Title of Invention	"UV-CURABLE COATING COMPOSITION AND COATED ARTICLES"
Abstract	An ultraviolet-curable coating composition obtained by blending (A) an at least tetrafunctional ultraviolet-curable (meth)acrylate which bears four or more (meth)acryloyl groups in the molecule and has a number-average molecular weight of 300 to 2,000 with (B) a lactone-modified polyhydric alcohol mono(meth)acrylate polymer which contains 20 to 60 % by mass of open-ring adducts of e-caprolactone and has a hydroxyl number resulting from the modification with lactone of 100 to 180 mgKOH/g and/or a lactone-modified polyester resin which contains 10 to 50 % by mass of open-ring adducts of lactone and has a hydroxyl number of 50 to 180 mgKOH/g, (C) a non-yellowing polyisocyanate and/or an amino resin, (D) a light stabilizer and (E) a photopolymerization initiator at a mass ratio of (A)/[(B)+(C)] ranging from 10:90 to 50:50 and at a (B)/(C) mass ratio ranging from 90:10 to 20:80 in such a way as to give a cured coating film which has a Knoop hardness of 10 to 18 and a molecular weight of the crosslinked resin component between crosslinks ranging from 150 to 300. The composition can give coating film excellent in scratch resistance, decorativeness, tight adhesion, and gasoline resistance at high productivity.

Title of Invention

"UV-CURABLE COATING COMPOSITION AND COATED ARTICLES"

Abstract

An ultraviolet-curable coating composition obtained by blending (A) an at least tetrafunctional ultraviolet-curable (meth)acrylate which bears four or more (meth)acryloyl groups in the molecule and has a number-average molecular weight of 300 to 2,000 with (B) a lactone-modified polyhydric alcohol mono(meth)acrylate polymer which contains 20 to 60 % by mass of open-ring adducts of e-caprolactone and has a hydroxyl number resulting from the modification with lactone of 100 to 180 mgKOH/g and/or a lactone-modified polyester resin which contains 10 to 50 % by mass of open-ring adducts of lactone and has a hydroxyl number of 50 to 180 mgKOH/g, (C) a non-yellowing polyisocyanate and/or an amino resin, (D) a light stabilizer and (E) a photopolymerization initiator at a mass ratio of (A)/[(B)+(C)] ranging from 10:90 to 50:50 and at a (B)/(C) mass ratio ranging from 90:10 to 20:80 in such a way as to give a cured coating film which has a Knoop hardness of 10 to 18 and a molecular weight of the crosslinked resin component between crosslinks ranging from 150 to 300. The composition can give coating film excellent in scratch resistance, decorativeness, tight adhesion, and gasoline resistance at high productivity.

