CA2624864A1 - Coating compositions having improved adhesion, coated substrates and methods related thereto - Google Patents
Coating compositions having improved adhesion, coated substrates and methods related thereto Download PDFInfo
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- CA2624864A1 CA2624864A1 CA 2624864 CA2624864A CA2624864A1 CA 2624864 A1 CA2624864 A1 CA 2624864A1 CA 2624864 CA2624864 CA 2624864 CA 2624864 A CA2624864 A CA 2624864A CA 2624864 A1 CA2624864 A1 CA 2624864A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Abstract
Coating compositions are provided which include a polysiloxane comprising at least one reactive functional group, at least one material comprising at least one reactive functional group, and at least one boron-containing compound. Also provided are multi-layer composite coatings formed from a basecoat deposited from a pigmented coating composition and a topcoat applied over the basecoat, the topcoat deposited from the aforementioned coating composition.
Methods for repairing a multi-layer composite coating and coated substrates are also provided. The compositions of the invention provide highly scratch resistant coatings, particularly highly scratch resistant color-plus-clear coatings, which have excellent intercoat adhesion to subsequently applied coating layers.
Methods for repairing a multi-layer composite coating and coated substrates are also provided. The compositions of the invention provide highly scratch resistant coatings, particularly highly scratch resistant color-plus-clear coatings, which have excellent intercoat adhesion to subsequently applied coating layers.
Description
COATING COMPOSITIONS HAVING IMPROVED
lo ADHESION, COATED SUBSTRATES AND
METHODS RELATED THERETO
This application is a divisional application of co-pending application Serial No. 2,455,804, filed July 29, 2002.
FIELD OF THE INVENTION
Certain embodiments-of the present invention are directed to coating compositions comprising at least one reactive functional group-containing polysiloxane, at least one reactant comprising at least one functional group that is reactive with the functional group(s) of the polysiloxane, and at least one boron-containing compound selected from boric acid, boric acid equivalents and mixtures thereof. Other embodiments of the present invention are directed to cured coatings formed from the foregoing coating compositions. Further embodiments are directed to substrates coated with the aforementioned compositions.
BACKGROUND OF THE INVENTION
Color-plus-clearcoating systems involving the application of a colored or pigmented basecoat to a substrate followed by application of a transparent or clearcoat over the basecoat have become increasingly popular as original finishes for a number of consumer products including, for example, automotive vehicles. The color-plus-clearcoating systems have outstanding appearance properties such as gloss and distinctness of image, due in large part to the clearcoat. Such color-plus-clearcoating systems have become popular for use with automotive vehicles, aerospace applications, floor io coverings such as ceramic tiles and wood flooring, packaging coatings and the like.
Topcoat coating compositions, particularly those used to form the transparent clearcoat in color-plus-clear coating systems for automotive applications, are subject to defects that occur during the assembly process as well as damage from numerous environmental elements. Such defects during the assembly process include paint defects in the application or curing of the basecoat or the clearcoat. Damaging environmental elements include acidic precipitation, exposure to ultraviolet radiation from sunlight, high relative humidity and high temperatures, defects due to contact with objects causing scratching of the coated surface, and defects due to impact -with small, hard objects resulting in chipping of the coating surface.
Further, elastomeric automotive parts and accessories, for example, elastomeric bumpers and body side moldings, are typically coated "off site"
and shipped to automobile assembly plants. The coating compositions applied to such elastomeric substrates are typically formulated to be very flexible so the coating can bend or flex with the substrate without cracking.
To achieve the requisite flexibility, coating compositions for use on elastomeric substrates often are formulated to produce coatings with lower crosslink densities or to include flexibilizing adjuvants which act to lower the overall film glass transition temperature (Tg). While acceptable flexibility properties can be achieved with these formulating techniques, they also can result in softer films that are susceptible to scratching. Consequently, great expense and care must be taken to package the coated parts to prevent scratching of the coated surfaces during shipping to automobile assembly plants.
U.S. Patent No. 6,235,858 BI discloses carbamate and/or urea functional polymers for use in coating compositions, especially clear coating compositions for color-plus-clear coating systems. Such polymers provide coatings with good resistance to damage caused by acidic precipitation.
U.S. Patent No. 5,853,809 discloses clearcoats in color-plus-clear io systems which have improved scratch resistance due to the inclusion in the coating composition of inorganic particles such as colloidal silicas which have been surface modified with a reactive coupling agent via covalent bonding.
A number of patents disclose the use of a surface active material, for example, a polysiloxane, in coating compositions to improve mar resistance of the cured coatings. U.S. Patent Nos. 5,939,491 and 6,225,434B1 disclose coating compositions comprising organic polysiloxanes having reactive functional groups. These polysiloxanes provide coatings with improved mar and scratch resistance.
A number of patents disclose the use of boric acid in polymeric compositions. For example, U.S. Patent Nos. 5,951,747 and 6,059,867 discloses the use of boric acid and borates in conjunction with a succinate in non-chromate, corrosion-inhibiting coating compositions for improved adhesion to metallic surfaces. Such compositions further include inhibitors such as phosphates, phosphosilicates, silicates, titanates, and zinc salts.
U.S. Patent No. 4,832,990 discloses a process for improving adhesion of polyolefins to metal substrates comprising mechanical cleaning of the metal surface, treating the metal surface with a water-alcohol solution containing an alkoxysilane and boric acid, thermally treating the acid treated substrate;
and subsequently treating the substrate with a polyolefin-based composition comprising zeolites and carbon black pigment. U.S. Patent No..5,073,455 discloses a thermoplastic laminated film which has improved adhesion to hydrophilic polymers, hydrophobic polymers and inorganic substaiices. The film comprise a base film of thermoplastic resin and a layer formed on the base film comprising a composition of one or more of water-soluble resins, water emulsified resins and water-dispersible resins, and an organic boron polymer or a mixture composed of an organic boron polymer and vinyl alcohol.
Multi-layer composite coatings are commonplace in modern coating lines. For example, a typical automotive coating system can include the sequential application of an electrodeposition primer, a primer-surfacer, a io color enhancing base coat, and a transparent top coat. In some instances, the electrodeposition primer is applied over a mill-applied weldable, thermosetting coating which has been applied to the coiled steel metal substrate from which the automobile body (or body parts, such as fenders, doors and hoods) has been formed. Also, adhesive coatings, for example, windshield adhesives, trim and molding adhesives and structural adhesives are sometimes applied to the cured top coats where necessary. Due to these mufti-layer- composite coating processes, it is necessary that the previously applied coating layer have excellent intercoat or interlayer-adhesion to the subsequently applied ccatir,.- layer(s).
Although the aforementioned coating compositions exhibit improvements for acid etch resistance and mar and scratch resistance, such compositions may not be readily recoatable. That is, when a subsequent coating is applied to the cured mar and scratch resistant coating composition, the intercoat adhesion between the cured coating and the subsequently applied coating can be quite poor.
For example, as mentioned above, on most vehicle coating lines the vehicle body is first given a corrosion inhibitive electrodepositable prinier coating commonly formed from a cationic electrodepositable coating composition. This electrodeposition primer is fully cured and, a primer-surfacer is typically applied to the cured electrodeposition primer. The primer-surfacer serves to enhance chip resistance of subsequently applied top coatings as well as to ensure good appearance of the top coatings. The top coats, either a monocoat or a color-plus-clear system, are then applied to the cured primer-surfacer coating. While most top coats have excellent intercoat adhesion to the primer-surfacer coating, some top coating compositions inherently can exhibit intercoat adhesion problems with some primer-surfacer coatings.
Also, due to the interest in cost-savings, there is recent interest in the automotive coatings market in eliminating the primer-surfacer step altogether.
That is, the top coats can be directly applied to the cured electrodeposition io primer. In such modified coating processes, the electrodeposition primer is required to meet stringent durability and appearance specifications.
Moreover, the cured electrodepositable primer must have excellent intercoat adhesion to the subsequently applied top coats (either monocoats or color coats of a color-plus-clear system).
On commercial automobile coating lines during application of the coating system, certain portions of the line can experience occasional process problems, for example, clearcoat applicator malfunctions, or curing oven faults where temperatures are out of specffication. While the color coat typically is "flash cured" to drive off solvent, but not fully cure the coating, once the clear coating has been applied, the color-plus-clear coating system typically is given a full cure (e.g., 250 F for 20 minutes) to simultaneously cure both the base coat and the top coat. In instances where the clear coat application system is malfunctioning, the auto body with the applied color coat will continue through the clear coat applicator station and into the clear coat curing oven, thereby fully curing the color coat. If this occurs, some automobile manufacturers elect to reapply the color coat over the fully cured color coat prior to application of the clearcoat. In such situations, the fully cured color coat can have poor intercoat adhesion with the subsequently applied color coat, even though the compositions may be the same.
Also, windshields and other items such as trim moldings typically are affixed to the body of a vehicle with an adhesive material, typically a moisture-cured material containing isocyanate group-containing polymers. Motor Vehicle Safety Standards (MVSS) require that these adhesives have complete adhesion to both the windshield and the coated substrate to which they are applied.. Similar adhesive compositions can be used as structural adhesives as well. Such adhesives, for example, are commercially available from Essex Specialty Products, Inc. of Auburn Hills, Michigan. These adhesive products adhere well to many cured top coating compositions used to coat vehicles such as automobiles. It is known, however, that these adhesive materials often do not completely adhere to some top coats, for io example, those formed from coating compositions based on carbamate and/or urea containing polymers. This necessitates the application of a primer coating to the cured carbamate and/or urea-based top coatirigs prior to application of the windshield adhesive to ensure compliance with the aforementioned Motor Vehicle Safety Standards. Such primer coatings are typically based on moisture-curable polymers similar to those comprising the adhesive. Use of such primer coatings has proven to be effective, but primer coating application adds an additional and expensive step to the windshield or trim installation process.
Moreover, as discussed previously, during the assembly process, the applied color-plus-clear coating can include surface defects in the clear coat surface which requires repair. Some automobile manufacturers elect to remove the defect and recoat the repair area with the same clear coat composition. In this instance, the cured clear coat must have excellent intercoat adhesion to the subsequently applied clear coat. It is known, however, that some clear coats when cured have poor intercoat adhesion with the subsequently applied repair clear coat.
In view of the foregoing, there obviously remains a need in the coating industry for coating compositions which have improved properties such as acid etch resistance and mar and scratch resistance while maintaining 3o excellent intercoat or interlayer adhesion to subsequently applied coatings and/or adhesives.
lo ADHESION, COATED SUBSTRATES AND
METHODS RELATED THERETO
This application is a divisional application of co-pending application Serial No. 2,455,804, filed July 29, 2002.
FIELD OF THE INVENTION
Certain embodiments-of the present invention are directed to coating compositions comprising at least one reactive functional group-containing polysiloxane, at least one reactant comprising at least one functional group that is reactive with the functional group(s) of the polysiloxane, and at least one boron-containing compound selected from boric acid, boric acid equivalents and mixtures thereof. Other embodiments of the present invention are directed to cured coatings formed from the foregoing coating compositions. Further embodiments are directed to substrates coated with the aforementioned compositions.
BACKGROUND OF THE INVENTION
Color-plus-clearcoating systems involving the application of a colored or pigmented basecoat to a substrate followed by application of a transparent or clearcoat over the basecoat have become increasingly popular as original finishes for a number of consumer products including, for example, automotive vehicles. The color-plus-clearcoating systems have outstanding appearance properties such as gloss and distinctness of image, due in large part to the clearcoat. Such color-plus-clearcoating systems have become popular for use with automotive vehicles, aerospace applications, floor io coverings such as ceramic tiles and wood flooring, packaging coatings and the like.
Topcoat coating compositions, particularly those used to form the transparent clearcoat in color-plus-clear coating systems for automotive applications, are subject to defects that occur during the assembly process as well as damage from numerous environmental elements. Such defects during the assembly process include paint defects in the application or curing of the basecoat or the clearcoat. Damaging environmental elements include acidic precipitation, exposure to ultraviolet radiation from sunlight, high relative humidity and high temperatures, defects due to contact with objects causing scratching of the coated surface, and defects due to impact -with small, hard objects resulting in chipping of the coating surface.
Further, elastomeric automotive parts and accessories, for example, elastomeric bumpers and body side moldings, are typically coated "off site"
and shipped to automobile assembly plants. The coating compositions applied to such elastomeric substrates are typically formulated to be very flexible so the coating can bend or flex with the substrate without cracking.
To achieve the requisite flexibility, coating compositions for use on elastomeric substrates often are formulated to produce coatings with lower crosslink densities or to include flexibilizing adjuvants which act to lower the overall film glass transition temperature (Tg). While acceptable flexibility properties can be achieved with these formulating techniques, they also can result in softer films that are susceptible to scratching. Consequently, great expense and care must be taken to package the coated parts to prevent scratching of the coated surfaces during shipping to automobile assembly plants.
U.S. Patent No. 6,235,858 BI discloses carbamate and/or urea functional polymers for use in coating compositions, especially clear coating compositions for color-plus-clear coating systems. Such polymers provide coatings with good resistance to damage caused by acidic precipitation.
U.S. Patent No. 5,853,809 discloses clearcoats in color-plus-clear io systems which have improved scratch resistance due to the inclusion in the coating composition of inorganic particles such as colloidal silicas which have been surface modified with a reactive coupling agent via covalent bonding.
A number of patents disclose the use of a surface active material, for example, a polysiloxane, in coating compositions to improve mar resistance of the cured coatings. U.S. Patent Nos. 5,939,491 and 6,225,434B1 disclose coating compositions comprising organic polysiloxanes having reactive functional groups. These polysiloxanes provide coatings with improved mar and scratch resistance.
A number of patents disclose the use of boric acid in polymeric compositions. For example, U.S. Patent Nos. 5,951,747 and 6,059,867 discloses the use of boric acid and borates in conjunction with a succinate in non-chromate, corrosion-inhibiting coating compositions for improved adhesion to metallic surfaces. Such compositions further include inhibitors such as phosphates, phosphosilicates, silicates, titanates, and zinc salts.
U.S. Patent No. 4,832,990 discloses a process for improving adhesion of polyolefins to metal substrates comprising mechanical cleaning of the metal surface, treating the metal surface with a water-alcohol solution containing an alkoxysilane and boric acid, thermally treating the acid treated substrate;
and subsequently treating the substrate with a polyolefin-based composition comprising zeolites and carbon black pigment. U.S. Patent No..5,073,455 discloses a thermoplastic laminated film which has improved adhesion to hydrophilic polymers, hydrophobic polymers and inorganic substaiices. The film comprise a base film of thermoplastic resin and a layer formed on the base film comprising a composition of one or more of water-soluble resins, water emulsified resins and water-dispersible resins, and an organic boron polymer or a mixture composed of an organic boron polymer and vinyl alcohol.
Multi-layer composite coatings are commonplace in modern coating lines. For example, a typical automotive coating system can include the sequential application of an electrodeposition primer, a primer-surfacer, a io color enhancing base coat, and a transparent top coat. In some instances, the electrodeposition primer is applied over a mill-applied weldable, thermosetting coating which has been applied to the coiled steel metal substrate from which the automobile body (or body parts, such as fenders, doors and hoods) has been formed. Also, adhesive coatings, for example, windshield adhesives, trim and molding adhesives and structural adhesives are sometimes applied to the cured top coats where necessary. Due to these mufti-layer- composite coating processes, it is necessary that the previously applied coating layer have excellent intercoat or interlayer-adhesion to the subsequently applied ccatir,.- layer(s).
Although the aforementioned coating compositions exhibit improvements for acid etch resistance and mar and scratch resistance, such compositions may not be readily recoatable. That is, when a subsequent coating is applied to the cured mar and scratch resistant coating composition, the intercoat adhesion between the cured coating and the subsequently applied coating can be quite poor.
For example, as mentioned above, on most vehicle coating lines the vehicle body is first given a corrosion inhibitive electrodepositable prinier coating commonly formed from a cationic electrodepositable coating composition. This electrodeposition primer is fully cured and, a primer-surfacer is typically applied to the cured electrodeposition primer. The primer-surfacer serves to enhance chip resistance of subsequently applied top coatings as well as to ensure good appearance of the top coatings. The top coats, either a monocoat or a color-plus-clear system, are then applied to the cured primer-surfacer coating. While most top coats have excellent intercoat adhesion to the primer-surfacer coating, some top coating compositions inherently can exhibit intercoat adhesion problems with some primer-surfacer coatings.
Also, due to the interest in cost-savings, there is recent interest in the automotive coatings market in eliminating the primer-surfacer step altogether.
That is, the top coats can be directly applied to the cured electrodeposition io primer. In such modified coating processes, the electrodeposition primer is required to meet stringent durability and appearance specifications.
Moreover, the cured electrodepositable primer must have excellent intercoat adhesion to the subsequently applied top coats (either monocoats or color coats of a color-plus-clear system).
On commercial automobile coating lines during application of the coating system, certain portions of the line can experience occasional process problems, for example, clearcoat applicator malfunctions, or curing oven faults where temperatures are out of specffication. While the color coat typically is "flash cured" to drive off solvent, but not fully cure the coating, once the clear coating has been applied, the color-plus-clear coating system typically is given a full cure (e.g., 250 F for 20 minutes) to simultaneously cure both the base coat and the top coat. In instances where the clear coat application system is malfunctioning, the auto body with the applied color coat will continue through the clear coat applicator station and into the clear coat curing oven, thereby fully curing the color coat. If this occurs, some automobile manufacturers elect to reapply the color coat over the fully cured color coat prior to application of the clearcoat. In such situations, the fully cured color coat can have poor intercoat adhesion with the subsequently applied color coat, even though the compositions may be the same.
Also, windshields and other items such as trim moldings typically are affixed to the body of a vehicle with an adhesive material, typically a moisture-cured material containing isocyanate group-containing polymers. Motor Vehicle Safety Standards (MVSS) require that these adhesives have complete adhesion to both the windshield and the coated substrate to which they are applied.. Similar adhesive compositions can be used as structural adhesives as well. Such adhesives, for example, are commercially available from Essex Specialty Products, Inc. of Auburn Hills, Michigan. These adhesive products adhere well to many cured top coating compositions used to coat vehicles such as automobiles. It is known, however, that these adhesive materials often do not completely adhere to some top coats, for io example, those formed from coating compositions based on carbamate and/or urea containing polymers. This necessitates the application of a primer coating to the cured carbamate and/or urea-based top coatirigs prior to application of the windshield adhesive to ensure compliance with the aforementioned Motor Vehicle Safety Standards. Such primer coatings are typically based on moisture-curable polymers similar to those comprising the adhesive. Use of such primer coatings has proven to be effective, but primer coating application adds an additional and expensive step to the windshield or trim installation process.
Moreover, as discussed previously, during the assembly process, the applied color-plus-clear coating can include surface defects in the clear coat surface which requires repair. Some automobile manufacturers elect to remove the defect and recoat the repair area with the same clear coat composition. In this instance, the cured clear coat must have excellent intercoat adhesion to the subsequently applied clear coat. It is known, however, that some clear coats when cured have poor intercoat adhesion with the subsequently applied repair clear coat.
In view of the foregoing, there obviously remains a need in the coating industry for coating compositions which have improved properties such as acid etch resistance and mar and scratch resistance while maintaining 3o excellent intercoat or interlayer adhesion to subsequently applied coatings and/or adhesives.
SUMMARY OF THE INVENTION
In one embodiment a coating composition formed from components comprising (a) at least one polysitoxane comprising at least one reactive functional group, the polysiloxane comprising a polymer of at least one of the following structural units (I):
(1) R',R2mSIO(4 n m)r wherein each R1, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, io which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of O<n<4, O<m<4 and 25(m+n)<4; (b) at least one reactant comprising at least one functional group that is reactive with the reactive functional -group of the polysiloxane (a); and (c) at least one compound selected from borates, is aluminates, titanates, zirconates, silicates, siloxanes, silanes and mixtures thereof, wherein each component is different.
In one embodiment, the present invention provides a coating composition formed from components comprising (a) at least one polysiloxane comprising at least one reactive functional group, the 20 polysiloxane comprising at least one of the structural units (!) as described above, wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 25 O<n<4, O<m<4 and 2<(m+n)<4; (b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one boron-containing compound selected from boric acid, boric acid equivalents and mixtures thereof, wherein each component is different.
30 In another embodiment, the present invention provides a coating composition formed from components comprising (a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the structural units (I), wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group, wherein m and n fulfill the requirements of O<n<4, O<m<4 and 2s(m+n)<4; (b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional group of the polysiloxane (a), the io curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin; (c) at least one boron-containing compound selected from boric acid, boric acid equivalents; and mixtures thereof; and (d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof, wherein each component is different.
The present invention also provides a coating composition formed from components cornprising (a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the structural uni s (f), wherein each R', which may be identical or different, 2o represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group, and a carbamate group, wherein m and n fulfill the requirements of O<n<4, O<m<4 and 2:5(m+n)<4; (b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional. group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;
(c) at least one boron-containing compound selected from boric acid and organic derivatives thereof; (d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof; and (e) at least one film-forming polymer selected from polyether polymers, polyester polymers, acrylic polymers and polyurethane polymers, said film-forming polymer having functional groups reactive with the functional groups of (a) and/or (b), wherein each component is different.
A further embodiment of the present invention provides a coating composition formed from components comprising (a) at least one polysiloxane having the following structure (11) or (111):
(!!) R R R R
- II !
lo R - Si - O - (-Si-O-)j -(Si -O)k -Si - R
I I I I
R R Ra R
or (I11) R R R R
I I I I
R-Si-O-(-Si-O-)j'-(Si-O)k'-Si-R
I I I I
Ra R Ra Ra wherein k has a value of at least 1; k' ranges from 0 to 75; j ranges from 0 to 5; j' ranges from 0 to 75; each R, which may be identical or different, is selected from H, OH, monovalent hydrocarbon groups, monovalent siloxane groups, and mixtures of any of the foregoing; and Ra comprises the following structure (IV):
(!V) -R3-X
wherein -R3 is selected from an alkylene group, an oxyalkylene group, an alkylene aryl group, an alkenylene group, an oxyalkenylene group, and an 3o alkenylene aryl group; and X represents a group which comprises at least one reactive functional group selected from a hydroxyl group and a carbarnate group; (b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the at least one functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin; (c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof; (d) a plurality of inorganic particles selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the foregoing, and mixtures thereof;
s and (e) at least one film-forming acrylic polymer having reactive functional groups selected from hydroxyl groups and carbamate groups, wherein each component is different.
Additionally, multi-component composite coatings formed from a basecoat deposited from a film-forming base coating composition and a top io coat which is applied over at least a portion of the basecoat and which is formed from any of the foregoing coating compositions is provided.
Another aspect of the present invention is a method of repairing a multi-layer composite coating comprising a base coat formed on a substrate from a film-forming base coating composition and a first top coat deposited 15 over at least a portion of the base coat, the first top coat formed from a first film-forming top coating composition comprising any of the foregoing coating compositions, the method comprising: locating an area of the composite =
coating which is flawed, applying a repair top coat film-forming composition to the flawed area after the flawed area has been prepared for repairing, 20 wherein the repair top coat film-forming composition comprises a film-forming composition which is the same or different from the first top coat film-forming composition.
Coated substrates comprising a substrate and having any of the foregoing coating compositions coated over at ieast a portion of the substrate 25 also are provided by the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions and so forth 30 used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of s equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set io forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Also, it should be understood that any numerical range recited as herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than I and a maximum value of equal to or less than 10.
20 As mentioned above, in one embodiment, the present invention is directed to a coating composition formed from components comprising (a) at least one polysiloxane comprising at least one reactive functional group, the ' polysiloxane comprising at least one of the following structural units (I):
(1) R1,R2mSIO(4.n-m)M
25 wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of O<n<4, 0<m<4 and 25(m+n)<4; (b) at least one reactant comprising at least 30 one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one compound selected from borates, aluminates, titanates, zirconates, silicates, siloxanes, silanes and mixtures thereof, wherein each component is different. Typically, the at least one compound (c) is selected from at least one of a borate and an alurriinate.
Examples of suitable borates are those discussed in detail below. Examples of titanates suitable for use in the compositions of the present invention include titanium isopropoxide, isopropyl triostearoyl titanate, dicyclo(dioct)pyrophosphato titanate, tetraisopropyl di(dioctyl)phosphito titanate. Suitable aluminates include aluminum alkoxides such as aluminum isoproxide, which is typically employed, and aluminum acetylacetonate, io Exemplary of a suitable silicate is tetraethyl orthosilicate. Suitable siloxanes include tetraisopropyidisiloxanes and tetramethylsiloxane. Suitable silanes include tetramethyl silyl ethers.
In one embodiment of the present invention, a polysiloxane (a) comprising one or more hydroxyl functional groups is reacted with an is aluminum alkoxide such as aluminum triisopropoxide.
In one embodiment, the present invention provides a coating composition forrried irom components comprising:(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of thie following structural uni~5 (1):
20 (I) . R1,R2mSIO(4-n-m)12 wherein each R1, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 25 0<n<4, 0<m<4 and 2:5(m+n)<4; (b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one boron-containing compound selected from boric acid, boric acid equivalents, organic derivatives thereof, and mixtures thereof, wherein each component is different.
30 The at least one boron-containing compound (c) can be selected from boric acid, boric acid equivaients, organic derivatives thereof, and mixtures thereof. As used herein, in the specification and in the claims, by "boric acid equivalents" is meant any of the humerous boron-containing compounds which can hydrolyze in aqueous media to form boric acid. Specific, but non-limiting examples of boric acid equivalents include boron oxides, for example, s B203; boric acid esters such as those obtained by the reaction of boric acid with an alcohol or phenol.
Suitable boron-containing compounds include those selected from boric acid, boric acid equivalents, and mixtures thereof. As used herein and in the claims, by "boric acid equivalents" is meant any of the io numerous boron-containing compounds which can hydrolyze in aqueous media to form boric acid. Specific, but non-limiting examples of boric acid equivalents include boron oxides, for example, B203; boric acid esters such as those obtained by the reaction of boric acid with an alcohol or phenol, for example, trimethyl borate, triethyi borate, tri-n-propyl borate, 15 tri-n-butyl borate, triphenyl borate, triisopropyl borate, tri-t-amyl borate, tri-2-cyclohexylcyclohexyl borate, triethanolamine borate, triisopropyfamine borate, and triisopropanolamine borate.
- Additionally, other amino-containing borates and tertiary amine salts of boric acid may be useful. Such boron-containing compounds 20 include, but are not limited to, 2-(beta-dimethylaminoisopropoxy)-4,5-dimethyl-1,3,2-dioxaborolane, 2-(beta-diethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborinane, 2-(beta-dimethylaminoethoxy)-4,4,6 trimethyl-1,3,2-dioxaborinane, 2-(betha-diisopropylaminoethoxy-1,3,2-dioxaborinane, 2-(beta-dibutylaminoethoxy)-4-methyl-1,3,2-dioxaborinane, 2-(gamma-25 dimethylaminopropoxy)-1,3,6,9-tetrapxa-2-boracycloundecane, and 2-(beta-d imethylaminoethoxy)-4,4-(4-hydorxybutyl)-1, 3,2-dioxaborotane.
Boric acid equivalents can also include metal salts of boric acid (i.e., metal borates) provided that such metal borates can readily dissociate in aqueous media to form boric acid.. Suitable examples of 30 metal borates include, for example, calcium borate, potassium borates such as potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate, sodium borates such as sodium perborate, sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium perborate, sodium hexaborate, and sodium octaborate, Likewise, ammonium borates can be useful.
Suitable boric acid equivalents can also include organic oligomeric and polymeric compounds comprising boron-containing moieties. Suitable examples include polymeric borate esters, such as those formed by reacting an active hydrogen-containing polymer, for example, a hydroxyl functional io group-containing acrylic polymer or polysiloxane polymer, with boric acid and/or a borate ester to form a polymer having borate ester groups.
Polymers suitable for this purpose can include any of a variety of active hydrogen-containing polymers such as those selected from at least one of acrylic polymers, polyester polymers, polyurethane polymers, polyether polymers and silicon-based polymers. By "silicon-based polymers" is meant a polymer comprising one or more -SiO- units in the backbone. Such silicon-based polymers can include hybrid polymers, such as those ccrnprisiiiy organic polymeric blocks with one or more -SiO- units in the backbone.
Examples of active hydrogen-containing pc'ymers suitablti for 20 purpose include polymers comprising functional groups selected from at least one of a hydroxyl group, an amine group, an epoxy group, a carbamate group, a urea group, and a carboxylic acid group. In a particular embodiment of the present invention, the boron-containing compound is formed by reacting boric acid and/or a borate ester with at least one polymer selected from an acrylic polyol, a polyester polyol, a polyurethane polyol, a polyether polyol, a polysiloxane polyol and mixtures thereof.
In one embodiment of the present invention, the boron-containing compound (c) comprises a polysiloxane borate ester formed from the following reactants: (A) at least one polysiloxane comprising at least one of the following structural units (I):
(I) R%R2mSiO(4_n.fiY2 wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical -or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of s O<n<4, O<m<4 and 2<(m+n)<4; and (B) at least one boron-containing compound selected from at least one of boric acid, a boric acid equivalent, and mixtures thereof.
It should be understood that the "at least one polysiloxane corriprising at least one structural unit (I)" above is a polymer that contains at least two Si io atoms per molecule. As used herein, the term "polymer" is meant to encompass oligomer, and includes without limitation both homopolymers and copolymers. It should also be understood that the at least one polysiloxane can include linear, branched, dendritic or cyclic polysiloxanes.
Moreover, as used herein, "formed from" denotes open, e.g., 15 "comprising," claim language. As such, it is intended that a composition "formed from" a list of recited components be a composition comprising at least these recited components, and can further comprise other, nonrecited components, during the composition's formation.
Also, as used herein, the term "reactive" refers to a functional group 20 that forms a covalent bond with another functional group under conditions sufficient to cure the composition.
As used herein, the phrase "each component is different" refers to components which do not have the same chemical structure as other components in the composition.
25 Each of m and n depicted in the at least one structural unit (1) above fulfill the requirements of O<n<4, O<m<4 and 2<(m+n)<4. When (m+n) is 3, the value represented by n can be 2 and the value represented by m is 1.
Likewise, when (m+n) is 2, the value represented by each of n and m is 1.
As used herein, the term "cure" as used in connection with a 30 composition, e.g., "composition when cured," shall mean that any crosslinkable components of the composition are at least partially crosslinked.
In certain embodiments of the present invention, the crosslink density of the crosslinkable components, i.e., the degree of crosslinking, ranges from 5% to 100% of complete crosslinking. In other embodiments, the crosslirik density ranges from 35% to 85% of full crosslinking. In other embodiments., the crosslink density ranges from 50% to 85% of full crosslinking. One skilled in the art will understand that the presence and degree of crosslinking, i.e., the crosslink density, can be determined by a variety of methods, such as dynamic mechanical thermal analysis (DMTA) using a TA Instruments DMA
2980 DMTA analyzer conducted under nitrogen. This method determines the io glass transition temperature and crosslink density of free films of coatings or polymers. These physical properties of a cured material are related to the structure of the crosslinked network.
As used herein, a "monovalent hydrocarbon group" means a monovalent group having a backbone repeat unit based exclusively on carbon. As used herein, "monovalent" refers to a substituent group that, as a substituent group, forms only one single, covalent bond. For example, a monovalent group on the at least one FolysPotcane vvi'i forni o,~.c covalent bond to a silicon atom in the backbone of the at least one polysiloxane polymer. As used herein, "hydrocarbon grou~s" are intendnd, to encompass both branched and unbranched hydrocarbon groups.
Thus, when referring to a "monovalent hydrocarbon group," the hydrocarbon group can be branched or unbranched, acyciic or cyciic, saturated or unsaturated, or aromatic, and can contain from I to 24 (or in the case of an aromatic group from 3 to 24) carbon atoms. Nonlimiting examples of such hydrocarbon groups include alkyl, alkoxy, aryl, alkaryl, and alkoxyaryl groups. Nonlimiting examples of lower alkyl groups include, for example, methyl, ethyl, propyl, and butyl groups. As used herein, "lower alkyl" refers to alkyl groups having from 1 to 6 carbon atoms. One or more of the hydrogen atoms of the hydrocarbon can be substituted with heteroatoms. As used 3o herein, "heteroatoms" means elements other than carbon, for example, oxygen, nitrogen, and halogen atoms.
In one embodiment a coating composition formed from components comprising (a) at least one polysitoxane comprising at least one reactive functional group, the polysiloxane comprising a polymer of at least one of the following structural units (I):
(1) R',R2mSIO(4 n m)r wherein each R1, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, io which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of O<n<4, O<m<4 and 25(m+n)<4; (b) at least one reactant comprising at least one functional group that is reactive with the reactive functional -group of the polysiloxane (a); and (c) at least one compound selected from borates, is aluminates, titanates, zirconates, silicates, siloxanes, silanes and mixtures thereof, wherein each component is different.
In one embodiment, the present invention provides a coating composition formed from components comprising (a) at least one polysiloxane comprising at least one reactive functional group, the 20 polysiloxane comprising at least one of the structural units (!) as described above, wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 25 O<n<4, O<m<4 and 2<(m+n)<4; (b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one boron-containing compound selected from boric acid, boric acid equivalents and mixtures thereof, wherein each component is different.
30 In another embodiment, the present invention provides a coating composition formed from components comprising (a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the structural units (I), wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group, wherein m and n fulfill the requirements of O<n<4, O<m<4 and 2s(m+n)<4; (b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional group of the polysiloxane (a), the io curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin; (c) at least one boron-containing compound selected from boric acid, boric acid equivalents; and mixtures thereof; and (d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof, wherein each component is different.
The present invention also provides a coating composition formed from components cornprising (a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the structural uni s (f), wherein each R', which may be identical or different, 2o represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group, and a carbamate group, wherein m and n fulfill the requirements of O<n<4, O<m<4 and 2:5(m+n)<4; (b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional. group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;
(c) at least one boron-containing compound selected from boric acid and organic derivatives thereof; (d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof; and (e) at least one film-forming polymer selected from polyether polymers, polyester polymers, acrylic polymers and polyurethane polymers, said film-forming polymer having functional groups reactive with the functional groups of (a) and/or (b), wherein each component is different.
A further embodiment of the present invention provides a coating composition formed from components comprising (a) at least one polysiloxane having the following structure (11) or (111):
(!!) R R R R
- II !
lo R - Si - O - (-Si-O-)j -(Si -O)k -Si - R
I I I I
R R Ra R
or (I11) R R R R
I I I I
R-Si-O-(-Si-O-)j'-(Si-O)k'-Si-R
I I I I
Ra R Ra Ra wherein k has a value of at least 1; k' ranges from 0 to 75; j ranges from 0 to 5; j' ranges from 0 to 75; each R, which may be identical or different, is selected from H, OH, monovalent hydrocarbon groups, monovalent siloxane groups, and mixtures of any of the foregoing; and Ra comprises the following structure (IV):
(!V) -R3-X
wherein -R3 is selected from an alkylene group, an oxyalkylene group, an alkylene aryl group, an alkenylene group, an oxyalkenylene group, and an 3o alkenylene aryl group; and X represents a group which comprises at least one reactive functional group selected from a hydroxyl group and a carbarnate group; (b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the at least one functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin; (c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof; (d) a plurality of inorganic particles selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the foregoing, and mixtures thereof;
s and (e) at least one film-forming acrylic polymer having reactive functional groups selected from hydroxyl groups and carbamate groups, wherein each component is different.
Additionally, multi-component composite coatings formed from a basecoat deposited from a film-forming base coating composition and a top io coat which is applied over at least a portion of the basecoat and which is formed from any of the foregoing coating compositions is provided.
Another aspect of the present invention is a method of repairing a multi-layer composite coating comprising a base coat formed on a substrate from a film-forming base coating composition and a first top coat deposited 15 over at least a portion of the base coat, the first top coat formed from a first film-forming top coating composition comprising any of the foregoing coating compositions, the method comprising: locating an area of the composite =
coating which is flawed, applying a repair top coat film-forming composition to the flawed area after the flawed area has been prepared for repairing, 20 wherein the repair top coat film-forming composition comprises a film-forming composition which is the same or different from the first top coat film-forming composition.
Coated substrates comprising a substrate and having any of the foregoing coating compositions coated over at ieast a portion of the substrate 25 also are provided by the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions and so forth 30 used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of s equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set io forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Also, it should be understood that any numerical range recited as herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than I and a maximum value of equal to or less than 10.
20 As mentioned above, in one embodiment, the present invention is directed to a coating composition formed from components comprising (a) at least one polysiloxane comprising at least one reactive functional group, the ' polysiloxane comprising at least one of the following structural units (I):
(1) R1,R2mSIO(4.n-m)M
25 wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of O<n<4, 0<m<4 and 25(m+n)<4; (b) at least one reactant comprising at least 30 one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one compound selected from borates, aluminates, titanates, zirconates, silicates, siloxanes, silanes and mixtures thereof, wherein each component is different. Typically, the at least one compound (c) is selected from at least one of a borate and an alurriinate.
Examples of suitable borates are those discussed in detail below. Examples of titanates suitable for use in the compositions of the present invention include titanium isopropoxide, isopropyl triostearoyl titanate, dicyclo(dioct)pyrophosphato titanate, tetraisopropyl di(dioctyl)phosphito titanate. Suitable aluminates include aluminum alkoxides such as aluminum isoproxide, which is typically employed, and aluminum acetylacetonate, io Exemplary of a suitable silicate is tetraethyl orthosilicate. Suitable siloxanes include tetraisopropyidisiloxanes and tetramethylsiloxane. Suitable silanes include tetramethyl silyl ethers.
In one embodiment of the present invention, a polysiloxane (a) comprising one or more hydroxyl functional groups is reacted with an is aluminum alkoxide such as aluminum triisopropoxide.
In one embodiment, the present invention provides a coating composition forrried irom components comprising:(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of thie following structural uni~5 (1):
20 (I) . R1,R2mSIO(4-n-m)12 wherein each R1, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 25 0<n<4, 0<m<4 and 2:5(m+n)<4; (b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one boron-containing compound selected from boric acid, boric acid equivalents, organic derivatives thereof, and mixtures thereof, wherein each component is different.
30 The at least one boron-containing compound (c) can be selected from boric acid, boric acid equivaients, organic derivatives thereof, and mixtures thereof. As used herein, in the specification and in the claims, by "boric acid equivalents" is meant any of the humerous boron-containing compounds which can hydrolyze in aqueous media to form boric acid. Specific, but non-limiting examples of boric acid equivalents include boron oxides, for example, s B203; boric acid esters such as those obtained by the reaction of boric acid with an alcohol or phenol.
Suitable boron-containing compounds include those selected from boric acid, boric acid equivalents, and mixtures thereof. As used herein and in the claims, by "boric acid equivalents" is meant any of the io numerous boron-containing compounds which can hydrolyze in aqueous media to form boric acid. Specific, but non-limiting examples of boric acid equivalents include boron oxides, for example, B203; boric acid esters such as those obtained by the reaction of boric acid with an alcohol or phenol, for example, trimethyl borate, triethyi borate, tri-n-propyl borate, 15 tri-n-butyl borate, triphenyl borate, triisopropyl borate, tri-t-amyl borate, tri-2-cyclohexylcyclohexyl borate, triethanolamine borate, triisopropyfamine borate, and triisopropanolamine borate.
- Additionally, other amino-containing borates and tertiary amine salts of boric acid may be useful. Such boron-containing compounds 20 include, but are not limited to, 2-(beta-dimethylaminoisopropoxy)-4,5-dimethyl-1,3,2-dioxaborolane, 2-(beta-diethylaminoethoxy)-4,4,6-trimethyl-1,3,2-dioxaborinane, 2-(beta-dimethylaminoethoxy)-4,4,6 trimethyl-1,3,2-dioxaborinane, 2-(betha-diisopropylaminoethoxy-1,3,2-dioxaborinane, 2-(beta-dibutylaminoethoxy)-4-methyl-1,3,2-dioxaborinane, 2-(gamma-25 dimethylaminopropoxy)-1,3,6,9-tetrapxa-2-boracycloundecane, and 2-(beta-d imethylaminoethoxy)-4,4-(4-hydorxybutyl)-1, 3,2-dioxaborotane.
Boric acid equivalents can also include metal salts of boric acid (i.e., metal borates) provided that such metal borates can readily dissociate in aqueous media to form boric acid.. Suitable examples of 30 metal borates include, for example, calcium borate, potassium borates such as potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate, sodium borates such as sodium perborate, sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium perborate, sodium hexaborate, and sodium octaborate, Likewise, ammonium borates can be useful.
Suitable boric acid equivalents can also include organic oligomeric and polymeric compounds comprising boron-containing moieties. Suitable examples include polymeric borate esters, such as those formed by reacting an active hydrogen-containing polymer, for example, a hydroxyl functional io group-containing acrylic polymer or polysiloxane polymer, with boric acid and/or a borate ester to form a polymer having borate ester groups.
Polymers suitable for this purpose can include any of a variety of active hydrogen-containing polymers such as those selected from at least one of acrylic polymers, polyester polymers, polyurethane polymers, polyether polymers and silicon-based polymers. By "silicon-based polymers" is meant a polymer comprising one or more -SiO- units in the backbone. Such silicon-based polymers can include hybrid polymers, such as those ccrnprisiiiy organic polymeric blocks with one or more -SiO- units in the backbone.
Examples of active hydrogen-containing pc'ymers suitablti for 20 purpose include polymers comprising functional groups selected from at least one of a hydroxyl group, an amine group, an epoxy group, a carbamate group, a urea group, and a carboxylic acid group. In a particular embodiment of the present invention, the boron-containing compound is formed by reacting boric acid and/or a borate ester with at least one polymer selected from an acrylic polyol, a polyester polyol, a polyurethane polyol, a polyether polyol, a polysiloxane polyol and mixtures thereof.
In one embodiment of the present invention, the boron-containing compound (c) comprises a polysiloxane borate ester formed from the following reactants: (A) at least one polysiloxane comprising at least one of the following structural units (I):
(I) R%R2mSiO(4_n.fiY2 wherein each R', which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical -or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of s O<n<4, O<m<4 and 2<(m+n)<4; and (B) at least one boron-containing compound selected from at least one of boric acid, a boric acid equivalent, and mixtures thereof.
It should be understood that the "at least one polysiloxane corriprising at least one structural unit (I)" above is a polymer that contains at least two Si io atoms per molecule. As used herein, the term "polymer" is meant to encompass oligomer, and includes without limitation both homopolymers and copolymers. It should also be understood that the at least one polysiloxane can include linear, branched, dendritic or cyclic polysiloxanes.
Moreover, as used herein, "formed from" denotes open, e.g., 15 "comprising," claim language. As such, it is intended that a composition "formed from" a list of recited components be a composition comprising at least these recited components, and can further comprise other, nonrecited components, during the composition's formation.
Also, as used herein, the term "reactive" refers to a functional group 20 that forms a covalent bond with another functional group under conditions sufficient to cure the composition.
As used herein, the phrase "each component is different" refers to components which do not have the same chemical structure as other components in the composition.
25 Each of m and n depicted in the at least one structural unit (1) above fulfill the requirements of O<n<4, O<m<4 and 2<(m+n)<4. When (m+n) is 3, the value represented by n can be 2 and the value represented by m is 1.
Likewise, when (m+n) is 2, the value represented by each of n and m is 1.
As used herein, the term "cure" as used in connection with a 30 composition, e.g., "composition when cured," shall mean that any crosslinkable components of the composition are at least partially crosslinked.
In certain embodiments of the present invention, the crosslink density of the crosslinkable components, i.e., the degree of crosslinking, ranges from 5% to 100% of complete crosslinking. In other embodiments, the crosslirik density ranges from 35% to 85% of full crosslinking. In other embodiments., the crosslink density ranges from 50% to 85% of full crosslinking. One skilled in the art will understand that the presence and degree of crosslinking, i.e., the crosslink density, can be determined by a variety of methods, such as dynamic mechanical thermal analysis (DMTA) using a TA Instruments DMA
2980 DMTA analyzer conducted under nitrogen. This method determines the io glass transition temperature and crosslink density of free films of coatings or polymers. These physical properties of a cured material are related to the structure of the crosslinked network.
As used herein, a "monovalent hydrocarbon group" means a monovalent group having a backbone repeat unit based exclusively on carbon. As used herein, "monovalent" refers to a substituent group that, as a substituent group, forms only one single, covalent bond. For example, a monovalent group on the at least one FolysPotcane vvi'i forni o,~.c covalent bond to a silicon atom in the backbone of the at least one polysiloxane polymer. As used herein, "hydrocarbon grou~s" are intendnd, to encompass both branched and unbranched hydrocarbon groups.
Thus, when referring to a "monovalent hydrocarbon group," the hydrocarbon group can be branched or unbranched, acyciic or cyciic, saturated or unsaturated, or aromatic, and can contain from I to 24 (or in the case of an aromatic group from 3 to 24) carbon atoms. Nonlimiting examples of such hydrocarbon groups include alkyl, alkoxy, aryl, alkaryl, and alkoxyaryl groups. Nonlimiting examples of lower alkyl groups include, for example, methyl, ethyl, propyl, and butyl groups. As used herein, "lower alkyl" refers to alkyl groups having from 1 to 6 carbon atoms. One or more of the hydrogen atoms of the hydrocarbon can be substituted with heteroatoms. As used 3o herein, "heteroatoms" means elements other than carbon, for example, oxygen, nitrogen, and halogen atoms.
As-used herein, "siloxane" means a group comprising a backbone comprising two or more -SiO- groups. For example, the siloxane groups represented by R', which is discussed above, and R, which is discussed below, can be branched or unbranched, and linear or cyclic. The siloxane groups can be substituted with pendant organic substituent groups, for example, alkyl, aryl, and alkaryl groups. The organic substituent groups can be substituted with heteroatoms, for example, oxygen, nitrogen, and halogen atoms, reactive functional groups, for example, those reactive functional groups discussed above with reference to R2, and mixtures of any of the io foregoing.
