CA2509837C - Coating composition - Google Patents
Coating composition Download PDFInfo
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- CA2509837C CA2509837C CA2509837A CA2509837A CA2509837C CA 2509837 C CA2509837 C CA 2509837C CA 2509837 A CA2509837 A CA 2509837A CA 2509837 A CA2509837 A CA 2509837A CA 2509837 C CA2509837 C CA 2509837C
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- coating composition
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- multifunctional
- silane
- functional
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
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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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Abstract
A coating composition comprising a reaction product of the following components: (a) at least one cyclic ether or anhydride; and (b) an alkoxysilane-functional polyacrylate, alkyd, polyester, epoxy, or a multifunctional polyol; and (c) at least one metal ester having the general formula Rm-M(OR~)n, in which M is Si, Al, Zr, or Ti, Mg, B, W. or Mo R is a hydrocarbon group of less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R~ is an alkyl or aryl group with less than 10 carbon atoms, m has values of 0, 1, 2 an 3 and correspondingly n is 4, 3, 2, or 1; and (d) at least one organofunctional alkoxysilane.
Description
COATING COMPOSITION
BACKGROUND
The present invention relates to new and improved formaldehyde and isocyanate-free room temperature, low temperature, heat and IR radiation curable compositions for use as coatings for wood, metal, plastics, ceramic, concrete, and other substrates. The coatings can be used, for example, for kitchen cabinets, automobiles, appliances, wood flooring, and several other applications.
It is well known that exposure to formaldehyde and isocyanate has significant health hazard issues. For example, under a court order OSHA has established long term (8 hours) and short term (15 minutes) PELs (permissible exposure limits) for formaldehyde. The rules require that any company marketing products that release free formaldehyde must label the containers and provide an MSDS showing how much formaldehyde is present. As formaldehyde has been declared a carcinogen, it is regulated as such.
Isocyanate-containing coatings, on the other hand, require special-breathing equipment for use to avoid respiratory system problems.
In the coatings industry, formaldehyde-containing polymers are commonly used as "crosslinking" resins that react with carboxyl or hydroxyl functional polymers such as polyesters or alkyd resins. Most of the current industrial finishes that require baking use coatings that contain some free formaldehyde. During the spraying process, workers can be exposed to some unsafe levels of free formaldehyde that comes from the paint. The coatings are then baked at temperatures > 275 F forming fully-crosslinked film. After the baking process, there is no longer any significant emission of free formaldehyde.
In the particular case of the wood finishing industry, it is not possible to bake the finishes at high temperature, and therefore a high level of acid catalyst is used to facilitate the crosslinking at room temperature. This type of coating is commonly termed a "conversion varnish". Typically, a conversion varnish creates a two stage release of free formaldehyde; namely, in the first stage, free formaldehyde is released from the coating itself during spraying and in a second stage, formaldehyde is released during the curing process. This second stage can last for several weeks. Many of these types of coatings are used by manufacturers in finishing kitchen cabinets, and for other indoor wood finishes.
Thus, it would be desirable to eliminate emission of free formaldehyde without compromising performance. In spite of the concerns, the performance and cost effectiveness of these types of coatings make it difficult to replace them. As regulations continue to be more stringent, it is anticipated that elimination of formaldehyde emission will become mandatory.
Additionally, numerous high performance, high solids coating compositions are based upon polymeric systems comprised of either polyester-based or polyacrylic-based polyols and crosslinking agents therefor. These coatings are generally supplied as "one-
BACKGROUND
The present invention relates to new and improved formaldehyde and isocyanate-free room temperature, low temperature, heat and IR radiation curable compositions for use as coatings for wood, metal, plastics, ceramic, concrete, and other substrates. The coatings can be used, for example, for kitchen cabinets, automobiles, appliances, wood flooring, and several other applications.
It is well known that exposure to formaldehyde and isocyanate has significant health hazard issues. For example, under a court order OSHA has established long term (8 hours) and short term (15 minutes) PELs (permissible exposure limits) for formaldehyde. The rules require that any company marketing products that release free formaldehyde must label the containers and provide an MSDS showing how much formaldehyde is present. As formaldehyde has been declared a carcinogen, it is regulated as such.
Isocyanate-containing coatings, on the other hand, require special-breathing equipment for use to avoid respiratory system problems.
In the coatings industry, formaldehyde-containing polymers are commonly used as "crosslinking" resins that react with carboxyl or hydroxyl functional polymers such as polyesters or alkyd resins. Most of the current industrial finishes that require baking use coatings that contain some free formaldehyde. During the spraying process, workers can be exposed to some unsafe levels of free formaldehyde that comes from the paint. The coatings are then baked at temperatures > 275 F forming fully-crosslinked film. After the baking process, there is no longer any significant emission of free formaldehyde.
In the particular case of the wood finishing industry, it is not possible to bake the finishes at high temperature, and therefore a high level of acid catalyst is used to facilitate the crosslinking at room temperature. This type of coating is commonly termed a "conversion varnish". Typically, a conversion varnish creates a two stage release of free formaldehyde; namely, in the first stage, free formaldehyde is released from the coating itself during spraying and in a second stage, formaldehyde is released during the curing process. This second stage can last for several weeks. Many of these types of coatings are used by manufacturers in finishing kitchen cabinets, and for other indoor wood finishes.
Thus, it would be desirable to eliminate emission of free formaldehyde without compromising performance. In spite of the concerns, the performance and cost effectiveness of these types of coatings make it difficult to replace them. As regulations continue to be more stringent, it is anticipated that elimination of formaldehyde emission will become mandatory.
Additionally, numerous high performance, high solids coating compositions are based upon polymeric systems comprised of either polyester-based or polyacrylic-based polyols and crosslinking agents therefor. These coatings are generally supplied as "one-
2 pack" or "two-pack" systems. In a typical one-pack system, all of the coating ingredients are combined into one storage stable mixture. In a typical two-pack system, a crosslinking agent is combined shortly before application with curing being conducted at ambient or elevated temperatures. Generally, two-pack systems have the advantages of corrosion and humidity resistance, short dry times and tough film thickness.
However, two-pack systems utilizing isocyanate crosslinkers or strong acid based crosslinkers have a number of disadvantages; for example, these two-pack systems require special handling and storage operations to avoid human exposure to the toxic isocyanates and acids. Further, the components of two-pack systems can only be mixed shortly prior to use. One-pack systems known in the art typically utilize resins which are susceptible to hydrolysis, which compromise the quality of the coating. Thus, it would be desirable to provide a one-pack, high solids, isocyanate-free system that has the desirable properties of the two-pack systems.
