WO2006138198A1 - Abrasion resistant coatings - Google Patents
Abrasion resistant coatings Download PDFInfo
- Publication number
- WO2006138198A1 WO2006138198A1 PCT/US2006/022704 US2006022704W WO2006138198A1 WO 2006138198 A1 WO2006138198 A1 WO 2006138198A1 US 2006022704 W US2006022704 W US 2006022704W WO 2006138198 A1 WO2006138198 A1 WO 2006138198A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- diacrylate
- composition according
- bisphenol
- glycol
- residues
- Prior art date
Links
Classifications
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
-
- 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]
-
- 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]
- Y10T428/31507—Of polycarbonate
-
- 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]
- Y10T428/31511—Of epoxy ether
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- 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]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- This invention pertains in general to radiation curable coating compositions.
- the invention pertains to coating compositions that form an abrasion resistant, protective finish for thermoplastic articles such as film, sheet, laminates, molded articles, and extruded profiles.
- thermoplastic polymers because of their physical, chemical, and mechanical properties, frequently are used to make shaped articles such as, for example, extruded film, sheet, profiles, formed products, composite structures, and laminates.
- An important criterion for thermoplastic polymers used in such applications is the ability to maintain a desirable appearance over the lifetime of the article.
- One way to impart abrasion resistance is to coat the article with a tough, hard, and clear coating that resists scratching and hazing from abrasion and rubbing.
- thermoplastic substrates include various thermoplastic polymers, unsaturated polyesters, epoxy resins, phenolics, melamines, acrylates, urethane-acrylates, rubbers, elastomers, and the like. In order for these coatings to be effective, they should be easy to apply to the thermoplastic article and should not degrade the physical or mechanical properties of the article such as, for example, its strength or toughness. Coating compositions have been developed which, when applied to a substrate and cured, impart a highly abrasion resistant surface to the substrate.
- abrasion resistant coatings can be prepared from acrylate monomers and cured or crosslinked by radiation. These radiation-curable coatings can exhibit superior hardness, and abrasion and chemical resistance. Radiation curable coatings can be rapidly cured without the use of ovens, and can be applied and processed in the absence of hazardous solvents. Radiation curable coatings also have been used to impart abrasion resistance to plastic lenses such as, for example, eyeglass lenses, to plastic panels and films, and to wood and furniture surfaces.
- the present invention provides coating composition that produces an abrasion and impact resistant protective finish to a thermoplastic substrate upon curing.
- the coating composition of the instant invention comprises a urethane acrylate, a flexible component, and an aromatic component in which the flexible component and aromatic component are present in a certain ratio.
- the present invention provides a coating composition for a thermoplastic substrate, comprising: (A) about 10 to about 60 weight percent of at least one flexible component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol selected from aliphatic diols containing 3 to 18 carbon atoms, polyalkylene ether glycols containing 3 to 50 carbon atoms, and cycloaliphatic diols containing 4 to 18 carbon atoms; (B) about 10 to about 60 weight percent of at least one aromatic component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol having a backbone comprising at least one residue of a bisphenol; and
- the above weight percentages are based upon the total weight of the composition excluding any additives.
- the coating composition is curable by thermal means or by radiation, such as, for example, by ultraviolet or electron beam radiation.
- the coating composition of the invention can further comprise at least one multifunctional acrylate such as, for example, one or more compounds selected trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxylated glycerol triacrylate, propoxylated, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate, and propoxylated dipentaerythritol hexaacrylate, and propoxy
- the invention provides a coating composition for a thermoplastic substrate comprising:
- the coating composition also may comprise additives such as, for example, UV absorbers and hindered amine light stabilizers (abbreviated herein as "HALS”) to impart additional weatherability and UV stability.
- HALS hindered amine light stabilizers
- the novel coating compositions of the present invention may be used advantageously on a wide range of thermoplastic substrates such as, for example, polyesters, polyamides, polycarbonates, cellulosics, and polyolefins, polysulfones, polyacetals, polyimides, and polyketones.
- the coating composition can be used to coat a shaped article, such as, for example, a sheet, film, bottle, tube, or profile, prepared from one or more thermoplastic polymers.
- the shaped article may contain one or more layers.
- the shaped article comprises a polyester comprising diacid residues which comprise at least 95 mole percent of the residues of terephthalic acid and diol residues which comprise about 10 to about 40 mole percent of the residues of 1 ,4- cyclohexanedimethanol, about 1 to about 25 mole percent of the residues of diethylene glycol, and about 35 to about 89 mole percent of the residues ethylene glycol.
- the coated article has enhanced resistance to abrasion and chemicals, excellent clarity, and toughness. Because the coating composition of the invention may be cured by radiation, thermoplastic articles can be cured quickly and at a temperature below the heat deflection temperature of the substrate.
- the present invention provides a coating composition for thermoplastic substrates that has enhanced resistance to abrasion and chemical resistance, without compromising other properties such as toughness and clarity. By utilizing radiation to cure these coatings, it is possible to initiate and complete curing in a short period of time while maintaining a temperature well below the heat deflection temperature of the substrate.
- the above weight percentages are based upon the total weight of the composition excluding any additives.
- additives include photoinitiators; slip agents; pigments, leveling agents; wetting agents; adhesion promoters; dispersion aids; anti-blocking agents; anti-caking agents; binders; curing agents; deaerators; diluents; dryers; emulsifiers; fillers; flatting agents; flow control agents; gloss agents; hardeners; lubricants; plasticizers; solvents; stabilizers; surfactants; viscosity modifiers; UV stabilizers; UV absorbers; water repellants, and the like.
- the coating composition of the invention comprises about 10 to about 60 weight percent, based on the total weight of the composition, excluding any additives, of at least one flexible component.
- the flexible component can comprise at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol selected from aliphatic diols containing 3 to 18 carbon atoms, polyalkylene ether glycols containing 3 to 50 carbon atoms, and cycloaliphatic diols containing about 4 to 18 carbon atoms.
- the substituted diols typically may comprise from 1 to 8 substituents independently selected from halo, hydroxy, oxo, Ci-Cio alkyl, C.2-C.10 alkenyl, C ⁇ -CIO aryl, and Ci-Cio alkoxy.
- esters that can be used as the flexible component include, but are not limited to, at least one diacrylate or dimethacrylate ester of diethylene glycol; 1 ,2-propanediol; dipropylene glycol; 1 ,3-propanediol; 2,2-dimethyl- 1 ,3-propanediol; 1 ,3-butanediol; decamethylene glycol; 1 ,4-butanediol; 1 ,5-pentanediol; 1 ,6-hexanediol; polyethylene glycol; polypropylene glycol; 2,2,4-trimethyl-l ,6-hexanedioI; thiodiethanol; 1 ,3-cycIohexanedimethanol; 1 ,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; triethylene glycol;
- the diacrylate esters of the cycloaliphatic diols i.e., 1 ,3- and 1 ,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-l ,3- cyclobutanediol, can be present as the pure cis or trans isomer or as a mixture of cis or trans isomers.
- the flexible component can comprise at least one diacrylate ester selected from 1 ,4-cyclohexane-dimethanol diacrylate; ethylene glycol diacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; polyethylene glycol diacrylate; polypropylene glycol diacrylate; dipolypropylene glycol diacrylate; trimethylolpropane diacrylate; ethoxylated trimethylolpropane diacrylate; propoxylated trimethylolpropane diacrylate; propoxylated neopentyl glycol diacrylate; ethoxylated neopentyl glycol diacrylate; tripolypropylene glycol diacrylate; 1 ,4-butanediol diacrylate; 1 ,3-propanediol diacrylate; 2,2- dimethyl-1 ,3-propanediol diacrylate; 1 ,6-hexanedio!
- the flexible component comprises 1 ,6-hexanediol diacrylate (abbreviated herein as "HDDA").
- HDDA 1 ,6-hexanediol diacrylate
- the coating composition also comprises about 10 to about 60 weight, based on the total weight of the composition excluding any additives, of at least one aromatic component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol having a backbone comprising at least one residue of a bisphenol.
- the substituted diols may contain from 1 to 8 substituents independently selected from halo, hydroxy, oxo, Ci-Cio alkyl, C2-C10 alkenyl, C ⁇ -Cio aryl, and Ci-Cio alkoxy.
- bisphenol as used herein, is understood to mean any methylenediphenol, i.e., HOCeH 4 CHbCeHUOH, such as, for example, /7,/7-methylenediphenol, and their substitution products, which are generally derived from condensation of two equivalent amounts of a phenol with an aldehyde or ketone.
- reduce as used herein, means any organic structure incorporated into a polymer, oligomer, monomer, ester, or plasticizer that originates from a chemical building block.
- the bisphenol residue can be a bisphenol A residue originating from the reaction of bisphenol A with epichlorohydrin to produce the diglycidyl ether of bisphenol A , which may be reacted further with acrylic acid to produce a bisphenol A epoxy acrylate.
- examples of bisphenols include, but are not limited to bisphenol (p,p- methylenediphenol), bisphenol F (a mixture of 2,2'-, 2,4'-, and 4,4'- dihydroxydiphenylmethane), and bisphenol S (4,4'- dihydroxydiphenylsulfone).
- the aromatic component (B) may comprise at least one compound selected from bisphenol A epoxy diacrylates and diacrylate esters of ethoxylated bisphenol, propoxylated bisphenol, ethoxylated bisphenol A, propoxylated bisphenol A, ethoxylated bisphenol F, propoxylated bisphenol F, ethoxylated bisphenol S, and propoxylated bisphenol S.
- These materials are typically prepared by condensing a bisphenol with one or more equivalents of ethylene or propylene oxide to form an adduct followed by esterification with acrylic acid, methacrylic acid, their corresponding acid chlorides, or anhydrides.
- These compounds are
- bisphenol epoxy acrylate means a compound prepared typically by reacting a diglycidyl ether of a bisphenol with acrylic acid, methacrylic acid or the anhydride of acrylic acid or methacrylic acid.
- glycidyl ethers may be oligomerized to form epoxy resins or further modified with diols, diacids, alkylene oxides such as, for example, ethylene oxide or propylene oxide, and then functionalized with acrylic or methacrylic acid, to produce diacrylate or dimethacrylate esters having a range of functionality, hydrophilicity, molecular weights, and viscosities.
- Bisphen ⁇ l epoxy acrylates typically do not have any free epoxy groups left from their synthesis but react through their acrylate ester end groups.
- the bisphenol epoxy acrylates of the present invention have molecular weights ranging from about 400 to about 1 500, but higher or lower molecular weights can be used depending upon the specific coating formulation.
- These acrylates are well known to persons having ordinary skill in the art and many of them are commercially available. Commercial examples of such compounds include NOVACURE ® 3701 , EBECRYL ® 3500, EBECRYL ® 600 (available from UCB Chemicals), and CNI 1 7 and CNl 1 5 (available from Sartomer Company).
- the aromatic component can comprise a bisphenol A epoxy diacrylate modified with at least one alkylene glycol or polyalkylene glycol containing 4 to 20 carbon atoms, one or more aliphatic dicarboxylic acids containing 2 to 20 carbon atoms, or a mixture thereof.
- the modified bisphenol epoxy diacrylate comprises the residues at least one aliphatic dicarboxylic acid containing 4 to 8 carbon atoms and propylene glycol.
- the aromatic component of invention comprises a bisphenol A epoxy diacrylate having the formula: wherein R is a radical having the formula:
- Urethane acrylates and meth acrylate s are known to the person skilled in the art and can be prepared according to known procedures, for example, by reacting a hydroxy- terminated polyurethane with acrylic acid or methacrylic acid, or by reacting an isocyanate-terminated prepolymer with hydroxyalkyl acrylates or methacrylates.
- Examples of commercially available urethane acrylates include those known under the trade designations UVITHANE 782, available from Morton Thiokol Chemical, EBECRYL ® 6600, EBECRYL ® 8400, and EBECRYL ® 8805, available from UCB Chemicals.
- hexafunctional is understood to mean the acrylate comprises oligomers having 6 acrylate ester groups.
- Examples of commercially available aliphatic urethane acrylates which can be used in the instant invention include, but are not limited to: EBECRYL ® 230, an aliphatic urethane; EBECRYL ® 244, an aliphatic urethane & 10% 1 ,6-hexanediol diacrylate; EBECRYL ® 265, an aliphatic urethane & 25% tripropyleneglycol diacrylate; EBECRYL ® 270, an aliphatic urethane; EBECRYL ® 285, an aliphatic urethane & 25% tripropyleneglycol diacrylate; EBECRYL ® 4830, an aliphatic urethane & 10%
- the inventive coating composition may further comprise at least one multifunctional acrylate having 3 or more acrylate ester groups.
- multifunctional acrylates include trimethylolpropane triacrylate, ethoxyiated or propoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxyiated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, ethoxyiated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxyiated pentaerythritol tetraacrylate, propoxylated dipentaerythritol hexaacrylate, ethoxyiated dipentaerythritol hexaacrylate, ethoxyiated dipentaerythritol hexaacrylate
- additives examples include, but are not limited to, photoinitiators; slip agents; leveling agents; wetting agents; adhesion promoters; anti-absorption agents; anti-foaming agents, such as, for example, mixtures of foam destroying polymers and polysiloxanes; accelerators; pigment dispersion aids; anti-blocking agents; anti-caking agents; anti-slip agents; anti-skinning agents; anti-static agents; anti- stripping agents; binders; curing agents; deaerators; diluents; dispersants; dryers; ernulsifiers; fillers; flatting agents; flow control agents; gloss agents; hardeners; lubricants; mar resistance aids; whiteners; plasticizers; solvents; stabilizers; surfactants; viscosity modifiers; UV stabilizers; UV absorbers; and water repellants.
- the coating composition may further comprise finely divided Si ⁇ 2, AI2O3, Zr ⁇ 2, or TiO ⁇ dispersed therein. These materials can modify the viscosity of the coating such that it may be applied easily and can enhance the abrasion resistance of the cured coating.
- the Si ⁇ 2 may comprise amorphous silica particles having an average surface area of 50 m 2 /g, and an average particle size of 40 ⁇ m.
- the Si ⁇ 2 can be a colloidal silica.
- Exemplary photoinitiators include, but are not limited to, those selected from organic peroxides, azo compounds, quinones, oc- hydroxy ketones, benzophenones, nitroso compounds, acyl halides, hydrazones, mercapto compounds, pyrylium compounds, triacylimidazoles, bisimidazoles, chloroalkyltriazines, benzoin ethers, benzil ketals, thioxanthones, and acetophenone derivatives, and mixtures thereof.