Full Text	SPECIFICATION ULTRAVIOLET-CURABLE COATING COMPOSITION AND COATED ARTICLE Field of technology The present invention relates to an ultraviolet-curable coating composition which can be used in the field that high degree of aesthetic decorative property and excellent properties of a paint film, for example, scratch resistance, gasoline resistance and excellent gloss-holding property in atmospheric exposure are required, and a coated article thereof. Background technology In recent years, as coating compositions for vehicles which requires high degree of aesthetic decorative property and board excellent properties of a paint film, solvent type or water-soluble type of acrylic resin / melamine resin coating compositions and acrylic resin / urethane resin coating compositions have been mainly utilized. Also, as different coating compositions from the thermosetting coating compositions described above, Japanese patent publication 1960210 discloses an ultraviolet-curable coating composition comprising an ultraviolet curable polyfunctional (meth)aerylate and acrylic resin, polyisocyanate compound, light stabilizer and photopolymerization initiator. And Japanese patent publication 2504061 discloses an ultraviolet-curable coating composition comprising an ultraviolet curable polyfunctional (meth) aerylate and acrylic resin, melamine resin or urea resin, light stabilizer and photopolymerization initiator. However, the acrylic resin / urethane resin coating compositions and the acrylic resin / melamine resin coating compositions described before are not necessarily sufficient in distinction of image of the paint film and are insufficient in view of productivity of the paint film because it takes long time to cure the coating composition. On the other hand, the ultraviolet-curable coating compositions of Japanese patent publication 1960210 and 2504061 give excellent distinction of image of the paint film and have high level productivity of the paint film, but can not give the paint film having excellent scratch resistance. The present invention has an object to provide the ultraviolet-curable coating composition which can give the paint film having not only excellent scratch resistance and high degree of aesthetic decorative property, but also excellent adhesion and excellent gasoline resistance, and have high level productivity of the paint film, and the coated article obtained by application of the ultraviolet-curable coating composition. Disclosure of the invention As a result of extensive investigations undertaken by the present inventors in order to solve the problems described above, it was found that the object of the present invention is achieved by using an ultraviolet-curable coating composition comprising a specific ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate, a specific lactone-modified polymer of polyhydric alcohol mono(meth)aerylate containing 20 to 60 percents by weight of a -caprolactone ring-opening addition product and/or a specific lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product, and a non-yellowing polyisocyanate compound and/or an amino resin, in a specific ratio and further, a light stabilizer and a photopolymerization initiator, and the components described above are formulated to obtain a cured paint film having a Knoop hardness of 10 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300. And thus the present invention is completed. That is to say, the present invention provides an ultraviolet-curable coating composition comprising: (A) an ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate having four or more (meth) acryloyl groups in the molecule and a number average molecular weight of 300 to 2,000, (B)a lactone-modified polymer of polyhydric alcohol mono(meth)aerylate containing 20 to 60 percents by weight of -caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 100 to 180 mgKOH/g, and/or a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g, (C)a non-yellowing polyisocyanate compound and/or an amino resin, (D)a light stabilizer and, (E)a photopolymerization initiator, wherein a weight ratio of component (A) against to a total weight of component Components (B) and (C) is 10 : 90 to 50 : 50, a weight ratio of component (B) against to component (C) is 90 : 10 to 20 : 80, and the components described above are formulated to obtain a cured paint film having a Knoop hardness of 10 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300. The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (B) is a lactone-modified polymer of polyhydric alcohol mono(meth)aerylate containing 20 to 60 percents by weight of  -caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 100 to 180 mgKOH/g. The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (B) is a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g. The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (C) is a non-yellowing polyisocyanate compound and the equivalent value of isocyanate group of ingredient (C) to the hydroxyl group of ingredient (B) is from 0.5 to 1.5. The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (C) is an amino resin. The present invention also provides a coated article obtained by applying the ultraviolet-curable coating composition as described above. In the present invention, the term, (meth)acryloyl group means acryloyl group and/or methacryloyl group. Also, the term, (meth)aery late means acrylate and/or methacrylate and the term, (meth)acrylic acid means acrylic acid and/or methacrylic acid. Preferable embodiment for practicing the invention The ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A), used in the present invention, has fourormore (meth) acryloyl groups in the molecule. When a polyfunctional (meth)acrylate having two (meth)acryloyl groups in the molecule is used, curability is insufficient and gasoline resistance is inferior. Also, when a polyfunctional (meth)acrylate having three (meth)acryloyl groups in the molecule is used and a large amount of ingredient (A) is formulated to obtain a cured paint film having a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300, the increase of curing shrinkage strain in the paint film is caused and adhesive property is inferior. Further, the number average molecular weight of ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) is from 300 to 2,000, preferably from 320 to 1,500. When the number average molecular weight is more than 2,000, leveling property of the paint film is inferior and it is difficult to obtain the high degree of aesthetic decorative property. On the other hand, when the number average molecular weight is less than 3 00, flexibility of the paint film is inferior and crack is easily caused in bending test. The ultraviolet curable four or more functional groups-containing polyfunctional (meth) aerylate of ingredient (A) includes a four or more functional groups-containing polyhydric alcohol (meth)acrylate obtained by esterification of tetravalent or more polyhydric alcohol with (meth)acrylic acid, a four or more functional groups-containing epoxy(meth)acrylate obtained by esterification of epoxy groups of fourormorefunctionalgroups-containingpolyfunctionalepoxy compound with (meth)acrylic acid, a four or more functional groups-containing polyurethane(meth)aerylate obtained by reaction of four or more functional groups-containing polyfunctional isocyanate compound with hydroxyl group-containing (meth)acrylate, and a four or more functional groups-containing melamine (meth) aery late obtained by reaction of methylolmelanine having four or more methylol groups in a molecule with hydroxyl group-containing (meth) aery late. The four or more functional groups-containing polyfunctional (meth)aerylate of ingredient (A) can be utilized singly or in combination of two or more members. The four or more functional groups-containing polyhydric alcohol (meth)acrylate includes pentaerythritol tetra( meth) aery late, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, xylitolpenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerildipentaerythritol hepta(meth)acrylate. Commercial compounds of four or more functional groups-containing polyhydric alcohol (meth)acrylate include KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 and KAYARAD DPCA-120 (all trade names, products of NIPPON KAYAKU CO. LTD..) . The four or more functional groups-containing polyfunctional epoxy compound used to prepare the four or more functional group-containing epoxy(meth)aerylate includes glycidyl ether epoxy resins such as phenol novolac type glycidyl ether epoxy resins, orthocresol novolac type glycidyl ether epoxy resins, bisphenol A novolac type glycidyl ether epoxy resins, brominated phenol novolac type glycidyl ether epoxy resins and tetraphenylol ethane type glycidyl ether epoxy resins. The four or more functional groups-containing polyfunctional isocyanate compound used to prepare the four or more functional group-containing polyurethane(meth)aerylate includes reaction products obtained by reaction of hexamethylene diisocyanate and/or isophorone diisocyanate with four or more functional groups-containing polyhydric alcohol such as pentaerythritol and dipentaerythritol. The methylolmelanine having four or more methylol groups in a molecule used to prepare the four or more functional group-containing melamine (meth)acrylate includes tetramethylolmelamine, pentamethylolmelamine and hexamethylolmelamine. The hydroxyl group-containing (meth)acrylate used to prepare the four or more functional group-containing polyurethane(meth)acrylate and the four or more functional group-containing melamine (meth) acrylate includes hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; polyhydric alcohol mono(meth)aerylates such as polyethyleneglycol mono(meth)aerylate, polypropyleneglycol mono(meth)aerylate, neopentylglycol mono(meth)acrylate and glycerin mono(meth)acrylate; ethyleneoxide and/or propyleneoxide addition products of hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. Among the four or more functional group-containing polyfunctional (meth)acrylates, the polyfunctional (meth)acrylate having the acryloyl group in the molecule has high curability compared with the polyfunctional (meth)acrylate having the methacryloyl group in the molecule. Therefore, the polyfunctional (meth)acrylate having the acryloyl group in the molecule is more preferably used in the present invention. Ingredient (A) can be utilized singly or in combination of two or more members. Ingredient (B) used in the present invention is a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 20 to 60 percents by weight of £ -caprolactone ring-opening addition product and having a hydroxy 1 value derived from the lactone modification of 100 to 180 mgKOH/g (hereinafter, it may be called "ingredient (Ba)"), and/or a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g (hereinafter, it may be called "ingredient (Bb)"), The content of a -caprolactone ring-opening addition product in ingredient (Ba) is 20 to 60 percents by weight, preferably 25 to 50 percents by weight. When the content of £-caprolactone ring-opening addition product is less than 20 percents by weight, the scratch resistance of the paint film is not sufficient. When the content of  -caprolactone ring-opening addition product is more than 60 percents by weight, hardness of the paint film is too low and the gasoline resistance of the paint film is inferior. The hydroxyl value derived from the lactone modification of ingredient (Ba) is 100 to 180 mgKOH/g, preferably 120 to 170 mgKOH/g. The term, "the hydroxyl value derived from the lactone modification" means the hydroxyl value of the hydroxyl group which exist in the end of the structure portion consisting of the  -caprolactone ring-opening addition product in the lactone-modified polymer of polyhydric alcohol mono(meth)acrylate and does not contain the hydroxyl value of the hydroxyl group in the other structure portion. When the hydroxyl value derived from the lactone modification is less than 100 mgKOH/g, the scratch resistance of the paint film is not sufficient. When the hydroxyl value derived from the lactone modification is more than 180 mgKOH/g, the compatibility with the four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) is inferior. The molecular weight of ingredient (Ba) is not limited particularly. The number average molecular weight of ingredient (Ba) is preferably about 2,000 to 20,000 in general. The lactone-modified polymer of polyhydric alcohol mono(meth)acrylate of ingredient (Ba) can be utilized singly or in combination of two or more members. The method for preparing ingredient (Ba) includes (1) a preparation method comprising homopolymerizing polycaprolactone-modified polyhydric alcohol mono(meth)aerylate obtained by ring-opening addition of e -caprolactone to the polyhydric alcohol mono (meth )acrylate or copolymerizing it and other copolymerizable vinyl monomer, and (2) a preparation method comprising ring-opening adding  -caprolactone to a homopolymer or a copolymer of polyhydric alcohol mono (meth) acrylate which is obtained by homopolymerizing polyhydric alcohol mono (meth) acrylate or copolymerizing it and other copolymerizable vinyl monomer. The polyhydric alcohol mono(meth)acrylate used in the methods (1) and (2) as described above includes 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, polyethyleneglycol mono(meth)acrylate, polypropyleneglycol mono(meth)acrylate, neopentylglycol mono(meth)acrylate and glycerin mono(meth)acrylate. The polyhydric alcohol mono(meth)acrylate can be utilized singly or in combination of two or more members. The polycaprolactone-modified polyhydric alcohol mono(meth)acrylate used in the method (1) as described above includes polycaprolactone-modified hydroxyalkyl mono(meth)acrylate and polycaprolactone-modified poly(oxyalkylene) mono(meth)acrylate. Commercial compounds of polycaprolactone-modified polyhydric alcohol mono(meth)acrylate include PLACCEL FA-1 (trade name, produced by Daicel Chemical Industries, LTD. , monomer obtained by ring-opening addition of one mole of -caprolactone to one mole of 2-hydroxyethyl acrylate), PLACCEL FM-1D, PLACCEL FM-2D, PLACCEL FM-3 and PLACCEL FM-4 (all trade names, produced by Daicel Chemical Industries, LTD. , monomer obtained by ring-opening addition of one mole, two moles, three moles or four moles of £ -caprolactone respectively to one mole of 2-hydroxyethyl methacrylate). The other copolymerizable vinyl monomers used in the methods (1) and (2) as described above include, for example, (meth)acrylic acid and alkyl substitution products thereof; alkyl(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)aerylate, butyl (meth)aerylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)aerylate and stearyl (meth)acrylate; hydroxyalkyl (meth)aerylates such as 2-hydroxyethyl (meth)aerylate and 3-hydroxypropyl (meth)acrylate; esters of dibasic acid such as itaconic acid, maleic acid and fumalic acid; styrene and nuclear-substituted styrenes such as vinyl toluene, dimethyl styrene and ethyl styrene; and (meth)aerylonitrile, (meth)aerylamide, vinyl acetate and vinyl chloride. The other copolymerizable monomer can be utilized singly or in combination of two or more members. In the polymerization for preparation of ingredient (Ba), a polymerization initiator can be utilized. The polymerization initiator includes organic peroxide polymerization initiators and azo polymerization initiators. The amount of the polymerization initiator is not limited particularly, but preferably 0.5 to 15 percents by weight to total amount of the monomers, in general. Ingredient (Ba) can be utilized singly or in combination of two or more members. The content of lactone ring-opening addition product in ingredient (Bb) is 10 to 50 percents by weight, preferably 15 to 40 percents by weight. When the content of lactone ring-opening addition product is less than 10 percents by weight, the scratch resistance of the paint film is not sufficient. When the content of lactone ring-opening addition product is more than 50 percents by weight, hardness of the paint film is too low and the gasoline resistance of the paint film is inferior. The hydroxyl value of ingredient (Bb) is 50 to 180 mgKOH/g, preferably 70 to 170 mgKOH/g. When the hydroxyl value is less than 50 mgKOH/g, the scratch resistance of the paint film is not sufficient. When the hydroxyl value is more than 180 mgKOH/g, the compatibility with the four or more functional groups-containing poly functional (meth) aery late of ingredient (A) is inferior. The molecular weight of ingredient (Bb) is not limited particularly. The number average molecular weight of ingredient (Bb) is preferably about 1,500 to 20,000, more preferably 1,500 to 5,000 in general. The method for preparing ingredient (Bb) includes a preparation method comprising ring-opening addition of a lactone to a polyester resin obtained by bonding a polybasic acid and a polyhydric alcohol. The polybasic acid used in the method described above includes, for example, aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, tetrachloro phthalic acid, naphthalene dicarboxylic acid, 4,4-diphenylmethane carboxylic acid; alicyclic polybasic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrotrimellitic acid and methyl hexahydroterephthalic acid; saturated and unsaturated aliphatic polybasic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebasic acid, dodecane dicarboxylic acid, pimelic acid, maleic acid, fumaric acid and itaconic acid. Also, anhydrides of the polybasic acids described above and ester-formable substitution product thereof, for example, ester of lower alkyl having 1 to 6 carbon atoms, can be utlized as the polybasic acid. The polybasic acid can be utilized singly or in combination of two or more members. Examples of the polyhydric alcohol described above are divalent alcohols and trivalent or more alcohols described below. The divalent alcohols include, for example, glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyl trimethylene glycol, tetramethylene glycol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol; polyether diols such as alkylene oxide addition products of bisphenol A, polyethylene glycol and polypropylene glycol; and monoepoxy compounds such as a-olefin epoxides like propylene oxide and butylene oxide and CARDURA E-10 (trade name, produced by SHELL chemical Co., glycidyl ester of synthetichigh branched saturated aliphatic acid ). Further, trivalent or more alcohols include, for example, glycerin, trimethylol ethane, trimethylol propane, diglycerin, pentaerythritol, dipentaerythritol and sorbitol. Also, compounds having two or more epoxy groups in the molecule like bisphenol A diglycidyl ether can be utilized as the trivalent or more alcohol. The polyhydric alcohol can be utilized singly or in combination of two or more members. For the polyester resins used for preparation of ingredient (Bb), saturated aliphatic fatty acids such as octyl acid, lauryl acid and stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and eleostearic acid; monobasic acids such as benzoic acid, abietic acid, acetic acid, propionic acid and butyric acid; hydroxycarboxylic acid compounds such as methylol propionic acid, pivalic acid, 12-hydroxystearic acid and ricinolic acid; and oils and fats such as linseed oil, castor oil, tall oil, cotton seed oil, soybean oil, olive oil and safflower oil can be utilized as other components according to needs, other than the components described above and before. The components described above can be utilized singly or in combination of two or more members. Lactones used for preparing ingredient (Bb) of the present invention, include  -caprolactone,  -butyrolactone, δ -valerolactone,  -valerolactone,  -caprolactone,  -nonanoic lactone and δ-dodecanolactone. In particular, -caprolactone is preferably used. The lactone can be utilized singly or in combination of two or more members. Ingredient (Bb) can be utilized singly or in combination of two or more members. ingredient (C) used in the present invention is a non-yellowing polyisocyanate compound and/or an amino resin. As the non-yellowing polyisocyanate compound, aliphatic and alicyclic polyisocyanate compounds are preferably used. Typical examples are reaction products of hexamethylene diisocyanate and/or isophorone diisocyanate with polyhydric alcohol and/or low molecular weight polyester polyol, isocyanurate compounds such as polymer of hexamethylene diisocyanate and/or isophorone diisocyanate and biuret compounds obtained by further reaction to the urethane bond. Also, blocked isocyanates in which the isocyanate groups in the polymers are masked with hydroxyl group-containing compounds, can be preferably utilized. Further, various non-yellowing polyisocyanate compounds such as polymers of diisocyanate compounds other than the compounds described above can be utilized. The non-yellowing polyisocyanate compound can be utilized singly or in combination of two or more members. As the amino resin, melamine resins or urea resins used generally for coating compositions can be utilized. The resins include melamine resins or urea resins which are ether if icated with lower alcohol such as methanol, n-butanol and isobutanol singly or in mixture thereof. The amino resin can be utilized singly or in combination two or more members. Further, the non-yellowing polyisocyanate compound and the amino resin can be used in combination. With respect to the content ratio of ingredient (A), ingredient (B) and ingredient (C), the weight ratio of ingredient (A) to the total weight of ingredient (B) and ingredient (C) is 10:90 to 50:50, preferably 15:85 to 45:55, more preferably 20:80 to 40:60, and the weight ratio of ingredient (B) to ingredient (C) is 90:10 to 20:80, preferably 80:20 to 30:70. When ingredient (C) is the non-yellowing polyisocyanate compound, the eguivalent value of the isocyanate group in ingredient (C) to one equivalent of hydroxyl group in ingredient (B) is preferably 0.5 to 1.5 equivalent, more preferably 0.6 to 1.2 equivalent. When the content of ingredient (A) is less than the lower limit in the range of the weight ratio of ingredient (A) to the total weight of ingredient (B) and ingredient (C), distinction of image of the cured paint film may be inferior. When the content of ingredient (A) is more than the upper limit of the range, the curing shrinkage of the paint f ilm is increased and the adhesive property is inferior. Further, when the weight ratio of ingredient (C) is less than the lower limit in the range of the weight ratio of ingredient (B) to ingredient (C), curability is not sufficient and gasoline resistance is inferior. When the weight ratio of ingredient (C) is more than the upper limit in the range, the curing shrinkage stress of the paint film is increased and the adhesive property is inferior. The light stabilizer of ingredient (D) used in the present invention is used for increasing weathering resistance of the paint film. The light stabilizer includes compounds which are dissolved or dispersed homogeneously in the paint film, does not cause curing inhibition at the time of ultraviolet-curable, and does not cause yellowing of the paint film. The light stabilizer includes ultraviolet absorbents and antioxidants. The ultraviolet absorbents include, for example, benzophenone or derivatives thereof, phenylsalicylate or derivatives thereof, benzotriazole or derivatives thereof, and cyanoacrylate or derivatives