Photopolymerizable coating composition and decorative film

Abstract

To provide a decorative film that can be used to decorate various molded articles, exhibiting excellent wear resistance and sunscreen resistance, and a photopolymerizable coating composition that enables the production of the decorative film.SOLUTION: A photopolymerizable coating composition contains (A): urethane methacrylate including two or more and four or less functional groups and having a weight average molecular weight of 1000 or more and 5000 or less; (B): urethane methacrylate prepared by reacting polytetramethylene glycol with diisocyanate and further reacting the same with methacrylate having a hydroxy group or an isocyanate group; (C): inorganic nanofiller: and (D): photopolymerization initiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photopolymerizable coating composition and a decorative film. [Background technology]

[0002] Decorating the surface of molded articles made from plastics, metals, and various other materials with a specific hard coating agent has been proposed for the purpose of imparting design features to the surface or protecting the surface (see, for example, Patent Document 1). However, due to the properties of the hard coating agent, there has been a problem in that, even if certain surface properties are obtained, excellent moldability cannot be obtained, because the decorative sheet is cured before injection molding.

[0003] Furthermore, a manufacturing method has been disclosed in which, with the aim of improving transferability to deep-draw shapes while achieving the above-mentioned surface properties, a transfer sheet having a protective layer made of an ionizing radiation-curable resin is vacuum-pressure molded in a mold, and then irradiated with ionizing radiation to cure the protective layer, followed by injection molding to obtain a resin molded product (see, for example, Patent Document 2). However, even this manufacturing method cannot fully meet the demands for more stringent surface properties and moldability, and further improvement is necessary. As such, high hardness and scratch resistance, and moldability are contradictory properties, and there is a need to ensure a high level of these contradictory properties.

[0004] Furthermore, in addition to natural stimuli such as wind, rain, and insects, which can cause quality deterioration in automobile interior and exterior parts, it is also necessary to address dirt caused by user contact. A particular problem is that the quality of automobile interior and exterior parts is deteriorated when skin care products such as hand cream and sunscreen cream adhere to the surface of automobile interior and exterior parts, and measures to address this problem are being considered (see, for example, Patent Documents 3 and 4). However, these products have not been sufficient to prevent surface deterioration caused by the adhesion of skin care products. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-249322 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-041480 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-018720 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-235236 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a decorative film that can provide excellent abrasion resistance and sunscreen resistance when used to decorate various molded products, and a photopolymerizable coating composition that can be used to produce the decorative film. [Means for solving the problem]

[0007] The present invention has the following configuration. [1] (A): a urethane (meth)acrylate having two or more and four or less functional groups and a weight average molecular weight of 1,000 or more and 5,000 or less; (B): urethane (meth)acrylate obtained by reacting polytetramethylene glycol with diisocyanate and then with a (meth)acrylate having a hydroxyl group or a (meth)acrylate having an isocyanate group; (C): inorganic nanofiller: and (D): Photopolymerization initiator 1. A photopolymerizable coating composition comprising: [2] The photopolymerizable coating composition according to [1], wherein (B) is a urethane (meth)acrylate having a structural unit represented by the following formula (1): TIFF0007767779000001.tif19169 (In formula (1), Y 1are independently groups represented by any one of the following formulas (1-1) to (1-4), and Y 2 are independently hydrogen or methyl, n is an integer of 1 to 50, and m is an integer of 1 to 30. TIFF0007767779000002.tif11484[3](E): A photopolymerizable silicone compound having a polyorganosiloxane skeleton and having a (meth)acryloyl group as a photopolymerizable unsaturated group at one or both ends thereof; and (F): Fluorine-containing photopolymerizable acrylic compound The photopolymerizable coating composition according to [1] or [2] above, further comprising at least one selected from the group consisting of: [4] The photopolymerizable coating composition according to any one of [1] to [3], wherein the weight ratio of (A) to (B) is 95 / 5 to 65 / 35, and the weight ratio of the total amount of (A) and (B) to (C) is 95 / 5 to 65 / 35. [5] The photopolymerizable coating composition according to any one of [1] to [4], wherein the weight average molecular weight of (B) is 1,000 to 20,000. [6] The photopolymerizable coating composition according to any one of [1] to [5], wherein (C) is at least one selected from the group consisting of silica, alumina, and zirconium, and has an average particle size of 1 nm or more and 100 nm or less. [7] The photopolymerizable coating composition according to any one of [3] to [6], wherein (F) comprises a photopolymerizable acrylic compound having a structural unit represented by the following formula (2) derived from a fluorosilsesquioxane derivative: TIFF0007767779000003.tif50138 (In equation (2), R f 1 ~R f 7are each independently a linear or branched fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; a fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen atom in the aryl is replaced by fluorine or trifluoromethyl; and A 1 is a group represented by the following formula (2-1) or formula (2-2): TIFF0007767779000004.tif40138 (In equation (2-1), Y 3 is alkylene having 2 to 10 carbon atoms, and R 6 is hydrogen, a linear alkyl having 1 to 5 carbon atoms or a branched alkyl having 3 to 5 carbon atoms, or an aryl having 6 to 10 carbon atoms. TIFF0007767779000005.tif31138 (In equation (2-2), Y 4 is a single bond or alkylene having 1 to 10 carbon atoms. [8] A decorative film having a coating layer made of a cured product obtained by curing the photopolymerizable coating composition according to any one of [1] to [7] above. [Effects of the Invention]