In one embodiment, the present invention is directed to any composition as previously described, wherein the at least one polysiloxane (A), which is used to form the polysiloxane borate ester, comprises at least two reactive functional groups. The at least one polysiloxane can have a reactive group equivalent weight ranging from 50 to1000 mg per gram of the at least one polysiloxane. In one embodiment, the at least one polysiloxane has a hydroxyl group equivalent weight ranging from 50 to 1000 mg k:OH per gram of the at least one polysiloxane. In another embodiment, the at least one polysiloxane has a hydroxyl group equivalent weight ranging frorY1100 to 300 mg KOH per gram of the at least one polysiloxane, while in another embodiment, the hydroxyl group equivalent weight ranges from 100 to 500 mg KOH per gram.
In another embodiment, the present invention is directed to any compositions as described above, wherein R2 (see structural unit I above), which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group such as an acrylate group and a methacrylate group, a maleimide group, a fumarate group, an onium salt group such as a sulfonium group and an amrrionium group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
In another embodiment, the present invention is directed to any composition as previously described, wherein at least one RZ group represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group. In yet another embodiment, the present invention is directed to any composition as previously described, wherein at least one R2 group represents a group comprising at least two reactive functional groups selected from a hydroxyl group and a carbamate to group. In another embodiment, the present invention is directed to any composition as previously described, wherein at least one R2 group represents a group comprising an oxyalkylene group and at least two hydroxyl groups.
In one embodiment, the present invention is directed to any composition as previously described, wherein the at least one poiysiloxane (A), which is used to form the polysiloxane borate ester, has the following structure (1)) or (111):
(11) R R R P.
! ! 1 R-Si-O-(-Si-O-), - (Si -O)k -Si- R
R R Re R
or (11{) R R R R
I I I I
R-Si-O-(-Si-O-)j'-(Si-O)k'-Si-R
~ ! ! !
Ra R Ra Re wherein: k has a value of at least 1; k' ranges from 0 to 75; j ranges from 0 to 75; j' ranges from 0 to 75; each R, which may be identical or different, is selected from H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and mixtures of any of the foregoing; and -Ra comprises the following structure (IV):
(IV) -R3-X
wherein - R3 is selected from an atkylene group, an oxyalkylene group, an s alkylene aryl group, an alkenylene group, an oxyalkenylene group, and an alkenylene aryl group; and X represents a group which comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a io urethane group, a vinyl group, an unsaturated ester group such as an acrylate group and a methacrylate group, a maleimide group, a fumarate group, an onium salt group such as a sulfonium group and an ammonium group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
In one embodiment of the present invention, X represents a group is which comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
As used herein, "alkylene" refers to an acyclic or cyclic, saturated 2o hydrocarbon group having a carbon chain length of from C2 to C25.
Nonlimiting examples of suitable alkylene groups include, but are not limited to, those derived from propenyl, 1-butenyl, 1 -pentenyl, 1 -decenyl, and 1-heneicosenyl, such as, for example (CH2)36 (CH2)4, (CH2)5, (CH2),o, and (CHz)23, respectively, as well as isoprene and myrcene.
25 As used herein, "oxyalkylene" refers to an alkylene group containing at least one oxygen atom bonded to, and interposed between, two carbori atoms and having an alkylene carbon chain length of from C2 to C25.
Nonlimiting examples of suitable oxyalkylene groups include those derived from trimethyfolpropane monoallyl ether,- trimethylolpropane diallyl ether, 30 pentaerythritol monoallyl ether, polyethoxylated allyl alcohol, and polypropoxylated allyl alcohol, such as -(CH2)30CH2C(CH2QH)2(CH2CH2-).
In one embodiment, the present invention is directed to any composition as previously described, wherein the at least one polysiloxane (A), which is used to form the polysiloxane borate ester, comprises at least two reactive functional groups. The at least one polysiloxane can have a reactive group equivalent weight ranging from 50 to1000 mg per gram of the at least one polysiloxane. In one embodiment, the at least one polysiloxane has a hydroxyl group equivalent weight ranging from 50 to 1000 mg k:OH per gram of the at least one polysiloxane. In another embodiment, the at least one polysiloxane has a hydroxyl group equivalent weight ranging frorY1100 to 300 mg KOH per gram of the at least one polysiloxane, while in another embodiment, the hydroxyl group equivalent weight ranges from 100 to 500 mg KOH per gram.
In another embodiment, the present invention is directed to any compositions as described above, wherein R2 (see structural unit I above), which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group such as an acrylate group and a methacrylate group, a maleimide group, a fumarate group, an onium salt group such as a sulfonium group and an amrrionium group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
In another embodiment, the present invention is directed to any composition as previously described, wherein at least one RZ group represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group. In yet another embodiment, the present invention is directed to any composition as previously described, wherein at least one R2 group represents a group comprising at least two reactive functional groups selected from a hydroxyl group and a carbamate to group. In another embodiment, the present invention is directed to any composition as previously described, wherein at least one R2 group represents a group comprising an oxyalkylene group and at least two hydroxyl groups.
In one embodiment, the present invention is directed to any composition as previously described, wherein the at least one poiysiloxane (A), which is used to form the polysiloxane borate ester, has the following structure (1)) or (111):
(11) R R R P.
! ! 1 R-Si-O-(-Si-O-), - (Si -O)k -Si- R
R R Re R
or (11{) R R R R
I I I I
R-Si-O-(-Si-O-)j'-(Si-O)k'-Si-R
~ ! ! !
Ra R Ra Re wherein: k has a value of at least 1; k' ranges from 0 to 75; j ranges from 0 to 75; j' ranges from 0 to 75; each R, which may be identical or different, is selected from H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and mixtures of any of the foregoing; and -Ra comprises the following structure (IV):
(IV) -R3-X
wherein - R3 is selected from an atkylene group, an oxyalkylene group, an s alkylene aryl group, an alkenylene group, an oxyalkenylene group, and an alkenylene aryl group; and X represents a group which comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a io urethane group, a vinyl group, an unsaturated ester group such as an acrylate group and a methacrylate group, a maleimide group, a fumarate group, an onium salt group such as a sulfonium group and an ammonium group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
In one embodiment of the present invention, X represents a group is which comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
As used herein, "alkylene" refers to an acyclic or cyclic, saturated 2o hydrocarbon group having a carbon chain length of from C2 to C25.
Nonlimiting examples of suitable alkylene groups include, but are not limited to, those derived from propenyl, 1-butenyl, 1 -pentenyl, 1 -decenyl, and 1-heneicosenyl, such as, for example (CH2)36 (CH2)4, (CH2)5, (CH2),o, and (CHz)23, respectively, as well as isoprene and myrcene.
25 As used herein, "oxyalkylene" refers to an alkylene group containing at least one oxygen atom bonded to, and interposed between, two carbori atoms and having an alkylene carbon chain length of from C2 to C25.
Nonlimiting examples of suitable oxyalkylene groups include those derived from trimethyfolpropane monoallyl ether,- trimethylolpropane diallyl ether, 30 pentaerythritol monoallyl ether, polyethoxylated allyl alcohol, and polypropoxylated allyl alcohol, such as -(CH2)30CH2C(CH2QH)2(CH2CH2-).
As used herein, "alkylene aryl" refers to an acyclic alkylene group substituted with at least one aryl group, for example, phenyl, and having an alkylene carbon chain length of C. to C25. The aryl group can be further substituted, if desired. Nonlimiting examples of suitable substituent groups for the aryl group include, but are not limited to, hydroxyl groups, benzyl groups, carboxylic acid groups, and aliphatic hydrocarbon groups.
Nonlimiting examples of suitable alkylene aryl groups include, but are not limited to, those derived from styrene and 3-isopropenyl-a,ac-dimethylbenzyl isocyanate, such as -(CH2)2C6H4- and -CH2CH(CH3)C6H3(C(CH3)2(NCO). As io used herein, "aikenylene" refers to an acyclic or cyclic hydrocarbon group having one or more double bonds and having an alkenylene carbon chain length of C2 to C25. Nonlimiting examples of suitable alkenylene groups include those derived from propargyl alcohol and acetylenic diols, for example, 2,4,7,9-tetramethyl-5-decyne-4,7-dioi which is commercially available from Air Products and Chemicals, Inc. of Allentown, Pennsylvania ,1 as SURFYNOL 104.
ForrnY'?.e 0 1) Grld I E?') a+L C{Ia cjIu ~im ailC, arld al"i: rl~: ::l~(] to it"llpiy that the parenthetical portions are necessarily blocks, although blocks may be used where desired. In some cases t~po?ysiloxane may ccr-nprise a varie-ty of sitoxane units. This is increasingly true as the number of siloxane units employed increases and especially true when mixtures of a number of different siloxane units are used. In those instances where a plurality of siloxane units are used and it is desired to form blocks, oligomers can be formed which can be joined to form the block compound. By judicious choice of reactants, compounds having an alternating structure or blocks of altemating structure may be used.
In one embodiment of the present invention the substituent group R3 represents an oxyalkylene group. In another embodiment, R3 represents an oxyalkylene group, and X represents a group which comprises at least two 3o reactive functional groups.
''Trade-mark In another embodiment of the present invention where the at least one polysiloxane (A) has the structure (II) or (III) described above, (j + k) ranges from 2 to 9. In yet another embodiment where the at least one polysiloxane have the structure (11) or (IfI) described above, (j + k) ranges from 2 to 3.
In another embodiment, where the at least one polysiloxane have the structure (Il) or (ltl) described above, (j' + k') ranges from 2 to 9. in another embodiment where the at least one polysiloxane has the structure (II) or (II{) described above, Q' + k') ranges from 2 to 3.
In yet another embodiment of the present invention, the substituent X
lo represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group. In another embodiment, the substituent X represents a group which comprises at least two hydroxyl groups. In yet another embodiment, X represents a group which corriprises at least one group selected from H, a monohydroxy-substituted organic group, and a group having the following structure (V):
(V) R'- (-CH2 OH)p wherein the substituent group R4 represents -CHZ C - R3 when p is 2 and the substituent group R3 represents a C, to C,, 2o alkylene group, or the substituent group R 4 represents -CH2- C -when p is 3, wherein at least a portion of X represents a group having the structure (V).
In another embodiment, where the polysiloxane (A) has the structure (I) or (II) described above, m is 2 and p is 2.
In another embodiment of the present invention, the polysiloxane (A) is formed from at least the following reactants: (i) at least one polysiloxane of the formula (VI):
(VI) R R R
I I I
R-Si-O-(-Si - O-)j-Si-R
, R R R
Nonlimiting examples of suitable alkylene aryl groups include, but are not limited to, those derived from styrene and 3-isopropenyl-a,ac-dimethylbenzyl isocyanate, such as -(CH2)2C6H4- and -CH2CH(CH3)C6H3(C(CH3)2(NCO). As io used herein, "aikenylene" refers to an acyclic or cyclic hydrocarbon group having one or more double bonds and having an alkenylene carbon chain length of C2 to C25. Nonlimiting examples of suitable alkenylene groups include those derived from propargyl alcohol and acetylenic diols, for example, 2,4,7,9-tetramethyl-5-decyne-4,7-dioi which is commercially available from Air Products and Chemicals, Inc. of Allentown, Pennsylvania ,1 as SURFYNOL 104.
ForrnY'?.e 0 1) Grld I E?') a+L C{Ia cjIu ~im ailC, arld al"i: rl~: ::l~(] to it"llpiy that the parenthetical portions are necessarily blocks, although blocks may be used where desired. In some cases t~po?ysiloxane may ccr-nprise a varie-ty of sitoxane units. This is increasingly true as the number of siloxane units employed increases and especially true when mixtures of a number of different siloxane units are used. In those instances where a plurality of siloxane units are used and it is desired to form blocks, oligomers can be formed which can be joined to form the block compound. By judicious choice of reactants, compounds having an alternating structure or blocks of altemating structure may be used.
In one embodiment of the present invention the substituent group R3 represents an oxyalkylene group. In another embodiment, R3 represents an oxyalkylene group, and X represents a group which comprises at least two 3o reactive functional groups.
''Trade-mark In another embodiment of the present invention where the at least one polysiloxane (A) has the structure (II) or (III) described above, (j + k) ranges from 2 to 9. In yet another embodiment where the at least one polysiloxane have the structure (11) or (IfI) described above, (j + k) ranges from 2 to 3.
In another embodiment, where the at least one polysiloxane have the structure (Il) or (ltl) described above, (j' + k') ranges from 2 to 9. in another embodiment where the at least one polysiloxane has the structure (II) or (II{) described above, Q' + k') ranges from 2 to 3.
In yet another embodiment of the present invention, the substituent X
lo represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group. In another embodiment, the substituent X represents a group which comprises at least two hydroxyl groups. In yet another embodiment, X represents a group which corriprises at least one group selected from H, a monohydroxy-substituted organic group, and a group having the following structure (V):
(V) R'- (-CH2 OH)p wherein the substituent group R4 represents -CHZ C - R3 when p is 2 and the substituent group R3 represents a C, to C,, 2o alkylene group, or the substituent group R 4 represents -CH2- C -when p is 3, wherein at least a portion of X represents a group having the structure (V).
In another embodiment, where the polysiloxane (A) has the structure (I) or (II) described above, m is 2 and p is 2.
In another embodiment of the present invention, the polysiloxane (A) is formed from at least the following reactants: (i) at least one polysiloxane of the formula (VI):
(VI) R R R
I I I
R-Si-O-(-Si - O-)j-Si-R
, R R R
wherein each substituent group R, which may be identical or different, represents a group selected frorri H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and mixtures of any of the foregoing; at least one of the groups represented by R is H, and j' ranges from 0 to 100, also can range from 0 to 10, and can further range from 0 to 5, such that the percent of SiH content of the polysiloxane ranges from 2 to 50 percent, and can range from 5 to 25 percent; and (ii) at least one molecule which comprises at least functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a Ao secondary amine group, an. amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group such as an acrylate group and a methacrylate group, a maleimide group, a fumarate group, an onium salt group such as a sulfonium group and an ammonium group, an anhydride group, a hydroxy alkylamide group, and an epoxy group 1s and at least one 'unsaturated bond capable of undergoing a hydrosilylation reaction. In another embodiment, the at least one functional group comprises h1;1roXy+~ ;rou-Pc.
It should be appreciated that the various R groups can be the same or different, and, in certain emtodirnents, the R croups will be entirely 20 monovalent hydrocarbon groups or will be a mixture of different groups such as, for example, monovalent hydrocarbon groups and hydroxyl groups.
In another embodiment, this reaction product is ungelled. As used herein, "ungelled" refers to a reaction product that is substantially free of crosslinking and has an intrinsic viscosity when dissolved in a suitable 25 solvent, as determined, for example, in accordance with ASTM-D1795 or ASTM-D4243. The intrinsic viscosity of the reaction product is an indication of its molecular weight. A gelled reaction product, on the other hand, since it is of an extremely high molecular weight, will have an intrinsic viscosity too high to measure. As used herein, a reaction product that is "substantially free 30 of crosslinking" refers to a reaction product that has a weight average molecular weight (Mw), as determined by gel permeation chromatography, of less than 1,000,000.
It also should be noted that the level of unsaturation containeci in reactant (ii) above, can be selected to obtain an ungelled reaction product.
In other words, when a polysiloxane containing silicon hydride (i) having a higher average value of Si-H functionality is used, reactant (ii) can have a lower level of unsaturation. For example, the polysiloxane containing silicon hydride (i) can be a low molecular weight material where j' ranges from 0 to 5 and the average value of Si-H functionality is two or less. In this case, io reactant (ii) can contain two or more unsaturated bonds capable of undergoing hydrosilylation reaction without the occurrence of gelation.
Nontimiting examples of polysiloxanes containing silicon hydride (i) include 1,1,3,3-tetramethyl disiloxane where n' is 0 and the average Si-H
functionality is two; and polymethyl polysiloxane containing silicon hydride, where n' ranges from 4 to 5 and the average Si-H functionality is approximately two, such as is commercially available from BASF Corporation as MASILWAX BASE .
Materials for use as reactant (ii) above can include hydroxyl furictional group-containing allyl ethers such as those selected from trimethylolpr=opane monoallyl ether, pentaerythritol monoallyl ether, trimethylolpropane diallyl ether, polyoxyalkylene alcohols such as polyethoxylated alcohol, polypropoxylated alcohol, and polybutoxylated alcohol, undecylenic acid-epoxy adducts, allyl glycidyl ether-carboxylic acid adducts, and mixtures of any of the foregoing. Mixtures of hydroxyl functional polyallyl ethers with hydroxyl functional monoallyl ethers or allyl alcohols are suitable as well.
In certain instances, reactant (ii) can contain at least one unsaturated bond in a terminal position. Reaction conditions and the ratio of reactants (i) and (ii) are selected so as to form the desired functional group.
The hydroxyl functional group-containing polysiloxane (A) can be prepared by reacting a polysiloxane containing hydroxyl functional groups with an anhydride to form the half-ester acid group under reaction conditions that favor only the reaction of the anhydride and the hydroxyl functional groups, and avoid further esterification from occurring. Nonlimiting examples of suitable anhydrides include hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, s succinic anhydride, chlorendic anhydride, alkenyl succinic anhydride, and substituted alkenyl anhydrides such as octenyl succinic anhydride, and mixtures of any of the foregoing.
The half-ester group-containing reaction product thus prepared can be further reacted with a monoepoxide to form a polysiloxane containing io secondary hydroxyl group(s). Nonlimiting examples of suitable monoepoxides are phenyl glycidyl ether, n-butyl glycidyl ether, cresy'l glycidyl ether, isopropyl glycidyl ether, glycidyl versatate, for example, CARDURA*E
available from Shell Chemical Co., and mixtures of any of the foregoing.
In another embodiment of the present invention, the at least one js polysiloxane (A) is a carbamate functional group-containing polysiloxane which comprises the reaction product of at least the following reactarits:
(i) at least one polysiloxane con.ai, ii: iy siiicon hydride of structure (VI) above where R and n' are as described above for that structure;
(ii) at least one hydroxyl func,ic~~~' r cup-containing rio: .erial t,aviag 20 one or more unsaturated bonds capable of undergoing hydrosilylation reaction as described above; and (iii) at least one low molecular weight carbamate functional maiterial, .
comprising the reaction product of an alcohol or glycol ether and a urea.
Examples of such "low molecular weight carbamate functional material"
25 include, but are not limited to, alkyl carbamate and hexyl carbamates, and glycol eth6r carbamates described in U.S. Patent Nos. 5,922,475 and 5,976,701.
The carbamate functional groups can be incorporated into the polysiloxane by reacting the hydroxyl functional group-containing polysiloxane 30 with the low molecular weight carbamate functional material via a "transcarbamoylation" process. The low molecular weight carbamate *Trade-mark functional material, which can be derived from an alcohol or glycol ether, can react with free hydroxyl groups of a polysiloxane polyol, that is, material having an average of two or more hydroxyl groups per molecule, yielding a carbamate functional polysiloxane (A) and the original alcohol or glycol ether.
Reaction conditions and the ratio of reactants (i), (ii) and (iii) are selected so as to form the desired groups.
The low molecular weight carbamate functional material can be prepared by reacting the alcohol or glycol ether with urea in the presence of a catalyst such as butyl stannoic acid. Nonlimiting examples of suitable io alcohols include lower molecular weight aliphatic, cycloaliphatic and aromatic alcohols, for example, methanol, ethanol, propanol, butanol, cyclohexanol, 2-ethylhexanol, and 3-methylbutanol. Nonlimiting examples of suitable glycol ethers include ethylene glycol methyl ether, and propylene glycol methyl ether. The incorporation of carbamate functional groups into the polysiloxane is also can be achieved by reacting isocyanic acid with free hydroxyl groups of the polysiloxane.
As aforementioned, in addition to or in lieu of hydroxyl or carbannate functional groups, the at least one polysiloxane (A) can contain one or more other reactive functional groups such as carboxyl groups, isocyanate groups, 20 blocked isocyanate groups, carboxylate groups, primary or secondary amine groups, amide groups, urea groups, urethane groups, an anhydride group, a hydroxy alkylamide group, epoxy groups, and mixtures of any of the foregoing.
When the at least one polysiloxane (A) contains carboxyl functional 25 groups, the at least one polysiloxane (A) can be prepared by reacting at least one polysiloxane containing hydroxyl functional groups as described above with a polycarboxylic acid or anhydride. Nonlimiting examples of polycarboxylic acids suitable for use include adipic acid, succinic acid, and dodecanedioic acid. Nonlimiting examples of suitable anhydrides include 30 those described above. Reaction conditions and the ratio of reactants are selected so as to form the desired functional groups.
In the case where at least one polysiloxane (A) contains one or more isocyanate functional groups, the at least one polysiloxane can be prepared by reacting at least one polysiloxane containing hydroxyl functional groups, as described above, with a polyisocyanate; such as a diisocyanate. Nonlimiting examples of suitable polyisocyanates include aliphatic polyisocyanates, such as, for example, aliphatic diisocyanates, for example, 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate; cycloaliphatic polyisocyanates, for example, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, and a,a-xyiylene diisocyanate; and aromatic polyisocyanates, to for example, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and tolyiene diisocyanate. These and other suitable polyisocyanates are described in more detail in U.S. Patent No. 4,046,729, at column 5, line 26 to column 6, line 28. Reaction conditions and the ratio of reactants are selected so as to form the desired functional groups.
The substituent X in structure (IV) can comprise an oligomeric or polymeric urethane or urea-containing material which is terminated with isocyanate, 17ydroxyl, primary or sccondary amine functional groups, or mixtures of any of the foregoing. When the substituent X comprises such f,unctionwl groups, the at least one polysitoxane can be the re2ct'son product of at least one polysiloxane polyol as described above, one or more polyisocyanates and, optionally, one or more compounds having at least two active hydrogen atoms per molecule selected from hydroxyl groups, primary amine groups, and secondary amine groups.
Nonlimiting examples of suitable polyisocyanates are those described .25 above. Nonlimiting examples of compounds having at least two active hydrogen atoms per molecule include polyols and polyamines containing primary or secondary amine groups.
Nonlimiting examples of suitable polyols include polyalkylene ether polyols, including thio ethers; polyester polyols, including polyhydroxy polyesteramides; and hydroxyl-containing polycaprolactones and hydroxy-containing acrylic interpolymers. Also useful are polyether polyols formed from the oxyalkylation of variQus polyols, for example, glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A, and the like, or higher polyols such as trimethylolpropane, pentaerythritol and the like. Polyester polyols also can be used. These and other suitable polyols are described in -U.S.
s Patent No. 4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 to column 9, line 66; and U.S. Patent No. 3,919,315 at column 2, line 64 to column 3, line 33.
Nonlimiting examples of suitable po{yamines include primary or secondary diamines or polyamines in which the groups attached to the io nitrogen atoms can be saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted-aliphatic, aliphatic-substituted-aromatic and heterocyclic.
Exemplary suitable aliphatic and alicyclic diamines include 1,2-ethylene diamine, 1,2-porphylene diamine, 1,8-octane diamine, isophorone diarnine, propane-2,2-cyclohexyl amine, and the like. Suitable aromatic diamines 15 include phenylene diamines and the toluene diamines, for example, o-phenylene diamine and p-tolylene diamine. These and other suitable polyamines are described in detail in U.S. Patent No. 4,046,729 at column 6, line 61 to column 7, line 26.
In one embodiment, the substituent group X of the structure (iV) can 20 comprise a polymeric ester-containing group which is terminated with hydroxyl or carboxylic acid functional groups. When X is such a group, at least one polysiloxane can be the reaction product of one or more polysiioxane polyols as described above, one or more materials comprising at least one carboxylic acid functional group, and one or more organic polyols.
25 Nonlimiting suitable examples of materials comprising at least one carboxylic acid functional group include carboxylic acid group-containing polymers well-known in the art, for example, carboxylic acid group-containing acrylic polymers, polyester polymers, and polyurethane polymers, such as those described in U.S. Patent No. 4,681,811. Nonlimiting examples of suitable 30 organic polyols include those described above.
It should be appreciated that the various R groups can be the same or different, and, in certain emtodirnents, the R croups will be entirely 20 monovalent hydrocarbon groups or will be a mixture of different groups such as, for example, monovalent hydrocarbon groups and hydroxyl groups.
In another embodiment, this reaction product is ungelled. As used herein, "ungelled" refers to a reaction product that is substantially free of crosslinking and has an intrinsic viscosity when dissolved in a suitable 25 solvent, as determined, for example, in accordance with ASTM-D1795 or ASTM-D4243. The intrinsic viscosity of the reaction product is an indication of its molecular weight. A gelled reaction product, on the other hand, since it is of an extremely high molecular weight, will have an intrinsic viscosity too high to measure. As used herein, a reaction product that is "substantially free 30 of crosslinking" refers to a reaction product that has a weight average molecular weight (Mw), as determined by gel permeation chromatography, of less than 1,000,000.
It also should be noted that the level of unsaturation containeci in reactant (ii) above, can be selected to obtain an ungelled reaction product.
In other words, when a polysiloxane containing silicon hydride (i) having a higher average value of Si-H functionality is used, reactant (ii) can have a lower level of unsaturation. For example, the polysiloxane containing silicon hydride (i) can be a low molecular weight material where j' ranges from 0 to 5 and the average value of Si-H functionality is two or less. In this case, io reactant (ii) can contain two or more unsaturated bonds capable of undergoing hydrosilylation reaction without the occurrence of gelation.
Nontimiting examples of polysiloxanes containing silicon hydride (i) include 1,1,3,3-tetramethyl disiloxane where n' is 0 and the average Si-H
functionality is two; and polymethyl polysiloxane containing silicon hydride, where n' ranges from 4 to 5 and the average Si-H functionality is approximately two, such as is commercially available from BASF Corporation as MASILWAX BASE .
Materials for use as reactant (ii) above can include hydroxyl furictional group-containing allyl ethers such as those selected from trimethylolpr=opane monoallyl ether, pentaerythritol monoallyl ether, trimethylolpropane diallyl ether, polyoxyalkylene alcohols such as polyethoxylated alcohol, polypropoxylated alcohol, and polybutoxylated alcohol, undecylenic acid-epoxy adducts, allyl glycidyl ether-carboxylic acid adducts, and mixtures of any of the foregoing. Mixtures of hydroxyl functional polyallyl ethers with hydroxyl functional monoallyl ethers or allyl alcohols are suitable as well.
In certain instances, reactant (ii) can contain at least one unsaturated bond in a terminal position. Reaction conditions and the ratio of reactants (i) and (ii) are selected so as to form the desired functional group.
The hydroxyl functional group-containing polysiloxane (A) can be prepared by reacting a polysiloxane containing hydroxyl functional groups with an anhydride to form the half-ester acid group under reaction conditions that favor only the reaction of the anhydride and the hydroxyl functional groups, and avoid further esterification from occurring. Nonlimiting examples of suitable anhydrides include hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, s succinic anhydride, chlorendic anhydride, alkenyl succinic anhydride, and substituted alkenyl anhydrides such as octenyl succinic anhydride, and mixtures of any of the foregoing.
The half-ester group-containing reaction product thus prepared can be further reacted with a monoepoxide to form a polysiloxane containing io secondary hydroxyl group(s). Nonlimiting examples of suitable monoepoxides are phenyl glycidyl ether, n-butyl glycidyl ether, cresy'l glycidyl ether, isopropyl glycidyl ether, glycidyl versatate, for example, CARDURA*E
available from Shell Chemical Co., and mixtures of any of the foregoing.
In another embodiment of the present invention, the at least one js polysiloxane (A) is a carbamate functional group-containing polysiloxane which comprises the reaction product of at least the following reactarits:
(i) at least one polysiloxane con.ai, ii: iy siiicon hydride of structure (VI) above where R and n' are as described above for that structure;
(ii) at least one hydroxyl func,ic~~~' r cup-containing rio: .erial t,aviag 20 one or more unsaturated bonds capable of undergoing hydrosilylation reaction as described above; and (iii) at least one low molecular weight carbamate functional maiterial, .
comprising the reaction product of an alcohol or glycol ether and a urea.
Examples of such "low molecular weight carbamate functional material"
25 include, but are not limited to, alkyl carbamate and hexyl carbamates, and glycol eth6r carbamates described in U.S. Patent Nos. 5,922,475 and 5,976,701.
The carbamate functional groups can be incorporated into the polysiloxane by reacting the hydroxyl functional group-containing polysiloxane 30 with the low molecular weight carbamate functional material via a "transcarbamoylation" process. The low molecular weight carbamate *Trade-mark functional material, which can be derived from an alcohol or glycol ether, can react with free hydroxyl groups of a polysiloxane polyol, that is, material having an average of two or more hydroxyl groups per molecule, yielding a carbamate functional polysiloxane (A) and the original alcohol or glycol ether.
Reaction conditions and the ratio of reactants (i), (ii) and (iii) are selected so as to form the desired groups.
The low molecular weight carbamate functional material can be prepared by reacting the alcohol or glycol ether with urea in the presence of a catalyst such as butyl stannoic acid. Nonlimiting examples of suitable io alcohols include lower molecular weight aliphatic, cycloaliphatic and aromatic alcohols, for example, methanol, ethanol, propanol, butanol, cyclohexanol, 2-ethylhexanol, and 3-methylbutanol. Nonlimiting examples of suitable glycol ethers include ethylene glycol methyl ether, and propylene glycol methyl ether. The incorporation of carbamate functional groups into the polysiloxane is also can be achieved by reacting isocyanic acid with free hydroxyl groups of the polysiloxane.
As aforementioned, in addition to or in lieu of hydroxyl or carbannate functional groups, the at least one polysiloxane (A) can contain one or more other reactive functional groups such as carboxyl groups, isocyanate groups, 20 blocked isocyanate groups, carboxylate groups, primary or secondary amine groups, amide groups, urea groups, urethane groups, an anhydride group, a hydroxy alkylamide group, epoxy groups, and mixtures of any of the foregoing.
When the at least one polysiloxane (A) contains carboxyl functional 25 groups, the at least one polysiloxane (A) can be prepared by reacting at least one polysiloxane containing hydroxyl functional groups as described above with a polycarboxylic acid or anhydride. Nonlimiting examples of polycarboxylic acids suitable for use include adipic acid, succinic acid, and dodecanedioic acid. Nonlimiting examples of suitable anhydrides include 30 those described above. Reaction conditions and the ratio of reactants are selected so as to form the desired functional groups.
In the case where at least one polysiloxane (A) contains one or more isocyanate functional groups, the at least one polysiloxane can be prepared by reacting at least one polysiloxane containing hydroxyl functional groups, as described above, with a polyisocyanate; such as a diisocyanate. Nonlimiting examples of suitable polyisocyanates include aliphatic polyisocyanates, such as, for example, aliphatic diisocyanates, for example, 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate; cycloaliphatic polyisocyanates, for example, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, and a,a-xyiylene diisocyanate; and aromatic polyisocyanates, to for example, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and tolyiene diisocyanate. These and other suitable polyisocyanates are described in more detail in U.S. Patent No. 4,046,729, at column 5, line 26 to column 6, line 28. Reaction conditions and the ratio of reactants are selected so as to form the desired functional groups.
The substituent X in structure (IV) can comprise an oligomeric or polymeric urethane or urea-containing material which is terminated with isocyanate, 17ydroxyl, primary or sccondary amine functional groups, or mixtures of any of the foregoing. When the substituent X comprises such f,unctionwl groups, the at least one polysitoxane can be the re2ct'son product of at least one polysiloxane polyol as described above, one or more polyisocyanates and, optionally, one or more compounds having at least two active hydrogen atoms per molecule selected from hydroxyl groups, primary amine groups, and secondary amine groups.
Nonlimiting examples of suitable polyisocyanates are those described .25 above. Nonlimiting examples of compounds having at least two active hydrogen atoms per molecule include polyols and polyamines containing primary or secondary amine groups.
Nonlimiting examples of suitable polyols include polyalkylene ether polyols, including thio ethers; polyester polyols, including polyhydroxy polyesteramides; and hydroxyl-containing polycaprolactones and hydroxy-containing acrylic interpolymers. Also useful are polyether polyols formed from the oxyalkylation of variQus polyols, for example, glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A, and the like, or higher polyols such as trimethylolpropane, pentaerythritol and the like. Polyester polyols also can be used. These and other suitable polyols are described in -U.S.
s Patent No. 4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 to column 9, line 66; and U.S. Patent No. 3,919,315 at column 2, line 64 to column 3, line 33.
Nonlimiting examples of suitable po{yamines include primary or secondary diamines or polyamines in which the groups attached to the io nitrogen atoms can be saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted-aliphatic, aliphatic-substituted-aromatic and heterocyclic.
Exemplary suitable aliphatic and alicyclic diamines include 1,2-ethylene diamine, 1,2-porphylene diamine, 1,8-octane diamine, isophorone diarnine, propane-2,2-cyclohexyl amine, and the like. Suitable aromatic diamines 15 include phenylene diamines and the toluene diamines, for example, o-phenylene diamine and p-tolylene diamine. These and other suitable polyamines are described in detail in U.S. Patent No. 4,046,729 at column 6, line 61 to column 7, line 26.
In one embodiment, the substituent group X of the structure (iV) can 20 comprise a polymeric ester-containing group which is terminated with hydroxyl or carboxylic acid functional groups. When X is such a group, at least one polysiloxane can be the reaction product of one or more polysiioxane polyols as described above, one or more materials comprising at least one carboxylic acid functional group, and one or more organic polyols.
25 Nonlimiting suitable examples of materials comprising at least one carboxylic acid functional group include carboxylic acid group-containing polymers well-known in the art, for example, carboxylic acid group-containing acrylic polymers, polyester polymers, and polyurethane polymers, such as those described in U.S. Patent No. 4,681,811. Nonlimiting examples of suitable 30 organic polyols include those described above.
To form the at least one polysiloxane (A) containing epoxy groups, at least one polysiloxane containing hydroxyl functional groups as described above can be further reacted with a polyepoxide. The polyepoxide can be an aliphatic or cycloaliphatic polyepoxide or mixtures of any of the foregoing.
Nonlimiting examples of polyepoxides suitable for use include epoxy functional acrylic copolymers prepared from at least one ethylenically unsaturated monomer comprising at least one epoxy group, for example glycidyl (meth)acrylate and allyl glycidyl ether, and one or more ethylenically unsaturated monomers which have no epoxy functionality. The preparation of io such epoxy functional acrylic copolymers is described in detail in U.S.
Patent No. 4,681,811 at column 4, line 52 to column 5, line 50. Reaction conditions and the ratio of reactants are selected so as to form the desired functional groups.
In the embodiment of the present invention where the boron-containing compound (c) is formed from the at least one functional group-containing polysiloxane (A) and the boron-containing compound (B), the at least one (A) can bo LuiTlf'30un6 (B) under condensation reaction conditions well known in the art. For example, mixing boric acid or a boric acid equivalent with ar7,'-vol and removing v_,~':,. r 2o by distillation either directly or in combination with a solvent. Other rriethods for preparing boric acid esters can be found in "Kirk-Othmer Encyclopedia of Chemical Technology" 4th edition, Vol 4, p 416; John Wiiey and sons; 1992.
Also, it should be understood, that the boron-containing compound (c) can be formed in situ. That is, the coating composition can comprise boric acid and/or a borate ester and an active hydrogen-containing reactant, such as a polymer or polysiloxane comprising hydroxyl functional groups, as separate components. The boron-containing compound (c) can then be formed, for example, by forming the condensate, i.e., the borate ester, within the composition at ambient temperature , or as the coating composition undergoes a curing reaction. When the boron-containing compound is formed in situ such as described immediately above, the coating composition can comprise the condensate reaction product (i.e., the borate ester), as well as the individual reactants used to form the borate ester, that is the boric acid and/or borate ester and the active hydrogen-containing reactant, as three separate ingredients.
The boron-containing compound (c), when added to the other components that form the coating composition, can be present in the coating composition in an amount sufficient to provide an amount of boron present in the composition of at least 0.001 weight percent, often at least 0.025 weight percent, usually at least 0.05 weight percent, and typically at least 0.10 weight to percent, based on total weight of the resin solids present in the composition.
Also, the boron-containing compound (c), when added to the other components that form the coating composition, can be present in the coating composition in an amount sufficient to provide an amount of boron present in the composition of less than 5 weight percent, often less than 3 weight percent, usually less than 2.5 weight percent, and typically less than 2 weight percent, based on total weight of the resin solids present in the composition.
The amount of boron-containing compound (c) is present in the composition in an amount sufficient to provide an amount of boron present in the composition that can range between any combination of these values inclusive of the recited values.
As previously mentioned, the present invention is directed to coating compositions comprising, in addition to the boron-containing compound (c) discussed in detail above, at least one functional group-containing polysiloxane (a) and at least one reactant (b) comprising at least one functional group that is reactive with the functional group(s) of the polysiloxane (a) (and, if desired, the boron-containing compound (c)).
The polysiloxane (a) can be any of the polysiloxanes described above with reference to polysiloxane (A) used to form the polysiloxane borate ester.
In one embodiment of the present invention, the polysiloxane (a) comprises at least one of the structural units (I), wherein R', R2, j and k are as described above for that structural unit. In a further embodiment of the present invention, the polysiloxane (a) comprises at least one polysiloxane having the structure (I) or (II), where R, R3, Ra, j, j', k, k', and X are as described above for these structures.
In one embodiment, the present invention is directed to coating s compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition such that the polysiloxane (a) is present in an amount ranging from 0.01 to 90 weight percent based on total weight of resin solids present in the composition. In another embodiment, the present io invention is directed to coating compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the polysiloxane (a) is present in the composition in an amount from at least weight percent based on total weight of resin solids present in the 15 composition.
In another embodiment, the present invention is directed to coating ccn Yas pi: ~~icu;~iy= cic;scrit~ed w~~~:,'in tile ai least one polysil~oxane (a), when added to the other components that form the composition, is p.resent in the composition in an amount such that the polysilot: :ne (r-) is 20 present in an amount from at least 5 weight percent based on total weight of resin solids present in the composition. In yet another embodiment, the present invention is directed to coating compositions as .previousiy described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition such 25 that the polysiloxane (a) is present in the composition in an amount from at least 10 weight percent based on total weight of resin solids present in the composition.
In one embodiment, the present invention is directed to coating compositions as previously described wherein the at least one polysiloxane 30 (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) present in the composition is less than 90 weight percent based on total weight of resin solids present in the composition. In another embodiment, the present invention is directed to coating compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) present in the composition is less than 80 weight percent based on total weight of resin solids present in the composition.
In another embodiment, the present invention is directed to coating io compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) present in the composition is less than 65 weight percent based on total weight of resin solids present in the composition. In yet another embodiment, the present invention is directed to coating compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) is less than 30 weight percent based on total weight of resin solids present in the composition.
As used herein pbased on total weight of the resin solids" of the composition means that the amount of the component added during the formation of the composition is based upon the total weight of the resin solids (non-volatiles) of the polysiloxane (a), any film-forming component and any curing agent present during the formation of the coating composition, but not including the particles, any solvent, or any additive solids such as hindered amine stabilizers, UV light absorbers, catalysts, pigments including pigment extenders and fillers, and flow modifiers.
As aforementioned, in addition to the components (a) and (c) 3o described in detail above, the components from which the coating composition of the present invention is formed can further comprise (b) at least one* reactant comprising at least one functional group that is reactive with at least one functional group'of the at least one polysiloxane (a), wherein each component is different. As used herein, the "at least one reactant"
refers to any material comprising a functional group that is reactive with at s least one functional group selected-from at least one functional group of the at least one polysiloxane (a) and, optionally, the at least one functional group-containing film-forming polymer discussed in detail below. If applicable the at least one reactant (b) may also be reactive with the reactive functional groups, if any, comprising the boron-containing compound (c) discussed io above.
In one embodiment, the at least one reactant (b) is selected from at least one curing agent. Dependent upon the reactive functional groups of component (a)(and/or component (c) if desired), this curing agent can be selected from an aminoplast resin, a polyisocyanate, a blocked isocyanate 15 compound, a polyepoxide, a polyacid, an anhydride, an amine, a polyol, and mixtures of any of the foregoing. In one embodiment, the at least one reuctUc ~: ~:,; is seiected iiorii an arninop{ast resin and a polyisocyanate.
In another embodiment, the present invention is directed to any composition as previously described wherein the cuTing is an 2o aminoplast. Aminoplast resins, which comprise phenoplasts, as curing agents for hydroxyl, carboxylic acid, and carbamate functional group-containing materials are well known in the art. Suitable aminoplasts, such as, for example, those discussed above, are known to those of ordinary skill in the art. Aminoplasts can be obtained from the condensation reaction of 25 formaldehyde with an amine or amide. Nonlimiting examples of amines or amides include melamine, urea, or benzoguanamine. Condensates with other amines or amides can be used; for example, aldehyde condensates of glycoluril, which give a high melting crystalline product useful in powder coatings. While the aldehyde used is most often formaldehyde, other 30 aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehyde can be used.
Nonlimiting examples of polyepoxides suitable for use include epoxy functional acrylic copolymers prepared from at least one ethylenically unsaturated monomer comprising at least one epoxy group, for example glycidyl (meth)acrylate and allyl glycidyl ether, and one or more ethylenically unsaturated monomers which have no epoxy functionality. The preparation of io such epoxy functional acrylic copolymers is described in detail in U.S.
Patent No. 4,681,811 at column 4, line 52 to column 5, line 50. Reaction conditions and the ratio of reactants are selected so as to form the desired functional groups.
In the embodiment of the present invention where the boron-containing compound (c) is formed from the at least one functional group-containing polysiloxane (A) and the boron-containing compound (B), the at least one (A) can bo LuiTlf'30un6 (B) under condensation reaction conditions well known in the art. For example, mixing boric acid or a boric acid equivalent with ar7,'-vol and removing v_,~':,. r 2o by distillation either directly or in combination with a solvent. Other rriethods for preparing boric acid esters can be found in "Kirk-Othmer Encyclopedia of Chemical Technology" 4th edition, Vol 4, p 416; John Wiiey and sons; 1992.
Also, it should be understood, that the boron-containing compound (c) can be formed in situ. That is, the coating composition can comprise boric acid and/or a borate ester and an active hydrogen-containing reactant, such as a polymer or polysiloxane comprising hydroxyl functional groups, as separate components. The boron-containing compound (c) can then be formed, for example, by forming the condensate, i.e., the borate ester, within the composition at ambient temperature , or as the coating composition undergoes a curing reaction. When the boron-containing compound is formed in situ such as described immediately above, the coating composition can comprise the condensate reaction product (i.e., the borate ester), as well as the individual reactants used to form the borate ester, that is the boric acid and/or borate ester and the active hydrogen-containing reactant, as three separate ingredients.
The boron-containing compound (c), when added to the other components that form the coating composition, can be present in the coating composition in an amount sufficient to provide an amount of boron present in the composition of at least 0.001 weight percent, often at least 0.025 weight percent, usually at least 0.05 weight percent, and typically at least 0.10 weight to percent, based on total weight of the resin solids present in the composition.
Also, the boron-containing compound (c), when added to the other components that form the coating composition, can be present in the coating composition in an amount sufficient to provide an amount of boron present in the composition of less than 5 weight percent, often less than 3 weight percent, usually less than 2.5 weight percent, and typically less than 2 weight percent, based on total weight of the resin solids present in the composition.
The amount of boron-containing compound (c) is present in the composition in an amount sufficient to provide an amount of boron present in the composition that can range between any combination of these values inclusive of the recited values.
As previously mentioned, the present invention is directed to coating compositions comprising, in addition to the boron-containing compound (c) discussed in detail above, at least one functional group-containing polysiloxane (a) and at least one reactant (b) comprising at least one functional group that is reactive with the functional group(s) of the polysiloxane (a) (and, if desired, the boron-containing compound (c)).
The polysiloxane (a) can be any of the polysiloxanes described above with reference to polysiloxane (A) used to form the polysiloxane borate ester.
In one embodiment of the present invention, the polysiloxane (a) comprises at least one of the structural units (I), wherein R', R2, j and k are as described above for that structural unit. In a further embodiment of the present invention, the polysiloxane (a) comprises at least one polysiloxane having the structure (I) or (II), where R, R3, Ra, j, j', k, k', and X are as described above for these structures.
In one embodiment, the present invention is directed to coating s compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition such that the polysiloxane (a) is present in an amount ranging from 0.01 to 90 weight percent based on total weight of resin solids present in the composition. In another embodiment, the present io invention is directed to coating compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the polysiloxane (a) is present in the composition in an amount from at least weight percent based on total weight of resin solids present in the 15 composition.
In another embodiment, the present invention is directed to coating ccn Yas pi: ~~icu;~iy= cic;scrit~ed w~~~:,'in tile ai least one polysil~oxane (a), when added to the other components that form the composition, is p.resent in the composition in an amount such that the polysilot: :ne (r-) is 20 present in an amount from at least 5 weight percent based on total weight of resin solids present in the composition. In yet another embodiment, the present invention is directed to coating compositions as .previousiy described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition such 25 that the polysiloxane (a) is present in the composition in an amount from at least 10 weight percent based on total weight of resin solids present in the composition.
In one embodiment, the present invention is directed to coating compositions as previously described wherein the at least one polysiloxane 30 (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) present in the composition is less than 90 weight percent based on total weight of resin solids present in the composition. In another embodiment, the present invention is directed to coating compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) present in the composition is less than 80 weight percent based on total weight of resin solids present in the composition.
In another embodiment, the present invention is directed to coating io compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) present in the composition is less than 65 weight percent based on total weight of resin solids present in the composition. In yet another embodiment, the present invention is directed to coating compositions as previously described wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount such that the amount of the polysiloxane (a) is less than 30 weight percent based on total weight of resin solids present in the composition.