- thermoplastic substrate Another embodiment of the invention is a coating composition for a thermoplastic substrate, comprising:
- the composition can comprise (A) about 20 to about 40 weight percent of a flexible component comprising dipropylene glycol diacrylate and 1 ,6-hexanediol diacrylate; (B) about 1 5 to about 40 weight percent of a bisphenol A epoxy acrylate modified with at least one alkylene glycol or polyalkylene glycol containing 4 to 20 carbon atoms, one or more aliphatic dicarboxylic acids containing 4 to 20 carbon atoms, or a mixture thereof; (C) about 5 to about 1 5 weight percent of at least one aliphatic urethane acrylate comprising the residues of pentaerythritol; and (D) about 5 to about 20 weight percent of a multifunctional acrylate comprising ethoxylated trimethylolpropane triacrylate containing
- R is a radical having the formula:
- the composition may further comprise a photoinitiator. Typical examples of photoinitiator levels are about 0.1 to about 5 weight percent, or preferably, about 0.5 to about 5 weight percent, based on the total weight of the composition.
- the coating composition also may further comprise S1O2 dispersed therein.
- one or more light stabilizers such as UV absorbers and reversible radical scavengers such as, for example, hindered amine (“HALS”) or hindered phenol light stabilizers also may be added to the coating composition to enhance weatherability and inhibit yellowing.
- HALS hindered amine
- hindered phenol light stabilizers are known to persons skilled in the art and many are commercially available.
- the hindered amine light stabilizers can have a high molecular weight such as, for example, those compounds having an N-substituted piperidinol nucleus and generally having a weight average molecular weight of about 400 to about 10,000 or, preferably, about 500 to about 5,000.
- Such hindered amine light stabilizers include high-molecular weight esters prepared from butanetetracarboxylic acid and an N-substituted piperidinol.
- the amount of the light stabilizer while varying according to the kind, generally ranges from about 0.5 to about 5 weight percent, based on the total weight of the coating composition.
- weight percentage ranges for the light stabilizer are about 0.6 to about 4 weight percent and about 0.7 to about 3 weight percent.
- examples of commercially available hindered amine light stabilizers that can be used in the invention include, but are not limited to: CYASORBTM UV-3529 (available from Cytec Industries), TINUVINTM 770 (available from Ciba Specialty Chemicals), TINUVINTM 1 23 (available from Ciba Specialty Chemicals), CHIMASSORBTM 1 19 (available from Ciba Specialty Chemicals), LOWILITETM 76 (available from Great Lakes Chemical Corp.), MARKTM LA 52 (available from Asahi Denka Co., Ltd.), MARKTM LA 62 (available from Asahi Denka Co., Ltd.), GOODRITETM UV- 31 59 (available from BF Goodrich Chemical Co.), MARKTM LA-63 (available from Adeca Argus), MARKTM LA-62 (available from Adeca Argus), and TINUVIN ® -622LD
- one or more UV absorbers may be added in an amount of about 0.5 to about 1 0 weight percent, preferably about 0.7 to about 9 weight percent, still preferably about 1 to about 8 weight percent, based on the total weight of the coating composition.
- Representative UV absorbers that can be added to the coating composition of the invention include, but are not limited to, one or more compounds having a maximum absorption in the range of 290-400 nm with a minimal absorbance between 400 and 700 nm.
- UV absorbers of cyanoacrylate type, benzotriazole type, aromatic triazine type, benzoxazinone type, benzophenone type, salicylic acid type, or hydroquinone type can be used.
- benzotriazole UV absorbers include, but are not limited to, 2-(3,5 ⁇ di-t-butyl-2- hydroxyphenyl)benzo-triazole, 2-[2-hydroxy ⁇ 3,5- bis(alpha,alpha- dimethylbenzyl)phenyl]-2H-benzotriazole, and 2— (3,5— di- t-amyl-2- hydroxyphenyl]-benzotriazole.
- benzophenone UV absorbers include, but are not limited to, 2- hydroxy-4- octyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4- methoxy-2'-carboxybenzophenone.
- Examples of salicylic acid UV absorbers include, but are not limited to, phenyl salicylate, p-octylphenyl salicylate, resorcinol monobenzoate, and 4-t-butylphenyl salicylate.
- Examples of cyanoacrylate UV absorbers include ethyl 2-cyano ⁇ 3,3-diphenylacrylate and 2-ethylhexyl ⁇ 2-cyano-3,3- diphenylacrylate.
- Examples of commercially availabe UV absorbers include, but are not limited to, CYASORBTM UV-1 164 (available from Cytec Industries) and TINUVINTM 1 577 (available from Ciba Specialty Chemicals).
- the present invention also provides a shaped article comprising the coating compositions described hereinabove, applied to at least one surface thereof, and cured by exposure to ultraviolet or electron beam radiation.
- the shaped article such as, for example, a sheet, film, tube, bottle, or profile, may be produced by extrusion, calendering, thermoforming, blow-molding, injection molding, casting, tentering, or blowing.
- the shaped article may comprise one or more layers.
- the shaped article will comprise at least one thermoplastic polymer selected from the following: polyester, polyamide, polycarbonate, cellulosic, polyolefin, polysulfone, polyacetal, polyimide, polyketone, polyvinyl chloride, polystyrene, polylactic acid, copolymers thereof, and blends thereof.
- thermoplastic as used herein with respect to the polymers of the shaped articles, it intended have its commonly understood meaning in the art, that is a property of a polymer wherein the polymer softens when exposed to heat and returns to its original condition when cooled to room temperature.
- the shaped article may comprise one or more polyesters such as, for example, poly(ethylene terephthalate), poly(butylene terephthalate), polyO ,3 ⁇ trimethylene terephthalate), poly(cyclohexylene terephthalate).
- the shaped articles of the invention may include polyesters from the condensation one of more aromatic diacids with one or more diols.
- polyester as used herein, is intended to include "copolyesters” and is understood to mean a synthetic polymer prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional hydroxyl compounds.
- the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as, for example, glycols and diols.
- the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxy substituents such as, for example, hydroquinone.
- the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
- dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester.
- the polyesters of present invention comprise dicarboxylic acid residues, diol residues, and repeating units.
- a "repeating unit" means an organic structure having a dicarboxylic acid and a diol residue bonded through a carbonyloxy group.
- the 1 ,3- and 1 ,4-cycIohexanedimethanol, and 2,2,4,4-tetramethyl-l ,3-cyclobutanediol may be used as a pure c/s or trans isomer or as a mixture of c/s and trans isomers.
- the polyesters generally will have inherent viscosity (I. V.) values in the range of about 0.5 dL/g to about 1 .4 dL/g. Additional examples of I.V. ranges include about 0.65 dL/g to about 1.0 dL/g and about 0.65 dL/g to about 0.85 dL/g.
- the reaction process may comprise two steps.
- the diol component and the dicarboxylic acid component such as, for example, dimethyl terephthalate
- the reaction product is heated under higher temperatures and under reduced pressure to form the polyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system.
- This second step, or polycondensation step is continued under higher vacuum and temperatures until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained.
- reaction rates of both stages are increased by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
- catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
- a three-stage manufacturing procedure similar to that described in U.S. Patent No. 5,290,631 , may also be used, particularly when a mixed monomer feed of acids and esters is employed.
- polyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components.
- the present invention also provides a method of coating a shaped article comprising applying the coating compositions described hereinabove to a surface of a shaped article and exposing the coated surface to radiation.
- the coating compositions are prepared by mixing the appropriate monomers, resins and additives in the desired proportions described above. Coating can be achieved by conventional techniques, including dipping, spraying, curtain coating, gravure and roll coating.
- the application methods are conventional and may be selected depending upon the nature of the substrate, desired thickness, and other factors.
- the coating is applied by using conventional gravure or roll coating techniques which produce thin coatings.
- Multiple coating layers may be applied to the substrate in a conventional manner as described above. For example, each respective coating layer may be applied individually to the substrate and cured prior to application of the next coating layer.
- the coating composition may be cured by thermal means, by radiation, or a combination thereof.
- conventional radiation curing techniques are employed in the present invention using any source of radiation capable of initiating photochemical reactions such as, for example, ultraviolet or electron beam radiation.
- Potential commercial applications of the coating composition of the invention include a variety of areas where the appearance of the plastic form or object is an important factor in its selection in use. These include flat sheet applications in areas such as building and construction, transportation, laminates, graphic arts, EILT (Encapsulated Image Layer Technology), appliances, point of purchase displays, sports, and recreation. In other application areas the coating can be applied and cured after an object has been molded such as, for example, in ophthalmic and cosmetic applications.
- the invention is further illustrated and described by the following examples.
- Example J A uniform mixture of materials was prepared using the materials listed in Table 1 . The weight percentages are calculated based on the total weight of the composition excluding the weight of any additives (e.g., SiO 2 and the DAROCUR photoinitiator).
- any additives e.g., SiO 2 and the DAROCUR photoinitiator.
- EBECRYL ® 1 290 was described by UCB Chemicals as a hexafunctional aliphatic urethane acrylate with an acrylated polyol diluent.
- the DAROCUR ® 1 1 73 initiator was described as 2-hydroxy-2-methylpropiophenone.
- the components of the formulation were each weighed out in an opaque NALGENE ® container. The formulation was then mixed by placing the container for at least 2 hours on a roller which was located in a heated chamber at a temperature of approximately 55 0 C. The container was then placed on a roller in the laboratory and allowed to roll overnight to insure that the formulation was well mixed.
- the coatings were applied to 1 /8 inch thick sheet prepared from a 70:30 (by weight) polyesterpolycarbonate blend.
- the polyester component of the blend contained about 100 mole% terephthalic acid, 62 mole% 1 ,4-cyclohexanedimethanol, and 38 mole% ethylene glycol.
- the coatings were applied using the RK automated draw down machine (Print-Coat Instruments, Ltd., England). A wire-wound rod with a very fine wound spring was used to draw a coating of approximately 5 microns wet film thickness. The speed of draw was set at "4".
- the Power PuckTM measures the total UV dosage Qoules/cm 2 ) and the peak UV intensity (watts/cm 2 ) for four UV ranges (UV-A: 320-390 nm, UV-B: 280-320 nm, UV-C: 250-260 nm, and UV-V: 395-445 nm). The following total peak UV readings were observed for the settings used in this experiment: UV-A 1 .6, UV-B 1 .5, UV-C 0.18, and UV-V 1 .1. [Para 46] Evaluation of the coatings - Initial Coating Characterization. The degree of cure of the coatings were verified to be acceptable using a K ⁇ nig Hardness test (ASTM D 4366).
- a crosshatched adhesion test was carried out according to ASTM D3359.
- the coating is scored with a razor knife 1 1 times horizontally and 1 1 times vertically (creating 100 squares).
- a piece of masking tape is adhered to the scored surface and then removed.
- the percent adhesion is then determined by counting the number of squares which remain adhered to the substrate.
- Example 1 showed 100% adhesion to polyester substrate.
- Examples 6 -16 Examples 6 - 1 6 were prepared, coated, cured, and analyzed as described in Example 1 . The weight percentages of the coating components, presented in Table 5, were calculated based on the total weight of the composition and included the weight of the DAROCUR ® ! 1 73 photoinitiator.
- Example 17 Example 1 7 was prepared, coated, and cured in a manner identical to Example 5 except that the following stabilizing additives were added to the formulation: 2 weight% T ⁇ NUVIN ® 400 and 1 weight% TINUVIN ® 123 (available from Ciba Specialty Chemicals). The weight percentages were based on the total weight of the coating composition. These additives, while compatible with the UV cure, improved the weatherability of the coating composition. The weatherability analysis was conducted on a QUV-SE Weathering Tester model QUV/se from Q-Panel Lab Products according to the ASTM method UVA-340 Gl 54 Cycle 1 . The weathering results from samples of this coating are presented in Table 8:
- Applicable ASTM methods include: o E 1 164 - Obtaining Spectrophotometric Data for Object-Color
- Comparative Examples I to 4 Comparative Examples 1 - 4 were prepared, coated, cured, and analyzed as described in Example 1 . These coatings utilized Example 5 as the starting composition for analyzing the effect of varying the concentration of either HDDA or of EBECRYL ® 3500 on the coating properties. The composition of these examples is presented in Table 9. The weight percentages are based on the total weight of the coating composition and include the weight of DAROCUR ® 1 173 photoinitiator.
- Table 10 presents the Taber Abrasion data for Comparative Examples 1 - 4:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Disclosed are radiation-curable, abrasion resistant coating compositions for thermoplastic substrates which provides superior abrasion, chemical, and impact resistance properties. The coating composition includes at least one flexible diacrylate component, at least one aromatic diacrylate component, and at least one urethane acrylate. Also disclosed are shaped articles having the coating composition applied to at least one surface and cured by exposure to radiation.
Description
ABRASION RESISTANT COATINGS . .
FIELD OF THE INVENTION
[Para 1 ] This invention pertains in general to radiation curable coating compositions. In particular, the invention pertains to coating compositions that form an abrasion resistant, protective finish for thermoplastic articles such as film, sheet, laminates, molded articles, and extruded profiles.
BACKGROUND OF THE INVENTION
[Para 2] Thermoplastic polymers, because of their physical, chemical, and mechanical properties, frequently are used to make shaped articles such as, for example, extruded film, sheet, profiles, formed products, composite structures, and laminates. An important criterion for thermoplastic polymers used in such applications is the ability to maintain a desirable appearance over the lifetime of the article. In particular, it is important for the thermoplastic material to maintain color, clarity, resistance to haze, and to resist scratching by mechanical abrasion. One way to impart abrasion resistance is to coat the article with a tough, hard, and clear coating that resists scratching and hazing from abrasion and rubbing. In addition to abrasion resistance, such a coating generally will provide protection against weathering and chemicals such as, for example, solvents, polishes, and cleaners.
[Para 3] Common coatings that are applied to thermoplastic substrates include various thermoplastic polymers, unsaturated polyesters, epoxy resins, phenolics, melamines, acrylates, urethane-acrylates, rubbers, elastomers, and the like. In order for these coatings to be effective, they should be easy to apply to the thermoplastic article and should not degrade the physical or mechanical properties of the article such as, for example, its strength or toughness. Coating compositions have been developed which, when applied to a substrate and cured, impart a highly abrasion resistant surface to the substrate. For example, abrasion resistant coatings can be prepared from acrylate monomers and cured or crosslinked by radiation. These radiation-curable coatings can exhibit superior hardness, and abrasion and chemical resistance. Radiation curable coatings can be rapidly cured without the use of ovens, and can be applied and processed in the absence of hazardous solvents. Radiation curable coatings also have been used to impart abrasion resistance to plastic lenses such as, for example, eyeglass lenses, to plastic panels and films, and to wood and furniture surfaces.