[0008] The decorative film of the present invention has excellent abrasion resistance and sunscreen resistance. In addition, by using the photopolymerizable coating composition of the present invention in a coating layer that is a surface protective layer of the decorative film, a decorative film with excellent abrasion resistance and sunscreen resistance can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below.

[0010] The photopolymerizable coating composition of the present invention contains the following (A) to (D): (A): a urethane (meth)acrylate having two or more and four or less functional groups and a weight average molecular weight of 1,000 or more and 5,000 or less. (B): Urethane (meth)acrylate obtained by reacting polytetramethylene glycol with diisocyanate and then with a (meth)acrylate having a hydroxyl group or a (meth)acrylate having an isocyanate group. (C): Inorganic nanofiller (D): Photopolymerization initiator

[0011] The photopolymerizable coating composition of the present invention may further contain at least one selected from the group consisting of the following (E) and (F): (E): A photopolymerizable silicone compound having a polyorganosiloxane skeleton and having a (meth)acryloyl group as a photopolymerizable unsaturated group at one or both ends of the skeleton. (F): Fluorine-containing photopolymerizable acrylic compound

[0012] In the photopolymerizable coating composition of the present invention, the weight ratio of (A) to (B) is 95 / 5 to 65 / 35, and preferably 90 / 10 to 70 / 30. A weight ratio of (A) to (B) within this range is preferable because it allows for a coating layer with excellent formability and sunscreen resistance to be obtained. The weight ratio of the total amount of (A) and (B) to (C) is 95 / 5 to 65 / 35, preferably 90 / 10 to 70 / 30, and more preferably 90 / 10 to 80 / 20. If the weight ratio of the total amount of (A) and (B) to (C) is within this range, a coating layer excellent in abrasion resistance and sunscreen resistance can be obtained, which is preferable.

[0013] In the present invention, the urethane (meth)acrylate (A), which is difunctional to tetrafunctional and has a weight average molecular weight of 1,000 to 5,000, is an oligomeric compound having reactive (meth)acryloyl groups at both ends, and can be obtained, for example, by reacting an isocyanate compound, a polyol, a (meth)acrylate having an isocyanate group, and a (meth)acrylate having a hydroxyl group.

[0014] As (A) used in the present invention, ultraviolet-curable urethane (meth)acrylate can be preferably used. The isocyanate compound is, for example, at least one selected from an aliphatic isocyanate compound and an alicyclic isocyanate compound, and the polyol is, for example, at least one selected from an ester polyol, an ether polyol, and a polycarbonate polyol.

[0015] Examples of the aliphatic isocyanate compound include hexamethylene diisocyanate, isocyanurate-modified hexamethylene diisocyanate, allophanate-modified hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0016] Examples of the alicyclic isocyanate compound include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hydrogenated xylenediisocyanate.

[0017] Examples of ester polyols include ester compounds obtained by reacting diols with dicarboxylic acids. Examples of the diols include 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, and 1,9-nonanediol. Examples of dicarboxylic acids include sebacic acid, adipic acid, dimer acid, succinic acid, azelaic acid, maleic acid, terephthalic acid, isophthalic acid, and citraconic acid, and anhydrides thereof may also be used.

[0018] Examples of ether polyols include polyether diols, poly(oxytetramethylene) glycols, and poly(oxybutylene) glycols. Examples of polyether diols include polypropylene glycols, polyethylene glycols, polytetramethylene glycols, and propylene-modified polytetramethylene glycols.

[0019] Examples of polycarbonate polyols include reaction products of carbonate derivatives and diols. Examples of carbonate derivatives include diaryl carbonates such as diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. Examples of diols include the compounds described above.

[0020] Examples of the (meth)acrylate having an isocyanate group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate.

[0021] Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, hydroxy polyester mono(meth)acrylate, and hydroxy polycarbonate mono(meth)acrylate.

[0022] Such urethane (meth)acrylate can be produced by the following reaction.

