COATING COMPOSITION AND METHOD OF COATING SUBSTRATES

Abstract: Coating compositions including (A) compounds of formula (I) wherein: R1 is a residue of an alpha-beta ethylenically unsaturated carboxylic acid; R2 is an alkylene group of 1-4 carbons or an alkoxylene group of 1-4 carbons; and n is an integer from 0 to 15; and (B) at least one dicarboxylic acid or anhydride, are provided, either in powder form, or as a solvent-borne coating composition in an organic solvent. The coating composition may also include acrylic and methacrylic monomers and/or styrenes. The coating resins provide excellent heat resistance and high temperature performance. Coated articles and methods of coating substrates with the resins are also provided.

Description: COATING COMPOSITION AND METHOD OF COATING SUBSTRATES. The invention relates to acrylic coating resins for use as coatings for rigid substrates which have excellent heat resistance and high temperature performance. Glycidyl methacrylate (GMA) acrylic powder coatings were introduced in the coatings industry in the 1970s, and are useful as protective coatings for metal. These thermoset, decorative powder coatings have recently found significant application in the automotive industry as primer surfacers, wheel coatings and as black-out coatings for automobile trim. Generally, GMA is polymerized with other monomers such as acrylates, methacrylates and other unsaturated monomers such as styrene and its derivatives. In most formulations, the crosslinker is a saturated aliphatic dicarboxylic acid. GMA powder, like other thermoset powder coatings is typically applied by electrostatic spraying, followed by curing at elevated temperature. Glycidyl methacrylate coatings are also available in solvent form and have application for coating metals and certain plastics, and are useful in industrial maintenance coatings. Conventional epoxy-functional (meth) acrylates, such as glycidyl methacrylate, have high volatility and toxicity. There is accordingly a need in the art to develop both solvent-borne and powder resin compositions with lower volatility and toxicity, as well as cured coatings exhibiting improved heat resistance and high temperature performance. According to WO 90 03987, a polyalicyclic acrylic acid ester derivative has been shown to be useful as a comonomer with an acrylic monomer in molding applications for optical materials. However, no formulations using polyalicyclic acrylic acid ester derivatives are known for solvent-borne or powder coatings . The invention is directed to a coating composition comprising : (A) a copolymerizable alpha-beta ethylenically unsaturated epoxide compound of formula (I) : wherein : - Ri is a residue of an alpha-beta ethylenically unsaturated carboxylic acid ; R 2 is an alkylene group having 1-4 carbons or an alkoxylene group having 1-4 carbons ; and n is an integer from 0 to 15 (which means n is 0 or an integer from 1 to 15) ; and (B) a crosslinker selected from the group of dicarboxylic acids and/or anhydrides or selected from the group of polyamides and/or polyamines. More particularly, the crosslinker (B) may be at least one dicarboxylic acid or anhydride or alternatively at least one compound selected from the group of polyamides and/or polyamines . The invention also includes compositions in a powder form, as well as solvent-borne coating resin compositions comprising a compound (A) of formula (I), a crosslinker (B) as defined above, and an organic solvent. The powder form and solvent-borne forms of the coating resin compositions may additionally contain comonomers such as acrylates, methacrylates and vinyl aromatic monomers, such as vinyl toluenes, styrene, styrene derivatives and the like, and mixtures of these co onomers . Further, the coating compositions may also contain dispersing aids, flow aids, pigments, catalysts and the like. The invention also comprises methods of coating substrates with the powder and solvent-borne compositions of the invention comprising the steps of a) applying said compositions to the substrate and b) curing the said compositions . The invention also comprises coated articles formed by coating substrates with the powder and solvent- borne compositions of the invention. More specifically, the invention also includes composition wherein the copolymerizable alpha-beta ethylenically unsaturated epoxide compound (A) is an epoxide-containing (meth) acrylate ester of formula (II) : wherein : - R 3 is a hydrogen or methyl group ; R 4 is an alkylene group of 1-4 carbons or an alkoxylene group of 1-4 carbons ; and n is an integer from 0 to 15. The invention