[Para 4] Although radiation curable coatings are quite hard and resistant to abrasion and scratching, they often can cause cracking and brittle failure of the entire article when subjected to impact. One approach to this brittleness and cracking problem is to use a softening comonomer (a monomer with a low second order transition temperature) to impart some
degree of flexibility to the coating. In achieving increased flexibility and reduced brittleness, however, the abrasion resistance of the coating can be reduced. A coating composition for thermoplastic substrates is needed, therefore, that provides excellent abrasion resistance and yet retains good clarity, resistance to impact, and toughness.
SUMMARY OF THE INVENTION
[Para 5] The present invention provides coating composition that produces an abrasion and impact resistant protective finish to a thermoplastic substrate upon curing. The coating composition of the instant invention comprises a urethane acrylate, a flexible component, and an aromatic component in which the flexible component and aromatic component are present in a certain ratio. Thus, in one embodiment, the present invention provides a coating composition for a thermoplastic substrate, comprising: (A) about 10 to about 60 weight percent of at least one flexible component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol selected from aliphatic diols containing 3 to 18 carbon atoms, polyalkylene ether glycols containing 3 to 50 carbon atoms, and cycloaliphatic diols containing 4 to 18 carbon atoms;
(B) about 10 to about 60 weight percent of at least one aromatic component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol having a backbone comprising at least one residue of a bisphenol; and
(C) at least one urethane acrylate; wherein the substituted diols contain 1 to 8 substituents independently selected from halo, hydroxy, oxo, Ci-Cio alkyl, C2-C10 alkenyl, Cδ-Cio aryl, and Ci-Cio alkoxy, and the composition has a weight ratio of flexible component :aromatic component of about 1 :3 to about 3:1 . The above weight percentages are based upon the total weight of the composition excluding any additives. The coating composition is curable by thermal means or by radiation, such as, for example, by ultraviolet or electron beam radiation.
[Para 6] In addition to the components described above, the coating composition of the invention, optionally, can further comprise at least one multifunctional acrylate such as, for example, one or more compounds selected trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxylated glycerol triacrylate, propoxylated, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol
hexaacrylate, and propoxylated dipentaerythritol hexaacrylate. The multifunctional acrylate permits additional crosslinking of the coating and allows for tayloring of the coating properties to meet the requirements of diverse applications.
[Para 7] In another embodiment, the invention provides a coating composition for a thermoplastic substrate comprising:
(A) about 20 to about 50 weight percent of a flexible component comprising at least one diacrylate ester selected from the following: 1 ,4-cyclohexanedimethanol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipolypropylene glycol diacrylate, tripolypropylene glycol diacrylate, 1 ,4-butanediol diacrylate, 1 ,3-propanediol diacrylate, 2,2-dimethyl-l ,3-propanediol diacrylate, 1 ,6-hexanediol diacrylate, and pentaerythritol diacrylate;
(B) about 1 5 to about 40 weight percent of an aromatic component comprising at least one bisphenol A epoxy diacrylate;
(C) about 5 to about 20 weight percent of at least one aliphatic urethane acrylate comprising the residues of at least one polyhydroxy compound selected from the following: trimethylolpropane, glycerol, pentaerythritol, and dipentaerythritol; and
(D) about 5 to about 25 weight percent of at least one multifunctional acrylate selected from the following: trimethylolpropane triacrylate,
ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrγlate, dipentaerythritol hexaacrylate, propoxylated trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate; wherein the weight percentages are based on the total weight of the composition, excluding any additives. The coating composition also may comprise additives such as, for example, UV absorbers and hindered amine light stabilizers (abbreviated herein as "HALS") to impart additional weatherability and UV stability.
[Para 8] The novel coating compositions of the present invention may be used advantageously on a wide range of thermoplastic substrates such as, for example, polyesters, polyamides, polycarbonates, cellulosics, and polyolefins, polysulfones, polyacetals, polyimides, and polyketones. The coating composition can be used to coat a shaped article, such as, for example, a sheet, film, bottle, tube, or profile, prepared from one or more thermoplastic polymers. The shaped article may contain one or more layers. In one aspect of the invention, for example, the shaped article comprises a polyester comprising diacid residues which comprise at least 95 mole percent of the residues of terephthalic acid and diol residues which comprise about 10 to about 40 mole percent of the residues of 1 ,4- cyclohexanedimethanol, about 1 to about 25 mole percent of the residues of diethylene glycol, and about 35 to about 89 mole percent of the residues
ethylene glycol. The coated article has enhanced resistance to abrasion and chemicals, excellent clarity, and toughness. Because the coating composition of the invention may be cured by radiation, thermoplastic articles can be cured quickly and at a temperature below the heat deflection temperature of the substrate.
DESCRIPTION OF THE INVENTION
[Para 9] The present invention provides a coating composition for thermoplastic substrates that has enhanced resistance to abrasion and chemical resistance, without compromising other properties such as toughness and clarity. By utilizing radiation to cure these coatings, it is possible to initiate and complete curing in a short period of time while maintaining a temperature well below the heat deflection temperature of the substrate. In a general embodiment, therefore, the instant invention provides a coating composition for a thermoplastic substrate, comprising: (A) about 10 to about 60 weight percent of at least one flexible component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol selected from aliphatic diols containing 3 to 18 carbon atoms, polyalkylene ether glycols containing 3 to 50 carbon atoms, and cycloaliphatic diols containing about 4 to 18 carbon atoms;
(B) about 10 to about 60 weight percent of at least one aromatic component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol having a backbone comprising at least one residue of a bisphenol; and
(C) at least one urethane acrylate; wherein the substituted diols contain 1 to 8 substituents independently selected from halo, hydroxy, oxo, Ci-Cio alky], C2-C10 alkenyl, Ce-Cio aryl, and Ci-Cio alkoxy, and the composition has a weight ratio of flexible component :aromatic component of about 1 :3 to about 3:1 . The above weight percentages are based upon the total weight of the composition excluding any additives.
[Para 10] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth 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, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range
specifically and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1 , 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1 .5, 2.3, 4.57, 6.1 1 3, etc., and the endpoints 0 and 10. Also, a range associated with chemical substituent groups such as, for example, "Ci to Cs hydrocarbons", is intended to specifically include and disclose Ci and Cs hydrocarbons as well as C2, C3, and C4 hydrocarbons. [Para 1 1] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
[Para 12] Unless indicated otherwise, the weight percentages of the polymerizable monomers and oligomers of the coating composition, as used herein with respect to the written description and the claims, are based upon the total weight of the coating composition and exclude the weight of any additives. The term "additives", as used herein, is intended to have its plain meaning as understood by persons of ordinary skill in the art, that is, a substance introduced into the coating composition or applied to its surface in order to modify or enhance a specific performance characteristic but is not incorporated into the base coating composition by copolymerization
with the other coating monomers or oligomers. Representative examples of additives include photoinitiators; slip agents; pigments, leveling agents; wetting agents; adhesion promoters; dispersion aids; anti-blocking agents; anti-caking agents; binders; curing agents; deaerators; diluents; dryers; emulsifiers; fillers; flatting agents; flow control agents; gloss agents; hardeners; lubricants; plasticizers; solvents; stabilizers; surfactants; viscosity modifiers; UV stabilizers; UV absorbers; water repellants, and the like. [Para 13] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include their plural referents unless the context clearly dictates otherwise. For example, reference a "polymer," or a "shaped article," is intended to include the processing or making of a plurality of polymers, or articles. References to a composition containing or including "an" ingredient or "a" polymer is intended to include other ingredients or other polymers, respectively, in addition to the one named. [Para 14] The terms "comprising" or "containing" or "including" are understood to mean that at least the named compound, element, particle, or method step, etc., is present in the composition or article or method, but does not exclude the presence of other compounds, catalysts, materials, particles, method steps, etc, even if the other such compounds, material, particles, method steps, etc., have the same function as what is named, unless expressly excluded in the claims.
[Para 1 5] It is also understood that the mention of one or more method steps does not preclude the presence of additional method steps before or after the combined recited steps or intervening method steps between those steps expressly identified. Moreover, the lettering of process steps or ingredients is a convenient means for identifying discrete activities or ingredients and the recited lettering can be arranged in any sequence, unless otherwise indicated.
[Para 16] The coating composition of the invention comprises about 10 to about 60 weight percent, based on the total weight of the composition, excluding any additives, of at least one flexible component. The flexible component can comprise at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol selected from aliphatic diols containing 3 to 18 carbon atoms, polyalkylene ether glycols containing 3 to 50 carbon atoms, and cycloaliphatic diols containing about 4 to 18 carbon atoms. The substituted diols typically may comprise from 1 to 8 substituents independently selected from halo, hydroxy, oxo, Ci-Cio alkyl, C.2-C.10 alkenyl, CΘ-CIO aryl, and Ci-Cio alkoxy. Representative examples of esters that can be used as the flexible component include, but are not limited to, at least one diacrylate or dimethacrylate ester of diethylene glycol; 1 ,2-propanediol; dipropylene glycol; 1 ,3-propanediol; 2,2-dimethyl- 1 ,3-propanediol; 1 ,3-butanediol; decamethylene glycol; 1 ,4-butanediol; 1 ,5-pentanediol; 1 ,6-hexanediol; polyethylene glycol; polypropylene glycol;
2,2,4-trimethyl-l ,6-hexanedioI; thiodiethanol; 1 ,3-cycIohexanedimethanol; 1 ,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; triethylene glycol; trimethylolpropane; tripropylene glycol; polycaprolactone diol; polyether polyols having a molecular weight up to about 3000; tetraethylene glycol; 2,2-bis(4-hydroxycyclohexyl)propane; and alkoxide adducts thereof. The diacrylate esters of the cycloaliphatic diols, i.e., 1 ,3- and 1 ,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-l ,3- cyclobutanediol, can be present as the pure cis or trans isomer or as a mixture of cis or trans isomers. In one embodiment, for example, the flexible component can comprise at least one diacrylate ester selected from 1 ,4-cyclohexane-dimethanol diacrylate; ethylene glycol diacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; polyethylene glycol diacrylate; polypropylene glycol diacrylate; dipolypropylene glycol diacrylate; trimethylolpropane diacrylate; ethoxylated trimethylolpropane diacrylate; propoxylated trimethylolpropane diacrylate; propoxylated neopentyl glycol diacrylate; ethoxylated neopentyl glycol diacrylate; tripolypropylene glycol diacrylate; 1 ,4-butanediol diacrylate; 1 ,3-propanediol diacrylate; 2,2- dimethyl-1 ,3-propanediol diacrylate; 1 ,6-hexanedio! diacrylate; and pentaerythritol diacrylate. In another example, the flexible component comprises 1 ,6-hexanediol diacrylate (abbreviated herein as "HDDA"). These acrylates are known to persons skilled in the art and some of them are
commercially available, for example, under the trade designations SR238, SR306, and SR9003, available from the Sartomer Company. [Para 1 7] The coating composition also comprises about 10 to about 60 weight, based on the total weight of the composition excluding any additives, of at least one aromatic component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol having a backbone comprising at least one residue of a bisphenol. The substituted diols may contain from 1 to 8 substituents independently selected from halo, hydroxy, oxo, Ci-Cio alkyl, C2-C10 alkenyl, Cβ-Cio aryl, and Ci-Cio alkoxy. The term "bisphenol", as used herein, is understood to mean any methylenediphenol, i.e., HOCeH4CHbCeHUOH, such as, for example, /7,/7-methylenediphenol, and their substitution products, which are generally derived from condensation of two equivalent amounts of a phenol with an aldehyde or ketone. The term "residue", as used herein, means any organic structure incorporated into a polymer, oligomer, monomer, ester, or plasticizer that originates from a chemical building block. Thus, for example, the bisphenol residue can be a bisphenol A residue originating from the reaction of bisphenol A with epichlorohydrin to produce the diglycidyl ether of bisphenol A , which may be reacted further with acrylic acid to produce a bisphenol A epoxy acrylate. In addition to bisphenol A (4,4'-isopropylidenediphenol), examples of bisphenols include, but are not limited to bisphenol (p,p-
methylenediphenol), bisphenol F (a mixture of 2,2'-, 2,4'-, and 4,4'- dihydroxydiphenylmethane), and bisphenol S (4,4'- dihydroxydiphenylsulfone).
[Para 18] For example, the aromatic component (B) may comprise at least one compound selected from bisphenol A epoxy diacrylates and diacrylate esters of ethoxylated bisphenol, propoxylated bisphenol, ethoxylated bisphenol A, propoxylated bisphenol A, ethoxylated bisphenol F, propoxylated bisphenol F, ethoxylated bisphenol S, and propoxylated bisphenol S. These materials are typically prepared by condensing a bisphenol with one or more equivalents of ethylene or propylene oxide to form an adduct followed by esterification with acrylic acid, methacrylic acid, their corresponding acid chlorides, or anhydrides. These compounds are known to persons skilled in the art and many are commercially available such as, for example, under the trade designations CD540, SR602, and SR349 from Sartomer Company.
[Para 19] The term "bisphenol epoxy acrylate", as used herein, means a compound prepared typically by reacting a diglycidyl ether of a bisphenol with acrylic acid, methacrylic acid or the anhydride of acrylic acid or methacrylic acid. These glycidyl ethers may be oligomerized to form epoxy resins or further modified with diols, diacids, alkylene oxides such as, for example, ethylene oxide or propylene oxide, and then functionalized with acrylic or methacrylic acid, to produce diacrylate or dimethacrylate esters
having a range of functionality, hydrophilicity, molecular weights, and viscosities. Bisphenσl epoxy acrylates typically do not have any free epoxy groups left from their synthesis but react through their acrylate ester end groups. Typically, the bisphenol epoxy acrylates of the present invention have molecular weights ranging from about 400 to about 1 500, but higher or lower molecular weights can be used depending upon the specific coating formulation. These acrylates are well known to persons having ordinary skill in the art and many of them are commercially available. Commercial examples of such compounds include NOVACURE® 3701 , EBECRYL® 3500, EBECRYL® 600 (available from UCB Chemicals), and CNI 1 7 and CNl 1 5 (available from Sartomer Company).
[Para 20] For example, the aromatic component can comprise a bisphenol A epoxy diacrylate modified with at least one alkylene glycol or polyalkylene glycol containing 4 to 20 carbon atoms, one or more aliphatic dicarboxylic acids containing 2 to 20 carbon atoms, or a mixture thereof. In another example, the modified bisphenol epoxy diacrylate comprises the residues at least one aliphatic dicarboxylic acid containing 4 to 8 carbon atoms and propylene glycol. In yet another embodiment, the aromatic component of invention comprises a bisphenol A epoxy diacrylate having the formula:
wherein R is a radical having the formula:
This material is available commercially from UBC Chemicals under the trade designation EBECRYL®3500.