thereof. Among them, benzotriazole based ultraviolet absorbents are preferable particularly. The antioxidants include phenol based antioxidants, organic phosphite based antioxidants, organic thioether based antioxidants and hindered amine based antioxidants. In particular, the hindered amine based antioxidants are preferable. The light stabilizer can be utilized singly or in combination of two or more members. The amount of the light stabilizer is preferably 0.5 to 5 parts by weight to 100 parts by weight of the total amount of ingredient (A), ingredient (B) and ingredient (C). Photopolymerization initiator of ingredient (E) used in the present invention includes benzoin or derivatives thereof, benzophenone or derivatives thereof, acetophenone or derivatives thereof, Michler's ketone, benzyl or derivatives thereof, tetraalkyl chiuram monosulfide and thioxane, having absorption in ultraviolet area of 260 to 450 nm. Among them, acetophenone or derivatives thereof are preferable particularly. The photopolymerization initiator can be utilized singly or in combination of two or more members. The amount of the photopolymerization initiator is preferably 0.5 to 5 parts by weight to 100 parts by weight of the total amount of ingredient (A), ingredient (B) and ingredient (C). The ultraviolet-curable coating composition of the present invention can be further formulated properly with one or not less than two members of dilution solvents for controlling viscosity, sensitizers of photopolymerization reaction such as amine compounds, urea compounds and sulfur compounds which are used generally for ultraviolet-curable coating composition, organic peroxides for proceeding the polymerization curing homogeneously, pigments, dyes and the like. In the ultraviolet-curable coating composition of the present invention, thecomponents described before are formulated to be able to obtain a cured paint film having a Knoop hardness of 10 to 18, preferably 11 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300, preferably 170 to 280. When the Knoop hardness of the cured paint film is less than 10, gasoline resistance is inferior. When the Knoop hardness of the cured paint film is more than 18, scratch resistance is inferior. When the molecular weight of intercrosslinking of crosslinked resin component in the cured paint film is less than 150, the curing shrinkage strain in the paint film is increased, adhesive property is inferior, and a graphic tape is easily cracked in the case that the ultraviolet-curable coating composition is applied on an article adhered with the graphic tape. On the other hand, when the molecular weight of intercrosslinking of crosslinked resin component in the cured paint film is more than 300, scratch resistance is inferior. Here the graphic tape is generally a graphic tape formed by providing such as printing and applying, of a display such as literatures of maker name, product name and the like, symbols, marks, figures and patterns on the surface of the substrate being a sheet of resin such as vinyl chloride resins and urethane resins, by applying a clear coating composition such as urethane resin clear coating composition on the surface of the display, by drying, and then by pattern-draw-molding. Also, the graphic tape includes graphic tapes formed by providing a display of metal vapor deposition such as aluminum vapor deposition and chromium vapor deposition on the surface of a sheet of resin such as polyethylene terephthalate resin. Knoop hardness is a hardness of the paint film measured at 20 °C by micro surface hardness meter ( produced by Shimazu Co., trade name "HMV-2000" ). As the value of Knoop hardness increases, the paint film becomes harder. The molecular weight of intercrosslinking of crosslinked resin component is a value obtained from dynamic regidity modulus in rubber area of the separated paint film, which is measured in condition of 110 Hz of frequency and 2 °C per minute of increasing rate of temperature by using a forced stretching vibration type viscoelasticity measuring device ( produced by Toyo Baldwin Co., trade name "REHOVTBRON DDV-II-EA" ) and is represented by the following formula. (Formula Removed) In the formula, Mc is the molecular weight of intercrosslinking of crosslinked resin component ( g/mol ), p is a density of the paint film ( g/cm3 ), G' is a dynamic rigidity in rubber area ( E'/3(dyne/cm2) ) and E' is a dynamic modulus of elasticity in rubber area (dyne/cm2). The method of applying the ultraviolet-curable coating composition of the present invention is not limited particularly. For example, after applying and curing a baking curing colored coating composition on an article to be coated beforehand, and adhering a graphic tape or the like on the surface of the baked colored paint film according to needs because of problems in design, the cured paint film can be obtained by applying the ultraviolet-curable coating composition on the coated article described above by methods such as spraying application, electrostatic application and curtain flow application, and irradiating ultraviolet light to cure. In this case, before the ultraviolet light is irradiated, preheating for removing solvents can be provided, or after the ultraviolet light is irradiated, afterheating can be provided. The temperature of preheating is not limited, but is preferably not less than 50 °C for increasing volatility of solvent. The temperature of afterheating is preferably not less than 80 °C for promoting curing of amino resin. The upper limit of temperature of the preheating or afterheating is not limited, but is preferably not more than 200 °C. The irradiation of ultraviolet light is conducted preferably by using an ultraviolet irradiation device, which can irradiate to the surface of three-dimensional coated article almost homogeneously. As ultraviolet light sources, high-pressure mercury lamps, metal halide lamps and the like can be used. The condition of ultraviolet light irradiation for curing the coated article includes a method of irradiating for long time with weak ultraviolet light and a method of irradiating for short time with strong ultraviolet light. Any one of the methods can be selected arbitrarily. When the weak ultraviolet light is irradiated for short time, the amount of ultraviolet energy for giving to the coated film runs short and therefore the curing is defective. When the strong ultraviolet light is irradiated for long time, the amount of ultraviolet energy for giving to the coated film is excess and therefore the paint film causes yellowing discoloration. Preferable amount of ultraviolet energy for curing the coated article is 100 to 5000 mJ/cm2. The thickness of the paint film obtained by applying the ultraviolet-curable coating composition of the present invention can be selected properly according to needs, but is preferably 10 to 200 µm of the dried thickness, in general. Coated articles obtained by applying the ultraviolet-curable coating composition of the present invention is not particularly limited, but include structures, wood articles, metallic articles, plastics articles, rubber articles, coated papers, ceramic articles and glass articles, specifically automobiles, parts for automobiles (for example, body, bumper, spoiler, mirror, wheel and inner package material, and these parts are made of various materials) , metal plates such as steel plates, two-wheel vehicles, parts for two-wheel vehicles, materials for road (for example, guard rail, traffic control sign and sound-proof wall) , materials for tunnel (for example, side wall plate) , marine vessels, railway vehicles, airplanes, furnitures, musical instruments, house-hold electric instruments, building materials, vessels, of f ice articles, sport articles and toys. Example The invention is explained in detail with reference to the following Examples; however, these Examples are intended to illustrate the invention and are not to be construed to limit the scope of the invention. Hereinafter, the term, "part" means "part by weight" and the term, "%" means "% by weight". Evaluation of the properties of the paint films in Examples and Comparative Examples was conducted as follows. (1) scratch resistance On a surface of the paint film, a skin was rubbed by reciprocating 1000 times under a load of 1 kg by using a RUBBING TESTER (produced by OHIRA RIKA Industry Co., Ltd. ). The scratch trace was observed by visual and the evaluation was conducted according to the following standard. O : The scratch trace was not observed. X : The scratch trace was observed. (2) distinction of image The distinction of image of the cured film was measured by a portable distinction of image and gloss meter PGD-IV produced by TOKYO KODEN Co., Ltd. When the value is not less than 0.9, the distinction of image is good. (3) adhesion The cutting lines were marked on the paint film by a cutting knife as the cut reached to the substrate under the paint film and 100 of cross-hathced square (lmmxlmm) were depicted. A pressure sensitive adhesive cellophane tape was adhered on the surface of the paint film, and then peeled rapidly from the surface of the paint film. The condition of the peeled surface of the paint film was observed and the adhesion was evaluated according to the following Standard. O: The peeling of the cross-cut marked paint film was not observed at all. X : The number of the peeling of the cross-cut marked paint film was not less than 10. (4) gasoline resistance The test piece was immersed in regular gasoline ( produced by NIPPON OIL CORPORATION.) at 20 °C for 24 hours. The appearance of the test piece was observed by visual. The gasoline resistance was evaluated according to the following standard. O: The abnormality on the paint film was not observed. X : The abnormality such as yellowing and blistering on the paint film was observed. (5) resistance against to graphic tape test The part of the paint film on which a graphic tape ( produced by SUMITOMO 3M Co. ) was adhered, was observed by visual. The resistance against to graphic tape test was evaluated according to the following standard. O: The abnormality on the paint film was not observed. X : The abnormality such as cracking and contraction on the paint film was observed. (Examples 1 to 13) Preparation of ultraviolet-curable coating composition The ultraviolet-curable coating compositions were prepared by mixing homogeneously all components of components (A) to (E) and SOLVESSO 100 indicated in Tables 1 to 4 in the ratio of the formulation amount indicated in Tables 1 to 4. Preparation of test pieces Acrylic resin / melamine resin based white coat solid coating composition (trade name "BELCOAT HS-1 WHITE", a product of BASF NO F Coatings Co., Ltd.) was applied by spraying to a PB-137 treated dull steel plate ( 70 mm in length, 150 mm in width and 0.8 mm in thickness ) in an amount to form a film having dried thickness of 40µm. After leaving the coated steel plate at room temperature for 10 minutes, the coated steel plate was baked at 140 °C for 30 minutes. A graphic tape ( produced by SUMITOMO 3M Co. ) was adhered or not adhered on a part of the surface of the coated steel plate and then the ultraviolet-curable coating compositions of Examples 1 to 13 were applied by spraying to coated steel plate adhered with the graphic tape or without the graphic tape in an amount to form a film having dried thickness of 60 µm. The coated steel plate was left at room temperature for 2 minutes. And then, the coated steel plate was heated for 3 minutes to reach the temperature of 70 °C by a far infrared heater ( produced by NIHON GAISHI Co. , Ltd., trade name "INFRASHUTAIN" ) and irradiated with ultraviolet light for 2 seconds by a metal halide lamp ( produced by NIPPON DENCHI Co., Ltd., 20 cm in length, 3 bulbs, 4.8 kw ) which is equipped at the distance of 20 cm from the coated steel plate. After this ultraviolet irradiation, the coated steel plate was heated for 5 minutes to reach the temperature of 120 °C by the far infrared heater to obtain test pieces. The properties of the obtained test pieces are shown in the low portion of Tables 1 to 4. Table 1 (Table Removed) The ultraviolet-curable coating compositions were prepared by mixing homogeneously all components of components (A) to (E) and SOLVESSO 100 indicated in Tables 5 to 11 in the ratio of the formulation amount indicated in Tables 5 to 11. Next, test pieces were prepared in the same method as described in Example 1 except that each of the coating composition of Comparative Examples 1 to 30 was used instead of the ultraviolet-curable coating composition of Example 1. The properties of the obtained test pieces are shown in the low portion of Tables 5 to 11. Table 5 (Table Removed) In Tables 1 to 11, the suffixed numerical characters indicate the following. 1: SR-295 ( trade name, produced by NIPPON KAYAKU Co.,Ltd., pentaerythritol tetraacrylate, number of functional groups: 4, number average molecular weight: 352 ) 2: KAYARAD PEG400DA ( trade name, produced by NIPPON KAYAKU Co. ,Ltd., polyethylene glycol diacrylate, number of functional groups: 2, number average molecular weight: 522 ) * 3: KAYARAD TMPTA (trade name, produced by NIPPON KAYAKU Co., Ltd., trimethylolpropane triacrylate, number of functional groups: 3, number average molecular weight: 296 ) 4: resin varnish (lactone-modified polymer of polyhydric alcohol mono (meth) aery late) containing 29 % of a -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value derived from the lactone modification of 140 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 27 parts of butyl methacrylate, 61 parts of PLACCEL FM-1D, 2 parts of acrylicacidand5partsof apolymerizationinitiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers. 5: resin varnish (lactone-modified polymer of polyhydric alcohol mono(meth)acrylate) containing 50 % of a nonvolatile matter, and having a hydroxyl value of 142 mgKOH/g and a number average molecular weight of 3, 000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 42 parts of butyl methacrylate, 13 parts of butylacrylate, 33 parts of 2-hydroxyethyl methacrylate, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL 0", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers. 6: resin varnish (lactone-modified polymer of polyhydric alcohol mono (meth) aery late) containing 14 .5 % of £ -caprolac tone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value derived from the lactone modification of 71 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 57 parts of butyl methacrylate, 31 parts of PLACCEL FM-1D, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers. 7: resin varnish (lactone-modified polymer of polyhydric alcohol mono'(meth)acrylate) containing 29 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value derived from the lactone modification of 140 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 27 parts of butyl acrylate, 61 parts of PLACCEL FM-1D, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers. * 8: resin varnish containing 21 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxy1 value derived from the lactone modification of 101 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 44 parts of butyl methacrylate, 44 parts of PLACCEL FM-1D, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers. 9: resinvarnish containing 20 % of -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value of 100 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging 400 parts of phthalic acid anhydride, 185 parts of trimethylol propane, 129 parts of adipic acid and 286 parts of 1,6-hexanediol into a reaction vessel equipped with a stirrer, a thermometer, a device for removing water produced in the reaction and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 220 °C for 6 hours while removing condensed water produced in the reaction to keep the temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 15 mgKOH/g, charging 500 parts of a mixture of xylene and isobutyl acetate (weight ratio: 90/10) and 231 parts of -caprolactone, heating the mixture to 140 °C, keeping the same temperature for 15 hours, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %. 10: resin varnish containing 50 % of a nonvolatile matter, and having a hydroxyl value of 100 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 2,4 00, which was prepared by charging 320 parts of phthalic acid anhydride, 122 parts of trimethylol propane, 210 parts of adipic acid and 348 parts of 1, 6-hexanediol into a reaction vessel equipped with a stirrer, a thermometer, a device for removing water produced in the react ion and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 220 °C for 6 hours while removing condensed water produced in the reaction to keep the temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 12 mgKOH/g, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %. * 11: resin varnish containing 20 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value of 4 0 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 2,500, which was prepared by charging 400 parts of phthalic acid anhydride, 20 parts of trimethylol propane, 140 parts of adipic acid and 440 parts of 1, 6-hexanediol into a reaction vessel equipped with a stirrer, a thermometer, a device for removing water produced in the reaction and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 220 °C for 6 hours while removing condensed water produced in the reaction to keep the temperature of 2 20 °C, cooling the mixture to 100 °C at the time that the acid value became to 15 mgKOH/g, charging 500 parts of a mixture of xylene and isobutyl acetate (weight ratio: 90/10) and 230 parts of -caprolactone, heating the mixture to 140 °C, keeping the same temperature for 15 hours, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %. * 12: resin varnish containing 40 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value of 100 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 2,800, which was prepared by charging 100 parts of phthalic acid anhydride, 278 parts of trimethylol propane, 427 parts of adipic acid and 195 parts of 1, 6-hexanediol into a reaction vessel equipped with a stirrer, a thermometer, a device for removing water produced in the reaction and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 2 20 °C for 6 hours while removing condensed water produced in the reaction to keep the temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 20 mgKOH/g, charging 500 parts of a mixture of xylene and isobutyl acetate (weight ratio: 90/10) and 592 parts of -caprolactone, heating the mixture to 140 °C, keeping the same temperature for 15 hours, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %. * 13: resin varnish containing 15 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value of 100 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 2,400, which was prepared by charging 600 parts of phthalic acid anhydride, 167 parts of trimethylol propane, 31 parts of adipic acid and 2 02 parts of ethylene glycol into a reaction vessel equipped with a stirrer, a thermometer, a device for removing water produced in the reaction and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 2 20 °C for 6 hours while removing produced condensed water to keep the temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 14 mgKOH/g, charging 500 parts of a mixture of xylene and isobutyl acetate (weight ratio: 90/10) and 163 parts of -caprolactone, heating themixture to 140 °C, keeping the same temperature for 15 hours, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %. * 14: DESMODURE N-75 (trade name, produced by BAYER Co., non-yellowing polyisocyanate compound (biuret compound of hexamethylene diisocyanate ), 75 % of nonvolatile matter, 16.6 % of NCO group content) 15: SUPER BECKAMINE L-116-70 (trade name, produced by DAINIPPON INK Chemical Industries, LTD., melamineresin, 70 % of nonvolatile matter) 16: DURANATE MF-K60X (trade name, produced by Asahi Kasei Corporation., blocked isocyanate, 60 % of nonvolatile matter, 6.6 % of NCO group content) 17: SANOL LS-292 (trade name, produced by SANKYO Co., hindered amine based antioxidant) 18: TINUVIN 900 (trade name, produced by CHIBA SPECIAL TY CHEMICALS INC., benzotriazole based ultraviolet absorbent) 19: IRGACURE 184 (trade name, produced by CHIBA SPECIA L T Y CHEMICALS INC., acetophenone based polymerization initiator) *20: SOLVESSO 100 (trade name, produced by EXXON Chemistry Co., aromatic solvent) As definite from the results indicated in Tables 1 to 11, in Examples 1 to 13 of theultraviolet-curable coating composition of the present invention, scratch resistance of the paint film is excellent and distinction of image, adhesion and gasoline resistance of the paint film are excellent. Further, when the ultraviolet-curable coating compos it ion is applied on the article to be coated which the graphic tape is adhered, abnormality such as cracking and contraction is not observed. Against, all of scratch resistance, distinction of image, adhesion, gasoline resistance and resistance of graphic tape test of the paint film can not be satisfied at the same time in Comparative Examples 1 to 30 which are not exmaple of the present invention. The ultraviolet-curable coating composition of the present invention can form the cured paint film having excellent scratch resistance and high degree of aesthetic decorative property, also excellent adhesion and gasoline resistance, and has high productivity of paint film. We Claim: 1. An ultraviolet-curable coating composition comprising: (A) an ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate having four or more (meth)acryloyl groups in the molecule and a number average molecular weight of 300 to 2,000. (B) a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 25 to 60 percents by weight of e-caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 120 to 180 mgKOH/g, and/or a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g, (C) a non-yellowing polyisocyanate compound and/or an amino resin, (D) a light stabilizer and, (E) a photopolymerization initiator, wherein a weight ratio of component (A) against to a total weight of components (B) and (C) is 10:90 to 50:50, a weight ratio of component (B) against to component (C) is 90:10 to 20:80, an amount of component (D) is 0.5 to 5 parts by weight to 100 parts by weight of the total amount of component (A), component (B), and component (C) and an amount of component (E) is 0.5 to 5 parts by weight to 100 parts by weight of the total amount of component (A), component (B), and component (C). 2. The ultraviolet-curable coating composition as claimed in claim 1, wherein ingredient (B) is a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 25 to 60 percents by weight of e-caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 120 to 180 mgKOH/g. 3. The ultraviolet-curable coating composition as claimed in claim 1, wherein ingredient (B) is a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g. 4. The ultraviolet-curable coating composition as claimed in any one of claims 1 to 3, wherein ingredient (C) is a non-yellowing polyisocyanate compound and the equivalent value of isocyanate group of ingredient (C) to the hydroxyl group of ingredient (B) is from 0.5 to 1.5. 5. The ultraviolet-curable coating composition as claimed in any one of claims 1 to 3, wherein ingredient (C) is an amino resin. 6. An ultraviolet-curable coating composition as claimed in any one of claims 1 to 5 which is used for applying to an article.