further includes a method of coating a substrate comprising (a) applying a composition comprising a copolymerizable, alpha-beta ethylenically unsaturated epoxide compound, a dicarboxylic acid or anhydride and an organic solvent to a substrate, (b) causing the solvent to flash off the coated substrate ; and (c) exposing the coated substrate to an elevated temperature for a sufficient amount of time at the selected temperature to cure the coating. The invention additionally comprises a coated article wherein a substrate is coated with the powder composition or the solvent-borne composition according to the claimed methods of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a coating prepared by laying a powder of the invention on a phosphate-treated steel panel inside a 0.051 mm (2 mil) polyester film template to control coating thickness. DETAILED DESCRIPTION OF THE INVENTION The copolymerizable alpha-beta ethylenically unsaturated epoxide compounds are suitable for use in preparing solvent-borne and powder coatings compositions and more particularly in preparing acrylic solvent-borne and powder coatings compositions. The copolymerizable alpha-beta ethylenically unsaturated epoxide compounds suitable for use in the invention are those having the general formula (I) as defined above and can be crosslinked by a crosslinker selected from at least one dicarboxylic acid and/or anhydride or a crosslinker selected from at least one polyamide and/or polyamine, in an organic solvent for solvent-borne coating compositions. More specifically, among the copolymerizable epoxide compounds (A) of formula (I) suitable for use in the invention are epoxy-containing (meth) acrylate esters having the formula (II) as defined above. Most preferably, the copolymerizable epoxide- containing (meth) acrylate esters of formula (II), suitable for use in the invention are (meth) acrylic esters of epoxidized dicyclopentadiene of formula (III) : The resin compositions of the invention include both solvent-borne resins and powder resins. In a first embodiment of the invention, the compositions are provided with at least one dicarboxylic acid and/or anhydride for crosslinking the composition. Solvent-borne compositions additionally comprise at least one organic solvent selected from the group consisting of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, and acetates. The powder and solvent-borne compositions of the invention may include other monomers which may be (co) polymerized and/or crosslinked with the copolymerizable alpha-beta ethylenically unsaturated epoxide compounds and more particularly with the epoxide- containing (meth) acrylate esters of the composition. Among the monomers suitable for use in the composition are acrylates, methacrylates, vinyl and vinyl aromatic monomers and their derivatives, such as styrene and styrene derivatives and the like, and mixtures of these monomers . Suitable acrylates, methacrylates, styrenes and styrene derivatives include, but are not limited to : vinyl monomers, such as vinyl acetate, styrene, vinyl toluenes, divinyl benzenes and the like ; acrylic and methacrylic esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2- hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,3- propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 2, 4-butanetriol tri (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,4- cyclohexanediol di (meth) acrylate, 1, 4-benzenediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, tri ethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2, 2-dimethyl-3-hydroxypropyl-2, 2-dimethyl-3-hydroxy- propionate, isobornyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, and the like. Among the acrylates, methacrylates and styrenes suitable for use in the invention, preferred are butyl acrylate, methyl methacrylate, vinyl toluenes and styrene, and the like. The comonomers are provided in an amount of about 30-90 wt based on the solids weight of the composition. Preferably, the comonomers are provided in an amount of about 50-80 wt% . Most preferably, the comonomers are provided in an amount of about 60-70 wt%. The copolymerizable alpha-beta ethylenically unsaturated epoxide compound and more particularly the epoxide-containing (meth) acrylate ester is provided in an amount of about 1-40 wt% based on the solids weight of the composition. Preferably, the copolymerizable unsaturated epoxide-containing (meth) acrylic ester is provided in an amount of about 10-25 wt% and most preferably in an amount of about 15 wt% . The copolymerizable alpha-beta ethylenically unsaturated epoxide compound and more