[0023] The isocyanate compound, polyol, and (meth)acrylate having a hydroxyl group can be reacted by charging them all at once.

[0024] Alternatively, a (meth)acrylate having a hydroxyl group may be reacted with these isocyanate compounds to produce a prepolymer having an excess of isocyanate groups, and then the remaining isocyanate groups may be reacted with a polyol compound.

[0025] Alternatively, a (meth)acrylate having an isocyanate group can be reacted with a polyol to produce a prepolymer having an excess of hydroxyl groups, and then the remaining hydroxyl groups can be reacted with an isocyanate compound.

[0026] Alternatively, an isocyanate compound can be reacted with a polyol to produce a prepolymer having an excess of isocyanate groups, and then the remaining isocyanate groups can be reacted with a (meth)acrylate compound having a hydroxyl group.

[0027] Alternatively, an isocyanate compound can be reacted with a polyol to produce a prepolymer having excess hydroxyl groups, which can then be reacted with a (meth)acrylate compound having residual hydroxyl groups and isocyanate groups.

[0028] The urethane (meth)acrylates produced by these methods have at least one of a polyether chain, a polyester chain, or a polycarbonate chain, and at least one of a urethane bond, a biuret bond, an allophanate bond, an isocyanurate bond, or an adduct structure.

[0029] The weight average molecular weight of the urethane (meth)acrylate thus produced is preferably 1,000 or more and 5,000 or less, and the number of functional groups is preferably 2 or more and 4 or less, from the viewpoint of imparting sunscreen resistance.

[0030] In the present invention, a commercially available product such as 8UX-116A manufactured by Taisei Fine Chemical Co., Ltd. can be used as (A).

[0031] In the present invention, (B), a urethane (meth)acrylate obtained by reacting polytetramethylene glycol with diisocyanate and then with a (meth)acrylate having a hydroxyl group or a (meth)acrylate having an isocyanate group, is an oligomeric compound having reactive (meth)acryloyl groups at both ends.

[0032] As (B) used in the present invention, an ultraviolet-curable urethane (meth)acrylate can be preferably used. From the viewpoint of imparting thermoformability, a urethane (meth)acrylate having a structural unit represented by the following formula (1) is more preferred. TIFF0007767779000006.tif19167 (In equation (1), Y 1 are independently groups represented by any one of the following formulas (1-1) to (1-4), and Y 2 are independently hydrogen or methyl, n is an integer of 1 to 50, and m is an integer of 1 to 30. TIFF0007767779000007.tif11484

[0033] Examples of polytetramethylene glycol include PTMG225, PTMG650, PTMG1000, PTMG2000, and PTMG3000 manufactured by Mitsubishi Chemical Corporation.

[0034] Examples of the aliphatic isocyanate compound, which is a diisocyanate, include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0035] Examples of the alicyclic isocyanate compound that is a diisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hydrogenated xylenediisocyanate.

[0036] Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, hydroxy polyester mono(meth)acrylate, and hydroxy polycarbonate mono(meth)acrylate.

[0037] Examples of the (meth)acrylate having an isocyanate group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate.

[0038] In producing such a urethane acrylate, the essential components thereof, that is, polytetramethylene glycol, diisocyanate, and (meth)acrylate having a hydroxyl group, can be reacted by charging them all at once.

[0039] Alternatively, an isocyanate compound can be reacted with polytetramethylene glycol to produce a prepolymer having an excess of isocyanate groups, and then the remaining isocyanate groups can be reacted with a (meth)acrylate having a hydroxyl group.

[0040] Alternatively, an isocyanate compound can be reacted with a polyol to produce a prepolymer having excess hydroxyl groups, which can then be reacted with a (meth)acrylate having the remaining hydroxyl groups and isocyanate groups.

[0041] The weight average molecular weight of the urethane (meth)acrylate thus produced is preferably 1,000 or more and 20,000 or less in terms of imparting thermoformability.

[0042] In the present invention, commercially available products such as SUA017, SUA023, and SUA030 manufactured by Asia Chemical Co., Ltd. can be used as (B).

[0043] In the present invention, the inorganic nanofiller (C) preferably has an average particle size of 1 to 100 nm, more preferably 25 to 75 nm, and particularly preferably 30 to 50 nm. Addition of the inorganic nanofiller improves abrasion resistance, and a particle size of 100 nm or less does not decrease transparency or impair appearance. Specifically, silica, alumina, and zirconium can be used. Examples of such inorganic fillers include Nissan Chemical Industries' "MEK-ST," "MEK-ST-L," "MEK-ST-40," "MEK-ST-ZL," "MEK-ST-UP," "IPA-ST," "IPA-ST-L," and "IPA-ST-UP," as well as BYK-Chemie's "BYK-3601," "BYK-3602," "BYK-3610," and "BYK-3611," and Mikuni Shikiso Co., Ltd.'s "MHI Series FM-215M."

