Photocurable resin composition, base material with cured coating film and method for producing the same

Abstract

To provide a photocurable resin composition capable of forming a cured coating film having excellent transparency, adhesion to a base material, hardness, visible light transmission properties and infrared absorption properties.MEANS: There is provided a photocurable resin composition comprising a urethane (meth)acrylate (A), a (meth)acrylate monomer (B), a photopolymerization initiator (C) and an infrared absorber (D), wherein the urethane (meth)acrylate (A) includes at least a urethane (meth)acrylate (a1) having a functional group number of 6 or more, the content of the urethane (meth)acrylate (a1) having a functional group number of 6 or more is 10 mass% or more and 40 mass% or less based on 100 mass% of the solid content of the photocurable resin composition, the (meth)acrylate monomer (B) includes at least a (meth)acrylate monomer (b1) having a functional group number of 5 or more and 6 or less, the content of the (meth)acrylate monomer (b1) having a functional group number of 5 or more and 6 or less is 20 mass% or more based on the total amount of the (meth)acrylate monomer (B), the (meth)acrylate monomer (B) may further include a (meth)acrylate monomer (b2) having a functional group number of 2 or less and the content of the (meth)acrylate monomer (b2) having a functional group number of 2 or less is less than 20 mass% based on the total amount of the (meth)acrylate monomer (B).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photocurable resin composition. The present invention also relates to a cured film formed from the photocurable resin composition, a substrate with the cured film, and a method for producing the substrate with the cured film.

Background Art

[0002] Conventionally, for the surfaces of windows of houses and vehicles, etc., a heat ray shielding film has been attached from the viewpoints of improving habitability and energy saving. Further, for a head-up display unit incorporated in a dashboard of a vehicle, a heat ray shielding film is used for the purpose of suppressing a temperature rise of a display due to intrusion of direct sunlight.

[0003] Such a heat ray shielding film is composed of, for example, a plastic film substrate typified by polyethylene terephthalate (PET) and a near-infrared absorption layer provided on one or both sides of the plastic film substrate. The near-infrared absorption layer is formed, for example, by coating and curing a photocurable resin composition (coating agent) having near-infrared absorption properties. Although it is effective to contain a specific near-infrared absorber in the coating agent for imparting near-infrared absorption properties, there is a problem that physical properties such as visible light transmittance and adhesion to a substrate are deteriorated. Further, when the crosslinking density of the near-infrared absorption layer is increased to improve the surface hardness, there is a problem that the adhesion to the substrate is deteriorated.

[0004] Therefore, as an infrared cut hard coat resin that achieves a balance between visible light transmittance and infrared absorption performance and has excellent heat-resistant adhesion to a polycarbonate film, a polyfunctional (meth)acrylate monomer (A) containing a 6-functional or higher (meth)acrylate monomer (a1), an infrared absorption component (B), and at least two types of intramolecular cleavage type photoinitiators (C) including an oxime ester type are included, and an infrared cut hard coat resin composition characterized in that the blending ratio of the (a1) with respect to the (A) is 35 to 80% by weight and an infrared cut hard coat film formed therefrom have been proposed (see Patent Document 1). Further, an infrared absorbing composition having an oxide (A) having infrared absorption ability, an acrylic compound (B) not containing fluorine, and an acrylic compound (C) containing fluorine has been proposed for forming an infrared absorption layer of a heat shielding film (see Patent Document 2).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present inventors have found a new problem that sufficient adhesion to a specific substrate (for example, a PET substrate) cannot be obtained in the development of a resin film excellent in transparency, hardness, visible light transmittance, and infrared absorption. In fact, the infrared cut hard coat film described in Patent Document 1 has good adhesion to a polycarbonate substrate but insufficient adhesion to a PET substrate.

[0007] The present invention has been made in view of the above-described background art and problems, and an object thereof is to provide a photocurable resin composition capable of forming a cured film excellent in transparency, substrate adhesion, hardness, visible light transmittance, and infrared absorption. **Means for Solving the Problems**

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a photocurable resin composition containing a specific urethane (meth)acrylate (A), a specific (meth)acrylate monomer (B), a photopolymerization initiator (C), and an infrared absorber (D). The present invention has been completed based on such findings.