[Para 21] The novel coating composition of the invention also comprises at least one urethane acrylate. For example, the coating composition of the present invention can comprise about 1 to about 25 weight percent or, or in another example, about 5 to about 20 weight percent of the urethane acrylate, based on the total weight of the composition excluding any additives. Urethanes acrylates are diacrylate esters of hydroxy terminated isocyanate extended polyesters or polyethers. Urethane acrylates and meth acrylate s are known to the person skilled in the art and can be prepared according to known procedures, for example, by reacting a hydroxy- terminated polyurethane with acrylic acid or methacrylic acid, or by reacting
an isocyanate-terminated prepolymer with hydroxyalkyl acrylates or methacrylates. Examples of commercially available urethane acrylates include those known under the trade designations UVITHANE 782, available from Morton Thiokol Chemical, EBECRYL® 6600, EBECRYL® 8400, and EBECRYL® 8805, available from UCB Chemicals.
[Para 22] The urethane acrylate can be an aliphatic urethane acrylate. The term "aliphatic urethane acrylate", as used herein, is intended to have its commonly understood meaning in the art, that of a urethane acrylate prepared from an aliphatic diisocyanate or polyisocyanate, i.e., an diisocyanate in which the isocyanate groups are connected by a aliphatic backbone. In one embodiment, for example, the aliphatic urethane acrylate comprises the residues of at least one polyhydroxy compound selected from trimethylolpropane, glycerol, pentaerythritol, and dipentaerythritol. It is also possible to use one or more hexafunctional urethane acrylates and methacrylates wherein the term "hexafunctional" is understood to mean the acrylate comprises oligomers having 6 acrylate ester groups. Examples of commercially available aliphatic urethane acrylates which can be used in the instant invention include, but are not limited to: EBECRYL® 230, an aliphatic urethane; EBECRYL® 244, an aliphatic urethane & 10% 1 ,6-hexanediol diacrylate; EBECRYL®265, an aliphatic urethane & 25% tripropyleneglycol diacrylate; EBECRYL®270, an aliphatic urethane; EBECRYL® 285, an aliphatic urethane & 25% tripropyleneglycol diacrylate; EBECRYL® 4830, an aliphatic
urethane & 10% tetraethyleneglycol diacrylate; EBECRYL® 4833, an aliphatic urethane & 10% N-vinyl-2-pyrrolidone; EBECRYL® 4834, an aliphatic urethane & 10% N-vinyl-2-pyrrolidone; EBECRYL® 4881 , an aliphatic urethane & 10% tetraethyleneglycol diacrylate; EBECRYL® 4883, an aliphatic urethane & 15% tripropyleneglycol diacrylate; EBECRYL® 8803-20R, an aliphatic urethane & 20% tripropyleneglycol diacrylate & 8% 2-(2- ethoxyethoxy)ethyl acrylate; EBECRYL®! 290, and EBECRYL® 8803. These products are available from UCB Chemicals. [Para 23] Typically, the flexible component (A) and the aromatic component (B) are each present in the coating composition at about 1 5 weight percent to about 55 weight percent based on the total weight of the composition excluding any additives. In another example, the coating composition can comprise about 20 weight percent to about 50 weight percent each of the flexible component (A) and aromatic component (B). The ratio by weight of the flexible component to the aromatic component desirably can be from about 1 :3 to about 3:1. In another example, the weight ratio of the flexible: aromatic component can be about 1 :2 to about 2:1 . In yet another example the weight ratio can be from about 1 :1.5 to about 1 .5:1.
[Para 24] To enhance crosslinking and hardness of the cured coating, the inventive coating composition may further comprise at least one multifunctional acrylate having 3 or more acrylate ester groups. Non-
limiting examples of multifunctional acrylates include trimethylolpropane triacrylate, ethoxyiated or propoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxyiated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, ethoxyiated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxyiated pentaerythritol tetraacrylate, propoxylated dipentaerythritol hexaacrylate, ethoxyiated dipentaerythritol hexaacrylate, and propoxylated dipentaerythritol hexaacrylate. In one embodiment, for example, the multifunctional acrylate comprises at least one ethoxyiated trimethylolpropane triacrylate containing 3 to 20 ethoxy groups. [Para 25] The coating composition also may comprise various additives as needed to alter or enhance certain properties such as, for example, to improve weatherability, components to improve abrasion resistance, additives to enhance appearance, and materials to improve toughness and mechanical properties. Examples of additives that may be used in the coating composition of the present invention include, but are not limited to, photoinitiators; slip agents; leveling agents; wetting agents; adhesion promoters; anti-absorption agents; anti-foaming agents, such as, for example, mixtures of foam destroying polymers and polysiloxanes; accelerators; pigment dispersion aids; anti-blocking agents; anti-caking agents; anti-slip agents; anti-skinning agents; anti-static agents; anti- stripping agents; binders; curing agents; deaerators; diluents; dispersants;
dryers; ernulsifiers; fillers; flatting agents; flow control agents; gloss agents; hardeners; lubricants; mar resistance aids; whiteners; plasticizers; solvents; stabilizers; surfactants; viscosity modifiers; UV stabilizers; UV absorbers; and water repellants. For example, the coating composition may further comprise finely divided Siθ2, AI2O3, Zrθ2, or TiO∑ dispersed therein. These materials can modify the viscosity of the coating such that it may be applied easily and can enhance the abrasion resistance of the cured coating. As an example, the Siθ2 may comprise amorphous silica particles having an average surface area of 50 m2/g, and an average particle size of 40 μm. In another example, the Siθ2 can be a colloidal silica.
[Para 26] While curing or polymerization of the coating composition of the invention can be achieved thermally, it is advantageous to cure the coating composition by radiation. It is understood by those skilled in the art that radiation curable coatings, although primarily cured by radiation energy, also may be cured or their cure accelerated by heating. Curing may be initiated by any source of ionizing radiation capable of producing free radicals, including gamma radiation, infrared, microwave, but more typically by electron beam or ultraviolet radiation. In one embodiment, for example, the coating composition is cured by exposure to ultraviolet radiation, typically in the 200-400 nm wavelength range. When polymerization is initiated by ultraviolet radiation, the coating composition will typically include a photoinitiator in accordance with known practices for UV curable
compositions. Exemplary photoinitiators include, but are not limited to, those selected from organic peroxides, azo compounds, quinones, oc- hydroxy ketones, benzophenones, nitroso compounds, acyl halides, hydrazones, mercapto compounds, pyrylium compounds, triacylimidazoles, bisimidazoles, chloroalkyltriazines, benzoin ethers, benzil ketals, thioxanthones, and acetophenone derivatives, and mixtures thereof. Some additional, representative examples of photoinitiators that may be used in the coating composition of the invention include one or more compounds selected from the following: 2,2-dimethoxy-l ,2-diphenyl-1 -ethanone; 2- hydroxy-2-methylpropiophenone; benzoin methyl ether; benzoin ethyl ether; benzoin isopropyl ether; benzoin phenyl ether; benzoin acetate; acetophenone; 2,2-dimethoxyacetophenone; 4-(phenylthio)acetophenone; 1 ,1 -dichloroacetophenone; benzil; benzil dimethyl ketal; benzil diethyl ketal; 2- methyl-anthraquinone; 2-ethylanthraquinone; 2- tertbutylanthraquinone; 1 - chloroanthraquinone; 2-amylanthraquinone; 2,4,6- trimethylbenzoyldiphenylphosphine oxide; benzophenone; 4,4'- bis(N,N'-dimethylamino)benzophenone; thioxanthones; 1 -phenyl-! ,2- propanedione-2-O-benzoyloxime; 1 -aminophenyl ketones; 1 - hydroxycyclohexyl phenyl ketone; phenyl (l -hydroxyisopropyl)ketone, 4- isopropylphenyl(l -hydroxyisopropyl)ketone; and chloroalkyl -S-triazines. Further examples of commercially available photoinitiators which may be used include 1 -hydrocyclohexyl phenyl ketone (IRGACURE® 184, available
from Ciba Specialty Chemicals), 2-hydroxy-2-methylpropiophenone (DAROCUR® 1 1 73, available from Ciba Specialty Chemicals), and 2,2- dichloro-l -(4-phenoxyphenyl) ethanone, and the like. When a photoinitiator is used, it is typically present from about 0.1 to about 5 weight percent based on the total weight of the coating composition. In another example the photoinitiator is present from about 0.5 to about 5 weight percent, based on the total weight of the composition.
[Para 27] Another embodiment of the invention is a coating composition for a thermoplastic substrate, comprising:
(A) about 20 to about 50 weight percent of a flexible component comprising at least one diacrylate ester selected from the following: 1 ,4-cyclohexanedimethanol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1 ,4-butanediol diacrylate,
1 ,3-propanediol diacrylate, 2,2-dimethyl-l ,3-propanediol diacrylate, 1 ,6-hexanediol diacrylate, and pentaerythritol diacrylate;
(B) about 1 5 to about 40 weight percent of an aromatic component comprising at least one bisphenol A epoxy diacrylate;
(C) about 5 to about 20 weight percent of at least one aliphatic urethane acrylate comprising the residues of at least one polyhydroxy
compound selected from the following: trimethylol propane, glycerol, pentaerythritol, and dipentaerythritol; and
(D) about 5 to about 25 weight percent of at least one multifunctional acrylate selected from the following: trimethylolpropane triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, propoxylated trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate; wherein the weight percentages are based on the total weight of the composition excluding any additives. The various aspects of the flexible component, aromatic component, urethane acrylate, multifunctional acrylates, additives, and photoinitiators are as described hereinabove. For example, in one embodiment, the composition can comprise (A) about 20 to about 40 weight percent of a flexible component comprising dipropylene glycol diacrylate and 1 ,6-hexanediol diacrylate; (B) about 1 5 to about 40 weight percent of a bisphenol A epoxy acrylate modified with at least one alkylene glycol or polyalkylene glycol containing 4 to 20 carbon atoms, one or more aliphatic dicarboxylic acids containing 4 to 20 carbon atoms, or a mixture thereof; (C) about 5 to about 1 5 weight percent of at least one aliphatic urethane acrylate comprising the residues of pentaerythritol; and (D) about 5 to about 20 weight percent of a multifunctional acrylate comprising ethoxylated trimethylolpropane triacrylate containing 3 to 20
ethoxy groups. In one embodiment, as described previously, the modified bisphenol A can have the formula:
[Para 28] . In another example, the composition may further comprise a photoinitiator. Typical examples of photoinitiator levels are about 0.1 to about 5 weight percent, or preferably, about 0.5 to about 5 weight percent, based on the total weight of the composition. The coating composition also may further comprise S1O2 dispersed therein. [Para 29] Although not critical to the invention, one or more light stabilizers, such as UV absorbers and reversible radical scavengers such as, for example, hindered amine ("HALS") or hindered phenol light stabilizers also may be added to the coating composition to enhance weatherability and
inhibit yellowing. Such UV absorbers and light stabilizers are known to persons skilled in the art and many are commercially available. While not limiting, the hindered amine light stabilizers can have a high molecular weight such as, for example, those compounds having an N-substituted piperidinol nucleus and generally having a weight average molecular weight of about 400 to about 10,000 or, preferably, about 500 to about 5,000. Such hindered amine light stabilizers include high-molecular weight esters prepared from butanetetracarboxylic acid and an N-substituted piperidinol. The amount of the light stabilizer, while varying according to the kind, generally ranges from about 0.5 to about 5 weight percent, based on the total weight of the coating composition. Further examples of weight percentage ranges for the light stabilizer are about 0.6 to about 4 weight percent and about 0.7 to about 3 weight percent. Examples of commercially available hindered amine light stabilizers that can be used in the invention include, but are not limited to: CYASORB™ UV-3529 (available from Cytec Industries), TINUVIN™ 770 (available from Ciba Specialty Chemicals), TINUVIN™ 1 23 (available from Ciba Specialty Chemicals), CHIMASSORB™ 1 19 (available from Ciba Specialty Chemicals), LOWILITE™ 76 (available from Great Lakes Chemical Corp.), MARK™ LA 52 (available from Asahi Denka Co., Ltd.), MARK™ LA 62 (available from Asahi Denka Co., Ltd.), GOODRITE™ UV- 31 59 (available from BF Goodrich Chemical Co.), MARK™ LA-63 (available from Adeca Argus), MARK™ LA-62 (available from Adeca Argus), and
TINUVIN®-622LD (available from Ciba-Geigy Oapan) Ltd.). Additional examples hindered amine light stabilizers that can be used are listed in the Plastic Additives Handbook 5th Edition (Hanser Gardner Publications, Inc., Cincinnati, OH, USA, 2001 ).
[Para 30] Typically, one or more UV absorbers may be added in an amount of about 0.5 to about 1 0 weight percent, preferably about 0.7 to about 9 weight percent, still preferably about 1 to about 8 weight percent, based on the total weight of the coating composition. Representative UV absorbers that can be added to the coating composition of the invention include, but are not limited to, one or more compounds having a maximum absorption in the range of 290-400 nm with a minimal absorbance between 400 and 700 nm. For example, UV absorbers of cyanoacrylate type, benzotriazole type, aromatic triazine type, benzoxazinone type, benzophenone type, salicylic acid type, or hydroquinone type can be used. Representative benzotriazole UV absorbers include, but are not limited to, 2-(3,5~di-t-butyl-2- hydroxyphenyl)benzo-triazole, 2-[2-hydroxy~3,5- bis(alpha,alpha- dimethylbenzyl)phenyl]-2H-benzotriazole, and 2— (3,5— di- t-amyl-2- hydroxyphenyl]-benzotriazole. Examples of benzophenone UV absorbers include, but are not limited to, 2- hydroxy-4- octyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4- methoxy-2'-carboxybenzophenone. Examples of salicylic acid UV absorbers include, but are not limited to, phenyl salicylate, p-octylphenyl salicylate,
resorcinol monobenzoate, and 4-t-butylphenyl salicylate. Examples of cyanoacrylate UV absorbers include ethyl 2-cyano~3,3-diphenylacrylate and 2-ethylhexyl~2-cyano-3,3- diphenylacrylate. Examples of commercially availabe UV absorbers include, but are not limited to, CYASORB™ UV-1 164 (available from Cytec Industries) and TINUVIN™ 1 577 (available from Ciba Specialty Chemicals).