[0044] In the present invention, the photopolymerization initiator (D) is not particularly limited as long as it is an initiator that generates radicals when exposed to active energy rays (active energy ray polymerization initiator), and examples thereof include alkylphenone-based photopolymerization initiators. Compounds used as photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, isopropyl benzoin ether, isobutyl benzoin ether, and 2,2-diethoxyacetophenone. , 2,2-Dimethoxy-2-phenylacetophenone, Camphorquinone, Benzanthrone, 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4'-Di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-Tri(t-butylperoxycarbonyl)benzophenone, 2,4,6-Trimethylbenzoyldiphenylphos Fin oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)] -2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6 -trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1 H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide can be mentioned. These compounds may be used alone, or it is also effective to use two or more of them in combination. The content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to the total amount (100 parts by mass) of the radical polymerizable resin.

[0045] In the present invention, the photopolymerizable silicone compound (E) having a polyorganosiloxane skeleton and (meth)acryloyl groups as photopolymerizable unsaturated groups at one or both ends is a group of silicone compounds also known as reactive silicone oils or polysiloxane macromonomers. These compounds are used in the field of polymer synthesis as raw materials for block copolymers and graft copolymers, as modifiers for molding resins, and as modifiers for paints. (E) improves the surface smoothness of the photopolymerizable coating composition of the present invention.

[0046] As such (E), a polyorganosiloxane compound having a terminal vinyl group is preferred, and a polydimethylsiloxane macromonomer having a (meth)acrylic group at the terminal is more preferred. As such (E), for example, "Silaplane FM-7711", "Silaplane FM-7721", "Silaplane FM-0711", "Silaplane FM-0721", "XP1457, the following formula (3)" (manufactured by JNC Corporation) can be used.

[0047] TIFF0007767779000008.tif51170

[0048] The photopolymerizable coating composition of the present invention preferably further contains a fluorine-containing photopolymerizable acrylic compound (F) in order to impart significant antifouling and water repellency to the surface protective layer, which is the coating layer. Examples of such fluorine-containing photopolymerizable acrylic compounds that can be used include "LE-600" manufactured by Toshin Chemical Industry Co., Ltd., "Viscoat 8FM" manufactured by Osaka Organic Chemical Industry Co., Ltd., "Megafac RS" manufactured by DIC Corporation, and "Fclear (registered trademark)" manufactured by Kanto Denka Kogyo Co., Ltd.

[0049] (F) is preferably a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by the following formula (2) (hereinafter sometimes abbreviated as fluorosilsesquioxane derivative (2)). TIFF0007767779000009.tif50138In equation (2), R f1 ~R f 7 are each independently a linear or branched fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; a fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen atom in the aryl is replaced by fluorine or trifluoromethyl; and A 1 is a group represented by the following formula (2-1) or formula (2-2). Specifically, R in Equation (2) f 1 ~R f 7 are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy)propyl, pentafluorophenylpropyl, pentafluorophenyl, or α,α,α-trifluoromethylphenyl, and R f 1 ~R f 7 are each independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

[0050] TIFF0007767779000010.tif40138

[0051] In formula (2-1), Y 3 is alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms, and R 6is hydrogen, linear alkyl having 1 to 5 carbon atoms or branched alkyl having 3 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and is preferably hydrogen or alkyl having 1 to 3 carbon atoms.

[0052] TIFF0007767779000011.tif31138

[0053] In formula (2-2), Y 4 is a single bond or alkylene having 1 to 10 carbon atoms.

[0054] The fluorosilsesquioxane derivative (2) is produced by the following method: First, a silicon compound (4) having trifunctional hydrolyzable groups, represented by the following formula (4), is hydrolyzed in an oxygen-containing organic solvent in the presence of an alkali metal hydroxide, followed by polycondensation, to produce a compound (5) represented by the following formula (5).

[0055] TIFF0007767779000012.tif51113

[0056] TIFF0007767779000013.tif47119

[0057] In formula (5), M is not particularly limited as long as it is an alkali metal, such as lithium, sodium, potassium, or cesium.

[0058] R in formulas (4) and (5) are each independently R in formula (2) f 1 ~R f 7and represents a linear or branched fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced with oxygen; a fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen atom is replaced with fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen atom in the aryl is replaced with fluorine or trifluoromethyl, and X in formula (4) is a hydrolyzable group. Examples of the hydrolyzable group include a methoxy group and an ethoxy group.