Full Text

SPECIFICATION ULTRAVIOLET-CURABLE COATING COMPOSITION AND COATED ARTICLE
Field of technology
The present invention relates to an ultraviolet-curable coating composition which can be used in the field that high degree of aesthetic decorative property and excellent properties of a paint film, for example, scratch resistance, gasoline resistance and excellent gloss-holding property in atmospheric exposure are required, and a coated article thereof.
Background technology
In recent years, as coating compositions for vehicles which requires high degree of aesthetic decorative property and board excellent properties of a paint film, solvent type or water-soluble type of acrylic resin / melamine resin coating compositions and acrylic resin / urethane resin coating compositions have been mainly utilized.
Also, as different coating compositions from the thermosetting coating compositions described above, Japanese patent publication 1960210 discloses an ultraviolet-curable coating composition comprising an ultraviolet curable polyfunctional (meth)aerylate and acrylic resin, polyisocyanate compound, light stabilizer and photopolymerization initiator. And Japanese patent publication 2504061 discloses an ultraviolet-curable coating composition comprising an ultraviolet curable polyfunctional (meth) aerylate and acrylic resin, melamine resin or urea resin, light stabilizer and
photopolymerization initiator.
However, the acrylic resin / urethane resin coating compositions and the acrylic resin / melamine resin coating compositions described before are not necessarily sufficient in distinction of image of the paint film and are insufficient in view of productivity of the paint film because it takes long time to cure the coating composition. On the other hand, the ultraviolet-curable coating compositions of Japanese patent publication 1960210 and 2504061 give excellent distinction of image of the paint film and have high level productivity of the paint film, but can not give the paint film having excellent scratch resistance.
The present invention has an object to provide the ultraviolet-curable coating composition which can give the paint film having not only excellent scratch resistance and high degree of aesthetic decorative property, but also excellent adhesion and excellent gasoline resistance, and have high level productivity of the paint film, and the coated article obtained by application of the ultraviolet-curable coating composition.
Disclosure of the invention
As a result of extensive investigations undertaken by the present inventors in order to solve the problems described above, it was found that the object of the present invention is achieved by using an ultraviolet-curable coating composition comprising a specific ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate, a specific lactone-modified polymer of polyhydric alcohol mono(meth)aerylate containing 20 to 60 percents by weight of
a -caprolactone ring-opening addition product and/or a specific lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product, and a non-yellowing polyisocyanate compound and/or an amino resin, in a specific ratio and further, a light stabilizer and a photopolymerization initiator, and the components described above are formulated to obtain a cured paint film having a Knoop hardness of 10 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300. And thus the present invention is completed.
That is to say, the present invention provides an
ultraviolet-curable coating composition comprising:
(A) an ultraviolet curable four or more functional
groups-containing polyfunctional (meth)acrylate having
four or more (meth) acryloyl groups in the molecule and a number
average molecular weight of 300 to 2,000,
(B)a lactone-modified polymer of polyhydric alcohol
mono(meth)aerylate containing 20 to 60 percents by weight
of -caprolactone ring-opening addition product and having
a hydroxyl value derived from the lactone modification of
100 to 180 mgKOH/g, and/or a lactone-modified polyester resin
containing 10 to 50 percents by weight of lactone ring-opening
addition product and having a hydroxyl value of 50 to 180
mgKOH/g,
(C)a non-yellowing polyisocyanate compound and/or an amino
resin, (D)a light stabilizer and, (E)a photopolymerization initiator, wherein a weight ratio of component (A) against to a total weight
of component Components (B) and (C) is 10 : 90 to 50 : 50, a weight ratio of component (B) against to component (C) is 90 : 10 to 20 : 80, and the components described above are formulated to obtain a cured paint film having a Knoop hardness of 10 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300.
The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (B) is a lactone-modified polymer of polyhydric alcohol mono(meth)aerylate containing 20 to 60 percents by weight of  -caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 100 to 180 mgKOH/g.
The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (B) is a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g.
The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (C) is a non-yellowing polyisocyanate compound and the equivalent value of isocyanate group of ingredient (C) to the hydroxyl group of ingredient (B) is from 0.5 to 1.5.
The present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (C) is an amino resin.
The present invention also provides a coated article obtained by applying the ultraviolet-curable coating composition as described above.
In the present invention, the term, (meth)acryloyl group means acryloyl group and/or methacryloyl group. Also, the term, (meth)aery late means acrylate and/or methacrylate and the term, (meth)acrylic acid means acrylic acid and/or methacrylic acid.
Preferable embodiment for practicing the invention
The ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A), used in the present invention, has fourormore (meth) acryloyl groups in the molecule. When a polyfunctional (meth)acrylate having two (meth)acryloyl groups in the molecule is used, curability is insufficient and gasoline resistance is inferior. Also, when a polyfunctional (meth)acrylate having three (meth)acryloyl groups in the molecule is used and a large amount of ingredient (A) is formulated to obtain a cured paint film having a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300, the increase of curing shrinkage strain in the paint film is caused and adhesive property is inferior.
Further, the number average molecular weight of ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) is from 300 to 2,000, preferably from 320 to 1,500. When the number average molecular weight is more than 2,000, leveling property of the paint film is inferior and it is difficult to obtain the high degree of aesthetic decorative property. On the other hand, when the number average molecular weight is less than 3 00, flexibility of the paint film is inferior and crack is easily caused in bending test.
The ultraviolet curable four or more functional groups-containing polyfunctional (meth) aerylate of ingredient (A) includes a four or more functional groups-containing polyhydric alcohol (meth)acrylate obtained by esterification of tetravalent or more polyhydric alcohol with (meth)acrylic acid, a four or more functional groups-containing epoxy(meth)acrylate obtained by esterification of epoxy groups of fourormorefunctionalgroups-containingpolyfunctionalepoxy compound with (meth)acrylic acid, a four or more functional groups-containing polyurethane(meth)aerylate obtained by reaction of four or more functional groups-containing polyfunctional isocyanate compound with hydroxyl group-containing (meth)acrylate, and a four or more functional groups-containing melamine (meth) aery late obtained by reaction of methylolmelanine having four or more methylol groups in a molecule with hydroxyl group-containing (meth) aery late. The four or more functional groups-containing polyfunctional (meth)aerylate of ingredient (A) can be utilized singly or in combination of two or more members.
The four or more functional groups-containing polyhydric
alcohol (meth)acrylate includes pentaerythritol
tetra( meth) aery late, ditrimethylolpropane tetra(meth)acrylate,
ethoxylated pentaerythritol tetra(meth)acrylate,
dipentaerythritol penta(meth)acrylate,
xylitolpenta(meth)acrylate, dipentaerythritol
hexa(meth)acrylate, glycerildipentaerythritol
hepta(meth)acrylate. Commercial compounds of four or more functional groups-containing polyhydric alcohol (meth)acrylate include KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 and
KAYARAD DPCA-120 (all trade names, products of NIPPON KAYAKU CO. LTD..) .
The four or more functional groups-containing polyfunctional epoxy compound used to prepare the four or more functional group-containing epoxy(meth)aerylate includes glycidyl ether epoxy resins such as phenol novolac type glycidyl ether epoxy resins, orthocresol novolac type glycidyl ether epoxy resins, bisphenol A novolac type glycidyl ether epoxy resins, brominated phenol novolac type glycidyl ether epoxy resins and tetraphenylol ethane type glycidyl ether epoxy resins.
The four or more functional groups-containing polyfunctional isocyanate compound used to prepare the four or more functional group-containing polyurethane(meth)aerylate includes reaction products obtained by reaction of hexamethylene diisocyanate and/or isophorone diisocyanate with four or more functional groups-containing polyhydric alcohol such as pentaerythritol and dipentaerythritol.
The methylolmelanine having four or more methylol groups in a molecule used to prepare the four or more functional group-containing melamine (meth)acrylate includes tetramethylolmelamine, pentamethylolmelamine and hexamethylolmelamine.
The hydroxyl group-containing (meth)acrylate used to prepare the four or more functional group-containing polyurethane(meth)acrylate and the four or more functional group-containing melamine (meth) acrylate includes hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; polyhydric
alcohol mono(meth)aerylates such as polyethyleneglycol mono(meth)aerylate, polypropyleneglycol mono(meth)aerylate, neopentylglycol mono(meth)acrylate and glycerin mono(meth)acrylate; ethyleneoxide and/or propyleneoxide addition products of hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate.
Among the four or more functional group-containing polyfunctional (meth)acrylates, the polyfunctional (meth)acrylate having the acryloyl group in the molecule has high curability compared with the polyfunctional (meth)acrylate having the methacryloyl group in the molecule. Therefore, the polyfunctional (meth)acrylate having the acryloyl group in the molecule is more preferably used in the present invention.
Ingredient (A) can be utilized singly or in combination of two or more members.
Ingredient (B) used in the present invention is a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 20 to 60 percents by weight of
£ -caprolactone ring-opening addition product and having a hydroxy 1 value derived from the lactone modification of 100 to 180 mgKOH/g (hereinafter, it may be called "ingredient (Ba)"), and/or a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g (hereinafter, it may be called "ingredient (Bb)"),
The content of a -caprolactone ring-opening addition product in ingredient (Ba) is 20 to 60 percents by weight,
preferably 25 to 50 percents by weight. When the content of £-caprolactone ring-opening addition product is less than 20 percents by weight, the scratch resistance of the paint film
is not sufficient. When the content of  -caprolactone ring-opening addition product is more than 60 percents by weight, hardness of the paint film is too low and the gasoline resistance of the paint film is inferior.
The hydroxyl value derived from the lactone modification of ingredient (Ba) is 100 to 180 mgKOH/g, preferably 120 to 170 mgKOH/g. The term, "the hydroxyl value derived from the lactone modification" means the hydroxyl value of the hydroxyl group which exist in the end of the structure portion consisting of the  -caprolactone ring-opening addition product in the lactone-modified polymer of polyhydric alcohol mono(meth)acrylate and does not contain the hydroxyl value of the hydroxyl group in the other structure portion. When the hydroxyl value derived from the lactone modification is less than 100 mgKOH/g, the scratch resistance of the paint film is not sufficient. When the hydroxyl value derived from the lactone modification is more than 180 mgKOH/g, the compatibility with the four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) is inferior.
The molecular weight of ingredient (Ba) is not limited particularly. The number average molecular weight of ingredient (Ba) is preferably about 2,000 to 20,000 in general.
The lactone-modified polymer of polyhydric alcohol mono(meth)acrylate of ingredient (Ba) can be utilized singly or in combination of two or more members.
The method for preparing ingredient (Ba) includes (1) a
preparation method comprising homopolymerizing polycaprolactone-modified polyhydric alcohol mono(meth)aerylate obtained by ring-opening addition of e -caprolactone to the polyhydric alcohol mono (meth )acrylate or copolymerizing it and other copolymerizable vinyl monomer, and (2) a preparation method comprising ring-opening adding  -caprolactone to a homopolymer or a copolymer of polyhydric alcohol mono (meth) acrylate which is obtained by homopolymerizing polyhydric alcohol mono (meth) acrylate or copolymerizing it and other copolymerizable vinyl monomer.
The polyhydric alcohol mono(meth)acrylate used in the methods (1) and (2) as described above includes 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, polyethyleneglycol mono(meth)acrylate, polypropyleneglycol mono(meth)acrylate, neopentylglycol mono(meth)acrylate and glycerin mono(meth)acrylate. The polyhydric alcohol mono(meth)acrylate can be utilized singly or in combination of two or more members.
The polycaprolactone-modified polyhydric alcohol mono(meth)acrylate used in the method (1) as described above includes polycaprolactone-modified hydroxyalkyl mono(meth)acrylate and polycaprolactone-modified poly(oxyalkylene) mono(meth)acrylate.
Commercial compounds of polycaprolactone-modified polyhydric alcohol mono(meth)acrylate include PLACCEL FA-1 (trade name, produced by Daicel Chemical Industries, LTD. , monomer obtained by ring-opening addition of one mole of -caprolactone to one mole of 2-hydroxyethyl acrylate), PLACCEL
FM-1D, PLACCEL FM-2D, PLACCEL FM-3 and PLACCEL FM-4 (all trade names, produced by Daicel Chemical Industries, LTD. , monomer obtained by ring-opening addition of one mole, two moles, three
moles or four moles of £ -caprolactone respectively to one mole of 2-hydroxyethyl methacrylate).
The other copolymerizable vinyl monomers used in the methods (1) and (2) as described above include, for example, (meth)acrylic acid and alkyl substitution products thereof; alkyl(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)aerylate, butyl (meth)aerylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)aerylate and stearyl (meth)acrylate; hydroxyalkyl (meth)aerylates such as 2-hydroxyethyl (meth)aerylate and 3-hydroxypropyl (meth)acrylate; esters of dibasic acid such as itaconic acid, maleic acid and fumalic acid; styrene and nuclear-substituted styrenes such as vinyl toluene, dimethyl styrene and ethyl styrene; and (meth)aerylonitrile, (meth)aerylamide, vinyl acetate and vinyl chloride. The other copolymerizable monomer can be utilized singly or in combination of two or more members.