[Para 31] The present invention also provides a shaped article comprising the coating compositions described hereinabove, applied to at least one surface thereof, and cured by exposure to ultraviolet or electron beam radiation. The shaped article such as, for example, a sheet, film, tube, bottle, or profile, may be produced by extrusion, calendering, thermoforming, blow-molding, injection molding, casting, tentering, or blowing. The shaped article may comprise one or more layers. [Para 32] Typically, the shaped article will comprise at least one thermoplastic polymer selected from the following: polyester, polyamide, polycarbonate, cellulosic, polyolefin, polysulfone, polyacetal, polyimide, polyketone, polyvinyl chloride, polystyrene, polylactic acid, copolymers thereof, and blends thereof. The term "thermoplastic" as used herein with respect to the polymers of the shaped articles, it intended have its commonly understood meaning in the art, that is a property of a polymer wherein the polymer softens when exposed to heat and returns to its original condition when cooled to room temperature. In one example, the
shaped article may comprise one or more polyesters such as, for example, poly(ethylene terephthalate), poly(butylene terephthalate), polyO ,3~ trimethylene terephthalate), poly(cyclohexylene terephthalate). In addition to the polyesters noted above, the shaped articles of the invention may include polyesters from the condensation one of more aromatic diacids with one or more diols. The term "polyester", as used herein, is intended to include "copolyesters" and is understood to mean a synthetic polymer prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional hydroxyl compounds. Typically the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as, for example, glycols and diols. Alternatively, the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxy substituents such as, for example, hydroquinone. Thus, the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. As used herein, therefore, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester.
[Para 33] The polyesters of present invention comprise dicarboxylic acid residues, diol residues, and repeating units. A "repeating unit", as used herein, means an organic structure having a dicarboxylic acid and a diol residue bonded through a carbonyloxy group. The polyesters of the present invention are prepared from the reaction of one or more diols with one or more dicarboxylic acids and contain substantially equal molar proportions of acid residues (100 mole%) and diol residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 30 mole% isophthalic acid, based on the total acid residues, means the polyester contains 30 mole% isophthalic acid out of a total of 100 mole% acid residues. Thus, there are 30 moles of isophthalic acid among every 100 moles of acid residues. In another example, a polyester containing 30 mole% ethylene glycol, based on the total diol residues, means the polyester contains 30 mole% ethylene glycol out of a total of 100 mole% diol residues. Thus, there are 30 moles of ethylene glycol among every 100 moles of diol residues. In a third example, a polyester containing 30 mole% of a monomer, which may be a dicarboxylic acid, a diol, or hydroxycarboxylic acid, based on the total repeating units, means that the polyester contains 30 mole% monomer out of a total of 100
mole% repeating units. Thus, there are 30 moles of monomer residues among every 100 moles of repeating units.
[Para 34] Examples of polyesters include those comprising (i) diacid residues comprising at least 80 mole percent, based on the total moles of diacid residues, of the residues of one or more dicarboxylic acids selected from: terephthalic acid, naphthalenedicarboxylic acid, 1 ,4- cyclohexanedicarboxylic acid, and isophthalic acid; and (ii) diol residues comprising 3 to 1 00 mole percent, based on the total moles of diol residues, of the residues of one or more diols selected from: 1 ,4- cyclohexanedimethanol, neopentyl glycol, and diethylene glycol; and 0 to 97 mole percent of one or more residues selected from: ethylene glycol, 1 ,2- propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 ,8-octanediol, 2,2,4-trimethyl-l ,3-pentanediol, 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol, 1 ,3-cyclohexanedimethanol, bisphenol A, and polyalkylene glycol. The 1 ,3- and 1 ,4-cycIohexanedimethanol, and 2,2,4,4-tetramethyl-l ,3-cyclobutanediol may be used as a pure c/s or trans isomer or as a mixture of c/s and trans isomers. The polyesters generally will have inherent viscosity (I. V.) values in the range of about 0.5 dL/g to about 1 .4 dL/g. Additional examples of I.V. ranges include about 0.65 dL/g to about 1.0 dL/g and about 0.65 dL/g to about 0.85 dL/g. The inherent viscosity is measured at 250C using 0.25 gram of polymer per 50 mL of a solvent composed of 60 weight percent phenol and 40 weight percent
tetrachloroethane. Typically, these copolyesters have a glass transition temperature between about 350C and about 1 5O0C. [Para 35] In one example, the shaped article can comprise a polyester having diacid residues comprising at least 95 mole percent of the residues of terephthalic acid and diol residues comprising about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol, about 1 to about 25 mole percent of the residues of diethylene glycol, and about 35 to about 89 mole percent of the residues ethylene glycol. In another example, the diacid residues can comprise from about 60 to 100 mole percent terephthalic acid and 0 to about 40 mole percent isophthalic acid. [Para 36] The polyesters of the present invention are prepared by procedures known to persons skilled in the art. For example, the polyesters of the instant invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, and the appropriate diol or diol mixtures using typical polycondensation reaction conditions. They may be made by continuous, semi-continuous, and batch modes of operation and may utilize a variety of reactor types such as, for example, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors. The reaction of the diol and dicarboxylic acid may be carried out using conventional polyester polymerization conditions or by melt phase processes, but those with sufficient crystallinity may be made by melt phase condensation followed by solid phase polycondensation techniques. For
example, when preparing the polyester by means of an ester interchange reaction, i.e., from the ester form of the dicarboxylic acid components, the reaction process may comprise two steps. In the first step, the diol component and the dicarboxylic acid component, such as, for example, dimethyl terephthalate, are reacted at elevated temperatures. Thereafter, the reaction product is heated under higher temperatures and under reduced pressure to form the polyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system. This second step, or polycondensation step, is continued under higher vacuum and temperatures until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained. The reaction rates of both stages are increased by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like. A three-stage manufacturing procedure, similar to that described in U.S. Patent No. 5,290,631 , may also be used, particularly when a mixed monomer feed of acids and esters is employed. In the preparation of polyester by direct esterification, i.e., from the acid form of the dicarboxylic acid component, polyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components.
[Para 37] To ensure that the reaction of the diol component and dicarboxylic acid component by an ester interchange reaction is driven to completion, it is sometimes desirable to employ about 1 .05 to about 2.5 moles of diol component to one mole dicarboxylic acid component. Persons of skill in the art will understand, however, that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction process occurs.
[Para 38] The cured coating composition of the present invention show excellent abrasion resistance and excellent resistance to methyl ethyl ketone (abbreviated herein as "MEK") yet while maintaining a ductile mode of failure in a reverse-sided, instrumented impact test. For example, the shaped article can be a sheet or film having the coating composition of the invention coated and cured thereon. Typically, this sheet or film will have a haze value of 20% or less after 100 cycles in accordance with ASTM procedure Dl 044. In another example, the sheet or film can exhibit a haze value of 1 5% or less after 100 cycles in accordance with ASTM procedure Dl 044. The shaped article also can exhibit excellent chemical and solvent resistance as exemplified after 300 methyl ethyl ketone double rubs in accordance with ASTM Procedure D3732.
[Para 39] The present invention also provides a method of coating a shaped article comprising applying the coating compositions described hereinabove to a surface of a shaped article and exposing the coated surface
to radiation. The coating compositions are prepared by mixing the appropriate monomers, resins and additives in the desired proportions described above. Coating can be achieved by conventional techniques, including dipping, spraying, curtain coating, gravure and roll coating. The application methods are conventional and may be selected depending upon the nature of the substrate, desired thickness, and other factors. In one embodiment of the invention, for example, the coating is applied by using conventional gravure or roll coating techniques which produce thin coatings. Multiple coating layers may be applied to the substrate in a conventional manner as described above. For example, each respective coating layer may be applied individually to the substrate and cured prior to application of the next coating layer.
[Para 40] As described hereinabove, the coating composition may be cured by thermal means, by radiation, or a combination thereof. Typically, conventional radiation curing techniques are employed in the present invention using any source of radiation capable of initiating photochemical reactions such as, for example, ultraviolet or electron beam radiation. [Para 41 ] Potential commercial applications of the coating composition of the invention include a variety of areas where the appearance of the plastic form or object is an important factor in its selection in use. These include flat sheet applications in areas such as building and construction, transportation, laminates, graphic arts, EILT (Encapsulated Image Layer
Technology), appliances, point of purchase displays, sports, and recreation. In other application areas the coating can be applied and cured after an object has been molded such as, for example, in ophthalmic and cosmetic applications. The invention is further illustrated and described by the following examples.
EXAMPLES
[Para 42] Example J - A uniform mixture of materials was prepared using the materials listed in Table 1 . The weight percentages are calculated based on the total weight of the composition excluding the weight of any additives (e.g., SiO2 and the DAROCUR photoinitiator).
Table 1
[Para 43] NANOCRYL® XP 21 /0768, available from Hanse Chemie, was specified by the manufacturer as containing 50 wt% SiO2 dispersed in a 50
wt% 1 ,6-hexanediol diacrylate ("HDDA") matrix. Ethoxylated trimethylolpropane triacrylate, EBECRYL® 3500, and EBECRYL® 1 290 are available from UCB Chemicals. DAROCUR® 1 1 73 is available from Ciba Specialty Chemicals. EBECRYL® 3500 was described by UCB Chemicals as a low viscosity difunctional, modified bisphenol-A epoxy acrylate. EBECRYL® 1 290 was described by UCB Chemicals as a hexafunctional aliphatic urethane acrylate with an acrylated polyol diluent. The DAROCUR® 1 1 73 initiator was described as 2-hydroxy-2-methylpropiophenone. [Para 44] The components of the formulation were each weighed out in an opaque NALGENE® container. The formulation was then mixed by placing the container for at least 2 hours on a roller which was located in a heated chamber at a temperature of approximately 550C. The container was then placed on a roller in the laboratory and allowed to roll overnight to insure that the formulation was well mixed. The coatings were applied to 1 /8 inch thick sheet prepared from a 70:30 (by weight) polyesterpolycarbonate blend. The polyester component of the blend contained about 100 mole% terephthalic acid, 62 mole% 1 ,4-cyclohexanedimethanol, and 38 mole% ethylene glycol. The coatings were applied using the RK automated draw down machine (Print-Coat Instruments, Ltd., England). A wire-wound rod with a very fine wound spring was used to draw a coating of approximately 5 microns wet film thickness. The speed of draw was set at "4".
[Para 45] The coated substrates were cured by passing them through a Fusion Model HP-6 High Power Six-Inch Ultraviolet Lamp System, using a belt speed of 24 ft/min and a power setting of 70% (of 500 Watts) with the "H" bulb to provide a dose of 1 .1 J/cm2. Before each use, the machine was characterized with a radiometer, a UV Power Puck™ (available from EIT Instruments). The Power Puck™ measures the total UV dosage Qoules/cm2) and the peak UV intensity (watts/cm2) for four UV ranges (UV-A: 320-390 nm, UV-B: 280-320 nm, UV-C: 250-260 nm, and UV-V: 395-445 nm). The following total peak UV readings were observed for the settings used in this experiment: UV-A 1 .6, UV-B 1 .5, UV-C 0.18, and UV-V 1 .1. [Para 46] Evaluation of the coatings - Initial Coating Characterization. The degree of cure of the coatings were verified to be acceptable using a Kδnig Hardness test (ASTM D 4366). A crosshatched adhesion test was carried out according to ASTM D3359. The coating is scored with a razor knife 1 1 times horizontally and 1 1 times vertically (creating 100 squares). Next, a piece of masking tape is adhered to the scored surface and then removed. The percent adhesion is then determined by counting the number of squares which remain adhered to the substrate. Example 1 showed 100% adhesion to polyester substrate.
[Para 47] Chemical resistance . The MEK Double Rub test was conducted on an instrument where the head of a ball peen hammer is covered with 16 folds of cheesecloth saturated in MEK. The covered hammer head was
rubbed 50 times over the surface of the coated sample. The instrument was then stopped, the coating was examined, and the cheesecloth was re- saturated with MEK. After the completion of 300 rubs, the test was complete. The Example 1 coating tested in the MEK Double Rub test remained intact for 300 rubs, exemplary of excellent chemical resistance. [Para 48] Abrasion Resistance - The Taber Abrasion Test ASTM Dl 044 was conducted for each of the acrylic coatings applied to the polyester sheet to analyze its resistance to abrasion. This test is generally accepted and recognized as a standard method for characterizing the ability of coated plastic sheet to resist scratching and abrasion. When this test is used for this purpose, the percent haze of a plastic sheet is usually measured over a range of 0 to 500 abrasive cycles, with a total weight of 500 grams on CS- 1 OF type wheels. A lower level of haze is indicative of greater resistance to abrasion.
[Para 49] For each coating, three replicates were run. Each coated panel was divided into quarters, to define a specific region for each of four haze measurements. After an initial measurement of haze, the panels were subjected to a specific number of abrasion cycles followed by a haze determination. To map out the dependence of the haze level on the number of abrasive cycles for each sample, this process was repeated until the panels have undergone a total of 500 cycles of abrasion. The Taber Abrasion results for the coated polyester sheet samples are presented in the Table 2:
Table 2
[Para 50] Toughness and ductility - To test the ductility and toughness of each coated sheet sample, a reverse sided instrumented impact test was employed using ASTM Method D-3763. A reverse sided configuration was utilized, with the coated side placed down, away from the side being impacted by the falling tup. In this manner, the coating was placed in tension during failure. This sample orientation results in a more accurate assessment of whether the presence of the coating on the surface of the sheet will cause a brittle or ductile failure when in use. In the instrumented impact test, the tup was weighted with a mass of 26.202 kg and was released from a height of 0.756 m. 5 samples were tested for example 1 : all 5 samples exhibited ductile failure with an average fracture energy of 41 .9 ft. lbs.
[Para 51 ] Examples 2, 3, 4, and 5: Examples 2, 3, 4, and 5 were prepared, coated, cured, and analyzed as described in Example 1 . The composition of these examples is described in Table 3. As described in Example 1 , the weight percentages of the polymerizable monomers and oligomers, which are provided in parentheses, are calculated based on the total weight of the
composition excluding the weight of any additives, e.g., Siθ2 and the photoinitiator. The weight percent values for NANOCRYL® XP 21 /0768, therefore, represent only the 1 ,6-hexanediol diacrylate component; the SiC-2 component of NANOCRYL® XP 21 /0768 was not included in the weight percentage calculations. Similarly, the weight of the DAROCUR® 1 1 73 photoinitiator also was excluded from the weight percentage calculations.
Table 3
[Para 52] Hexanediol diacrylate was obtained from the UCB Chemicals Group. The Taber Abrasion results for Examples 2 - 5 are presented in Table 4.
Table 4: Taber Abrasion Results
Cycles Example 2 Example 3 Example 4 Example 5
0 0.69 0.66 0.77 0.24
50 1 .24 1 .34 1 .50 1 .41
1 00 1 .46 1 .61 1 .83 1 .83
200 1 .76 1 .98 2.26 2.55
500 2.31 2.49 2.86 3.53
[Para 53] The reverse sided instrumented impact analysis for Examples 2 - 5 showed ductile behavior for all of the samples tested for each Example. The fracture energy averaged 35.4, 31 .0, 36.1 , and 33.9 ft. lbs., respectively, for Examples 2, 3, 4, and 5. The coatings for Examples 2 - 5 tested in the MEK Double Rub test remained intact for 300 rubs, thus showing excellent chemical resistance.