Accordingly, it is an object of the present invention to provide room temperature or low temperature curable compositions which exhibit high performance characteristics such as corrosion and humidity resistance, tough film properties, and no formaldehyde evolution upon curing. It is another object of this invention to provide coating compositions comprising these room temperature or low temperature curable compositions. The compositions of this invention can be cured effectively at lower temperatures without the use of toxic crosslinking agents, and do not liberate formaldehyde on curing. It is also an object of this invention to provide a one-pack, high solids, isocyanate-free system that has the desirable properties of a two-pack isocyanate system.
However, two-pack systems utilizing isocyanate crosslinkers or strong acid based crosslinkers have a number of disadvantages; for example, these two-pack systems require special handling and storage operations to avoid human exposure to the toxic isocyanates and acids. Further, the components of two-pack systems can only be mixed shortly prior to use. One-pack systems known in the art typically utilize resins which are susceptible to hydrolysis, which compromise the quality of the coating. Thus, it would be desirable to provide a one-pack, high solids, isocyanate-free system that has the desirable properties of the two-pack systems.
Accordingly, it is an object of the present invention to provide room temperature or low temperature curable compositions which exhibit high performance characteristics such as corrosion and humidity resistance, tough film properties, and no formaldehyde evolution upon curing. It is another object of this invention to provide coating compositions comprising these room temperature or low temperature curable compositions. The compositions of this invention can be cured effectively at lower temperatures without the use of toxic crosslinking agents, and do not liberate formaldehyde on curing. It is also an object of this invention to provide a one-pack, high solids, isocyanate-free system that has the desirable properties of a two-pack isocyanate system.
3 SUMMARY OF THE INVENTION
The present invention is particularly directed to a one-pack, high solids, isocyanate-free coating composition comprising the reaction product of the following components: (a) at least one cycloaliphatic diepoxide; and (b) a polyacrylate, alkyd, polyester, epoxy or a multifunctional polyol having alkoxysilane functionality; and (c) at least one metal ester having the general formula Rm-M(OR')n, wherein M
is Si, Al, Zr, Ti, Mg, B, W or Mo, and where Rm is a hydrocarbon group of less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R' is an alkyl or aryl group of less than 10 carbon atoms, in has values of 0, 1, 2 and 3 and correspondingly n is 4, 3, 2, or 1; and (d) at least one organofunctional alkoxysilane; and (e) a reaction product of a multifunctional polyol and a compound selected from the group consisting of an isocyanate-functional silane, a multifunctional orthosilicate, and a metal ester. The coating composition can further comprise a hydroxy-functional polymer and/or a silicate such as tetraethyl orthosilicate, and/or an alkyd polymer.
DESCRIPTION OF THE INVENTION
In accordance with the present invention, new and improved curable compositions are provided, said compositions comprising at least one at least one cyclic ether or anhydride, an alkoxysilane-functional polyacrylate, alkyd, polyester, epoxy, or a multifunctional polyol; and at least one metal ester having the general formula Rm-M(OR')n, in which M is Si, Al, Zr, Ti, Mg, B , W or Mo; Rm is a hydrocarbon group of
The present invention is particularly directed to a one-pack, high solids, isocyanate-free coating composition comprising the reaction product of the following components: (a) at least one cycloaliphatic diepoxide; and (b) a polyacrylate, alkyd, polyester, epoxy or a multifunctional polyol having alkoxysilane functionality; and (c) at least one metal ester having the general formula Rm-M(OR')n, wherein M
is Si, Al, Zr, Ti, Mg, B, W or Mo, and where Rm is a hydrocarbon group of less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R' is an alkyl or aryl group of less than 10 carbon atoms, in has values of 0, 1, 2 and 3 and correspondingly n is 4, 3, 2, or 1; and (d) at least one organofunctional alkoxysilane; and (e) a reaction product of a multifunctional polyol and a compound selected from the group consisting of an isocyanate-functional silane, a multifunctional orthosilicate, and a metal ester. The coating composition can further comprise a hydroxy-functional polymer and/or a silicate such as tetraethyl orthosilicate, and/or an alkyd polymer.
DESCRIPTION OF THE INVENTION
In accordance with the present invention, new and improved curable compositions are provided, said compositions comprising at least one at least one cyclic ether or anhydride, an alkoxysilane-functional polyacrylate, alkyd, polyester, epoxy, or a multifunctional polyol; and at least one metal ester having the general formula Rm-M(OR')n, in which M is Si, Al, Zr, Ti, Mg, B , W or Mo; Rm is a hydrocarbon group of
4 less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R' is an alkyl or aryl group of less than 10 carbon atoms, m has values of 0, 1, 2 an 3 and correspondingly n is 4, 3, 2, or 1; and at least one organofunctional alkoxysilane.
The cyclic ether useful for this invention can be a cycloaliphatic epoxide or cycloaliphatic diepoxide, multifunctional glycidyl epoxide, multifunctional glycidyl diepoxide, epoxidized oils or polymers containing an oxirane ring. In a preferred embodiment, the cyclic ether is a cycloaliphatic diepoxide, and can be described by the general formula:
0 ~
Where R = - CH2 - O - C(O) - C4Hs - C(O) - O -CH2- ; - C(O) - O- CH2 -Other cyclic ethers or cycloaliphatic epoxides useful for this invention can be 3,4-epoxy cyclohexylmethyl-3,4-epoxycyclohexyl carboxylate and bis-(3,4-epoxycyclohexylmethyl) adipate (commercially available as ERLTM-4221 and ERL-4299, respectively, from Dow Chemical Company), various glycidyl ethers such as diglycidyl ether, butyl glycidyl ether, bis-A-epoxy resins, and the like.
The alkoxysilane-functional polyacrylate is represented by the, formula:
[R 1 ] -C - C [R2] -Si - [OR3]3 wherein Rl is an organic acrylic polymer, R2 is a divalent organic radical, and R3 is a monovalent radical that can include heteroatoms (e.g., oxygen, nitrogen, sulfur), including but not limited to, alkyl (linear or branched), cycloalkyl, aryl, allyl, or aralkyL
The silicon alkoxide functionality pendant in the acrylic polymer can be available for further crosslinking.
The alkoxysilane-functional polyacrylate can be prepared by methods known in the art. Preferably, the alkoxysilane-functional polyacrylates are made utilizing alkoxysilanes represented by the general formula:
[R4]x - Si - [R5]4_,, In the above formula, R4 is an ethylenically unsaturated organic moiety and R5 is an alkoxy or an acetoxy group; and x is a positive integer from 1 to 3.
Alternatively, multifunctional polyols such as a reactive silanated polyol can be utilized, such as the TONE polyol or any other hydroxyl functional polymers such as polyesters, alkyds, and hydroxy functional epoxies.