[0059] Preferably, R in formulas (4) and (5) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy)propyl, pentafluorophenylpropyl, pentafluorophenyl, or α,α,α-trifluoromethylphenyl.

[0060] More preferably, each R in formula (4) is independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

[0061] Next, the compound (5) is reacted with a compound (6) represented by formula (6) to obtain a fluorosilsesquioxane derivative (2).

[0062] TIFF0007767779000014.tif43122

[0063] The group X in the formula (6) is a group represented by the above formula (2-1) or formula (2-2).

[0064] Among such fluorosilsesquioxane derivatives (2), γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane represented by the following formula (2-3) is preferred.

[0065] TIFF0007767779000015.tif56162 In formula (2-3), F 3 is -CH2CH2CF3.

[0066] The introduction of a fluorosilsesquioxane derivative (2) such as γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane into a coating layer of a laminate film can further improve the antifouling function of the coating layer. When the fluorosilsesquioxane derivative (2) is incorporated into a photopolymerizable acrylic compound that does not have a urethane unit and contains fluorine atoms, it may be directly mixed with other photopolymerizable acrylic compounds that do not have urethane units and contain fluorine atoms, or an oligomer produced by crosslinking and / or polymerizing the fluorosilsesquioxane derivative (2) with a photopolymerizable acrylic compound that does not have urethane units may be mixed with other photopolymerizable acrylic compounds that do not have urethane units and contain fluorine atoms.

[0067] Generally, a polymer containing fluorosilsesquioxane derivative (2) units is prepared in advance by copolymerizing the fluorosilsesquioxane derivative (2) with one or more acrylate copolymerization components selected from monofunctional acrylates, bifunctional acrylates, and polyfunctional acrylates, and this polymer is used as part of a fluorine-containing photopolymerizable acrylic compound. In this case, the polymer containing fluorosilsesquioxane derivative (2) units is blended in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the urethane acrylate.

[0068] As the one or more acrylate copolymerization components described above, compounds generally called photocurable acrylic monomers can be used, for example, monofunctional acrylates such as (meth)acrylic acid, (meth)acrylic acid esters, and hydroxyl group-containing (meth)acrylic acid esters, difunctional acrylates such as (poly)alkylene glycol di(meth)acrylates, and trifunctional or higher polyfunctional acrylates such as pentaerythritol triacrylate, as well as oligomers obtained by polymerizing these.

[0069] [Use of photopolymerizable coating composition] By applying the photopolymerizable coating composition of the present invention to the surface of various articles, followed by drying and UV irradiation, a surface protective layer can be formed that imparts abrasion resistance and sunscreen resistance to the surface of the article. There are no particular restrictions on the articles on which a surface protective layer can be formed, but laminate films are particularly advantageous in that the liquid photopolymerizable coating composition of the present invention can be easily applied. Furthermore, among laminate films, decorative films that require thermoformability are particularly useful as articles that utilize a surface protective layer. The decorative film provided with a surface protective layer will be described below.

[0070] [Surface protection layer] Examples of treatments for curing photopolymerizable coating compositions include curing treatments such as ultraviolet irradiation and electron beam irradiation. When the coating film contains a solvent, it is generally preferable to heat the coating film at a temperature in the range of 70 to 200°C for several minutes to remove any remaining solvent, and then perform the curing treatment. For curing by ultraviolet irradiation, the coating film may be irradiated with ultraviolet rays having a wavelength of 200 to 400 nm from a UV lamp (e.g., a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, or a high-power metal halide lamp) for a short period of time (several seconds to several tens of seconds). For curing by electron beam irradiation, the coating solution may be irradiated with a low-energy electron beam from a self-shielded low-energy electron accelerator of 300 keV or less. The thickness of the coating layer is generally 1 to 100 μm, preferably 2 to 50 μm, and more preferably 3 to 30 μm.

[0071] [Base material layer] The substrate film is preferably a film formed of a thermoplastic resin. Examples of thermoplastic resins include polyurethane resins, polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and norbornene resins. One or more types of thermoplastic resins may be laminated. Polyester resins, polyolefin resins, (meth)acrylic resins, and polycarbonate resins are particularly preferred. A laminate of multiple types of these substrate films may also be used, such as a PMMA / PC two-layer film obtained by co-extrusion of a polycarbonate resin and a (meth)acrylic resin. The thickness of the substrate film is not particularly limited, but when the present invention is used as a laminate, the thickness of the substrate film is preferably 25 to 1000 μm, more preferably 100 to 400 μm. When the thickness of the substrate film is 25 μm or more, the mechanical strength of the substrate is sufficient, making it possible to form a layer on the substrate. Furthermore, when the thickness is 1000 μm or less, the thickness of the laminate does not become too thick.