In the polymerization for preparation of ingredient (Ba), a polymerization initiator can be utilized. The polymerization initiator includes organic peroxide polymerization initiators and azo polymerization initiators. The amount of the polymerization initiator is not limited particularly, but preferably 0.5 to 15 percents by weight to total amount of the monomers, in general. Ingredient (Ba) can be utilized singly or in combination of two or more members.
The content of lactone ring-opening addition product in ingredient (Bb) is 10 to 50 percents by weight, preferably 15
to 40 percents by weight. When the content of lactone ring-opening addition product is less than 10 percents by weight, the scratch resistance of the paint film is not sufficient. When the content of lactone ring-opening addition product is more than 50 percents by weight, hardness of the paint film is too low and the gasoline resistance of the paint film is inferior.
The hydroxyl value of ingredient (Bb) is 50 to 180 mgKOH/g, preferably 70 to 170 mgKOH/g. When the hydroxyl value is less than 50 mgKOH/g, the scratch resistance of the paint film is not sufficient. When the hydroxyl value is more than 180 mgKOH/g, the compatibility with the four or more functional groups-containing poly functional (meth) aery late of ingredient (A) is inferior.
The molecular weight of ingredient (Bb) is not limited particularly. The number average molecular weight of ingredient (Bb) is preferably about 1,500 to 20,000, more preferably 1,500 to 5,000 in general.
The method for preparing ingredient (Bb) includes a preparation method comprising ring-opening addition of a lactone to a polyester resin obtained by bonding a polybasic acid and a polyhydric alcohol.
The polybasic acid used in the method described above includes, for example, aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, tetrachloro phthalic acid, naphthalene dicarboxylic acid, 4,4-diphenylmethane carboxylic acid; alicyclic polybasic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrotrimellitic acid and methyl hexahydroterephthalic
acid; saturated and unsaturated aliphatic polybasic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebasic acid, dodecane dicarboxylic acid, pimelic acid, maleic acid, fumaric acid and itaconic acid. Also, anhydrides of the polybasic acids described above and ester-formable substitution product thereof, for example, ester of lower alkyl having 1 to 6 carbon atoms, can be utlized as the polybasic acid. The polybasic acid can be utilized singly or in combination of two or more members.
Examples of the polyhydric alcohol described above are divalent alcohols and trivalent or more alcohols described below.
The divalent alcohols include, for example, glycols such
as ethylene glycol, propylene glycol, diethylene glycol,
triethylene glycol, 1,4-butanediol, 1,3-butanediol,
2,3-butanediol, 1,2-butanediol, 1,5-pentanediol,
1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyl trimethylene
glycol, tetramethylene glycol, 3-methyl-4,5-pentanediol,
2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol,
1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol; polyether diols such as alkylene oxide addition products of bisphenol A, polyethylene glycol and polypropylene glycol; and monoepoxy
compounds such as a-olefin epoxides like propylene oxide and butylene oxide and CARDURA E-10 (trade name, produced by SHELL chemical Co., glycidyl ester of synthetichigh branched saturated aliphatic acid ).
Further, trivalent or more alcohols include, for example, glycerin, trimethylol ethane, trimethylol propane, diglycerin, pentaerythritol, dipentaerythritol and sorbitol. Also,
compounds having two or more epoxy groups in the molecule like bisphenol A diglycidyl ether can be utilized as the trivalent or more alcohol. The polyhydric alcohol can be utilized singly or in combination of two or more members.
For the polyester resins used for preparation of ingredient (Bb), saturated aliphatic fatty acids such as octyl acid, lauryl acid and stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and eleostearic acid; monobasic acids such as benzoic acid, abietic acid, acetic acid, propionic acid and butyric acid; hydroxycarboxylic acid compounds such as methylol propionic acid, pivalic acid, 12-hydroxystearic acid and ricinolic acid; and oils and fats such as linseed oil, castor oil, tall oil, cotton seed oil, soybean oil, olive oil and safflower oil can be utilized as other components according to needs, other than the components described above and before. The components described above can be utilized singly or in combination of two or more members.
Lactones used for preparing ingredient (Bb) of the present invention, include  -caprolactone,  -butyrolactone, δ -valerolactone,  -valerolactone,  -caprolactone,  -nonanoic lactone and δ-dodecanolactone. In particular, -caprolactone is preferably used. The lactone can be utilized singly or in combination of two or more members.
Ingredient (Bb) can be utilized singly or in combination of two or more members.
ingredient (C) used in the present invention is a non-yellowing polyisocyanate compound and/or an amino resin.
As the non-yellowing polyisocyanate compound, aliphatic and alicyclic polyisocyanate compounds are preferably used.
Typical examples are reaction products of hexamethylene diisocyanate and/or isophorone diisocyanate with polyhydric alcohol and/or low molecular weight polyester polyol, isocyanurate compounds such as polymer of hexamethylene diisocyanate and/or isophorone diisocyanate and biuret compounds obtained by further reaction to the urethane bond. Also, blocked isocyanates in which the isocyanate groups in the polymers are masked with hydroxyl group-containing compounds, can be preferably utilized. Further, various non-yellowing polyisocyanate compounds such as polymers of diisocyanate compounds other than the compounds described above can be utilized. The non-yellowing polyisocyanate compound can be utilized singly or in combination of two or more members.
As the amino resin, melamine resins or urea resins used generally for coating compositions can be utilized. The resins include melamine resins or urea resins which are ether if icated with lower alcohol such as methanol, n-butanol and isobutanol singly or in mixture thereof. The amino resin can be utilized singly or in combination two or more members.
Further, the non-yellowing polyisocyanate compound and the amino resin can be used in combination.
With respect to the content ratio of ingredient (A), ingredient (B) and ingredient (C), the weight ratio of ingredient (A) to the total weight of ingredient (B) and ingredient (C) is 10:90 to 50:50, preferably 15:85 to 45:55, more preferably 20:80 to 40:60, and the weight ratio of ingredient (B) to ingredient (C) is 90:10 to 20:80, preferably 80:20 to 30:70.
When ingredient (C) is the non-yellowing polyisocyanate compound, the eguivalent value of the isocyanate group in
ingredient (C) to one equivalent of hydroxyl group in ingredient
(B) is preferably 0.5 to 1.5 equivalent, more preferably 0.6
to 1.2 equivalent.
When the content of ingredient (A) is less than the lower limit in the range of the weight ratio of ingredient (A) to the total weight of ingredient (B) and ingredient (C), distinction of image of the cured paint film may be inferior. When the content of ingredient (A) is more than the upper limit of the range, the curing shrinkage of the paint f ilm is increased and the adhesive property is inferior. Further, when the weight ratio of ingredient
(C) is less than the lower limit in the range of the weight ratio
of ingredient (B) to ingredient (C), curability is not sufficient
and gasoline resistance is inferior. When the weight ratio of
ingredient (C) is more than the upper limit in the range, the
curing shrinkage stress of the paint film is increased and the
adhesive property is inferior.
The light stabilizer of ingredient (D) used in the present invention is used for increasing weathering resistance of the paint film. The light stabilizer includes compounds which are dissolved or dispersed homogeneously in the paint film, does not cause curing inhibition at the time of ultraviolet-curable, and does not cause yellowing of the paint film. The light stabilizer includes ultraviolet absorbents and antioxidants. The ultraviolet absorbents include, for example, benzophenone or derivatives thereof, phenylsalicylate or derivatives thereof, benzotriazole or derivatives thereof, and cyanoacrylate or derivatives thereof. Among them, benzotriazole based ultraviolet absorbents are preferable particularly. The antioxidants include phenol based antioxidants, organic phosphite based antioxidants,
organic thioether based antioxidants and hindered amine based antioxidants. In particular, the hindered amine based antioxidants are preferable.
The light stabilizer can be utilized singly or in combination of two or more members. The amount of the light stabilizer is preferably 0.5 to 5 parts by weight to 100 parts by weight of the total amount of ingredient (A), ingredient (B) and ingredient (C).
Photopolymerization initiator of ingredient (E) used in the present invention includes benzoin or derivatives thereof, benzophenone or derivatives thereof, acetophenone or derivatives thereof, Michler's ketone, benzyl or derivatives thereof, tetraalkyl chiuram monosulfide and thioxane, having absorption in ultraviolet area of 260 to 450 nm. Among them, acetophenone or derivatives thereof are preferable particularly.
The photopolymerization initiator can be utilized singly or in combination of two or more members. The amount of the photopolymerization initiator is preferably 0.5 to 5 parts by weight to 100 parts by weight of the total amount of ingredient (A), ingredient (B) and ingredient (C).
The ultraviolet-curable coating composition of the present invention can be further formulated properly with one or not less than two members of dilution solvents for controlling viscosity, sensitizers of photopolymerization reaction such as amine compounds, urea compounds and sulfur compounds which are used generally for ultraviolet-curable coating composition, organic peroxides for proceeding the polymerization curing homogeneously, pigments, dyes and the like.
In the ultraviolet-curable coating composition of the
present invention, thecomponents described before are formulated to be able to obtain a cured paint film having a Knoop hardness of 10 to 18, preferably 11 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300, preferably 170 to 280. When the Knoop hardness of the cured paint film is less than 10, gasoline resistance is inferior. When the Knoop hardness of the cured paint film is more than 18, scratch resistance is inferior. When the molecular weight of intercrosslinking of crosslinked resin component in the cured paint film is less than 150, the curing shrinkage strain in the paint film is increased, adhesive property is inferior, and a graphic tape is easily cracked in the case that the ultraviolet-curable coating composition is applied on an article adhered with the graphic tape. On the other hand, when the molecular weight of intercrosslinking of crosslinked resin component in the cured paint film is more than 300, scratch resistance is inferior. Here the graphic tape is generally a graphic tape formed by providing such as printing and applying, of a display such as literatures of maker name, product name and the like, symbols, marks, figures and patterns on the surface of the substrate being a sheet of resin such as vinyl chloride resins and urethane resins, by applying a clear coating composition such as urethane resin clear coating composition on the surface of the display, by drying, and then by pattern-draw-molding. Also, the graphic tape includes graphic tapes formed by providing a display of metal vapor deposition such as aluminum vapor deposition and chromium vapor deposition on the surface of a sheet of resin such as polyethylene terephthalate resin.
Knoop hardness is a hardness of the paint film measured at 20 °C by micro surface hardness meter ( produced by Shimazu Co., trade name "HMV-2000" ). As the value of Knoop hardness increases, the paint film becomes harder.
The molecular weight of intercrosslinking of crosslinked resin component is a value obtained from dynamic regidity modulus in rubber area of the separated paint film, which is measured in condition of 110 Hz of frequency and 2 °C per minute of increasing rate of temperature by using a forced stretching vibration type viscoelasticity measuring device ( produced by Toyo Baldwin Co., trade name "REHOVTBRON DDV-II-EA" ) and is represented by the following formula.
(Formula Removed)
In the formula, Mc is the molecular weight of intercrosslinking of crosslinked resin component ( g/mol ), p is a density of the paint film ( g/cm3 ), G' is a dynamic rigidity in rubber area ( E'/3(dyne/cm2) ) and E' is a dynamic modulus of elasticity in rubber area (dyne/cm2).
The method of applying the ultraviolet-curable coating composition of the present invention is not limited particularly. For example, after applying and curing a baking curing colored coating composition on an article to be coated beforehand, and adhering a graphic tape or the like on the surface of the baked colored paint film according to needs because of problems in design, the cured paint film can be obtained by applying the ultraviolet-curable coating composition on the coated article described above by methods such as spraying application, electrostatic application and curtain flow application, and irradiating ultraviolet light to cure. In this case, before the
ultraviolet light is irradiated, preheating for removing solvents can be provided, or after the ultraviolet light is irradiated, afterheating can be provided. The temperature of preheating is
not limited, but is preferably not less than 50 °C for increasing volatility of solvent. The temperature of afterheating is
preferably not less than 80 °C for promoting curing of amino resin. The upper limit of temperature of the preheating or afterheating is not limited, but is preferably not more than 200 °C.
The irradiation of ultraviolet light is conducted preferably by using an ultraviolet irradiation device, which can irradiate to the surface of three-dimensional coated article almost homogeneously. As ultraviolet light sources, high-pressure mercury lamps, metal halide lamps and the like can be used. The condition of ultraviolet light irradiation for curing the coated article includes a method of irradiating for long time with weak ultraviolet light and a method of irradiating for short time with strong ultraviolet light. Any one of the methods can be selected arbitrarily. When the weak ultraviolet light is irradiated for short time, the amount of ultraviolet energy for giving to the coated film runs short and therefore the curing is defective. When the strong ultraviolet light is irradiated for long time, the amount of ultraviolet energy for giving to the coated film is excess and therefore the paint film causes yellowing discoloration. Preferable amount of ultraviolet
energy for curing the coated article is 100 to 5000 mJ/cm2. The thickness of the paint film obtained by applying the ultraviolet-curable coating composition of the present invention can be selected properly according to needs, but is preferably 10 to 200 µm of the dried thickness, in general.
Coated articles obtained by applying the ultraviolet-curable coating composition of the present invention is not particularly limited, but include structures, wood articles, metallic articles, plastics articles, rubber articles, coated papers, ceramic articles and glass articles, specifically automobiles, parts for automobiles (for example, body, bumper, spoiler, mirror, wheel and inner package material, and these