The metal esters which have been found useful in the practice of the invention may be represented by the formula Rm-(OR)x, in which M is silicon, aluminum, zirconium, titanium, magnesium, boron, tungsten, or molybdenum; Rm is a hydrocarbon group of less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R' is an alkyl or aryl group of less than 10 carbon atoms, m has values of 0, 1, 2 an 3 and correspondingly n is 4, 3, 2, or 1.
Representative metal esters that can be used in the practice of this invention include tetra-isopropyl titanate (commercially available as Tyzor TPT, DuPont), tetra-n-butyl titanate (commercially available as Tyzor TBT, DuPont), tetraethyl titanate, tetra-2-ethylhexyl titanate, tetra-n-butyl zirconate, tetra-n-butyl titanate, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, orthosilicate, tetraethylortho silicate and tetraisopropyl zirconate.
Other useful metal esters of the type described are known in the art. The preferred metal esters are tetraisopropyl titanate, tetraisobutyl titanate, tetraisopropyl zirconate, and tetraisobutyl zirconate.
Organofunctional alkoxysilanes that have been found useful in the practice of the present invention include beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (SILQUESTTM
A 186), gamma-glycidoxypropyltrimethoxysilane (SILQUEST A-187 or Z 6040);
vinyltriethoxysilane (SILQI EST Al51); vinyl-tris-(2-methoxyethoxy) silane (SILQUEST A 172); gamma-methacryloxypropyltrimethoxy silane (SILQUEST A174);
methyltriethoxysilane (SILQUEST A- 162); methyltrimethoxysilane (SILQUEST A-1630); gamma-isocyanatopropyltriethoxysilane (SILQUEST A1310); and vinyltriacetoxy silane. (All of the above Sll!QUES1`i"' compounds are commercially available from OSI
Specialties, Inc., Danbury, CT). Other useful oganofunctional alkoxysilanes such as glycidyl epoxy, cycloaliphatic epoxy, methyl, methacrylato propoyl, vinyl, mercapto, isocyanato and amino functional silanes, and others known to the art, can be used. It has been found that the further addition of an isocyanatosilane modified polyol can improve pencil hardness and abrasion resistance of the coating.
The coating composition can further comprise the reaction product of a multifunctional polyol and (1) an isocyanate-functional silane; (2) a multifunctional orthosilicate; and/or (3) a metallic alkoxide.
While not intending to be bound by any theory, it is believed that the improvement in film formation and drying takes place when the metal ester reacts with atmospheric moisture and goes through hydrolysis to form a metal network. For example, titanium isopropoxide reacts with atmospheric moisture and goes through hydrolysis and condensation reactions to form a titanic network. The mechanism by which this occurs could be a combination of the silane and tetraorthoethyl silicate, wherein the silane and the ortho silicate hydrolyze to form a crosslinked network of the silica and titania. Also, use of a cycloapliphatic epoxy provides improvement in the hardness and chemical resistance through a crosslinking between the titanium oxide and the epoxy ring as well as with alkoxy silane functionality.
According to this invention, use of the cycloaliphatic epoxysilane is beneficial for coatings for wood floors used by manufacturers of wood flooring, and for automotive topcoats.
The coating compositions used in the practice of this invention are prepared by simply admixing or blending the cyclic ether such as cycloaliphatic (di)epoxide (or multifunctional glycidyl (di)epoxide); the alkoxysilane-functional polyacrylate, alkyd, polyester, epoxy, or multifunctional polyol; the metal ester crosslinker; and the organofunctional alkoxysilane at room temperature (i.e., 25 Q. Other additives such as leveling agents, colorants, viscosity modifiers, etc. may also be included in the composition by simple mixing. The preferred order of addition of the ingredients is to add the cycloaliphatic (di)epoxide to the reactive organofunctional alkoxysilane, and then the metal ester is added slowly at the end under constant agitation.
The coating composition of this invention can comprise 1-50% by weight of the alkoxysilane-functional polyacrylate (or alkyd, polyester, epoxy, or multifunctional polyol), 1-50% by weight of the cyclic ether (e.g., cycloaliphatic (di)epoxide or multifunctional glycidyl (di)epoxide), 1-70% by weight of the organofunctional alkoxysilane, and 1-40% by weight of the metal ester.
The coating composition of this invention can further comprise 1 to 50 weight percent of one or more of the following: (1) a hydroxy-functional polymer; (2) a silicate such as tetraethyl orthosilicate; (3) a silicone hydride functional polymer such as polyhydridomethylsiloxane; (4) an alkyd polymer; (5) a compounds having primary, secondary, or tertiary amine functionality; (6) a compound having alpha,beta unsaturated polymers; and/or (7) the reaction product of a multifunctional polyol and (a) an isocyanate-functional silane, (b) multifunctional orthosilicate, or (c) metallic alkoxide.
In one embodiment of this invention, a silicate such as tetraethyl orthosilicate is added to the coating composition to provide improved hardness properties. The silicate can be added to the composition with constant mixing. Preferably, the silicate is present at between 1.0 weight percent and 20 weight percent, based on the total weight of the coating composition.
In another embodiment of this invention, the composition of this invention can be used with a variety of oils, polyether polyols, alkyds, amines, polyesters, cycloaliphatic epoxides, glycidyl epoxides, silanes, acrylics, silicon alkoxides, isocyanate functional silanes, glycol ethers, polypropylene, polyethylene, polyvinyl chloride, polyvinyl acetates, and any other hydroxy functional polymers to produce coatings having much improved chemical resistance, corrosion resistance, hardness and drying properties.
In the case of wood floors and automotive topcoats, it has also been found that the addition of a reaction product of an isocyanate-functional silane and a multifunctional polyol is also desirable. For example, an isocyanate-functional silane such as Silquest A-1310 is reacted with a multifunctional polyol such as Tone 0301 polyol to provide a silane-functional urethane. The silane-functional urethane is then added to the coating composition to promote further crosslinking between the silane groups. If present, the silane-functional urethane is added in an amount of between 1.0 weight percent and 20 weight percent, based on the total weight percent of the final coating composition.
Typically, after admixing or blending, the coating composition can be applied directly to the substrate. The coatings of the present invention may be applied to any substrate in any desired thickness to impart abrasion resistance, solvent resistance, and corrosion resistance. Applications of the coatings of this invention include stains, floor finish topcoats, sanding sealers, conversion varnish for kitchen cabinets, automotive topcoat, epoxy primers, and flattening agents.