[0072] [Decorative film manufacturing] The decorative film of the present invention is produced by applying a surface protective layer to a substrate layer and curing the layer by the above-described method, such as gravure coating, bar coating, spray coating, spin coating, roll coating, die coating, knife coating, air knife coating, hot melt coating, or curtain coating.

[0073] The decorative film of the present invention can be used to impart design features to the surface of molded articles made from plastic, metal, and various other materials, or to protect the surface. A substrate layer, such as the laminate film described above, coated with a surface protective layer may be used, or a printed layer may be provided to impart design features. The printed layer includes various decorations, such as metallic tones, letters, pictures, and patterns. It can be provided on the surface of the substrate layer opposite the surface protective layer. Such decorative films can be used, for example, in film insert molding, laminate injection press molding, film in-mold molding, TOM molding, vacuum molding, and the like. [Example]

[0074] [Preparation of a polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units, an example of component (F)] First, γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane was synthesized using the following procedure. Trifluoropropyltrimethoxysilane (100 g), THF (500 mL), deionized water (10.5 g), and sodium hydroxide (7.9 g) were charged into a 1 L four-neck flask equipped with a reflux condenser, thermometer, and dropping funnel. The mixture was heated in an oil bath from room temperature to the reflux temperature of the THF while stirring with a magnetic stirrer. Stirring was continued for 5 hours after the start of reflux to complete the reaction. The flask was then removed from the oil bath and allowed to stand at room temperature overnight. It was then placed back in the oil bath and heated and concentrated at constant pressure until a solid precipitated.

[0075] The precipitated product was collected by filtration using a pressure filter equipped with a membrane filter having a pore size of 0.5 μm, and then washed once with THF and dried in a vacuum dryer at 80° C. for 3 hours to obtain 74 g of a colorless powdery solid.

[0076] The resulting solid (65 g), dichloromethane (491 g), and triethylamine (8.1 g) were placed in a 1 L four-neck flask equipped with a reflux condenser, thermometer, and dropping funnel, and cooled to 3°C in an ice bath. Next, γ-methacryloxypropyltrichlorosilane (21.2 g) was added. After confirming that the heat generation had subsided, the flask was removed from the ice bath and allowed to age overnight at room temperature. After washing three times with ion-exchanged water, the dichloromethane layer was dehydrated with anhydrous magnesium sulfate, and the magnesium sulfate was removed by filtration. The mixture was concentrated using a rotary evaporator until a viscous solid precipitated, and 260 g of methanol was added and stirred until a powder was obtained. The powder was filtered using a pressure filter equipped with 5 μm filter paper and dried in a vacuum dryer at 65°C for 3 hours, yielding 41.5 g of a colorless powdery solid. GPC analysis of the resulting solid was performed. 1 H-NMR measurement confirmed the formation of γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane {formula (2-3)}.

[0077] TIFF0007767779000016.tif56162In equation (2-3), F 3 is -CH2CH2CF3.

[0078] Next, a polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units was synthesized by the following procedure.

[0079] Compound 5 (25 g), Silaplane FM0721 (6.3 g, JNC Corporation), 2-hydroxyethyl methacrylate (18.8 g), methyl methacrylate (12.5 g), and methyl ethyl ketone (62 g) were added to a nitrogen-sealed four-neck round-bottom flask equipped with a reflux condenser and a dropping funnel. The mixture was refluxed and degassed in an oil bath for 15 minutes. Polymerization was then initiated by adding a solution of azobisisobutyronitrile (0.48 g) and mercaptoacetic acid (0.054 g) dissolved in methyl ethyl ketone (4.8 g). Three hours after the start of polymerization, a solution of azobisisobutyronitrile (0.48 g) dissolved in methyl ethyl ketone (4.3 g) was added and the mixture was aged for 5 hours to obtain a copolymer solution. Furthermore, paramethoxyphenol (0.16 g) and dibutyltin dilaurate (0.15 g, Showa Denko K.K.) were dissolved in methyl ethyl ketone (1.5 g) and added as a polymerization inhibitor, and then Karenz AOI (26.4 g) was added dropwise using a dropping funnel so that the liquid temperature was 35 to 50°C, and the mixture was then aged at 45°C for 3 hours.

[0080] After that, methanol (9 g) was added and treated, and then paramethoxyphenol (0.16 g) was added, and the mixture was diluted with methyl isobutyl ketone (107.3 g) to obtain a 30 wt % solution of the target polymer (A-1).