particularly the epoxide-containing (meth) acrylate monomer (ester) may be crosslinked with at least one dicarboxylic acid and/or anhydride. The dicarboxylic acids and anhydrides may generally be aliphatic dicarboxylic acids and anhydrides. The aliphatic dicarboxylic acids or anhydrides suitable for use in the present invention are not particularly restricted. Examples of the aliphatic dicarboxylic acids and anhydrides suitable for use in the invention include dodecanedioic acid, malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, glutaric acid, sebacic acid, succinic acid, brassylic acid, dicarboxylic acids of the general formula COOH- (CH 2 ) p -COOH, wherein p is an integer of about 1-14, and the like. A preferred dicarboxylic acid is dodecanedioic acid. The dicarboxylic acid is provided in an amount sufficient to crosslink the copolymerizable alpha-beta ethylenically unsaturated epoxide compound and preferably the epoxide-containing (meth) acrylate monomer. Generally, the dicarboxylic acids or anhydrides are present in an amount of 5-25 wt% based on the weight of the composition. Preferably, the dicarboxylic acids or anhydrides are added in an amount of 5-15 wt%. Most preferably, the dicarboxylic acids or anhydrides are provided in an amount of 10 wt%. The solvent-borne coating resin compositions of the invention are provided in organic solvents. The organic solvents useful in the invention as solvents for the solvent-borne coating resins compositions, will depend largely on the application for which the coating resin composition will be applied. Examples of the solvents which may be used in the invention, include organic alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, such as benzene, xylene, toluene, and the like, acetates such as butyl acetate, ethyl acetate, and the like, and mixtures thereof. Of the organic solvents useful in the present invention, xylene and butyl acetate and mixtures thereof are preferred. The solvent-borne coating resin compositions of the invention may also include pigments, such as titanium dioxide (Ti0 2 ) and the like ; dispersing acids, such as Anti-Terra U Dispersing Aid, and the like ; and catalysts, such as p-toluenesulfonic acid catalyst (p-TSA) and the like. In use, a solvent-borne coating resin composition containing the copolymerizable alpha-beta ethylenically unsaturated epoxide compound, more preferably the epoxide-containing (meth) acrylate ester monomer and optionally, a comonomer, such as acrylate, methacrylate and/or styrene, is blended with a dicarboxylic acid or anhydride in a solvent. The composition may contain other additives such as pigments, dispersing aids, and catalysts. The substrate to be coated is coated with the solvent-borne coating resin composition. The solvent is allowed to flash off, and the coating on the coated substrate is allowed to cure by exposing the coated substrate to elevated temperature. Generally, the elevated temperature is about 100-300°C for 1 minute to 2 hours. Preferably, the temperature is about 150-250°C for 10 minutes to 1 hour and most preferably at about 200°C. The polymerization or curing time depends on the precise formulation and the temperature at which polymerization is allowed to proceed. For embodiments exposed to a temperature of about 200 °C, the polymerization time may be from about 15 minutes to about 1 hour. Generally, the polymerization time will be about 30 minutes. The powder coating resins compositions of the invention may be prepared for use in coating substrates for high-temperature curing. The powder coating compositions comprise the copolymerizable alpha-beta ethylenically unsaturated epoxide compounds which preferably may be epoxide-containing (meth) acrylate ester monomers, dry-blended with a dicarboxylic acid or anhydride, and optionally, a comonomer, such as acrylates, methacrylates, and/or styrenes. The composition may also include pigments, such as titanium dioxide (Ti0 2 ) and the like ; flow promoting agents, such as Modaflow Flow Aid, and the like ; and catalysts, such as p-TSA (p-toluene sulfonic acid), and the like. Pigments, such as titanium dioxide, when added are typically provided in an amount of about 0 to 30 wt% . Flow aids, generally added in an amount of about 2 wt% or less, are useful in forming a smooth coating, substantially free of pinholes and "orange peel". Typical concentrations for flow aids are about 0.5 to 2 wt%. Catalysts, which promote more rapid curing, are generally added in an amount of about 0 to 0.02 wt%. The blended composition may be ground to a selected particle size. Particle size is selected based