EXAMPLES
Example I
Preparation of a Polyacr ly ate A polyacrylate of this invention can be made by mixing the following components at 160 C:
Component Styrene 50 parts Butyl acrylate 30 parts Hydroxy Propyl Methacrylate 50 parts Butyl Acetate 100 parts VasoTM 67 1 part Example 2 Preparation of a Silanated Polyaq late The following coating composition was prepared utilizing the polyacrylate of Example 1:
Component Weight Percent Propylene glycol 3.8 n-butyl acetate 48.0 Example 1 Acrylic 31.6 Silquest A-186 1.0 EPONTM 815 16.0 BykTM 370 0.7 Titanium n-butoxide 10 The resulting coating composition is coated onto a surface of wood by spray technique (standard kitchen cabinet oak) and cured at ambient temperature. This one-pack coating was analyzed under the KCMA specifications (KCMA-A 161.1-2000) with the following results, as compared to a commercially available two-pack acid-catalyzed alkyd urea system:
Example 2 Comm. Available One-pack Two-pack Dry to touch 15 mins. 15 minx 1 hr @ 120 F Stackable Stackable Chemical resistance PASS PASS
Edge soak test PASS PASS
(24 hr immersion) Cold Check PASS PASS
(5 cycles) Heat resistance PASS PASS
(24 hrs @ 12(r F) Example 3 Preparation of a Silanated Polyol A multifunctional polyol, and in particular, a silanated polyol, is made by mixing together the following:
Component Caprolactone-based polyester polyol (TONE 0301 polyol) 100 grams Isocyanate-functional silane 30 grams (A-1310) Dibutyl tin dilaurate 0.1 gram The above mixture is heated for 1 hr. @ 230 F and is monitored using FTIR
until all of the isocyanate is reacted.
Example 4 Preparation of a Coating Composition A coating composition utilizing the silanated polyol of Example 3 is prepared as follows:
Component Weight Percent Silanated polyol of Example 3 20.7 1,3-di(3,4-epoxycyclohexyl)-2-propanone (ERL4221) 11.5 SILQUEST A-186 47.6 Titanium n-butoxide 20.0 The above components are added under constant mixing. The resulting coating composition is coated onto a surface of a metal at 2.9 mil film thickness, and cured at ambient temperature. The resulting coating has a pencil hardness of H, gloss of 129 at 60 degrees, table abrasion after 2200 cycles, CS 17 wheels, 1000 gram weight of 0.1813 gram loss.
Example 5 Preparation of a Silanated Acrylic Resin A silanated acrylic resin can be prepared as follows:
In a flask, 220.0 grams of butyl acetate and 0.5 grams of Vazo-52 initiator (available from Du Pont is blended. The temperature is raised to 115 C, and the following blend is added over a two hour period while stirring and increasing the temperature to 128 C:
Component Weight Percent Butyl Acrylate 106 grams Styrene 276 grams Silquest A-174 43 grams After the above components are added, 0.5 grams of dodecyl mercaptan is added.
After a total of 3.5 hours since the initial blend, 2.0 grams of Vazo-52 are added and after an additional 1 hour at 128 C, butyl acetate is added. The mixture is heated until the monomer conversion is complete.
Example 6 Preparation of a Coating Composition The following coating composition was prepared utilizing the silanated acrylic in Example 5 Component Weight Percent n-Butyl Acetate 28.0 Butyl PropasolTM 5.0 Example 5 Silanated acrylic 54.0 Silquest A-186 1.0 Silane 1-1630 2.5 Byk 370 0.7 Wacker's TesTM - 28 5.0 Zirconium n-butoxide 5.0 Example 7 Preparation of a Sealer for Untreated Wood Component Weight Percent SilrezTM SY-409 (comm. avail. from Wacker) 16.67 Tes - 28 (comm. avail. from Wacker) 16.67 Aluminum - s - Butoxide 16.67 Odorless mineral Sprit 50.00 The resulting coating composition is coated onto a surface of oak wood by spray or brush application and cured at ambient temperature. The coating can be sanded within 1 hr.
Examples 8-13 were prepared as coating compositions at differing gloss finishes, such as satin, gloss, high gloss. The components were blended together at room temperature.
Component Weight Percent Butyl Propasol 64.8 Silane A-162 49.4 Silanated Polyol of Example 3 1.01 Silquest A-186 26.49 ERL-4221 17.65 Zirconium n-butoxide 20.00 Component Weight Percent Butyl Propasol 44.08 Silane A-162 5.10 Silanated Polyol of Example 3 10.42 SILQUEST A-186 16.41 ERL-4221 10.93 Titanium n-Butoxide 13.08 Component Weight Percent Silanated Polyol of Example 3 16.8 ERL-4221 16.47 Butyl Propasol 17.29 Silane A-162 2.94 TS-100 (Fumed Amorphous Silica) 2.30 Wacker TES-28 1.62 Silquest A-186 22.55 Zirconium N-butoxide 20.00 Component Weight Percent Silanated Polyol of Example 3 17.53 ERL-4221 16.36 Butyl Propasol 14.34 Silane A-162 3.50 TS-100 (Fumed Amorphous Silica) 1.46 Wacker TES-28 23.36 Silquest A-186 20.45 Zirconium N-butoxide 20.00 Polymer Formulation for Hi hg~ Gloss Component Weight Percent Tone Polyol 0301 5.58 ERL-4299 (Bakelite resin) 20.10 Silquest A-186 Silane 60.32 Tetra Orthosilicate 11.76 Cab-O-Sil ' TS 610 fumed silica 2.23 Polymer Formulation for Satin Finish Component Weight Percent Tone Polyol 0301 5.28 ERL-4299 (Bakelite resin) 19.00 Silquest A-186 Silane 57.02 Tetra Orthosilicate 6.02 Cab-O-Sil TS 610 fumed silica 2.11 Crosslinker Formulation Component Weight Percent CoatosiliM 1770 Modified Epoxysilane 33.75 Zirconium N-Butoxide (AKZ-945) 33.12 Tyzor Tetrabutyl Titanate 33.12 Coating Formulation Component Weight Percent High Gloss Polymer of Example 11 71.45 Polymer of Example 13 28.55 Coating Formulation Component Weight Percent Satin Polymer of Example 12 71.45 Polymer of Example 13 28.55 Samples from the above examples were tested for physical and chemical properties, with the following results:
Comm. Comm. Comm. Ex.4 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Avail. Avail. 2K Avail. Oil 2K Water- Modified Urethane borne Urethane Satin Satin Gloss Gloss Gloss Gloss Semi- Semi-Gloss Gloss 2K W/B 2K W/B 1K-Solv 1K-solv 1K- 1K-soly 1K-solv 1K-soly solv Ureth. Aziridine Alkyd- Alkoxy Alkoxy Alkoxy- Alkoxy- Alkoxy-Urethane -Si -Si Si Si Si NVM % 35.19 36.96 46.21 78.25 . 75.67 71.62 74.63 68.84 DFT
30-Bar 0.67 0.55 0.73 0.89 0.91 0.86 1 60-Bar 1.17 1.318 1.32 2.02 2.1 1.96 1.91 90-Bar 1.73 1.72 1.66 4.633 2.51 2.33 2.73 2.62 GLOSS
30-Bar 15.4 20.1 130 129 132 65.2 46 60-Bar 16.1 131 127 131 68.8 42.9 90-Bar 16.8 40.2 132 129 127 129 69.6 67.9 PENCIL HARDNESS
30-Bar 4H H-2H B-1-1B HB-F 3H-4H H H
60-Bar 4H H-2H <6B B 2H-3H 2H-3H 2H-3H
90-Bar 2H H-2H <6B H B 2H-3H H 2H-3H
Adhesion 5B 5B 5B 5B 5B 5B 5B
TABER 31.5 150.1 152.7 108.8 105.9 71.4 The above examples are offered to illustrate the present invention. Various cyclic ethers, alkoxysilanes, silanated acrylics, and metal alkoxides may be used in a wide range of proportions and concentrations, and cured using different temperatures and cycles.