As used herein pbased on total weight of the resin solids" of the composition means that the amount of the component added during the formation of the composition is based upon the total weight of the resin solids (non-volatiles) of the polysiloxane (a), any film-forming component and any curing agent present during the formation of the coating composition, but not including the particles, any solvent, or any additive solids such as hindered amine stabilizers, UV light absorbers, catalysts, pigments including pigment extenders and fillers, and flow modifiers.
As aforementioned, in addition to the components (a) and (c) 3o described in detail above, the components from which the coating composition of the present invention is formed can further comprise (b) at least one* reactant comprising at least one functional group that is reactive with at least one functional group'of the at least one polysiloxane (a), wherein each component is different. As used herein, the "at least one reactant"
refers to any material comprising a functional group that is reactive with at s least one functional group selected-from at least one functional group of the at least one polysiloxane (a) and, optionally, the at least one functional group-containing film-forming polymer discussed in detail below. If applicable the at least one reactant (b) may also be reactive with the reactive functional groups, if any, comprising the boron-containing compound (c) discussed io above.
In one embodiment, the at least one reactant (b) is selected from at least one curing agent. Dependent upon the reactive functional groups of component (a)(and/or component (c) if desired), this curing agent can be selected from an aminoplast resin, a polyisocyanate, a blocked isocyanate 15 compound, a polyepoxide, a polyacid, an anhydride, an amine, a polyol, and mixtures of any of the foregoing. In one embodiment, the at least one reuctUc ~: ~:,; is seiected iiorii an arninop{ast resin and a polyisocyanate.
In another embodiment, the present invention is directed to any composition as previously described wherein the cuTing is an 2o aminoplast. Aminoplast resins, which comprise phenoplasts, as curing agents for hydroxyl, carboxylic acid, and carbamate functional group-containing materials are well known in the art. Suitable aminoplasts, such as, for example, those discussed above, are known to those of ordinary skill in the art. Aminoplasts can be obtained from the condensation reaction of 25 formaldehyde with an amine or amide. Nonlimiting examples of amines or amides include melamine, urea, or benzoguanamine. Condensates with other amines or amides can be used; for example, aldehyde condensates of glycoluril, which give a high melting crystalline product useful in powder coatings. While the aldehyde used is most often formaldehyde, other 30 aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehyde can be used.
The aminoplast contains imino and methylol groups and in certain instances at least a portion of the methylol groups are etherified with an alcohol to modify the cure response. Any monohydric alcohol can be employed for this purpose including methanol, ethanol, n-butyl alcohol, s isobutanol, and hexanol.
Nonlimiting examples of aminoplasts include melamine-, urea-, or benzoguanamine-formaldehyde condensates, in certain instances monomeric and at least partially etherified with one or more alcohols containing from one to four carbon atoms. Nonlimiting examples of suitable aminoplast resins are io commercially available, for example, from Cytec Industries, Inc. under the trademark CYMELO and from Solutia, Inc. under the trademark RESIMENE .
In another embodiment, the present invention is directed to coating compositions as previously described wherein the curing agent comprises an is aminoplast resin which, when added to the other components that forrn the composition, is generally present in an amount ranging from 2 weight percent to 65 weight percent, can be present in an amount ranging from 5 weight percent to 50 weight percent, and typically is present in an amount ranging from 5 weight percent to 40 weight percent based on total weight of resin 2o solids present in the composition.
In yet another embodiment, the present invention is directed to coating compositions as previously described wherein the at least one reactant (b) comprises a polyisocyanate curing agent. As used herein, unless othennrise indicated, the term "polyisocyanate" is intended to include blocked (or 25 capped) polyisocyanates as well as unblocked isocyanates. The polyisocyanate can be an aliphatic or an aromatic polyisocyanate, or a mixture of the foregoing two. Diisocyanates can be used, although higher polyisocyanates such as isocyanurates of diisocyanates are often used.
Higher polyisocyanates also can be used in combination with diisocyanates.
30 Isocyanate prepolymers, for example, reaction products of polyisocyanates with polyols also can be used. Mixtures of polyisocyanate curing agents can be used.
If the polyisocyanate is blocked or capped, any suitable aliphatic, cycloaliphatic, or aromatic alkyl monoalcohol known to those skilled in the art can be used as a capping agent for the polyisocyanate. Other suitable capping agents include oximes and lactams. When used, the polyisocyanate curing agent is typically present, when added to the other components which form the coating composition, in an amount ranging from 5 to 65 weight percent, can be present in an amount ranging from 10 to 45 weight percent, lo and often are present in an amount ranging from 15 to 40 percent by weight based on the total weight of resin solids present in the composition.
Other useful curing agents comprise blocked isocyanate compounds such as, for example, the tricarbamoyl triazine compounds described in detail in U.S. Patent No. 5,084,541. When used, the blocked polyisocyante curing agent can be present, when added to the other components in the composition, in an amount ranging up to 20 weight percent, and can be present in an amount ranging from 1 to 20 weight perc--'. r-, "e, total weight of resin solids present in the composition.
In one embodiment, the present invention is directed to film-forming compositions as previously described, wherein the at least one reactant (b) comprises as a curing agent both an aminoplast resin and a polyisocyanate.
Anhydrides as curing agents for hydroxyl functional group-containing materials also are we(I known in the art and can be used in the present invention. Nonlimiting examples of anhydrides suitable for use as curing agents in the compositions of the invention include those having at least two carboxyiic acid anhydride groups per molecule which are derived from a mixture of monomers comprising an ethylenically unsaturated carboxylic acid anhydride and at least one vinyl co-monomer, for example, styrene, alpha-methyl styrene, vinyl toluene, and the like. Nonlimiting examples of suitable ethylenically unsaturated carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, and itaconic anhydride. Alternatively, the anhydride can be an anhydride adduct of a diene polymer such as maleinized polybutadiene or a maleinized copolymer of butadiene, for example, a butadiene/styrene copolymer. These and other suitable anhydride curing agents are described in U.S. Patent No. 4,798,746 at column 10, lines 16-50;
and in U.S. Patent No. 4,732,790 at column 3, lines 41-57.
Polyepoxides as curing agents for carboxylic acid functional group-containing materials are well known in the art. Nonlimiting examples of io poiyepoxides suitable for use in the compositions of the present invention comprise polyglycidyl esters (such as acrylics from glycidyl methacrylate), polyglycidyl ethers of polyhydric phenois and of aliphatic alcohols, which can be prepared by etherification of the polyhydric phenol, or aliphatic alcohol with an epihalohydrin such as epichlorohydrin in the presence of alkali. These and is other suitable polyepoxides are described in U.S. Patent No. 4,681,811 at column 5, lines 33 to 58.
Suitable curing agents for epoxy functional group-containing materials comprise polyacid curing agents, such as the acid group-containing acrylic polymers prepared from an ethylenically unsaturated monomer containing at 20 least one carboxylic acid group and at least one ethylenically unsaturated monomer which is free from carboxylic acid groups. Such acid functional acrylic polymers can have an acid number ranging from 30 to 150. Acid functional group-containing polyesters can be used as well. The above-described polyacid curing agents are described in further detaif in U.S.
Patent 25 No. 4,681,811 at column 6, line 45 to column 9, line 64.
Also well known in the art as curing agents for isocyanate functional group-containing materials are polyols, that is, materials having two or more hydroxyl groups per molecule, different from component (b) when component 30 (b) is a polyol. Nonlimiting examples of such materials suitable for use in the compositions of the invention include polyalkylene ether polyols, including thio ethers; potyester polyols, including polyhydroxy polyesteramides; and hydroxyl-containing polycaprolaotohes and hydroxy-containing acrylic copolymers. Also useful are polyether polyols formed from the oxyalkylation of various polyols, for example, glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A and the like, or higher polyols such as trim ethyl olpropane, pentaerythritol, and the like. Polyester polyols also can be used. These and other suitable polyol curing agents are described in U.S.
Patent No. 4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 to column 9, line 66; and U.S. Patent No. 3,919,315 at column 2, line 64 to io column 3, line 33.
Polyamines also can be used as curing agents for isocyanate functional group-containing materials. Nonlimiting examples of suitable polyamine curing agents include primary or secondary diamines or polyamines in which the radicals attached to the nitrogen atoms can be is saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted-aliphatic, aliphatic-substituted-aromatic, and heterocyclic. Nonlimiting , ~,Qr '"..;fi: a!E' c.+'~7ti~.tic and :C, i, Cjla1Ci11i1t S tõClUIa(; 11,2-EillyiE i1e diamine, 1,2-porphylene diamine, 1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like.
2o aromatic diamines include phenylene diamines and the toluene diamines, for example, o-phenylene diamine and p-tolylene diamine. These and other suitable polyamines described in detail in U.S. Patent No. 4,046,729 at column 6, line 61 to column 7, line 26.
25 When desired, appropriate mixtures of curing agents may be used. It should be mentioned that compositions can be formulated as a one-component composition where a curing agent such as an aminoplast resin and/or a blocked isocyanate compound such as those described above is admixed with other composition components. The one-component 30 composition can be storage stable as formulated. Alternatively, compositions can be formulated as a two-component composition where a polyisocyanate curing agent such as those described above can be added to a pre-forrned admixture of the other composition components just prior to application. The pre-formed admixture can comprise curing agents such as aminoplast resins and/or blocked isocyarrate compounds such as those described above.
In another embodiment in which the coating is cured by actinic radiation or the combination of actinic radiation and thermal energy, the components from which the coating composition are formed further can comprise at least one photoinitiator or photosensitizer which provides free radicals or cations to initiate the polymerization process. Useful io photoinitiators have an adsorption in the range of 150 to 2,000 nm. Non-limiting examples of useful photoinitiators include benzoin, benzophenone, hydroxy benzophenone, anthraquinone, thioxanthone, substituted berizoins such as butyl isomers of benzoin ethers, a,a-diethoxyacetophenone, Ia,a-dimethoxy-a-phenylacetophenone, 2-hydroxy-2-methyl-l-phenyl propane 1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.
In a further embodiment, the present invention is directed to coating compositions as previously described which further comprise at least one reactive functional group-containing, film forming polymer. This film forming polymer can be different from and in addition to the at least one polysiloxane (a), the at least one reactant.(b), and the boron-containing compound (c).
This film-forming polymer can have at least one functional group reactive with at least one functional group selected from the at least one reactive functional group of the at least one polysiloxane (a), the at least one functional group of the reactant (b), and, if desired, the boron-containing compound (c). In one embodiment, this at least one additional polymer can be selected from at least one of polyether polymers, polyester polymers, acrylic polymers, silicon-based polymers, and polyurethane polymers.
In a particular embodiment of the present invention, the film-forrriing polymer can comprise at least one reactive functional group selected from a 3o hydroxyl group, a carboxyl group, an isocyanate group, a blocked.
isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, ari unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
In another embodiment of the present invention, the film-fomling s polymer comprises at least one reactive functional group selected from a hydroxyl group, a carbamate group, an epoxy group, an isocyanate group, and a carboxy( group. In another embodiment, the polymer comprises at least one reactive functional group selected from a hydroxyl group, and a carbamate group.
The film-forming polymer can comprise a mixture of any of the foregoing reactive functional groups.
Suitable film-forming polymers suitable for use as the at least one reactive functional group-containing film-forming polymer can include any of a variety of functional polymers known in the art. For example, suitable hydroxyl group-containing polymers can include acrylic polyols, polyester polyols, polyurethane polyols, polyether polyols, and mixtures thereof. In a particular embodiment of the present invention, the film-forming polymer is an acrylic p o';oi ha,;ing a i;-dro;:,~! equivaie-~i vv~:~y~it rc~il~a;i ij froni 1i~vt1 to 100 grams per solid equivalent, preferably 500 to 150 grams per solid equivalent.
S -".ab1e hydroxyl qrou,_, ~:)d/or carbo;:yi group-conta:.i;ng acr%';c polymers can be prepared from polymerizable ethylenically unsaturated monomers and are typically copolymers of (meth)acrylic acid and/or hydroxylalkyl esters of (meth)acrylic acid with one or more other polymerizable ethylenically unsaturated monomers such as alkyl esters of (meth)acrylic acid including methyl (meth)acryiate, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethyl hexylacrylate, and vinyl aromatic compounds such as styrene, alpha-methyl styrene, and vinyl toluene. As used herein, "(meth)acrylate" and like terms is intended to include both acrylates and methacrylates.
In a one embodiment of the present invention the acrylic polymer can be prepared from ethylenicaily unsaturated; beta-hydroxy ester functional monomers. Such monomers can be derived from the reaction of an ethylenically unsaturated acid functional monomer, such as monocarboxylic acids, for example, acrylic acid, and an epoxy compound which does not participate in the free radical initiated polymerization with the unsaturated acid monomer. Examples of such epoxy compounds include glycidyl ethers and esters. Suitable glycidyl ethers include glycidyl ethers of alcohols and phenols such as butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether and the like. Suitable glycidyl esters include those which are commercially available from Shell Chemical Company under the trade-mark CARDURA E;
io and from Exxon Chemical Company under the trade-mark GLYDEXX-10.
Aiternatively, the beta-hydroxy ester functional monomers can be prepared from an ethylenically unsaturated, epoxy functional monomer, for exarnple glycidy! (meth)acrylate and allyl glycidyl ether, and a saturated carboxylic acid, such as a saturated monocarboxylic acid, for example isostearic acid.
is Epoxy functional groups can be incorporated into the polymer prepared from polymerizable ethylenically unsaturated monomers by copolymerizing oxirane group-containing monomers, for example glycidyl (meth)acrylate and allyl glycidyl ether, with other polyrnerizable ethylenically unsaturated monomers, such as those discussed above. Preparation of such epoxy 20 functional acrylic polymers is described in detail in U.S. Patent No.
4,001,156 at columns 3 to 6.
Carbamate functional groups can be incorporated into the polymer prepared from polymerizable ethylenically unsaturated monomers by copolymerizing, for example, the above-described ethylenically unsaturated 25 monomers with a carbamate functional vinyl monomer such as a carbamate functional alkyl ester of methacrylic acid. - Useful carbamate functional alkyl esters can be prepared by reacting, for example, a hydroxyalkyl carbamate, such as the reaction product of ammonia and ethylene carbonate or propylene carbonate, with methacrylic anhydride. Other useful carbamate 3o functional vinyl monomers include, for instance, the reaction product of hydroxyethyl methacrylate, isophorone dilsocyanate, and hydroxypropyl carbamate; or the reaction product of hydroxypropyl methacrylate, isophoro,.a diisocyanate, and methanol. Still other carbamate functional vinyl monomers may be used, such as the reaction product of isocyanic acid (HNCO) with a hydroxyl functional acrylic or methacrylic monomer such as hydroxyethyl acrylate, and those described in U.S. Patent No. 3,479,328. Carbamate functional groups can also be incorporated into the acrylic polymer by reacting a hydroxyl functional acrylic polymer with a low m o l e c u l a r we i g h t alkyl carbamate such as methyl carbamate. Pendant carbamate groups can also be incorporated into the acrylic polymer by a io "transcarbamoylation" reaction in which a hydroxyl functional acrylic polymer is reacted with a low molecular weight carbamate derived from an alcohol or a glycol ether. The carbamate groups exchange with the hydroxyl groups yielding the carbamate functional acrylic polymer and the originaf alcohol or glycol ether. Also, hydroxyl functional acrylic polymers can be reacted with isocyanic acid to provide pendent carbamate groups. Utkewise, hydroxyl functional acrylic polymers can be reacted with urea to provide pendent carbamate groups.
The pofy~,'ners prepared from polyr-nerizable ethylenicaliy unsaturated monomers can be prepared by solution polymerization techniques, which are ~;; well-known to i'",ose skilled in ttie art, in t'7:; presence of suitable catalysts such as organic peroxides or azo compounds, for example, benzoyl peroxide or N,N-azobis(isobutylronitrile). The polymerization can be carried out in an organic solution in which the monomers are soluble by techniques conventional in the art. Altematively, these polymers can be prepared by aqueous emulsion or dispersion polymerization techniques which are well-known in the art. The ratio of reactants and reaction conditions are selected to result in an acrylic polymer with the desired pendent functionality.
Polyester polymers are also useful in the coating compositions of the invention as the film-forming polymer. Useful polyester polymers typically include the condensation products of polyhydric alcohols and polycarboxylic acids. Suitable polyhydric alcohols can include ethylene glycol, neopentyl glycol, trimethylol propane, and pentaerythritol. Suitable polycarboxylic acids can include adipic acid, 1,4-c,yclohexyt dicarboxylic acid, and hexahydrophthalic acid. Besides the polycarboxylic acids mentioned above, functional equivalents of the acids such as anhydrides where they exist or lower alkyl esters of the acids such as the methyl esters can be used. Also, small amounts of monocarboxylic acids such as stearic acid can be used. The ratio of reactants and reaction conditions are selected to result in a polyester polymer with the desired pendent functionality, i.e., carboxyl or hydroxyl functionality.
For example, hydroxyl group-containing polyesters can be prepared by reacting an anhydride of a dicarboxylic acid such as hexahydrophthalic anhydride with a diol such as neopentyl glycol in a 1:2 molar ratio. Where it is desired to enhance air-drying, suitable drying oil fatty acids may be used and include those derived from linseed oil, soya bean oil, tall oil, dehydrated castor oit, or tung oil.
Carbamate functional polyesters can be prepared by first formirig a hydroxyalkyl carbamate that can be reacted with the polyacids and poYyols used in forming the polyester. Alternatively, terminal carbamate functional groups can be incorporated into the polyester by reacting isocyanic acid with 2o a hydroxy functional polyester. Also, carbamate functionality can be incorporated into the polyester by reacting a hydroxyl polyester with a urea.
Additionally, carbamate groups can be incorporated into the polyester by a transcarbamoylation reaction. Preparation of suitable carbamate functional group-containing polyesters are those described in U.S. Patent No. 5,593,733 at column 2, line 40 to column 4, line 9.
Polyurethane polymers containing terminal isocyanate or hydroxyl groups also can be used as the polymer (d) in the coating compositions of the invention. The polyurethane polyols or NCO-terminated polyurethanes which can be used are those prepared by reacting polyols including polymeric potyots with polyisocyanates. Polyureas containing terminal isocyanate or primary and/or secondary amine groups which also can be used are those prepared by reacting polyamines including polymeric polyamines with polyisocyanates. The hydroxyl/isocyanate or aminersocyanate equivalent ratio is adjusted and reaction conditions are selected to obtain the desired terminal groups. Examples of suitable polyisocyanates include those s described in U.S. Patent No. 4,046,729 at column 5, line 26 to column 6, line 28. Examples of suitable polyols include those described in U.S. Patent No. 4,046,729 at column 7, line 52 to column 10, line 35. Examples of suitable polyamines include those described in U.S. Patent No. 4,046,729 at column 6, line 61 to column 7, line 32 and in U.S. Patent No. 3,799,854 Io at column 3, lines 13 to 50.
Carbamate functional groups can be introduced into the polyurethane polymers by reacting a polyisocyanate with a polyester having hydroxyl functionality and containing pendent carbamate groups. Alternatively, the is polyurethane can be prepared by reacting a polyisocyanate with a polyester polyol and a hydroxyalkyl carbamate or isocyanic acid as separate reactants.
Examples of suitable polyisocyanates are aromatic isocyanates, such as 4,4'-dipl-i enylrroethane diisocyanate, 1,3-phenylene diisocyanate and toluene diisocyanate, and aliphatic polyisocyanates, such as 1,4-tetramethylene 2o diisoc~,'anate and 1,6-hex:.:-4-,athylene diisocyanate. Cyclc=~,ipiiatic diisocyanates, such as 1,4-cyclohexyl diisocyanate and isophorone diisocyanate also can be employed.
Examples of suitable polyether polyols include polyalkylene ether polyols such as those having the following structural formulas (VI() or (Vlil):
25 (VII) 1 r R
or (Ulll) H 0 [cH2 CHr OH
s R
wherein the substituent R is hydrogen or a lower alkyl group containing from 1 to 5 carbon atoms including mixed substituents, and r has a value typically s ranging from 2 to 6 and s has a value ranging from 8 to 100 or higher.
Exemplary polyalkylene ether polyols include poiy(oxytetramethylene) glycols, poly(oxytetraethylene) glycols, poly(oxy-1,2-propylene) glycols, and poly(oxy-1,2-butylene) glycols.
Also useful are polyether polyols formed from oxyalkylation of various io polyols, for example, glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A, and the like, or other higher polyols such as trimethylolpropane, pentaerythritoi, ~nd Polyofs of higher functionality which can be utilized as indicated can be made, for instance, by oxyalkylation of compounds such as sucrose or sorbitof. One commonly utilized oxyalkylation is method is reaction of a polyol with an aliCylene oxide, for exampSe, pfnpySene or ethylene oxide, in the presence of an acidic or basic catalyst. Specific examples of polyethers include those sold under trade-marks TERATHANE
and TERACOL, available from E. I. Du Pont de Nemours and Company, Inc.
Generally, the polymers having reactive functional groups which are 20 useful in the coating compositions of the invention have a weight average molecular weight (Mw) typically ranging from 1000 to 20,000 preferably 1500 to 15,000 and more preferably 2000 to 12,000 as determined by gel permeation chromatography using a polystyrene standard.
It should be mentioned that when both (a) and (d) are present, the 25 reactive functional groups of (a) and (d) can be the same or different, but both must be reactive with the functional groups of the curing agent (b). Examples of such reactive functional groups include hydroxyl, carboxylic acid, isocyanate, carboxylate, primary amine, secondary amine, amide, carbamate, and epoxy functional groups. Hydroxyl and/or carbamate functional group-containing polymers are preferred.
The polymer having reactive functional groups, if employed, can be present in the coating compositions of the invention in an amount of at least percent by weight, usually at least 5 percent by weight, and typically at least percent by weight based on weight of total resin solids in the coating composition. Also, the polymer having reactive functional groups can be present in the coating compositions of the invention in an amount less than 80 percent by weight, usually less than 60 percent by weight, and typically io less than 50 percent by weight based on weight of total resin solids in the coating composition. The amount of the polymer having reactive functional groups present in the coating compositions of the present invention can range between any combination of these values inclusive of the recited values.
The coating compositions of the present invention can be solvent-based compositions, water-based compositions, in solid particulate form, that is, a powder composition, in the form of a powder slurry or an aqueous dispersion. The components of the present invention used to form the compositions of the present invention can be dissolved or dispersed in an organic solvent. Nonlimiting examples of suitable organic solvents include alcohols, such as butanol; ketones, such as methyl amyl ketone; aromatic hydrocarbons, such as xylene; and glycol ethers, such as, ethylene glycol monobutyl ether; esters; other solvents; and mixtures of any of the foregoing.
In solvent based compositions, the organic solvent is generally present in amounts ranging from 5 to 80 percent by weight based on total weight of the resin solids of the components which form the composition, and can be present in an amount ranging from 30 to 50 percent by weight. The compositions as described above can have a total solids content ranging from 40 to 75 percent by weight based on total weight of the resin solids of the components which form the composition, and can have a total solids content ranging from 50 to 70 percent by weight. Alternatively, the inventive compositions can be in solid particulate form suitable for use as a powder coating, or suitable for disper,sion in a liquid medium such as water for use as a powder slurry.
In a further embodiment, the film-forming compositions as previously s described further comprise a catalyst which is present during the composition's formation. In one embodiment, the catalyst is present in an amount sufficient to accelerate the reaction between at least one reactive functional group of the at least one reactant (b) and/or at least one reactive functional group of the at least one polysiloxane (a) and/or the boron-io containing compound (c), if appropriate, and/or the functional group-containing film-forming polymer, if used.
Nonlimiting examples of suitable catalysts include acidic materials, for example, acid phosphates, such as phenyl acid phosphate, and substituted or unsubstituted sulfonic ac;ft such as dodecylbenzene sulfonic acid or para-15 toluene sulfonic acid. Non-limiting examples of suitable catalysts for reactions between isocyanate groups and active hydrogen-containing materials, for example, those comprising hydroxyl groups, include tin catalysts such as dibutyl tin dilaurate and dibutyl tin oxide. Non-limiting examples of epoxy acid base catalysts include tertiary amines such as N,N'-2o dimethyldodecyl amine catalysts. In another embodiment, the catalyst can be a phosphatized polyester or a phosphatized epoxy. In this embodiment, the catalyst can be, for example, the reaction product of phosphoric acid and a bisphenol A digiycidyl ether having two hydrogenated phenolic rings, such as DRH-151, which is commercially available from Shell Chemical Co. The 25 catalyst can be present, when added to the other components that form the composition, in an amount ranging from 0.1 to 5.0 percent by weight, and is typically present in an amount ranging from 0.5 to 1.5 percent by weight based on the total weight of resin solids present in the composition.
In another embodiment, additional components can be present during 30 the formation of the compositions as previously described. These additional components include, but are not limited to, particles different from components (a), (b) and (c), flexibilizers, plasticizers, surface active agents, thixotropic agents, rheology control modifiers, anti-gassing agents, organic cosolvents, flow controllers, hindered amine light stabilizers, anti-oxidants, UV
light absorbers, coloring agents or tints, and similar additives conventional in s the art, as well as mixtures of any of the foregoing can be included in the composition. These additional ingredients can be present, when added to the other components that form the composition, in an amount up to 40 percent by weight based on the total weight of resin solids present in the composition.
In one embodiment, the present invention is directed to io compositions as previously described wherein the composition further comprises a plurality of particles. In another embodiment, the preserit invention is directed to any composition as previously described wherein the particles have an average particle size of less than 100 microns prior to incorporation into the composition. In another embodiment, the present is invention is directed to any composition as previously described wherein the particles have an average particle size ranging from 1 to less than 1000 nanometers prior to incorporation into the composition. In yet another embodiment, the present invention is directed to any composition as previously described wherein the particles have an average particle size 2o ranging from 1 to 100 nanometers prior to incorporation into the composition.
In another embodiment, the present invention is directed to any composition as previously described wherein the particles have an average particle size ranging from 5 to 50 nanometers prior to incorporation into the composition. In another embodiment, the present invention is directed to any 25 composition as previously described wherein the particles have an average particle size ranging from 5 to 25 nanometers prior to incorporation into the composition.
In an embodiment where the average particle size of the particles is greater than one micron, the average particle size can be measured 30 according to known laser scattering techniques. For example, the average particle size of such particles is measured using a Horiba Model LA 900 laser *Trade-mark diffraction particle size instrument, which uses a helium-neon laser with a wave length of 633 nm to measure the size of the particles and assumes the particle has a spherical shape, i.e., the "particle size" refers to the smallest sphere that will completely enclose the particle.
s In an embodiment of the present invention wherein the size of the particles is less than or equal to one micron, the average particle size can be determined by visually examining an electron micrograph of a transmission electron microscopy ("TEM") image, measuring the diameter of the particles in the image, and calculating the average particle size based on the io magnification of the TEM image. One of ordinary skill in the art will understand how to prepare such a TEM image, and a description of one such method is disclosed in the examples set forth below. In one nonlimiting embodiment of the present invention, a TEM image with 105,000X
ma ;nificatican is ,prc~Q'uced, =~nd a conv , ic ;~ factor is ollzained by dividing the i,s magnification by 1000. Upon visual inspection, the diameter of the particles is measured aniflimeters, and the measurement is converted to nanometers using the conversion factor. The diameter of the particle refers to the smallest diameter sphere that will completely enclose the particle.
The shape (or morphology) of the particles can vary depending upon 20 the specific embodiment of the present invention and its intended application.
For example generally spherical morphologies (such as solid beads, microbeads, or hollow spheres), can be used, as well as particles that are cubic, platy, or acicular (elongated or fibrous). Additionally, the particles can have an internal structure that is hollow, porous or void free, or a combination 25 of any of the foregoing, e.g., a hollow center with porous or solid walls.
For more information on suitable particle characteristics see H. Katz et al.
(Ed.), Handbook of Fillers and Plastics (1987) at pages 9-10.
It will be recognized by one skilled in the art that mixtures of one or 30 more particles having different average particle sizes can be incorporated into the compositions in accordance with the present Invention to impart the desired properties and characteristics to the compositions. For example, particles of varying particle sizes can be used in the compositions according to the present invention.
The particles can be formed from materials selected from polymeric and nonpolymeric inorganic materials, polymeric and nonpolymeric organic materials, composite materials, and mixtures of any of the foregoing. As used herein, the term "polymeric inorganic material" means a polymeric material having a backbone repeat unit based on an element or elements other than carbon. For more information see James Mark et al., Inorganic Polymers, io Prentice Hall Polymer Science and Engineering Series, (1992) at page 5.
As used herein, the term "polymeric organic materials" means synthetic polymeric materials, semisynthetic polymeric materials and natural polymeric materials, all of which have a backbone repeat unit based on carbon.
is An "organic material," as used herein, means carbon containing compounds wherein the carbon is typically bonded to itself and to hydrogen, and often to other elements as well, and excludes binary compounds such as the carbon oxides, ttie carbides, carbon disulfide, etc.; such ternary compounds as the metallic cyanides, metallic carbonyls, phosgene, carbonyl 2o sulfide, etc.; and carbon-containing ionic compounds such as metaiiif.:
carbonates, for example, calcium carbonate and sodium carbonate. See R.
Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at pages 761-762, and M. Silberberg, Chemistry The Molecular Nature of Matter and Change (1996) at page 586.
As used herein, the term "inorganic material" means any material that is not an organic material.
As used herein, the term "composite material" means a, combination of two or more differing materials. The particles formed from composite materials generally have a hardness at their surface that is different from the hardness of the internal portions of the particle beneath its surface. More specifically, the surface of the particle can be modified in any manner well known in the art, including, but not limited to, chemically or physically changing its surface characteristics using techniques known in the art.
For example, a particle can be formed from a primary material that is coated, clad or encapsulated with one or more secondary materials to form a composite particle that has a softer surface. In yet another alternative embodiment, particles formed from composite materials can be formed from a primary material that is coated, clad or encapsulated with a different form of the primary material. For more information on particles useful in the present io invention, see G. Wypych, Handbook of Fillers, 2nd Ed. (1999) at pages 15-202.
The particles suitable for use in the compositions of the invention can comprise inorganic elements or compounds known in the art. Suitable particles can -te for;ried from ceramic materials, metallic materials, and is mixtures of any of the foregoing. Suitable ceramic materials comprise metal oxides, metal nitrides, metal carbides, metal me'.-1 7,iticates, metal borides, metal carbonates, and mtixtuces of any of the focegoing. Spectific, nonlimiting examples of metal nitrides are, for example, boron nitride;
specific, nonlimiting examples of metal oxides are, for example, zinc oxide;
norilimiting 2o examples of suitable metal sulfides are, for example, molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide; nonlimiting suitable examples of metal silicates are, for example, aluminum silicates and magnesium silicates such as vermiculite.
The particles can comprise, for example, a core of essentially a single 25 inorganic oxide such as silica in colloidal, fumed, or amorphous form, alumina or colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, e.g., colloidal or amorphous zirconia, and mixtures of any of the foregoing; or an inorganic oxide of one type upon which is deposited an organic oxide of another type. It should be understood that when the 30 composition of the invention is employed as. a transparent topcoat, for example, as a clearcoat in a multi-component composite coating composition, particles should not seriously interfere with the optical properties of the composition. As used herein; "transparent" means that the cured coating has a BYK Haze index of less than 50 as measured using a BYK/Haze Gloss instrument.
Nonpolymeric, inorganic materials useful in forming the particles of the present invention comprise inorganic materials selected from graphite, metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates, and hydroxides. A nonlimiting example of a useful inorganic oxide is zinc oxide. Nonlimiting examples of suitable inorganic sulfides include io molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide.
Nonlimiting examples of useful inorganic siiicates include aluminum silicates and magnesium silicates, such as vermiculite. Nonlimiting examples of suitable metals include molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, alloys, and mixtures of any of the foregoing.
In one embodiment, the present invention is directed to any composition as previously described wherein the particles are selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia, and mixtures of any of the foregoing. In another embodiment, the present invention is directed to any composition as previously described wherein the particles include colloidal silica. As disclosed above, these materials can be surface treated or untreated.
The composition can comprise precursors suitable for forming silica particles in situ by a sol-gel process. The composition according to the present invention can comprise alkoxy silanes which can be hydrolyzed to form silica particles in situ. For example, tetraethylortho silicate can be hydrolyzed with an acid such as hydrochloric acid and condensed to form silica particles. Other useful particles include surface-modified silicas such as are described in U.S. Patent No. 5,853,809 at cblumn 6, line 51 to'column 8, line 43.
Nonlimiting examples of aminoplasts include melamine-, urea-, or benzoguanamine-formaldehyde condensates, in certain instances monomeric and at least partially etherified with one or more alcohols containing from one to four carbon atoms. Nonlimiting examples of suitable aminoplast resins are io commercially available, for example, from Cytec Industries, Inc. under the trademark CYMELO and from Solutia, Inc. under the trademark RESIMENE .
In another embodiment, the present invention is directed to coating compositions as previously described wherein the curing agent comprises an is aminoplast resin which, when added to the other components that forrn the composition, is generally present in an amount ranging from 2 weight percent to 65 weight percent, can be present in an amount ranging from 5 weight percent to 50 weight percent, and typically is present in an amount ranging from 5 weight percent to 40 weight percent based on total weight of resin 2o solids present in the composition.
In yet another embodiment, the present invention is directed to coating compositions as previously described wherein the at least one reactant (b) comprises a polyisocyanate curing agent. As used herein, unless othennrise indicated, the term "polyisocyanate" is intended to include blocked (or 25 capped) polyisocyanates as well as unblocked isocyanates. The polyisocyanate can be an aliphatic or an aromatic polyisocyanate, or a mixture of the foregoing two. Diisocyanates can be used, although higher polyisocyanates such as isocyanurates of diisocyanates are often used.
Higher polyisocyanates also can be used in combination with diisocyanates.
30 Isocyanate prepolymers, for example, reaction products of polyisocyanates with polyols also can be used. Mixtures of polyisocyanate curing agents can be used.
If the polyisocyanate is blocked or capped, any suitable aliphatic, cycloaliphatic, or aromatic alkyl monoalcohol known to those skilled in the art can be used as a capping agent for the polyisocyanate. Other suitable capping agents include oximes and lactams. When used, the polyisocyanate curing agent is typically present, when added to the other components which form the coating composition, in an amount ranging from 5 to 65 weight percent, can be present in an amount ranging from 10 to 45 weight percent, lo and often are present in an amount ranging from 15 to 40 percent by weight based on the total weight of resin solids present in the composition.
Other useful curing agents comprise blocked isocyanate compounds such as, for example, the tricarbamoyl triazine compounds described in detail in U.S. Patent No. 5,084,541. When used, the blocked polyisocyante curing agent can be present, when added to the other components in the composition, in an amount ranging up to 20 weight percent, and can be present in an amount ranging from 1 to 20 weight perc--'. r-, "e, total weight of resin solids present in the composition.
In one embodiment, the present invention is directed to film-forming compositions as previously described, wherein the at least one reactant (b) comprises as a curing agent both an aminoplast resin and a polyisocyanate.
Anhydrides as curing agents for hydroxyl functional group-containing materials also are we(I known in the art and can be used in the present invention. Nonlimiting examples of anhydrides suitable for use as curing agents in the compositions of the invention include those having at least two carboxyiic acid anhydride groups per molecule which are derived from a mixture of monomers comprising an ethylenically unsaturated carboxylic acid anhydride and at least one vinyl co-monomer, for example, styrene, alpha-methyl styrene, vinyl toluene, and the like. Nonlimiting examples of suitable ethylenically unsaturated carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, and itaconic anhydride. Alternatively, the anhydride can be an anhydride adduct of a diene polymer such as maleinized polybutadiene or a maleinized copolymer of butadiene, for example, a butadiene/styrene copolymer. These and other suitable anhydride curing agents are described in U.S. Patent No. 4,798,746 at column 10, lines 16-50;
and in U.S. Patent No. 4,732,790 at column 3, lines 41-57.
Polyepoxides as curing agents for carboxylic acid functional group-containing materials are well known in the art. Nonlimiting examples of io poiyepoxides suitable for use in the compositions of the present invention comprise polyglycidyl esters (such as acrylics from glycidyl methacrylate), polyglycidyl ethers of polyhydric phenois and of aliphatic alcohols, which can be prepared by etherification of the polyhydric phenol, or aliphatic alcohol with an epihalohydrin such as epichlorohydrin in the presence of alkali. These and is other suitable polyepoxides are described in U.S. Patent No. 4,681,811 at column 5, lines 33 to 58.
Suitable curing agents for epoxy functional group-containing materials comprise polyacid curing agents, such as the acid group-containing acrylic polymers prepared from an ethylenically unsaturated monomer containing at 20 least one carboxylic acid group and at least one ethylenically unsaturated monomer which is free from carboxylic acid groups. Such acid functional acrylic polymers can have an acid number ranging from 30 to 150. Acid functional group-containing polyesters can be used as well. The above-described polyacid curing agents are described in further detaif in U.S.
Patent 25 No. 4,681,811 at column 6, line 45 to column 9, line 64.
Also well known in the art as curing agents for isocyanate functional group-containing materials are polyols, that is, materials having two or more hydroxyl groups per molecule, different from component (b) when component 30 (b) is a polyol. Nonlimiting examples of such materials suitable for use in the compositions of the invention include polyalkylene ether polyols, including thio ethers; potyester polyols, including polyhydroxy polyesteramides; and hydroxyl-containing polycaprolaotohes and hydroxy-containing acrylic copolymers. Also useful are polyether polyols formed from the oxyalkylation of various polyols, for example, glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A and the like, or higher polyols such as trim ethyl olpropane, pentaerythritol, and the like. Polyester polyols also can be used. These and other suitable polyol curing agents are described in U.S.
Patent No. 4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 to column 9, line 66; and U.S. Patent No. 3,919,315 at column 2, line 64 to io column 3, line 33.
Polyamines also can be used as curing agents for isocyanate functional group-containing materials. Nonlimiting examples of suitable polyamine curing agents include primary or secondary diamines or polyamines in which the radicals attached to the nitrogen atoms can be is saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted-aliphatic, aliphatic-substituted-aromatic, and heterocyclic. Nonlimiting , ~,Qr '"..;fi: a!E' c.+'~7ti~.tic and :C, i, Cjla1Ci11i1t S tõClUIa(; 11,2-EillyiE i1e diamine, 1,2-porphylene diamine, 1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like.
2o aromatic diamines include phenylene diamines and the toluene diamines, for example, o-phenylene diamine and p-tolylene diamine. These and other suitable polyamines described in detail in U.S. Patent No. 4,046,729 at column 6, line 61 to column 7, line 26.
25 When desired, appropriate mixtures of curing agents may be used. It should be mentioned that compositions can be formulated as a one-component composition where a curing agent such as an aminoplast resin and/or a blocked isocyanate compound such as those described above is admixed with other composition components. The one-component 30 composition can be storage stable as formulated. Alternatively, compositions can be formulated as a two-component composition where a polyisocyanate curing agent such as those described above can be added to a pre-forrned admixture of the other composition components just prior to application. The pre-formed admixture can comprise curing agents such as aminoplast resins and/or blocked isocyarrate compounds such as those described above.
In another embodiment in which the coating is cured by actinic radiation or the combination of actinic radiation and thermal energy, the components from which the coating composition are formed further can comprise at least one photoinitiator or photosensitizer which provides free radicals or cations to initiate the polymerization process. Useful io photoinitiators have an adsorption in the range of 150 to 2,000 nm. Non-limiting examples of useful photoinitiators include benzoin, benzophenone, hydroxy benzophenone, anthraquinone, thioxanthone, substituted berizoins such as butyl isomers of benzoin ethers, a,a-diethoxyacetophenone, Ia,a-dimethoxy-a-phenylacetophenone, 2-hydroxy-2-methyl-l-phenyl propane 1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.
In a further embodiment, the present invention is directed to coating compositions as previously described which further comprise at least one reactive functional group-containing, film forming polymer. This film forming polymer can be different from and in addition to the at least one polysiloxane (a), the at least one reactant.(b), and the boron-containing compound (c).
This film-forming polymer can have at least one functional group reactive with at least one functional group selected from the at least one reactive functional group of the at least one polysiloxane (a), the at least one functional group of the reactant (b), and, if desired, the boron-containing compound (c). In one embodiment, this at least one additional polymer can be selected from at least one of polyether polymers, polyester polymers, acrylic polymers, silicon-based polymers, and polyurethane polymers.
In a particular embodiment of the present invention, the film-forrriing polymer can comprise at least one reactive functional group selected from a 3o hydroxyl group, a carboxyl group, an isocyanate group, a blocked.
isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, ari unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.
In another embodiment of the present invention, the film-fomling s polymer comprises at least one reactive functional group selected from a hydroxyl group, a carbamate group, an epoxy group, an isocyanate group, and a carboxy( group. In another embodiment, the polymer comprises at least one reactive functional group selected from a hydroxyl group, and a carbamate group.
The film-forming polymer can comprise a mixture of any of the foregoing reactive functional groups.
Suitable film-forming polymers suitable for use as the at least one reactive functional group-containing film-forming polymer can include any of a variety of functional polymers known in the art. For example, suitable hydroxyl group-containing polymers can include acrylic polyols, polyester polyols, polyurethane polyols, polyether polyols, and mixtures thereof. In a particular embodiment of the present invention, the film-forming polymer is an acrylic p o';oi ha,;ing a i;-dro;:,~! equivaie-~i vv~:~y~it rc~il~a;i ij froni 1i~vt1 to 100 grams per solid equivalent, preferably 500 to 150 grams per solid equivalent.
S -".ab1e hydroxyl qrou,_, ~:)d/or carbo;:yi group-conta:.i;ng acr%';c polymers can be prepared from polymerizable ethylenically unsaturated monomers and are typically copolymers of (meth)acrylic acid and/or hydroxylalkyl esters of (meth)acrylic acid with one or more other polymerizable ethylenically unsaturated monomers such as alkyl esters of (meth)acrylic acid including methyl (meth)acryiate, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethyl hexylacrylate, and vinyl aromatic compounds such as styrene, alpha-methyl styrene, and vinyl toluene. As used herein, "(meth)acrylate" and like terms is intended to include both acrylates and methacrylates.
In a one embodiment of the present invention the acrylic polymer can be prepared from ethylenicaily unsaturated; beta-hydroxy ester functional monomers. Such monomers can be derived from the reaction of an ethylenically unsaturated acid functional monomer, such as monocarboxylic acids, for example, acrylic acid, and an epoxy compound which does not participate in the free radical initiated polymerization with the unsaturated acid monomer. Examples of such epoxy compounds include glycidyl ethers and esters. Suitable glycidyl ethers include glycidyl ethers of alcohols and phenols such as butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether and the like. Suitable glycidyl esters include those which are commercially available from Shell Chemical Company under the trade-mark CARDURA E;
io and from Exxon Chemical Company under the trade-mark GLYDEXX-10.
Aiternatively, the beta-hydroxy ester functional monomers can be prepared from an ethylenically unsaturated, epoxy functional monomer, for exarnple glycidy! (meth)acrylate and allyl glycidyl ether, and a saturated carboxylic acid, such as a saturated monocarboxylic acid, for example isostearic acid.
is Epoxy functional groups can be incorporated into the polymer prepared from polymerizable ethylenically unsaturated monomers by copolymerizing oxirane group-containing monomers, for example glycidyl (meth)acrylate and allyl glycidyl ether, with other polyrnerizable ethylenically unsaturated monomers, such as those discussed above. Preparation of such epoxy 20 functional acrylic polymers is described in detail in U.S. Patent No.
4,001,156 at columns 3 to 6.
Carbamate functional groups can be incorporated into the polymer prepared from polymerizable ethylenically unsaturated monomers by copolymerizing, for example, the above-described ethylenically unsaturated 25 monomers with a carbamate functional vinyl monomer such as a carbamate functional alkyl ester of methacrylic acid. - Useful carbamate functional alkyl esters can be prepared by reacting, for example, a hydroxyalkyl carbamate, such as the reaction product of ammonia and ethylene carbonate or propylene carbonate, with methacrylic anhydride. Other useful carbamate 3o functional vinyl monomers include, for instance, the reaction product of hydroxyethyl methacrylate, isophorone dilsocyanate, and hydroxypropyl carbamate; or the reaction product of hydroxypropyl methacrylate, isophoro,.a diisocyanate, and methanol. Still other carbamate functional vinyl monomers may be used, such as the reaction product of isocyanic acid (HNCO) with a hydroxyl functional acrylic or methacrylic monomer such as hydroxyethyl acrylate, and those described in U.S. Patent No. 3,479,328. Carbamate functional groups can also be incorporated into the acrylic polymer by reacting a hydroxyl functional acrylic polymer with a low m o l e c u l a r we i g h t alkyl carbamate such as methyl carbamate. Pendant carbamate groups can also be incorporated into the acrylic polymer by a io "transcarbamoylation" reaction in which a hydroxyl functional acrylic polymer is reacted with a low molecular weight carbamate derived from an alcohol or a glycol ether. The carbamate groups exchange with the hydroxyl groups yielding the carbamate functional acrylic polymer and the originaf alcohol or glycol ether. Also, hydroxyl functional acrylic polymers can be reacted with isocyanic acid to provide pendent carbamate groups. Utkewise, hydroxyl functional acrylic polymers can be reacted with urea to provide pendent carbamate groups.
The pofy~,'ners prepared from polyr-nerizable ethylenicaliy unsaturated monomers can be prepared by solution polymerization techniques, which are ~;; well-known to i'",ose skilled in ttie art, in t'7:; presence of suitable catalysts such as organic peroxides or azo compounds, for example, benzoyl peroxide or N,N-azobis(isobutylronitrile). The polymerization can be carried out in an organic solution in which the monomers are soluble by techniques conventional in the art. Altematively, these polymers can be prepared by aqueous emulsion or dispersion polymerization techniques which are well-known in the art. The ratio of reactants and reaction conditions are selected to result in an acrylic polymer with the desired pendent functionality.