on the application, but typical particle size is about 5-100 μm. In use, the powder coating resin compositions may be applied to a substrate to be coated by any known means, such as by corona discharge or triboelectric charging, and the like, at an elevated temperature, such as in a forced air oven. Generally, curing takes place at an elevated temperature, such as 60-250°C. Preferably, the cure is achieved at a temperature of about 100-200°C. Most preferably, the temperature is about 150°C. It will be understood by persons skilled in the art that the temperature of the cure may be adjusted based on the precise composition of the resin and the time required for curing. Some adjustment for these factors will be easily achieved by modifying the conditions of the cure depending on the desired cure dynamics. In another embodiment of the invention, useful for industrial coatings for metal, the unsaturated alpha- beta ethylenically unsaturated epoxide compounds, more preferably epoxide-containing (meth) acrylate esters may be used as a comonomer for coatings that can be crosslinked with polyamides and/or polyamines at ambient temperature or at elevated temperatures. These compositions may also include other comonomers such as acrylates, methacrylates and vinyl or vinyl aromatic monomers, such as vinyl toluenes, styrene and styrene derivatives. In this embodiment of the invention, the unsaturated epoxide compound or more particularly the epoxide-containing (meth) acrylate ester is present in an amount of about 1-60 wt% based on the weight of the composition. Preferably, the unsaturated epoxide compound or epoxide-containing (meth) acrylate ester is present in an amount of about 10-40 wt% and most preferably is present in an amount of about 15-25 wt%. The polyamides and/or polyamines in this embodiment may be present in an amount of about 5-50 wt% based on the weight of the composition. Preferably, the polyamides and/or polyamines are present in an amount of about 10-40 wt% and most preferably in an amount of about 15-25 wt%. Suitable polyamides and/or polyamines include, but are not limited to : ethyleneamines, propyleneamines, higher alkyleneamines, Mannich Bases, amines from adducts of amines with epoxy, adducts with acrylonitrile, ketimines, arylaliphatic amines, alicyclic aliphatic amines, cycloaliphatic amines, unsaturated fatty acid derivatives of alkylene amines and the like. Of the polyamides and polyamines suitable for use in the invention, preferred are ethyleneamines such as diethylenetriamine and triethylenetetraamine . In this embodiment, the aforementioned acrylates, methacrylates, vinyl aromatic monomers, such as vinyl toluenes, styrene and styrene derivatives may be provided in an amount of about 1-60 wt% based on the solids weight of the composition. Preferably, these comonomers are provided in an amount of about 10-40 wt% and most preferably in an amount of about 15-25 wt% . Other additives of this embodiment may include pigments and dispersing aids as described in the previous embodiments . The compositions containing polyamines and/or polyamides may be cured at ambient temperature or at elevated temperature. Suitable temperatures are from about 25° to about 150°C. In use, the unsaturated epoxide compounds or more particularly the epoxide-containing (meth) acrylate esters are blended with the polyamines and/or polyamides and are crosslinked at ambient temperature to about 150 °C. Coating resins compositions may also be prepared to include a UV initiator and a cationic photoinitiator for crosslinking in a hybrid cure system with ultraviolet light and heat. These coating compositions may include at least one UV initiator and/or at least one cationic photoinitiator . Cationic curing provides a high rate of curing. The cationic initiators suitable for use in the invention include sulfonium and iodonium salts. These sulfonium and iodonium salts, upon exposure to ultraviolet light, decompose to yield an acid catalyst. Examples of cationic initiators include diaryliodonium hexafluoro- antimonate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, cyclopentadiene hexafluorophosphate and the like. When employing a cationic photoinitiator, the cationic photoinitiator is typically present in an amount of about 0.5 to 1 wt%. In these applications, UV light is applied, which partially cures the compositions. Exposure to elevated temperatures completes the curing process. UV initiators include benzoin ethers, benzil ketals, acetophenones, phosphine oxide, and benzophenone, as well as others known in the art. In use, for powder coating compositions, the