Any pigments, fillers and other additives compatible with the composition of the present invention may be employed in any amount.
The cyclic ether useful for this invention can be a cycloaliphatic epoxide or cycloaliphatic diepoxide, multifunctional glycidyl epoxide, multifunctional glycidyl diepoxide, epoxidized oils or polymers containing an oxirane ring. In a preferred embodiment, the cyclic ether is a cycloaliphatic diepoxide, and can be described by the general formula:
0 ~
Where R = - CH2 - O - C(O) - C4Hs - C(O) - O -CH2- ; - C(O) - O- CH2 -Other cyclic ethers or cycloaliphatic epoxides useful for this invention can be 3,4-epoxy cyclohexylmethyl-3,4-epoxycyclohexyl carboxylate and bis-(3,4-epoxycyclohexylmethyl) adipate (commercially available as ERLTM-4221 and ERL-4299, respectively, from Dow Chemical Company), various glycidyl ethers such as diglycidyl ether, butyl glycidyl ether, bis-A-epoxy resins, and the like.
The alkoxysilane-functional polyacrylate is represented by the, formula:
[R 1 ] -C - C [R2] -Si - [OR3]3 wherein Rl is an organic acrylic polymer, R2 is a divalent organic radical, and R3 is a monovalent radical that can include heteroatoms (e.g., oxygen, nitrogen, sulfur), including but not limited to, alkyl (linear or branched), cycloalkyl, aryl, allyl, or aralkyL
The silicon alkoxide functionality pendant in the acrylic polymer can be available for further crosslinking.
The alkoxysilane-functional polyacrylate can be prepared by methods known in the art. Preferably, the alkoxysilane-functional polyacrylates are made utilizing alkoxysilanes represented by the general formula:
[R4]x - Si - [R5]4_,, In the above formula, R4 is an ethylenically unsaturated organic moiety and R5 is an alkoxy or an acetoxy group; and x is a positive integer from 1 to 3.
Alternatively, multifunctional polyols such as a reactive silanated polyol can be utilized, such as the TONE polyol or any other hydroxyl functional polymers such as polyesters, alkyds, and hydroxy functional epoxies.
The metal esters which have been found useful in the practice of the invention may be represented by the formula Rm-(OR)x, in which M is silicon, aluminum, zirconium, titanium, magnesium, boron, tungsten, or molybdenum; Rm is a hydrocarbon group of less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R' is an alkyl or aryl group of less than 10 carbon atoms, m has values of 0, 1, 2 an 3 and correspondingly n is 4, 3, 2, or 1.
Representative metal esters that can be used in the practice of this invention include tetra-isopropyl titanate (commercially available as Tyzor TPT, DuPont), tetra-n-butyl titanate (commercially available as Tyzor TBT, DuPont), tetraethyl titanate, tetra-2-ethylhexyl titanate, tetra-n-butyl zirconate, tetra-n-butyl titanate, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, orthosilicate, tetraethylortho silicate and tetraisopropyl zirconate.
Other useful metal esters of the type described are known in the art. The preferred metal esters are tetraisopropyl titanate, tetraisobutyl titanate, tetraisopropyl zirconate, and tetraisobutyl zirconate.
Organofunctional alkoxysilanes that have been found useful in the practice of the present invention include beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (SILQUESTTM
A 186), gamma-glycidoxypropyltrimethoxysilane (SILQUEST A-187 or Z 6040);
vinyltriethoxysilane (SILQI EST Al51); vinyl-tris-(2-methoxyethoxy) silane (SILQUEST A 172); gamma-methacryloxypropyltrimethoxy silane (SILQUEST A174);
methyltriethoxysilane (SILQUEST A- 162); methyltrimethoxysilane (SILQUEST A-1630); gamma-isocyanatopropyltriethoxysilane (SILQUEST A1310); and vinyltriacetoxy silane. (All of the above Sll!QUES1`i"' compounds are commercially available from OSI
Specialties, Inc., Danbury, CT). Other useful oganofunctional alkoxysilanes such as glycidyl epoxy, cycloaliphatic epoxy, methyl, methacrylato propoyl, vinyl, mercapto, isocyanato and amino functional silanes, and others known to the art, can be used. It has been found that the further addition of an isocyanatosilane modified polyol can improve pencil hardness and abrasion resistance of the coating.
The coating composition can further comprise the reaction product of a multifunctional polyol and (1) an isocyanate-functional silane; (2) a multifunctional orthosilicate; and/or (3) a metallic alkoxide.
While not intending to be bound by any theory, it is believed that the improvement in film formation and drying takes place when the metal ester reacts with atmospheric moisture and goes through hydrolysis to form a metal network. For example, titanium isopropoxide reacts with atmospheric moisture and goes through hydrolysis and condensation reactions to form a titanic network. The mechanism by which this occurs could be a combination of the silane and tetraorthoethyl silicate, wherein the silane and the ortho silicate hydrolyze to form a crosslinked network of the silica and titania. Also, use of a cycloapliphatic epoxy provides improvement in the hardness and chemical resistance through a crosslinking between the titanium oxide and the epoxy ring as well as with alkoxy silane functionality.
According to this invention, use of the cycloaliphatic epoxysilane is beneficial for coatings for wood floors used by manufacturers of wood flooring, and for automotive topcoats.
The coating compositions used in the practice of this invention are prepared by simply admixing or blending the cyclic ether such as cycloaliphatic (di)epoxide (or multifunctional glycidyl (di)epoxide); the alkoxysilane-functional polyacrylate, alkyd, polyester, epoxy, or multifunctional polyol; the metal ester crosslinker; and the organofunctional alkoxysilane at room temperature (i.e., 25 Q. Other additives such as leveling agents, colorants, viscosity modifiers, etc. may also be included in the composition by simple mixing. The preferred order of addition of the ingredients is to add the cycloaliphatic (di)epoxide to the reactive organofunctional alkoxysilane, and then the metal ester is added slowly at the end under constant agitation.