[Para 54] Examples 6 -16: Examples 6 - 1 6 were prepared, coated, cured, and analyzed as described in Example 1 . The weight percentages of the coating components, presented in Table 5, were calculated based on the total weight of the composition and included the weight of the DAROCUR®! 1 73 photoinitiator.
[Para 55] Dipropylene glycol diacrylate available from UCB Chemicals. The coatings prepared in examples 6 - 1 6 were tested in the MEK Double Rub test as described in example 1 . Each of the coatings tested remained intact for 300 rubs, thus showing excellent chemical resistance. The Taber Abrasion results for Examples 6 - 1 6 are presented in Table 6:
Table 6
[Para 56] The coated samples for Examples 6 - 1 6 were tested in the reverse sided instrumented impact study as described in Example 1 . For each of the Examples which exhibited 100% ductile failure, the average fracture energy was calculated. The results to this evaluation are presented in Table 7:
Table 7
[Para 57] Example 17: Example 1 7 was prepared, coated, and cured in a manner identical to Example 5 except that the following stabilizing additives were added to the formulation: 2 weight% TΪNUVIN® 400 and 1 weight% TINUVIN® 123 (available from Ciba Specialty Chemicals). The weight percentages were based on the total weight of the coating composition. These additives, while compatible with the UV cure, improved the weatherability of the coating composition. The weatherability analysis was conducted on a QUV-SE Weathering Tester model QUV/se from Q-Panel Lab
Products according to the ASTM method UVA-340 Gl 54 Cycle 1 . The weathering results from samples of this coating are presented in Table 8:
Table 8
[Para 58] The b* values were obtained from testing performed on a
HunterLab UltraScan Sphere 8000 running Hunter's Universal software. The default testing conditions are D65 (daylight, 6500 0 K), Large Area View (I " diameter), Reflectance Mode, Specular Included, and 10 ° observer.
Applicable ASTM methods include: o E 1 164 - Obtaining Spectrophotometric Data for Object-Color
Evaluation o E 308 - Computing the Colors of Objects by Using the CIE System.
(This method covers the calculations for going from spectra and CIE
standard observer and CIE standard illuminant to colorimetric property values like CIE L*, a*, b*.) o D 2244 - Calculation of Color Differences o E 31 3 - Yellowness and Whiteness Index
[Para 59] Comparative Examples I to 4: Comparative Examples 1 - 4 were prepared, coated, cured, and analyzed as described in Example 1 . These coatings utilized Example 5 as the starting composition for analyzing the effect of varying the concentration of either HDDA or of EBECRYL®3500 on the coating properties. The composition of these examples is presented in Table 9. The weight percentages are based on the total weight of the coating composition and include the weight of DAROCUR® 1 173 photoinitiator.
Table 9
[Para 60] The reverse sided instrumented impact results for Comparative Examples 1 - 4 are presented in Table 1 1 :
Table 1 1
[Para 61] In the MEK double rub test, the coatings of Comparative Examples 2 and 3 remained intact for 300 cycles of rubbing. The coatings of Comparative Examples 1 and 4, however, failed after 100 cycles. In comparison with Example 5, none of Comparative Examples 1 -4 pass both the MEK double rub test and the reverse sided impact test.
Claims
What is claimed is:
[Clai m 1 ] A coating composition for a thermoplastic substrate, comprising:
(A) about 1 0 to about 60 weight percent of at least one flexible component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol selected from aliphatic diols containing 3 to about 1 8 carbon atoms, polyalkylene ether glycols containing 3 to 50 carbon atoms, and cycloaliphatic diols containing about 4 to about 18 carbon atoms;
(B) about 1 0 to about 60 weight percent of at least one aromatic component comprising at least one diacrylate or dimethacrylate ester of a substituted or unsubstituted, linear or branched, diol having a backbone comprising at least one residue of a bisphenol; and
(C) at least one urethane acrylate; wherein said substituted diols contain 1 to 8 substituents independently selected from halo, hydroxy, oxo, Ci-Cio alkyl, C2-C10 alkenyl, C.6-C10 aryl, and Ci-Cio alkoxy, said composition has a weight ratio of flexible component :aromatic component of about 1 :3 to about 3:1 , and said weight percentages are based upon the total weight of said composition excluding any additives.
[Claim 2] The composition according to claim 1 which is curable by radiation.
[Claim 3] The composition according to claim 2 wherein said radiation comprises ultraviolet or electron beam radiation.
[Claim 4] The composition according to claim 1 which comprises about 15 weight percent to about 55 weight percent each of said flexible component (A) and aromatic component (B).
[Claim 5] The composition according to claim 4 which comprises about 20 weight percent to about 50 weight percent each of said flexible component (A) and aromatic component (B).
[Claim 6] The composition according to claim 1 wherein said weight ratio is about 1 :2 to about 2:1.
[Claim 7] The composition according to claim 1 wherein said weight ratio is about 1 :1.5 to about 1.5:1.
[Claim 8] The composition according to claim 3 wherein said flexible component (A) comprises at least one diacrylate or dimethacrylate ester of at least one diol selected from the following: diethylene glycol; 1 ,2- propanediol; dipropylene glycol; 1 ,3-propanediol; 2,2-dimethyl-l ,3- propanediol; 1 ,3-butanediol; decamethylene glycol; 1 ,4-butanediol; 1 ,5- pentanediol; 1 ,6-hexanediol; polyethylene glycol; polypropylene glycol; 2,2,4-trimethyl-l ,6-hexanediol; thiodiethanol; 1 ,3-cyclohexanedimethanol; 1 ,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; triethylene glycol; trimethylolpropane; tripropylene glycol; polycaprolactone diol; polyether polyols having a molecular weight of up to about 3000; tetraethylene glycol; 2,2-bis(4-hydroxycyclohexyl)propane; and alkoxide adducts thereof.
[Claim 9] The composition according to claim 8 wherein said flexible component (A) comprises at least one diacrylate ester selected from the following: 1 ,4-cyclohexane-dimethanol diacrylate; ethylene glycol diacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; polyethylene glycol diacrylate; polypropylene glycol diacrylate; dipolypropylene glycol diacrylate; trimethylolpropane diacrylate; ethoxylated trimethylolpropane diacrylate; propoxylated trimethylolpropane diacrylate; propoxylated neopentyl glycol diacrylate; ethoxylated neopentyl glycol diacrylate; tripolypropylene glycol diacrylate; tripolypropylene glycol diacrylate; 1 ,4-butanediol diacrylate; 1 ,3-propanediol diacrylate; 2,2- dimethyl-1 ,3-propanediol diacrylate; 1 ,6-hexanediol diacrylate; and pentaerythritol diacrylate.
[Claim 1 0] The composition according to claim 9 wherein said flexible component (A) comprises 1 ,6-hexanediol diacrylate.
[Claim 1 1 ] The composition according to claim 1 wherein said bisphenol comprises at least one compound selected from the following: bisphenol, bisphenol A, bisphenol F, and bisphenol S.
[Claim 1 2] The composition according to claim 1 1 wherein said aromatic component (B) comprises at least one compound selected from bisphenol A epoxy diacrylates and diacrylate esters of ethoxylated bisphenol, propoxylated bisphenol, ethoxylated bisphenol A, propoxylated bisphenol A, ethoxylated bisphenol F, propoxylated bisphenol F, ethoxylated bisphenol S, and propoxylated bisphenol S.
[Claim 1 3] The composition according to claim 12 wherein said aromatic component (B) comprises at least one bisphenol A epoxy diacrylate modified with at least one alkylene glycol or polyalkylene glycol containing 4 to 20 carbon atoms, one or more aliphatic dicarboxylic acids containing 2 to 20 carbon atoms, or a mixture thereof.
[Claim 1 4] The composition according to claim 13 wherein said modified bisphenol A epoxy diacrylate comprises residues of at least one aliphatic dicarboxylic acid containing 4 to 8 carbon atoms and propylene glycol.
[Claim 1 5] The composition according to claim 14 wherein said bisphenol A epoxy diacrylate has the formula:
[Claim 1 6] The composition according to claim 1 which comprises about 1 to about 25 weight percent of said urethane acrylate.
[Claim 1 7] The composition according to claim 16 which comprises about 5 to about 20 weight percent of said urethane acrylate.
[Claim 1 8] The composition according to claim 16 wherein said urethane acrylate is an aliphatic urethane acrylate.
[Claim 1 9] The composition according to claim 1 8 wherein said aliphatic urethane acrylate comprises residues of at least one polyhydroxy compound selected from the following: trimethylolpropane, glycerol, pentaerythritol, and dipentaerythritol.
[Claim 20] The composition according to claim 19 wherein said aliphatic urethane acrylate comprises at least one hexafunctional aliphatic urethane acrylate.
[Claim 21 ] The composition according to claim 1 7 which further comprises at least one multifunctional acrylate selected from the following: trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate, and propoxylated dipentaerythritol hexaacrylate.
[Claim 22] The composition according to claim 21 wherein said multifunctional acrylate comprises at least one ethoxylated trimethylolpropane triacrylate containing 3 to 20 ethoxy groups.
[Claim 23] The composition according to claim 1 which further comprises SiO2 dispersed therein.
[Claim 24] The composition according to claim 2 which further comprises at least one photoinitiator selected from the following: 2,2-dimethoxy-l ,2- diphenyl-1 -ethanone; 2-hydroxy-2-methylpropiophenone; benzoin methyl ether; benzoin ethyl ether; benzoin isopropyl ether; benzoin phenyl ether; benzoin acetate; acetophenone; 2,2-dimethoxyacetophenone; 4- (phenylthio)acetophenone; 1 ,1 -dichloroacetophenone; benzil; benzil dimethyl ketal; benzil diethyl ketal; 2- methylanthraquinone; 2- ethylanthraquinone; 2-tertbutylanthraquinone; 1 - chloroanthraquinone; 2- amylanthraquinone; 2,4,6- trimethylbenzoyldiphenylphosphine oxide; benzophenone; 4,4'-bis(N,N'-dimethylamino)benzophenone; thioxanthones; 1 -phenyl-! ,2~propanedione-2-O-benzoyloxime; 1 -aminophenyl ketones; 1 -hydroxycyclohexyl phenyl ketone; phenyl (l -hydroxyisopropyl)ketone; 4- isopropylphenyl(l -hydroxyisopropyl)ketone; and chloroalkyl-S-triazines.
[Clai m 25] The composition according to claim 24 wherein said photoinitiator comprises 2-hydroxy-2-methylpropiophenone.
[Claim 26] A coating composition for a thermoplastic substrate according to claim 1 , comprising:
(A) about 20 to about 50 weight percent of a flexible component comprising at least one diacrylate ester selected from the following: 1 ,4-cyclohexanedimethanol diacrylate, ethylene glycol diacryiate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipolypropylene glycol diacrylate, tripolypropylene glycol diacrylate, 1 ,4-butanediol diacrylate, 1 ,3-propanediol diacrylate, 2,2-dimethyl-l ,3-propanediol diacrylate, 1 ,6-hexanediol diacrylate, and pentaerythritol diacrylate;
(B) about 1 5 to about 40 weight percent of an aromatic component comprising at least one bisphenol A epoxy diacrylate;
(C) about 5 to about 20 weight percent of at least one aliphatic urethane acrylate comprising the residues of at least one polyhydroxy compound selected from the following: trimethylolpropane, glycerol, pentaerythritol, and dipentaerythritol; and (D) about 5 to about 25 weight percent of at least one multifunctional acrylate selected from the following: trimethylolpropane triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, propoxylated trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate; wherein said weight percentages are based on the total weight of said composition excluding any additives.
[Claim 27] The composition according to claim 26 further comprising at least one photoinitiator.
[Claim 28] The composition according to claim 27 which comprises
(A) about 20 to about 40 weight percent of a flexible component comprising dipropylene glycol diacrylate and 1 ,6-hexanediol di acrylate;
(B) about 1 5 to about 40 weight percent of a bisphenol A epoxy acrylate modified with at least one alkylene glycol or polyalkylene glycol containing 4 to 20 carbon atoms, one or more aliphatic dicarboxylic acids containing 4 to 20 carbon atoms, or a mixture thereof
(C) about 5 to about 1 5 weight percent of at least one aliphatic urethane acrylate comprising the residues of pentaerythritol; and (D) about 5 to about 20 weight percent of a multifunctional acrylate comprising ethoxylated trimethylolpropane triacrylate containing 3 to 20 ethoxy groups.
[Claim 29] The composition according to claim 28 further comprising S1O2 dispersed therein.
[Clai m 30] The composition according to claim 29 wherein said modified bisphenol epoxy acrylate has the formula:
[Claim 31 ] The composition according to claim 30 further comprising a UV absorber or hindered amine light stabilizer.
[Claim 32] A shaped article comprising the composition of claim 27 applied to at least one surface thereof and cured by exposure to ultraviolet or electron beam radiation.
[Claim 33] The shaped article according to claim 32 which comprises at least one thermoplastic polymer selected from the following: polyester, polyamide, polycarbonate, cellulosic, polyolefin, polysulfone, polyacetal, polyimide, polyketone, polylactic acid, copolymers thereof, and blends thereof.
[Claim 34] The shaped article according to claim 33 which comprises one or more layers.
[Claim 35] The shaped article according to claim 33 wherein said thermoplastic polymer comprises at least one polyester.
[Claim 36] The shaped article according to claim 35 wherein said polyester comprises one or more polyesters selected from the following: poly(ethylene terephthalate), poly(butylene terephthalate), polyO ,3-trimethylene terephthalate), and poly(cyclohexylene terephthalate).
[Claim 37] The shaped article according to claim 35 where said polyester comprises
(i) diacid residues comprising at least 80 mole percent, based on the total moles of diacid residues, of the residues of one or more dicarboxylic acids selected from: terephthalic acid, naphthalenedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, and isophthalic acid; and
(ii) diol residues comprising about 3 to about 100 mole percent, based on the total moles of diol residues, of the residues of one or more diols selected from 1 ,4-cyclohexanedimethanol, neopentyl glycol, and diethylene glycol; and 0 to 97 mole percent of the residues of one or more of diols selected from: ethylene glycol; 1 ,2-propanediol; 1 ,3- propanediol; 1 ,4-butanediol; 1 ,5-pentanediol; 1 ,6-hexanediol; 1 ,8- octanediol; 2,2,4-trimethyl-l ,3-pentanediol; 2,2,4,4-tetramethyl- 1 ,3-cyclo-butanediol; 1 ,3-cyclohexanedimethanol; bisphenol A; and polyalkylene glycol.
[Claim 38] The shaped article according to claim 37 wherein said diacid residues comprise at least 95 mole percent of the residues of terephthalic acid; said the diol residues comprise about 1 0 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol, about 1 to about 25 mole percent of the residues of diethylene glycol, and about 35 to about 89 mole percent of the residues ethylene glycol.