parts are made of various materials) , metal plates such as steel plates, two-wheel vehicles, parts for two-wheel vehicles, materials for road (for example, guard rail, traffic control sign and sound-proof wall) , materials for tunnel (for example, side wall plate) , marine vessels, railway vehicles, airplanes, furnitures, musical instruments, house-hold electric instruments, building materials, vessels, of f ice articles, sport articles and toys.
Example
The invention is explained in detail with reference to the following Examples; however, these Examples are intended to illustrate the invention and are not to be construed to limit the scope of the invention. Hereinafter, the term, "part" means "part by weight" and the term, "%" means "% by weight".
Evaluation of the properties of the paint films in Examples and Comparative Examples was conducted as follows. (1) scratch resistance
On a surface of the paint film, a skin was rubbed by reciprocating 1000 times under a load of 1 kg by using a RUBBING TESTER (produced by OHIRA RIKA Industry Co., Ltd. ). The scratch trace was observed by visual and the evaluation was conducted
according to the following standard. O : The scratch trace was not observed. X : The scratch trace was observed.
(2) distinction of image
The distinction of image of the cured film was measured by a portable distinction of image and gloss meter PGD-IV produced
by TOKYO KODEN Co., Ltd. When the value is not less than 0.9, the distinction of image is good.
(3) adhesion
The cutting lines were marked on the paint film by a cutting knife as the cut reached to the substrate under the paint film and 100 of cross-hathced square (lmmxlmm) were depicted. A pressure sensitive adhesive cellophane tape was adhered on the surface of the paint film, and then peeled rapidly from the surface of the paint film. The condition of the peeled surface of the paint film was observed and the adhesion was evaluated according to the following Standard.
O: The peeling of the cross-cut marked paint film was not observed at all.
X : The number of the peeling of the cross-cut marked paint film was not less than 10.
(4) gasoline resistance
The test piece was immersed in regular gasoline ( produced by NIPPON OIL CORPORATION.) at 20 °C for 24 hours. The appearance of the test piece was observed by visual. The gasoline resistance was evaluated according to the following standard. O: The abnormality on the paint film was not observed. X : The abnormality such as yellowing and blistering on the paint film was observed.
(5) resistance against to graphic tape test
The part of the paint film on which a graphic tape ( produced by SUMITOMO 3M Co. ) was adhered, was observed by visual. The resistance against to graphic tape test was evaluated according to the following standard.
O: The abnormality on the paint film was not observed. X : The abnormality such as cracking and contraction on the paint film was observed. (Examples 1 to 13) Preparation of ultraviolet-curable coating composition
The ultraviolet-curable coating compositions were prepared by mixing homogeneously all components of components (A) to (E) and SOLVESSO 100 indicated in Tables 1 to 4 in the ratio of the formulation amount indicated in Tables 1 to 4. Preparation of test pieces
Acrylic resin / melamine resin based white coat solid coating composition (trade name "BELCOAT HS-1 WHITE", a product of BASF NO F Coatings Co., Ltd.) was applied by spraying to a PB-137 treated dull steel plate ( 70 mm in length, 150 mm in width and 0.8 mm in thickness ) in an amount to form a film having dried
thickness of 40µm. After leaving the coated steel plate at room temperature for 10 minutes, the coated steel plate was baked
at 140 °C for 30 minutes. A graphic tape ( produced by SUMITOMO 3M Co. ) was adhered or not adhered on a part of the surface of the coated steel plate and then the ultraviolet-curable coating compositions of Examples 1 to 13 were applied by spraying to coated steel plate adhered with the graphic tape or without the graphic tape in an amount to form a film having dried thickness of 60 µm. The coated steel plate was left at room temperature
for 2 minutes. And then, the coated steel plate was heated for 3 minutes to reach the temperature of 70 °C by a far infrared heater ( produced by NIHON GAISHI Co. , Ltd., trade name "INFRASHUTAIN" ) and irradiated with ultraviolet light for 2 seconds by a metal halide lamp ( produced by NIPPON DENCHI Co., Ltd., 20 cm in length, 3 bulbs, 4.8 kw ) which is equipped at the distance of 20 cm from the coated steel plate. After this ultraviolet irradiation, the coated steel plate was heated for
5 minutes to reach the temperature of 120 °C by the far infrared heater to obtain test pieces. The properties of the obtained test pieces are shown in the low portion of Tables 1 to 4.
Table 1
(Table Removed)
The ultraviolet-curable coating compositions were prepared by mixing homogeneously all components of components (A) to (E) and SOLVESSO 100 indicated in Tables 5 to 11 in the ratio of the formulation amount indicated in Tables 5 to 11.
Next, test pieces were prepared in the same method as described in Example 1 except that each of the coating composition
of Comparative Examples 1 to 30 was used instead of the ultraviolet-curable coating composition of Example 1. The properties of the obtained test pieces are shown in the low portion of Tables 5 to 11.
Table 5
(Table Removed)
In Tables 1 to 11, the suffixed numerical characters indicate the following.
*1: SR-295 ( trade name, produced by NIPPON KAYAKU Co.,Ltd., pentaerythritol tetraacrylate, number of functional groups: 4,
number average molecular weight: 352 )
*2: KAYARAD PEG400DA ( trade name, produced by NIPPON KAYAKU Co. ,Ltd., polyethylene glycol diacrylate, number of functional groups: 2, number average molecular weight: 522 )
* 3: KAYARAD TMPTA (trade name, produced by NIPPON KAYAKU Co., Ltd., trimethylolpropane triacrylate, number of functional groups: 3, number average molecular weight: 296 )
*4: resin varnish (lactone-modified polymer of polyhydric alcohol mono (meth) aery late) containing 29 % of a -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value derived from the lactone modification of 140 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 27 parts of butyl methacrylate, 61 parts of PLACCEL FM-1D, 2 parts of acrylicacidand5partsof apolymerizationinitiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers.
*5: resin varnish (lactone-modified polymer of polyhydric alcohol mono(meth)acrylate) containing 50 % of a nonvolatile matter, and having a hydroxyl value of 142 mgKOH/g and a number average molecular weight of 3, 000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating
under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 42 parts of butyl methacrylate, 13 parts of butylacrylate, 33 parts of 2-hydroxyethyl methacrylate, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL 0", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers.
*6: resin varnish (lactone-modified polymer of polyhydric alcohol mono (meth) aery late) containing 14 .5 % of £ -caprolac tone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value derived from the lactone modification of 71 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 57 parts of butyl methacrylate, 31 parts of PLACCEL FM-1D, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers.
* 7: resin varnish (lactone-modified polymer of polyhydric alcohol mono'(meth)acrylate) containing 29 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value derived from the lactone modification of 140 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped
with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 27 parts of butyl acrylate, 61 parts of PLACCEL FM-1D, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers.
* 8: resin varnish containing 21 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxy1 value derived from the lactone modification of 101 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging a mixture of xylene and isobutyl acetate (weight ratio: 90/10) into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping vessel of monomer, and heating under stirring until the reflux, and dropping a solution consisting of 10 parts of styrene, 44 parts of butyl methacrylate, 44 parts of PLACCEL FM-1D, 2 parts of acrylic acid and 5 parts of a polymerization initiator ( produced by NOF CORPORATION, trade name "PERBUTYL O", t-butylperoxy-2-ethylhexanoate ) at constant velocity, and copolymerizing the monomers.
*9: resinvarnish containing 20 % of -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value of 100 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 3,000, which was prepared by charging 400 parts of phthalic acid anhydride, 185 parts of trimethylol propane, 129 parts of adipic acid and 286 parts of 1,6-hexanediol into a reaction vessel equipped with a stirrer,
a thermometer, a device for removing water produced in the reaction and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 220 °C for 6 hours while removing condensed water produced in the reaction to keep the
temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 15 mgKOH/g, charging 500 parts of a mixture of xylene and isobutyl acetate (weight ratio: 90/10)
and 231 parts of -caprolactone, heating the mixture to 140 °C, keeping the same temperature for 15 hours, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %.
*10: resin varnish containing 50 % of a nonvolatile matter, and having a hydroxyl value of 100 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 2,4 00, which was prepared by charging 320 parts of phthalic acid anhydride, 122 parts of trimethylol propane, 210 parts of adipic acid and 348 parts of 1, 6-hexanediol into a reaction vessel equipped with a stirrer, a thermometer, a device for removing water produced in the react ion and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 220 °C for 6 hours while removing condensed water produced in the reaction to keep the temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 12 mgKOH/g, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %.
* 11: resin varnish containing 20 % of  -caprolactone
ring-opening addition product and 50 % of a nonvolatile matter,
and having a hydroxyl value of 4 0 mgKOH/g, an acid value of 12
mgKOH/g and a number average molecular weight of 2,500, which
was prepared by charging 400 parts of phthalic acid anhydride,
20 parts of trimethylol propane, 140 parts of adipic acid and
440 parts of 1, 6-hexanediol into a reaction vessel equipped with
a stirrer, a thermometer, a device for removing water produced
in the reaction and a introduction tube of nitrogen gas, and
heating under stirring in the atmosphere of nitrogen gas until
the temperature reached to 160 °C, keeping the mixture to the
temperature of 160 °C for 1 hour, increasing the temperature to
220 °C for 6 hours while removing condensed water produced in
the reaction to keep the temperature of 2 20 °C, cooling the mixture
to 100 °C at the time that the acid value became to 15 mgKOH/g,
charging 500 parts of a mixture of xylene and isobutyl acetate
(weight ratio: 90/10) and 230 parts of -caprolactone, heating the mixture to 140 °C, keeping the same temperature for 15 hours, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %.
* 12: resin varnish containing 40 % of  -caprolactone
ring-opening addition product and 50 % of a nonvolatile matter,
and having a hydroxyl value of 100 mgKOH/g, an acid value of
12 mgKOH/g and a number average molecular weight of 2,800, which
was prepared by charging 100 parts of phthalic acid anhydride,
278 parts of trimethylol propane, 427 parts of adipic acid and
195 parts of 1, 6-hexanediol into a reaction vessel equipped with
a stirrer, a thermometer, a device for removing water produced
in the reaction and a introduction tube of nitrogen gas, and
heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 2 20 °C for 6 hours while removing condensed water produced in the reaction to keep the temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 20 mgKOH/g, charging 500 parts of a mixture of xylene and isobutyl acetate (weight ratio: 90/10) and 592 parts of -caprolactone, heating the mixture to 140 °C, keeping the same temperature for 15 hours, and diluting the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %.
* 13: resin varnish containing 15 % of  -caprolactone ring-opening addition product and 50 % of a nonvolatile matter, and having a hydroxyl value of 100 mgKOH/g, an acid value of 12 mgKOH/g and a number average molecular weight of 2,400, which was prepared by charging 600 parts of phthalic acid anhydride, 167 parts of trimethylol propane, 31 parts of adipic acid and 2 02 parts of ethylene glycol into a reaction vessel equipped with a stirrer, a thermometer, a device for removing water produced in the reaction and a introduction tube of nitrogen gas, and heating under stirring in the atmosphere of nitrogen gas until the temperature reached to 160 °C, keeping the mixture to the temperature of 160 °C for 1 hour, increasing the temperature to 2 20 °C for 6 hours while removing produced condensed water to keep the temperature of 220 °C, cooling the mixture to 100 °C at the time that the acid value became to 14 mgKOH/g, charging 500 parts of a mixture of xylene and isobutyl acetate (weight ratio: 90/10) and 163 parts of -caprolactone, heating themixture to 140 °C, keeping the same temperature for 15 hours, and diluting
the mixture by adding a mixture of xylene and isobutyl acetate (weight ratio: 90/10) as the nonvolatile matter was 50 %. * 14: DESMODURE N-75 (trade name, produced by BAYER Co., non-yellowing polyisocyanate compound (biuret compound of hexamethylene diisocyanate ), 75 % of nonvolatile matter, 16.6 % of NCO group content)
15: SUPER BECKAMINE L-116-70 (trade name, produced by DAINIPPON INK Chemical Industries, LTD., melamineresin, 70 % of nonvolatile matter)
*16: DURANATE MF-K60X (trade name, produced by Asahi Kasei Corporation., blocked isocyanate, 60 % of nonvolatile matter, 6.6 % of NCO group content)
*17: SANOL LS-292 (trade name, produced by SANKYO Co., hindered amine based antioxidant)
*18: TINUVIN 900 (trade name, produced by CHIBA SPECIAL
TY CHEMICALS INC., benzotriazole based ultraviolet absorbent)
*19: IRGACURE 184 (trade name, produced by CHIBA SPECIA
L T Y CHEMICALS INC., acetophenone based polymerization
initiator)
*20: SOLVESSO 100 (trade name, produced by EXXON Chemistry Co.,
aromatic solvent)
As definite from the results indicated in Tables 1 to 11, in Examples 1 to 13 of theultraviolet-curable coating composition of the present invention, scratch resistance of the paint film is excellent and distinction of image, adhesion and gasoline resistance of the paint film are excellent. Further, when the ultraviolet-curable coating compos it ion is applied on the article to be coated which the graphic tape is adhered, abnormality such
as cracking and contraction is not observed.
Against, all of scratch resistance, distinction of image, adhesion, gasoline resistance and resistance of graphic tape test of the paint film can not be satisfied at the same time in Comparative Examples 1 to 30 which are not exmaple of the present invention.
The ultraviolet-curable coating composition of the present invention can form the cured paint film having excellent scratch resistance and high degree of aesthetic decorative property, also excellent adhesion and gasoline resistance, and has high productivity of paint film.