Polyester polymers are also useful in the coating compositions of the invention as the film-forming polymer. Useful polyester polymers typically include the condensation products of polyhydric alcohols and polycarboxylic acids. Suitable polyhydric alcohols can include ethylene glycol, neopentyl glycol, trimethylol propane, and pentaerythritol. Suitable polycarboxylic acids can include adipic acid, 1,4-c,yclohexyt dicarboxylic acid, and hexahydrophthalic acid. Besides the polycarboxylic acids mentioned above, functional equivalents of the acids such as anhydrides where they exist or lower alkyl esters of the acids such as the methyl esters can be used. Also, small amounts of monocarboxylic acids such as stearic acid can be used. The ratio of reactants and reaction conditions are selected to result in a polyester polymer with the desired pendent functionality, i.e., carboxyl or hydroxyl functionality.
For example, hydroxyl group-containing polyesters can be prepared by reacting an anhydride of a dicarboxylic acid such as hexahydrophthalic anhydride with a diol such as neopentyl glycol in a 1:2 molar ratio. Where it is desired to enhance air-drying, suitable drying oil fatty acids may be used and include those derived from linseed oil, soya bean oil, tall oil, dehydrated castor oit, or tung oil.
Carbamate functional polyesters can be prepared by first formirig a hydroxyalkyl carbamate that can be reacted with the polyacids and poYyols used in forming the polyester. Alternatively, terminal carbamate functional groups can be incorporated into the polyester by reacting isocyanic acid with 2o a hydroxy functional polyester. Also, carbamate functionality can be incorporated into the polyester by reacting a hydroxyl polyester with a urea.
Additionally, carbamate groups can be incorporated into the polyester by a transcarbamoylation reaction. Preparation of suitable carbamate functional group-containing polyesters are those described in U.S. Patent No. 5,593,733 at column 2, line 40 to column 4, line 9.
Polyurethane polymers containing terminal isocyanate or hydroxyl groups also can be used as the polymer (d) in the coating compositions of the invention. The polyurethane polyols or NCO-terminated polyurethanes which can be used are those prepared by reacting polyols including polymeric potyots with polyisocyanates. Polyureas containing terminal isocyanate or primary and/or secondary amine groups which also can be used are those prepared by reacting polyamines including polymeric polyamines with polyisocyanates. The hydroxyl/isocyanate or aminersocyanate equivalent ratio is adjusted and reaction conditions are selected to obtain the desired terminal groups. Examples of suitable polyisocyanates include those s described in U.S. Patent No. 4,046,729 at column 5, line 26 to column 6, line 28. Examples of suitable polyols include those described in U.S. Patent No. 4,046,729 at column 7, line 52 to column 10, line 35. Examples of suitable polyamines include those described in U.S. Patent No. 4,046,729 at column 6, line 61 to column 7, line 32 and in U.S. Patent No. 3,799,854 Io at column 3, lines 13 to 50.
Carbamate functional groups can be introduced into the polyurethane polymers by reacting a polyisocyanate with a polyester having hydroxyl functionality and containing pendent carbamate groups. Alternatively, the is polyurethane can be prepared by reacting a polyisocyanate with a polyester polyol and a hydroxyalkyl carbamate or isocyanic acid as separate reactants.
Examples of suitable polyisocyanates are aromatic isocyanates, such as 4,4'-dipl-i enylrroethane diisocyanate, 1,3-phenylene diisocyanate and toluene diisocyanate, and aliphatic polyisocyanates, such as 1,4-tetramethylene 2o diisoc~,'anate and 1,6-hex:.:-4-,athylene diisocyanate. Cyclc=~,ipiiatic diisocyanates, such as 1,4-cyclohexyl diisocyanate and isophorone diisocyanate also can be employed.
Examples of suitable polyether polyols include polyalkylene ether polyols such as those having the following structural formulas (VI() or (Vlil):
25 (VII) 1 r R
or (Ulll) H 0 [cH2 CHr OH
s R
wherein the substituent R is hydrogen or a lower alkyl group containing from 1 to 5 carbon atoms including mixed substituents, and r has a value typically s ranging from 2 to 6 and s has a value ranging from 8 to 100 or higher.
Exemplary polyalkylene ether polyols include poiy(oxytetramethylene) glycols, poly(oxytetraethylene) glycols, poly(oxy-1,2-propylene) glycols, and poly(oxy-1,2-butylene) glycols.
Also useful are polyether polyols formed from oxyalkylation of various io polyols, for example, glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A, and the like, or other higher polyols such as trimethylolpropane, pentaerythritoi, ~nd Polyofs of higher functionality which can be utilized as indicated can be made, for instance, by oxyalkylation of compounds such as sucrose or sorbitof. One commonly utilized oxyalkylation is method is reaction of a polyol with an aliCylene oxide, for exampSe, pfnpySene or ethylene oxide, in the presence of an acidic or basic catalyst. Specific examples of polyethers include those sold under trade-marks TERATHANE
and TERACOL, available from E. I. Du Pont de Nemours and Company, Inc.
Generally, the polymers having reactive functional groups which are 20 useful in the coating compositions of the invention have a weight average molecular weight (Mw) typically ranging from 1000 to 20,000 preferably 1500 to 15,000 and more preferably 2000 to 12,000 as determined by gel permeation chromatography using a polystyrene standard.
It should be mentioned that when both (a) and (d) are present, the 25 reactive functional groups of (a) and (d) can be the same or different, but both must be reactive with the functional groups of the curing agent (b). Examples of such reactive functional groups include hydroxyl, carboxylic acid, isocyanate, carboxylate, primary amine, secondary amine, amide, carbamate, and epoxy functional groups. Hydroxyl and/or carbamate functional group-containing polymers are preferred.
The polymer having reactive functional groups, if employed, can be present in the coating compositions of the invention in an amount of at least percent by weight, usually at least 5 percent by weight, and typically at least percent by weight based on weight of total resin solids in the coating composition. Also, the polymer having reactive functional groups can be present in the coating compositions of the invention in an amount less than 80 percent by weight, usually less than 60 percent by weight, and typically io less than 50 percent by weight based on weight of total resin solids in the coating composition. The amount of the polymer having reactive functional groups present in the coating compositions of the present invention can range between any combination of these values inclusive of the recited values.
The coating compositions of the present invention can be solvent-based compositions, water-based compositions, in solid particulate form, that is, a powder composition, in the form of a powder slurry or an aqueous dispersion. The components of the present invention used to form the compositions of the present invention can be dissolved or dispersed in an organic solvent. Nonlimiting examples of suitable organic solvents include alcohols, such as butanol; ketones, such as methyl amyl ketone; aromatic hydrocarbons, such as xylene; and glycol ethers, such as, ethylene glycol monobutyl ether; esters; other solvents; and mixtures of any of the foregoing.
In solvent based compositions, the organic solvent is generally present in amounts ranging from 5 to 80 percent by weight based on total weight of the resin solids of the components which form the composition, and can be present in an amount ranging from 30 to 50 percent by weight. The compositions as described above can have a total solids content ranging from 40 to 75 percent by weight based on total weight of the resin solids of the components which form the composition, and can have a total solids content ranging from 50 to 70 percent by weight. Alternatively, the inventive compositions can be in solid particulate form suitable for use as a powder coating, or suitable for disper,sion in a liquid medium such as water for use as a powder slurry.
In a further embodiment, the film-forming compositions as previously s described further comprise a catalyst which is present during the composition's formation. In one embodiment, the catalyst is present in an amount sufficient to accelerate the reaction between at least one reactive functional group of the at least one reactant (b) and/or at least one reactive functional group of the at least one polysiloxane (a) and/or the boron-io containing compound (c), if appropriate, and/or the functional group-containing film-forming polymer, if used.
Nonlimiting examples of suitable catalysts include acidic materials, for example, acid phosphates, such as phenyl acid phosphate, and substituted or unsubstituted sulfonic ac;ft such as dodecylbenzene sulfonic acid or para-15 toluene sulfonic acid. Non-limiting examples of suitable catalysts for reactions between isocyanate groups and active hydrogen-containing materials, for example, those comprising hydroxyl groups, include tin catalysts such as dibutyl tin dilaurate and dibutyl tin oxide. Non-limiting examples of epoxy acid base catalysts include tertiary amines such as N,N'-2o dimethyldodecyl amine catalysts. In another embodiment, the catalyst can be a phosphatized polyester or a phosphatized epoxy. In this embodiment, the catalyst can be, for example, the reaction product of phosphoric acid and a bisphenol A digiycidyl ether having two hydrogenated phenolic rings, such as DRH-151, which is commercially available from Shell Chemical Co. The 25 catalyst can be present, when added to the other components that form the composition, in an amount ranging from 0.1 to 5.0 percent by weight, and is typically present in an amount ranging from 0.5 to 1.5 percent by weight based on the total weight of resin solids present in the composition.
In another embodiment, additional components can be present during 30 the formation of the compositions as previously described. These additional components include, but are not limited to, particles different from components (a), (b) and (c), flexibilizers, plasticizers, surface active agents, thixotropic agents, rheology control modifiers, anti-gassing agents, organic cosolvents, flow controllers, hindered amine light stabilizers, anti-oxidants, UV
light absorbers, coloring agents or tints, and similar additives conventional in s the art, as well as mixtures of any of the foregoing can be included in the composition. These additional ingredients can be present, when added to the other components that form the composition, in an amount up to 40 percent by weight based on the total weight of resin solids present in the composition.
In one embodiment, the present invention is directed to io compositions as previously described wherein the composition further comprises a plurality of particles. In another embodiment, the preserit invention is directed to any composition as previously described wherein the particles have an average particle size of less than 100 microns prior to incorporation into the composition. In another embodiment, the present is invention is directed to any composition as previously described wherein the particles have an average particle size ranging from 1 to less than 1000 nanometers prior to incorporation into the composition. In yet another embodiment, the present invention is directed to any composition as previously described wherein the particles have an average particle size 2o ranging from 1 to 100 nanometers prior to incorporation into the composition.
In another embodiment, the present invention is directed to any composition as previously described wherein the particles have an average particle size ranging from 5 to 50 nanometers prior to incorporation into the composition. In another embodiment, the present invention is directed to any 25 composition as previously described wherein the particles have an average particle size ranging from 5 to 25 nanometers prior to incorporation into the composition.
In an embodiment where the average particle size of the particles is greater than one micron, the average particle size can be measured 30 according to known laser scattering techniques. For example, the average particle size of such particles is measured using a Horiba Model LA 900 laser *Trade-mark diffraction particle size instrument, which uses a helium-neon laser with a wave length of 633 nm to measure the size of the particles and assumes the particle has a spherical shape, i.e., the "particle size" refers to the smallest sphere that will completely enclose the particle.
s In an embodiment of the present invention wherein the size of the particles is less than or equal to one micron, the average particle size can be determined by visually examining an electron micrograph of a transmission electron microscopy ("TEM") image, measuring the diameter of the particles in the image, and calculating the average particle size based on the io magnification of the TEM image. One of ordinary skill in the art will understand how to prepare such a TEM image, and a description of one such method is disclosed in the examples set forth below. In one nonlimiting embodiment of the present invention, a TEM image with 105,000X
ma ;nificatican is ,prc~Q'uced, =~nd a conv , ic ;~ factor is ollzained by dividing the i,s magnification by 1000. Upon visual inspection, the diameter of the particles is measured aniflimeters, and the measurement is converted to nanometers using the conversion factor. The diameter of the particle refers to the smallest diameter sphere that will completely enclose the particle.
The shape (or morphology) of the particles can vary depending upon 20 the specific embodiment of the present invention and its intended application.
For example generally spherical morphologies (such as solid beads, microbeads, or hollow spheres), can be used, as well as particles that are cubic, platy, or acicular (elongated or fibrous). Additionally, the particles can have an internal structure that is hollow, porous or void free, or a combination 25 of any of the foregoing, e.g., a hollow center with porous or solid walls.
For more information on suitable particle characteristics see H. Katz et al.
(Ed.), Handbook of Fillers and Plastics (1987) at pages 9-10.
It will be recognized by one skilled in the art that mixtures of one or 30 more particles having different average particle sizes can be incorporated into the compositions in accordance with the present Invention to impart the desired properties and characteristics to the compositions. For example, particles of varying particle sizes can be used in the compositions according to the present invention.
The particles can be formed from materials selected from polymeric and nonpolymeric inorganic materials, polymeric and nonpolymeric organic materials, composite materials, and mixtures of any of the foregoing. As used herein, the term "polymeric inorganic material" means a polymeric material having a backbone repeat unit based on an element or elements other than carbon. For more information see James Mark et al., Inorganic Polymers, io Prentice Hall Polymer Science and Engineering Series, (1992) at page 5.
As used herein, the term "polymeric organic materials" means synthetic polymeric materials, semisynthetic polymeric materials and natural polymeric materials, all of which have a backbone repeat unit based on carbon.
is An "organic material," as used herein, means carbon containing compounds wherein the carbon is typically bonded to itself and to hydrogen, and often to other elements as well, and excludes binary compounds such as the carbon oxides, ttie carbides, carbon disulfide, etc.; such ternary compounds as the metallic cyanides, metallic carbonyls, phosgene, carbonyl 2o sulfide, etc.; and carbon-containing ionic compounds such as metaiiif.:
carbonates, for example, calcium carbonate and sodium carbonate. See R.
Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at pages 761-762, and M. Silberberg, Chemistry The Molecular Nature of Matter and Change (1996) at page 586.
As used herein, the term "inorganic material" means any material that is not an organic material.
As used herein, the term "composite material" means a, combination of two or more differing materials. The particles formed from composite materials generally have a hardness at their surface that is different from the hardness of the internal portions of the particle beneath its surface. More specifically, the surface of the particle can be modified in any manner well known in the art, including, but not limited to, chemically or physically changing its surface characteristics using techniques known in the art.
For example, a particle can be formed from a primary material that is coated, clad or encapsulated with one or more secondary materials to form a composite particle that has a softer surface. In yet another alternative embodiment, particles formed from composite materials can be formed from a primary material that is coated, clad or encapsulated with a different form of the primary material. For more information on particles useful in the present io invention, see G. Wypych, Handbook of Fillers, 2nd Ed. (1999) at pages 15-202.
The particles suitable for use in the compositions of the invention can comprise inorganic elements or compounds known in the art. Suitable particles can -te for;ried from ceramic materials, metallic materials, and is mixtures of any of the foregoing. Suitable ceramic materials comprise metal oxides, metal nitrides, metal carbides, metal me'.-1 7,iticates, metal borides, metal carbonates, and mtixtuces of any of the focegoing. Spectific, nonlimiting examples of metal nitrides are, for example, boron nitride;
specific, nonlimiting examples of metal oxides are, for example, zinc oxide;
norilimiting 2o examples of suitable metal sulfides are, for example, molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide; nonlimiting suitable examples of metal silicates are, for example, aluminum silicates and magnesium silicates such as vermiculite.
The particles can comprise, for example, a core of essentially a single 25 inorganic oxide such as silica in colloidal, fumed, or amorphous form, alumina or colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, e.g., colloidal or amorphous zirconia, and mixtures of any of the foregoing; or an inorganic oxide of one type upon which is deposited an organic oxide of another type. It should be understood that when the 30 composition of the invention is employed as. a transparent topcoat, for example, as a clearcoat in a multi-component composite coating composition, particles should not seriously interfere with the optical properties of the composition. As used herein; "transparent" means that the cured coating has a BYK Haze index of less than 50 as measured using a BYK/Haze Gloss instrument.
Nonpolymeric, inorganic materials useful in forming the particles of the present invention comprise inorganic materials selected from graphite, metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates, and hydroxides. A nonlimiting example of a useful inorganic oxide is zinc oxide. Nonlimiting examples of suitable inorganic sulfides include io molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide.
Nonlimiting examples of useful inorganic siiicates include aluminum silicates and magnesium silicates, such as vermiculite. Nonlimiting examples of suitable metals include molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, alloys, and mixtures of any of the foregoing.
In one embodiment, the present invention is directed to any composition as previously described wherein the particles are selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia, and mixtures of any of the foregoing. In another embodiment, the present invention is directed to any composition as previously described wherein the particles include colloidal silica. As disclosed above, these materials can be surface treated or untreated.
The composition can comprise precursors suitable for forming silica particles in situ by a sol-gel process. The composition according to the present invention can comprise alkoxy silanes which can be hydrolyzed to form silica particles in situ. For example, tetraethylortho silicate can be hydrolyzed with an acid such as hydrochloric acid and condensed to form silica particles. Other useful particles include surface-modified silicas such as are described in U.S. Patent No. 5,853,809 at cblumn 6, line 51 to'column 8, line 43.
In one embodiment of the present invention, the particles have a hardness value greater than the hardness value of materials that can abrade a polymeric coating or a polymeric substrate. Examples of materials that can abrade the polymeric coating or polymeric substrate include, but are not limited to, dirt, sand, rocks, glass, carwash brushes, and the like. The hardness values of the particles and the materials that can abrade the polymeric coating or polymeric substrate can be determined by any conventional hardness measurement method, such as Vickers or Brinell hardness, but is preferably determined according to the original Mohs' io hardness scale which indicates the relative scratch resistance of the surface of a material on a scale of one to ten. The Mohs' hardness values of several nonlimiting examples of particles formed from inorganic materials suitable for use in the present invention are given in Table A below.
Table A
Particle material Mohs' hardness (original scale) Boron nitride 21 Graphite 0.5-12 Molybdenum disulfide 13 Talc 1-1.54 Mica 2.8-3.2 Kaolinite 2.0-2.56 Gypsum 1.6-2' Caicite (calcium carbonate) 3 Calcium fluoride 49 zinc oxide 4=510 Aluminum 2.511 Copper 2.5-312 Iron 4-513 Gold 2.5-3"
Nickel 5'S
Palladium 4.816 Platinum 4=3"
Silver 2=5-4' Zinc sulfide 3=5-4 9 K. Ludema, Friction, Wear, Lubrication, (1996) at page 27.
2 R. Weast (Ed_), Handbook of Chemistry and Ph~, CRC Press (1 z'at page F-22.
3R. Lewis, Sr., HaWley's Condensed Chemical DictionaN, (12th Ed. 1993) at page 793.
4 Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at page 1113.
Hawley's Condensed Chemical Dictionarti, (12th Ed. 1993) at page 784.
Handbook of Chemistry and Physics at page F-22.
' Handbook of ChemistrY and Physics at page F-22.
Friction. Wear. Lubrication at page 27.
9 Friction. Wear. Lubrication at page 27.
Friction. Wear, Lubrication at page 27.
"Friction. Wear. Lubrication at page 27.
12 Handbook of Chemistry and Physics at page F-22.
"Handbook of Chemistry and Physics at page F-22.
'" Handbook of Chemistrv and Physics at page F-22.
Handbook of Chemistrv and Physics at page F-22.
16 Handbook of Chemistry and Physics at page F-22.
"Handbook of Chemistrv and Physics at page F-22.
18 Handbook of Chemistry and Physics at page F-22.
19 R. Weast (Ed.), Handbook of Chemistrv and Physics, CRC Press (715' Ed.
1990) at page 4-158.
Particle material Mohs' hardness (original scale) Boron nitride 21 Graphite 0.5-12 Molybdenum disulfide 13 Talc 1-1.54 Mica 2.8-3.2 Kaolinite 2.0-2.56 Gypsum 1.6-2' Caicite (calcium carbonate) 3 Calcium fluoride 49 zinc oxide 4=510 Aluminum 2.511 Copper 2.5-312 Iron 4-513 Gold 2.5-3"
Nickel 5'S
Palladium 4.816 Platinum 4=3"
Silver 2=5-4' Zinc sulfide 3=5-4 9 K. Ludema, Friction, Wear, Lubrication, (1996) at page 27.
2 R. Weast (Ed_), Handbook of Chemistry and Ph~, CRC Press (1 z'at page F-22.
3R. Lewis, Sr., HaWley's Condensed Chemical DictionaN, (12th Ed. 1993) at page 793.
4 Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at page 1113.
Hawley's Condensed Chemical Dictionarti, (12th Ed. 1993) at page 784.
Handbook of Chemistry and Physics at page F-22.
' Handbook of ChemistrY and Physics at page F-22.
Friction. Wear. Lubrication at page 27.
9 Friction. Wear. Lubrication at page 27.
Friction. Wear, Lubrication at page 27.
"Friction. Wear. Lubrication at page 27.
12 Handbook of Chemistry and Physics at page F-22.
"Handbook of Chemistry and Physics at page F-22.
'" Handbook of Chemistrv and Physics at page F-22.
Handbook of Chemistrv and Physics at page F-22.
16 Handbook of Chemistry and Physics at page F-22.
"Handbook of Chemistrv and Physics at page F-22.
18 Handbook of Chemistry and Physics at page F-22.
19 R. Weast (Ed.), Handbook of Chemistrv and Physics, CRC Press (715' Ed.
1990) at page 4-158.
In one embodiment, the Mohs' hardness value of the particles is greater than 5. In certain embodiments, the Mohs' hardness value off the particles, such as silica, is greater than 6.
As mentioned above, the Mohs' hardness scale relates to the resistance of a material to scratching. The present invention therefore further contemplates particles that have a hardness at their surface that- is different from the hardness of the internal portions of the particle beneath its surface.
More specifically, and as discussed above, the surface of the particle can be modified in any manner well known in the art, including, but not limited to, to chemically changing the particle's surface characteristics using techniques known in the art such that the surface hardness of the particle is greater the hardness of the materials that can abrade the polymeric coating or polymeric substrate while the hardness of the particle beneath the surface is less than the hJness oi the r;ater'.-~:As that cUn ab;ac-3 the polymeric coating or polymeric substrate.
As another alierr+ntive, a particle cari be formed from a prif-nary material that is coated, clad or encapsulated with one or more secondary materials to form a composite material that has a harder surface.
Alternatively, a particle can be formed from a primary material that is coated, clad or encapsulated with a differing form of the primary material to form a composite material that has a harder surface.
In one example, and without limiting the present invention, an inorganic particle formed from an inorganic material such as silicon carbide or aluminum nitride can be provided with.a silica, carbonate or nanoclay coating to form a useful composite particle. In another nonlimiting example, a silane coupling agent with alkyl side chains can'interact with the surface of an inorganic particle formed from an inorganic oxide to provide a useful composite particle having a "softer" surface. Other examples include cladding, encapsulating or coating particles formed from nonpolymeric or polymeric materials with differing* nonpolymeric or polymeric materials. A
specific nonlimiting example of such composite particles is DUALITET"", which is a synthetic polymeric particle coated with calcium carbonate that is commercially available from Pierce and Stevens Corporation of Buffalo, NY.
In one nonlimiting embodiment of the invention, the particles are formed from solid lubricant materials. As used herein, the term "solid s lubricant" means any solid used between two surfaces to provide protection from damage during relative movement or to reduce friction and wear. In one embodiment, the solid lubricants are inorganic solid lubricants. As used herein, "inorganic solid lubricant" means that the solid lubricants have a characteristic crystalline habit which causes them to shear into thin, flat plates io which readily slide over one another and thus produce an antifriction lubricating effect. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12 th Ed. 1993) at page 712. Friction is the resistance to sliding one solid over another. F. Clauss, Solid Lubricants and Self-Lubricating Solids (1972) at page 1.
In one nonlimiting embodiment of the invention, the particles have a lamellar structure. Particles having a lamellar structure are composed of sheets or plates of atoms in hexagonal array, with strong bonding within the sheet and weak van der Waals bonding between sheets, providing low shear strength between sheets. A.nonlimiting example of a lamellar structure is a hexagonal crystal structure. Inorganic solid particles having a lamellar fullerene (i.e., buckyball) structure also are useful in the present invention.
Nonlimiting examples of suitable materials having a lamellar structure that are useful in forming the particles of the present invention include boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, and mixtures of any of the foregoing. Suitable metal dichalcogenides include molybdenum disuifide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures of any of the foregoing.
The particles can be formed from nonpolymeric, organic materials.
Nonlimiting examples of nonpolymeric, organic materials useful in the present invention include, but are not limited to, stearates (such as zinc stearate and aluminum stearate), diamond, carbon black, and stearamide.
The particles can be formed from inorganic polymeric materials.
Nonlimiting examples of-useful inorganic polymeric materials include s polyphosphazenes, polysilanes, polysiloxane, polygeremanes, polymeric sulfur, polymeric selenium, silicones, and mixtures of any of the foregoing. A
specific, nonlimiting example of a particle formed from an inorganic polymeric material suitable for use in the present invention is TosPEARt_20, which is a particle formed from cross-linked siloxanes and is commercially available from io Toshiba Silicones Company, Ltd. of Japan.
The particles can be formed from synthetic, organic polymeric materials. Nonlimiting examples of suitable organic polymeric materials include, but are not limited to, thermoset materials and thermoplastic materials. A!~=_,sed ",a"'t ~T-:terial is a material that softens 15 when exposed to heat and returns to its original condition when cooled to room temperature. Nonlimitin~.-~ examples of suitable thermoplastic materials include thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonates, polyolefins such as polyethylene, polypropylene, and polyisobutene, acrylic 20 polymers such as copolymer.s of styrene and an acrylic acid monomer, and polymers containing methacrylate, polyamides, thermoplastic polyurethanes, vinyl polymers, and mixtures of any of the foregoing.
Nonlimiting examples of suitable thermoset materials include thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, 25 thermoset polyurethanes, and mixtures of any of the foregoing. A specific, nonlimiting example of a synthetic polymeric particle formed from an epoxy material is an epoxy microgel particle. As used herein, a"thermoset" material is a material that material solidifies or "sets" irreversibly when heated. A
thermoset material has formed a crosslinked network. As used herein, a 20 See R. J. Perry "Applications for Cross-Linked Siloxane Particles"
Chemtech, February 1999 at pages 39-44.
As mentioned above, the Mohs' hardness scale relates to the resistance of a material to scratching. The present invention therefore further contemplates particles that have a hardness at their surface that- is different from the hardness of the internal portions of the particle beneath its surface.
More specifically, and as discussed above, the surface of the particle can be modified in any manner well known in the art, including, but not limited to, to chemically changing the particle's surface characteristics using techniques known in the art such that the surface hardness of the particle is greater the hardness of the materials that can abrade the polymeric coating or polymeric substrate while the hardness of the particle beneath the surface is less than the hJness oi the r;ater'.-~:As that cUn ab;ac-3 the polymeric coating or polymeric substrate.
As another alierr+ntive, a particle cari be formed from a prif-nary material that is coated, clad or encapsulated with one or more secondary materials to form a composite material that has a harder surface.
Alternatively, a particle can be formed from a primary material that is coated, clad or encapsulated with a differing form of the primary material to form a composite material that has a harder surface.
In one example, and without limiting the present invention, an inorganic particle formed from an inorganic material such as silicon carbide or aluminum nitride can be provided with.a silica, carbonate or nanoclay coating to form a useful composite particle. In another nonlimiting example, a silane coupling agent with alkyl side chains can'interact with the surface of an inorganic particle formed from an inorganic oxide to provide a useful composite particle having a "softer" surface. Other examples include cladding, encapsulating or coating particles formed from nonpolymeric or polymeric materials with differing* nonpolymeric or polymeric materials. A
specific nonlimiting example of such composite particles is DUALITET"", which is a synthetic polymeric particle coated with calcium carbonate that is commercially available from Pierce and Stevens Corporation of Buffalo, NY.
In one nonlimiting embodiment of the invention, the particles are formed from solid lubricant materials. As used herein, the term "solid s lubricant" means any solid used between two surfaces to provide protection from damage during relative movement or to reduce friction and wear. In one embodiment, the solid lubricants are inorganic solid lubricants. As used herein, "inorganic solid lubricant" means that the solid lubricants have a characteristic crystalline habit which causes them to shear into thin, flat plates io which readily slide over one another and thus produce an antifriction lubricating effect. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12 th Ed. 1993) at page 712. Friction is the resistance to sliding one solid over another. F. Clauss, Solid Lubricants and Self-Lubricating Solids (1972) at page 1.
In one nonlimiting embodiment of the invention, the particles have a lamellar structure. Particles having a lamellar structure are composed of sheets or plates of atoms in hexagonal array, with strong bonding within the sheet and weak van der Waals bonding between sheets, providing low shear strength between sheets. A.nonlimiting example of a lamellar structure is a hexagonal crystal structure. Inorganic solid particles having a lamellar fullerene (i.e., buckyball) structure also are useful in the present invention.
Nonlimiting examples of suitable materials having a lamellar structure that are useful in forming the particles of the present invention include boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, and mixtures of any of the foregoing. Suitable metal dichalcogenides include molybdenum disuifide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures of any of the foregoing.
The particles can be formed from nonpolymeric, organic materials.
Nonlimiting examples of nonpolymeric, organic materials useful in the present invention include, but are not limited to, stearates (such as zinc stearate and aluminum stearate), diamond, carbon black, and stearamide.
The particles can be formed from inorganic polymeric materials.
Nonlimiting examples of-useful inorganic polymeric materials include s polyphosphazenes, polysilanes, polysiloxane, polygeremanes, polymeric sulfur, polymeric selenium, silicones, and mixtures of any of the foregoing. A
specific, nonlimiting example of a particle formed from an inorganic polymeric material suitable for use in the present invention is TosPEARt_20, which is a particle formed from cross-linked siloxanes and is commercially available from io Toshiba Silicones Company, Ltd. of Japan.
The particles can be formed from synthetic, organic polymeric materials. Nonlimiting examples of suitable organic polymeric materials include, but are not limited to, thermoset materials and thermoplastic materials. A!~=_,sed ",a"'t ~T-:terial is a material that softens 15 when exposed to heat and returns to its original condition when cooled to room temperature. Nonlimitin~.-~ examples of suitable thermoplastic materials include thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonates, polyolefins such as polyethylene, polypropylene, and polyisobutene, acrylic 20 polymers such as copolymer.s of styrene and an acrylic acid monomer, and polymers containing methacrylate, polyamides, thermoplastic polyurethanes, vinyl polymers, and mixtures of any of the foregoing.
Nonlimiting examples of suitable thermoset materials include thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, 25 thermoset polyurethanes, and mixtures of any of the foregoing. A specific, nonlimiting example of a synthetic polymeric particle formed from an epoxy material is an epoxy microgel particle. As used herein, a"thermoset" material is a material that material solidifies or "sets" irreversibly when heated. A
thermoset material has formed a crosslinked network. As used herein, a 20 See R. J. Perry "Applications for Cross-Linked Siloxane Particles"
Chemtech, February 1999 at pages 39-44.
polymeric material is "crosslinked" if it at least partially forms a polymeric network. One skilled in the art will understand that the presence and degree of crosslinking (crosslink density) can be determined by a variety of methods, such as dynamic mechanical thermal analysis (DMTA) using a TA
Instruments DMA 2980 analyzer conducted under nitrogen such as is described above. This method determines the glass transition temperature and crosslink density of free films of coatings or polymers. These physical properties of a cured material are related to the structure of the crosslinked network.
The particles also can be hollow particles formed from materials selected from polymeric and nonpolymeric inorganic materials, polymeric and nonpolymeric organic materials, composite materials, and mixtures of any of the foregoing. Nonlimiting examples of suitable materials from which the hollow particles can be formed are described above.
In an embodiment of the present invention, the at least one polysiloxane (a) is nonreactive with the particles.
In one embodiment, the present invention is directed to any composition as previously described wherein the particles, when added to the other components that form the composition, are present in the composition in an amount ranging from 0.01 to 75 weight percent based on the totaf weight of the resin solids of the components which form the composition. In another embodiment, the present invention is directed to any composition as previously described wherein the particles, when added to the other components that form the composition, are present in the composition in an amount of at least 0.1 weight percent, can be present in the composition in an amount greater than 0.5 weight percent, and are typically present in the composition in an amount greater than 5 weight percent based on the total weight of the resin solids of the components which form the composition.
In yet another embodiment, the present invention is directed to any composition as previously described wherein, the particles, when added to the other components of the composition, are present in the composition in an amount less than 75 weight percent, can be present in the composition in an amount less than 50 weight percent, can be present in the composition in an amount less than 20 weight percent, and are typically present in the composition in an amount less than 10 weight percent based on the total s weight of the resin solids of the components which form the composition.
The amount of the particles present in the compositions may range between any combination of these values inclusive of the recited values.
Prior to incorporation, one class of particles which can be used according to the present invention includes sols, such as an organosol, of the io particles. These sols can be of a wide variety of small-particle, colloidal silicas having an average particle size in ranges such as identified above.
The colloidal silicas can be surface modified during or after the particles are initially formed. These surface modified silicas may contain on their surface chAmical!y honded c-)rhon-containing moieties, as well ac.; such is groups as anhydrous :>;v2 groups and SiOH groups, various ionic groups physically associated or chem-cally bonded within the surface of the silica, adsorbed organic groups, or combinations of any of the foregoing, depending on the characteristics of the particular silica desired. Such surface modified silicas are described in detail in U.S. Patent No. 4,680,204.
Such materials can be prepared by a variety of techniques in various forms, nonlimiting examples comprise organosols and mixed sols. As used herein the term "mixed sols" is intended to include those dispersions of colloidal silica in which the dispersing medium comprises both an organic liquid and water. Such small particle colloidal silicas are readily available, are essentially colorless and have refractive indices which permit their inclusion in compositions that, without additional pigments or components known in the art to color or decrease the transparency of such compositions, result in colorless, transparent coatings. .
Suitable nonlimiting examples of particles include colloidal silicas, such as those commercially available from Nissan Chemical Company under the trademark ORGANOSILICASOLSTM such as ORGANOSILICASOLTM MT-1%1.
and from Clariant Corporation as HIGHLINKTM; colloidal aluminas, such as those commercially available from Nalco Chemical under the trademark NALCO 8676 ; and colloidal zirconias, such as those commercially available from Nissan Chemical Company under the trademark HIT-32M .
The particles can be incorporated into the compositions of the invention in the form of a stable dispersion. When the particles are in a colloidal form, the dispersions can be prepared by dispersing the particles in a carrier under agitation and solvent that is present can be removed under 1o vacuum at ambient temperatures. In certain embodiments, the carrier can be other than a solvent, such as the surface active agents described in detail below, including, but not limited to a polysiloxane containing reactive functional groups, including, but not limited to, the at least one polysiloxane (a).
Alternatively, the dispersions can be prepared as described in U.S.
Patent Nos. 4,522,958 or 4,526,910. The particles can be "cold-blended"
with the at least one polysiloxane (a) prior to incorporation into the iiiventive cor7iposi'Lions. Alternatively, tfie particles can be post-added to an admixture of any remaining composition components (including, but not limited to, the at least one polysiloxane (a)) an.' dispersed ?'.-;ein osina dispersing techniques well-known in the art.
When the particles are in other than colloidal form, for example, but not limited to, agglomerate form, the dispersions can be prepared by dispersing the agglomerate in the carrier, for example, but not limited to, the at least one polysiloxane (a), to stably disperse the particles therein. Dispersion techniques such as grinding, milling, microfluidizing, ultrasounding,, or any other pigment dispersing techniques well known in the art of coatings formulation can be used. Alternatively, the particles can be dispersed by any other dispersion techniques known in the art. If desired, the particles in other than colloidal form can be post-added to an admixture of other composition components and dispersed therein using any dispersing techniques known in the art.
The particles can be present in a dispersion, suspension or emulsion in a carrier. Nonlimiting examples of suitable carriers include, but are not limited to, water, solvents, surfactants, or a mixture of any of the foregoing.
In yet another embodiment of the present invention, at least one adjuvant surface active agent can be present during the formation of the compositions as previously described. Further, as used herein, by "surface active agent" is meant any material which tends to lower the solid surface io tension or surface energy of the "cured" composition or coating. That is, the cured composition or coating formed from a composition comprising a surface active agent has a lower solid surface tension or surface energy than a cured coating formed from the analogous composition which does not contain the surface active aaent.
For purposes of the present invention, solid -surface tension can be measured according to the Owens-Wendt method using a Rame'-Hart Contact Angle Goniometer with distilled water and methylene iodide as reagents. Generally, a 0.02 cc drop of one reagent is placed upon the cured coating surface and the contact angle and its complement are measured using a standard microscope equipped with the goniometer. The contact angle and its complement are measured for each of three drops. The process is then repeated using the other reagent. An average 'value is calculated for the six measurements for each of the reagents. The solid surface tension is then calculated using the Owens-Wendt equation:
{y 1(1+cos0)}/2 =(yldysd)V2+ (y1PySp)In where y I is the surface tension of the liquid (methylene iodide = 50.8, distilled water = 72.8) and y d and y are the dispersion and polar components (methylene iodide 7 = 49.5, y P= 1.3; distilled water y d= 21.8, y P= 51.0);
the values for cD measured and the cos (D determined. Two equations are then setup, one for methylene iodide and one for water. The only unknowns are y and y S p. The two equations are then solved for the two unknowns. The two components combined rqpresent the total solid surface tension.
The at least one adjuvant surface active agent can be selected from amphiphilic, reactive functional group-containing polysiloxanes such as are s described above, amphiphilic fluoropolymers, and mixtures of any of the foregoing. With reference to water-soluble or water-dispersible amphiphilic materials, the term "amphiphilic" means a polymer having a generally hydrophilic polar end and a water-insoluble generally hydrophobic end.
Nonlimiting examples of suitable functional group-containing polysiloxanes for i o use as surface active agents include those polysiloxanes described above.
Nonlimiting examples of suitable amphiphilic fluoropolymers include fluoroethylene-alkyl vinyl ether alternating copolymers (such as those described in U.S. Patent No. 4,345,057) available from Asahi Glass Company under the trade-mark LUMIFLON; fluorosurfactants, such as the is fluoroaliphatic polymeric esters commercially available from 3M of St.
Paul, Minnesota under the trade-mark FLUORAD; functionalized perfluorinated niaterials, such as 1 H, 1 H-perfluoro-nonanol commercially available from FluoroChem UISA; a>>c1 periiuorinated (:iieth)acryiat:; resi+Is.
Nonlimiting examples of other adjuvant surface active agents suitable 20 for use in the composition or coating of the presen' invention ca-r include anionic, nonionic and cationic surface active agents.
Nonlimiting examples of suitable anionic surface active agents include sulfates or sulfonates. Specific nonlimiting examples include higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates 25 containing from 10 to 16 carbon atoms in the alkyl group and a straight- or branched-chain, e.g., the sodium salts of decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl benzene sulfonate and the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate. Other nonlimiting examples of 30 suitable anionic surface active agents include olefin sulfonates, including long chain alkenylene sulfonates, long chain hydroxyalkane sulfonates, and mixtures of any of the foregoing. Nonlimiting examples of other sulfate or sulfonate detergents are parpffin sulfonates such as the reaction products of alpha olefins and bisulfites (e.g.,I sodium bisulfite). Also comprised are sulfates of higher alcohols, such as sodium lauryl sulfate, sodium tallow s alcohol sulfate, or sulfates of mono-or di-glycerides of fatty acids (e.g., stearic monoglyceride monosulfate), alkyl poly(ethoxy)ether sulfates including, but not iimited to, the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having 1-5 ethenoxy groups per molecule); latiryl or other higher alkyl glyceryl ether sulfonates; aromatic poly(ethenoxy)ether io suifates including, but not limited to, the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having 1-20 oxyethylene groups per molecule). Further nonlimiting examples include salts of sulfated aliphatic alcohol, alkyl ether sulfate or alkyl aryl ethoxy sulfate available from Rhone-c Ur:d :. the gE,-i:F ,rade-m: A ABEX. ate mono-or di-ester 15 type anionic surface active agents also can be used. These anionic surface acti'r agen's are well knov~n in the art and are com-nerciaiiy ava:lab;eund.:r the general trade designation GAFAC* from GAF Corporation and under the general trade designation TRITON* from Rohm & Haas Company.
Nonlimiting examples of nonionic surface active agents suitable for use 20 in the cured composition or coating of the present invention include those containing ether linkages and which are represented by the following general formula: RO(R'O)nH; wherein the substituent group R represents a hydrocarbon group containing 6 to 60 carbon atoms, the substituent group R' represents an alkylene group containing 2 or 3 carbon atoms, and mixtures of 25 any of the foregoing, and n is an integer ranging from 2 to 100. Such nonionic surface active agents can be prepared by treating fatty alcohols or alkyl-substituted phenols with an excess of ethylene or propylene oxide. The alkyl carbon chain may contain from 14 to 40 carbon atoms and may be derived from a long chain fatty alcohol such as oleyl alcohol or stearyl alcohol.
so Nonionic polyoxyethylene surface active agents of the type represented by the formula above are commercially available under the general trade *Trade-mark designation SURFYNOL from Air Products Chemicals, Inc.; PLURONIC Or TETRONIC from BASF Corporation; TERGtTOL from Union Carbide; and SURFONIC from Huntsman Corporation. Other nonlimiting examples of suitable nonionic surface active agents include block copolymers of ethylene oxide and propylene oxide based on a glycol such as ethylene glycol or propylene glycol including, but not limited to, those available from BASF
Corporation under the general trade designation PLURONIC .
As indicated above, cationic surface active agents also can be used.
Nonlimiting examples of cationic surface active agents suitable for use in the io compositions of the present invention include acid salts of alkyl a.mines such as ARMAC HT, an acetic acid salt of n-alkyl amine available from Akzo Nobel Chemicals; imidazoline derivatives such as CALGENE C-100 available from Calgene Chemicals Inc.; ethoxylated amines or amides such as DETHOX Amine C-5, a cocoamine ethoxylate available from Deforest 15- Enterprises; ethoxylated fatty amines such as ETHOX TAM available from Ethox Chemicals, Inc.; and glyceryl esters such as LEXEMUL AR, a glyceryl stearate/stearaidoethyl diethylamine available from !nolex Chemical Co.
Other examples of suitable surface active agents can include polyacrylates. Nonlimiting examples of suitable polyacrylates include 2o homopolymers and copolymers of acrylate monomers, for example polybutylacrylate and copolymers derived from acrylate monomers (sUch as ethyl (meth)acrylate, 2-ethylhexylacrylate, butyl (meth)acrylate and isobutyl acrylate), and hydroxy ethyl(meth)acrylate and (meth)acrylic acid monomers.
In one embodiment, the polyacrylate can have amino and hydroxy 25 functionality. Suitable amino and hydroxyl functional acrylates are discin--cpr+
in Example 26 below and in U.S. Patent No. 6,013,733. Another example of a useful amino and hydroxyl functional copolymer is a copolymer of hydroxy ethyl acrylate, 2-ethylhexylacrylate, isobutyl acrylate and dimethylamino ethylmethacrylate. In another 30 embodiment, the polyacrylate can have acid functionality, which can be provided, for example, by including acid functional monomers such as (meth)acrylic acid in the components used to prepare the polyacrylate. In another embodiment, the polyacrylate can have acid functionality and hydroxyl functionality, which can'be provided, for example, by including acid functional monomers such as (meth)acrylic acid and hydroxyl functional monomers such as hydroxy ethyl (meth)acrylate in the components used to prepare the polyacrylate.
Suitable flow additives include silicones such as BYK*310 or BYK*307, which are commercially available from Byk-Chemie. Suitable rheology control agents include cellulose acetate butyrate and fumed silicas such as R812 io which is commercially available from Degussa Chemical.
In yet another embodiment, the present invention is directed to a coated substrate comprising a substrate and a composition coated over at least a portion of the substrate, wherein the composition is selected from any cf ~he f~r-.f-ning composit ens. In still another embodiment, the present invention is uirected to a method of coating a substrate which comprises applying a composition over at least a portion of the rubstrate, wherein the composition is selected from any of the foregoing compositions. In another embodiment, the present invention is directed to a method of coating a substrate further comprising a step of curing the composition after application to the substrate. The components used to form the compositions in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
As used herein, a composition "over" at least a portion of a substrate refers to a composition directly applied to at least a portion of the substrate, as well as a composition applied to any coating or adhesion promoter material which was previously applied to at least a portion of the substrate.
The coating compositions of the present invention can be applied over virtually any flexible substrate including plastic, and polymeric substrates such as elastomeric substrates. In one.embodiment, the present invention is 3o directed to a coated substrate as previously described wherein the coated substrate is a flexible elastomeric substrate. In still another embodiment, the *Trade-mark present invention is directed to coated substrates as previously described wherein the coated substrate is a polymeric substrate. The components used to form the compositions in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
A further embodiment of the present invention is directed to a coated automobile substrate comprising an automobile substrate and a composition coated over at least a portion of the automobile substrate, wherein the composition is selected from any of the foregoing compositions. In yet io another embodiment, the present invention is directed to a method of making a coated automobile substrate comprising providing an automobile substrate and applying over at least a portion of the automotive substrate a composition selected from any of the foregoing compositions. Again, the components used to form the compositions in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
Suitable polymeric or flexible elastomeric substrates can include any of the thermoplastic or thermoset synthetic materials weii known in the art.
Nonlimiting examples of suitable flexible elastomeric substrate materials incfude polyethylene, polypropylene, thermoplastic polyole in ("TPO"'), reaction injected molded polyurethane ("RIM") and thermoplastic polyurethane ("TPU").
Nonlimiting examples of thermoset materials useful as substrates in connection with the present invention include polyesters, epoxides, phenolics, polyurethanes such as "RIM" thermoset materials, and mixtures of any of the foregoing. Nonlimiting examples of suitable thermoplastic materials include thermoplastic polyolefins such as polyethylene, polypropylene, polyamides such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, acrylic polymers, vinyl polymers, polycarbonates, acrylonitrile-butadiene-styrene ("ABS") copolymers, ethylene propylene diene terpolymer ("EPDM") rubber, copolymers, and mixtures of any of the foregoing.
Instruments DMA 2980 analyzer conducted under nitrogen such as is described above. This method determines the glass transition temperature and crosslink density of free films of coatings or polymers. These physical properties of a cured material are related to the structure of the crosslinked network.