[0081] The resulting polymer (A-1) had a weight-average molecular weight of Mw 42,000 and a polydispersity index of Mw / Mn 1.9. The weight-average molecular weight and polydispersity index were measured using gel permeation chromatography (GPC, model number: Alliance 2695, manufactured by Waters Corporation, column: Shodex GPC KF-804L x 2 (in series), guard column: KF-G). GPC analysis confirmed that the resulting polymer (A-1) contained γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units and had acryloyl groups in the side chains.

[0082] [Preparation of Photopolymerizable Urethane Acrylate Composition] The following components were selected as shown in Table 1 and mixed in the weight ratios shown in Table 1. The diluent used was "methyl 2-hydroxyisobutyrate" manufactured by Mitsubishi Gas Chemical Company, Inc., and the components were diluted to a coating solution containing a concentration of 25% by weight. The weight ratios shown in the table are all solid masses. (A): Photopolymerizable urethane (meth)acrylate polymer "8UX-116A" manufactured by Taisei Fine Chemical Co., Ltd. (B): Asia Industries "SUA-030" (C): Nissan Chemical silica filler "MEK-ST-L" (D): “Omnirad127D” manufactured by IGM Resins (E): JNC "FM-7711" (F): "RS-75A" manufactured by DIC Corporation, "XUA-008" manufactured by JNC Corporation (Polymer (A-1) produced by the above-mentioned method. A polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units and having an acryloyl group in the side chain).

[0083] [Manufacturing decorative films] Each of the above coating solutions was applied to the PMMA surface of a 300 μm thick PMMA / PC two-layer film (Wavelock Advanced Technology PMMA / PC two-layer film "AW-10FSU") using a wire bar coater manufactured by RDS Webster, and dried at 80°C for 3 minutes. After that, an 8kW x 1-lamp UV curing conveyor ESC-801G1 manufactured by iGraphics Co., Ltd. was used to apply the coating solution to the PMMA surface of the film, with an integrated light dose of 1000 mJ / cm. 2 The photopolymerizable coating liquid was cured by 50°C for 1 hour at 2 ...

[0084] [Decorative film evaluation] The decorative film described above was evaluated from the following viewpoints and by the following methods, and the results are shown in Table 1.

[0085] (1) Sunscreen resistance A 50 mm x 50 mm test piece was cut from the resulting decorative film, and a commercially available sunscreen cream (Neutrogena ULTRA SHEER SUNSCREEN SPF45) was applied at a concentration of 2.0 g / 100 cm on the surface protective layer. 2 The amount of sunscreen cream applied was uniformly thick. Two pieces of white cloth were placed on top of an aluminum plate on the surface with the sunscreen cream attached. In this state, the entire test object including the decorative film was left to heat in a thermostatic chamber at 80°C for 4 hours. After heating, the aluminum plate and white cloth were removed, and the sunscreen adhering to the surface protection layer was then removed with a neutral detergent. The condition of the decorative film after the sunscreen cream had been removed was evaluated according to the following criteria. ◎: The condition is the same as before the sunscreen cream was applied, and no changes or deformations were observed. 〇: Traces of sunscreen cream or dissolved residue are observed on some parts of the applied surface. ×: Traces of sunscreen cream or dissolved residue are observed over the entire applied surface.

[0086] (2) Adhesion after sunscreen cream resistance test The coating surface that had undergone the sunscreen cream resistance test above was subjected to a cross-cut test at 1mm intervals on the decorative film in accordance with JIS K5600-6. The state of the grid formed by the cross-cuts was visually observed, and the state of adhesion between the surface protective layer of the decorative film and the PMMA / PC substrate was judged according to the following criteria. ◎: No peeling is observed within the grid, and the surface is well adhered to the substrate. ○: Partial peeling is observed within the lattice. ×: Peeling is observed over the entire grid.

[0087] (3) Scratch resistance The haze (H1) of a 120 mm x 50 mm test piece cut from the resulting decorative film was measured using a haze meter NDH-5000SP manufactured by Nippon Denshoku Industries Co., Ltd. The test piece for which the haze H1 was measured was placed in an abrasion resistance tester C manufactured by Imoto Manufacturing Co., Ltd., IMC-1557, and the coating layer was subjected to an abrasion treatment. The abrasion conditions were #0000 steel wool, a load of 400 g, and 15 back-and-forth strokes. The haze (H2) of the test piece after the abrasion treatment was measured using the same method as for measuring the haze H1 before the abrasion treatment. The degree of change in transparency (ΔH) was calculated from the values ​​of H1 and H2, as shown in the following formula. A smaller ΔH indicates higher scratch resistance. ΔH = |H1-H2| A ΔH of 20% or less is practically preferable.