[Claim 39] The shaped article according to claim 38 wherein said diacid residues comprise from about 60 to about 100 mole percent terephthalic acid and 0 to about 40 mole percent isophthalic acid.
[Claim 40] The shaped article according to claim 37 wherein said article is produced by extrusion, calendering, thermoforming, blow-molding, injection molding, casting, tentering, or blowing.
[Claim 41 ] The shaped article according to claim 40 wherein article is a sheet, film, tube, bottle, or profile.
[Claim 42] The shaped article according to claim 41 which is a film or sheet having a haze value of 20% or less after 100 cycles in accordance with ASTM procedure Dl 044.
[Claim 43] The shaped article of claim 42 which exhibits a haze value of 1 5% or less after 100 cycles in accordance with ASTM procedure Dl 044.
[Clai m 44] The shaped article of claim 43 which exhibits solvent resistance after 300 methyl ethyl ketone double rubs in accordance with ASTM Procedure D3732.
[Clai m 45] A method of coating a shaped article comprising applying the coating composition of claim 28 to a surface of a shaped article and exposing said surface to radiation.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008516967A JP2008546872A (en) | 2005-06-16 | 2006-06-12 | Abrasion resistant coating |
EP20060772849 EP1891169A1 (en) | 2005-06-16 | 2006-06-12 | Abrasion resistant coatings |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/160,267 US7375144B2 (en) | 2005-06-16 | 2005-06-16 | Abrasion resistant coatings |
US11/160,267 | 2005-06-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006138198A1 true WO2006138198A1 (en) | 2006-12-28 |
Family
ID=37084699
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2006/022704 WO2006138198A1 (en) | 2005-06-16 | 2006-06-12 | Abrasion resistant coatings |
Country Status (5)
Country | Link |
---|---|
US (1) | US7375144B2 (en) |
EP (1) | EP1891169A1 (en) |
JP (1) | JP2008546872A (en) |
CN (1) | CN101198659A (en) |
WO (1) | WO2006138198A1 (en) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7375144B2 (en) | 2005-06-16 | 2008-05-20 | Eastman Chemical Company | Abrasion resistant coatings |
WO2009086301A1 (en) * | 2007-12-27 | 2009-07-09 | Baxter International Inc. | Radiation curable coatings |
WO2010090715A1 (en) * | 2009-02-06 | 2010-08-12 | Eastman Chemical Company | Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol |
WO2010100051A1 (en) * | 2009-03-04 | 2010-09-10 | Basf Se | Radiation curable coating compounds comprising diacrylate |
US8168721B2 (en) | 2009-02-06 | 2012-05-01 | Eastman Chemical Company | Coating compositions containing tetramethyl cyclobutanediol |
FR2972633A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
FR2972632A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
FR2972636A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
FR2972634A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
FR2972635A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
US8324316B2 (en) | 2009-02-06 | 2012-12-04 | Eastman Chemical Company | Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom |
US9029461B2 (en) | 2009-02-06 | 2015-05-12 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
US9029460B2 (en) | 2009-02-06 | 2015-05-12 | Stacey James Marsh | Coating compositions containing acrylic and aliphatic polyester blends |
US9487619B2 (en) | 2014-10-27 | 2016-11-08 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
WO2017031298A1 (en) * | 2015-08-19 | 2017-02-23 | 3M Innovative Properties Company | Composite article and methods of making the same |
WO2017031294A1 (en) * | 2015-08-19 | 2017-02-23 | 3M Innovative Properties Company | Composite article including a multilayer barrier assembly and methods of making the same |
US9598602B2 (en) | 2014-11-13 | 2017-03-21 | Eastman Chemical Company | Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds |
US9650539B2 (en) | 2014-10-27 | 2017-05-16 | Eastman Chemical Company | Thermosetting compositions based on unsaturated polyesters and phenolic resins |
EP2401337B1 (en) * | 2009-02-27 | 2018-05-09 | PPG Industries Ohio, Inc. | Biomass derived radiation curable liquid coatings |
US9988553B2 (en) | 2016-02-22 | 2018-06-05 | Eastman Chemical Company | Thermosetting coating compositions |
US10011737B2 (en) | 2016-03-23 | 2018-07-03 | Eastman Chemical Company | Curable polyester polyols and their use in thermosetting soft feel coating formulations |
US10526444B2 (en) | 2015-09-25 | 2020-01-07 | Eastman Chemical Company | Polymers containing cyclobutanediol and 2,2-bis(hydroxymethyl)alkylcarboxylic acid |
US10676565B2 (en) | 2015-05-19 | 2020-06-09 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
US11584113B2 (en) | 2015-08-19 | 2023-02-21 | 3M Innovative Properties Company | Composite article including a multilayer barrier assembly and methods of making the same |
Families Citing this family (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7956154B2 (en) * | 2005-09-27 | 2011-06-07 | Dow Global Technologies Llc | Polymers incorporating 1,3 and 1,4 cyclohexanedimethanol |
WO2007084297A2 (en) | 2006-01-12 | 2007-07-26 | 3M Innovative Properties Company | Light-collimating film |
ZA200806228B (en) * | 2006-02-03 | 2009-11-25 | Dow Global Technologies Inc | 1,3/1,4-cyclohexane dimethanol based monomers and polymers |
US20080176972A1 (en) * | 2007-01-19 | 2008-07-24 | David Hews | Radiation cured elastomeric urethane acrylate films and the process for making same |
JP2010516888A (en) * | 2007-01-31 | 2010-05-20 | ダウ グローバル テクノロジーズ インコーポレイティド | Polyester coil coating composition |
DE102007028601A1 (en) | 2007-06-19 | 2008-12-24 | Evonik Röhm Gmbh | Reactive mixture for coating moldings by means of reaction injection molding and coated molding |
US7883092B2 (en) * | 2007-12-31 | 2011-02-08 | Scientific Games International, Inc. | Energy cured coating |
US20090181242A1 (en) | 2008-01-11 | 2009-07-16 | Enniss James P | Exterior window film |
US20100003523A1 (en) * | 2008-07-02 | 2010-01-07 | Sabic Innovative Plastics Ip B.V. | Coated Film for Insert Mold Decoration, Methods for Using the Same, and Articles Made Thereby |
KR101363783B1 (en) * | 2008-11-14 | 2014-02-17 | 엘지디스플레이 주식회사 | Photosensitive resin composition for imprinting process and method of forming organic layer over substrate |
EP2389420B1 (en) * | 2009-01-26 | 2014-04-30 | Sun Chemical Corporation | Uv curable ink for a plastic glazing system |
EP2228414A1 (en) | 2009-03-13 | 2010-09-15 | Bayer MaterialScience AG | UV-curable, wear resistant and antistatic coating filled with carbon nanotubes |
KR101548791B1 (en) * | 2009-09-25 | 2015-08-31 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Photosensitive resin composition for resist material, and photosensitive resin laminate |
KR101134383B1 (en) * | 2009-11-27 | 2012-04-09 | 현대자동차주식회사 | Coating agent for Poly?methyl methacrylate?pannel nano imprinting having superior anti-light reflection |
WO2011143519A1 (en) * | 2010-05-13 | 2011-11-17 | Pennsylvania College Of Technology | Bio-derived polymers having improved processability and method for the production thereof |
AU2011250831A1 (en) * | 2010-12-03 | 2012-06-21 | Bayer Intellectual Property Gmbh | Security and/or valuable documents with a top layer with a scratch-resistant finish |
KR20120061758A (en) * | 2010-12-03 | 2012-06-13 | 바이엘 머티리얼사이언스 아게 | Security and?or Valuable Documents With a Top Layer With a Scratch-resistant Finish |
US8999509B2 (en) * | 2011-04-27 | 2015-04-07 | Cpfilms Inc. | Weather resistant exterior film composite |
RU2458953C1 (en) * | 2011-06-30 | 2012-08-20 | Государственное образовательное учреждение высшего профессионального образования "Московский государственный университет инженерной экологии" (ГОУ ВПО "МГУИЭ") | Photopolymeric acrylic oligomer-oligomer composition, wear-resistant coating on organic glass for glasing elements of buildings, structures and vehicles based thereon and method of producing wear-resistant coating |
US10000588B2 (en) * | 2011-07-28 | 2018-06-19 | Eastman Chemical Company | Coating for the inner surface of plastic bottles for protection against degradation from volatile organic compounds |
KR101168073B1 (en) * | 2011-09-28 | 2012-07-24 | 이성권 | Photocuring hard-coating composition and high hardness sheet employing the same |
TWI446609B (en) | 2011-11-15 | 2014-07-21 | Ind Tech Res Inst | Dye sensitized solar cell |
KR101389967B1 (en) * | 2012-05-31 | 2014-04-30 | 주식회사 엘지화학 | Method of preparing of hard coating film |
KR101379491B1 (en) | 2012-05-31 | 2014-04-01 | 주식회사 엘지화학 | Hard coating film and method of preparing of hard coating film |
KR101501686B1 (en) | 2012-05-31 | 2015-03-11 | 주식회사 엘지화학 | Hard coating film |
US9446562B2 (en) | 2012-06-22 | 2016-09-20 | Sabic Global Technologies B.V. | Coated film for insert mold decoration, methods for using the same, and articles made thereby |
KR101470465B1 (en) | 2012-08-23 | 2014-12-08 | 주식회사 엘지화학 | Hard coating film |
EP2912121B1 (en) | 2012-10-29 | 2019-09-25 | Ariste Medical, LLC | Polymer coating compositions and coated products |
FR2998789B1 (en) | 2012-12-05 | 2015-01-16 | Oreal | METHOD FOR MAKING NAILS WITH PHOTORETICULABLE VARNISH COMPOSITIONS |
FR2998784B1 (en) | 2012-12-05 | 2015-02-13 | Oreal | HIGH-GLOSS PHOTORETICULAR COSMETIC COMPOSITION |
FR2998788B1 (en) | 2012-12-05 | 2015-01-16 | Oreal | NEW PHOTORETICULABLE VARNISH COMPOSITIONS AS BASE LAYER |
FR2998790B1 (en) | 2012-12-05 | 2015-01-09 | Oreal | PHOTORETICULABLE COMPOSITION FOR NAIL MAKE-UP |
FR2998791B1 (en) | 2012-12-05 | 2015-01-16 | Oreal | METHOD FOR MAKING NAILS WITH PHOTORETICULABLE VARNISH COMPOSITIONS |
FR2998797B1 (en) | 2012-12-05 | 2015-02-13 | Oreal | PHOTORETICULATE COSMETIC COMPOSITION NOT COLLAPSIBLE |
JP5629025B2 (en) * | 2013-01-23 | 2014-11-19 | デクセリアルズ株式会社 | Hydrophilic laminate, and production method thereof, antifouling laminate, article, production method thereof, and antifouling method |
KR101540657B1 (en) | 2013-05-31 | 2015-07-30 | 주식회사 케이씨씨 | Photocurable coating composition and molded article comprisng a cured coating layer formed from the same |
KR102326487B1 (en) * | 2013-09-24 | 2021-11-15 | 소마아루 가부시끼가이샤 | A Coating Composition and A Hard Coating Film Using The Same |
KR101686567B1 (en) * | 2013-10-23 | 2016-12-14 | 제일모직 주식회사 | Photosensitive resin composition and light blocking layer using the same |
FR3013975B1 (en) | 2013-12-04 | 2015-11-20 | Oreal | PHOTORETICULABLE VARNISH COMPOSITIONS AND METHODS OF APPLICATION |
TWI665087B (en) * | 2014-02-19 | 2019-07-11 | 荷蘭商薩比克全球科技公司 | Multilayer sheet, methods for making and using the same, and articles comprising the multilayer sheet |
AU2015249769A1 (en) | 2014-04-22 | 2016-11-10 | Ariste Medical, Llc. | Methods and processes for application of drug delivery polymeric coatings |
US9820931B2 (en) | 2014-10-13 | 2017-11-21 | L'oreal | Latex nail compositions having low amounts of photo-initiator |
US9636293B2 (en) | 2014-10-13 | 2017-05-02 | L'oréal | Latex nail compositions having low amounts of photo-initiator |
US9649272B2 (en) | 2014-10-13 | 2017-05-16 | L'oréal | Latex nail compositions having low amounts of photo-initiator |
KR101974615B1 (en) * | 2014-10-29 | 2019-05-02 | 나노-디멘션 테크놀로지스, 엘티디. | Suspension polymerization compositions, methods and use thereof |
JP6654348B2 (en) * | 2015-02-05 | 2020-02-26 | 株式会社ブリヂストン | Laminate and conductive roller |
US20160289979A1 (en) * | 2015-04-03 | 2016-10-06 | Armstrong World Industries, Inc. | Scratch resistant coating composition with a combination of hard particles |
US10822811B2 (en) * | 2015-04-03 | 2020-11-03 | Armstrong World Industries, Inc. | Scratch resistant coating |
ES2957658T3 (en) * | 2016-07-26 | 2024-01-23 | Ppg Ind Ohio Inc | Polyurethane coating compositions containing 1,1-diactivated vinyl compounds and related coatings and processes |
CN110791081B (en) * | 2019-10-09 | 2022-05-13 | 浙江闪铸三维科技有限公司 | Preparation method of elastic photosensitive resin for 3D printing |
CN112831268B (en) * | 2019-11-25 | 2022-07-12 | 万华化学集团股份有限公司 | Photo-curing water-based paint resin and preparation method thereof |
US20220389248A1 (en) * | 2021-05-25 | 2022-12-08 | Mighty Buildings, Inc. | Composition and production method for 3d printing construction material |
CN115304985A (en) * | 2022-08-15 | 2022-11-08 | 广东新纪源复合材料股份有限公司 | Acrylate wear-resistant anti-fouling coating and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5888649A (en) * | 1996-01-11 | 1999-03-30 | Avery Dennison Corporation | Radiation-curable release coating compositions |
EP1106627A1 (en) * | 1999-12-08 | 2001-06-13 | Ciba SC Holding AG | Novel phosphine oxide photoinitiator systems and curable compositions with low color |
Family Cites Families (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2890202A (en) * | 1953-07-20 | 1959-06-09 | Pittsburgh Plate Glass Co | Method of preparing acrylate esters of epoxy resins |
US3317465A (en) * | 1963-06-26 | 1967-05-02 | Robertson Co H H | Combination catalyst-inhibitor for betahydroxy carboxylic esters |
US3373221A (en) * | 1964-11-04 | 1968-03-12 | Shell Oil Co | Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates |
US3256226A (en) * | 1965-03-01 | 1966-06-14 | Robertson Co H H | Hydroxy polyether polyesters having terminal ethylenically unsaturated groups |
GB1301890A (en) | 1969-08-04 | 1973-01-04 | ||
US4065587A (en) * | 1976-05-11 | 1977-12-27 | Scm Corporation | U.V. Curable poly(ether-urethane) polyacrylates and wet-look polymers prepared therefrom |