The coating composition of this invention can comprise 1-50% by weight of the alkoxysilane-functional polyacrylate (or alkyd, polyester, epoxy, or multifunctional polyol), 1-50% by weight of the cyclic ether (e.g., cycloaliphatic (di)epoxide or multifunctional glycidyl (di)epoxide), 1-70% by weight of the organofunctional alkoxysilane, and 1-40% by weight of the metal ester.
The coating composition of this invention can further comprise 1 to 50 weight percent of one or more of the following: (1) a hydroxy-functional polymer; (2) a silicate such as tetraethyl orthosilicate; (3) a silicone hydride functional polymer such as polyhydridomethylsiloxane; (4) an alkyd polymer; (5) a compounds having primary, secondary, or tertiary amine functionality; (6) a compound having alpha,beta unsaturated polymers; and/or (7) the reaction product of a multifunctional polyol and (a) an isocyanate-functional silane, (b) multifunctional orthosilicate, or (c) metallic alkoxide.
In one embodiment of this invention, a silicate such as tetraethyl orthosilicate is added to the coating composition to provide improved hardness properties. The silicate can be added to the composition with constant mixing. Preferably, the silicate is present at between 1.0 weight percent and 20 weight percent, based on the total weight of the coating composition.
In another embodiment of this invention, the composition of this invention can be used with a variety of oils, polyether polyols, alkyds, amines, polyesters, cycloaliphatic epoxides, glycidyl epoxides, silanes, acrylics, silicon alkoxides, isocyanate functional silanes, glycol ethers, polypropylene, polyethylene, polyvinyl chloride, polyvinyl acetates, and any other hydroxy functional polymers to produce coatings having much improved chemical resistance, corrosion resistance, hardness and drying properties.
In the case of wood floors and automotive topcoats, it has also been found that the addition of a reaction product of an isocyanate-functional silane and a multifunctional polyol is also desirable. For example, an isocyanate-functional silane such as Silquest A-1310 is reacted with a multifunctional polyol such as Tone 0301 polyol to provide a silane-functional urethane. The silane-functional urethane is then added to the coating composition to promote further crosslinking between the silane groups. If present, the silane-functional urethane is added in an amount of between 1.0 weight percent and 20 weight percent, based on the total weight percent of the final coating composition.
Typically, after admixing or blending, the coating composition can be applied directly to the substrate. The coatings of the present invention may be applied to any substrate in any desired thickness to impart abrasion resistance, solvent resistance, and corrosion resistance. Applications of the coatings of this invention include stains, floor finish topcoats, sanding sealers, conversion varnish for kitchen cabinets, automotive topcoat, epoxy primers, and flattening agents.
EXAMPLES
Example I
Preparation of a Polyacr ly ate A polyacrylate of this invention can be made by mixing the following components at 160 C:
Component Styrene 50 parts Butyl acrylate 30 parts Hydroxy Propyl Methacrylate 50 parts Butyl Acetate 100 parts VasoTM 67 1 part Example 2 Preparation of a Silanated Polyaq late The following coating composition was prepared utilizing the polyacrylate of Example 1:
Component Weight Percent Propylene glycol 3.8 n-butyl acetate 48.0 Example 1 Acrylic 31.6 Silquest A-186 1.0 EPONTM 815 16.0 BykTM 370 0.7 Titanium n-butoxide 10 The resulting coating composition is coated onto a surface of wood by spray technique (standard kitchen cabinet oak) and cured at ambient temperature. This one-pack coating was analyzed under the KCMA specifications (KCMA-A 161.1-2000) with the following results, as compared to a commercially available two-pack acid-catalyzed alkyd urea system:
Example 2 Comm. Available One-pack Two-pack Dry to touch 15 mins. 15 minx 1 hr @ 120 F Stackable Stackable Chemical resistance PASS PASS
Edge soak test PASS PASS
(24 hr immersion) Cold Check PASS PASS
(5 cycles) Heat resistance PASS PASS
(24 hrs @ 12(r F) Example 3 Preparation of a Silanated Polyol A multifunctional polyol, and in particular, a silanated polyol, is made by mixing together the following:
Component Caprolactone-based polyester polyol (TONE 0301 polyol) 100 grams Isocyanate-functional silane 30 grams (A-1310) Dibutyl tin dilaurate 0.1 gram The above mixture is heated for 1 hr. @ 230 F and is monitored using FTIR
until all of the isocyanate is reacted.
Example 4 Preparation of a Coating Composition A coating composition utilizing the silanated polyol of Example 3 is prepared as follows:
Component Weight Percent Silanated polyol of Example 3 20.7 1,3-di(3,4-epoxycyclohexyl)-2-propanone (ERL4221) 11.5 SILQUEST A-186 47.6 Titanium n-butoxide 20.0 The above components are added under constant mixing. The resulting coating composition is coated onto a surface of a metal at 2.9 mil film thickness, and cured at ambient temperature. The resulting coating has a pencil hardness of H, gloss of 129 at 60 degrees, table abrasion after 2200 cycles, CS 17 wheels, 1000 gram weight of 0.1813 gram loss.
Example 5 Preparation of a Silanated Acrylic Resin A silanated acrylic resin can be prepared as follows:
In a flask, 220.0 grams of butyl acetate and 0.5 grams of Vazo-52 initiator (available from Du Pont is blended. The temperature is raised to 115 C, and the following blend is added over a two hour period while stirring and increasing the temperature to 128 C:
Component Weight Percent Butyl Acrylate 106 grams Styrene 276 grams Silquest A-174 43 grams After the above components are added, 0.5 grams of dodecyl mercaptan is added.
After a total of 3.5 hours since the initial blend, 2.0 grams of Vazo-52 are added and after an additional 1 hour at 128 C, butyl acetate is added. The mixture is heated until the monomer conversion is complete.
Example 6 Preparation of a Coating Composition The following coating composition was prepared utilizing the silanated acrylic in Example 5 Component Weight Percent n-Butyl Acetate 28.0 Butyl PropasolTM 5.0 Example 5 Silanated acrylic 54.0 Silquest A-186 1.0 Silane 1-1630 2.5 Byk 370 0.7 Wacker's TesTM - 28 5.0 Zirconium n-butoxide 5.0 Example 7 Preparation of a Sealer for Untreated Wood Component Weight Percent SilrezTM SY-409 (comm. avail. from Wacker) 16.67 Tes - 28 (comm. avail. from Wacker) 16.67 Aluminum - s - Butoxide 16.67 Odorless mineral Sprit 50.00 The resulting coating composition is coated onto a surface of oak wood by spray or brush application and cured at ambient temperature. The coating can be sanded within 1 hr.