[0009] That is, according to the present invention, the following inventions are provided. [1] A photocurable resin composition containing a urethane (meth)acrylate (A), a (meth)acrylate monomer (B), a photopolymerization initiator (C), and an infrared absorber (D), wherein the urethane (meth)acrylate (A) contains at least a urethane (meth)acrylate (a1) having 6 or more functional groups, and the content of the urethane (meth)acrylate (a1) having 6 or more functional groups is 10% by mass or more and 40% by mass or less with respect to 100% by mass of the solid content of the photocurable resin composition, the (meth)acrylate monomer (B) contains at least a (meth)acrylate monomer (b1) having 5 or more and 6 or less functional groups, and the content of the (meth)acrylate monomer (b1) having 5 or more and 6 or less functional groups is 20% by mass or more with respect to the total amount of the (meth)acrylate monomer (B), the (meth)acrylate monomer (B) may further contain a (meth)acrylate monomer (b2) having 2 or less functional groups, and the content of the (meth)acrylate monomer (b2) having 2 or less functional groups is less than 20% by mass with respect to the total amount of the (meth)acrylate monomer (B). [2] The photocurable resin composition according to [1], wherein the content of the (meth)acrylate monomer (B) is 10% by mass or more and 60% by mass or less based on 100% by mass of the solid content of the photocurable resin composition. [3] The photocurable resin composition according to [1] or [2], wherein the (meth)acrylate monomer (B) further contains a (meth)acrylate monomer (b3) having 3 or more and 4 or less functional groups. [4] The infrared absorber (D) is represented by the general formula: M x W y O z (In the formula, M is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb; W is tungsten; O is oxygen; 0.001 ≦ x / y ≦ 1; 2.0 < z / y ≦ 3.0), and is a composite tungsten oxide, and the photocurable resin composition according to any one of [1] to [3]. [5] The photocurable resin composition according to any one of [1] to [4], wherein the content of the infrared absorber (D) is 2% by mass or more and 40% by mass or less based on 100% by mass of the solid content of the photocurable resin composition. [6] The photocurable resin composition according to any one of [1] to [5], further comprising inorganic particles (E). [7] The photocurable resin composition according to [6], wherein the inorganic particles (E) at least contain nanosilica (e1) having an average primary particle diameter of 5 nm or more and less than 70 nm and nanosilica (e2) having an average primary particle diameter of 70 nm or more and less than 300 nm. [8] The photocurable resin composition according to any one of [1] to [7], further comprising a leveling agent (F). [9] The photocurable resin composition according to any one of [1] to [8], further comprising a dispersant (G).

[10] The photocurable resin composition according to any one of [1] to [9], which is used as a paint.

[11] A cured film formed from the photocurable resin composition according to any one of [1] to

[10] .

[12] A substrate with a cured film having a cured film formed from the photocurable resin composition according to any one of [1] to

[10] on at least a part of the substrate surface.

[13] A coating step of applying the photocurable resin composition according to any one of [1] to

[10] to at least one surface of the substrate, A curing step of curing the photocurable resin composition by ultraviolet irradiation to form a cured film after the coating step, A method for manufacturing a substrate with a cured film, including the above steps.

Advantages of the Invention

[0010] According to the present invention, a photocurable resin composition capable of forming a cured film excellent in transparency, substrate adhesion, hardness, visible light transmittance, and infrared absorption can be provided. Further, according to the present invention, a cured film formed from such a photocurable resin composition, a substrate with the cured film, and a method for manufacturing the substrate with the cured film can also be provided.

[0011] A film provided with a cured film formed from the photocurable resin composition of the present invention is attached to optical members such as windows and displays of vehicles and buildings, and by cutting infrared rays, it is possible to suppress the rise in indoor temperature and the thermal deterioration of members. Further, such a film provided with a cured film exhibits high light absorption in the infrared wavelength region and high transparency in the visible light wavelength region, so high visibility can be obtained even when applied to optical members such as displays.