alpha-beta ethylenically unsaturated epoxide compound or preferably the epoxide-containing (meth) acrylate ester is blended with other cycloaliphatic monomers, a UV initiator (e.g., benzophenone) and a cationic photoinitiator. The composition is formed into a powder, which is applied to the substrate. The coating is partially cured by exposure to UV light by any conventional method, and cure is completed by applying heat (such as in a forced air oven) at temperatures of about 40-80°C, preferably about SO- 70°C, and most preferably at about 60°C. The copolymerizable alpha-beta ethylenically unsaturated epoxide compounds or preferably the epoxide- containing (meth) acrylate esters of the invention confer a significant advantage over conventional epoxy-functional (meth) acrylate esters, such as glycidyl methacrylate. A comparison was made in Table 1 of dicyclopentadiene methacrylate epoxide with glycidyl methacrylate to demonstrate the advantages of the copolymerizable epoxide- containing (meth) acrylate esters of the invention. Additionally, experiments were conducted to demonstrate the excellent properties of coating compositions formed in accordance with aspects of the invention. Viscosity was measured with a Brookfield LVT viscometer. Percent volatiles was measured according to ASTM D2369, which measures weight loss after 1 hour at 110°C. Glass transition temperature was measured by differential scanning calorimetry (DSC) in which a specimen was cured with 0.5 wt% Vazo 67 at 100°C for 3 hours. Autopolymerization was also measured by DSC. The advantageous aspects of the invention will become apparent from the following examples, which are intended to be illustrative of the invention, and are not to be construed as limiting the scope of the invention, which is defined by the appended claims. Table 1 EXAMPLES In the following examples, resins were prepared and evaluated by several tests : 60° Gloss was measured using a Micro-Triglossmeter from Byk-Gardner ; Pencil Hardness, Reverse Impact and Cross-Hatch Adhesion were each measured by ASTM methods ; and the MEK double rub method was used to measure Solvent Resistance. The first set of examples demonstrates the invention in use as a solvent-borne coating. EXAMPLE 1 An acrylic terpolymer was prepared by combining 6.17 moles of butyl acrylate, 1.14 moles methyl methacrylate and 1.0 moles of dicyclopentadiene methacrylate epoxide in solution at 100 - 120 °C using an azonitrile initiator. The resulting terpolymer had an epoxide equivalent weight of approximately 1200. The terpolymer coating resin prepared was formulated into a solvent-borne acrylic white enamel coating, as shown in Table 2, by mixing with Ti0 2 , dispersing aid, solvent and pTSA catalyst on an air-driven high shear mixer. Dodecanedioic acid was added and the mixture was mixed in a laboratory 3-roll mill. A drawdown was prepared on chrome-treated aluminium panel using a # 10 wire wound drawdown rod for testing coating properties. The panel sat at 25°C for 30 minutes to allow the solvent to flash off. The panel was then baked in a forced air oven at 200°C for 1 hour. The panel was subjected to the following tests : 60° Gloss was measured using a micro-triglossmeter from Byk-Gardner. Solvent Resistance was measured using the MEK double rub method, in which a paper towel is saturated with MEK solvent and is wiped back and forth across the surface of the film coating with nominal pressure. One wipe back and forth constitues a double-rub. Reverse Impact, Pencil Hardness and Cross-Hatch Adhesion were measured following the ASTM method. The results are shown in Table 2. COMPARATIVE EXAMPLE 1 An acrylic terpolymer was prepared by combining 6.8 moles of butyl acrylate, 1.25 moles methyl methacrylate and 1.0 mole of glycidyl methacrylate in solution at 100 - 120°C using an azonitrile initiator. The resulting terpolymer had an epoxide equivalent weight of approximately 1200. The terpolymer coating resin prepared was formulated into a solvent-borne acrylic white enamel coating, as shown in Table 2, by mixing with Ti0 2 , dispersing aid, solvent and p-toluenesulfonic acid catalyst (p-TSA catalyst) on an air-driven high shear mixer. Dodecanedioic acid was added and the mixture was mixed in a laboratory 3-roll mill. A drawdown was prepared on chrome-treated aluminium panel using a # 10 wire wound drawdown rod for testing coating properties. The panel sat at 25°C for 30 minutes to allow the solvent to flash off. The panel was then baked in a forced air oven at 200°C for 1 hour. The panel was subjected to the same tests as Example 1. The results are shown in Table 