JPS54129034A (en) | 1978-03-30 | 1979-10-06 | Kao Corp | Coating resin composition curable with actinic energy radiation |
US4308119A (en) * | 1979-02-21 | 1981-12-29 | Panelgraphic Corporation | Abrasion-resistant optical coating composition containing pentaerythritol based polyacrylates and cellulose esters |
JPS573875A (en) * | 1980-06-11 | 1982-01-09 | Tamura Kaken Kk | Photopolymerizable ink composition |
JPS57158235A (en) * | 1981-03-26 | 1982-09-30 | Toray Ind Inc | Plastic molding |
US4481093A (en) * | 1981-10-13 | 1984-11-06 | Desoto, Inc. | Ultraviolet curable basecoats for vacuum metallization |
US4416750A (en) * | 1981-10-13 | 1983-11-22 | Desoto, Inc. | Ultraviolet curable basecoats for vacuum metallization |
US4472019A (en) * | 1982-12-28 | 1984-09-18 | Desoto, Inc. | Topcoats for buffer-coated optical fiber using urethane acrylate and epoxy acrylate and vinyl monomer |
US4563438A (en) * | 1983-05-06 | 1986-01-07 | Ciba Geigy Corporation | Liquid mixture of photoinitiators |
JPS6020972A (en) | 1983-07-13 | 1985-02-02 | Matsushita Electric Ind Co Ltd | Coating composition |
DE3418282A1 (en) * | 1984-05-17 | 1985-11-21 | Hoechst Ag, 6230 Frankfurt | DECORATIVE PLATE WITH IMPROVED SURFACE PROPERTIES |
US4557980A (en) * | 1984-08-21 | 1985-12-10 | Martin Processing, Inc. | Radiation curable coating for film structure |
JPS6262832A (en) | 1985-09-14 | 1987-03-19 | Nissha Printing Co Ltd | Production of film having ultraviolet-curable coating layer |
JP2649799B2 (en) | 1987-04-06 | 1997-09-03 | 大日本印刷株式会社 | Hydrophilic film-forming composition, hydrophilic film thereof and method for producing the same |
EP0329791B1 (en) * | 1987-07-28 | 1995-01-11 | Nippon Kayaku Kabushiki Kaisha | Photosensitive resin composition and color filter |
US5213875A (en) * | 1987-09-30 | 1993-05-25 | Westinghouse Electric Corp. | UV conformal coatings |
JP2632874B2 (en) | 1987-10-20 | 1997-07-23 | 大日本印刷株式会社 | Decorative sheet |
FR2633217A1 (en) * | 1988-06-23 | 1989-12-29 | Tyerman David | PROCESS FOR MANUFACTURING A PROTECTIVE AND / OR DECORATIVE COATING MATERIAL AND COATING CARRIED OUT ACCORDING TO THIS PROCESS |
US5254395A (en) * | 1988-08-23 | 1993-10-19 | Thor Radiation Research, Inc. | Protective coating system for imparting resistance to abrasion, impact and solvents |
US5114783A (en) * | 1988-08-23 | 1992-05-19 | Thor Radiation Research, Inc. | Protective coating system for imparting resistance to abrasion, impact and solvents |
JPH02222902A (en) | 1988-11-07 | 1990-09-05 | Mitsubishi Rayon Co Ltd | Manufacture of lens sheet |
FR2649111B1 (en) * | 1989-06-29 | 1991-09-13 | Poudres & Explosifs Ste Nale | METHOD FOR MANUFACTURING RADIORETICULATING COATINGS, NEW RADIORETICULABLE COMPOSITIONS AND NEW CARBONATES |
EP0423713A3 (en) * | 1989-10-18 | 1991-12-18 | Takeda Chemical Industries, Ltd. | Photocurable adhesive and production of laminated articles using the same |
JPH03152181A (en) | 1989-11-09 | 1991-06-28 | Teijin Chem Ltd | Cloud-preventive composition |
DE3940898A1 (en) | 1989-12-11 | 1991-06-13 | Wilde Dental Gmbh | Hand-formable, light-curable sheet material - contains di- or tri- or poly-functional (meth)acrylate], mono- or di-functional urethane-acrylate oligomer, fillers, photoinitiators, etc. |
US5045572A (en) * | 1990-01-26 | 1991-09-03 | Gaf Chemicals Corporation | Radiation curable cross linkable compositions containing an aliphatic polyfunctional alkenyl ether |
US5492733A (en) * | 1990-03-05 | 1996-02-20 | International Paper Company | High gloss ultraviolet curable coating |
US5373033A (en) * | 1990-04-20 | 1994-12-13 | Sola International Holdings Limited | Casting composition |
JP2987887B2 (en) | 1990-06-29 | 1999-12-06 | 東洋紡績株式会社 | Radiation-curable resin composition |
DE59209143D1 (en) * | 1991-03-27 | 1998-02-26 | Ciba Geigy Ag | Photosensitive mixture based on acrylates |
EP0505737A1 (en) | 1991-03-27 | 1992-09-30 | General Electric Company | UV curable abrasion resistant coating compositions and method |
MX9201528A (en) | 1991-04-03 | 1992-10-01 | Red Spot Paint & Varnish | UV CURABLE MIXING COMPOSITIONS AND PROCESSES |
AU1997392A (en) * | 1991-05-15 | 1992-12-30 | Andrew A. Sokol | Finishing composition which is curable by uv light and method of using same |
US5183831A (en) * | 1991-08-22 | 1993-02-02 | Ciba-Geigy Corporation | Radiation curable composition with high temperature oil resistance |
EP0565044B1 (en) * | 1992-04-06 | 1999-03-10 | Mitsubishi Chemical Corporation | Ultraviolet-curing covering composition with hardwearing properties |
TW418346B (en) * | 1993-03-05 | 2001-01-11 | Ciba Sc Holding Ag | Photopolymerisable compositions containing tetraacrylates |
BE1006883A3 (en) | 1993-03-05 | 1995-01-17 | Solvay | Surface protection method for items made of thermoplastic material with asurface treatment |
JPH06270350A (en) | 1993-03-24 | 1994-09-27 | Sekisui Jushi Co Ltd | Surface-modified polycarbonate resin molded piece |
US5580647A (en) * | 1993-12-20 | 1996-12-03 | Minnesota Mining And Manufacturing Company | Abrasive articles incorporating addition polymerizable resins and reactive diluents |
US5883212A (en) * | 1996-05-08 | 1999-03-16 | Rexam Graphics, Inc. | Conductivity exaltation in radiation cured electrically conductive coatings |
DE19709467C1 (en) * | 1997-03-07 | 1998-10-15 | Basf Coatings Ag | Coating compositions and processes for producing multicoat paint systems |
US6228133B1 (en) * | 1998-05-01 | 2001-05-08 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
US6284835B1 (en) * | 1999-07-09 | 2001-09-04 | Lilly Industries, Inc. | High impact coatings |
US6265132B1 (en) * | 1999-10-20 | 2001-07-24 | Rohm And Haas Company | Photoimageable composition containing flexible oligomer |
US6268111B1 (en) * | 1999-10-20 | 2001-07-31 | Rohm And Haas Company | Photoimageable composition having photopolymerizeable binder oligomer |
US7375144B2 (en) | 2005-06-16 | 2008-05-20 | Eastman Chemical Company | Abrasion resistant coatings |
-
2005
- 2005-06-16 US US11/160,267 patent/US7375144B2/en not_active Expired - Fee Related
-
2006
- 2006-06-12 CN CNA2006800210639A patent/CN101198659A/en active Pending
- 2006-06-12 JP JP2008516967A patent/JP2008546872A/en not_active Withdrawn
- 2006-06-12 EP EP20060772849 patent/EP1891169A1/en not_active Withdrawn
- 2006-06-12 WO PCT/US2006/022704 patent/WO2006138198A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5888649A (en) * | 1996-01-11 | 1999-03-30 | Avery Dennison Corporation | Radiation-curable release coating compositions |
EP1106627A1 (en) * | 1999-12-08 | 2001-06-13 | Ciba SC Holding AG | Novel phosphine oxide photoinitiator systems and curable compositions with low color |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7375144B2 (en) | 2005-06-16 | 2008-05-20 | Eastman Chemical Company | Abrasion resistant coatings |
WO2009086301A1 (en) * | 2007-12-27 | 2009-07-09 | Baxter International Inc. | Radiation curable coatings |
US8324316B2 (en) | 2009-02-06 | 2012-12-04 | Eastman Chemical Company | Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom |
WO2010090715A1 (en) * | 2009-02-06 | 2010-08-12 | Eastman Chemical Company | Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol |
US8163850B2 (en) | 2009-02-06 | 2012-04-24 | Eastman Chemical Company | Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol |
US8168721B2 (en) | 2009-02-06 | 2012-05-01 | Eastman Chemical Company | Coating compositions containing tetramethyl cyclobutanediol |
US9029460B2 (en) | 2009-02-06 | 2015-05-12 | Stacey James Marsh | Coating compositions containing acrylic and aliphatic polyester blends |
US9029461B2 (en) | 2009-02-06 | 2015-05-12 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
US8524834B2 (en) | 2009-02-06 | 2013-09-03 | Eastman Chemical Company | Coating compositions containing tetramethyl cyclobutanediol |
US8519055B2 (en) | 2009-02-06 | 2013-08-27 | Eastman Chemical Company | Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol |
EP2401337B1 (en) * | 2009-02-27 | 2018-05-09 | PPG Industries Ohio, Inc. | Biomass derived radiation curable liquid coatings |
WO2010100051A1 (en) * | 2009-03-04 | 2010-09-10 | Basf Se | Radiation curable coating compounds comprising diacrylate |
FR2972636A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
FR2972634A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
WO2012130600A1 (en) * | 2011-03-15 | 2012-10-04 | L'oreal | Photo-crosslinkable nail varnishes free of unsaturated monomers |
WO2012130603A1 (en) * | 2011-03-15 | 2012-10-04 | L'oreal | Photo-crosslinkable nail varnishes free of unsaturated monomers |
WO2012130602A1 (en) * | 2011-03-15 | 2012-10-04 | L'oreal | Photo-crosslinkable nail varnishes free of unsaturated monomers |
WO2012130601A1 (en) * | 2011-03-15 | 2012-10-04 | L'oreal | Photo-crosslinkable nail varnishes free of unsaturated monomers |
FR2972635A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
FR2972633A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
FR2972632A1 (en) * | 2011-03-15 | 2012-09-21 | Oreal | PHOTORETICULABLE NAIL VARNISH EXEMPT FROM UNSATURATED MONOMERS |
WO2012130604A1 (en) * | 2011-03-15 | 2012-10-04 | L'oreal | Photo-crosslinkable nail varnishes free of unsaturated monomers |
US9487619B2 (en) | 2014-10-27 | 2016-11-08 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
US9650539B2 (en) | 2014-10-27 | 2017-05-16 | Eastman Chemical Company | Thermosetting compositions based on unsaturated polyesters and phenolic resins |
US9598602B2 (en) | 2014-11-13 | 2017-03-21 | Eastman Chemical Company | Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds |
US10676565B2 (en) | 2015-05-19 | 2020-06-09 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
WO2017031294A1 (en) * | 2015-08-19 | 2017-02-23 | 3M Innovative Properties Company | Composite article including a multilayer barrier assembly and methods of making the same |
KR101909426B1 (en) | 2015-08-19 | 2018-10-17 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Composite article and manufacturing method thereof |
WO2017031298A1 (en) * | 2015-08-19 | 2017-02-23 | 3M Innovative Properties Company | Composite article and methods of making the same |
US11584113B2 (en) | 2015-08-19 | 2023-02-21 | 3M Innovative Properties Company | Composite article including a multilayer barrier assembly and methods of making the same |
US11752749B2 (en) | 2015-08-19 | 2023-09-12 | 3M Innovative Properties Company | Composite article including a multilayer barrier assembly and methods of making the same |
US10526444B2 (en) | 2015-09-25 | 2020-01-07 | Eastman Chemical Company | Polymers containing cyclobutanediol and 2,2-bis(hydroxymethyl)alkylcarboxylic acid |
US9988553B2 (en) | 2016-02-22 | 2018-06-05 | Eastman Chemical Company | Thermosetting coating compositions |
US10011737B2 (en) | 2016-03-23 | 2018-07-03 | Eastman Chemical Company | Curable polyester polyols and their use in thermosetting soft feel coating formulations |
Also Published As
Publication number | Publication date |
---|---|
CN101198659A (en) | 2008-06-11 |
US7375144B2 (en) | 2008-05-20 |
EP1891169A1 (en) | 2008-02-27 |
US20060286383A1 (en) | 2006-12-21 |
JP2008546872A (en) | 2008-12-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7375144B2 (en) | Abrasion resistant coatings | |
US9109137B2 (en) | Radiation curable (meth) acrylated compounds | |
KR102329391B1 (en) | Photocurable resin composition, cured film formed of composition and base material with coating film, and method for producing cured film and base material with coating film | |
US9540310B2 (en) | Radiation curable (meth)acrylated compounds | |
US20130131268A1 (en) | Radiation curable liquid composition for low gloss coatings | |
EP1846526B1 (en) | Powder coatings | |
EP1355994A2 (en) | Radiation curable coating for thermoplastic substrates | |
WO2007125746A1 (en) | Active energy ray-curable coating composition and molded article having cured coating film of the composition | |
AU671254B2 (en) | UV curable blend compositions and processes | |
WO2003080745A1 (en) | Uv-curable coating composition and coated articles | |
US20070231577A1 (en) | Coatings for polycarbonate windows | |
JP4985560B2 (en) | Water and oil repellent wood building materials | |
JP5996560B2 (en) | Active energy ray-curable resin composition | |
RU2235108C1 (en) | Compositions based on emulsified ultraviolet-cured resins and employment thereof as varnish layer for floor and wall finishing | |
KR20200140295A (en) | Curable resin composition | |
EP3211049B1 (en) | Coating composition | |
JPH029614B2 (en) | ||
JP3660410B2 (en) | Emulsion coating composition | |
ES2691554T3 (en) | Water-based, soft-touch, radiation-polymerizable coatings | |
JPS62236832A (en) | Coating composition of excellent adhesion | |
JPH09111151A (en) | Emulsion coating composition | |
JP2798261B2 (en) | Ultraviolet-curable polycarbonate resin coating composition and method for producing plastic molded article having cured coating with modified surface properties | |
JP4256119B2 (en) | Light-shielding application film, UV curable adhesive film, and application method using the film | |
JPH04332767A (en) | Curable coating composition | |
JPH04117418A (en) | Urethane resin composition and coating material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200680021063.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2006772849 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2008516967 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |