Coating agent, layered product, and article having layered product

Abstract

The purpose of the present invention is to obtain a layered product having excellent weathering resistance.　This coating agent contains: a dimer acid di(meth)acrylate-based resin; a polyfunctional (meth)acrylate-based compound; a photopolymerization initiator; and a photostabilizer represented by formula (1). In addition, this layered product comprises: a coating layer formed on a substrate layer using the coating agent; a substrate layer formed using a thermoplastic polyurethane; and, on the opposite side of the substrate layer from the side on which the coating layer is formed, an adhesive layer formed using at least one resin selected from among an acrylic-based resin, a urethane-based resin, a rubber-based resin and a silicone-based resin.

Description

Coating agent, laminate, and article comprising the laminate

[0001] The present invention relates to a coating agent used for surface protection or surface design modification of articles that are primarily used outdoors, and to a laminate obtained by using this coating agent.

[0002] Since articles used outdoors are exposed to ultraviolet rays, wind and rain, and are prone to deterioration and scratches, extremely strict weather resistance is required for films used to protect the surfaces of articles. For example, when attached to the body or headlights of an automobile, the protective film itself must maintain transparency for a long period of time from the viewpoint of visibility under light irradiation and safety. To solve these problems, a protective film has been disclosed that can be easily attached to plastics whose transparency has been reduced due to aging, weathering, etc. (see, for example, Patent Document 1).

[0003] However, even when the protective film is used, there is a problem that the surface of the film is deteriorated, resulting in a decrease in gloss, color, transparency, and the like.

[0004] International Publication No. 2017 / 047600

[0005] In view of the above, an object of the present invention is to obtain a laminate such as a protective film that has excellent weather resistance.

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result have found that a coating agent can be obtained that maintains the color and transparency of a laminate even when exposed to ultraviolet light or wind and rain, i.e., provides a laminate with excellent weather resistance, by using a di(meth)acrylate (DDDA) and a polyfunctional (meth)acrylate having a dimer acid skeleton with highly hydrophobic properties as resin components of the coating agent and adding a light stabilizer with a specific structure to the coating agent, and thus completed the present invention.

[0007] The coating agent according to a first aspect of the present invention contains a dimer acid di(meth)acrylate resin, a polyfunctional (meth)acrylate compound, a photopolymerization initiator, and a light stabilizer represented by formula (1). (In formula (1), n ​​is an integer of 4 to 12, each R is independently alkyl having 1 to 5 carbon atoms or alkoxy having 4 to 10 carbon atoms, and Me is methyl.

[0008] A coating agent according to a second aspect of the present invention is the coating agent according to the first aspect of the present invention, further comprising an ultraviolet absorber.

[0009] A coating agent according to a third aspect of the present invention is the coating agent according to the first or second aspect of the present invention, wherein the polyfunctional (meth)acrylate compounds are trifunctional acrylate compounds.

[0010] The laminate 10 according to the fourth aspect of the present invention comprises a substrate layer and a coating layer formed on the substrate layer using the coating agent according to any one of the first to third aspects of the present invention. This configuration results in a laminate with significantly improved weather resistance. In this specification, "on the surface side" means that the laminate may be laminated in contact with the substrate or may be laminated via another layer. "On the surface" means that the laminate is laminated in contact with the substrate.

[0011] A laminate 10 according to a fifth aspect of the present invention comprises a coating layer formed on a substrate layer using the coating agent according to any one of the first to third aspects of the present invention, the coating layer being made of a cured product of the coating agent, and a substrate layer formed using thermoplastic polyurethane.

[0012] The laminate 10 according to the sixth aspect of the present invention comprises: a coating layer formed on a substrate layer using the coating agent according to any one of the first to third aspects of the present invention; a substrate layer formed using thermoplastic polyurethane; and an adhesive layer formed on the surface of the substrate layer opposite to the surface on which the coating layer is formed using at least one resin selected from acrylic, urethane, rubber, and silicone resins.

[0013] The laminate 10 according to the seventh aspect of the present invention is the coating agent according to any one of the fourth to sixth aspects of the present invention, which further contains at least one reactive silicone compound selected from the group consisting of siloxanes having acryloyl groups at both ends or one end.

[0014] The laminate 10 according to the eighth aspect of the present invention is the coating agent according to any one of the fourth to seventh aspects of the present invention, which further contains at least one fluorine compound selected from the group consisting of fluorosilsesquioxane monomers and fluorosilsesquioxane polymers.

[0015] In the laminate 10 according to the ninth aspect of the present invention, the fluorosilsesquioxane polymer described in the eighth aspect of the present invention is an addition polymer of a fluorosilsesquioxane monomer having at least one addition polymerizable functional group, or an addition copolymer of a fluorosilsesquioxane monomer having one addition polymerizable functional group and an addition polymerizable monomer.

[0016] An article according to a tenth aspect of the present invention is an article in which the laminate 10 according to any one of the sixth to ninth aspects of the present invention is attached to a surface by the adhesive layer.

[0017] By using the coating agent of the present invention on the surface of a substrate layer to form a coating layer that functions as a protective layer, a laminate can be obtained that does not develop appearance defects such as cracks even when exposed to ultraviolet rays, wind and rain, and can exhibit excellent weather resistance.

[0018] The laminate of the present invention has excellent weather resistance due to the coating layer. Furthermore, by attaching the laminate of the present invention to the surface of an article such as an adherend (an object to be attached), the surface of the article can be protected.

[0019] FIG. 1 is a diagram schematically showing the layer structure of a laminate 10 according to a second embodiment of the present invention.

[0020] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, identical or similar reference numerals are used to designate identical or corresponding parts, and redundant explanations will be omitted. Furthermore, the present invention is not limited to the following embodiments.

[0021] [Coating Agent] The coating agent according to the first embodiment of the present invention contains a dimer acid di(meth)acrylate resin, polyfunctional (meth)acrylate compounds, a photopolymerization initiator, and a light stabilizer represented by formula (1). For example, as shown in FIG. 1 , by applying the coating agent to a substrate layer 11 and curing it, a coating layer 12 with excellent acid resistance and elongation can be formed, resulting in a laminate with excellent weather resistance. The coating agent may further contain an ultraviolet absorber, and may also contain a fluorine compound or a reactive silicone compound as an antifouling agent. From the viewpoint of further improving weather resistance, it is preferable to contain an ultraviolet absorber. From the viewpoint of improving the antifouling properties of the coating layer 12 and imparting excellent slip properties, it is preferable to contain an antifouling agent. The coating agent may further contain a solvent and an additive. Of the components contained in the coating agent, the dimer acid di(meth)acrylate resin, polyfunctional (meth)acrylate compounds, and photopolymerization initiator are sometimes referred to as curable components.

[0022] 1, the laminate 10 according to the second embodiment of the present invention includes a base layer 11 having a coating layer 12, and an adhesive layer 13. The laminate 10 preferably includes a release film 14 during production, but the release film 14 is peeled off when the laminate 10 is attached to the surface of an adherend.

[0023] [Coating Layer 12] The coating layer 12 is formed by applying a coating agent containing a dimer acid di(meth)acrylate resin, polyfunctional (meth)acrylate compounds, a photopolymerization initiator, and a light stabilizer represented by formula (1), optionally containing an ultraviolet absorber, a reactive silicone compound, and a fluorine compound antifouling agent, to the surface of the substrate layer 11, followed by drying and curing. When a reactive silicone compound and a fluorine compound are contained, the silicone and fluorine contained in the reactive silicone compound and the fluorine compound accumulate at the interface with the air in the coating layer 12. The thickness of the coating layer 12 is typically 0.5 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm, and particularly preferably 1 to 5 μm. A thickness of 0.5 μm or more of the coating layer 12 provides sufficient acid resistance, while a thickness of 100 μm or less provides sufficient elongation without the laminate becoming too thick.

[0024] [Coating Method of Coating Agent] A wet coating method that uniformly coats the coating agent is preferably used for coating. Examples of wet coating methods that can be used include gravure coating and die coating. The gravure coating method involves immersing a gravure roll with a textured surface in a coating solution, scraping off the coating agent adhering to the textured areas of the gravure roll with a doctor blade, and allowing the solution to accumulate in the textured areas, allowing it to be accurately measured and transferred to the substrate layer. The gravure coating method allows for a thin coating of a low-viscosity solution. The die coating method involves applying pressure to the solution by extruding it from a coating head called a die. The die coating method enables high-precision coating. Furthermore, because the solution is not exposed to the air during application, changes in the concentration of the coating agent due to drying are less likely to occur. Other wet coating methods include spin coating, bar coating, reverse coating, roll coating, slit coating, dipping, spray coating, kiss coating, reverse kiss coating, air knife coating, curtain coating, and rod coating. The coating method can be appropriately selected from these methods depending on the required film thickness. Furthermore, by using a wet coating method, coating can be performed at a line speed of several tens of meters per minute (e.g., about 20 m / min), which allows for mass production and improves production efficiency.

[0025] [Substrate Layer 11] The substrate layer 11 constituting the laminate of the present invention 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. Specifically, thermoplastic polyurethane, polycaprolactone (PCL), acrylic acid polymer, polyester, polyacrylonitrile, polyether ketone, polystyrene, polyvinyl acetate, or derivatives thereof are preferred. These resins may be used alone or in combination. The substrate layer 11 is preferably formed using thermoplastic polyurethane. Examples of thermoplastic polyurethanes include polycaprolactone-based thermoplastic polyurethanes using polycaprolactone polyol as a polyhydroxy compound, polycarbonate-based thermoplastic polyurethanes using polycarbonate polyol, and polyether-based thermoplastic polyurethanes using polyether polyol, among which polycaprolactone-based thermoplastic polyurethanes are preferably used. Specific examples of trade names of thermoplastic polyurethanes include Argotec 49510 and Argotec 49510-DV manufactured by Argotec, Esmer URSPX86, Esmer URSPX93, and Esmer URSPX98 manufactured by Nihon Matai Co., Ltd., and DUS202, DUS213, DUS235, DUS501, DUS601, DUS605, DUS614, and DUS615 manufactured by Seedam Co., Ltd. Examples of such a polymer include US203, DUS220, DUS701, XUS2086, XUS2098, DUS451, DUS450, Unigrand XN2001, XN2002, and XN2004 manufactured by Japan Unipolymer Co., Ltd., N4900 manufactured by Nupro, SNY97-CLB manufactured by Okura Kogyo Co., Ltd., and PP277+375 and PP386+375 manufactured by DinZing (Dingji Advanced Materials) Co., Ltd.

[0026] The thickness of the substrate layer 11 is not particularly limited, but is typically 25 to 300 μm, preferably 100 to 200 μm, and more preferably 100 to 150 μm. If the thickness of the substrate layer 11 is 25 μm or more, the substrate layer has sufficient mechanical strength, making it possible to form a layer on the substrate layer. Furthermore, if the thickness is 300 μm or less, the thickness of the laminate will not be too large.

[0027] [Dimer Acid Di(meth)acrylate Resin] The dimer acid di(meth)acrylate resin is an active energy ray-curable resin that preferably has a (meth)acryloyl group and a dimer acid, which is a dimer of an unsaturated fatty acid having 18 carbon atoms, as its basic skeleton, and examples thereof include ultraviolet-curable resins. In the present specification, "(meth)acrylate" refers to acrylate or methacrylate, "(meth)acrylo" refers to acrylo or methacrylo, and "(meth)acrylic" refers to acrylic or methacrylic. The dimer acid di(meth)acrylate resin can be obtained from a compound derived from a dimer acid by a common ester synthesis method such as a dehydration condensation method, an acid chloride method, or an ester exchange method. The dimer acid is preferably produced by dimerizing an unsaturated fatty acid having 18 carbon atoms, such as oleic acid or linoleic acid. Active energy ray-curable resins using dimer diol, a saturated alkylene diol having 36 carbon atoms obtained by reducing dimer acid, can also be obtained by a similar reaction. Dimer diol modified with ethylene oxide or propylene oxide can also be used as an active energy ray-curable resin by introducing a (meth)acrylate group using a general ester synthesis method. Furthermore, dimer diamine obtained by dimer diol or the borrowing hydrogen method can also be used as an active energy ray-curable resin by reacting it with an isocyanate monomer having a (meth)acrylate group. From the viewpoint of excellent weather resistance, the content of the dimer acid di(meth)acrylate resin is preferably 1 to 65 parts by weight, more preferably 5 to 55 parts by weight, per 100 parts by weight of the total amount of the curable component, fluorine compound, and reactive silicone compound.

[0028] [Polyfunctional (meth)acrylate compounds] Polyfunctional (meth)acrylate compounds are compounds having two or more (meth)acryloyl groups (excluding dimer acid di(meth)acrylate resins). Examples of polyfunctional (meth)acrylate compounds include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid. Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide (EO)-modified trimethylolpropane tri(meth)acrylate, propylene oxide (PO)-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, phenylethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol diacrylate, 1,3-adamantanedimethanol di(meth)acrylate, o-xylylene di(meth)acrylate, m-xylylene di(meth)acrylate, p-xylylene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy) ) isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, and the like.Examples of trade names manufactured by Toagosei Co., Ltd. include Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245, Aronix M-305, M-306, Aronix M-309, Aronix M-313, Aronix M-315, Aronix M-321, Aronix M-325, M-350, and M-360. From the viewpoint of excellent weather resistance, the content of the polyfunctional (meth)acrylate compound is preferably 30 to 95 parts by weight, more preferably 40 to 85 parts by weight, per 100 parts by weight of the total amount of the curable component, fluorine compound, and reactive silicone compound.

[0029] [Photopolymerization initiator] The photopolymerization initiator is not particularly limited, and a photoradical polymerization initiator that generates radicals when exposed to active energy rays can be used, such as 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, 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-trimethylbenzoyldiphenylphosphine 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-[p-N,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-(1H-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(methyoxycarbonyl)benzophenone, Examples of suitable photopolymerization initiators include 4,4'-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. These compounds may be used alone, or a mixture of two or more compounds is also effective. From the viewpoint of excellent weather resistance, the content of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the total amount of the curable component, fluorine compound, and reactive silicone compound.

[0030] [Light stabilizer represented by formula (1)] In formula (1), n ​​is an integer of 4 to 12, each R is independently alkyl having 1 to 5 carbon atoms or alkoxy having 4 to 10 carbon atoms, and Me is methyl. In formula (1), preferably, n is an integer of 6 to 12, each R is independently alkyl having 1 to 3 carbon atoms or alkoxy having 6 to 8 carbon atoms, more preferably, n is an integer of 6 to 10, and each R is independently linear alkyl having 1 to 3 carbon atoms or linear alkoxy having 6 to 8 carbon atoms, or cyclohexyloxy. Preferred examples of the light stabilizer represented by formula (1) (hereinafter, may be referred to as light stabilizer (1)) include TINUVIN 765 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate), TINUVIN 292 (compound name: a mixture of approximately 75% by weight of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and approximately 25% by weight of methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate), and TINUVIN 123 (compound name: a reaction product of decanedioic acid, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester (in the presence of 1,1-dimethylethyl hydroperoxide and octane)), both of which are trade names of BASF. From the viewpoint of excellent weather resistance, the content of the light stabilizer (1) is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the total amount of the curable component, the fluorine compound, and the reactive silicone compound.

[0031] [Ultraviolet Absorber] The coating agent of the present invention may further contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylates, triazines, and dibenzoylresorcinols.

[0032] Examples of benzotriazoles include TINUVIN PS, TINUVIN 99-2, TINUVIN 326, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, and TINUVIN Carboprotect, both manufactured by BASF. Examples of hydroxyphenyltriazines include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479, both manufactured by BASF. Examples of benzophenones include ADEKASTAB1413, both manufactured by ADEKA Corporation, and Sumisorb130, both manufactured by Sumika Chemtex Co., Ltd. Examples of salicylates include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate. Examples of cyanoacrylates include 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and ethyl 2-cyano-3,3-diphenylacrylate. Examples of triazines include ADEKASTAB LA-46 and ADEKASTAB LA-F70 (trade names) manufactured by ADEKA Corporation, and an example of dibenzoylresorcinols is 4,6-dibenzoylresorcinol. These ultraviolet absorbers may be used alone or in combination. It is preferable to appropriately select the type and combination of ultraviolet absorbers based on the wavelength of ultraviolet light to be absorbed. From the viewpoint of excellent weather resistance, the content of the ultraviolet absorber is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the total amount of the curable component, the fluorine compound, and the reactive silicone compound.

[0033] [Fluorine Compound] As the fluorine compound, preferably, at least one selected from the group consisting of fluorosilsesquioxane monomers and fluorosilsesquioxane polymers can be used. Fluorosilsesquioxane Monomer In the present invention, the fluorosilsesquioxane monomer is a fluorosilsesquioxane monomer having at least one polymerizable functional group. The fluorosilsesquioxane monomer may be any fluorosilsesquioxane monomer as long as it has the property of easily accumulating at the interface between air and a solid (or liquid) in a hydrophobic atmosphere (for example, in air). Furthermore, the effects of the present invention can be fully achieved as long as the fluorosilsesquioxane monomer accumulates at the interface. Due to the excellent surface accumulation properties of such fluorosilsesquioxane monomers, the surface of the coating layer 12 can be modified effectively in small amounts. The fluorosilsesquioxane monomer used in the present invention is a fluorosilsesquioxane monomer represented by the formula [(R １ -SiO １．５ ) ｎ ] in the substituent (R １ ) with a fluoroalkyl group (R ｆ ) can be used. Specifically, an example of the fluorosilsesquioxane monomer is a fluorosilsesquioxane monomer having a cage molecular structure represented by the following formula (2):

[0034]

[0035] In formula (2), taking into consideration the solubility in a solvent, R ｆ The number of carbon atoms in R is preferably 1 to 8. ｆ may be a straight-chain group or a branched group. Specifically, the straight-chain group may be —CH ２ CH ２ CF ３ , -CH ２ CH ２ CF ２ CF ３ , -CH ２ CH ２ CF ２ CF ２ CF ３ , -CH ２ CH ２ CF２ CF ２ CF ２ CF ３ , -CH ２ CH ２ CF ２ CF ２ CF ２ CF ２ CF ３ , -CH ２ CH ２ CF ２ CF ２ CF ２ CF ２ CF ２ CF ３ , as a branched group, —CH ２ CH ２ CF (CF ３ ) ２ , -CH ２ CH (CF ３ )CF ２ CF ３ , -CH(CF ３ ) CH ２ CF ２ CF ３ , -CH ２ C (CF ３ ) ２ CF ３ , -C(CF ３ ) ２ CH ２ CF ３ -CH ２ CH ２ CF ２ CF (CF ３ ) ２ , -CH ２ CH ２ CF (CF ３ )CF ２ CF ３ , -CH ２ CH ２ C (CF ３ ) ２ CF ３ Examples of such compounds include R ｆ may be different groups or may all be the same group.

[0036] Although the above formula (2) illustrates a fluorosilsesquioxane monomer having "3-(methacryloyloxy)propyl" at one Si, the polymerizable functional group is not limited to this. For example, when the position of "3-(methacryloyloxy)propyl" is designated as Z, this position can be replaced with another functional group. Specifically, Z can be hydrogen, a hydroxyl group, an alkenyl, or a halogen (chlorine, bromine, iodine), an alkoxy, a phenoxy, a polyalkyleneoxy, -COOH, 2-oxapropane-1,3-dioyl, an alkoxycarbonyl, an alkenyloxycarbonyl, an oxiranyl, a 3,4-epoxycyclohexyl, an oxetanyl, an oxetanylene, -NH-, -NH ２ , —CN, —NCO, alkynyl, cycloalkenyl, acryloyloxy, methacryloyloxy, urethane acryloyl, urethane methacryloyl, —SH and —PH ２ Furthermore, Z may be any of the above groups (hydrogen to -PH ２ ) may also be used. The alkylene bonded to Si is not particularly limited, but is preferably an alkylene having 1 to 8 carbon atoms, and particularly preferably propylene having 3 carbon atoms. However, the selection range does not include groups having an alkanoyloxy group, groups having a sulfonyl halide, and groups having an α-haloester group. Particularly preferred is a fluorosilsesquioxane monomer having at least two polymerizable functional groups bonded to Si. For example, while the above formula (2) illustrates a fluorosilsesquioxane monomer having "3-(methacryloyloxy)propyl" on one Si, it is more preferred to use a fluorosilsesquioxane monomer having this "3-(methacryloyloxy)propyl" on at least one other Si. Furthermore, the polymerizable functional group is preferably a radically polymerizable functional group.

[0037] Fluorosilsesquioxane Polymer In the present invention, the fluorosilsesquioxane polymer is an oligomer, prepolymer, or polymer of a fluorosilsesquioxane monomer and has at least one polymerizable functional group. Since the fluorosilsesquioxane polymer has at least one polymerizable functional group, it corresponds to a so-called macromonomer or macromer. When only one type of fluorosilsesquioxane monomer is used, the fluorosilsesquioxane polymer can be a fluorosilsesquioxane homopolymer. It can also be a copolymer with other common monomers (e.g., addition-polymerizable monomers). A copolymer of fluorosilsesquioxane monomers having different polymerizable functional groups may also be used. In this case, any known polymerization method can be used. However, the fluorosilsesquioxane polymer after polymerization has at least one polymerizable functional group. Furthermore, the polymerizable functional group is preferably a radically polymerizable functional group.

[0038] That is, the fluorosilsesquioxane monomer of the above formula (2) may have an addition-polymerizable functional group as Z. Alternatively, Z may have an addition-polymerizable functional group connected via an alkylene. Examples of the addition-polymerizable functional group include groups having a terminal olefin-type or internal olefin-type radically polymerizable functional group; groups having a cationically polymerizable functional group such as vinyl ether or propenyl ether; and groups having an anionically polymerizable functional group such as vinyl carboxyl or cyanoacryloyl, with radically polymerizable functional groups being preferred.

[0039] The radically polymerizable functional group is not particularly limited as long as it is a group that undergoes radical polymerization, and includes methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide, etc., and among these, groups containing (meth)acrylic or styryl are preferred. Examples of the radically polymerizable functional group containing (meth)acrylic include a group represented by the following formula (3). In formula (3), Y １represents alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms, and more preferably propylene. X represents hydrogen or alkyl having 1 to 3 carbon atoms, and preferably hydrogen or methyl.

[0040] Examples of the radically polymerizable functional group having styryl include a group represented by the following formula (4): ２ represents a single bond or alkylene having 1 to 10 carbon atoms, preferably a single bond or alkylene having 1 to 6 carbon atoms, more preferably a single bond or ethylene. Vinyl is bonded to any carbon atom of the benzene ring, and preferably Y ２ It is bonded to the carbon in the para position.

[0041]

[0042] The addition polymerizable monomer may be one having a crosslinkable functional group or one not having a crosslinkable functional group. The addition polymerizable monomer having a crosslinkable functional group may be any compound having one or more addition polymerizable double bonds, and may be any of a vinyl compound, a vinylidene compound, and a vinylene compound. More specifically, examples thereof include a (meth)acrylic acid compound and a styrene compound.

[0043] Examples of the (meth)acrylic acid compound include (meth)acrylic acid and (meth)acrylic acid esters, as well as (meth)acrylic acid amides and (meth)acrylonitrile.

[0044] Examples of the (meth)acrylic acid compound of the addition polymerizable monomer include (meth)acrylates having a crosslinkable functional group, such as epoxy (i.e., oxiranyl) groups such as glycidyl and epoxycyclohexyl, oxetanyl groups, isocyanato groups, acid anhydrides, carboxyl groups, and hydroxyl groups, with epoxy (i.e., oxiranyl) groups such as glycidyl and oxetanyl groups being preferred. The (meth)acrylates having the above-mentioned crosslinkable functional group include (meth)acrylic acid, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; epoxy-containing (meth)acrylates such as glycidyl (meth)acrylate; alicyclic epoxy-containing (meth)acrylates such as 3,4-epoxycyclohexylmethyl (meth)acrylate; oxetanyl-containing (meth)acrylates such as 3-ethyl-3-(meth)acryloyloxymethyloxetane; 2-(meth)acryloyloxyethyl isocyanate; γ-(methacryloyloxymethyl)-2 ... (meth)acrylate-2-aminoethyl, 2-(2-bromopropionyloxy)ethyl (meth)acrylate, 2-(2-bromoisobutyryloxy)ethyl (meth)acrylate; 1-(meth)acryloxy-2-phenyl-2-(2,2,6,6-tetramethyl-1-piperidinyloxy)ethane, 1-(4-((4-(meth)acryloxy)ethoxyethyl)phenylethoxy)piperidine, 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate, 2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate.

[0045] Examples of the styrene compound having one addition-polymerizable double bond include styrene compounds having a crosslinkable functional group. Such crosslinkable functional groups include epoxy (i.e., oxiranyl) such as glycidyl, oxetanyl, halo, amino, isocyanato, acid anhydride, carboxyl, hydroxyl, thiol, and siloxy. Examples of the styrene compound having a crosslinkable functional group include o-aminostyrene, p-styrene chlorosulfonic acid, styrenesulfonic acid and its salts, vinylphenylmethyldithiocarbamate, 2-(2-bromopropionyloxy)styrene, 2-(2-bromoisobutyryloxy)styrene, 1-(2-((4-vinylphenyl)methoxy)-1-phenylethoxy)-2,2,6,6-tetramethylpiperidine, and compounds represented by the following formula:

[0046]

[0047] In addition to the above-mentioned addition polymerizable monomers, addition polymerizable monomers other than the above-mentioned addition polymerizable monomers can also be used in combination as necessary in order to control the compatibility with the curable resin, the leveling property, the amount of crosslinkable functional groups in the copolymer, and the like.

[0048] Examples of the addition-polymerizable monomer having no crosslinkable functional group include a (meth)acrylic acid compound having one addition-polymerizable double bond and no crosslinkable functional group, and a styrene compound having one addition-polymerizable double bond and no crosslinkable functional group. Examples of such (meth)acrylic acid compounds include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, methyl ... alkyl (meth)acrylates such as methyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and toluyl (meth)acrylate; aryl alkyl (meth)acrylates such as benzyl (meth)acrylate; alkoxy alkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, and 3-methoxybutyl (meth)acrylate; and ethylene oxide adducts of (meth)acrylic acid.

[0049] The (meth)acrylic acid compound having one addition-polymerizable double bond and no crosslinkable functional group further includes fluoroalkyl (meth)acrylates such as trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

[0050] Furthermore, examples of (meth)acrylic acid compounds having one addition polymerizable double bond and no crosslinkable functional group include (meth)acrylic acid compounds having a silsesquioxane skeleton. Specific examples of such (meth)acrylic acid compounds having a silsesquioxane skeleton include 3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaisobutyl-pentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３]octasiloxane-1-yl)propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxan-1-yloxy)dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate. Specific examples of the styrene compound having one addition polymerizable double bond and no crosslinkable functional group include styrene, vinyltoluene, α-methylstyrene, and p-chlorostyrene.

[0051] Examples of the styrene compound having one addition-polymerizable double bond and no crosslinkable functional group further include styrene compounds containing silsesquioxane. Examples of such styrene compounds containing silsesquioxane include 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane, and 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ octasiloxanes having a 4-vinylphenyl group (T8 type silsesquioxanes), such as 3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３]octasiloxane-1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yl)ethylstyrene, 3-((3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene, 3-((3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene, and 3-((3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ ]octasiloxanes having a 4-vinylphenylethyl group (T8 type silsesquioxanes), such as (octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene;

[0052] Further, examples of addition polymerizable monomers other than the above-mentioned addition polymerizable monomers include macromonomers having a main chain derived from styrene, (meth)acrylic acid ester, siloxane, and alkylene oxide, such as ethylene oxide or propylene oxide, and having one polymerizable double bond.

[0053] Examples of the addition-polymerizable monomer also include compounds having two addition-polymerizable double bonds. Examples of the compounds having two addition-polymerizable double bonds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and the like. p) Di(meth)acrylate monomers such as acrylate, bis[(meth)acryloyloxyethoxy]bisphenol A, bis[(meth)acryloyloxyethoxy]tetrabromobisphenol A, bis[(meth)acryloxypolyethoxy]bisphenol A, 1,3-bis(hydroxyethyl)5,5-dimethylhydantoin, 3-methylpentanediol di(meth)acrylate, di(meth)acrylate of a hydroxypivalic acid ester neopentyl glycol compound, and bis[(meth)acryloyloxypropyl]tetramethyldisiloxane, and divinylbenzene. Further examples include macromonomers having a main chain derived from styrene, (meth)acrylic acid ester, siloxane, and alkylene oxide, for example, ethylene oxide or propylene oxide, and having two polymerizable double bonds.

[0054] Examples of the addition-polymerizable monomer include compounds having three or more addition-polymerizable double bonds. Examples of the compound having three or more addition-polymerizable double bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, tris(2-hydroxyethyl isocyanate) tri(meth)acrylate, tris(diethylene glycol) trimellit tri(meth)acrylate, 3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaethyltricyclo[7.3.3.1 ５，１１ ]heptasiloxane, 3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1 ５，１１ ]heptasiloxane, 3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaisooctyltricyclo[7.3.3.1 ５，１１ ]heptasiloxane, 3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.1 ５，１１ ]heptasiloxane, 3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.1 ５，１１ ]heptasiloxane, octakis(3-(meth)acryloyloxypropyldimethylsiloxy)octasilsesquioxane, and octakis(3-(meth)acryloyloxypropyl)octasilsesquioxane. Further examples include macromonomers having a main chain derived from styrene, (meth)acrylic acid ester, siloxane, and alkylene oxide, for example, ethylene oxide or propylene oxide, and having three or more polymerizable double bonds.

[0055] The addition-polymerizable monomer is preferably a (meth)acrylic acid compound, more preferably a (meth)acrylic acid ester, and even more preferably a lower alkyl (e.g., carbon number 1 to 3) ester of (meth)acrylic acid or an ester having a crosslinkable functional group.

[0056] The polymer is an addition polymer of a fluorosilsesquioxane monomer or an addition copolymer with other addition-polymerizable monomers. In the case of a copolymer, it may be an ordered copolymer such as a block copolymer or a random copolymer, but a random copolymer is preferred. In addition, the polymer may have a crosslinked structure or may be a graft copolymer.

[0057] The content of the fluorine compound is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component, fluorine-based compound, and reactive silicone compound. If the content is 0.1 part by weight or more, the antifouling properties of the coating layer 12 can be improved and slipperiness can be imparted to the coating layer 12, while if the content is 10 parts by weight or less, the flexibility of the coating layer 12 can be reduced, avoiding poor self-repairing properties.

[0058] [Solvent] The dimer acid di(meth)acrylate resin, polyfunctional (meth)acrylate compounds, photopolymerization initiator, light stabilizer (1), UV absorber (if necessary), and fluorine compound contained in the coating agent of the present invention may be dissolved in a solvent such as an organic solvent. The solvent is not particularly limited. Common organic solvents can be used. Examples of the solvent include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran (THF), diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, etc.), carbonate solvents (ethylene carbonate, ester, propylene carbonate, etc.), amide solvents (N,N-dimethylformamide, N,N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5, and 6 or more carbon atoms), perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine-containing solvents (fluoroethers, fluoropolyethers, fluoroketones, fluoroalcohols), aromatic fluorine-containing solvents (α,α,α-trifluorotoluene, hexafluorobenzene), and water.

[0059] These solvents may be used alone or in combination. For example, a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone can be used. Adding a solvent such as methyl ethyl ketone can improve the workability of homogenizing the solution during the preparation of the coating agent. Furthermore, improved solubility can stabilize the coating agent. The mixing ratio (by weight) can be, for example, methyl isobutyl ketone / methyl ethyl ketone = 1 to 99 / 99 to 1, preferably 20 to 80 / 80 to 20. The content of the solvent used as a diluent is preferably 20 to 500 parts by weight, more preferably 50 to 400 parts by weight, per 100 parts by weight of the total amount of the curable components, fluorine compound, and reactive silicone compound of the coating agent that forms the coating layer.

[0060] [Additives] Various additives may be added to the coating agent as needed. For example, a filler may be added to impart hardness and scratch resistance to the coating layer. A leveling agent may be added to improve application properties, or a reactive silicone may be added to improve squeegeeing during application. Other additives may be added, such as a light stabilizer other than the light stabilizer (1) and an antifoaming agent. More specifically, the coating agent may further contain optional components such as an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiator aid, a leveling agent, a wettability improver, a surfactant, a plasticizer, a light stabilizer other than the light stabilizer (1), an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler (such as silica or alumina), or an organic filler, as long as they do not adversely affect the effects of the coating layer formed by the coating agent.

[0061] Examples of the leveling agent include commercially available acrylic surface conditioners BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, and BYK-3550 (all trade names: manufactured by BYK Japan Co., Ltd.). Examples of silicone surface conditioners include BYK-UV3500 and BYK-UV-3570 (all trade names: manufactured by BYK Japan Co., Ltd.), and TEGO. Examples of suitable acrylic resins include Rad2100, 2200N, 2250, 2500, 2600, and 2700 (all trade names: manufactured by Evonik Degussa Japan Co., Ltd.), X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X-22-2426, X-22-164A, and X-22-164C (all trade names: manufactured by Shin-Etsu Chemical Co., Ltd.).

[0062] Examples of light stabilizers other than the light stabilizer (1) include hindered benzoate-based light stabilizers and hindered amine-based light stabilizers (HALS) other than the light stabilizer (1).

[0063] Examples of the hindered benzoate light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and 2,4-di-t-amylphenyl-3,5-di-t-butyl-4-hydroxybenzoate. Examples of hindered amine light stabilizers (HALS) other than the light stabilizer (1) include BASF's trade name: TINUVIN (registered trademark) 5100 (a neutral general-purpose HALS), TINUVIN 152 (compound name: 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine), and TINUVIN 144 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl] methyl]butylmalonate), TINUVIN 111FDL (a mixture of about 50% by weight, TINUVIN 622, compound name: (butanedioic acid polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl)ethanol), and about 50% by weight, CHIMASSORB 119, compound name: N-N'-N''-N'''-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine), or ADEKA STAB (trade name, manufactured by ADEKA Corporation) LA series, specifically LA-52 ((5)-6116), LA-57 ((5)-5555), LA-62 ((5)-5711), LA-67 ((5)-5755), LA-82 ((5)-6023), LA-87 ((5)-6022). The numbers in parentheses are the numbers of existing chemical substances.

[0064] Examples of commercially available inorganic fillers (trade names) include MEK-ST-40, MEK-ST-L, MEK-ST-ZL, PGM-AC-2140Y, PGM-AC-4130Y, AS-200, and AS-520 manufactured by Nissan Chemical Industries, Ltd., and anatase TiO manufactured by CIK Nanotech Co., Ltd. ２ , Al ２ O ３, ZnO, ZrO ２ , cobalt blue, zirconium oxide, barium titanate, titanium oxide, silica, alumina, and MUA filler manufactured by Mikuni Shikiso Co., Ltd. Examples of organic fillers include commercially available products (trade names) such as the Techpolymer MBX series and SBX series manufactured by Sekisui Plastics Co., Ltd., Art Pearl crosslinked acrylic beads and Art Pearl crosslinked urethane beads manufactured by Negami Chemical Industries Co., Ltd., and Ganz Pearl manufactured by Aica Kogyo Co., Ltd. These fillers may be used alone or in combination.

[0065] [Reactive Silicone Compound] Reactive silicone compounds are a group of silicone compounds, also known as reactive silicone oils or polysiloxane macromonomers. They are used in the field of polymer synthesis as raw materials for block copolymers and graft copolymers, as resin modifiers, and as paint modifiers. This component can improve the surface smoothness of the coating agent of the present invention and improve squeegeeability during application. Preferred examples of such components include polyorganosiloxane compounds containing terminal vinyl groups, and more preferably polydimethylsiloxane macromonomers having methacryloyl groups at their ends. The content of the reactive silicone compound is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of the curable component, fluorine-based compound, and reactive silicone compound. A content of 0.01 parts by weight or more can improve the surface smoothness and antifouling properties of the coating layer 12, impart slipperiness, and improve squeegeeability during application. A content of 10 parts by weight or less can avoid a decrease in the flexibility of the coating layer 12 and poor self-repairing properties.

[0066] Other components may be added to the coating agent of the present invention. Examples of such other components include thermoplastic resins and rubbers. By adding thermoplastic resins and rubbers, the properties of the coating layer (mechanical properties, surface and interface properties, compatibility, etc.) can be improved. Commercial products of the reactive silicone compound include X-22-164A (number average molecular weight 860, manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164B (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.), X-24-164E (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.), X-24-8201 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.), both-end type Silaplane FM-7711 (manufactured by JNC Corporation), both-end type Silaplane FM-7721 (manufactured by JNC Corporation), both-end type Silaplane FM-7725 (manufactured by JNC Corporation), and one-end type Silaplane FM-7716 (manufactured by JNC Corporation). Silaplane FM-0711 (manufactured by JNC Corporation), single-end type Silaplane FM-0721 (number average molecular weight 5000, manufactured by JNC Corporation), single-end type Silaplane FM-0725 (number average molecular weight 10000, manufactured by JNC Corporation), single-end type Silaplane TM-0701 (number average molecular weight 423, manufactured by JNC Corporation), single-end type Silaplane TM-0701T (number average molecular weight 423, manufactured by JNC Corporation), BYK-UV3500 (manufactured by BYK Japan Co., Ltd.), BYK-UV3510 (manufactured by BYK Japan Co., Ltd.), BYK-UV3570 (manufactured by BYK Japan Co., Ltd.), TEGO Examples of such a tertiary fluoride include TEGO Rad2100 (manufactured by Tego Chemie Service Co., Ltd.), TEGO Rad2200N (manufactured by Tego Chemie Service Co., Ltd.), TEGO Rad2250 (manufactured by Tego Chemie Service Co., Ltd.), TEGO Rad2500 (manufactured by Tego Chemie Service Co., Ltd.), TEGO Rad2600 (manufactured by Tego Chemie Service Co., Ltd.), TEGO Rad2600 (manufactured by Tego Chemie Service Co., Ltd.), and TEGO Rad2700 (manufactured by Tego Chemie Service Co., Ltd.).

[0067] Examples of thermoplastic resins include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly(meth)acrylate resin, ultra-high molecular weight polyethylene, poly-4-methylpentene, syndiotactic polystyrene, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, and polyarylate (U Polymer: a trade name manufactured by Unitika Ltd., Vectra: poly Examples of the polymerizable polymer include polyimides (such as Kapton, a product name of Toray Industries, Inc., and AURUM, a product name of Mitsui Chemicals, Inc.), polyetherimides and polyamideimides, polyamides such as nylon 6, nylon 6,6, nylon 6,10, nylon MXD6, and nylon 6,T (all product names: manufactured by DuPont), polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate, and fluororesins such as polytetrafluoroethylene and polyvinylidene fluoride.

[0068] The coating agent used to form the coating layer 12 must be in liquid form. Therefore, if the coating agent contains solids, it can be used in liquid form by dissolving it in a solvent, as described above. The concentration of the curable component in the coating agent can be selected so that the viscosity of the coating agent is appropriate for the coating method, such as wet coating. The concentration is preferably 1 to 80 wt %, more preferably 3 to 75 wt %, and even more preferably 3 to 60 wt %. The concentration of the curable component in the coating agent can be adjusted by using a solvent. Common organic solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used as the solvent. Note that if the coating agent contains a fluorine compound, a fluorine-based organic solvent may be used if the solubility in the solvent is reduced due to factors such as the length of the fluoroalkyl group of the fluorine compound.

[0069] [Curing Method] Examples of curing treatments for curing the coating agent include ultraviolet irradiation, heating, 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 tens of minutes to remove any remaining solvent from the coating film before carrying out the curing treatment. For curing by ultraviolet irradiation, the coating liquid may be irradiated with ultraviolet light 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 liquid may be irradiated with a low-energy electron beam from a self-shielded low-energy electron accelerator of 300 keV or less.

[0070] [Adhesive Layer 13] As shown in Figure 1, the adhesive layer 13 is formed by applying an adhesive to the side opposite to the side of the base layer 11 on which the coating layer 12 is provided. The adhesive layer 13 may be formed directly on the surface of the base layer 11, or may be laminated between the adhesive layer 13 and the base layer 11 via another layer. The adhesive used in the adhesive layer 13 can be an acrylic adhesive, a rubber adhesive, a urethane adhesive, a silicone adhesive, or the like. For applications requiring long-term durability from the perspective of product design, an acrylic adhesive, which has excellent heat resistance and weather resistance, is preferred. In the adhesive layer 13, unevenness is provided on the adhesive surface in terms of adhesion properties to the article to be adhered.

[0071] Examples of acrylic adhesives include acrylic adhesives containing an acrylic copolymer obtained by copolymerizing a monomer component having a functional group such as a carboxyl group or a hydroxyl group with a monomer component mainly composed of an acrylic acid ester. Examples of acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Examples of alkyl (meth)acrylates include acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, isobornyl (meth)acrylate, and 1-adamantyl (meth)acrylate. These alkyl (meth)acrylates can be used alone or in combination.

[0072] The alkyl (meth)acrylate can be copolymerized with the following monomer components. Examples of copolymerizable monomer components include carboxyl group-containing monomers such as itaconic acid, maleic acid, crotonic acid, isocrotonic acid, fumaric acid, (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate; glycidyl group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; acrylonitrile and methacrylonite. nitrogen-containing monomers such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, (meth)acryloylmorpholine, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-cyclohexylmaleimide, N-phenylmaleimide, N-acryloylpyrrolidine, and t-butylaminoethyl (meth)acrylate; styrene and styrene derivatives; and vinyl acetate. If necessary, one or more of these monomers can be copolymerized with a (meth)acrylic acid ester and used.

[0073] The pressure-sensitive adhesive used in the present invention is preferably an acrylic copolymer composed of at least one monomer selected from the group consisting of butyl acrylate and 2-ethylhexyl acrylate and at least one carboxyl group-containing monomer selected from the group consisting of acrylic acid and methacrylic acid. To improve heat resistance and weather resistance, the pressure-sensitive adhesive used in the present invention may contain additives such as methyl acrylate, vinyl acetate, methyl methacrylate, and acrylonitrile. Furthermore, to further improve various physical properties such as weather resistance, ultraviolet absorbers, light stabilizers, and the like may be added as needed. The proportion of these additives added is preferably 10 to 80 wt %, more preferably 20 to 70 wt %, and even more preferably 30 to 60 wt %, based on the total weight of the pressure-sensitive adhesive.

[0074] The weight-average molecular weight (Mw) of the acrylic copolymer is preferably 50,000 to 2,000,000, more preferably 100,000 to 1,500,000, and even more preferably 150,000 to 1,000,000.The number-average molecular weight (Mn) is preferably 10,000 to 500,000, more preferably 10,000 to 400,000, and even more preferably 10,000 to 300,000.

[0075] The composition that will become the adhesive layer 13 can be applied to the release film 14 or the base layer 11 by a commonly used method such as gravure coating, bar coating, spray coating, spin coating, roll coating, die coating, knife coating, air knife coating, hot melt coating, curtain coating, etc. The thickness of the adhesive layer 13 is typically 10 to 100 μm, preferably 15 to 50 μm, more preferably 25 to 45 μm, and particularly preferably 35 to 40 μm, in terms of adhesion after application.

[0076] The adhesive layer 13 physically forms surface irregularities by adhering a release film 14 on which irregularities have been formed and transferring the irregularities.

[0077] [Release Film 14] The release film 14 may be a resin film such as polyethylene terephthalate, polyethylene, or polypropylene, coated on one or both sides with a release agent such as a silicone resin, a fluorine-based resin, or a carbamate containing a long-chain alkyl group. Alternatively, a plastic film such as a polyester resin or a polyolefin resin, or a paper with a pore-sealing treatment such as cellophane or glassine paper may be used. The thickness of the release film 14 varies slightly depending on the material used, but is typically 10 to 250 μm, preferably 20 to 200 μm, and more preferably 50 to 75 μm.

[0078] [Article] The article according to the third embodiment of the present invention is an article having the laminate of the present invention attached to its surface via the pressure-sensitive adhesive layer. The article before the laminate of the present invention is attached is used as an adherend. Examples of articles that can be used as adherends include lighting fixtures for vehicles such as automobiles, motorcycles, and trains, as well as aircraft and ships. The laminate of the present invention is effective for protecting the painted surfaces of various main body parts of these articles, particularly transparent plastic parts of parts exposed to danger from flying debris (sand, stones, etc.) and insects (such as the tip and other tip surfaces of the front hood, rocker panels, etc.).

[0079] The present invention will be described in detail below using examples, but the present invention is not limited to the contents described in the following examples.

[0080] [Production of Fluorosilsesquioxane Polymer Containing γ-Methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane Units, a Fluorine Compound] First, γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane was synthesized according to 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 temperature at which the THF refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from 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. After that, the mixture was placed back into the oil bath and heated and concentrated at constant pressure until a solid precipitated. The precipitated product was collected by filtration using a pressure filter equipped with a 0.5 μm pore size membrane filter. The resulting solid was then washed once with THF and dried in a vacuum dryer at 80°C for 3 hours, yielding 74 g of a colorless, powdery solid. 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, a thermometer, and a dropping funnel, and cooled to 3°C in an ice bath. γ-Methacryloxypropyltrichlorosilane (21.2 g) was then added, and 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 deionized 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 filter paper having a retention particle size of 5 μm, and then dried in a vacuum dryer at 65° C. for 3 hours to obtain 41.5 g of a colorless powdery solid. １ H-NMR measurement was carried out, and the production of γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane (5) represented by the following formula (5) was confirmed.

[0081]

[0082] Next, a polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units was synthesized by the following procedure. Into a nitrogen-sealed four-neck round-bottom flask equipped with a reflux condenser and a dropping funnel, the above-mentioned γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane (5) (25 g), Silaplane FM-0721 (a polydimethylsiloxane macromonomer having a methacryloxy group at one end and a number-average molecular weight of Mn 5,000, 6.3 g, trade name of JNC Corporation), 2-hydroxyethyl methacrylate (18.8 g), methyl methacrylate (12.5 g), and methyl ethyl ketone (62 g) were added, and the mixture was refluxed and degassed in an oil bath for 15 minutes. Then, a solution of azobisisobutyronitrile (0.48 g) and mercaptoacetic acid (0.054 g) dissolved in methyl ethyl ketone (4.8 g) was added to initiate polymerization. Three hours after the start of polymerization, azobisisobutyronitrile (0.48 g) was dissolved in methyl ethyl ketone (4.3 g) and 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, manufactured by Resonac Co., Ltd.) were dissolved in methyl ethyl ketone (1.5 g) as polymerization inhibitors and added, followed by dropwise addition of Karenz AOI (acryloyloxyethyl isocyanate, 26.4 g, manufactured by Resonac Co., Ltd.) using a dropping funnel so that the liquid temperature was 35 to 50°C, and the mixture was aged at 45°C for 3 hours after the dropwise addition. Methanol (9 g) was then added and treated, followed by the addition of paramethoxyphenol (0.16 g). This was then diluted with methyl isobutyl ketone (107.3 g) to obtain a 30 wt% solution of the target fluorosilsesquioxane polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units and having acryloyl groups in its side chains (hereinafter, sometimes referred to as "XUA008"). The resulting XUA008 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), manufactured by Resonac Corporation; guard column: KF-G, manufactured by Resonac Corporation). GPC analysis confirmed that the obtained XUA008 was a polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units and having acryloyl groups in the side chains.

[0083] [Preparation of Dimer Acid Di(meth)acrylate Resin] Dimer diol di(meth)acrylate derived from dimer diol, a derivative of dimer acid, was prepared as follows. Dimer diol (trade name: Pripol 2033, manufactured by Croda Japan Co., Ltd., 284.4 g, 500 mmol) was dissolved in dry acetone (450 ml) under a nitrogen atmosphere in a 1-liter three-neck flask equipped with a mechanical stirrer and a dropping funnel. Triethylamine (101.2 g, 1 mol) was added to the solution, and the solution was cooled to 4°C on an ice bath. Acryloyl chloride (90.5 g, 1 mol) solvated in dry acetone (100 ml) was charged into the dropping funnel and added dropwise to the stirred reaction solution over the course of 60 minutes, maintaining an internal temperature T<10°C. The solution was stirred on ice for an additional 2 hours, then allowed to return to room temperature and stirred for 4 hours. Most of the solvent was removed by evaporator, and the remaining residue was dissolved in CH ２ Cl ２ This solution was solvated in 1 L of 5 wt % HCl aqueous solution (800 ml) and H ２ The isolated organic material was washed with anhydrous MgSO. ４ After drying on a lid, filtering, and removing the solvent with an evaporator, dimer diol di(meth)acrylate (DDDA) was obtained.

[0084] [Preparation of Coating Agent] The materials were mixed and stirred according to the compositions shown in Table 1 to prepare a coating agent of the present invention and a comparative coating agent. The materials used are listed below. Dimer acid di(meth)acrylate resin: DDDA: Dimer diol di(meth)acrylate produced by the method described above. Multifunctional (meth)acrylate compounds: M309: Aronix (registered trademark) M309, manufactured by Toagosei Co., Ltd. Trimethylolpropane triacrylate. Photopolymerization initiator: Irgacure (registered trademark) 127, manufactured by BASF 2-hydroxy-1-(4-((4-(2-hydroxy-2-methylpropanoyl)phenyl)methyl)phenyl)-2-methylpropan-1-one. Fluorine compound: XUA008: XUA008 produced by the method described above. A polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units and having an acryloyl group in the side chain. The parts by weight of XUA008 in Table 1 are the parts by weight of the solid content of a 30 wt% solution of XUA008. Reactive silicone compounds: FM-7711: Trade name of JNC Corporation; Silaplane (registered trademark) FM-7711. A polydimethylsiloxane macromonomer having a number average molecular weight of Mn 1,000 and having methacryloxy groups at both ends. Light stabilizer (1): Tinuvin (registered trademark) 292: Trade name of a light stabilizer manufactured by BASF. TINUVIN 292 (compound name: a mixture of approximately 75% by weight of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and approximately 25% by weight of methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate). Ultraviolet absorbers - Tinuvin (registered trademark) 479: trade name of ultraviolet absorber manufactured by BASF. Hydroxyphenyltriazine-based ultraviolet absorber. - Tinuvin (registered trademark) 384-2: trade name of ultraviolet absorber manufactured by BASF. Benzotriazole-based ultraviolet absorber. - Tinuvin (registered trademark) 400: trade name of ultraviolet absorber manufactured by BASF. Hydroxyphenyltriazine-based ultraviolet absorber. Diluent (solvent) - Diluent (solvent): methyl isobutyl ketone. Other components - Tinuvin (registered trademark) 770: trade name of light stabilizer manufactured by BASF.Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0085] [Preparation of Coating Agent A0] As the dimer acid di(meth)acrylate resin, 27.7 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of solids at an effective concentration of 30.0 wt %), which is a fluorosilsesquioxane polymer obtained by the method described above, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under its product name) were used as the reactive silicone compound. Further, to this, 2.0 parts by weight of a light stabilizer (1) manufactured by BASF under the trade name "TINUVIN 292," 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2" and 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400," and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the total weight of the curable component, fluorine compound, and z silicone compound was 100 parts by weight. In this way, the coating agent A0 shown in Table 1 was obtained.

[0086] [Preparation of Coating Agent B0] As the dimer acid di(meth)acrylate resin, 27.8 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used, 65.1 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used as a polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 7.0 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used as a photopolymerization initiator, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under its product name) was used as a reactive silicone compound. Further, to this, 5.0 parts by weight of a light stabilizer (1) manufactured by BASF under the trade name "TINUVIN 292," 5.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2," and 5.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400" were added, and 30 parts by weight of methyl isobutyl ketone was added as a diluent (solvent), to obtain the coating agent B0 shown in Table 1.

[0087] [Preparation of Coating Agent C0] As the dimer acid di(meth)acrylate resin, 46.2 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 46.3 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt%), which is a fluorosilsesquioxane polymer obtained by the above-mentioned method, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under its product name) were used as the reactive silicone compound. Further, to this, 2.5 parts by weight of a light stabilizer (1) manufactured by BASF under the trade name "TINUVIN 292," 2.5 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2" and 2.5 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400," and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the total weight of the curable component, fluorine compound, and reactive silicone compound was 100 parts by weight. In this way, the coating agent C0 shown in Table 1 was obtained.

[0088] [Preparation of Coating Agent D0] As the dimer acid di(meth)acrylate resin, 9.2 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 83.3 parts by weight of an ultraviolet-curable resin (trifunctional acrylate) manufactured by Toagosei Co., Ltd., under the trade name "Aronix M309," was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the trade name "Irgacure 127," was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt%), which is a fluorosilsesquioxane polymer obtained by the above-mentioned method, and 0.1 parts by weight of Silaplane FM-7711 (trade name manufactured by JNC Corporation) were used as the reactive silicone compound. Further, to this, 2.0 parts by weight of a light stabilizer (1) manufactured by BASF under the trade name "TINUVIN 292," 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2" and 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400," and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the total weight of the curable component, fluorine compound, and reactive silicone compound was 100 parts by weight. In this way, the coating agent D0 shown in Table 1 was obtained.

[0089] [Preparation of Coating Agent E0] As the dimer acid di(meth)acrylate resin, 27.8 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used, 65.1 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used as a polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 7.0 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used as a photopolymerization initiator, and further 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under the product name) was used as a reactive silicone compound. Further, to this, 2.0 parts by weight of a light stabilizer (1) manufactured by BASF under the trade name "TINUVIN 292," 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2" and 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400," and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the total weight of the curable component, fluorine compound, and reactive silicone compound was 100 parts by weight. In this way, the coating agent E0 shown in Table 1 was obtained.

[0090] [Preparation of Coating Agent F0] As the dimer acid di(meth)acrylate resin, 27.8 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used as a polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 7.0 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used as a photopolymerization initiator, and further 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under the product name) was used as a reactive silicone compound. Further, to this, 1.5 parts by weight of a light stabilizer (1) manufactured by BASF under the trade name "TINUVIN 292," 1.5 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 497," and 1.5 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400" were added, and 30 parts by weight of methyl isobutyl ketone was added as a diluent (solvent), so that the coating agent F0 shown in Table 1 was obtained.

[0091] [Preparation of Coating Agent G0] As the dimer acid di(meth)acrylate resin, 27.7 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt %), which is a fluorosilsesquioxane polymer obtained by the above-mentioned method, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under its product name) were used as the reactive silicone compound. Further, to this, 1.5 parts by weight of a light stabilizer (1) manufactured by BASF under the trade name "TINUVIN 292," 1.5 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2" and 1.5 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400," and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the total weight of the curable component, fluorine compound, and reactive silicone compound was 100 parts by weight. In this way, the coating agent G0 shown in Table 1 was obtained.

[0092] [Preparation of Coating Agent H0] As the dimer acid di(meth)acrylate resin, 27.7 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compounds, which are trifunctional acrylate compounds, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd., under the trade name "Aronix M309," was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the trade name "Irgacure 127," was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt%), which is a fluorosilsesquioxane polymer obtained by the above-mentioned method, and 0.1 parts by weight of Silaplane FM-7711 (trade name manufactured by JNC Corporation) were used as the reactive silicone compound. Further, to a total weight of 100 parts by weight of the curable component, fluorine compound, and reactive silicone compound, 2.0 parts by weight of a light stabilizer manufactured by BASF under the trade name "TINUVIN 770" as a light stabilizer, 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2" and 2.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400" as ultraviolet absorbers, and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added. In this way, coating agent H0 shown in Table 1 was obtained.

[0093] [Preparation of Coating Agent I0] As the dimer acid di(meth)acrylate resin, 27.7 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt%), which is a fluorosilsesquioxane polymer obtained by the above-mentioned method, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under its product name) were used as the reactive silicone compound. Further, to this, 2.0 parts by weight of a BASF light stabilizer (trade name "TINUVIN 770") as a light stabilizer, 2.0 parts by weight of a BASF ultraviolet absorber (trade name "TINUVIN 497") and 2.0 parts by weight of a BASF ultraviolet absorber (trade name "TINUVIN 400") as ultraviolet absorbers, and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the coating agent 10 shown in Table 1 was obtained.

[0094] [Preparation of Coating Agent J0] As the dimer acid di(meth)acrylate resin, 27.7 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt%) obtained by the above-mentioned method, which is a fluorosilsesquioxane polymer, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation, product name) were used as the reactive silicone compound. Further, to this, 5.0 parts by weight of a light stabilizer manufactured by BASF under the trade name "TINUVIN 770" as a light stabilizer, 5.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 384-2" and 5.0 parts by weight of an ultraviolet absorber manufactured by BASF under the trade name "TINUVIN 400" as ultraviolet absorbers, and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the coating agent J0 shown in Table 1 was obtained.

[0095] [Preparation of Coating Agent K0] As the dimer acid di(meth)acrylate resin, 27.7 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt%) obtained by the above-mentioned method, which is a fluorosilsesquioxane polymer, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation, product name) were used as the reactive silicone compound. Further, to this, 1.5 parts by weight of a BASF light stabilizer (trade name "TINUVIN 770") as a light stabilizer, 1.5 parts by weight of a BASF ultraviolet absorber (trade name "TINUVIN 497") and 1.5 parts by weight of a BASF ultraviolet absorber (trade name "TINUVIN 400") as ultraviolet absorbers, and 30 parts by weight of methyl isobutyl ketone as a diluent (solvent) were added, so that the coating agent K0 shown in Table 1 was obtained.

[0096] [Preparation of Coating Agent L0] As the dimer acid di(meth)acrylate resin, 27.7 parts by weight of the "dimer diol di(meth)acrylate" synthesized above was used; as the polyfunctional (meth)acrylate compound, which is a trifunctional acrylate compound, 64.8 parts by weight of an ultraviolet-curable resin manufactured by Toagosei Co., Ltd. under the product name "Aronix M309" was used; as the photopolymerization initiator, 6.9 parts by weight of a photopolymerization initiator manufactured by BASF under the product name "Irgacure 127" was used; and further, as the fluorine compound, 0.5 parts by weight of XUA008 (as the weight of the solid content at an effective concentration of 30.0 wt %), which is a fluorosilsesquioxane polymer obtained by the above-mentioned method, and 0.1 parts by weight of Silaplane FM-7711 (manufactured by JNC Corporation under its product name) were used. Further, 30 parts by weight of methyl isobutyl ketone was added as a diluent (solvent) to make the total weight of the curable component, fluorine compound, and reactive silicone compound 100 parts by weight, thereby obtaining the coating agent K0 shown in Table 1.

[0097] Examples 1 to 7, Comparative Examples 1 to 5 Preparation of Laminates A commercially available acrylic pressure-sensitive adhesive (Avery Dennison, product name: S8721) was applied by die coating to one side of a substrate layer (thermoplastic polyurethane film manufactured by Argotec, product name "ARGOGUARD49510") and dried at 70°C for 3 minutes. In this way, a 40 μm thick adhesive layer was formed on one side of the substrate layer. Next, the open surface of the adhesive layer was pressed against a 75 μm thick polyethylene terephthalate film (release film: release liner) that had been release-treated with a silicone resin using a rubber roller, and the resulting film was aged at 45°C for 1 day. In this way, laminates A, B, C, D, E, F, G, H, I, J, K, and L were obtained, each having the substrate layer, adhesive layer, and release film bonded together in this order. Photopolymerizable coating agents A0, B0, C0, D0, E0, F0, G0, H0, I0, J0, K0, and L0 were applied to the open surface of the substrate layer using a wire bar coater No. 12 manufactured by R.D.S. Webster, and dried at 80°C for 3 minutes. Thereafter, a Fusion UV lamp-equipped belt conveyor curing unit (manufactured by Heraeus) was used to apply the coatings at an integrated light dose of 500 mJ / cm. ２The coating agent was cured by heating at 400°C for 1 hour. In this manner, a coating layer having a thickness of 0.5 to 5.0 μm was formed on the substrate layer, and laminates (Examples 1, 2, 3, 4, 5, 6, 7, Comparative Examples 1, 2, 3, 4, and 5) in which the coating layer, substrate layer, adhesive layer, and release film layer were contacted in this order were obtained.

[0098] [Weather resistance test of laminate] The laminate was used to test the laminate in an accelerated weather resistance tester "Super Xenon Weather Meter SX75Z" manufactured by Suga Test Instruments Co., Ltd. (lamp: 7.5 kW xenon lamp, irradiance: 180 W / m ２ An accelerated weather resistance test was carried out under the following conditions: black panel temperature: 63°C; test conditions: UV irradiation (irradiation + water spray (18 minutes) → irradiation only (102 minutes) 1 cycle repeated for 2 hours); and the total light transmittance (%), haze, and color were measured before and after 2000 hours of the accelerated weather resistance test.

[0099] [Evaluation of Laminate] The laminate obtained was evaluated before and after the accelerated weather resistance test from the following viewpoints. The results are shown in Table 1.

[0100] 1) Total Light Transmittance (%) As an index of the transparency of the laminate, the total light transmittance was measured in accordance with JIS K 7361-1 using a haze meter (NDH-5000SP, product name, manufactured by Nippon Denshoku Industries Co., Ltd.) The release film of the laminate was peeled off before the accelerated weather resistance test and after 2000 hours of the accelerated weather resistance test, and the laminate was attached to a polycarbonate resin plate (manufactured by Teijin Limited, product name: Panlite PC-1151, thickness 2.0 mm) via the adhesive layer, and the measurement was performed in this state.

[0101] 2) Haze As an index of the transparency of the laminate, haze was measured in accordance with the standard of JIS K 7361-1 using a haze meter (NDH-5000SP, product name, manufactured by Nippon Denshoku Industries Co., Ltd.) The release film of the laminate was peeled off before the accelerated weather resistance test and after 2000 hours of the accelerated weather resistance test, and the measurement was carried out in a state where the target laminate was attached to a polycarbonate resin plate (manufactured by Teijin Limited, product name: Panlite PC-1151, thickness 2.0 mm) via the adhesive layer.

[0102] 3) Color As an index of the color of the laminate, a spectrophotometer / colorimeter (SD 7000, product name of Nippon Denshoku Industries Co., Ltd.) was used in accordance with the standard of JIS Z 8729 to measure the color of the laminate. ＊ The release film of the laminate was peeled off before the accelerated weather resistance test and after 2000 hours of the accelerated weather resistance test, and the measurement was carried out in a state where the laminate was attached to a polycarbonate resin plate (trade name: Panlite PC-1151, manufactured by Teijin Limited, thickness 2.0 mm) via the adhesive layer.

[0103]

[0104] As shown in Table 1, the laminates produced in Examples 1 to 7, which used TINUVIN 292 as the light stabilizer represented by formula (1), showed small differences in total light transmittance (%), haze, and color before and after the accelerated weather resistance test, i.e., excellent weather resistance was obtained.

[0105] On the other hand, as shown in Table 1, the laminates produced in Comparative Examples 1 to 5 did not use the light stabilizer represented by formula (1), and therefore showed large differences in haze and color before and after the accelerated weather resistance test.

[0106] The laminate of the present invention has excellent weather resistance and can be used for outdoor applications, including vehicles such as automobiles, motorcycles, and trains, as well as ships, windows, digital signage, and outdoor touch panels. It can also be used indoors, protecting floorboards, kitchen and bathroom walls, packaging, and office supplies. Additionally, the surface of the protected article can be made smooth, improving its design.

[0107] REFERENCE SIGNS LIST 10 Laminate 11 Base material layer 12 Coating layer 13 Adhesive layer 14 Release film s1 Surface ss Fluorine compound, reactive silicone compound

Claims

1. A coating agent comprising a dimer acid di(meth)acrylate resin, a polyfunctional (meth)acrylate compound, a photopolymerization initiator, and a light stabilizer represented by formula (1). In formula (1), n ​​is an integer of 4 to 12, each R is independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 4 to 10 carbon atoms, and Me is methyl.

2. The coating agent according to claim 1, further comprising an ultraviolet absorber.

3. The coating agent according to claim 1, wherein the polyfunctional (meth)acrylate compounds are trifunctional acrylate compounds.

4. A laminate comprising a substrate layer and a coating layer made of a cured product of the coating agent according to any one of claims 1 to 3 formed on the substrate layer.

5. A laminate comprising a coating layer made of a cured product of the coating agent formed on a substrate layer using the coating agent according to any one of claims 1 to 3, and a substrate layer formed using thermoplastic polyurethane.

6. A laminate comprising: a coating layer formed on a base layer using the coating agent according to any one of claims 1 to 3 and made of a cured product of the coating agent; a base layer formed using thermoplastic polyurethane; and an adhesive layer formed on the surface of the base layer opposite to the surface on which the coating layer is formed using at least one resin selected from acrylic, urethane, rubber, and silicone resins.

7. The laminate according to claim 4, wherein the coating agent further contains at least one reactive silicone compound selected from the group consisting of siloxanes having acryloyl groups at both or one of the ends.

8. The laminate according to claim 4, wherein the coating agent further contains at least one fluorine compound selected from the group consisting of fluorosilsesquioxane monomers and fluorosilsesquioxane polymers.

9. The laminate of claim 8, wherein the fluorosilsesquioxane polymer is an addition polymer of a fluorosilsesquioxane monomer having at least one addition polymerizable functional group, or an addition copolymer of a fluorosilsesquioxane monomer having one addition polymerizable functional group and an addition polymerizable monomer.

10. An article having the laminate according to claim 6 attached to a surface by the adhesive layer.

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