Examples 8-13 were prepared as coating compositions at differing gloss finishes, such as satin, gloss, high gloss. The components were blended together at room temperature.
Component Weight Percent Butyl Propasol 64.8 Silane A-162 49.4 Silanated Polyol of Example 3 1.01 Silquest A-186 26.49 ERL-4221 17.65 Zirconium n-butoxide 20.00 Component Weight Percent Butyl Propasol 44.08 Silane A-162 5.10 Silanated Polyol of Example 3 10.42 SILQUEST A-186 16.41 ERL-4221 10.93 Titanium n-Butoxide 13.08 Component Weight Percent Silanated Polyol of Example 3 16.8 ERL-4221 16.47 Butyl Propasol 17.29 Silane A-162 2.94 TS-100 (Fumed Amorphous Silica) 2.30 Wacker TES-28 1.62 Silquest A-186 22.55 Zirconium N-butoxide 20.00 Component Weight Percent Silanated Polyol of Example 3 17.53 ERL-4221 16.36 Butyl Propasol 14.34 Silane A-162 3.50 TS-100 (Fumed Amorphous Silica) 1.46 Wacker TES-28 23.36 Silquest A-186 20.45 Zirconium N-butoxide 20.00 Polymer Formulation for Hi hg~ Gloss Component Weight Percent Tone Polyol 0301 5.58 ERL-4299 (Bakelite resin) 20.10 Silquest A-186 Silane 60.32 Tetra Orthosilicate 11.76 Cab-O-Sil ' TS 610 fumed silica 2.23 Polymer Formulation for Satin Finish Component Weight Percent Tone Polyol 0301 5.28 ERL-4299 (Bakelite resin) 19.00 Silquest A-186 Silane 57.02 Tetra Orthosilicate 6.02 Cab-O-Sil TS 610 fumed silica 2.11 Crosslinker Formulation Component Weight Percent CoatosiliM 1770 Modified Epoxysilane 33.75 Zirconium N-Butoxide (AKZ-945) 33.12 Tyzor Tetrabutyl Titanate 33.12 Coating Formulation Component Weight Percent High Gloss Polymer of Example 11 71.45 Polymer of Example 13 28.55 Coating Formulation Component Weight Percent Satin Polymer of Example 12 71.45 Polymer of Example 13 28.55 Samples from the above examples were tested for physical and chemical properties, with the following results:
Comm. Comm. Comm. Ex.4 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Avail. Avail. 2K Avail. Oil 2K Water- Modified Urethane borne Urethane Satin Satin Gloss Gloss Gloss Gloss Semi- Semi-Gloss Gloss 2K W/B 2K W/B 1K-Solv 1K-solv 1K- 1K-soly 1K-solv 1K-soly solv Ureth. Aziridine Alkyd- Alkoxy Alkoxy Alkoxy- Alkoxy- Alkoxy-Urethane -Si -Si Si Si Si NVM % 35.19 36.96 46.21 78.25 . 75.67 71.62 74.63 68.84 DFT
30-Bar 0.67 0.55 0.73 0.89 0.91 0.86 1 60-Bar 1.17 1.318 1.32 2.02 2.1 1.96 1.91 90-Bar 1.73 1.72 1.66 4.633 2.51 2.33 2.73 2.62 GLOSS
30-Bar 15.4 20.1 130 129 132 65.2 46 60-Bar 16.1 131 127 131 68.8 42.9 90-Bar 16.8 40.2 132 129 127 129 69.6 67.9 PENCIL HARDNESS
30-Bar 4H H-2H B-1-1B HB-F 3H-4H H H
60-Bar 4H H-2H <6B B 2H-3H 2H-3H 2H-3H
90-Bar 2H H-2H <6B H B 2H-3H H 2H-3H
Adhesion 5B 5B 5B 5B 5B 5B 5B
TABER 31.5 150.1 152.7 108.8 105.9 71.4 The above examples are offered to illustrate the present invention. Various cyclic ethers, alkoxysilanes, silanated acrylics, and metal alkoxides may be used in a wide range of proportions and concentrations, and cured using different temperatures and cycles.
Any pigments, fillers and other additives compatible with the composition of the present invention may be employed in any amount.
Claims (17)
1. A one-pack, high solids, isocyanate-free coating composition comprising the reaction product of the following components:
(a) at least one cycloaliphatic diepoxide; and (b) a polyacrylate, alkyd, polyester, epoxy or a multifunctional polyol having alkoxysilane functionality; and (c) at least one metal ester having the general formula Rm-M(OR')n, wherein M is Si, Al, Zr, Ti, Mg, B, W or Mo, and where Rm is a hydrocarbon group of less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R' is an alkyl or aryl group of less than 10 carbon atoms, m has values of 0, 1, 2 and 3 and correspondingly n is 4, 3, 2, or 1; and (d) at least one organofunctional alkoxysilane; and (e) a reaction product of a multifunctional polyol and a compound selected from the group consisting of an isocyanate-functional silane, a multifunctional orthosilicate, and a metal ester.
(a) at least one cycloaliphatic diepoxide; and (b) a polyacrylate, alkyd, polyester, epoxy or a multifunctional polyol having alkoxysilane functionality; and (c) at least one metal ester having the general formula Rm-M(OR')n, wherein M is Si, Al, Zr, Ti, Mg, B, W or Mo, and where Rm is a hydrocarbon group of less than 10 carbon atoms or a group comprising hydrogen, carbon and oxygen of less than 20 carbon atoms, R' is an alkyl or aryl group of less than 10 carbon atoms, m has values of 0, 1, 2 and 3 and correspondingly n is 4, 3, 2, or 1; and (d) at least one organofunctional alkoxysilane; and (e) a reaction product of a multifunctional polyol and a compound selected from the group consisting of an isocyanate-functional silane, a multifunctional orthosilicate, and a metal ester.
2. The coating composition of claim 1, further comprising the reaction product of a multifunctional polyol and an isocyanate-functional silane.
3. The coating composition of claim 1, further comprising the reaction product of a multifunctional polyol and a multifunctional orthosilicate.
4. The coating composition of claim 1, further comprising the reaction product of a multifunctional polyol and a metal ester.
5. The coating composition of claim 1, wherein the cycloaliphatic diepoxide is selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate and bis-(3,4-epoxycyclohexylmethyl)-adipate.