We Claim:
1. An ultraviolet-curable coating composition comprising:
(A) an ultraviolet curable four or more functional groups-containing
polyfunctional (meth)acrylate having four or more (meth)acryloyl groups in the
molecule and a number average molecular weight of 300 to 2,000.
(B) a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 25 to 60 percents by weight of e-caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 120 to 180 mgKOH/g, and/or a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g,
(C) a non-yellowing polyisocyanate compound and/or an amino resin,
(D) a light stabilizer and,
(E) a photopolymerization initiator,
wherein a weight ratio of component (A) against to a total weight of components (B) and (C) is 10:90 to 50:50, a weight ratio of component (B) against to component (C) is 90:10 to 20:80, an amount of component (D) is 0.5 to 5 parts by weight to 100 parts by weight of the total amount of component (A), component (B), and component (C) and an amount of component (E) is 0.5 to 5 parts by weight to 100 parts by weight of the total amount of component (A), component (B), and component (C).
2. The ultraviolet-curable coating composition as claimed in claim 1, wherein ingredient (B) is a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 25 to 60 percents by weight of e-caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 120 to 180 mgKOH/g.
3. The ultraviolet-curable coating composition as claimed in claim 1, wherein ingredient (B) is a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g.
4. The ultraviolet-curable coating composition as claimed in any one of claims 1 to 3, wherein ingredient (C) is a non-yellowing polyisocyanate compound and the equivalent value of isocyanate group of ingredient (C) to the hydroxyl group of ingredient (B) is from 0.5 to 1.5.
5. The ultraviolet-curable coating composition as claimed in any one of claims 1
to 3, wherein ingredient (C) is an amino resin.
6. An ultraviolet-curable coating composition as claimed in any one of claims 1 to 5 which is used for applying to an article.