[0088] (4) Heat moldability Tensile tests were conducted in a thermostatic chamber using a Shimadzu AGS-X tensile testing machine. Dumbbell-shaped test specimens (JIS-K7113 No. 2 test specimens, parallel section width 6±0.4 mm, parallel section length 33±2 mm, gauge length 25±1 mm) were cut from the resulting decorative film. The resulting dumbbell-shaped test specimens were then attached to the tensile testing machine with a chuck distance of 80 mm and held in a thermostatic chamber at 120°C for 3 minutes. The test was then conducted at a tensile speed of 50 mm / min, and the difference between the gauge length (L1) at which cracks occurred and the initial gauge length (25 mm) was measured. The elongation upon heating, ΔL, was calculated using the following formula. A larger ΔL indicates better formability. ΔL(%)=(L1-25) / 25 × 100 A ΔL of 70% or more is practically preferable.

[0089] (5) Surface hardness The hardness of the surface protective layer was measured by a pencil hardness test in accordance with JIS K 5600. In practice, hardness of H or higher is preferred.

[0090] TIFF0007767779000017.tif93170

[0091] As shown in Table 1, in the laminated film in which a coating layer was formed using the photopolymerizable coating composition of the present invention, a coating film with excellent sunscreen resistance, abrasion resistance, and heat formability was formed. On the other hand, Comparative Example 1, which did not contain (C), had insufficient abrasion resistance, and Comparative Example 2, which did not contain (B) or (C), had insufficient abrasion resistance and heat moldability. [Industrial Applicability]

[0092] The photopolymerizable coating composition of the present invention has a good balance of abrasion resistance, moldability, sunscreen cream resistance, surface hardness, and adhesion. Such a photopolymerizable coating composition of the present invention is useful as a surface protective layer for automotive interior and exterior parts that require high functionality and design, such as instrument panels, emblems, radiator grilles, and various garnishes. It is expected that the present invention will enable the production of automotive interior and exterior parts that can withstand the increasingly sophisticated requirements of recent years.

Claims

1. (A): a difunctional to tetrafunctional urethane (meth)acrylate having a weight average molecular weight of 1,000 to 5,000; (B): a urethane (meth)acrylate obtained by reacting polytetramethylene glycol with a diisocyanate and then reacting the resulting mixture with a (meth)acrylate having a hydroxyl group or a (meth)acrylate having an isocyanate group; (C): inorganic nanofiller; and (D): Photopolymerization initiator Contains (E): a photopolymerizable silicone compound having a polyorganosiloxane skeleton and having a (meth)acryloyl group as a photopolymerizable unsaturated group at one or both ends of the skeleton; and (F): Fluorine-containing photopolymerizable acrylic compound Further comprising at least one selected from the group consisting of Photopolymerizable coating composition.

2. 2. The photopolymerizable coating composition according to claim 1, wherein (B) is a urethane (meth)acrylate having a structural unit represented by the following formula (1): (In formula (1), Y １ are independently groups represented by any one of the following formulas (1-1) to (1-4), and Y ２ are independently hydrogen or methyl, n is an integer from 1 to 50, and m is an integer from 1 to 30.

3. 3. The photopolymerizable coating composition according to claim 1, wherein the weight ratio of (A) to (B) is 95 / 5 to 65 / 35, and the weight ratio of the total amount of (A) and (B) to (C) is 95 / 5 to 65 / 35.

4. 4. The photopolymerizable coating composition according to claim 1, wherein the weight average molecular weight of (B) is 1,000 to 20,000.

5. 5. The photopolymerizable coating composition according to claim 1, wherein (C) is at least one selected from the group consisting of silica, alumina, and zirconium, and has an average particle size of 1 nm or more and 100 nm or less.

6. The photopolymerizable coating composition according to any one of claims 3 to 5, wherein (F) comprises a photopolymerizable acrylic compound having a structural unit represented by the following formula (2) derived from a fluorosilsesquioxane derivative: (In formula (2), R ｆ １ ~R ｆ ７ are each independently a linear fluoroalkyl having 1 to 20 carbon atoms or a branched fluoroalkyl having 3 to 20 carbon atoms in which any methylene may be replaced by oxygen; a fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen atom in the aryl is replaced by fluorine or trifluoromethyl; and A １ is a group represented by the following formula (2-1) or formula (2-2): (In formula (2-1), Y ３ is alkylene having 2 to 10 carbon atoms, and R ６ is hydrogen, a linear alkyl having 1 to 5 carbon atoms or a branched alkyl having 3 to 5 carbon atoms, or an aryl having 6 to 10 carbon atoms. (In formula (2-2), Y ４ is a single bond or alkylene having 1 to 10 carbon atoms.

7. A decorative film comprising a coating layer made of a cured product obtained by curing the photopolymerizable coating composition according to any one of claims 1 to 6.

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