6. The coating composition of claim 1, further comprising a hydroxy-functional polymer.
7. The coating composition of claim 1, further comprising a silicone hydride functional polymer.
8. The coating composition of claim 7, wherein the silicone hydride is polyhydridomethylsiloxane.
9. The coating composition of claim 1, further comprising a compound having primary, secondary or tertiary amine functionality.
10. The coating composition of claim 1, further comprising an alpha,beta unsaturated polymer.
11. The coating composition of claim 10, wherein the alpha,beta unsaturated polymer is selected from the group consisting of acrylate-functional silanes, methacrylate-functional silanes, acrylic urethane, and acrylated urethane silanes.
12. The coating composition of claim 1, wherein the polyacrylate having alkoxysilane-functionality is represented by the formula:
[R1] -C - C [R2] -Si - [OR3]3 wherein R1 is an organic acrylic polymer, R2 is a divalent organic radical, and R3 is a monovalent radical that can comprise heteroatoms, and can comprise linear or branched alkyl, cycloalkyl, aryl, allyl, or aralkyl, and wherein the silicon alkoxide functionality is pendant in the acrylic polymer available for further crosslinking.
[R1] -C - C [R2] -Si - [OR3]3 wherein R1 is an organic acrylic polymer, R2 is a divalent organic radical, and R3 is a monovalent radical that can comprise heteroatoms, and can comprise linear or branched alkyl, cycloalkyl, aryl, allyl, or aralkyl, and wherein the silicon alkoxide functionality is pendant in the acrylic polymer available for further crosslinking.
13. The coating composition of claim 1, wherein the organofunctional alkoxysilane is selected from the group consisting of beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane;
gamma-glycidoxypropyltrimethoxy; vinyltriethoxysilane; vinyltris (2-methoxyethoxy) silane;
gamma-methacryloxy-propyltrimethoxy silane; and vinyltriacetoxy silane.
gamma-glycidoxypropyltrimethoxy; vinyltriethoxysilane; vinyltris (2-methoxyethoxy) silane;
gamma-methacryloxy-propyltrimethoxy silane; and vinyltriacetoxy silane.
14. The coating composition of claim 1, wherein the metal ester is selected from the group consisting of tetra-isopropyl titanate; tetra-n-butyl titanate; tetra-n-butyl zirconate, tetraethyl titanate, tetraethyl zirconate, tetra 2-ethylhexyl titanate, aluminumisopropoxide, aluminum n-butoxide, aluminum-s-butoxide, orthosilicate, tetraethylorthosilicate, and tetraisopropyl zirconate.
15. The coating composition of claim 1, further comprising an alkyd, polyester, or polyamine, polyamide, polyepoxide, or another single or multifunctional hydroxyl group containing compound.
16. The coating composition of claim 1, further comprising compounds having silicate-, ortho-silicate-, or silicone alkoxide functionality.
17. The coating composition of claim 12, wherein the heteroatoms are selected from oxygen, nitrogen and sulfur.
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| US60/435,840 | 2002-12-20 | ||
| PCT/US2003/040819 WO2004058907A1 (en) | 2002-12-20 | 2003-12-19 | Coating composition |
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| US7435777B2 (en) * | 2005-12-30 | 2008-10-14 | Columbia Insurance Company | Low-VOC compositions containing a polymeric latex, coatings made therefrom, substrates containing same, and methods for making same |
| KR101249090B1 (en) * | 2006-11-14 | 2013-03-29 | 삼성전자주식회사 | Composition for Preparing Organic Insulator and the Organic Insulator prepared by using the same |
| WO2009019296A1 (en) | 2007-08-09 | 2009-02-12 | Akzo Nobel Coatings International B.V. | High solids epoxy coating composition |
| BR112012016126A2 (en) * | 2009-12-29 | 2016-05-31 | 3M Innovative Properties Co | polyurethane nanocomposites |
| JP5963607B2 (en) * | 2012-08-10 | 2016-08-03 | 石塚硝子株式会社 | Organic inorganic adhesive composition |
| US9683125B2 (en) * | 2013-01-03 | 2017-06-20 | Basf Coatings Gmbh | One-component, curable coating compositions, processes for making and using them, and coatings and articles prepared with them |
| EP3687831A1 (en) * | 2017-09-26 | 2020-08-05 | Avery Dennison Retail Information Services, LLC | Heat transfer label |
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| US4042749A (en) * | 1974-10-08 | 1977-08-16 | Minnesota Mining And Manufacturing Company | Article having abrasion resistant surface formed from the reaction product of a silane and a metal ester |
| US4084021A (en) * | 1974-10-08 | 1978-04-11 | Minnesota Mining And Manufacturing Company | Method for rendering substrates resistant to abrasion |
| US4069368A (en) * | 1976-10-01 | 1978-01-17 | Minnesota Mining And Manufacturing Company | Workable and curable epoxy-terminated silane films |
| US4151344A (en) * | 1977-12-29 | 1979-04-24 | Phillips Petroleum Company | Release substrate |
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| KR20030016951A (en) * | 2001-08-23 | 2003-03-03 | 조욱제 | Liquid coating agent |
-
2003
- 2003-12-19 DE DE60319277T patent/DE60319277T2/en not_active Expired - Lifetime
- 2003-12-19 US US10/741,617 patent/US7399352B2/en not_active Expired - Fee Related
- 2003-12-19 MX MXPA05006553A patent/MXPA05006553A/en active IP Right Grant
- 2003-12-19 CA CA2509837A patent/CA2509837C/en not_active Expired - Fee Related
- 2003-12-19 AU AU2003297440A patent/AU2003297440A1/en not_active Abandoned
- 2003-12-19 WO PCT/US2003/040819 patent/WO2004058907A1/en active IP Right Grant
- 2003-12-19 BR BRPI0316867-0A patent/BR0316867B1/en not_active IP Right Cessation
- 2003-12-19 EP EP03814271A patent/EP1585795B1/en not_active Expired - Fee Related
- 2003-12-19 CN CN200380106753.0A patent/CN1729261A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE60319277T2 (en) | 2009-02-12 |
| CA2509837A1 (en) | 2004-07-15 |
| CN1729261A (en) | 2006-02-01 |
| AU2003297440A1 (en) | 2004-07-22 |
| WO2004058907A1 (en) | 2004-07-15 |
| DE60319277D1 (en) | 2008-04-03 |
| BR0316867B1 (en) | 2014-04-29 |
| US7399352B2 (en) | 2008-07-15 |
| MXPA05006553A (en) | 2005-08-16 |
| EP1585795B1 (en) | 2008-02-20 |
| BR0316867A (en) | 2005-10-18 |
| US20040210022A1 (en) | 2004-10-21 |
| EP1585795A1 (en) | 2005-10-19 |
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| EEER | Examination request | ||
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| MKLA | Lapsed |
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