The particles also can be hollow particles formed from materials selected from polymeric and nonpolymeric inorganic materials, polymeric and nonpolymeric organic materials, composite materials, and mixtures of any of the foregoing. Nonlimiting examples of suitable materials from which the hollow particles can be formed are described above.
In an embodiment of the present invention, the at least one polysiloxane (a) is nonreactive with the particles.
In one embodiment, the present invention is directed to any composition as previously described wherein the particles, when added to the other components that form the composition, are present in the composition in an amount ranging from 0.01 to 75 weight percent based on the totaf weight of the resin solids of the components which form the composition. In another embodiment, the present invention is directed to any composition as previously described wherein the particles, when added to the other components that form the composition, are present in the composition in an amount of at least 0.1 weight percent, can be present in the composition in an amount greater than 0.5 weight percent, and are typically present in the composition in an amount greater than 5 weight percent based on the total weight of the resin solids of the components which form the composition.
In yet another embodiment, the present invention is directed to any composition as previously described wherein, the particles, when added to the other components of the composition, are present in the composition in an amount less than 75 weight percent, can be present in the composition in an amount less than 50 weight percent, can be present in the composition in an amount less than 20 weight percent, and are typically present in the composition in an amount less than 10 weight percent based on the total s weight of the resin solids of the components which form the composition.
The amount of the particles present in the compositions may range between any combination of these values inclusive of the recited values.
Prior to incorporation, one class of particles which can be used according to the present invention includes sols, such as an organosol, of the io particles. These sols can be of a wide variety of small-particle, colloidal silicas having an average particle size in ranges such as identified above.
The colloidal silicas can be surface modified during or after the particles are initially formed. These surface modified silicas may contain on their surface chAmical!y honded c-)rhon-containing moieties, as well ac.; such is groups as anhydrous :>;v2 groups and SiOH groups, various ionic groups physically associated or chem-cally bonded within the surface of the silica, adsorbed organic groups, or combinations of any of the foregoing, depending on the characteristics of the particular silica desired. Such surface modified silicas are described in detail in U.S. Patent No. 4,680,204.
Such materials can be prepared by a variety of techniques in various forms, nonlimiting examples comprise organosols and mixed sols. As used herein the term "mixed sols" is intended to include those dispersions of colloidal silica in which the dispersing medium comprises both an organic liquid and water. Such small particle colloidal silicas are readily available, are essentially colorless and have refractive indices which permit their inclusion in compositions that, without additional pigments or components known in the art to color or decrease the transparency of such compositions, result in colorless, transparent coatings. .
Suitable nonlimiting examples of particles include colloidal silicas, such as those commercially available from Nissan Chemical Company under the trademark ORGANOSILICASOLSTM such as ORGANOSILICASOLTM MT-1%1.
and from Clariant Corporation as HIGHLINKTM; colloidal aluminas, such as those commercially available from Nalco Chemical under the trademark NALCO 8676 ; and colloidal zirconias, such as those commercially available from Nissan Chemical Company under the trademark HIT-32M .
The particles can be incorporated into the compositions of the invention in the form of a stable dispersion. When the particles are in a colloidal form, the dispersions can be prepared by dispersing the particles in a carrier under agitation and solvent that is present can be removed under 1o vacuum at ambient temperatures. In certain embodiments, the carrier can be other than a solvent, such as the surface active agents described in detail below, including, but not limited to a polysiloxane containing reactive functional groups, including, but not limited to, the at least one polysiloxane (a).
Alternatively, the dispersions can be prepared as described in U.S.
Patent Nos. 4,522,958 or 4,526,910. The particles can be "cold-blended"
with the at least one polysiloxane (a) prior to incorporation into the iiiventive cor7iposi'Lions. Alternatively, tfie particles can be post-added to an admixture of any remaining composition components (including, but not limited to, the at least one polysiloxane (a)) an.' dispersed ?'.-;ein osina dispersing techniques well-known in the art.
When the particles are in other than colloidal form, for example, but not limited to, agglomerate form, the dispersions can be prepared by dispersing the agglomerate in the carrier, for example, but not limited to, the at least one polysiloxane (a), to stably disperse the particles therein. Dispersion techniques such as grinding, milling, microfluidizing, ultrasounding,, or any other pigment dispersing techniques well known in the art of coatings formulation can be used. Alternatively, the particles can be dispersed by any other dispersion techniques known in the art. If desired, the particles in other than colloidal form can be post-added to an admixture of other composition components and dispersed therein using any dispersing techniques known in the art.
The particles can be present in a dispersion, suspension or emulsion in a carrier. Nonlimiting examples of suitable carriers include, but are not limited to, water, solvents, surfactants, or a mixture of any of the foregoing.
In yet another embodiment of the present invention, at least one adjuvant surface active agent can be present during the formation of the compositions as previously described. Further, as used herein, by "surface active agent" is meant any material which tends to lower the solid surface io tension or surface energy of the "cured" composition or coating. That is, the cured composition or coating formed from a composition comprising a surface active agent has a lower solid surface tension or surface energy than a cured coating formed from the analogous composition which does not contain the surface active aaent.
For purposes of the present invention, solid -surface tension can be measured according to the Owens-Wendt method using a Rame'-Hart Contact Angle Goniometer with distilled water and methylene iodide as reagents. Generally, a 0.02 cc drop of one reagent is placed upon the cured coating surface and the contact angle and its complement are measured using a standard microscope equipped with the goniometer. The contact angle and its complement are measured for each of three drops. The process is then repeated using the other reagent. An average 'value is calculated for the six measurements for each of the reagents. The solid surface tension is then calculated using the Owens-Wendt equation:
{y 1(1+cos0)}/2 =(yldysd)V2+ (y1PySp)In where y I is the surface tension of the liquid (methylene iodide = 50.8, distilled water = 72.8) and y d and y are the dispersion and polar components (methylene iodide 7 = 49.5, y P= 1.3; distilled water y d= 21.8, y P= 51.0);
the values for cD measured and the cos (D determined. Two equations are then setup, one for methylene iodide and one for water. The only unknowns are y and y S p. The two equations are then solved for the two unknowns. The two components combined rqpresent the total solid surface tension.
The at least one adjuvant surface active agent can be selected from amphiphilic, reactive functional group-containing polysiloxanes such as are s described above, amphiphilic fluoropolymers, and mixtures of any of the foregoing. With reference to water-soluble or water-dispersible amphiphilic materials, the term "amphiphilic" means a polymer having a generally hydrophilic polar end and a water-insoluble generally hydrophobic end.
Nonlimiting examples of suitable functional group-containing polysiloxanes for i o use as surface active agents include those polysiloxanes described above.
Nonlimiting examples of suitable amphiphilic fluoropolymers include fluoroethylene-alkyl vinyl ether alternating copolymers (such as those described in U.S. Patent No. 4,345,057) available from Asahi Glass Company under the trade-mark LUMIFLON; fluorosurfactants, such as the is fluoroaliphatic polymeric esters commercially available from 3M of St.
Paul, Minnesota under the trade-mark FLUORAD; functionalized perfluorinated niaterials, such as 1 H, 1 H-perfluoro-nonanol commercially available from FluoroChem UISA; a>>c1 periiuorinated (:iieth)acryiat:; resi+Is.
Nonlimiting examples of other adjuvant surface active agents suitable 20 for use in the composition or coating of the presen' invention ca-r include anionic, nonionic and cationic surface active agents.
Nonlimiting examples of suitable anionic surface active agents include sulfates or sulfonates. Specific nonlimiting examples include higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates 25 containing from 10 to 16 carbon atoms in the alkyl group and a straight- or branched-chain, e.g., the sodium salts of decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl benzene sulfonate and the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate. Other nonlimiting examples of 30 suitable anionic surface active agents include olefin sulfonates, including long chain alkenylene sulfonates, long chain hydroxyalkane sulfonates, and mixtures of any of the foregoing. Nonlimiting examples of other sulfate or sulfonate detergents are parpffin sulfonates such as the reaction products of alpha olefins and bisulfites (e.g.,I sodium bisulfite). Also comprised are sulfates of higher alcohols, such as sodium lauryl sulfate, sodium tallow s alcohol sulfate, or sulfates of mono-or di-glycerides of fatty acids (e.g., stearic monoglyceride monosulfate), alkyl poly(ethoxy)ether sulfates including, but not iimited to, the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having 1-5 ethenoxy groups per molecule); latiryl or other higher alkyl glyceryl ether sulfonates; aromatic poly(ethenoxy)ether io suifates including, but not limited to, the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having 1-20 oxyethylene groups per molecule). Further nonlimiting examples include salts of sulfated aliphatic alcohol, alkyl ether sulfate or alkyl aryl ethoxy sulfate available from Rhone-c Ur:d :. the gE,-i:F ,rade-m: A ABEX. ate mono-or di-ester 15 type anionic surface active agents also can be used. These anionic surface acti'r agen's are well knov~n in the art and are com-nerciaiiy ava:lab;eund.:r the general trade designation GAFAC* from GAF Corporation and under the general trade designation TRITON* from Rohm & Haas Company.
Nonlimiting examples of nonionic surface active agents suitable for use 20 in the cured composition or coating of the present invention include those containing ether linkages and which are represented by the following general formula: RO(R'O)nH; wherein the substituent group R represents a hydrocarbon group containing 6 to 60 carbon atoms, the substituent group R' represents an alkylene group containing 2 or 3 carbon atoms, and mixtures of 25 any of the foregoing, and n is an integer ranging from 2 to 100. Such nonionic surface active agents can be prepared by treating fatty alcohols or alkyl-substituted phenols with an excess of ethylene or propylene oxide. The alkyl carbon chain may contain from 14 to 40 carbon atoms and may be derived from a long chain fatty alcohol such as oleyl alcohol or stearyl alcohol.
so Nonionic polyoxyethylene surface active agents of the type represented by the formula above are commercially available under the general trade *Trade-mark designation SURFYNOL from Air Products Chemicals, Inc.; PLURONIC Or TETRONIC from BASF Corporation; TERGtTOL from Union Carbide; and SURFONIC from Huntsman Corporation. Other nonlimiting examples of suitable nonionic surface active agents include block copolymers of ethylene oxide and propylene oxide based on a glycol such as ethylene glycol or propylene glycol including, but not limited to, those available from BASF
Corporation under the general trade designation PLURONIC .
As indicated above, cationic surface active agents also can be used.
Nonlimiting examples of cationic surface active agents suitable for use in the io compositions of the present invention include acid salts of alkyl a.mines such as ARMAC HT, an acetic acid salt of n-alkyl amine available from Akzo Nobel Chemicals; imidazoline derivatives such as CALGENE C-100 available from Calgene Chemicals Inc.; ethoxylated amines or amides such as DETHOX Amine C-5, a cocoamine ethoxylate available from Deforest 15- Enterprises; ethoxylated fatty amines such as ETHOX TAM available from Ethox Chemicals, Inc.; and glyceryl esters such as LEXEMUL AR, a glyceryl stearate/stearaidoethyl diethylamine available from !nolex Chemical Co.
Other examples of suitable surface active agents can include polyacrylates. Nonlimiting examples of suitable polyacrylates include 2o homopolymers and copolymers of acrylate monomers, for example polybutylacrylate and copolymers derived from acrylate monomers (sUch as ethyl (meth)acrylate, 2-ethylhexylacrylate, butyl (meth)acrylate and isobutyl acrylate), and hydroxy ethyl(meth)acrylate and (meth)acrylic acid monomers.
In one embodiment, the polyacrylate can have amino and hydroxy 25 functionality. Suitable amino and hydroxyl functional acrylates are discin--cpr+
in Example 26 below and in U.S. Patent No. 6,013,733. Another example of a useful amino and hydroxyl functional copolymer is a copolymer of hydroxy ethyl acrylate, 2-ethylhexylacrylate, isobutyl acrylate and dimethylamino ethylmethacrylate. In another 30 embodiment, the polyacrylate can have acid functionality, which can be provided, for example, by including acid functional monomers such as (meth)acrylic acid in the components used to prepare the polyacrylate. In another embodiment, the polyacrylate can have acid functionality and hydroxyl functionality, which can'be provided, for example, by including acid functional monomers such as (meth)acrylic acid and hydroxyl functional monomers such as hydroxy ethyl (meth)acrylate in the components used to prepare the polyacrylate.
Suitable flow additives include silicones such as BYK*310 or BYK*307, which are commercially available from Byk-Chemie. Suitable rheology control agents include cellulose acetate butyrate and fumed silicas such as R812 io which is commercially available from Degussa Chemical.
In yet another embodiment, the present invention is directed to a coated substrate comprising a substrate and a composition coated over at least a portion of the substrate, wherein the composition is selected from any cf ~he f~r-.f-ning composit ens. In still another embodiment, the present invention is uirected to a method of coating a substrate which comprises applying a composition over at least a portion of the rubstrate, wherein the composition is selected from any of the foregoing compositions. In another embodiment, the present invention is directed to a method of coating a substrate further comprising a step of curing the composition after application to the substrate. The components used to form the compositions in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
As used herein, a composition "over" at least a portion of a substrate refers to a composition directly applied to at least a portion of the substrate, as well as a composition applied to any coating or adhesion promoter material which was previously applied to at least a portion of the substrate.
The coating compositions of the present invention can be applied over virtually any flexible substrate including plastic, and polymeric substrates such as elastomeric substrates. In one.embodiment, the present invention is 3o directed to a coated substrate as previously described wherein the coated substrate is a flexible elastomeric substrate. In still another embodiment, the *Trade-mark present invention is directed to coated substrates as previously described wherein the coated substrate is a polymeric substrate. The components used to form the compositions in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
A further embodiment of the present invention is directed to a coated automobile substrate comprising an automobile substrate and a composition coated over at least a portion of the automobile substrate, wherein the composition is selected from any of the foregoing compositions. In yet io another embodiment, the present invention is directed to a method of making a coated automobile substrate comprising providing an automobile substrate and applying over at least a portion of the automotive substrate a composition selected from any of the foregoing compositions. Again, the components used to form the compositions in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
Suitable polymeric or flexible elastomeric substrates can include any of the thermoplastic or thermoset synthetic materials weii known in the art.
Nonlimiting examples of suitable flexible elastomeric substrate materials incfude polyethylene, polypropylene, thermoplastic polyole in ("TPO"'), reaction injected molded polyurethane ("RIM") and thermoplastic polyurethane ("TPU").
Nonlimiting examples of thermoset materials useful as substrates in connection with the present invention include polyesters, epoxides, phenolics, polyurethanes such as "RIM" thermoset materials, and mixtures of any of the foregoing. Nonlimiting examples of suitable thermoplastic materials include thermoplastic polyolefins such as polyethylene, polypropylene, polyamides such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, acrylic polymers, vinyl polymers, polycarbonates, acrylonitrile-butadiene-styrene ("ABS") copolymers, ethylene propylene diene terpolymer ("EPDM") rubber, copolymers, and mixtures of any of the foregoing.
If desired, the polymeric substrates described above can have an adhesion promoter present on the surface of the substrate over which the coating compositions of the present invention are applied. To facilitate adhesion of organic coatings to polymeric substrates, the substrate can be s pretreated using an adhesion promoter layer or tie coat, e.g., a thin layer 0.25 mils (6.35 microns) thick, or by flame or corona pretreatment.
Suitable adhesion promoters include chlorinated polyolefin adhesion promoters such as are described in U.S. Patent Nos. 4,997,882; 5,319,032;
and 5,397,602. Other useful adhesion promoting coatings are to disclosed in U.S. Patent Nos. 6,001,469 (a coating composition containing a saturated polyhydroxylated polydiene polymer having terminal hydroxyl groups), 5,863,646 (a coating composition having a blend of a saturated polyhydroxylated polydiene polymer and a chlorinated in) ~-1,j ~-,, 13F,9:1:' ,.]iing comm~it~~~n ;7avjr=~~ ~',n adhesion 15 promoting material obtained by reacting a chlorinated polyolefin, maleic acid anhvr-iride, acryl or meth,.-~cryl modified hv,'rorrnated polybutadiene containing at least one acryloyl group or methacryloyl group per unit molecule, and organic peroxide).
When the substrates are used as components to fabricate automotive 20 vehicles (including, but not limited to, automobiles, trucks and tractors) they can have any shape, and can be selected from the flexible substrates described above. Typical shapes of automotive body components can include body side moldings, fenders, bumpers, and trim for automotive vehicles.
25 In a further embodiment, the present invention is directed to coated automotive substrates as previously described wherein the coated automotive substrate is a body side molding. In another embodiment, the present invention is directed to coated automotive substrates as previously described wherein the coated automotive substrate is a fender.ln another embodiment, 30 the present invention is directed to coated automotive substrates as previously described wherein the coated automotive substrate is a bumper.
Suitable adhesion promoters include chlorinated polyolefin adhesion promoters such as are described in U.S. Patent Nos. 4,997,882; 5,319,032;
and 5,397,602. Other useful adhesion promoting coatings are to disclosed in U.S. Patent Nos. 6,001,469 (a coating composition containing a saturated polyhydroxylated polydiene polymer having terminal hydroxyl groups), 5,863,646 (a coating composition having a blend of a saturated polyhydroxylated polydiene polymer and a chlorinated in) ~-1,j ~-,, 13F,9:1:' ,.]iing comm~it~~~n ;7avjr=~~ ~',n adhesion 15 promoting material obtained by reacting a chlorinated polyolefin, maleic acid anhvr-iride, acryl or meth,.-~cryl modified hv,'rorrnated polybutadiene containing at least one acryloyl group or methacryloyl group per unit molecule, and organic peroxide).
When the substrates are used as components to fabricate automotive 20 vehicles (including, but not limited to, automobiles, trucks and tractors) they can have any shape, and can be selected from the flexible substrates described above. Typical shapes of automotive body components can include body side moldings, fenders, bumpers, and trim for automotive vehicles.
25 In a further embodiment, the present invention is directed to coated automotive substrates as previously described wherein the coated automotive substrate is a body side molding. In another embodiment, the present invention is directed to coated automotive substrates as previously described wherein the coated automotive substrate is a fender.ln another embodiment, 30 the present invention is directed to coated automotive substrates as previously described wherein the coated automotive substrate is a bumper.
In another embodiment, the present invention is directed to coated automotive substrates as previously described wherein the coated automotive substrate is trim. The componerits used to form the compositions used to coat the automotive substrates in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
In another embodiment, the present invention is directed to multi-component composite coating compositions comprising a basecoat deposited from a base coating composition, which, typically is pigmented, and a topcoat io deposited from any of the coating compositions of the present invention previously described above. In one embodiment, the present invention is directed to a multi-component composite coating composition as previously described, wherein the topcoating composition is transparent after curing and is selected from any of the compositions previously described. The components used to form the topcoating composition in these embodiments can be selected from the coating components discussed above, and additional components also can be selected from those recited above.
The basecoat and transparent topcoat (i.e., clearcoat) compositions used in the multi-component composite coating compositions of the present invention in certain instances can be formulated into liquid high solids coating compositions, that is, compositions containing 40 percent, or greater than 50 percent by weight resin solids. The solids content can be determined by heating a sample of the composition to 105 C to 110 C for 1-2 hours to drive off the volatile material, and subsequently measuring relative weight loss. As aforementioned, although the compositions can be liquid coating compositions, they also can be formulated as powder coating compositions.
The coating composition of the basecoat in the color-plus-clear system can be any of the compositions useful in coatings applications, particularly automotive applications. The coating composition of the basecoat can comprise a resinous binder and a pigment to act as the'colorant. Nonlimiting vxaitiN~eti vr fesinous ninaers are acryuc poiymers, polyesters, alkyds, and polyurethanes.
The resinous binders for the basecoat can be organic solvent-based materials such as those described in U.S. Patent No. 4,220,679, note column 2, line 24 continuing through column 4, line 40. Also, water-based coating compositions such as those described in U.S. Patent Nos. 4,403,003, 4,147,679 and 5,071,904 can be used as the binder in the basecoat composition.
The basecoat composition can comprise one or more pigments as colorants. Nonlimiting examples of suitable metallic pigments include aluminum flake, copper bronze flake, and metal oxide coated mica.
Besides the metallic pigments, the basecoat compositions can contain color pigments con~ 1 -~ntionally used in surface coatings such as, for examt.: : -ranic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, and carbon Nack; and ora?nic pinments such as phthalocyanine blue and phthalocyanine green.
Optional ingredients in the basecoat composition can comprise those which are well known in the art of formulating surface coatings and can comprise surface active agents, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts, and other customary auxiliaries. Nonlimiting examples of these materials and suitable amounts are described in U.S. Patent Nos. 4,220,679; 4,403,003; 4,147,769;
and 5,071,904.
The basecoat compositions can be applied to the substrate by any conventional coating technique such as brushing, spraying, dipping, or flowing. Spray techniques and equipment for.air, spraying,. airless spray, and electrostatic spraying in either manual or automatic methods, known in the art can be used.
During application of the basecoat to the substrate, the film thickness of the basecoat formed on the substrate can range from 0.1 to 5 mils. In another embodiment, the film thickness of the basecoat formed on the substrate can range 0.1 to 1 mils, and can be 0.4 mils.
After forming a film of the basecoat on the substrate, the basecoat can be cured or alternatively given a drying step in which solvent is driven out of the basecoat film by heating or an air drying period before application of the clearcoat. Suitable drying conditions may depend on the particular basecoat composition, and on the ambient humidity if the composition is water-borne, but a drying time from 1 to 15 minutes at a temperature of 75 to 200 F (211 to 93 C) can be adequate.
The transparent or clear topcoat composition can be applied to the basecoat by any conventional coating technique, including, but not limited to, compressed air spraying, electrostatic spraying, and either manual or automatic methods. The transparent topcoat can be applied to a cured or to a dried basecoat before the basecoat has been cured. In the latter instance, is the two coatings can then be heated to cure both coating layers simultaneously. Typical curing conditions can range from 50 F to 475 F
(10 C to 246 F) for 1 to 30 minutes. The clearcoating thickness (dry film thickness) can be 1 to 6 mils.
A second tr.., coat coating composi,:on can be appi',.d t,3 the first topcoat to form a "clear-on-clear" topcoat. The first topcoat coating composition can be applied over the basecoat as described above. 'rhe second topcoat coating composition can be applied to a cured or to a dried first topcoat before the basecoat and first topcoat have been cured. The basecoat, the first topcoat and the second topcoat can then be heated to cure 2s the three coatings simultaneously.
It should be understood that the second transparent topcoat and the first transparent topcoat coating compositions can be the same or different provided that, when applied wet-on-wet, one topcoat does not substantially interfere with the curing of the other for example by inhibiting solvent/water 3o evaporation from a lower layer. Moreover, the first topcoat, the second topcoat or both can be the film-forming composition of the present invention.
In another embodiment, the present invention is directed to multi-component composite coating compositions comprising a basecoat deposited from a base coating composition, which, typically is pigmented, and a topcoat io deposited from any of the coating compositions of the present invention previously described above. In one embodiment, the present invention is directed to a multi-component composite coating composition as previously described, wherein the topcoating composition is transparent after curing and is selected from any of the compositions previously described. The components used to form the topcoating composition in these embodiments can be selected from the coating components discussed above, and additional components also can be selected from those recited above.
The basecoat and transparent topcoat (i.e., clearcoat) compositions used in the multi-component composite coating compositions of the present invention in certain instances can be formulated into liquid high solids coating compositions, that is, compositions containing 40 percent, or greater than 50 percent by weight resin solids. The solids content can be determined by heating a sample of the composition to 105 C to 110 C for 1-2 hours to drive off the volatile material, and subsequently measuring relative weight loss. As aforementioned, although the compositions can be liquid coating compositions, they also can be formulated as powder coating compositions.
The coating composition of the basecoat in the color-plus-clear system can be any of the compositions useful in coatings applications, particularly automotive applications. The coating composition of the basecoat can comprise a resinous binder and a pigment to act as the'colorant. Nonlimiting vxaitiN~eti vr fesinous ninaers are acryuc poiymers, polyesters, alkyds, and polyurethanes.
The resinous binders for the basecoat can be organic solvent-based materials such as those described in U.S. Patent No. 4,220,679, note column 2, line 24 continuing through column 4, line 40. Also, water-based coating compositions such as those described in U.S. Patent Nos. 4,403,003, 4,147,679 and 5,071,904 can be used as the binder in the basecoat composition.
The basecoat composition can comprise one or more pigments as colorants. Nonlimiting examples of suitable metallic pigments include aluminum flake, copper bronze flake, and metal oxide coated mica.
Besides the metallic pigments, the basecoat compositions can contain color pigments con~ 1 -~ntionally used in surface coatings such as, for examt.: : -ranic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, and carbon Nack; and ora?nic pinments such as phthalocyanine blue and phthalocyanine green.
Optional ingredients in the basecoat composition can comprise those which are well known in the art of formulating surface coatings and can comprise surface active agents, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts, and other customary auxiliaries. Nonlimiting examples of these materials and suitable amounts are described in U.S. Patent Nos. 4,220,679; 4,403,003; 4,147,769;
and 5,071,904.
The basecoat compositions can be applied to the substrate by any conventional coating technique such as brushing, spraying, dipping, or flowing. Spray techniques and equipment for.air, spraying,. airless spray, and electrostatic spraying in either manual or automatic methods, known in the art can be used.
During application of the basecoat to the substrate, the film thickness of the basecoat formed on the substrate can range from 0.1 to 5 mils. In another embodiment, the film thickness of the basecoat formed on the substrate can range 0.1 to 1 mils, and can be 0.4 mils.
After forming a film of the basecoat on the substrate, the basecoat can be cured or alternatively given a drying step in which solvent is driven out of the basecoat film by heating or an air drying period before application of the clearcoat. Suitable drying conditions may depend on the particular basecoat composition, and on the ambient humidity if the composition is water-borne, but a drying time from 1 to 15 minutes at a temperature of 75 to 200 F (211 to 93 C) can be adequate.
The transparent or clear topcoat composition can be applied to the basecoat by any conventional coating technique, including, but not limited to, compressed air spraying, electrostatic spraying, and either manual or automatic methods. The transparent topcoat can be applied to a cured or to a dried basecoat before the basecoat has been cured. In the latter instance, is the two coatings can then be heated to cure both coating layers simultaneously. Typical curing conditions can range from 50 F to 475 F
(10 C to 246 F) for 1 to 30 minutes. The clearcoating thickness (dry film thickness) can be 1 to 6 mils.
A second tr.., coat coating composi,:on can be appi',.d t,3 the first topcoat to form a "clear-on-clear" topcoat. The first topcoat coating composition can be applied over the basecoat as described above. 'rhe second topcoat coating composition can be applied to a cured or to a dried first topcoat before the basecoat and first topcoat have been cured. The basecoat, the first topcoat and the second topcoat can then be heated to cure 2s the three coatings simultaneously.
It should be understood that the second transparent topcoat and the first transparent topcoat coating compositions can be the same or different provided that, when applied wet-on-wet, one topcoat does not substantially interfere with the curing of the other for example by inhibiting solvent/water 3o evaporation from a lower layer. Moreover, the first topcoat, the second topcoat or both can be the film-forming composition of the present invention.
The first transparent topcoat coating composition can be virtually any transparent topcoating composition known to those skilled in the art. The first transparent topcoat composition can be water-borne or solventborne, or, alternatively, in solid particulate form, i.e., a powder coating.
s Nonlimiting examples of suitable first topcoating compositions include crosslinkable coating compositions comprising at least-one thermosettable coating material and at least one curing agent. Suitable waterborne clearcoats are disclosed in U.S. Patent No. 5,098,947 and are based on water-soluble acrylic resins. Useful solvent borne clearcoats are disclosed io in U.S. Patent Nos. 5,196,485 and 5,814,410 and include polyepoxides and polyacid curing agents. Suitable powder clearcoats are described in U.S. Patent No. 5,663,240 and include epoxy functional acrylic copolymers and polycarboxylic acid curing agents.
15 Typically, after forming the first topcoat over th- hasecoat, the first topcoat is given a drying step in which solvent is driven out of the film by heating or, alternatively, an air drying period or curing step before application of the second topcoat. Suitable drying conditions will depend on the particular first topcoat composition, and on the ambient humidity if the 20 composition is water-borne, but, in general, a drying time from 1 to 15 minutes at a temperature of 75 F to 200 F (21 C to 93 C) will be adequate.
The film-forming composition of the present invention when employed as a second topcoat coating composition can be applied as described above for the first topcoat by any conventional coating application technique.
Curing 25 conditions can be those described above for the topcoat. The second topcoating dry film thickness can range from 0.1 to 3 mils (7.5 micrometers to 75 micrometers).
It should be mentioned that the coating compositions of the present invention can be advantageously formulated as a "monocoat", that is a 30 coating which forms essentially one coating layer when applied to a substrate.
The monocoat coating composition can be pigmented. Nonlimiting examples of suitable pigments include those mentioned above. When employed as a monocoat, the coating compositions of the present invention can be applied (by any of the conventional application techniques discussed above) in two or more successive coats, and, in certain instances can be applied with only an ambient flash period between coats. The multi-coats when cured can form essentially one coating layer.
In another embodiment, the coating compositions of the present invention also can be useful as decorative or protective coatings for pigmented piastic (elastomeric) substrates, such as those described above, io or mold-in-color ("MIC") plastic substrates. In these applications, the compositions can be applied directly to the plastic substrate or included in the molding matrix. Optionally, an adhesion promoter can first be applied directly to the plastic or elastomeric substrate and the composition applied as a topcoat thereover, as discussed above. The compositions of the present t s invention also can be advantageously formulated as pigmented coating compositions for use as primer coatings, as basecoats in multi-component co;::po:,iic ccutirtgs, ar;U-1 GJ i.-1onocoat iuPcaais including pigments or colorants. The components used to form the compositions in these embodiments can be selected from the coating components discussed t *-_ve, 20 and additional components also can be selected from those recited above.
In embodiments of the present invention directed to automotive applications, the cured compositions can be, for example, the electrodeposition coating, the primer coating, the basecoat, and/or the topcoat. Suitable topcoats include monocoats and basecoat/clearcoat 25 composites. Monocoats are formed from_one or more layers of a colored coating composition. Basecoat/clearcoat composites comprise one or more layers of a colored basecoat composition, and one or more layers of a clearcoating composition, wherein the basecoat composition has at least one component which is different from the clearcoat composition. In the 3o embodiments of the present invention directed to automotive applications, the clearcoat can be transparent after application.
s Nonlimiting examples of suitable first topcoating compositions include crosslinkable coating compositions comprising at least-one thermosettable coating material and at least one curing agent. Suitable waterborne clearcoats are disclosed in U.S. Patent No. 5,098,947 and are based on water-soluble acrylic resins. Useful solvent borne clearcoats are disclosed io in U.S. Patent Nos. 5,196,485 and 5,814,410 and include polyepoxides and polyacid curing agents. Suitable powder clearcoats are described in U.S. Patent No. 5,663,240 and include epoxy functional acrylic copolymers and polycarboxylic acid curing agents.
15 Typically, after forming the first topcoat over th- hasecoat, the first topcoat is given a drying step in which solvent is driven out of the film by heating or, alternatively, an air drying period or curing step before application of the second topcoat. Suitable drying conditions will depend on the particular first topcoat composition, and on the ambient humidity if the 20 composition is water-borne, but, in general, a drying time from 1 to 15 minutes at a temperature of 75 F to 200 F (21 C to 93 C) will be adequate.
The film-forming composition of the present invention when employed as a second topcoat coating composition can be applied as described above for the first topcoat by any conventional coating application technique.
Curing 25 conditions can be those described above for the topcoat. The second topcoating dry film thickness can range from 0.1 to 3 mils (7.5 micrometers to 75 micrometers).
It should be mentioned that the coating compositions of the present invention can be advantageously formulated as a "monocoat", that is a 30 coating which forms essentially one coating layer when applied to a substrate.
The monocoat coating composition can be pigmented. Nonlimiting examples of suitable pigments include those mentioned above. When employed as a monocoat, the coating compositions of the present invention can be applied (by any of the conventional application techniques discussed above) in two or more successive coats, and, in certain instances can be applied with only an ambient flash period between coats. The multi-coats when cured can form essentially one coating layer.
In another embodiment, the coating compositions of the present invention also can be useful as decorative or protective coatings for pigmented piastic (elastomeric) substrates, such as those described above, io or mold-in-color ("MIC") plastic substrates. In these applications, the compositions can be applied directly to the plastic substrate or included in the molding matrix. Optionally, an adhesion promoter can first be applied directly to the plastic or elastomeric substrate and the composition applied as a topcoat thereover, as discussed above. The compositions of the present t s invention also can be advantageously formulated as pigmented coating compositions for use as primer coatings, as basecoats in multi-component co;::po:,iic ccutirtgs, ar;U-1 GJ i.-1onocoat iuPcaais including pigments or colorants. The components used to form the compositions in these embodiments can be selected from the coating components discussed t *-_ve, 20 and additional components also can be selected from those recited above.
In embodiments of the present invention directed to automotive applications, the cured compositions can be, for example, the electrodeposition coating, the primer coating, the basecoat, and/or the topcoat. Suitable topcoats include monocoats and basecoat/clearcoat 25 composites. Monocoats are formed from_one or more layers of a colored coating composition. Basecoat/clearcoat composites comprise one or more layers of a colored basecoat composition, and one or more layers of a clearcoating composition, wherein the basecoat composition has at least one component which is different from the clearcoat composition. In the 3o embodiments of the present invention directed to automotive applications, the clearcoat can be transparent after application.
In another embodiment, the present invention is directed to a method for making a multi-component composite comprising (a) applying a pigmented composition to a substrate to form a basecoat; and (b) applying a topcoating composition over at least a portion of the basecoat to form a topcoat thereon, s wherein the topcoating composition is selected from any of the compositions described above. The components used to form the topcoating composition in this embodiment can be selected from the coating components discussed above, and additional components also can be selected from those recited above.
In one embodiment, the present invention is directed to a method of repairing a multi-layer composite coating comprising a base coat formed on a substrate from a film-forming base coating composition and a first top coat 4-.i-,)osited, over at least a portion of the base coat, }"n first top coat forrn-_~:1 from a first fcim-rorming top coating composition comprising any of the foregoing coating compositions, the method comprising locating an ariaa of ttze composite coating which is lawed, and applying a repair top coat film-forming composition to the flawed area after the flawed area has been prepared for repairing. The repair top coat film-forming composition can comprise a film-forming composition which is the same or different frorn the first top coat film-forming composition. The flawed area can be any coating blemish that-cannot be polished out, for example dirt particles in the coating surface. The flawed area typically can be abraded or sanded to remove such coating blemishes. In a repair carried out in accordance with the method of the present invention, the first top coating can provide excellent intercoat adhesion with the subsequently applied repair top coating.
The coatings formed from the compositions according to the present invention can have outstanding appearance properties and initial scratch (mar) resistance properties, as well as post-weathering or "retained" scratch (mar) resistance, which can be evaluated by measuring the gloss of coated substrates before and after abrading of the coated substrates. Moreover, the coatings formed from the compositions according to the present invention can have excellent intercoat adhesion, both to previously applied coatings as well as to subsequently applied coatirigs.
In one embodiment, the present invention is directed to methods of improving the scratch resistance of a polymeric substrate or polymer coated substrate comprising applying to at least a portion of the substrate any of the previously described inventive compositions, and curing the composition to form a cured coating on the substrate.
In another embodiment, the present invention is directed to a method for retaining the gloss of a polymeric substrate or polymer coated substrate to after a predetermined period of time comprising applying to the substrate comprising any of the inventive compositions described for the substrate. This predetermined period of time can generally be at least 6 months and can be at least one year. In another embodiment, the present invention is directed to a method for revitalizing the gloss of a polymeric substrate or polymer coated is substrate comprising applying to the substrate any of the inventive compositions described above.
The initial 201 gloss of a cured coated substrate according to the present invention can be measured with a 200 NOVO-GLOSS"'20 statistical glossmeter, available from Gardner Instrument Company, Inc. The coated 20 substrate can be subjected to scratch testing by linearly scratching the coating or substrate with a weighted abrasive paper for ten double rub.s using an Atlas AATCC*Scratch Tester, Model CM-5, available from Atlas Electrical Devices Company of Chicago, Illinois. The abrasive paper is 3M 281 Q
WETORDRYTM PRODUCTIONT"' 9 micron polishing paper sheets, which 25 are commercially available from 3M Company of St. Paul, Minnesota. Panels are then rinsed with tap water and carefully patted dry with a paper towel.
The 200 gloss is measured on the scratched area of each test panel. The number reported is the percent of the initial gloss retained after scratch testing, i.e., 100% X scratched gloss / initial gloss. This test method is fully 3o disclosed in the examples that follow.
In certain embodiments, the cured composition or coating of the '"Trade-mark present ihvention has an initial 20 gloss (as measured using a 20 NOVO-GLOSS 20 statistical glossmeter, available from Gardner Instrument Company) of greater than 40, can be greater than 50, and is often greater than 70. This high gloss composition can be curable under ambient or thermal conditions or by radiation curing techniques, for example, by actinic radiation. In one embodiment, the high gloss composition is curable by ambient or thermal conditions.
Moreover, the cured topcoat formed from the compositions of the present invention can exhibit excellent initial scratch (mar) resistance, as we1l io as post-weathering scratch (mar) resistance properties. The cured topcoat can have an initial scratch (mar) resistance value (as measured by first determining the initial 20 gloss as described above, linearly abrading the r! _~
cured coating surf, p_n'p :r for ten double using an Atlas AATCC Scratch i-ester, Mode1 CM-5, available from Atlas is Electrical Devices Company, and measuring the 20 g!oss as c~n~cribe i above for the abraded surface) such that after scratch (mar) testing greater than 30 percent of initial 20 gloss is retained, in certain instances greater than 40 percent of initial 20 gloss is retained, and in other instances greater than 60 percent of initial 20 gloss is retained after abrading the coating 20 surface (that is, 100% X scratched gloss / initial gloss).
Also, the cured topcoat formed from the compositions of the present invention can have a post-weathering scratch (mar) resistance (as measured using the scratch test method described above after the unscratched test panels were subjected to simulated weathering by QUV exposure to UVA-340 25 bulbs in a weathering cabinet available from Q Panel Company) such that greater than 30 percent of initial 200 gloss is retained is retained after weathering for 250 hours. In another embodiment, greater than 50 percent of initial 20 gloss is retained, an often greater than 70 percent of initial 20 gloss is retained after weathering for 250 hours.
30 The compositions of the present invention can advantageously be used to form the transparent topcoat (i.e., clearcoat) in a cured multi-component composite coating comprising a basecoat deposited from a pigmented coating composition and the topcoat deposited from a topcoat coating composition. As used herein, "transparent" means that the cured coating has a BYK Haze index of less than 50 as measured using a BYK
s Haze/Gloss Instrument. When so employed, the cured topcoat can be deposited from any of the previously described compositions of the present invention.
The coating compositions of the present invention can provide flexible cured coatings. Flexibility testing can be conducted according to the following io "Flexibility Test Method." The coating is applied to a flexible polymeric test panel and cured. For flex testing, a 1-inch by 4-inch piece is cut from the coated test panel. At a temperature of 70 F (21 C) 5 F, the piece is subjected to a mandrel bend using a'/2 inch diameter steel mandrel, such that the two ends of the 4-inch long test piece contacted one another. The test 1s panel is then rated for flexibility by visual inspection for coating cracking on a scale of 0 to 10. A "10" rating is recorded where there is no visible paint cracking; a"9" E-ating has less than five interrupted short line cracks; an "8"
has interrupted line cracks with a maximum of four uninterrupted line cracks;
a "6" has five to ten uninterrupted line cracks; a"41 " has more t;c~ 1'7 20 uninterrupted line cracks; and a "0" represents fracture of the substrate.
In one embodiment, the coating compositions when cured have a flexibility rating of at least 6 at 70 F. In another embodiment, the coating compositions when cured have a flexibility rating of at least 8 at 70 F, while in yet another embodiment, the coating compositions when cured have a flexibility rating of 25 at least 9 at 70 F.
Moreover, the coating compositions of the present invention can provide cured coatings having excellent intercoat or interlayer adhesion to subsequently applied coating layers. For example, any of the aforementioned coating compositions can be applied as a transparent clearcoat in a color-30 plus-clear coating system as discussed above. In the event of damage to the cured coating system causing a surface defect, it may be necessary to prepare the damaged area for repair with a subsequently applied clear coat composition. The coating compositions of the present invention can provide excellent intercoat adhesion between the first clear coat layer and the subsequently applied repair clear coat layer. Likewise, when used as a top coat composition, the coating compositions of the present invention also provide excellent interlayer adhesion between the cured top coat and a subsequently applied windshield adhesive without the intervening step of applying an adhesion promoting primer.
Illustrating the invention are the following examples which, however, 1o are not to be considered as limiting the invention to their details. Unless otherwise indicated, all parts and percentages in the following examples, as well as throughout the specification, are by weight.
EXAMPLES
RESIN COMPOSITIONS
POLYSILOXANE POLYOL
EXAMPLE AA
This example describes the preparation of a polysiloxane polyol which was subsequently used to form respective silica dispersions of Examples A
and B, and the polysiloxane borates used in the thermosetting compositions of the present invention. The polysiloxane polyol was a product of the hydrosilylation of a reactive silicone fluid having an approximate degree of polymerization of 3 to 7, i.e., (Si-O), to (Si-O)7. The polysiloxane polyol was prepared-from a proportionately scaled-up batch of the following mixture of ingredients in the ratios indicated:
Ingredients Equivalent Parts By Weight Weight Equivalents (kilograms) Charge I:
=
Trimethylolpropane monoallyl 174.0 756.0 131.54 ether Charqe II:
MASILWAX BASE' 156.72 594.8 93.21 Charge 111: 10 ppm Chloroplatinic acid 0.23 Toluene OL--d Isopropanol ' Polysiloxane-containing silicon hydride, commercially available from BASF
Corporation.
2 Equivalent weight based on mercuric bichloride determination.
To a suitable reaction vessel equipped with a means for maintaining a nitrogen blanket, Charge I and an amount of sodium acetate equivalent to 20 io to 25 ppm of total monomer solids was added at ambient conditions and the temperature was gradually increased to 75 C under a nitrogen blanket. At that temperature, about 5.0% of Charge II was added under agitation, followed by the addition of Ciiarge Ili, equivalent to 10 ppm of active platinum based on total monomer solids. The reaction was then allowed to exotherm ts to 95 C at which time the remainder of Charge II was added at a rate such that the temperature did not exceed 95 C. After completion of this addition, the reaction temperature was maintained at 95 C and monitored by infrared spectroscopy for disappearance of the silicon hydride absorption band (Si-H, 2150 cm-').
SILICA DISPERSIONS
EXAMPLE A
This example describes the preparation of a colloidal silica dispersion used as a component in the thermosetting compositions of the present invention..-The colloidal silica dispersion was prepared as follows. A
suitable reaction vessel was equipped for vacuum distillation and flushed with N2. To the reaction flask was added 3150 g of the polysiloxane polyol of Example AA
described above, 4500 g of ORGANOSILICASOLT"" MT-ST colloidal silica s (which is commercially available from Nissan Chemicals) and 1440 g of methyl amyl ketone. The mean particle size of the silica particles was about 10-20 nanometers, as disclosed at http//www.snowtex.com /organo _types.html (June 2, 2000). The resulting mixture was vacuum distilled at 25 C for a period of 8 hours.
to EXAMPLE B
This example describes the preparation of a colloidal silica dispersion used as a component in the thermosetting compositions of the present ts inventijn. The coi;oidai siiica dispersion was prepared as follows. A 4-neck reaction flask equipped for vacuum distillation was flushed with N2. To the ;o,j ::0-i .4 g of :he poiysiioxane tetrol described above, 3752.9 g of ORGANOSILICASOLT"" MT-ST colloidal silica (which is commercially available from Nissan Chemicals) and 900.6 g of methyl amyl 2o ketone. The resulting mixture was vacuum distilled at 70 mm Hg and 31 C.
ADHESION PROMOTER COMPOSITtONS
The following Examples C through H describe the preparation of various adhesion promoting compositions used in the coating compositions of 25 the present invention. Each adhesion promoting composition was prepared as described below.
EXAMPLE C
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following -30 materials were charged to the flask and blended under agitation: 180.4 g of the polysilxoane polyol of Example AA, 300.9 g of isopropyl alcohol and 25.8 g of boric acid. The mixture was heated to reflux at a temperature of 79 C, and 200 rim1 of solvent was removed over 0.25 hours. The resulting material was cooled and measured to have 49.8 % solids and contained 3.0% water.
EXAMPLE D
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following materials were charged to the flask and blended under agitation: 3241.4 g of the polysiloxane polyol of Example AA, 5415.3 g of isopropyl alcohol and 463.9 g of boric acid. The mixture was heated to reflux at a temperature of io 73 C, and 3607.7 g of solvent was removed over a period of 1.5 hours. The resulting material was cooled and measured to have 56.0% solids and contained 2.5% water.
EXAMPLE E
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following rz~~~'eri.~'s v,r:;Ye charaed to the fiasl; a,id blLnided under t:;-ji iio, -': 180.3 g oi polysiloxane polyol of Example AA, 300.7 g of isopropyl alcohol and 25.8 g of boric acid. The mixture was heated to reflu'y: at a temperature 79 C, ~-nd 2'0 ml of solvent was removed over a period of 0.25 hours. The resulting material was cooled and measured to have 49.5 % solids and contained 3.0%
water.
EXAMPLE F
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following materials were charged to the flask and blended under agitation: 1575.5 g Dowanol*PM, and 144.8 g of Boric acid2. The mixture was heated to reflux at a temperature of 110 C, and held for a period 2 hours. Thereafter, 632.3 g of solvent was removed over a period of 0.5 hours. The resulting material was cooled and measured to have11.2% solids and contained 5.0% water.