2. Table 2 The second set of examples demonstrates the use of the invention as an acrylic powder coating. EXAMPLE 2 An acrylic powder coating resin was prepared by combining 1.0 moles of butyl acrylate, 3.25 moles of methyl methacrylate and 4.24 moles of styrene and 1.06 moles of dicyclopentadiene methacrylate epoxide. The resulting tetrapolymer coating resin was formulated into an acrylic powder coating formulation, as shown in Table 3, by dry blending with the Ti0 2 , p-TSA catalyst, dodecanedioic acid and a Modaflow agent in a one pint epoxy-lined aluminium can on a shaker for 10 minutes. The formulation was then ground to fine particles using a mortar and pestle. The coating was prepared in the laboratory by laying the powder on a phosphate-treated steel panel inside of a 0.051 mm (2 mil) polyester film template to control coating thickness as shown in Figure 1. A second phosphate-treated steel panel was placed on top of the template and then the coating was cured in a hydraulic press at 150°C for 20 minutes under 2 metric tons of pressure. The coatings were subjected to 60°C Gloss, Solvent Resistance and Cross-Hatch Adhesion tests as performed for Example 1 and Comparative Example 1. The results are shown in Table 3. COMPARATIVE EXAMPLE 2 An acrylic powder coating resin was prepared by combining 1.0 moles of butyl acrylate, 3.25 moles methyl methacrylate, and 4.24 moles of styrene, and 1.06 moles of glycidyl methacrylate. The resulting tetrapolymer coating resin was formulated into an acrylic powder coating formulation, as shown in Table 3, by dry blending with the Ti0 2 , p-TSA catalyst, dodecanedioic acid and a Modaflow agent in a one pint epoxy-lined aluminium can on a shaker for 10 minutes. The formulation was then ground to fine particles using a mortar and pestle. The coating was prepared in the laboratory by laying the powder on a phosphate-treated steel panel inside of a 0.051 mm (2 mil) polyester film template to control coating thickness as shown in Figure 1. A second phosphate-treated steel panel was placed on top of the template and then the coating was cured in a hydraulic press at 150 °C for 20 minutes under 2 metric tons of pressure. The coatings were subjected to 60°C Gloss, Solvent Resistance and Cross-Hatch Adhesion tests as performed for Example 1 and Comparative Example 1. The results are shown in Table 3. Table 3

Claims: CLAIMS A coating composition comprising (A) A copolymerizable alpha-beta ethylenically unsaturated epoxide compound of formula (I) : wherein : - Ri is a residue of an alpha-beta ethylenically unsaturated carboxylic acid ; R 2 is an alkylene group having 1-4 carbons or an alkoxylene group having 1-4 carbons ; and n is an integer from 0 to 15 ; and (B) a crosslinker selected from the group of dicarboxylic acids and/or anhydrides or selected from the group of polyamides and/or polyamines. 2 - The coating composition of Claim 1, further comprising at least one monomer selected from the group consisting of acrylates, methacrylates and vinyl aromatic monomers and derivatives. 3 - The coating composition of claims 1 or 2 wherein the said compound (A), as defined in claim 1, is present in the form of a copolymer formed by copolymerization with monomers as defined in claim 2. 4 - The coating composition according to any one of Claims 1 to 3, wherein said composition is a powder coating composition. 5 - The coating composition according to any one of Claims 1 to 3, further comprising an organic solvent, thereby forming a solvent-borne coating composition. 6 - The coating composition of Claim 5, wherein said organic solvent is selected from the group consisting of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, and acetates. 7 - The coating composition of Claims 5 or 6, wherein said organic solvent is selected from the group consisting of xylene, butyl acetate and mixtures thereof. 8 - The coating composition according to any one of Claims 1 to 4, further comprising at least one compound selected from the group consisting of catalysts, flow aids and pigments. 9 - The coating composition according to any one of Claims 5 to 7 , further comprising at least one compound selected from the group consisting of catalysts, dispersing aids and pigments. 10 - The coating composition of Claims 8 or 9, wherein said catalyst is p-toluenesulfonic acid. 11 - A coating composition according to any one of claims 1 to 10 wherein said compound (A) , as defined in claim 1, is a (meth) acrylic ester defined by formula (II): wherein: R 3 is a hydrogen or methyl group ; R 4 is an alkylene group of 1-4 carbons or an alkoxylene group of 1-4 carbons ; and n is an integer from 0 to 15. 