Documents:

2313-DELNP-2004-Correspondence Others-(12-10-2011).pdf

2313-DELNP-2004-GPA-(12-10-2011).pdf

3213-DELNP-2004-Abstract-(08-06-2010).pdf

3213-delnp-2004-abstract.pdf

3213-delnp-2004-claims (24-01-2011).pdf

3213-DELNP-2004-Claims-(08-06-2010).pdf

3213-delnp-2004-claims.pdf

3213-delnp-2004-Correspondence Others-(25-02-2011).pdf

3213-DELNP-2004-Correspondence-Others-(07-07-2010).pdf

3213-DELNP-2004-Correspondence-Others-(08-06-2010).pdf

3213-DELNP-2004-Correspondence-Others-(24-01-2011).pdf

3213-DELNP-2004-Correspondence-Others-(25-02-2011).pdf

3213-delnp-2004-Correspondence-Others-(27-04-2011).pdf

3213-delnp-2004-correspondence-others.pdf

3213-delnp-2004-description (complete).pdf

3213-delnp-2004-form-1.pdf

3213-delnp-2004-Form-13-(25-02-2011).pdf

3213-delnp-2004-Form-13.pdf

3213-delnp-2004-form-2.pdf

3213-delnp-2004-form-26.pdf

3213-DELNP-2004-Form-3-(07-07-2010).pdf

3213-DELNP-2004-Form-3-(24-01-2011).pdf

3213-delnp-2004-form-3.pdf

3213-delnp-2004-form-5.pdf

3213-delnp-2004-pct-210.pdf

3213-delnp-2004-pct-301.pdf

3213-delnp-2004-pct-308.pdf

3213-DELNP-2004-Petition 137-(24-01-2011).pdf

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Patent Number

255505

Indian Patent Application Number

3213/DELNP/2004

PG Journal Number

09/2013

Publication Date

01-Mar-2013

Grant Date

27-Feb-2013

Date of Filing

18-Oct-2004

Name of Patentee

BASF COATINGS JAPAN LTD.

Applicant Address

296, SHIMOKURATA-CHO, TOTSUKA-KU, YOKOHAMS-SHI, KANAGAWA 244-0815 (JAPAN)

Inventors:

#	Inventor's Name	Inventor's Address
1	TSUNODA, TAKESHI	447-1-103, SHIMOKURATA-CHO, TOTSUKA-KU, YOKOHAMA-SHI, KANAGAWA 244-0815 (JP)
2	MITSUMUNE, SHINJI	2-8-24-205, KUGENUMATACHIBANA, FUJISAWA-SHI, KANAGAWA 251-0024 (JAPAN)

PCT International Classification Number

C09D 4/06

PCT International Application Number

PCT/JP2003/03438

PCT International Filing date

2003-03-20

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2002-80289	2002-03-22	Japan
2	2002-155717	2002-05-29	Japan
3	2002-318723	2002-10-31	Japan