"Trade-mark EXAMPLE G
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following ingredients were charged to the flask and blended under agitation: 454.7 g of acrylic polyol (prepared from 14.5% butyl acrylate, 14.5% butyl methacrylate, 27.6% isobornyl methacrylate, 22.6% hydroxypropyl methacrylate, 20.4%
hydroxyethyl methacrylate, and 0.4% acrylic acid, having a resin solids of 69.7%, Mw 3227 and hydroxyl value of 101), 97.2 g of isopropyl alcohol and io 2.06 g of boric acid. The mixture was heated to reflux at a temperature of 93 C, and held for a period of 1 hour. Thereafter, 62 g of solvent was removed over a period of 0.25 hours. The resulting material was cooled and me,asured 69.3 % solids and contained 0.1% water.
EXAMPLE H
r-r-sec; reaciion flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following materials were charged to the flask and blended under agitation: 360.5 g of the polysiloxane polyol of Example AA, 601.7 g of isopropyl alcohol and 13.6 g of aluminum isopropoxide (available from Aldrich Chemical Co.). The mixture was heated to reflux at a temperature of 81 C, and, thereafter, 401.8 g of solvent was removed over a period of 1 hour. The resulting material was cooled and measured to have 53.32 % solids THERMOSETTING COATING COMPOSITIONS
ONE COMPONENT COMPOSITIONS:
This example describes the preparation of a resinous binder pre-mix used in the one-package thermosetting coating compositions of Examples 4-6 below. Each of the ingredients was added sequentially and mixed under mild agitation.
Ingredient Parts by weight Solid weight (grams) (grams) Methyl n-amyl ketone 18.0 ----Butyl Cellosolve acetate' 18.0 ---Butyl CarbitolS acetate2 4.0 ---TINUVIN 384g 1.58 1.50 TINUVIN 4004 1.76 1.50 TINUVIN 2925 0.40 0.40 TINUVIN 123 0.40 0.40 Silica dispersion of Example A 13.2 10.0 LUWIPAL 018' 41.1 30.0 TACTe 9.4 5.0 Polybutyl acryfate9 0.50 fl.'.Q
Biocked acid catalyst1Q 2.50 1.00 ' 2-Butoxyethyl acetate solventcommercially available from Union Carbide Corp.
io 2 2-(2-Butoxyethoxy) ethyl acetate commercially available from Union Carbide Corp.
3 Substituted benzotriazo;e UV light staloi~izer commcrciaily avaifabi-e-fronn Ciba Specialty Chemicals Corp.
" Substituted triazine UV light stabilizer commercially available from Ciba Specialty Chemicals Corp.
5 Sterically hindered amine light stabilizer commercially available from Ciba Specialty Chemicals Corp.
s Bis-(1-octyloxy-2,2,6,6-tetramethyl-4-pipe(dinyl) sebacate hindered aminoether light stabilizer available from Ciba Specialty Chemicals Corp.
' High imino, butylated melamine formaldehyde resin commercially available from BASF Corp.
e Tris (alkyl carbamoyl) triazine available from Cytec Industries, Inc. The alkyl substituent was mixed methyl and butyl.
e A flow control agent having a Mw of about 6700 and a Mn of about 2600 made in xylene at 62.5% solids available from E. 1. duPont de Nemours and Company.
10 Dodecyl benzene sulfonic acid solution, blocked with diisopropanol amine to 91 %
total neutralization, 40 percent in ethanol.
In one embodiment, the present invention is directed to a method of repairing a multi-layer composite coating comprising a base coat formed on a substrate from a film-forming base coating composition and a first top coat 4-.i-,)osited, over at least a portion of the base coat, }"n first top coat forrn-_~:1 from a first fcim-rorming top coating composition comprising any of the foregoing coating compositions, the method comprising locating an ariaa of ttze composite coating which is lawed, and applying a repair top coat film-forming composition to the flawed area after the flawed area has been prepared for repairing. The repair top coat film-forming composition can comprise a film-forming composition which is the same or different frorn the first top coat film-forming composition. The flawed area can be any coating blemish that-cannot be polished out, for example dirt particles in the coating surface. The flawed area typically can be abraded or sanded to remove such coating blemishes. In a repair carried out in accordance with the method of the present invention, the first top coating can provide excellent intercoat adhesion with the subsequently applied repair top coating.
The coatings formed from the compositions according to the present invention can have outstanding appearance properties and initial scratch (mar) resistance properties, as well as post-weathering or "retained" scratch (mar) resistance, which can be evaluated by measuring the gloss of coated substrates before and after abrading of the coated substrates. Moreover, the coatings formed from the compositions according to the present invention can have excellent intercoat adhesion, both to previously applied coatings as well as to subsequently applied coatirigs.
In one embodiment, the present invention is directed to methods of improving the scratch resistance of a polymeric substrate or polymer coated substrate comprising applying to at least a portion of the substrate any of the previously described inventive compositions, and curing the composition to form a cured coating on the substrate.
In another embodiment, the present invention is directed to a method for retaining the gloss of a polymeric substrate or polymer coated substrate to after a predetermined period of time comprising applying to the substrate comprising any of the inventive compositions described for the substrate. This predetermined period of time can generally be at least 6 months and can be at least one year. In another embodiment, the present invention is directed to a method for revitalizing the gloss of a polymeric substrate or polymer coated is substrate comprising applying to the substrate any of the inventive compositions described above.
The initial 201 gloss of a cured coated substrate according to the present invention can be measured with a 200 NOVO-GLOSS"'20 statistical glossmeter, available from Gardner Instrument Company, Inc. The coated 20 substrate can be subjected to scratch testing by linearly scratching the coating or substrate with a weighted abrasive paper for ten double rub.s using an Atlas AATCC*Scratch Tester, Model CM-5, available from Atlas Electrical Devices Company of Chicago, Illinois. The abrasive paper is 3M 281 Q
WETORDRYTM PRODUCTIONT"' 9 micron polishing paper sheets, which 25 are commercially available from 3M Company of St. Paul, Minnesota. Panels are then rinsed with tap water and carefully patted dry with a paper towel.
The 200 gloss is measured on the scratched area of each test panel. The number reported is the percent of the initial gloss retained after scratch testing, i.e., 100% X scratched gloss / initial gloss. This test method is fully 3o disclosed in the examples that follow.
In certain embodiments, the cured composition or coating of the '"Trade-mark present ihvention has an initial 20 gloss (as measured using a 20 NOVO-GLOSS 20 statistical glossmeter, available from Gardner Instrument Company) of greater than 40, can be greater than 50, and is often greater than 70. This high gloss composition can be curable under ambient or thermal conditions or by radiation curing techniques, for example, by actinic radiation. In one embodiment, the high gloss composition is curable by ambient or thermal conditions.
Moreover, the cured topcoat formed from the compositions of the present invention can exhibit excellent initial scratch (mar) resistance, as we1l io as post-weathering scratch (mar) resistance properties. The cured topcoat can have an initial scratch (mar) resistance value (as measured by first determining the initial 20 gloss as described above, linearly abrading the r! _~
cured coating surf, p_n'p :r for ten double using an Atlas AATCC Scratch i-ester, Mode1 CM-5, available from Atlas is Electrical Devices Company, and measuring the 20 g!oss as c~n~cribe i above for the abraded surface) such that after scratch (mar) testing greater than 30 percent of initial 20 gloss is retained, in certain instances greater than 40 percent of initial 20 gloss is retained, and in other instances greater than 60 percent of initial 20 gloss is retained after abrading the coating 20 surface (that is, 100% X scratched gloss / initial gloss).
Also, the cured topcoat formed from the compositions of the present invention can have a post-weathering scratch (mar) resistance (as measured using the scratch test method described above after the unscratched test panels were subjected to simulated weathering by QUV exposure to UVA-340 25 bulbs in a weathering cabinet available from Q Panel Company) such that greater than 30 percent of initial 200 gloss is retained is retained after weathering for 250 hours. In another embodiment, greater than 50 percent of initial 20 gloss is retained, an often greater than 70 percent of initial 20 gloss is retained after weathering for 250 hours.
30 The compositions of the present invention can advantageously be used to form the transparent topcoat (i.e., clearcoat) in a cured multi-component composite coating comprising a basecoat deposited from a pigmented coating composition and the topcoat deposited from a topcoat coating composition. As used herein, "transparent" means that the cured coating has a BYK Haze index of less than 50 as measured using a BYK
s Haze/Gloss Instrument. When so employed, the cured topcoat can be deposited from any of the previously described compositions of the present invention.
The coating compositions of the present invention can provide flexible cured coatings. Flexibility testing can be conducted according to the following io "Flexibility Test Method." The coating is applied to a flexible polymeric test panel and cured. For flex testing, a 1-inch by 4-inch piece is cut from the coated test panel. At a temperature of 70 F (21 C) 5 F, the piece is subjected to a mandrel bend using a'/2 inch diameter steel mandrel, such that the two ends of the 4-inch long test piece contacted one another. The test 1s panel is then rated for flexibility by visual inspection for coating cracking on a scale of 0 to 10. A "10" rating is recorded where there is no visible paint cracking; a"9" E-ating has less than five interrupted short line cracks; an "8"
has interrupted line cracks with a maximum of four uninterrupted line cracks;
a "6" has five to ten uninterrupted line cracks; a"41 " has more t;c~ 1'7 20 uninterrupted line cracks; and a "0" represents fracture of the substrate.
In one embodiment, the coating compositions when cured have a flexibility rating of at least 6 at 70 F. In another embodiment, the coating compositions when cured have a flexibility rating of at least 8 at 70 F, while in yet another embodiment, the coating compositions when cured have a flexibility rating of 25 at least 9 at 70 F.
Moreover, the coating compositions of the present invention can provide cured coatings having excellent intercoat or interlayer adhesion to subsequently applied coating layers. For example, any of the aforementioned coating compositions can be applied as a transparent clearcoat in a color-30 plus-clear coating system as discussed above. In the event of damage to the cured coating system causing a surface defect, it may be necessary to prepare the damaged area for repair with a subsequently applied clear coat composition. The coating compositions of the present invention can provide excellent intercoat adhesion between the first clear coat layer and the subsequently applied repair clear coat layer. Likewise, when used as a top coat composition, the coating compositions of the present invention also provide excellent interlayer adhesion between the cured top coat and a subsequently applied windshield adhesive without the intervening step of applying an adhesion promoting primer.
Illustrating the invention are the following examples which, however, 1o are not to be considered as limiting the invention to their details. Unless otherwise indicated, all parts and percentages in the following examples, as well as throughout the specification, are by weight.
EXAMPLES
RESIN COMPOSITIONS
POLYSILOXANE POLYOL
EXAMPLE AA
This example describes the preparation of a polysiloxane polyol which was subsequently used to form respective silica dispersions of Examples A
and B, and the polysiloxane borates used in the thermosetting compositions of the present invention. The polysiloxane polyol was a product of the hydrosilylation of a reactive silicone fluid having an approximate degree of polymerization of 3 to 7, i.e., (Si-O), to (Si-O)7. The polysiloxane polyol was prepared-from a proportionately scaled-up batch of the following mixture of ingredients in the ratios indicated:
Ingredients Equivalent Parts By Weight Weight Equivalents (kilograms) Charge I:
=
Trimethylolpropane monoallyl 174.0 756.0 131.54 ether Charqe II:
MASILWAX BASE' 156.72 594.8 93.21 Charge 111: 10 ppm Chloroplatinic acid 0.23 Toluene OL--d Isopropanol ' Polysiloxane-containing silicon hydride, commercially available from BASF
Corporation.
2 Equivalent weight based on mercuric bichloride determination.
To a suitable reaction vessel equipped with a means for maintaining a nitrogen blanket, Charge I and an amount of sodium acetate equivalent to 20 io to 25 ppm of total monomer solids was added at ambient conditions and the temperature was gradually increased to 75 C under a nitrogen blanket. At that temperature, about 5.0% of Charge II was added under agitation, followed by the addition of Ciiarge Ili, equivalent to 10 ppm of active platinum based on total monomer solids. The reaction was then allowed to exotherm ts to 95 C at which time the remainder of Charge II was added at a rate such that the temperature did not exceed 95 C. After completion of this addition, the reaction temperature was maintained at 95 C and monitored by infrared spectroscopy for disappearance of the silicon hydride absorption band (Si-H, 2150 cm-').
SILICA DISPERSIONS
EXAMPLE A
This example describes the preparation of a colloidal silica dispersion used as a component in the thermosetting compositions of the present invention..-The colloidal silica dispersion was prepared as follows. A
suitable reaction vessel was equipped for vacuum distillation and flushed with N2. To the reaction flask was added 3150 g of the polysiloxane polyol of Example AA
described above, 4500 g of ORGANOSILICASOLT"" MT-ST colloidal silica s (which is commercially available from Nissan Chemicals) and 1440 g of methyl amyl ketone. The mean particle size of the silica particles was about 10-20 nanometers, as disclosed at http//www.snowtex.com /organo _types.html (June 2, 2000). The resulting mixture was vacuum distilled at 25 C for a period of 8 hours.
to EXAMPLE B
This example describes the preparation of a colloidal silica dispersion used as a component in the thermosetting compositions of the present ts inventijn. The coi;oidai siiica dispersion was prepared as follows. A 4-neck reaction flask equipped for vacuum distillation was flushed with N2. To the ;o,j ::0-i .4 g of :he poiysiioxane tetrol described above, 3752.9 g of ORGANOSILICASOLT"" MT-ST colloidal silica (which is commercially available from Nissan Chemicals) and 900.6 g of methyl amyl 2o ketone. The resulting mixture was vacuum distilled at 70 mm Hg and 31 C.
ADHESION PROMOTER COMPOSITtONS
The following Examples C through H describe the preparation of various adhesion promoting compositions used in the coating compositions of 25 the present invention. Each adhesion promoting composition was prepared as described below.
EXAMPLE C
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following -30 materials were charged to the flask and blended under agitation: 180.4 g of the polysilxoane polyol of Example AA, 300.9 g of isopropyl alcohol and 25.8 g of boric acid. The mixture was heated to reflux at a temperature of 79 C, and 200 rim1 of solvent was removed over 0.25 hours. The resulting material was cooled and measured to have 49.8 % solids and contained 3.0% water.
EXAMPLE D
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following materials were charged to the flask and blended under agitation: 3241.4 g of the polysiloxane polyol of Example AA, 5415.3 g of isopropyl alcohol and 463.9 g of boric acid. The mixture was heated to reflux at a temperature of io 73 C, and 3607.7 g of solvent was removed over a period of 1.5 hours. The resulting material was cooled and measured to have 56.0% solids and contained 2.5% water.
EXAMPLE E
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following rz~~~'eri.~'s v,r:;Ye charaed to the fiasl; a,id blLnided under t:;-ji iio, -': 180.3 g oi polysiloxane polyol of Example AA, 300.7 g of isopropyl alcohol and 25.8 g of boric acid. The mixture was heated to reflu'y: at a temperature 79 C, ~-nd 2'0 ml of solvent was removed over a period of 0.25 hours. The resulting material was cooled and measured to have 49.5 % solids and contained 3.0%
water.
EXAMPLE F
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following materials were charged to the flask and blended under agitation: 1575.5 g Dowanol*PM, and 144.8 g of Boric acid2. The mixture was heated to reflux at a temperature of 110 C, and held for a period 2 hours. Thereafter, 632.3 g of solvent was removed over a period of 0.5 hours. The resulting material was cooled and measured to have11.2% solids and contained 5.0% water.
"Trade-mark EXAMPLE G
A four-neck reaction flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following ingredients were charged to the flask and blended under agitation: 454.7 g of acrylic polyol (prepared from 14.5% butyl acrylate, 14.5% butyl methacrylate, 27.6% isobornyl methacrylate, 22.6% hydroxypropyl methacrylate, 20.4%
hydroxyethyl methacrylate, and 0.4% acrylic acid, having a resin solids of 69.7%, Mw 3227 and hydroxyl value of 101), 97.2 g of isopropyl alcohol and io 2.06 g of boric acid. The mixture was heated to reflux at a temperature of 93 C, and held for a period of 1 hour. Thereafter, 62 g of solvent was removed over a period of 0.25 hours. The resulting material was cooled and me,asured 69.3 % solids and contained 0.1% water.
EXAMPLE H
r-r-sec; reaciion flask equipped with stirrer, temperature probe, Dean Stark trap and reflux condenser was flushed with N2. The following materials were charged to the flask and blended under agitation: 360.5 g of the polysiloxane polyol of Example AA, 601.7 g of isopropyl alcohol and 13.6 g of aluminum isopropoxide (available from Aldrich Chemical Co.). The mixture was heated to reflux at a temperature of 81 C, and, thereafter, 401.8 g of solvent was removed over a period of 1 hour. The resulting material was cooled and measured to have 53.32 % solids THERMOSETTING COATING COMPOSITIONS
ONE COMPONENT COMPOSITIONS:
This example describes the preparation of a resinous binder pre-mix used in the one-package thermosetting coating compositions of Examples 4-6 below. Each of the ingredients was added sequentially and mixed under mild agitation.
Ingredient Parts by weight Solid weight (grams) (grams) Methyl n-amyl ketone 18.0 ----Butyl Cellosolve acetate' 18.0 ---Butyl CarbitolS acetate2 4.0 ---TINUVIN 384g 1.58 1.50 TINUVIN 4004 1.76 1.50 TINUVIN 2925 0.40 0.40 TINUVIN 123 0.40 0.40 Silica dispersion of Example A 13.2 10.0 LUWIPAL 018' 41.1 30.0 TACTe 9.4 5.0 Polybutyl acryfate9 0.50 fl.'.Q
Biocked acid catalyst1Q 2.50 1.00 ' 2-Butoxyethyl acetate solventcommercially available from Union Carbide Corp.
io 2 2-(2-Butoxyethoxy) ethyl acetate commercially available from Union Carbide Corp.
3 Substituted benzotriazo;e UV light staloi~izer commcrciaily avaifabi-e-fronn Ciba Specialty Chemicals Corp.
" Substituted triazine UV light stabilizer commercially available from Ciba Specialty Chemicals Corp.
5 Sterically hindered amine light stabilizer commercially available from Ciba Specialty Chemicals Corp.
s Bis-(1-octyloxy-2,2,6,6-tetramethyl-4-pipe(dinyl) sebacate hindered aminoether light stabilizer available from Ciba Specialty Chemicals Corp.
' High imino, butylated melamine formaldehyde resin commercially available from BASF Corp.
e Tris (alkyl carbamoyl) triazine available from Cytec Industries, Inc. The alkyl substituent was mixed methyl and butyl.
e A flow control agent having a Mw of about 6700 and a Mn of about 2600 made in xylene at 62.5% solids available from E. 1. duPont de Nemours and Company.
10 Dodecyl benzene sulfonic acid solution, blocked with diisopropanol amine to 91 %
total neutralization, 40 percent in ethanol.
This example describes the preparation of a resinous binder pre-mix used in the one-package thermosetting coating composition of Examples 7-9 described below. Each of the ingredients was added sequentally and mixed s under mild agitation.
Ingredient Parts by weight Solid weight (grams) (grams) ' Methyl n-amyl ketone 16.0 ---Butyl Cellosolve acetate 16.0 ---Butyt Carbitol acetate 3.50 ----TINUVINO 9281 3.00 3.00 TINUVIN'* 292 0.40 0.40 Silica Dispersion of Example 10.3 7.0 B
RESIMENE 757 2 41.2 40.0 0.50 ; - - 0.30 Blocked acid ca, .;yst 2.50 1.00 ' 2-(2H-Benzotriazol-2y1)-6-(1-methyl-1-phenyiethyl)-4-(1,1,3,3-tetramethylbuty!)phenol UV
absorbr?r avn'1;-,;hiU 'r ~m Ciba !~,ae~~nO~ Ch r_:-~
Z rvle:nylated and butylated melamine-formaldehyde resin available frcm Cytec Industries, Inc.
Ingredient Parts by weight Solid weight (grams) (grams) ' Methyl n-amyl ketone 16.0 ---Butyl Cellosolve acetate 16.0 ---Butyt Carbitol acetate 3.50 ----TINUVINO 9281 3.00 3.00 TINUVIN'* 292 0.40 0.40 Silica Dispersion of Example 10.3 7.0 B
RESIMENE 757 2 41.2 40.0 0.50 ; - - 0.30 Blocked acid ca, .;yst 2.50 1.00 ' 2-(2H-Benzotriazol-2y1)-6-(1-methyl-1-phenyiethyl)-4-(1,1,3,3-tetramethylbuty!)phenol UV
absorbr?r avn'1;-,;hiU 'r ~m Ciba !~,ae~~nO~ Ch r_:-~
Z rvle:nylated and butylated melamine-formaldehyde resin available frcm Cytec Industries, Inc.
This example describes the preparation of a resinous binder pre-mix used in the preparation of thermosetting coating compositions of Examples 7-9 described below. The resins were admixed and blended under mild agitation.
Ingredient Parts by weight Solid weight (grams) (grams) Carbamoylated acrylic' 44.4 28.0 Carbamoylated polyester2 38.9 28.0 1 (58% butyl methacrylate/40 % hydroxypropyl acrylate/2% methyl styrene dimer) 64 /> solids in a solvent blend of (50% DOWANOL PM/50% propanoic acid, 3-ethoxy ethyl ester), 75%
carbamoylated with methyl carbamate.
2(10.6% trimethylol propane/22.7% 2,2,4-trimethyl-1,3-pentanediol/17.5%
neopentyl glycoV49.2% hexahydrophthalic anhydride) 69% solids in a solvent blend of (44%
Dowanol PM/56% Dowanol PM Acetate) 75% carbamoylated with methyl carbamate.
The preparation of various one-package thermosetting coating compositions are described below in the following Tables 1 and 2. The amounts listed are the total parts by weight in grams and the amount within parenthesis are percentages by weight based on weight of solids. Each component was mixed sequentially with agitation. Comparative coating compositions which do not contain a boron-cor~,'aining compound are indicated using. an TABLE I
Ingredient Example 4* Example 5 Example 6 Example 1 pre-mix 110.8 (50.1) 110.8 (50.1) 110.8 (50.1) Acrylic resin' 89.9 (58.0) 88.4 (57.0) 83.7 (54.0) Siloxane Borate of --- 2.01 (1.00) 8.0 (4.00) Example C
::Redlrction _ Methyl n-amyl ketone 5.4 4.79 3.07 Butyl CellosolveO 5.4 4.79 3.07 acetate Butyl Carbitol acetate 1.2 1.06 0.68 Spray viscosity2 (sec) 28.4 28.2 28.1 Paint temperature ( F) 73.3 73.5 73.1 Theory % Solids3 50.8 51.0 51.6 ' Acrylic regin (30% styrene, 19.9% hydroxyethyl methacrylate, 28.7% CarduraE
(available from Shell Chemical Co.), 9.5% acrylic acid, and 12% ethylhexyl acrylate) at 65% solids in SOLVESSO*100 (avaiiable from Exxon Chemicals America), prepared in Example A of US Patent No. 5,965,670.
2 Viscosity measured in seconds with a #4 FORD efflux cup at ambient temperature.
3 Theory % Solids of a coating is determined by taking the solid weight of the coating formulation divided by the sum of the parts by weight of the coating formulation and the reducing solvent weight Ingredient Example 7* Example 8 Example 9 Example 2 pre-mix 93.4 (51.7) 93.4 (51.7) 93.4 (51.7) Example 3 pre-mix 83.3 (56.0) 81.8 (55.0) 77.4 (52.0) Siloxane Borate of -- 1.79 (1.00) 7.1 (4.00) Example D
Methyl n-amyl ketone 2.00 ---- ----Butyl Cellosfllve 2.00 ---- -duly+ _.; t71t0lO 0.50 '--- -Reductioii Inforimation Methyl n-amyl ketone 3.03' _ 4.7 3.83 3utyl 3.::'3 :3.33 ~
acetate Butyl Carbitola acetate 0.67 1.04 0.85 Spray viscosity' (sec) 28.4 28.7 28.1 Paint temperature ( F) 72.4 72.3 72.0 Theory % So!ids2 57.3 57.5 57.8 Viscosity measured in seconds with a #4 FORD efflux cup at ambient temperature.
2 Theory % Solids of a coating is determined by taking the solid weight of the coating formulation divided by the sum of the parts by weight of the coating formulation and the reducing solvent weight.
TESTING
The film forming compositions of Examples 4-9 were spray applied to a pigmented basecoat to form color-plus-clear composite coatings over primed electrocoated steel panels. The panels used were cold rolled steel pariels (size 4 inches x 12 inches (10.16 cm by 30.48 cm)). The steel panels for Examples 4-6 were coated with ED5000 electrocoat, available from PPG
Industries, Inc, and SUPERMAR primer, available from Herbects/DuPont.
The ED5000 electrocoat test panels are available as APR22986 from ACT
Laboratories, Inc. of Hillsdale, Michigan. Examples 7-9 utilized steel panels *rrade-rrark that were coated with ED5240 electrocoat and FCP6579 primer, both available from PPG Industries, Inc. The test panels are available as APR40017 from ACT Laboratories, Inc. of Hillsdale, Michigan.
The basecoat used for Examples 4-6 was Nero Vulcano*UR806/A, black pigmented solvent-based acrylic/melamine basecoat, available from PPG Industries, Inc. Examples 7-9 used ODCT6373 Ebony Black, a black pigmented solvent-based acrylic/melamine basecoat, available from PPG
Industries, Inc.
The Nero Vulcano UR806/A basecoat was automated spray applied in to one coat to the electrocoated and primed steel panels at ambient temperature (about 70 F (21 C)). A dry film thickness of about 0.5 to 0.7 mils (about 13 to 18 micrometers) was targeted. After the basecoat application, a ninety second air flash at ambient temperature was given before applying the clearcoat. The ODCT6373 Ebony Black basecoat was automated spray applied in two coats to the electrocoated and primed steel panels at ambient temperature (about 70 F (21 C)). A ninety second air flash at ambient A dryA iilill thickness of about 0.6 to 0.8 mils (about 15 to 20 micrometers) was targeted.
t-.fler the secon-d bas' ecoat application, a ninety seco7!d air f'....sh at 20 temperature was given before applying the clearcoat.
The clear coating compositions of Examples 4-9 were each automated spray applied to a basecoated panel at ambient temperature in two coats with a ninety second ambient flash between applications. Examples 4-6 were targeted for a 1.5 to 1.7 mils (about 38 to 43 micrometers) dry film thickness, and Examples 7-9 were targeted for a 1.7 to 1.9 mils (about 43 to 48 micrometers) dry film thickness. All coatings were allowed to air flash at ambient temperature for ten minutes. Panels prepared from each coating were baked for thirty minutes at 285 F (141 C) to fully cure the coating(s).
The panels were baked in a horizontal position.
To test for recoat adhesion, an original basecoated and clearcoated panel, as described above, was given another layer of basecoat and "Trade-mark clearcoat-or clearcoat only. Examples 4-6 were recoated with Nero Vulcano UR806/A and Examples 4-6,'depending on the respective original panel.
Examples 7-9 were recoated with ODCT6373 Ebony Black and Examples 7-9, depending on the respective original panel. For example, an Example 4 clearcoat over Nero Vulcano UR806/A original (prepared above) was recoated with Nero Vulcano UR806/A and Example 4 clearcoat. Half' of an original panel from each clear coating was basecoated and clearcoated and the other half of the panel was clearcoated only. To recoat the panels half .and half, the bottom halves of the original panels were covered with aluminum io foil and then the respective basecoats were automated spray applied as described above. The foil was removed, resulting in an original panel with the upper half coated in basecoat and the bottom half still with only the original coating layers. The respective clearcoat was then automated spray applied to tite eri,:F c panel as described above. t he rL~;ultir:g pane': _; , rare half coated in basecoat/ clearcoat from the original spray application and another layer of ~.asecoatl c!earcoat Tru;,x ~~)a coat --p:ay p <p:;cuiticn (aiCii~;C). The uLher half of the resu{titig panel was coated in basecoat,' clearcoat from the original spray application and another layer of clearcoat from the recoat spray application (B/C//C).
Test results for the coatings are reported below in Table 3. As mentioned above the coating compositions of Examples 4-6 were applied over Nero Vulcano UR806/A basecoat and Examples 7-9 were applied over ODCT6373 Ebony Black basecoat.
Ingredient Parts by weight Solid weight (grams) (grams) Carbamoylated acrylic' 44.4 28.0 Carbamoylated polyester2 38.9 28.0 1 (58% butyl methacrylate/40 % hydroxypropyl acrylate/2% methyl styrene dimer) 64 /> solids in a solvent blend of (50% DOWANOL PM/50% propanoic acid, 3-ethoxy ethyl ester), 75%
carbamoylated with methyl carbamate.
2(10.6% trimethylol propane/22.7% 2,2,4-trimethyl-1,3-pentanediol/17.5%
neopentyl glycoV49.2% hexahydrophthalic anhydride) 69% solids in a solvent blend of (44%
Dowanol PM/56% Dowanol PM Acetate) 75% carbamoylated with methyl carbamate.
The preparation of various one-package thermosetting coating compositions are described below in the following Tables 1 and 2. The amounts listed are the total parts by weight in grams and the amount within parenthesis are percentages by weight based on weight of solids. Each component was mixed sequentially with agitation. Comparative coating compositions which do not contain a boron-cor~,'aining compound are indicated using. an TABLE I
Ingredient Example 4* Example 5 Example 6 Example 1 pre-mix 110.8 (50.1) 110.8 (50.1) 110.8 (50.1) Acrylic resin' 89.9 (58.0) 88.4 (57.0) 83.7 (54.0) Siloxane Borate of --- 2.01 (1.00) 8.0 (4.00) Example C
::Redlrction _ Methyl n-amyl ketone 5.4 4.79 3.07 Butyl CellosolveO 5.4 4.79 3.07 acetate Butyl Carbitol acetate 1.2 1.06 0.68 Spray viscosity2 (sec) 28.4 28.2 28.1 Paint temperature ( F) 73.3 73.5 73.1 Theory % Solids3 50.8 51.0 51.6 ' Acrylic regin (30% styrene, 19.9% hydroxyethyl methacrylate, 28.7% CarduraE
(available from Shell Chemical Co.), 9.5% acrylic acid, and 12% ethylhexyl acrylate) at 65% solids in SOLVESSO*100 (avaiiable from Exxon Chemicals America), prepared in Example A of US Patent No. 5,965,670.
2 Viscosity measured in seconds with a #4 FORD efflux cup at ambient temperature.
3 Theory % Solids of a coating is determined by taking the solid weight of the coating formulation divided by the sum of the parts by weight of the coating formulation and the reducing solvent weight Ingredient Example 7* Example 8 Example 9 Example 2 pre-mix 93.4 (51.7) 93.4 (51.7) 93.4 (51.7) Example 3 pre-mix 83.3 (56.0) 81.8 (55.0) 77.4 (52.0) Siloxane Borate of -- 1.79 (1.00) 7.1 (4.00) Example D
Methyl n-amyl ketone 2.00 ---- ----Butyl Cellosfllve 2.00 ---- -duly+ _.; t71t0lO 0.50 '--- -Reductioii Inforimation Methyl n-amyl ketone 3.03' _ 4.7 3.83 3utyl 3.::'3 :3.33 ~
acetate Butyl Carbitola acetate 0.67 1.04 0.85 Spray viscosity' (sec) 28.4 28.7 28.1 Paint temperature ( F) 72.4 72.3 72.0 Theory % So!ids2 57.3 57.5 57.8 Viscosity measured in seconds with a #4 FORD efflux cup at ambient temperature.
2 Theory % Solids of a coating is determined by taking the solid weight of the coating formulation divided by the sum of the parts by weight of the coating formulation and the reducing solvent weight.
TESTING
The film forming compositions of Examples 4-9 were spray applied to a pigmented basecoat to form color-plus-clear composite coatings over primed electrocoated steel panels. The panels used were cold rolled steel pariels (size 4 inches x 12 inches (10.16 cm by 30.48 cm)). The steel panels for Examples 4-6 were coated with ED5000 electrocoat, available from PPG
Industries, Inc, and SUPERMAR primer, available from Herbects/DuPont.
The ED5000 electrocoat test panels are available as APR22986 from ACT
Laboratories, Inc. of Hillsdale, Michigan. Examples 7-9 utilized steel panels *rrade-rrark that were coated with ED5240 electrocoat and FCP6579 primer, both available from PPG Industries, Inc. The test panels are available as APR40017 from ACT Laboratories, Inc. of Hillsdale, Michigan.
The basecoat used for Examples 4-6 was Nero Vulcano*UR806/A, black pigmented solvent-based acrylic/melamine basecoat, available from PPG Industries, Inc. Examples 7-9 used ODCT6373 Ebony Black, a black pigmented solvent-based acrylic/melamine basecoat, available from PPG
Industries, Inc.
The Nero Vulcano UR806/A basecoat was automated spray applied in to one coat to the electrocoated and primed steel panels at ambient temperature (about 70 F (21 C)). A dry film thickness of about 0.5 to 0.7 mils (about 13 to 18 micrometers) was targeted. After the basecoat application, a ninety second air flash at ambient temperature was given before applying the clearcoat. The ODCT6373 Ebony Black basecoat was automated spray applied in two coats to the electrocoated and primed steel panels at ambient temperature (about 70 F (21 C)). A ninety second air flash at ambient A dryA iilill thickness of about 0.6 to 0.8 mils (about 15 to 20 micrometers) was targeted.
t-.fler the secon-d bas' ecoat application, a ninety seco7!d air f'....sh at 20 temperature was given before applying the clearcoat.
The clear coating compositions of Examples 4-9 were each automated spray applied to a basecoated panel at ambient temperature in two coats with a ninety second ambient flash between applications. Examples 4-6 were targeted for a 1.5 to 1.7 mils (about 38 to 43 micrometers) dry film thickness, and Examples 7-9 were targeted for a 1.7 to 1.9 mils (about 43 to 48 micrometers) dry film thickness. All coatings were allowed to air flash at ambient temperature for ten minutes. Panels prepared from each coating were baked for thirty minutes at 285 F (141 C) to fully cure the coating(s).
The panels were baked in a horizontal position.
To test for recoat adhesion, an original basecoated and clearcoated panel, as described above, was given another layer of basecoat and "Trade-mark clearcoat-or clearcoat only. Examples 4-6 were recoated with Nero Vulcano UR806/A and Examples 4-6,'depending on the respective original panel.
Examples 7-9 were recoated with ODCT6373 Ebony Black and Examples 7-9, depending on the respective original panel. For example, an Example 4 clearcoat over Nero Vulcano UR806/A original (prepared above) was recoated with Nero Vulcano UR806/A and Example 4 clearcoat. Half' of an original panel from each clear coating was basecoated and clearcoated and the other half of the panel was clearcoated only. To recoat the panels half .and half, the bottom halves of the original panels were covered with aluminum io foil and then the respective basecoats were automated spray applied as described above. The foil was removed, resulting in an original panel with the upper half coated in basecoat and the bottom half still with only the original coating layers. The respective clearcoat was then automated spray applied to tite eri,:F c panel as described above. t he rL~;ultir:g pane': _; , rare half coated in basecoat/ clearcoat from the original spray application and another layer of ~.asecoatl c!earcoat Tru;,x ~~)a coat --p:ay p <p:;cuiticn (aiCii~;C). The uLher half of the resu{titig panel was coated in basecoat,' clearcoat from the original spray application and another layer of clearcoat from the recoat spray application (B/C//C).
Test results for the coatings are reported below in Table 3. As mentioned above the coating compositions of Examples 4-6 were applied over Nero Vulcano UR806/A basecoat and Examples 7-9 were applied over ODCT6373 Ebony Black basecoat.
Adhesion Recoat Adhesion2 Windshield Promoter Adhesion3 (B) Example Elemental 20 Gloss' B/C//B/C B/C//C (% cohesive # Weight % failure) on Resin Solids 4* 0 91 0 td 0 td ----0.02 91 2/3 0 ---6 0.08 91 4+ 4 7* 0 86 2+ 0 0 8 0.02 86 5- 3+ 100 9 0.08 84 5 5 100 20 gloss was measured with a Statistical Novo-Gloss 20 gloss meter, available from Paul N. Gardner Company, Inc.
5 2 Recoat adhesion tests the adhesion of the recoat layer (either basecoat/clearcoat or clearcoat only) to the original layers (steel/ electrodeposition/ primer/
basecoatl clearcoat). A multi-blade claw with 2.0 mm spaced teeth (blade and handle/blade holder are available from Paul N. Gardner Company, Inc.) was used to scribe the cured coating. Two sets of scribes were made by scribing the second set on top of and perpendicular to the first set. Detached flakes and ribbons of coating were wiped off the panel and strapping tape (3M #898 available from Minnesota, Mining and Manufacturing Co. - 3M) was smoothed firmly over the crosshatch marking.
Within 90 seconds of application, the tape was removed in one continuous motion directed toward the tester and as paraflel to the panel as possible. The scribed area was inspected and rated for removal of the recoat layer to the substrate accorciing to the following scale:
5= The edges of the cuts are completely smooth and l~ttic-:
squares is detached.
4 = Small flakes of coating are detached at intersections. Less than five percent of the area is affected.
3 = Small flakes of the coating are detached along edges and at intersections of cuts. The area affected is five to fifteen percent of the lattice.
2= The coating has flaked along the edges and on parts of the squares.
The area affected is fifteen to thirty-five percent of the lattice.
1 = The coating has flaked along the edges of cuts in large ribbons and whole squares have detached. The area affected is thirty-five to sixty-five percent of the lattice.
0 = Flaking and detachment worse than rating 1. Over sixty-five percent of the lattice is affected.
Td = Total delamination, The adhesion between a coating and a windshield adhesive used in the automotive industry was determined using the Quick Knife test. Wthin 1 to 4 hours of the tinal thirty minute bake cycle, a bead of the B-ETASEAL*15625 urethane adhesive (Supplied by Essex Specialty Products Inc.) was applied to the surface of the clearcoat of a basecoated and clearcoated panel, prepared as described above.
The plastic nozzle (supplied with adhesive) was prepared for the urethane by cutting the tip at - 80 angle. The opening measured approximately 5mm in diameter. On *Trade-mark the long end of the cut edge, a notch approximately 5mm wide by 2mm high was cut.
The tube of urethane was placed in a battery powered caulking gun and a small amount was squeezed from the tube into a paper cup for disposal. The caulking gun was set at - 90% speed for a steady flow of adhesive. The plastic tip was placed on the panel with the notch facing away from the person applying the bead. With the tip held firmly on the panel at the same angle (80 ) as the cut nozzle, a steady bead was applied down the length of the panel. The bead was flat where it contacted the panel. After the bead was laid, the panel was placed in a ventilated hood where it remained undisturbed for at least 72 hours @ 20 - 50% relative humidity in order to cure. After the bead cured, the adhesive bead was cut with a razor blade knife. A
small section was cut at the beginning of the bead to make it easier to grasp.
To cut the bead, the small beginning section was pulled back at approximately a 1800 angle and slices were made in the adhesive at a 60 to 80 angle in a quick motion.
The blade was kept in contact with the clearcoat at all times during. The adhesive bead continued to be pulled while the adhesive was being cut at -1/2" intervals. A
minimum of 10 cuts was made. After making slices to the adhesive bead, the panel was rated for % Cohesive Failure (% C.F.) of the bead to the panel. (Cohesive Failure occurs when the integrity of the adhesive bead is lost as a result of cutting and pulling rather than the bond between the adhesive bead and the clearcoat surface.) Failures were reported as a total % along the bead. For example, if there ~rl~c ?!7 /Q of the urath.-nE e rAmaining on the parM, then 4 %ffas reported as 20% C'7.
if the en'Liri-, ;. ~... : ;be Nu'R;:U'off, it was c,..cjnside~-c!d to be 0%
C.F. The --_;rcA
result was a minimum of 90% or higher cohesion.
Tc J~ R 7 < , above in Tab!- 3 iI~;stracL a t ;a: :t the one-package coating compositions of tine present invention improves as the amount of polysiloxane borate increases in the composition, while similar comparative compositions which do not contain the polysiloxane borate have poor or no recoat adhesion. - Further, the data illustrate that while the comparative composition of Example 7 exhibits very poor (0%) windshield adhesion, the compositions of the present invention (Examples 8 and 9) exhibit excellent (100%) windshield adhesion.
The following Examples 10 through 13 presented in Table 4 below describe the preparation of thermosetting coating compositions based on epoxy containing acrylic resins cured with acid functional curing agents in combination with aminoplast resins. The compositions were prepared by admixing the following ingredients under mild agitation. Note, those comparative compositions which do not contain a boron-containing compound (i.e., Comparative Examples 10 and 13) are designated with an Example Example Example Example 10* 11 12 13*
Materials Solids Soin. Solids Soln. Solids Soln. Solids Soln.
Resin Wt. Resin Wt. Resin Wt. Resin Wt.
+ + + +
Additive Additive Additive Additive n-pentyl - 25 - 25 - 25 - 15 propionate' DOWANOL - - - - - - - 11.2 TINUVIN -3283 3 3 3 3 3 3 2.7 2.7 Colloidal silica 10.5 10.5 10.5 - -dispersion of Example A
60% GMA 42.9 67 39.05 61 37.05 58 - -resin"
50% GMA - - - - - - 56.25 87.9 resins Primarv <rnyf - - - - - - - ~.~
a4coho{' CYMEL 202' 3 3.8 3 3.8 3 3.8 2.05 2.6 CYLIN!iU 10 20 10 20 10 20 - -20G0$
fumed silica - - - - - - 12.9 dispersion9 Isostearic 4 4 4 4 4 4 4.1 4.1 Acid10 ' PE7JTEK"" 34.25 50.4 34.1 50 32.1 47.2 34.2 50.3 Siloxane - - 4 8.1 8 16.2 - -Borate of Example A
TINUVIN 123 0.4 0.4 0.4 0.4 0.4 0.4 0.35 0.35 Polybutyl - - - - - - 0.51 0.85 acrylate OX-6012 - - - - - - 0.04 0.08 Multiflow (50% 0.025 0.05 0.025 0.05 0.025 0.05 0.09 0.18 soin. of MODAFLC7M' D'am ,~thyl 0.3 0.3 0.3 0.3 0.3 0.3 0.32 0.32 cocoamine14 ' Available from Dow Chemical Co.
2 Dipropylene glycol monomethyl ether, available from Dow Chemical Co.
Trade-rrark 3 2-(2'-Hydroxy-3',5'-dtert-amylphenyl) benzotriazole UV light stabilizer available from Ciba Specialty Chemicals Corp.
Acrylic resin comprising 60% glycidyl methacrylate, 31 % n-butyl methacrylate, 0.2% methyl methacrylate, 7% styrene, 2% diphenyl-2,4-methyl-4 pentene-1, 66%
solids in dipropylene glycol monomethyl ether and n-amyl propionate.
5 Acrylic resin comprising 50% glycidyl methacrylate, 41 % n-butyl methacrylate, 0.2% methyl methacrylate, 7% styrene, 2% diphenyl-2,4-methyl-4 pentene-1, 64%
solids in dipropylene glycol monorriethyl ether and n-amyl propionate.
6 Available from Dow Chemical Co.
' Melamine available from Cytec Industries, Inc.
8 Available from Cytec Industries, Inc.
9 R-812 silica from Degussa dispersed in n-amyl alcohol and a trimethylol propane/methylhexahydrophthalic anhydride half ester of Example G in US patent #
5,256,452.
10 Available from Uniqema.
Polyester prepared from 83% 4-methyl hexahydrophthalic anhydride and 17%
pentaerythritol, 67% solids in n-propyl alcohol and n-amyl propionate.
12 Available from Kusumoto, a King Industries distributor.
13 Available from Solutia.
14 Available from Albemarle Corp.
.,,:: ci~aicoats prE--r-ared as described ..<ocve were reduced,,vith DOWANOL DPM to a spray viscosity of 26 seconds at ambient temperature ii ~. a:~ ~Y 7+00r f (26 G)), 1 ci t oi d }?.
TESTING
The film forming compositions of Examples 10-13 were spray applied to a pigmented basecoat to form color-plus-clear composite coatings over electrocoated steel panels. The panels used were cold rolled steel panels (size 4 inches x 12 inches (10.16 cm by 30.48 cm)). The steel panels for Examples 10-13 were coated with ED5000 electrocoat, available from PPG
Industries, Inc. These prepared test panels are available as APR23884 from ACT Laboratories, Inc. of Hillsdale, Michigan.
The basecoat used for Examples 10-13 was HWB-9517, black pigmented waterborne basecoat, available from PPG Industries, Inc. The HWB-9517 basecoat was automated spray applied in one coat to the electrocoated steel panels at ambient temperature (i.e., at approximately 76 F (25 C) and 30% relative humidity). A dry film thickness of about 0.5 to 0.7 mils (about 13 to 18 micrometers) was targeted. The basecoat was allowed tczflash ambiently for about 5minutes and then prebaked for five minutes at 200 F (93 C).
The clear coating compositions of Examples 10-13 were each automated spray applied to a basecoated panel at ambient temperature in two coats with a 60 second ambient flash between applications. Coatings of Examples 10-13 were targeted for a 1.8 to 2 mils (about 46 to 51 micrometers) dry film thickness. All coatings were allowed to air flash at ambient temperature for ten minutes. Panels prepared from each coating were baked for thirty minutes at 285 F (141 C) to fully cure the coating(s).
to The panels were baked in a horizontal position.
To test for recoat adhesion, an original basecoated and clearcoated panel, as described above, was given another layer of basecoat and clearcoat or clearcoat only. Examples 10-13 virere recoated with HWB-9517 basecoat. To recoat the panels half and half, the right halves of the original panels were covered with masking tape and then the respective basecoats were automated spray applied as described above. The tape was removed, resulting in an oriainal pane! thc r'~41: h~!r fo?!r=d i.,1 ha ~-,d t')r I
half still with only the original coating layers. The respective clearcoat was then automated spray applied to the entire panel as described above. The 2o resulting panels were half coated in basecoat/ clearcoat from the original spray application and another layer of basecoat/ clearcoat from the recoat spray application (B/C//B/C). The other half of the resulting panel was coated in basecoat/ clearcoat from the original spray application and another layer of clearcoat from the recoat spray application (c~/C(!C). Test data is presented below in the following Table 5.
5 2 Recoat adhesion tests the adhesion of the recoat layer (either basecoat/clearcoat or clearcoat only) to the original layers (steel/ electrodeposition/ primer/
basecoatl clearcoat). A multi-blade claw with 2.0 mm spaced teeth (blade and handle/blade holder are available from Paul N. Gardner Company, Inc.) was used to scribe the cured coating. Two sets of scribes were made by scribing the second set on top of and perpendicular to the first set. Detached flakes and ribbons of coating were wiped off the panel and strapping tape (3M #898 available from Minnesota, Mining and Manufacturing Co. - 3M) was smoothed firmly over the crosshatch marking.
Within 90 seconds of application, the tape was removed in one continuous motion directed toward the tester and as paraflel to the panel as possible. The scribed area was inspected and rated for removal of the recoat layer to the substrate accorciing to the following scale:
5= The edges of the cuts are completely smooth and l~ttic-:
squares is detached.
4 = Small flakes of coating are detached at intersections. Less than five percent of the area is affected.
3 = Small flakes of the coating are detached along edges and at intersections of cuts. The area affected is five to fifteen percent of the lattice.
2= The coating has flaked along the edges and on parts of the squares.
The area affected is fifteen to thirty-five percent of the lattice.
1 = The coating has flaked along the edges of cuts in large ribbons and whole squares have detached. The area affected is thirty-five to sixty-five percent of the lattice.
0 = Flaking and detachment worse than rating 1. Over sixty-five percent of the lattice is affected.
Td = Total delamination, The adhesion between a coating and a windshield adhesive used in the automotive industry was determined using the Quick Knife test. Wthin 1 to 4 hours of the tinal thirty minute bake cycle, a bead of the B-ETASEAL*15625 urethane adhesive (Supplied by Essex Specialty Products Inc.) was applied to the surface of the clearcoat of a basecoated and clearcoated panel, prepared as described above.
The plastic nozzle (supplied with adhesive) was prepared for the urethane by cutting the tip at - 80 angle. The opening measured approximately 5mm in diameter. On *Trade-mark the long end of the cut edge, a notch approximately 5mm wide by 2mm high was cut.
The tube of urethane was placed in a battery powered caulking gun and a small amount was squeezed from the tube into a paper cup for disposal. The caulking gun was set at - 90% speed for a steady flow of adhesive. The plastic tip was placed on the panel with the notch facing away from the person applying the bead. With the tip held firmly on the panel at the same angle (80 ) as the cut nozzle, a steady bead was applied down the length of the panel. The bead was flat where it contacted the panel. After the bead was laid, the panel was placed in a ventilated hood where it remained undisturbed for at least 72 hours @ 20 - 50% relative humidity in order to cure. After the bead cured, the adhesive bead was cut with a razor blade knife. A
small section was cut at the beginning of the bead to make it easier to grasp.
To cut the bead, the small beginning section was pulled back at approximately a 1800 angle and slices were made in the adhesive at a 60 to 80 angle in a quick motion.
The blade was kept in contact with the clearcoat at all times during. The adhesive bead continued to be pulled while the adhesive was being cut at -1/2" intervals. A
minimum of 10 cuts was made. After making slices to the adhesive bead, the panel was rated for % Cohesive Failure (% C.F.) of the bead to the panel. (Cohesive Failure occurs when the integrity of the adhesive bead is lost as a result of cutting and pulling rather than the bond between the adhesive bead and the clearcoat surface.) Failures were reported as a total % along the bead. For example, if there ~rl~c ?!7 /Q of the urath.-nE e rAmaining on the parM, then 4 %ffas reported as 20% C'7.
if the en'Liri-, ;. ~... : ;be Nu'R;:U'off, it was c,..cjnside~-c!d to be 0%
C.F. The --_;rcA
result was a minimum of 90% or higher cohesion.
Tc J~ R 7 < , above in Tab!- 3 iI~;stracL a t ;a: :t the one-package coating compositions of tine present invention improves as the amount of polysiloxane borate increases in the composition, while similar comparative compositions which do not contain the polysiloxane borate have poor or no recoat adhesion. - Further, the data illustrate that while the comparative composition of Example 7 exhibits very poor (0%) windshield adhesion, the compositions of the present invention (Examples 8 and 9) exhibit excellent (100%) windshield adhesion.
The following Examples 10 through 13 presented in Table 4 below describe the preparation of thermosetting coating compositions based on epoxy containing acrylic resins cured with acid functional curing agents in combination with aminoplast resins. The compositions were prepared by admixing the following ingredients under mild agitation. Note, those comparative compositions which do not contain a boron-containing compound (i.e., Comparative Examples 10 and 13) are designated with an Example Example Example Example 10* 11 12 13*
Materials Solids Soin. Solids Soln. Solids Soln. Solids Soln.
Resin Wt. Resin Wt. Resin Wt. Resin Wt.
+ + + +
Additive Additive Additive Additive n-pentyl - 25 - 25 - 25 - 15 propionate' DOWANOL - - - - - - - 11.2 TINUVIN -3283 3 3 3 3 3 3 2.7 2.7 Colloidal silica 10.5 10.5 10.5 - -dispersion of Example A
60% GMA 42.9 67 39.05 61 37.05 58 - -resin"
50% GMA - - - - - - 56.25 87.9 resins Primarv <rnyf - - - - - - - ~.~
a4coho{' CYMEL 202' 3 3.8 3 3.8 3 3.8 2.05 2.6 CYLIN!iU 10 20 10 20 10 20 - -20G0$
fumed silica - - - - - - 12.9 dispersion9 Isostearic 4 4 4 4 4 4 4.1 4.1 Acid10 ' PE7JTEK"" 34.25 50.4 34.1 50 32.1 47.2 34.2 50.3 Siloxane - - 4 8.1 8 16.2 - -Borate of Example A
TINUVIN 123 0.4 0.4 0.4 0.4 0.4 0.4 0.35 0.35 Polybutyl - - - - - - 0.51 0.85 acrylate OX-6012 - - - - - - 0.04 0.08 Multiflow (50% 0.025 0.05 0.025 0.05 0.025 0.05 0.09 0.18 soin. of MODAFLC7M' D'am ,~thyl 0.3 0.3 0.3 0.3 0.3 0.3 0.32 0.32 cocoamine14 ' Available from Dow Chemical Co.
2 Dipropylene glycol monomethyl ether, available from Dow Chemical Co.
Trade-rrark 3 2-(2'-Hydroxy-3',5'-dtert-amylphenyl) benzotriazole UV light stabilizer available from Ciba Specialty Chemicals Corp.
Acrylic resin comprising 60% glycidyl methacrylate, 31 % n-butyl methacrylate, 0.2% methyl methacrylate, 7% styrene, 2% diphenyl-2,4-methyl-4 pentene-1, 66%
solids in dipropylene glycol monomethyl ether and n-amyl propionate.
5 Acrylic resin comprising 50% glycidyl methacrylate, 41 % n-butyl methacrylate, 0.2% methyl methacrylate, 7% styrene, 2% diphenyl-2,4-methyl-4 pentene-1, 64%
solids in dipropylene glycol monorriethyl ether and n-amyl propionate.
6 Available from Dow Chemical Co.
' Melamine available from Cytec Industries, Inc.
8 Available from Cytec Industries, Inc.
9 R-812 silica from Degussa dispersed in n-amyl alcohol and a trimethylol propane/methylhexahydrophthalic anhydride half ester of Example G in US patent #
5,256,452.
10 Available from Uniqema.
Polyester prepared from 83% 4-methyl hexahydrophthalic anhydride and 17%
pentaerythritol, 67% solids in n-propyl alcohol and n-amyl propionate.
12 Available from Kusumoto, a King Industries distributor.
13 Available from Solutia.
14 Available from Albemarle Corp.
.,,:: ci~aicoats prE--r-ared as described ..<ocve were reduced,,vith DOWANOL DPM to a spray viscosity of 26 seconds at ambient temperature ii ~. a:~ ~Y 7+00r f (26 G)), 1 ci t oi d }?.
TESTING
The film forming compositions of Examples 10-13 were spray applied to a pigmented basecoat to form color-plus-clear composite coatings over electrocoated steel panels. The panels used were cold rolled steel panels (size 4 inches x 12 inches (10.16 cm by 30.48 cm)). The steel panels for Examples 10-13 were coated with ED5000 electrocoat, available from PPG
Industries, Inc. These prepared test panels are available as APR23884 from ACT Laboratories, Inc. of Hillsdale, Michigan.
The basecoat used for Examples 10-13 was HWB-9517, black pigmented waterborne basecoat, available from PPG Industries, Inc. The HWB-9517 basecoat was automated spray applied in one coat to the electrocoated steel panels at ambient temperature (i.e., at approximately 76 F (25 C) and 30% relative humidity). A dry film thickness of about 0.5 to 0.7 mils (about 13 to 18 micrometers) was targeted. The basecoat was allowed tczflash ambiently for about 5minutes and then prebaked for five minutes at 200 F (93 C).
The clear coating compositions of Examples 10-13 were each automated spray applied to a basecoated panel at ambient temperature in two coats with a 60 second ambient flash between applications. Coatings of Examples 10-13 were targeted for a 1.8 to 2 mils (about 46 to 51 micrometers) dry film thickness. All coatings were allowed to air flash at ambient temperature for ten minutes. Panels prepared from each coating were baked for thirty minutes at 285 F (141 C) to fully cure the coating(s).
to The panels were baked in a horizontal position.
To test for recoat adhesion, an original basecoated and clearcoated panel, as described above, was given another layer of basecoat and clearcoat or clearcoat only. Examples 10-13 virere recoated with HWB-9517 basecoat. To recoat the panels half and half, the right halves of the original panels were covered with masking tape and then the respective basecoats were automated spray applied as described above. The tape was removed, resulting in an oriainal pane! thc r'~41: h~!r fo?!r=d i.,1 ha ~-,d t')r I
half still with only the original coating layers. The respective clearcoat was then automated spray applied to the entire panel as described above. The 2o resulting panels were half coated in basecoat/ clearcoat from the original spray application and another layer of basecoat/ clearcoat from the recoat spray application (B/C//B/C). The other half of the resulting panel was coated in basecoat/ clearcoat from the original spray application and another layer of clearcoat from the recoat spray application (c~/C(!C). Test data is presented below in the following Table 5.
Clearcoat 200 Gloss Elemental MVSS Recoat Recoat composition weight % primerless Adhesion Adhesion on resin adhesion %pass %pass solids % pass B/C//B/C BIC//C
Example 11 72 0.08 data 30 50 unavailable Example 12 72 0.16 88 100 100 Example 10* 83 0 100 0 0 Example 13* 83 0 100 100 100 * Comparative examples The data presented in Table 5 above illustrate that the epoxy-acid clear coat controls of Comparative Examples 10 and 13 pass MVSS
primeriess adhesion. However, these same the clearcoating of Exarnple 10 exhibits very poor recoat adhesion when recoated either with a subsequently arnlied repair b~~-_-coat/clearcoat system or a repair cle-rl-oat. By contrast, ta LE,e coating compositions of the present invention which contain the polysiloxane borate, exhibit improved recoat adhesion and 100% recoat adhesion (see Exa,Yipies 11 and 12, respective:Jy).
TWO-COMPONENT COATING COMPOSITIONS
COMPARATIVE EXAtAPEE 14 This comparative example describes the preparation of a two-component clearcoat composition which does not contain an adhesion promoting-compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Ceilosolve acetate 10.0 -Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin' 58.2 42.2 CYMEL 202 18.8 15.0 Polysiloxane polyol of Example AA 11.0 11.0 Phenyl Acid Phosphate Catalyst2 0.7 0.5 DesmrodurN33004* 27.1 27.1 ' Acrylic polyol prepared from 14.5% butyl acrylate, 14.5% butyl methacrylate, 27.6%
isobomyl methacrylate, 22.6% hydroxypropyl methacrylate, 20.4% hydroxyethyl methacrylate, and 0.4% acrylic acid, having resin solids of 69.7%, Mw 3227 and a hydroxyl value of 101.
2 Phenyl acid phosphate solution, 75 percent in isopropanol.
3 Isocyanurate of hexamethylene diisocyanate available from Bayer Corp.
This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane borate as an +-i promol;r,g compouind. The coating compasitiori was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Cellosolve R acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 Polysiloxane polyol of Example AA 10.0 10.0 Siloxane Borate of Example E 2.4 1.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 "'TradWafc This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane borate as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 --Butyl Cellosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dipersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 ,,f F~ _ AA 9.0 9.0 _---~~,~~a: _ ate of Exa. J;pie E 4.9 2.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27_ 1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane borate as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Buty{ CellosolveO acetate 10.0 ---Butyl Carbitol acetate 5.0 --Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cymel 202 18.8 15.0 Po{ysiloxane polyol of Example AA 7.0 7.0 Siloxane Borate of Example E 9.8 4.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains a boric acid as an adhesion promoting compound. The coating composition was prepared by s admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 Butyl Cellosolve acetate 10.01 --Butyl Carbitol acetate 5.0 --Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 Polysiloxane poiyol of Example AA 11.0 11.0 Boric acid (20% solution in 1.3 0.3 methanol) Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describ6s the preparation of a two-component clearcoat composition of the present invention which contains a boric acid as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Cellosotve8 acetate 10.0 --Butyt Carbito{ acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 Polysiloxane polyol of Fynr=.~ule AA 11.0 11.0 3oric acid (2(~ j 4:.- n in 5.0 1.0 methanol) Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 2:.:
Example 11 72 0.08 data 30 50 unavailable Example 12 72 0.16 88 100 100 Example 10* 83 0 100 0 0 Example 13* 83 0 100 100 100 * Comparative examples The data presented in Table 5 above illustrate that the epoxy-acid clear coat controls of Comparative Examples 10 and 13 pass MVSS
primeriess adhesion. However, these same the clearcoating of Exarnple 10 exhibits very poor recoat adhesion when recoated either with a subsequently arnlied repair b~~-_-coat/clearcoat system or a repair cle-rl-oat. By contrast, ta LE,e coating compositions of the present invention which contain the polysiloxane borate, exhibit improved recoat adhesion and 100% recoat adhesion (see Exa,Yipies 11 and 12, respective:Jy).
TWO-COMPONENT COATING COMPOSITIONS
COMPARATIVE EXAtAPEE 14 This comparative example describes the preparation of a two-component clearcoat composition which does not contain an adhesion promoting-compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Ceilosolve acetate 10.0 -Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin' 58.2 42.2 CYMEL 202 18.8 15.0 Polysiloxane polyol of Example AA 11.0 11.0 Phenyl Acid Phosphate Catalyst2 0.7 0.5 DesmrodurN33004* 27.1 27.1 ' Acrylic polyol prepared from 14.5% butyl acrylate, 14.5% butyl methacrylate, 27.6%
isobomyl methacrylate, 22.6% hydroxypropyl methacrylate, 20.4% hydroxyethyl methacrylate, and 0.4% acrylic acid, having resin solids of 69.7%, Mw 3227 and a hydroxyl value of 101.
2 Phenyl acid phosphate solution, 75 percent in isopropanol.
3 Isocyanurate of hexamethylene diisocyanate available from Bayer Corp.
This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane borate as an +-i promol;r,g compouind. The coating compasitiori was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Cellosolve R acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 Polysiloxane polyol of Example AA 10.0 10.0 Siloxane Borate of Example E 2.4 1.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 "'TradWafc This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane borate as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 --Butyl Cellosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dipersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 ,,f F~ _ AA 9.0 9.0 _---~~,~~a: _ ate of Exa. J;pie E 4.9 2.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27_ 1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane borate as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Buty{ CellosolveO acetate 10.0 ---Butyl Carbitol acetate 5.0 --Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cymel 202 18.8 15.0 Po{ysiloxane polyol of Example AA 7.0 7.0 Siloxane Borate of Example E 9.8 4.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains a boric acid as an adhesion promoting compound. The coating composition was prepared by s admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 Butyl Cellosolve acetate 10.01 --Butyl Carbitol acetate 5.0 --Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 Polysiloxane poiyol of Example AA 11.0 11.0 Boric acid (20% solution in 1.3 0.3 methanol) Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describ6s the preparation of a two-component clearcoat composition of the present invention which contains a boric acid as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Cellosotve8 acetate 10.0 --Butyt Carbito{ acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cyme1202 18.8 15.0 Polysiloxane polyol of Fynr=.~ule AA 11.0 11.0 3oric acid (2(~ j 4:.- n in 5.0 1.0 methanol) Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 2:.:
This example describ6s the preparation of a two-component clearcoat composition of the present invention which contains triisopropyl borate as an.
adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 --Butyl Cellosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cymel 202 18.8 15.0 Polysiloxane polyol of Example AA 11.0 11.0 Triisopropyl Borate' 0.9 0.9 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 ' Available from Aldrich Chemical Co.
adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 --Butyl Cellosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cymel 202 18.8 15.0 Polysiloxane polyol of Example AA 11.0 11.0 Triisopropyl Borate' 0.9 0.9 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 ' Available from Aldrich Chemical Co.
EXAMPL.E 21 This example describes the preparation of a two-component clearcoat composition of the present invention which contains DOWANOL PM borate as an adhesion promoting compound. The coating composition was prepared s by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Cellosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cymel 202 18.8 15.0 Pr%kysil~xar ,Iyo! -r- AA 1-10 11.0 F 2.2 Phenyl Acid Phospha'ce Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains an acrylic borate as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Ceiiosolve acetate 10.0 ---Butyi Carbitot acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acryiic Borate of Example G 60.9 42.2 Cymel 202 18.8 15.0 Polysiloxane polyol of Example AA 11.0 11.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane aluminum isopropoxide as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Celiosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 -Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 t--~~'ic Resin of Example 1A 58.'' 42.2 y i;ymel 202 15.0 Polysiloxane po;yei c=f Example AA -- -- +
Si{oxane Aluminum isopropoxide of 42.9 22.9 Exam01e P
__ Phenyl Acid ;~~icsph_at_e Catalyst 0.7 0.5 -4 DesrnodurN'?00 27.1 The clearcoats Examp!es 14 through 23 described above were reduced in viscosity to about 25 seconds on a #4 Ford efflux cup at ambient temperature using methyl n-amyl ketone.
TESTING
is The film forming compositions of Examples 14-23 were spray applied to a pigmented basecoat to form coior-plus-clear composite coatings over primed electrocoated steel panels. The panels used were cold rolled steel panels (size 4 inches x 12 inches (10.16 cm by 30.48 cm)). The steel panels for Examples 14-23 were coated with ED5050B electrocoat, available from PPG Industries, Inc, and 1177225A primer surfacer, also available from PPG
Industries, Inc or coated with ED5000 electrocoat, available from PPG
Industries, fnc, and GPXH5379 primer surfacer, also available from PPG
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Cellosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acrylic Resin of Example 14 58.2 42.2 Cymel 202 18.8 15.0 Pr%kysil~xar ,Iyo! -r- AA 1-10 11.0 F 2.2 Phenyl Acid Phospha'ce Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains an acrylic borate as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Ceiiosolve acetate 10.0 ---Butyi Carbitot acetate 5.0 ---Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 Acryiic Borate of Example G 60.9 42.2 Cymel 202 18.8 15.0 Polysiloxane polyol of Example AA 11.0 11.0 Phenyl Acid Phosphate Catalyst 0.7 0.5 DesmodurN3300 27.1 27.1 This example describes the preparation of a two-component clearcoat composition of the present invention which contains a siloxane aluminum isopropoxide as an adhesion promoting compound. The coating composition was prepared by admixing the following ingredients sequentially under mild agitation.
Ingredient Parts by Weight Solid Weight (grams) (grams) Methyl n-amyl ketone 30.0 ---Butyl Celiosolve acetate 10.0 ---Butyl Carbitol acetate 5.0 -Tinuvin 928 3.0 3.0 Tinuvin 292 0.5 0.5 Silica dispersion of Example A 8.8 6.7 t--~~'ic Resin of Example 1A 58.'' 42.2 y i;ymel 202 15.0 Polysiloxane po;yei c=f Example AA -- -- +
Si{oxane Aluminum isopropoxide of 42.9 22.9 Exam01e P
__ Phenyl Acid ;~~icsph_at_e Catalyst 0.7 0.5 -4 DesrnodurN'?00 27.1 The clearcoats Examp!es 14 through 23 described above were reduced in viscosity to about 25 seconds on a #4 Ford efflux cup at ambient temperature using methyl n-amyl ketone.
TESTING
is The film forming compositions of Examples 14-23 were spray applied to a pigmented basecoat to form coior-plus-clear composite coatings over primed electrocoated steel panels. The panels used were cold rolled steel panels (size 4 inches x 12 inches (10.16 cm by 30.48 cm)). The steel panels for Examples 14-23 were coated with ED5050B electrocoat, available from PPG Industries, Inc, and 1177225A primer surfacer, also available from PPG
Industries, Inc or coated with ED5000 electrocoat, available from PPG
Industries, fnc, and GPXH5379 primer surfacer, also available from PPG
lndustries, Inc. The test panels are available as APR39754 or APR39375 from ACT Laboratories, Inc. of Hillsdale, Michigan.
The basecoat used for Examples 14-23 was Obsidian Schwarz*, black pigmented waterborne basecoat, available from BASF Corporation. The Obsidian Schwarz basecoat was automated spray applied in two coats with approximately 30 second flash between coats to the efectrocoated and primed steel panels at about 70 F (21 C) temperature and about 60% relative humidity. A dry film thickness of about 0.5 to 0.6 mils (about 12 to 16 micrometers) was targeted. The basecoat was allowed to flash ambiently for io about five minutes and then prebaked for five minutes at 176 F (80 C).
The clear coating compositions of Examples 14-23 were each automated spray applied to a basecoated panel at ambient temperature in two coats with about a 30 second ambient flash between coats. Examples 1-were targeted for a 1.5 to 2.0 mils (about 38 to 51 micrometers) dry film j5 thickness. All coatings were allowed to air flash at ambient temperature for ten minutes. Panels prepared from each coating were baked for 30 minutes at 285 F (141 C) to fullv cure the coatin~(s) horizontal position.
To test for recoat adhesion, an original basecoated and clearcoated panel, as described above, was given another layer of basecoat and clearcoat or clearcoat only. With the condition of sanding, the right half of the panel was sanded with 1200 grit sand paper and the left hulf -vras not sar~dcd thus giving sanded and non-sanded areas. Half of an original panel from each clear coating was basecoated and clearcoated and ti-7e other half of ttie panel was clearcoated only. To recoat the panels half and half, the bottom halves of the original panels were covered with aluminum foil and then the top halves were recoated with Obsidian Schwarz basecoat using the same.conditions as above. The foil was removed, resulting in an original panel with the upper half coated in basecoat and the bottom half still with only the original coating layers. The respective clearcoat was then automated spray applied to the entire panel as described above. The resulting panels were half coated in *Trade-mark basecoat/_clearcoat from the original spray application and another layer of basecoat/ clearcoat from the recoat spray application (B/C//B/C). The other half of the resulting panel was coated in basecoat/ clearcoat from the original spray application and another layer of clearcoat from the recoat spray s application (B/C//C). Test data is reported below in the following Table 6.
Recoat Adhesion - Cross Hatch Adhesion 30/285 F // 30/285 F
promoter Sanded Non-Sanded Example # Elemental 20 Gloss B/C// B/C// B/C// B/C//
Weight % B/C C B/C C
on resin -solids 14* 0 84 5 5 0 0 15 0.02 84 5 5 5 0 ~ ;.-, 17 - G. 84 5 5 5 5-18 0.04 84 5 5 5 0 19 0.15 35 5 5 5-, ._ ~------- ' _ .__._--- - . ----._..-- .----- --- - --------_ 20 0.04 85 -- --- 5 0 21 0.04 85 --- -- 5 0 22 0.03 85 - --- -- 5 0 23 0.10 82 5 5 5 0 * Designates a comparative example.
The data presented above in Table 6 illustrate that the inclusion in a two-component clearcoating composition of the adhesion promoting composition of Examples C through H above provide excellent adhesion where a basecoat/clearcoat system is recoated with a repair basecoat/clearcoat system. Further, the data for Examples 14-22 illustrate that the inclusion of the polysiloxane borate and boric acid (where the composition also comprises a polysiloxane) at levels of elemental boron of 0.08 or greater, show excellent adhesion where a basecoat/clearcoat system is repaired with a clearcoat.
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not .
limited to the particular embodiments disclosed, but it is intended to cover modifications which are within the spirit and scope of the invention, as defined by the appended claims.
s
The basecoat used for Examples 14-23 was Obsidian Schwarz*, black pigmented waterborne basecoat, available from BASF Corporation. The Obsidian Schwarz basecoat was automated spray applied in two coats with approximately 30 second flash between coats to the efectrocoated and primed steel panels at about 70 F (21 C) temperature and about 60% relative humidity. A dry film thickness of about 0.5 to 0.6 mils (about 12 to 16 micrometers) was targeted. The basecoat was allowed to flash ambiently for io about five minutes and then prebaked for five minutes at 176 F (80 C).
The clear coating compositions of Examples 14-23 were each automated spray applied to a basecoated panel at ambient temperature in two coats with about a 30 second ambient flash between coats. Examples 1-were targeted for a 1.5 to 2.0 mils (about 38 to 51 micrometers) dry film j5 thickness. All coatings were allowed to air flash at ambient temperature for ten minutes. Panels prepared from each coating were baked for 30 minutes at 285 F (141 C) to fullv cure the coatin~(s) horizontal position.
To test for recoat adhesion, an original basecoated and clearcoated panel, as described above, was given another layer of basecoat and clearcoat or clearcoat only. With the condition of sanding, the right half of the panel was sanded with 1200 grit sand paper and the left hulf -vras not sar~dcd thus giving sanded and non-sanded areas. Half of an original panel from each clear coating was basecoated and clearcoated and ti-7e other half of ttie panel was clearcoated only. To recoat the panels half and half, the bottom halves of the original panels were covered with aluminum foil and then the top halves were recoated with Obsidian Schwarz basecoat using the same.conditions as above. The foil was removed, resulting in an original panel with the upper half coated in basecoat and the bottom half still with only the original coating layers. The respective clearcoat was then automated spray applied to the entire panel as described above. The resulting panels were half coated in *Trade-mark basecoat/_clearcoat from the original spray application and another layer of basecoat/ clearcoat from the recoat spray application (B/C//B/C). The other half of the resulting panel was coated in basecoat/ clearcoat from the original spray application and another layer of clearcoat from the recoat spray s application (B/C//C). Test data is reported below in the following Table 6.
Recoat Adhesion - Cross Hatch Adhesion 30/285 F // 30/285 F
promoter Sanded Non-Sanded Example # Elemental 20 Gloss B/C// B/C// B/C// B/C//
Weight % B/C C B/C C
on resin -solids 14* 0 84 5 5 0 0 15 0.02 84 5 5 5 0 ~ ;.-, 17 - G. 84 5 5 5 5-18 0.04 84 5 5 5 0 19 0.15 35 5 5 5-, ._ ~------- ' _ .__._--- - . ----._..-- .----- --- - --------_ 20 0.04 85 -- --- 5 0 21 0.04 85 --- -- 5 0 22 0.03 85 - --- -- 5 0 23 0.10 82 5 5 5 0 * Designates a comparative example.
The data presented above in Table 6 illustrate that the inclusion in a two-component clearcoating composition of the adhesion promoting composition of Examples C through H above provide excellent adhesion where a basecoat/clearcoat system is recoated with a repair basecoat/clearcoat system. Further, the data for Examples 14-22 illustrate that the inclusion of the polysiloxane borate and boric acid (where the composition also comprises a polysiloxane) at levels of elemental boron of 0.08 or greater, show excellent adhesion where a basecoat/clearcoat system is repaired with a clearcoat.
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not .
limited to the particular embodiments disclosed, but it is intended to cover modifications which are within the spirit and scope of the invention, as defined by the appended claims.
s
Claims (3)
1. A coating composition formed from components comprising:
(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising a polymer of at least one of the following structural units (I):
(1) R1n R 2m SiO(4-n-m)/2 wherein each R1, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<n<4, 0<m<4 and
(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising a polymer of at least one of the following structural units (I):
(1) R1n R 2m SiO(4-n-m)/2 wherein each R1, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<n<4, 0<m<4 and
2<=(m+n)<4;
(b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one borate, aluminate, titanate, zirconate, silicate, siloxane, silane, or mixture thereof, wherein each component is different.
2. A coating composition according to claim 1, wherein the compound (c) comprises at least one of a borate and an aluminate.
(b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and (c) at least one borate, aluminate, titanate, zirconate, silicate, siloxane, silane, or mixture thereof, wherein each component is different.
2. A coating composition according to claim 1, wherein the compound (c) comprises at least one of a borate and an aluminate.
3. A coating composition according to claim 2, wherein the compound (c) comprises aluminum alkoxide.
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US09/919,198 | 2001-07-31 | ||
CA 2455804 CA2455804C (en) | 2001-07-31 | 2002-07-29 | Coating compositions having improved adhesion, coated substrates and methods related thereto |
CA 2624864 CA2624864A1 (en) | 2001-07-31 | 2002-07-29 | Coating compositions having improved adhesion, coated substrates and methods related thereto |
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US (1) | US6623791B2 (en) |
EP (1) | EP1417273B1 (en) |
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KR (2) | KR100618737B1 (en) |
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CA (2) | CA2455804C (en) |
DE (1) | DE60237691D1 (en) |
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Families Citing this family (116)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6221367B1 (en) * | 1992-06-15 | 2001-04-24 | Emisphere Technologies, Inc. | Active agent transport systems |
US6824879B2 (en) | 1999-06-10 | 2004-11-30 | Honeywell International Inc. | Spin-on-glass anti-reflective coatings for photolithography |
KR100804873B1 (en) | 1999-06-10 | 2008-02-20 | 얼라이드시그날 인코퍼레이티드 | Spin-on-glass anti-reflective coatings for photolithography |
US6268457B1 (en) | 1999-06-10 | 2001-07-31 | Allied Signal, Inc. | Spin-on glass anti-reflective coatings for photolithography |
US6633769B2 (en) * | 2000-07-24 | 2003-10-14 | Symbol Technologies, Inc. | Wireless access point software system |
DE10055549A1 (en) * | 2000-11-09 | 2002-05-29 | Basf Coatings Ag | Color and / or effect multi-layer coating, process for their preparation and their use |
US6592998B2 (en) * | 2001-07-31 | 2003-07-15 | Ppg Industries Ohio, Inc. | Multi-layer composites formed from compositions having improved adhesion, coating compositions, and methods related thereto |
KR100953927B1 (en) * | 2001-09-04 | 2010-04-22 | 다이니폰 인사츠 가부시키가이샤 | Coating composition, coating formed therefrom, anti-reflection coating, anti-reflection film, and image display device |
CN1606713B (en) | 2001-11-15 | 2011-07-06 | 霍尼韦尔国际公司 | Spincoating antireflection paint for photolithography |
CN100437784C (en) * | 2002-05-29 | 2008-11-26 | Tdk株式会社 | Optical information medium and production method therefor |
US7141618B2 (en) | 2002-06-03 | 2006-11-28 | Ppg Industries Ohio, Inc. | Coating compositions with modified particles and methods of using the same |
WO2004076568A1 (en) * | 2003-02-25 | 2004-09-10 | Chemetall Gmbh | Method for coating metallic surfaces with a composition that is rich in polymers |
CN100519414C (en) * | 2003-05-12 | 2009-07-29 | 日挥触媒化成株式会社 | Applying fluid for forming transparent coating film and base material with transparent coating film, and display device |
US20040231843A1 (en) * | 2003-05-22 | 2004-11-25 | Simpson Nell A. A. | Lubricant for use in a wellbore |
US7605194B2 (en) * | 2003-06-24 | 2009-10-20 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
US7635727B2 (en) * | 2003-06-24 | 2009-12-22 | Ppg Industries Ohio, Inc. | Composite transparencies |
US8053159B2 (en) | 2003-11-18 | 2011-11-08 | Honeywell International Inc. | Antireflective coatings for via fill and photolithography applications and methods of preparation thereof |
DE10361878A1 (en) * | 2003-12-19 | 2005-07-14 | Ami-Agrolinz Melamine International Gmbh | Flame retardant mixture for lignocellulosic composites |
US7276549B2 (en) * | 2004-01-12 | 2007-10-02 | United States Gypsum Company | Surface enhancing coating for gypsum-containing floor underlayments |
US20100184911A1 (en) * | 2009-01-22 | 2010-07-22 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
WO2005103172A2 (en) | 2004-04-15 | 2005-11-03 | Avery Dennison Corporation | Dew resistant coatings |
US7354650B2 (en) * | 2004-05-28 | 2008-04-08 | Ppg Industries Ohio, Inc. | Multi-layer coatings with an inorganic oxide network containing layer and methods for their application |
JP2008508097A (en) * | 2004-08-03 | 2008-03-21 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for coating metal surface with anticorrosion coating |
JP5502278B2 (en) * | 2004-10-01 | 2014-05-28 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | Carbamate-functional silica compound and process for its preparation and use of the compound |
WO2007114808A1 (en) * | 2006-03-31 | 2007-10-11 | Sdc Coatings, Inc. | Coating compositions, articles, and methods of coating articles |
KR20070084142A (en) * | 2004-10-12 | 2007-08-24 | 에스디씨 코우팅스 인코포레이티드 | Coating compositions, articles, and methods of coating articles |
US7806977B2 (en) * | 2004-10-29 | 2010-10-05 | Millennium Inorganic Chemicals, Inc. | Compositions and methods comprising titanium dioxide pigments and coupling agents |
US8101014B2 (en) * | 2004-11-10 | 2012-01-24 | Chemetall Gmbh | Process for coating metallic surfaces with a multicomponent aqueous composition |
EP1815044B1 (en) | 2004-11-10 | 2019-06-19 | Chemetall GmbH | Method for coating metallic surfaces with an aqueous composition comprising silanes silanols siloxanes and polysiloxanes and said composition |
US20060099332A1 (en) * | 2004-11-10 | 2006-05-11 | Mats Eriksson | Process for producing a repair coating on a coated metallic surface |
US7910022B2 (en) | 2006-09-15 | 2011-03-22 | Performance Indicator, Llc | Phosphorescent compositions for identification |
US20060159925A1 (en) | 2004-12-20 | 2006-07-20 | Satish Agrawal | High-intensity, persistent thermochromic compositions and objects, and methods for creating the same |
US20080138615A1 (en) | 2005-04-04 | 2008-06-12 | Thomas Kolberg | Method for Coating Metallic Surfaces with an Aqueous Composition and Said Composition |
US7713628B2 (en) * | 2005-05-31 | 2010-05-11 | Chemque, Inc. | Actinic radiation curable coating compositions |
DE102005034350A1 (en) * | 2005-07-22 | 2007-01-25 | Consortium für elektrochemische Industrie GmbH | Paints containing particles |
US7569254B2 (en) * | 2005-08-22 | 2009-08-04 | Eastman Kodak Company | Nanocomposite materials comprising high loadings of filler materials and an in-situ method of making such materials |
US7745010B2 (en) | 2005-08-26 | 2010-06-29 | Prc Desoto International, Inc. | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods |
DE102005045228A1 (en) | 2005-09-22 | 2007-04-05 | Basf Coatings Ag | Use of phosphonic diesters and diphosphonic diesters, and silane-containing, curable mixtures containing phosphonic and Diphosphonsäurediester |
DE102005045150A1 (en) | 2005-09-22 | 2007-04-05 | Basf Coatings Ag | Use of phosphonic diesters and diphosphonic diesters and thermally curable mixtures containing phosphonic diester and Diphosphonsäurediester |
EP1968790B1 (en) * | 2006-01-06 | 2012-10-24 | Avery Dennison Corporation | High gloss laminates for decorative automotive parts |
US8278390B2 (en) * | 2006-03-23 | 2012-10-02 | Dow Corning Corporation | Coatings with carbinol-functional siloxane resin |
JP4566149B2 (en) * | 2006-03-27 | 2010-10-20 | スリーエム イノベイティブ プロパティズ カンパニー | Method for producing independent glass film |
JP4573790B2 (en) * | 2006-03-27 | 2010-11-04 | スリーエム イノベイティブ プロパティズ カンパニー | Method for producing independent glass film |
US20070237902A1 (en) * | 2006-04-10 | 2007-10-11 | Ragunathan Kaliappa G | Adhesion-promoting compositions and methods of promoting adhesion between a coating and a substrate |
DE102006024823A1 (en) | 2006-05-29 | 2007-12-06 | Basf Coatings Ag | Use of curable mixtures containing silane-containing compounds and phosphonic or Diphosphonsäurediester as adhesion promoters |
JP4039682B2 (en) * | 2006-06-09 | 2008-01-30 | 日東電工株式会社 | Adhesive for polarizing plate, polarizing plate, method for producing the same, optical film, and image display device |
DE102006030059A1 (en) * | 2006-06-29 | 2008-01-17 | Basf Coatings Ag | Process for producing multicoat color and / or effect paint systems |
US9095878B2 (en) | 2006-08-02 | 2015-08-04 | Ford Motor Company | Coating compositions and methods of applying the same |
TW200811237A (en) * | 2006-08-11 | 2008-03-01 | Momentive Performance Mat Inc | Composition, associated method and article |
US20080039542A1 (en) * | 2006-08-11 | 2008-02-14 | General Electric Company | Composition and associated method |
US8029894B2 (en) * | 2006-08-18 | 2011-10-04 | Ppg Industries Ohio, Inc. | Multi-layer composites formed from compositions having improved adhesion |
US7547894B2 (en) | 2006-09-15 | 2009-06-16 | Performance Indicator, L.L.C. | Phosphorescent compositions and methods for identification using the same |
EP2122638B1 (en) * | 2006-12-19 | 2012-11-07 | Dow Global Technologies LLC | Improved composites and methods for conductive transparent substrates |
US9193880B2 (en) * | 2006-12-19 | 2015-11-24 | Dow Global Technologies Llc | Adhesion promotion additives and methods for improving coating compositions |
CN101553351B (en) | 2006-12-19 | 2012-09-05 | 陶氏环球技术公司 | Encapsulated panel assemblies and method for making same |
CA2675576A1 (en) * | 2007-02-13 | 2008-08-21 | Basf Corporation | Coating system for achieving excellent mvss adhesion |
US8642246B2 (en) | 2007-02-26 | 2014-02-04 | Honeywell International Inc. | Compositions, coatings and films for tri-layer patterning applications and methods of preparation thereof |
US7857905B2 (en) | 2007-03-05 | 2010-12-28 | Momentive Performance Materials Inc. | Flexible thermal cure silicone hardcoats |
DE102007014720A1 (en) | 2007-03-23 | 2008-09-25 | Basf Coatings Japan Ltd., Yokohama | Phosphonate-containing two-component paint system, its preparation and use |
DE602008000155D1 (en) * | 2007-03-26 | 2009-11-05 | Graco Childrens Prod Inc | Child calming device with low frequency tone chamber |
US8460795B2 (en) | 2007-04-12 | 2013-06-11 | Ppg Industries Ohio, Inc. | Curable film-forming compositions demonstrating burnish resistance and low gloss |
KR101490536B1 (en) * | 2007-04-24 | 2015-02-11 | 다우 글로벌 테크놀로지스 엘엘씨 | Universal primer compositions and methods |
RU2418811C2 (en) * | 2007-04-24 | 2011-05-20 | Дау Глобал Текнолоджиз, Инк. | Single-component glass primer containing oxazolidine |
KR20100037093A (en) * | 2007-07-12 | 2010-04-08 | 다우 글로벌 테크놀로지스 인크. | Colored primer compositions and methods |
US7842128B2 (en) | 2007-09-13 | 2010-11-30 | Performance Indicatior LLC | Tissue marking compositions |
US8039193B2 (en) | 2007-09-13 | 2011-10-18 | Performance Indicator Llc | Tissue markings and methods for reversibly marking tissue employing the same |
US20090104473A1 (en) * | 2007-10-19 | 2009-04-23 | John D. Jarrell | Novel compositions and related methods, coatings, and articles |
WO2009067100A1 (en) * | 2007-11-21 | 2009-05-28 | Momentive Performance Materials Inc. | Organosilicone compositions and methods for preparing them |
CN101903483B (en) | 2007-12-18 | 2014-09-10 | 陶氏环球技术公司 | Protective coating for window glass having enhanced adhesion to glass bonding adhesives |
MX2011001064A (en) * | 2008-07-29 | 2011-03-24 | Du Pont | Surface active blocked isocyanates and coating compositions thereof. |
WO2010096110A1 (en) * | 2008-10-29 | 2010-08-26 | Dow Global Technologies, Inc. | Low energy surface bonding system containing a primer with long open time |
US8507050B2 (en) * | 2008-11-12 | 2013-08-13 | Ppg Industries Ohio, Inc. | Methods for depositing ultra thin coatings exhibiting low haze and methods for the preparation of such coatings |
CA2749599C (en) | 2009-01-20 | 2014-10-07 | Ppg Industries Ohio, Inc. | Transparent, colorless infrared radiation absorbing compositions comprising non-stoichiometric tungsten oxide nanoparticles |
US8633292B2 (en) * | 2009-03-26 | 2014-01-21 | Signet Armorlite | Polyurethane-based photochromic optical materials |
US8288466B2 (en) * | 2009-05-13 | 2012-10-16 | E I Du Pont De Nemours And Company | Composite of a polymer and surface modified hexagonal boron nitride particles |
US8440292B2 (en) * | 2009-05-13 | 2013-05-14 | E I Du Pont De Nemours And Company | Multi-layer article for flexible printed circuits |
US8784980B2 (en) * | 2009-05-13 | 2014-07-22 | E I Du Pont De Nemours And Company | Film prepared from a casting composition comprising a polymer and surface modified hexagonal boron nitride particles |
US8258346B2 (en) * | 2009-05-13 | 2012-09-04 | E I Du Pont De Nemours And Company | Surface modified hexagonal boron nitride particles |
WO2010144444A2 (en) * | 2009-06-08 | 2010-12-16 | Saint-Gobain Performance Plastics Corporation | Articles containing silicone compositions and methods of making such articles |
US8557877B2 (en) | 2009-06-10 | 2013-10-15 | Honeywell International Inc. | Anti-reflective coatings for optically transparent substrates |
US20110111147A1 (en) * | 2009-11-06 | 2011-05-12 | Ajjer Llc | Variable emissivity coatings and their applications |
KR100970461B1 (en) * | 2010-02-09 | 2010-07-16 | 엘베스트지에이티 주식회사 | Organic inorganic hybrid type composition of coating agent for anticorrosion and manufacturing method of the same |
WO2011112699A1 (en) | 2010-03-09 | 2011-09-15 | University Of Virginia Patent Foundation | Viscoelastic silicone rubber compositions |
US20110223220A1 (en) | 2010-03-15 | 2011-09-15 | Ppg Industries Ohio, Inc. | Dispersions of encapsulated particles and methods for their production and use |
US20110244382A1 (en) | 2010-04-06 | 2011-10-06 | Christopher Alyson M | Hydrophobic silica particles and method of producing same |
US8901198B2 (en) | 2010-11-05 | 2014-12-02 | Ppg Industries Ohio, Inc. | UV-curable coating compositions, multi-component composite coatings, and related coated substrates |
US8513321B2 (en) | 2010-11-05 | 2013-08-20 | Ppg Industries Ohio, Inc. | Dual cure coating compositions, methods of coating a substrate, and related coated substrates |
US9012557B1 (en) * | 2011-01-14 | 2015-04-21 | William C. Hiscox | Method of making and treating synthetic sporting surfaces |
EP2691487B1 (en) | 2011-03-31 | 2014-12-24 | Akzo Nobel Coatings International B.V. | Foul preventing coating composition |
US20120301647A1 (en) * | 2011-05-23 | 2012-11-29 | Ppg Industries Ohio, Inc. | Phosphatized polyesters and coating compositions containing the same |
US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
US9550864B2 (en) | 2011-08-10 | 2017-01-24 | University Of Virginia Patent Foundation | Viscoelastic silicon rubber compositions |
US8871848B2 (en) * | 2011-11-16 | 2014-10-28 | Ppg Industries Ohio, Inc. | Coating compositions for golf balls and coated golf balls |
US9222050B1 (en) | 2012-02-29 | 2015-12-29 | Rand Innovations, Llc | Lubricant composition, method of preparing the same, and firearm cleaner including the same |
US9581922B2 (en) | 2012-03-26 | 2017-02-28 | Cabot Corporation | Treated fumed silica |
BR112014029193A2 (en) * | 2012-05-22 | 2017-06-27 | Dsm Ip Assets Bv | composition and process for producing a porous inorganic oxide coating |
US9453134B2 (en) * | 2012-08-27 | 2016-09-27 | Agfa Graphics Nv | Recycling of radiation cured printed matter |
MX2015004550A (en) * | 2012-10-12 | 2015-07-17 | Basf Se | Lubricant compositions comprising boroxines to improve fluoropolymer seal compatibility. |
US10093829B2 (en) * | 2012-10-19 | 2018-10-09 | Ppg Industries Ohio, Inc. | Curable film-forming compositions demonstrating burnish resistance and low gloss, and methods of improving burnish resistance of a substrate |
US9228151B1 (en) * | 2012-11-07 | 2016-01-05 | Rand Innovations, Llc | Lubricant additive composition, lubricant, and method of preparing the same |
US10221283B2 (en) * | 2013-01-18 | 2019-03-05 | Georgetown University | Amino-substituted polysiloxanes combined with polymerizable and unpolymerizable organic acids |
US9273214B1 (en) | 2013-03-04 | 2016-03-01 | Mark Figliozzi | Removable spray coating and application method |
EP4039851A1 (en) * | 2013-03-16 | 2022-08-10 | PRC-Desoto International, Inc. | Azole compounds as corrosion inhibitors |
US9359471B2 (en) | 2014-04-21 | 2016-06-07 | Gaco Western, LLC | Foam compositions |
JP6803842B2 (en) | 2015-04-13 | 2020-12-23 | ハネウェル・インターナショナル・インコーポレーテッドHoneywell International Inc. | Polysiloxane formulations and coatings for optoelectronic applications |
WO2017152156A1 (en) | 2016-03-04 | 2017-09-08 | Penn Color, Inc. | Coatings for reducing heat absorption |
KR102024252B1 (en) * | 2016-09-09 | 2019-09-23 | 주식회사 엘지화학 | Pressure Sensitive Adhesive composition using foldable display |
KR102024253B1 (en) | 2016-09-09 | 2019-09-23 | 주식회사 엘지화학 | Pressure Sensitive Adhesive composition using foldable display |
WO2018048240A1 (en) * | 2016-09-09 | 2018-03-15 | 주식회사 엘지화학 | Adhesive composition for foldable display |
WO2018048243A1 (en) * | 2016-09-09 | 2018-03-15 | 주식회사 엘지화학 | Adhesive composition for foldable display |
JP6836770B2 (en) * | 2016-09-13 | 2021-03-03 | トーヨーポリマー株式会社 | Anti-fog coating composition and anti-fog film |
JP6772421B1 (en) * | 2019-02-27 | 2020-10-21 | 関西ペイント株式会社 | Thermosetting paint compositions and painted articles |
CN110437740B (en) * | 2019-08-08 | 2021-01-05 | 陕西宝塔山油漆股份有限公司 | High-decoration acrylic polysiloxane coating and preparation method thereof |
US20210246316A1 (en) * | 2020-02-10 | 2021-08-12 | Axalta Coating Systems Ip Co., Llc | Primer compositions and methods of coating a substrate |
CN114806406A (en) * | 2022-04-25 | 2022-07-29 | 开封夸克新材料有限公司 | Environment-friendly siloxane anti-corrosion temperature-resistant coating |
WO2023237605A1 (en) * | 2022-06-09 | 2023-12-14 | Basf Coatings Gmbh | Low temperature curable multilayer coating systems with excellent appearance |
Family Cites Families (262)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2587295A (en) | 1952-02-26 | Alkyd-polysiloxane resins | ||
US2860074A (en) | 1958-11-11 | Vevyl resin-acrylic ester-organopoly- | ||
US1873945A (en) | 1930-03-29 | 1932-08-23 | Ig Farbenindustrie Ag | Materials coated with lacquers, lacquers, and a process of producing coatings |
US2584340A (en) | 1950-01-07 | 1952-02-05 | Dow Corning | Reaction of organosilane with glycerine-dicarboxylic acid ester and dicarboxylic acid |
US2901449A (en) | 1950-07-06 | 1959-08-25 | Siemens Ag | Organosilicon condensation products and processes for producing them |
US3127363A (en) * | 1955-08-05 | 1964-03-31 | Process for the manufacture of elasto- | |
US2978437A (en) | 1957-06-12 | 1961-04-04 | Pittsburgh Plate Glass Co | Water-insoluble condensation products of aldehydes and acrylamide interpolymers |
US3203919A (en) | 1962-09-19 | 1965-08-31 | Du Pont | Acrylic/siloxane copolymer, polysiloxane composition containing same, and article coated with the composition |
US3317460A (en) | 1963-04-01 | 1967-05-02 | Dow Corning | Hydroxyorganosiloxanes and copolymers |
DE1193504B (en) | 1964-04-24 | 1965-05-26 | Bundesrep Deutschland | Process for the preparation of polysiloxanes with terminal diketone groups |
DE1545040A1 (en) | 1964-11-02 | 1970-07-23 | Tondeo Werk Noss A | Blade cover for razor blades and process for producing the coating substance and for applying it to the razor blades |
GB1080549A (en) | 1964-12-29 | 1967-08-23 | Ici Ltd | Improvements in or relating to light transmitting polymeric sheet |
US3398174A (en) | 1965-02-03 | 1968-08-20 | Dow Corning | Method of synthesizing organosilicon compounds |
US3450792A (en) | 1966-09-20 | 1969-06-17 | Desoto Inc | Heat-hardenable condensates of polyalkoxy siloxanes with unsaturated polyesters modified with lipophilic monomer |
US3479328A (en) | 1966-11-18 | 1969-11-18 | Ashland Oil Inc | Novel monomers and polymers |
US3655602A (en) | 1967-08-16 | 1972-04-11 | Desoto Inc | Silicone-containing hydrophylic resins dispersible in water |
US3539658A (en) | 1967-11-13 | 1970-11-10 | Desoto Inc | Air drying polyurethane coating composition comprising organic polyisocyanate mixed with a resinous polyhydric alcohol having an organosilicon resinous material condensed therein |
US3551830A (en) | 1968-10-22 | 1970-12-29 | Du Pont | Glossy microporous sheet material |
US3627836A (en) | 1968-11-15 | 1971-12-14 | Stauffer Wacker Silicone Corp | Modified organopolysiloxanes with mono and polyolefinic cross-linked particles generated in situ |
US3577265A (en) | 1968-11-18 | 1971-05-04 | Ford Motor Co | Vinyl resin-siloxane coated article |
US3577263A (en) | 1968-11-18 | 1971-05-04 | Ford Motor Co | Epoxy resin-siloxane coated article |
GB1293331A (en) | 1969-01-13 | 1972-10-18 | Union Carbide Corp | Addition process for producing siloxane alcohols |
US3687872A (en) | 1970-03-17 | 1972-08-29 | Gen Electric | Borosilicone materials and epoxy resins cured therewith |
US3919315A (en) | 1970-06-13 | 1975-11-11 | Bayer Ag | New aminophenylamidines, their production and their medicinal use |
US3799854A (en) | 1970-06-19 | 1974-03-26 | Ppg Industries Inc | Method of electrodepositing cationic compositions |
US3668183A (en) | 1970-11-03 | 1972-06-06 | Union Carbide Corp | Production of polyenamines |
US3644566A (en) | 1970-11-17 | 1972-02-22 | Cook Paint & Varnish Co | Silicon acrylic copolymers |
US3832183A (en) * | 1971-02-17 | 1974-08-27 | Polaroid Corp | Polymer encapsulated silver halide grains |
US4025407A (en) | 1971-05-05 | 1977-05-24 | Ppg Industries, Inc. | Method for preparing high solids films employing a plurality of curing mechanisms |
US3719634A (en) * | 1971-06-18 | 1973-03-06 | Dow Corning | Room temperature vulcanizable silicone elastomers containing metal hydrocarbonoxides |
US3772240A (en) | 1971-06-18 | 1973-11-13 | Dow Corning | Silicone elastomers containing boric acid |
BE795106A (en) | 1972-02-07 | 1973-08-07 | Ici Ltd | NITROGEN COMPOUNDS AND THEIR USE |
AU466953B2 (en) | 1972-05-24 | 1975-11-13 | Dulux Australia Limited | Thermosetting coating compositions |
US4001156A (en) | 1972-08-03 | 1977-01-04 | Ppg Industries, Inc. | Method of producing epoxy group-containing, quaternary ammonium salt-containing resins |
US4089763A (en) | 1973-04-24 | 1978-05-16 | Imperial Chemical Industries Limited | Method of repairing teeth using a composition which is curable by irradiation with visible light |
US3964936A (en) | 1974-01-02 | 1976-06-22 | Amchem Products, Inc. | Coating solution for metal surfaces |
US4221697A (en) | 1974-05-29 | 1980-09-09 | Imperial Chemical Industries Limited | Composite materials |
US3986997A (en) | 1974-06-25 | 1976-10-19 | Dow Corning Corporation | Pigment-free coating compositions |
US4027073A (en) | 1974-06-25 | 1977-05-31 | Dow Corning Corporation | Pigment-free coating compositions |
US4025456A (en) | 1974-09-20 | 1977-05-24 | Union Carbide Corporation | Polysiloxane-polyoxyalkylene block copolymers |
US4093673A (en) | 1974-11-14 | 1978-06-06 | Ppg Industries, Inc. | Coating compositions composed of hydroxyfunctional polymers or copolymers and alkoxysilanes |
US4046729A (en) | 1975-06-02 | 1977-09-06 | Ppg Industries, Inc. | Water-reduced urethane coating compositions |
US4121011A (en) | 1975-11-28 | 1978-10-17 | Raychem Corporation | Polymeric article coated with a thermochromic paint |
NL179063C (en) | 1975-12-15 | 1986-07-01 | Akzo Nv | PROCESS FOR PREPARING A HIGH SOLID CONTENT PIGMENT-CONTAINING COMPOSITION |
US4147679A (en) | 1976-06-02 | 1979-04-03 | Ppg Industries, Inc. | Water-reduced urethane coating compositions |
NL176864C (en) | 1976-11-25 | 1985-06-17 | Akzo Nv | PROCESS FOR THE PREPARATION OF A THIXOTROPE COATING COMPOSITION |
US4177315A (en) | 1977-03-04 | 1979-12-04 | E. I. Du Pont De Nemours And Company | Coated Polymeric substrates |
JPS53111336A (en) | 1977-03-11 | 1978-09-28 | Toray Ind Inc | Coating composition |
NZ186925A (en) | 1977-04-25 | 1979-12-11 | Ici Ltd | Top-coating based on a basecoat and top-coat compositions not requiring an intermediate baking operation |
NL7707669A (en) | 1977-07-08 | 1979-01-10 | Akzo Nv | METHOD OF COVERING A SUBSTRATE WITH A RADIATION HARDABLE COATING COMPOSITION. |
AT350685B (en) | 1977-12-27 | 1979-06-11 | Vianova Kunstharz Ag | PROCESS FOR THE PRODUCTION OF WATER-SOLUBLE POLYSILOXANE-MODIFIED PAINT BINDERS |
JPS54135824A (en) | 1978-03-31 | 1979-10-22 | Akzo Nv | Liquid coating composition |
IL55710A (en) | 1978-09-30 | 1981-11-30 | Brandenberger Hansruedy | Manufacture of bodies of synthetic resin material with a refined surface |
US4239798A (en) | 1978-11-01 | 1980-12-16 | General Electric Company | Abrasion resistant silicone coated polycarbonate article |
US4279800A (en) | 1979-04-19 | 1981-07-21 | Akzo Nv | High solids pigmented coating composition containing a blend of ester diols and a curing agent |
US4271062A (en) | 1979-04-19 | 1981-06-02 | Akzo N.V. | Pigment-containing coating composition having a high solids content |
US4369300A (en) | 1979-11-26 | 1983-01-18 | Union Carbide Corporation | Acrylated urethane silicone compositions |
ATE5728T1 (en) | 1979-12-21 | 1984-01-15 | Imperial Chemical Industries Plc | POLYMERIZATION PROCESSES FOR THE PREPARATION OF HIGH REFRACTION INDEX POLYMERIC MICROPARTICLES AND COATING LAYERS CONTAINING THESE MICROPARTICLES. |
DE3008138A1 (en) | 1980-03-04 | 1981-09-10 | Wacker-Chemie GmbH, 8000 München | METHOD FOR PRODUCING SILICONE MODIFIED RESINS |
GB2073609B (en) | 1980-04-14 | 1984-05-02 | Ici Ltd | Coating process |
US4308060A (en) | 1980-05-12 | 1981-12-29 | Talbot Milford C | Method and composition for an improved cleaning and polishing compound having a solid form |
US4348462A (en) | 1980-07-11 | 1982-09-07 | General Electric Company | Abrasion resistant ultraviolet light curable hard coating compositions |
JPS6021686B2 (en) | 1980-08-08 | 1985-05-29 | 旭硝子株式会社 | Fluorine-containing copolymer that can be cured at room temperature |
US4310600A (en) | 1980-08-29 | 1982-01-12 | American Hoechst Corp. | Polyester film having abrasion resistant radiation curable silicone coating |
US4478876A (en) | 1980-12-18 | 1984-10-23 | General Electric Company | Process of coating a substrate with an abrasion resistant ultraviolet curable composition |
JPS57149290A (en) | 1981-03-13 | 1982-09-14 | Shin Etsu Chem Co Ltd | Production of glycerol-modified silicone |
US4410594A (en) | 1981-04-10 | 1983-10-18 | General Electric Company | Ultraviolet radiation stabilized coated polycarbonate article |
US4491508A (en) | 1981-06-01 | 1985-01-01 | General Electric Company | Method of preparing curable coating composition from alcohol, colloidal silica, silylacrylate and multiacrylate monomer |
US4395461A (en) | 1981-10-23 | 1983-07-26 | General Electric Company | Method for making silicon coated polycarbonates and article obtained therefrom |
DE3151350A1 (en) | 1981-12-24 | 1983-07-07 | Bayer Ag, 5090 Leverkusen | PLASTIC MOLDED BODIES EQUIPPED WITH A 3-LAYER COVER AND A METHOD FOR PRODUCING THE EQUIPMENT |
US4418182A (en) | 1981-12-28 | 1983-11-29 | Ford Motor Company | High solids coatings from new tetrahydroxy oligomers |
US4465815A (en) | 1981-12-28 | 1984-08-14 | Ford Motor Company | Polyhydroxy oligomers for high solids coatings II |
EP0088193B1 (en) | 1981-12-28 | 1985-04-10 | Ford Motor Company Limited | Coating composition and tetrahydroxy oligomer precursor therefor |
US4413086A (en) | 1982-03-04 | 1983-11-01 | Ppg Industries, Inc. | Coating compositions containing organosilane-polyol |
US4598111A (en) | 1982-03-18 | 1986-07-01 | Glasurit America, Inc. | Coating composition containing cross-linked microparticles |
US4477536A (en) | 1982-03-18 | 1984-10-16 | Glasurit America, Inc. | Process for preparing a multilayer coating |
US4481126A (en) | 1982-07-26 | 1984-11-06 | The Procter & Gamble Company | No rinse liquid car cleaner with solid polymers |
US4512677A (en) | 1982-07-26 | 1985-04-23 | The Procter & Gamble Company | No rinse liquid car cleaner kit with liquid cleaner and bristle pad |
US4403093A (en) | 1982-09-28 | 1983-09-06 | Ppg Industries, Inc. | Polyesters |
US4408018A (en) | 1982-10-29 | 1983-10-04 | Rohm And Haas Company | Acetoacetate functionalized polymers and monomers useful for crosslinking formulations |
US4499150A (en) | 1983-03-29 | 1985-02-12 | Ppg Industries, Inc. | Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups |
US4499151A (en) | 1983-03-29 | 1985-02-12 | Ppg Industries, Inc. | Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups |
GB2140018B (en) | 1983-05-21 | 1986-03-19 | Dow Corning | Organosiloxane-oxyalkylene copolymers |
US4677004A (en) | 1983-09-06 | 1987-06-30 | Ppg Industries, Inc. | Color plus clear coating system utilizing inorganic microparticles |
US4522958A (en) | 1983-09-06 | 1985-06-11 | Ppg Industries, Inc. | High-solids coating composition for improved rheology control containing chemically modified inorganic microparticles |
US4526910A (en) | 1983-09-06 | 1985-07-02 | Ppg Industries, Inc. | High-solids coating composition for improved rheology control containing inorganic microparticles |
AU556491B2 (en) | 1983-09-06 | 1986-11-06 | Ppg Industries, Inc. | Coating |
US4680204A (en) | 1983-09-06 | 1987-07-14 | Ppg Industries, Inc. | Color plus clear coating system utilizing inorganic microparticles |
US4652470A (en) | 1983-09-06 | 1987-03-24 | Ppg Industries, Inc. | Color plus clear coating system utilizing inorganic microparticles |
US4518522A (en) | 1983-09-19 | 1985-05-21 | Mobay Chemical Corporation | Blocked polyisocyanates with improved storage stability |
AU565336B2 (en) | 1983-10-26 | 1987-09-10 | Nippon Paint Co., Ltd. | Clear top coat for use on color base |
CA1284538C (en) | 1983-11-12 | 1991-05-28 | Hisaki Tanabe | Coating composition having improved weathering resistance and recoating property and resinous composition to be used therein |
US4520144A (en) | 1984-02-06 | 1985-05-28 | Desoto, Inc. | Polydimethylsiloxane-modified polyepoxides |
US4569966A (en) | 1984-04-19 | 1986-02-11 | Ppg Industries, Inc. | Polymeric microparticles |
DE3432149A1 (en) | 1984-05-25 | 1985-11-28 | Nippon Paint Co., Ltd., Osaka | COATING COMPOSITIONS FOR TOP LAYERS |
US4702860A (en) | 1984-06-15 | 1987-10-27 | Nauchno-Issledovatelsky Institut Kabelnoi Promyshlennosti Po "Sredazkabel" | Current-conducting composition |
US4592816A (en) | 1984-09-26 | 1986-06-03 | Rohm And Haas Company | Electrophoretic deposition process |
US5116418A (en) | 1984-12-03 | 1992-05-26 | Industrial Progress Incorporated | Process for making structural aggregate pigments |
CA1275208C (en) | 1985-01-25 | 1990-10-16 | Roger W. Lange | Silica coating |
NL8500476A (en) | 1985-02-20 | 1986-09-16 | Akzo Nv | THIXOTROPE COATING COMPOSITION. |
US4618657A (en) | 1985-03-11 | 1986-10-21 | Desoto, Inc. | Heat curable polysiloxane release coatings which stratify when baked and paper coated therewith |
US4728690A (en) | 1985-03-19 | 1988-03-01 | Th. Goldschmidt Ag | Process for producing molded polyurethane parts |
US5276068A (en) | 1985-03-29 | 1994-01-04 | Jeneric/Pentron, Inc. | Dental resin materials |
JPS61228015A (en) | 1985-04-01 | 1986-10-11 | Yokohama Rubber Co Ltd:The | Epoxy resin composition |
DE3521618A1 (en) | 1985-06-15 | 1986-12-18 | Bayer Ag, 5090 Leverkusen | POLYISOCYANATE PREPARATION IN WATER AND THEIR USE AS ADDITIVES FOR AQUEOUS ADHESIVES |
EP0207775B1 (en) | 1985-07-02 | 1990-04-11 | Toray Industries, Inc. | Ornamental articles having a coating membrane |
US4640940A (en) | 1985-08-13 | 1987-02-03 | Loctite Corporation | Polyol terminated silicones and derivatives thereof |
US4681811A (en) | 1985-08-19 | 1987-07-21 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents in the clear coat |
US4665116A (en) | 1985-08-28 | 1987-05-12 | Turtle Wax, Inc. | Clear cleaner/polish composition |
JPS6279873A (en) | 1985-10-02 | 1987-04-13 | Nippon Paint Co Ltd | Metallic painting method |
US4754014A (en) | 1986-01-06 | 1988-06-28 | E. I. Du Pont De Nemours And Company | Polysiloxane graft copolymers, flexible coating compositions comprising same and branched polysiloxane macromers for preparing same |
US4673718A (en) | 1986-01-06 | 1987-06-16 | E. I. Du Pont De Nemours And Company | Polysiloxane graft copolymers, flexible coating compositions comprising same and branched polysiloxane macromers for preparing same |
US4804732A (en) | 1986-01-06 | 1989-02-14 | E. I. Du Pont De Nemours And Company | Polysiloxane graft copolymers, flexible coating compositions comprising same and branched polysiloxane macromers for preparing same |
US4713410A (en) | 1986-01-13 | 1987-12-15 | Desoto, Inc. | Silicone release coating emulsions which stratify when baked |
JP2632675B2 (en) | 1986-02-04 | 1997-07-23 | 大日本インキ化学工業株式会社 | Resin composition for coating |
US4689383A (en) | 1986-03-18 | 1987-08-25 | Thoratec Laboratories Corp. | Hydroxyl-functional disiloxanes and polysiloxane oligomers |
JPS6335798A (en) | 1986-07-31 | 1988-02-16 | Nippon Steel Corp | Organic composite steel sheet having excellent cation electrodeposition paintability |
FR2602776B1 (en) | 1986-08-12 | 1988-11-10 | Rhone Poulenc Chimie | DIORGANOPOLYSILOXANE WITH BETA-KETOESTER FUNCTION USEFUL AS STABILIZER OF VINYL POLYCHLORIDE POLYMERS |
US4732790A (en) | 1986-08-21 | 1988-03-22 | Ppg Industries, Inc. | Color plus clear application of thermosetting high solids coating composition of hydroxy-functional epoxies and anhydrides |
IT1214578B (en) | 1986-12-11 | 1990-01-18 | Eniricerche Spa | POLIOLEFINE. METAL SURFACES COATING PROCEDURE WITH |
US4873298A (en) | 1986-12-16 | 1989-10-10 | E. I. Du Pont De Nemours And Company | Polysiloxane graft copolymers, flexible coating compositions comprising same and branched polysiloxane macromers for preparing same II |
US4870140A (en) | 1986-12-16 | 1989-09-26 | E. I. Du Pont De Nemours And Company | Polyester graft copolymers, flexible coating compositions comprising same and branched polyester macromers for preparing same II |
US4839443A (en) | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
US4766185A (en) | 1987-04-22 | 1988-08-23 | E. I. Du Pont De Nemours And Company | Polysiloxane graft copolymers, flexible coating compositions comprising same and branched polysiloxane macromers for preparing same - II |
JPH0764539B2 (en) | 1987-08-07 | 1995-07-12 | 信越化学工業株式会社 | Method for producing organic solvent-dispersed silica sol |
US4927868A (en) | 1987-08-19 | 1990-05-22 | Ppg Industries, Inc. | High solids coating compositions containing a polyepoxide and a copolymer of an alpha-olefin and an olefinically unsaturated monoanhydride |
US4798746A (en) | 1987-08-24 | 1989-01-17 | Ppg Industries, Inc. | Basecoat/clearcoat method of coating utilizing an anhydride additive in the thermoplastic polymer-containing basecoat for improved repairability |
GB2211762B (en) | 1987-11-13 | 1991-11-13 | Kobe Steel Ltd | Zinc alloy-plated corrosion preventive steel sheet having an organic coating layer thereon and a method for making the same |
US4822828A (en) | 1987-11-23 | 1989-04-18 | Hoechst Celanese Corporation | Radiation curable coating composition based on a silica/vinyl-functional silanol dispersion |
JP2632167B2 (en) | 1987-11-30 | 1997-07-23 | 鐘淵化学工業株式会社 | Thermosetting composition |
US5073455A (en) | 1988-01-26 | 1991-12-17 | Toyo Boseki Kabushiki Kaisha | Thermoplastic laminated film |
LU87127A1 (en) | 1988-02-08 | 1989-09-20 | Oreal | COSMETIC APPLICATION OF BETA-KETOESTER FUNCTIONAL POLYSILOXANES AND COMPOSITIONS IMPLEMENTED |
EP0329260B1 (en) | 1988-02-19 | 1995-06-21 | Nippon Paint Co., Ltd. | Resinous composition for coating use |
NL8800748A (en) | 1988-03-25 | 1989-10-16 | Stamicarbon | COMPOSITION CONTAINING ULTRAVIOLET LIGHT-CURABLE UNSATURATED MONOMERS AND / OR OLIGOMERS, A PHOTO INITIATOR AND COLLOIDAL SILICA WITH AN ORGANOSILANE COMPOUND AND THE USE OF THIS COMPOSITION IN COATINGS. |
US5104929A (en) | 1988-04-11 | 1992-04-14 | Minnesota Mining And Manufacturing Company | Abrasion resistant coatings comprising silicon dioxide dispersions |
US5914162A (en) | 1988-04-11 | 1999-06-22 | Minnesota Mining And Manufacturing Company | Coating for metal surfaces of unsaturated polymer and colloidal inorganic particles |
US5258424A (en) | 1988-06-15 | 1993-11-02 | Nippon Paint Co., Ltd. | Aqueous coating composition capable of forming a coating with improved moisture permeability |
JPH0260935A (en) | 1988-08-29 | 1990-03-01 | Shin Etsu Chem Co Ltd | Siloxane compound having two hydroxyls on one end |
DE3829587A1 (en) | 1988-09-01 | 1990-03-15 | Bayer Ag | COATING AGENT, A PROCESS FOR THE PRODUCTION THEREOF, AND THE USE OF SELECTED TWO-COMPONENT POLYURETHANE SYSTEMS AS BINDER FOR SUCH COATING AGENTS |
US4892906A (en) | 1988-09-28 | 1990-01-09 | Ppg Industries, Inc. | Urethane coating composition |
EP0365098B1 (en) | 1988-10-21 | 1993-12-08 | Akzo Nobel N.V. | Waterborne coatings and binder systems for use therein |
JP2756804B2 (en) | 1988-12-01 | 1998-05-25 | 東レ・ダウコーニング・シリコーン株式会社 | Polishing agent |
DE3841848A1 (en) | 1988-12-13 | 1990-06-21 | Bayer Ag | Inorganic Pigments with Improved Properties |
US5084541A (en) | 1988-12-19 | 1992-01-28 | American Cyanamid Company | Triazine crosslinking agents and curable compositions |
US5141555A (en) | 1989-02-15 | 1992-08-25 | Minnesota Mining And Manufacturing Company | Buffing composition |
JPH064311B2 (en) | 1989-02-27 | 1994-01-19 | 川崎製鉄株式会社 | Organic coated steel sheet with excellent corrosion resistance |
JPH0696792B2 (en) | 1989-03-06 | 1994-11-30 | 株式会社神戸製鋼所 | Manufacturing method of resin coated rustproof steel plate with excellent electrodeposition coating property |
JPH02255688A (en) | 1989-03-29 | 1990-10-16 | Toshiba Silicone Co Ltd | Hydroxyl group-containing organosilicon compound |
JP2777190B2 (en) | 1989-05-18 | 1998-07-16 | 日産自動車株式会社 | Composite coating |
US5071904A (en) | 1989-05-30 | 1991-12-10 | Ppg Industries, Inc. | Waterborne coating compositions for automotive applications |
JP2727230B2 (en) | 1989-06-05 | 1998-03-11 | 戸田工業株式会社 | Paint composition |
CA2018237C (en) | 1989-07-14 | 2000-05-09 | Antony P. Wright | Radiation curable acryloxyfunctional silicone coating composition |
US5162420A (en) | 1989-07-31 | 1992-11-10 | Ppg Industries, Inc. | Aqueous compositions based on acid-functional acrylic silanol polymers |
JP2862576B2 (en) | 1989-08-14 | 1999-03-03 | 日産自動車株式会社 | Cationic electrodeposition coating composition |
US5213846A (en) | 1989-09-27 | 1993-05-25 | Dai Nippon Toryo Co., Ltd. | Corrison resistant coating composition |
DE4001783A1 (en) | 1990-01-23 | 1991-07-25 | Bayer Ag | POLYISOCYANATE MIXTURES, A PROCESS FOR THEIR PRODUCTION AND THEIR USE AS A BINDER FOR COATING AGENTS OR AS A REACTION PARTNER FOR ISOCYANATE GROUPS OR CARBOXYL GROUPS REACTIVE COMPOUNDS |
US5258225A (en) | 1990-02-16 | 1993-11-02 | General Electric Company | Acrylic coated thermoplastic substrate |
US5114756A (en) | 1990-04-27 | 1992-05-19 | E. I. Du Pont De Nemours And Company | Conductive epoxypolyamide coating composition |
US5066698A (en) | 1990-05-10 | 1991-11-19 | E. I. Du Pont De Nemours And Company | Coating composition of an acrylic polymer, a crosslinking agent and a silane oligomer |
DE4017075A1 (en) | 1990-05-26 | 1991-11-28 | Basf Lacke & Farben | VARNISHES AND USE OF THESE VARNISHES AS TOP COATINGS FOR LACQUERING AUTOMOTIVE BODIES |
JP3133357B2 (en) | 1990-06-11 | 2001-02-05 | 日本エーアールシー株式会社 | Coating composition for forming high-refractive-index abrasion-resistant film and molded article using the composition |
JP3108427B2 (en) | 1990-07-30 | 2000-11-13 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing carbinol group-containing organopolysiloxane |
US5389718A (en) | 1990-07-30 | 1995-02-14 | Miles Inc. | Two-component aqueous polyurethane dispersions |
US5268256A (en) | 1990-08-02 | 1993-12-07 | Ppg Industries, Inc. | Photoimageable electrodepositable photoresist composition for producing non-tacky films |
US5220047A (en) | 1990-09-17 | 1993-06-15 | Union Carbide Chemicals & Plastics Technology Corporation | Carbamate silicon compounds as latent coupling agents and process for preparation and use |
US5108832A (en) | 1990-09-28 | 1992-04-28 | Ppg Industries, Inc. | Flexible intumescent coating composition |
US5104922A (en) | 1990-10-22 | 1992-04-14 | E. I. Du Pont De Nemours And Company | Stable aqueous aluminum flake dispersion |
US5445871A (en) | 1990-10-30 | 1995-08-29 | Kansai Paint Co., Ltd. | Surface-modified plastic plate |
JPH0671579B2 (en) | 1990-11-28 | 1994-09-14 | 株式会社神戸製鋼所 | Resin coated steel sheet with excellent electrodeposition and weldability |
US5387642A (en) | 1991-01-19 | 1995-02-07 | Bayer Aktiengesellschaft | Aqueous binder composition and a process for its preparation |
DE4101696A1 (en) | 1991-01-22 | 1992-07-23 | Bayer Ag | USE OF TWO-COMPONENT SYSTEMS FOR PRODUCING BURNING COATINGS |
US5194487A (en) | 1991-01-22 | 1993-03-16 | Miles Inc. | Two-component aqueous polyurethane dispersions with reduced solvent content and coatings prepared therefrom with improved gloss |
US5085694A (en) | 1991-03-04 | 1992-02-04 | Dow Corning Corporation | Polish compositions |
US5154759A (en) | 1991-04-11 | 1992-10-13 | Dow Corning Corporation | Polish containing amine functional siloxane |
US5110891A (en) | 1991-04-11 | 1992-05-05 | Dow Corning Corporation | Amine functional siloxanes |
WO1992019655A1 (en) | 1991-04-29 | 1992-11-12 | Ppg Industries, Inc. | A stable, one-package, non-gelled coating composition curable under ambient conditions |
US5196485A (en) | 1991-04-29 | 1993-03-23 | Ppg Industries, Inc. | One package stable etch resistant coating |
US5256452A (en) | 1991-04-29 | 1993-10-26 | Ppg Industries, Inc. | One package stable etch resistant coating process |
US5212273A (en) | 1991-06-20 | 1993-05-18 | Ppg Industries, Inc. | Crosslinked polymeric microparticles; their method of preparation and use in coating compositions |
JPH0737575B2 (en) | 1991-06-27 | 1995-04-26 | 信越化学工業株式会社 | Silicone putty composition |
US5235018A (en) | 1991-07-22 | 1993-08-10 | Miles Inc. | Polyisocyanates containing allophanate and isocyanurate groups, a process for their production and their use in two-component coating compositions |
US5174813A (en) | 1991-11-07 | 1992-12-29 | Dow Corning Corporation | Polish containing derivatized amine functional organosilicon compounds |
FR2684367B1 (en) | 1991-12-02 | 1994-03-11 | Hoechst Ste Fse | PROCESS FOR OBTAINING A DISPERSED SILICA SOL IN A LOWER ALCANOL AND APPLICATION OF THE ORGANOSOL THUS OBTAINED, IN PARTICULAR FOR THE PREPARATION OF ORGANIC GLASS SURFACE COATING COMPOSITIONS. |
US5248789A (en) | 1992-03-26 | 1993-09-28 | Ppg Industries, Inc. | Epoxy silicone |
US5260469A (en) | 1992-03-26 | 1993-11-09 | Ppg Industries, Inc. | Organo-siloxane with modified solubility |
US5378735A (en) | 1992-04-06 | 1995-01-03 | Mitsubishi Petrochemical Company, Ltd. | Ultraviolet-curing covering composition with hardwearing properties |
JP3099099B2 (en) | 1992-04-20 | 2000-10-16 | 関西ペイント株式会社 | Paint composition and coating method |
US5258063A (en) | 1992-05-11 | 1993-11-02 | Dow Corning Corporation | Polish containing silylated derivatives of organic amines and epoxides |
JPH05320571A (en) | 1992-05-20 | 1993-12-03 | Nippon Paint Co Ltd | Water-based paint composition, multi-layer coating film and method for forming multi-layer coating film |
JP2741823B2 (en) | 1992-05-27 | 1998-04-22 | 松下電器産業株式会社 | Surface treatment agent and method of using the same |
JPH05331412A (en) | 1992-06-03 | 1993-12-14 | Sumitomo Metal Ind Ltd | Coating composition |
US5322890A (en) | 1992-06-30 | 1994-06-21 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Room temperature cross-linkage aqueous composition |
US5461102A (en) | 1992-07-07 | 1995-10-24 | Kanegafuchi Chemical Industry Co., Ltd. | Aqueous dispersion composition and production thereof |
JP2616640B2 (en) | 1992-07-16 | 1997-06-04 | 信越化学工業株式会社 | Additive for water-based paint |
DE69322560T2 (en) | 1992-08-04 | 1999-08-19 | Shinetsu Chemical Co | Polymer composition curable at room temperature |
DE4227030A1 (en) | 1992-08-14 | 1994-02-17 | Basf Lacke & Farben | Polymers suitable as binders |
US5286835A (en) | 1992-08-24 | 1994-02-15 | Allied-Signal Inc. | Preparation of vinyl ether terminated polyesters |
JPH06145602A (en) | 1992-09-02 | 1994-05-27 | Nippon Paint Co Ltd | Thermosetting coating composition |
AU663967B2 (en) | 1992-09-09 | 1995-10-26 | Nippon Paint Co., Ltd. | A curable resin composition, a coating composition and a process for forming a coating film |
CA2107715A1 (en) | 1992-10-06 | 1994-04-07 | Hiroyuki Naito | Solvent-free organosiloxane composition and its use |
US5356669A (en) | 1992-10-23 | 1994-10-18 | Basf Corporation | Composite color-plus-clear coating utilizing carbamate-functional polymer composition in the clearcoat |
US6235858B1 (en) | 1992-10-30 | 2001-05-22 | Ppg Industries Ohio, Inc. | Aminoplast curable film-forming compositions providing films having resistance to acid etching |
TW242644B (en) | 1992-10-30 | 1995-03-11 | Ppg Industries Inc | |
JP2816076B2 (en) | 1993-01-21 | 1998-10-27 | 日本ペイント株式会社 | Dispersion of colloidal particles and aqueous coating composition |
US5589129A (en) | 1993-02-19 | 1996-12-31 | Kabushiki Kaisha Toshiba | Method of manufacturing a molding using a filler or an additive concentrated on an arbitrary portion or distributed at a gradient concentration |
DE4491656T1 (en) | 1993-03-19 | 1995-10-05 | Mazda Motor | Low solvent type resin composition, a coating composition containing this resin composition, and a method of applying this coating composition |
US5308494A (en) | 1993-03-24 | 1994-05-03 | E. I. Du Pont De Nemours And Company | Method for improving filter efficiency |
US5328975A (en) | 1993-04-02 | 1994-07-12 | Ppg Industries, Inc. | Ultraviolet radiation absorbing coating |
US5407707A (en) | 1993-11-01 | 1995-04-18 | Ppg Industries, Inc. | Powder coating composition based on epoxy containing polymers and polyacid curing agents |
US5470504A (en) | 1994-01-21 | 1995-11-28 | Bardahl Manufacturing Corporation | Siloxane polymer compositions |
WO1995019997A1 (en) | 1994-01-25 | 1995-07-27 | Eastern Michigan University | Polymeric vehicle effective for providing solventless coating compositions |
AU1733695A (en) | 1994-01-25 | 1995-08-08 | Eastern Michigan University | Polymeric vehicle for high solids coatings |
JP3376567B2 (en) | 1994-01-26 | 2003-02-10 | 関西ペイント株式会社 | Two-part aqueous coating composition |
DE4407321A1 (en) | 1994-03-04 | 1995-09-07 | Blanco Gmbh & Co Kg | Plastic molded parts with a plastic matrix filled with inorganic fillers |
JP3276152B2 (en) | 1994-04-29 | 2002-04-22 | ピーピージー インダストリーズ オハイオ, インコーポレイテッド | Flexible aminoplast-curable coating film forming composition providing a coating film having acid etching resistance |
US5976701A (en) | 1994-04-29 | 1999-11-02 | Ppg Industries Ohio, Inc. | Flexible aminoplast-curable film-forming compositions and composite coating |
US5709950A (en) | 1994-04-29 | 1998-01-20 | Ppg Industries, Inc. | Color-plus-clear composite coatings that contain polymers having carbamate functionality |
US5468802A (en) | 1994-07-18 | 1995-11-21 | Ppg Industries, Inc. | Low volatile organic content automotive refinish coating composition |
US5418476A (en) | 1994-07-28 | 1995-05-23 | At&T Corp. | Low voltage output buffer with improved speed |
EP0699721B1 (en) | 1994-09-01 | 2002-05-15 | Toda Kogyo Corporation | Modified polysiloxane coated inorganic particles |
DE4432260C1 (en) | 1994-09-10 | 1995-06-22 | Herberts Gmbh | Scratch-resistant, acid-resistant top-coat material |
JPH08113696A (en) | 1994-10-14 | 1996-05-07 | Toray Dow Corning Silicone Co Ltd | Powder-coating resin composition |
JPH08259574A (en) | 1995-03-22 | 1996-10-08 | Toray Dow Corning Silicone Co Ltd | Radically polymerizable oligosiloxane containing alicyclic epoxy group and its production |
JPH08269391A (en) | 1995-03-31 | 1996-10-15 | Mazda Motor Corp | One package coating composition and coating method of the same |
US5886082A (en) | 1995-04-05 | 1999-03-23 | Kansai Paint Co., Ltd. | Aqueous coating composition |
CN1071366C (en) | 1995-04-28 | 2001-09-19 | 日本油脂Basf涂料株式会社 | Coating composition, process for preparing the composition, and process for preparing dispersion of inorganic oxide sol |
JP3521431B2 (en) | 1995-05-09 | 2004-04-19 | 大日本インキ化学工業株式会社 | Curable resin composition |
US5571297A (en) | 1995-06-06 | 1996-11-05 | Norton Company | Dual-cure binder system |
US5998541A (en) | 1995-06-14 | 1999-12-07 | Matsushita Electric Industrial Co., Ltd. | Finishing agents and method of using the same |
US5798409A (en) | 1995-10-03 | 1998-08-25 | Minnesota Mining & Manufacturing Company | Reactive two-part polyurethane compositions and optionally self-healable and scratch-resistant coatings prepared therefrom |
US5766769A (en) | 1995-10-06 | 1998-06-16 | Basf Corporation | Curable composition for coatings |
US6059867A (en) | 1995-10-10 | 2000-05-09 | Prc-Desoto International, Inc. | Non-chromate corrosion inhibitors for aluminum alloys |
EP0859872B1 (en) | 1995-10-10 | 2002-06-19 | Prc-Desoto International, Inc. | Non-chromate corrosion inhibitors for aluminum alloys |
JP3458205B2 (en) | 1995-11-20 | 2003-10-20 | 関西ペイント株式会社 | High solid content coating composition and method for forming top coat using the same |
US5593733A (en) | 1995-11-21 | 1997-01-14 | Ppg Industries, Inc. | Coating composition containing polyester polymers with terminal carbamate groups and polymeric polyol derived from ethylenically unsaturated monomers |
JP3796286B2 (en) | 1996-01-22 | 2006-07-12 | 関西ペイント株式会社 | Painting method |
US6013733A (en) | 1996-02-16 | 2000-01-11 | Ppg Industries Ohio, Inc. | Coating of film-forming resin and functional flow control copolymer |
US5780530A (en) | 1996-03-19 | 1998-07-14 | Nippon Paint Co., Ltd. | Thermosetting resin composition |
US5948541A (en) | 1996-04-04 | 1999-09-07 | Kennametal Inc. | Boron and nitrogen containing coating and method for making |
US5976716A (en) | 1996-04-04 | 1999-11-02 | Kennametal Inc. | Substrate with a superhard coating containing boron and nitrogen and method of making the same |
US5998543A (en) | 1996-05-28 | 1999-12-07 | Eastman Chemical Company | Stable amino-containing polymer latex blends |
JP3789555B2 (en) | 1996-06-19 | 2006-06-28 | ポリプラスチックス株式会社 | Polyacetal resin composition |
US6297331B1 (en) | 1996-06-22 | 2001-10-02 | Th. Goldschmidt Ag | Organosiloxanyl derivatives of alkanediol monovinyl ethers, process for their preparation, their modification and their use as paint additives |
US5693724A (en) | 1996-07-01 | 1997-12-02 | Basf Corporation | Low VOC curable coating composition utilizing carbamate-functional compound |
US5693723A (en) | 1996-07-01 | 1997-12-02 | Basf Corporation | Low voc curable coating composition utilizing carbamate-functional compound |
US5853809A (en) | 1996-09-30 | 1998-12-29 | Basf Corporation | Scratch resistant clearcoats containing suface reactive microparticles and method therefore |
EP0832947B1 (en) | 1996-09-30 | 2003-05-14 | Basf Corporation | Scratch resistant clearcoats containing surface reactive microparticles and method therefor |
US5942556A (en) | 1996-11-27 | 1999-08-24 | Ppg Industries Ohio, Inc. | Stabilized radiation curable compositions based on unsaturated ester and vinyl ether compounds |
US6013724A (en) | 1997-03-05 | 2000-01-11 | Nippon Paint Co., Ltd. | Raindrop fouling-resistant paint film, coating composition, film-forming method, and coated article |
DE19709467C1 (en) | 1997-03-07 | 1998-10-15 | Basf Coatings Ag | Coating compositions and processes for producing multicoat paint systems |
DE19715426A1 (en) | 1997-04-14 | 1998-10-15 | Bayer Ag | Colloidal metal oxides containing blocked isocyanate groups |
US5922475A (en) | 1997-04-29 | 1999-07-13 | Ppg Industries Ohio, Inc. | Color-plus-clear composite coating compositions containing alkylolated or etherified carbanate functional polymers |
WO1999005213A1 (en) | 1997-07-25 | 1999-02-04 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
US6225434B1 (en) | 1997-08-01 | 2001-05-01 | Ppg Industries Ohio, Inc. | Film-forming compositions having improved scratch resistance |
US5939491A (en) | 1997-08-01 | 1999-08-17 | Ppg Industries Ohio, Inc. | Curable compositions based on functional polysiloxanes |
US6121378A (en) | 1997-08-21 | 2000-09-19 | Mitsui Chemicals, Inc. | Thermosetting powder paint composition |
US6045870A (en) | 1997-09-03 | 2000-04-04 | Kansai Paint Co., Ltd. | High solid coating composition and method for forming topcoat using same |
US6080816A (en) | 1997-11-10 | 2000-06-27 | E. I. Du Pont De Nemours And Company | Coatings that contain reactive silicon oligomers |
DE19800528A1 (en) | 1998-01-09 | 1999-07-15 | Bayer Ag | Coating system made of UV-curing urethane (meth) acrylate isocyanate groups |
US6005045A (en) | 1998-02-24 | 1999-12-21 | Ppg Industries Ohio, Inc. | Waterborne, ambient temperature curable film-forming compositions |
KR100338136B1 (en) | 1998-03-03 | 2002-05-24 | 울프 크라스텐센, 스트라쎄 로텐베르그 | New(meth) acrylate esters of organosiloxane polyols, process for their prepartion and their use as radiation-curable coating materials |
US6239212B1 (en) | 1998-10-23 | 2001-05-29 | Basf Corporation. | Clearcoat composition and method for intercoat adhesion |
-
2001
- 2001-07-31 US US09/919,198 patent/US6623791B2/en not_active Expired - Lifetime
-
2002
- 2002-07-29 KR KR1020067009568A patent/KR100618737B1/en active IP Right Grant
- 2002-07-29 CA CA 2455804 patent/CA2455804C/en not_active Expired - Lifetime
- 2002-07-29 EP EP20020748263 patent/EP1417273B1/en not_active Expired - Lifetime
- 2002-07-29 CA CA 2624864 patent/CA2624864A1/en not_active Abandoned
- 2002-07-29 ES ES02748263T patent/ES2350198T3/en not_active Expired - Lifetime
- 2002-07-29 AU AU2002317592A patent/AU2002317592A1/en not_active Abandoned
- 2002-07-29 DE DE60237691T patent/DE60237691D1/en not_active Expired - Lifetime
- 2002-07-29 WO PCT/US2002/023964 patent/WO2003011992A2/en active Application Filing
- 2002-07-29 KR KR20047001583A patent/KR100618738B1/en active IP Right Grant
- 2002-07-29 JP JP2003517172A patent/JP4148891B2/en not_active Expired - Lifetime
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- 2007-11-13 JP JP2007294938A patent/JP2008111129A/en not_active Withdrawn
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AU2002317592A1 (en) | 2003-02-17 |
KR20060066135A (en) | 2006-06-15 |
KR20040030907A (en) | 2004-04-09 |
ES2350198T3 (en) | 2011-01-20 |
US6623791B2 (en) | 2003-09-23 |
EP1417273B1 (en) | 2010-09-15 |
KR100618738B1 (en) | 2006-08-31 |
WO2003011992A2 (en) | 2003-02-13 |
CA2455804C (en) | 2008-07-08 |
CA2455804A1 (en) | 2003-02-13 |
KR100618737B1 (en) | 2006-09-01 |
AU2002317592A8 (en) | 2005-10-13 |
EP1417273A2 (en) | 2004-05-12 |
JP2004536947A (en) | 2004-12-09 |
US20020086168A1 (en) | 2002-07-04 |
JP2008111129A (en) | 2008-05-15 |
JP4148891B2 (en) | 2008-09-10 |
WO2003011992A3 (en) | 2003-06-05 |
DE60237691D1 (en) | 2010-10-28 |
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