12 - A coating composition according to any one of claims 1 to 11 wherein the said copolymerizable compound (A) as defined in claim 1, is a (meth) acrylic ester of epoxidized dicyclopentadiene, defined by the formula (III) : 13 - A coating composition according to any one of claims 1 to 12 wherein the crosslinker (B) , as defined in claim 1, is at least one dicarboxylic acid and/or anhydride . 14 - A coating composition according to any one of claims 1 to 12 wherein the crosslinker (B) , as defined in claim 1, is at least one comonomer selected from the group consisting of polyamides and polyamines. 15 - A composition according to any one of claims 1 to 14 further including at least one UV initiator and/or at least one cationic photoinitiator for crosslinking in a hybrid cure system with ultraviolet light and heat. 16 - A method of coating a substrate, comprising the steps of : (a) applying a coating composition, as defined according to any one of claims 1 to 15, to a substrate, thereby forming a coating on said substrate ; and (b) curing the said coating composition. 17 - A method of coating a substrate comprising : (a) applying a composition to a substrate thereby forming a coating on said substrate, said composition comprising : (i) a copolymerizable, alpha-beta ethylenically unsaturated epoxide compound having formula (I) as defined in claim 1 (ii) at least one monomer selected from the group consisting of acrylates, methacrylates and vinyl aromatic monomers and derivatives ; and (iii) at least one dicarboxylic acid or anhydride; (iv) at least one organic solvent ; (b) causing solvent to flash off said coated substrate ; and (c) exposing said coated substrate to an elevated temperature for a sufficient amount of time at said temperature to cure said coating. A method of coating a substrate comprising: (a) applying a powder composition to a substrate thereby forming a coating on said substrate, said powder composition comprising : (i) a copolymerizable, alpha-beta ethylenically unsaturated epoxide compound of formula (I) as defined in claim 1 ; (ii) at least one monomer selected from the group consisting of acrylates, methacrylates and vinyl aromatic monomers and derivatives ; (iii)at least one dicarboxylic acid or anhydride ; and (b) exposing said coated substrate to an elevated temperature for a sufficient amount of time at said temperature to cure said coating. 19 - The method of Claims 17 or 18, wherein said elevated temperature is about 100-300°C. 20 - A method of coating a substrate comprising : (a) applying a powder composition to a substrate thereby forming a coating on said substrate, said powder composition comprising : (i) a copolymerizable, alpha-beta ethylenically unsaturated epoxide compound of formula (I) as defined in claim 1 ; (ii) at least one UV initiator ; (iv) at least one cationic photoinitiator ; (b) exposing said coated substrate to UV light to partially cure said coating ; and (c) exposing said coated substrate to an elevated temperature for a sufficient amount of time at said temperature to cure said coating. 21 - The method according to Claim 20, wherein said composition further comprises at least one other cycloaliphatic epoxy monomer. 22 - The method of Claims 20 or 21, wherein said cationic photoinitiator is selected from the group consisting of diaryliodoniu hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate and cyclopentadiene hexafluoro- phosphate . 23 - The method according to any one of Claims 20 to 22 wherein said UV initiator is selected from the group consisting of benzoin ethers, benzil ketals, acetophenones, phosphine oxide and benzophenone. 24 - The method according to any one of Claims 20 to 23, wherein said elevated temperature is about 40-80 °C. 25 - A coated article comprising a substrate coated with a cured coating resin composition, formed from a coating composition defined according to any one of claims 1 to 15, wherein said coating composition is exposed to an elevated temperature. 26 - A coated article according to claim 25 wherein said cured resin composition is formed from a composition comprising as crosslinker (B) defined in claim 1, at least one compound selected from the group consisting of polyamines and polyamides and wherein said composition is exposed to an ambient or elevated temperature.

Inventors: BAILEY MICHAEL A, COSTIN RICHARD C, BAILEY, MICHAEL, A., COSTIN, RICHARD, C.
Applicants: CRAY VALLEY SA, SARTOMER CO INC, CRAY VALLEY S.A., SARTOMER COMPANY, INC.
Application year: 2000
Main classification: C08G59
IPC codes: C08G59, C09D163