Embodiments for Carrying Out the Invention

[0012] Hereinafter, the present invention will be described in more detail. In this specification, “(meth)acrylate” represents acrylate and methacrylate, “(meth)acrylic” represents acrylic and methacrylic, and “(meth)acryloyl” represents acryloyl and methacryloyl. "Solid content" refers to the component that constitutes the cured film when the volatile components such as organic solvents are removed from the photocurable resin composition.

[0013] <Photocurable resin composition> The photocurable resin composition according to the present invention contains urethane (meth)acrylate (A), (meth)acrylate monomer (B), photoinitiator (C), and infrared absorber (D). In the present invention, by including the components (A) to (D) in the photocurable resin composition, a cured film excellent in transparency, substrate adhesion, hardness, visible light transmittance, and infrared absorption can be formed. Further, the photocurable resin composition according to the present invention may further contain inorganic particles (E), leveling agent (F), dispersant (G), ultraviolet absorber (H), light stabilizer (I), and the like. Such a photocurable resin composition can be applied to various fields where both visible light transmittance and infrared absorption are required, and can be used, for example, in window films for vehicles and buildings and optical members such as displays. Hereinafter, each component constituting the photocurable resin composition will be described in detail.

[0014] (Urethane (meth)acrylate (A)) Urethane (meth)acrylate (A) has an acryloyl group (CH2=CHCO-) and / or a methacryloyl group (CH2=C(CH3)-CO-) as functional groups in the molecule, and a urethane bond (-NH·COO-). Urethane (meth)acrylate is not particularly limited, and can be obtained, for example, by reacting a polyisocyanate, a hydroxyl group-containing (meth)acrylate, and, if necessary, a polyol other than the hydroxyl group-containing (meth)acrylate. Urethane (meth)acrylate (A) is preferably an oligomer or a polymer, and more preferably an oligomer.

[0015] The above polyisocyanate is obtained by reacting a polyol with a diisocyanate. The polyol, which is a synthetic raw material of the polyisocyanate, is not particularly limited. For example, polyester polyol, polyether polyol, polycarbonate polyol, etc. may be mentioned. It may be used alone of these, or two or more kinds may be used in combination.

[0016] There are no particular restrictions on the production method of the polyester polyol. For example, those obtained by known methods such as polycondensation reaction of a diol with a dicarboxylic acid or a dicarboxylic acid chloride, or esterification of a diol or a dicarboxylic acid followed by transesterification reaction can be used. The diol used in the synthesis of the polyester polyol is not particularly limited. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dibropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, etc. may be mentioned. The dicarboxylic acid used in the synthesis of the polyester polyol is not particularly limited. For example, adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dimaleic acid, terephthalic acid, isophthalic acid, phthalic acid, etc. may be mentioned.

[0017] The polyether polyol is not particularly limited. For example, polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide random copolymer, etc. may be mentioned.

[0018] The polycarbonate polyol is not particularly limited, and examples thereof include reaction products obtained by polycondensing the following component A and component B. That is, component A is not particularly limited, and examples thereof include diols such as 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol, dipropylene glycol, diethylene glycol, or reaction products of these diols with dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, hexahydrophthalic acid, etc. Component B is not particularly limited, and examples thereof include aromatic carbonates or aliphatic carbonates such as diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, phenyltolyl carbonate, phenylchlorophenyl carbonate, 2-tolyl-4-tolyl carbonate, dimethyl carbonate, diethyl carbonate, diethylene carbonate, ethylene carbonate, etc.

[0019] The diisocyanate, which is a raw material for synthesizing the polyisocyanate, is not particularly limited, and a linear or alicyclic aliphatic diisocyanate or an aromatic diisocyanate can be used. Specifically, for example, isocyanate group-containing linear hydrocarbons such as tetramethylene diisocyanate, hexamethylene diisocyanate; isocyanate group-containing branched-chain hydrocarbons such as 2,2,4-trimethylhexamethylene diisocyanate; isocyanate group-containing cyclic hydrocarbons such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate; isocyanate group-containing aromatic hydrocarbons such as p-phenylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 1,3-xylene diisocyanate, dianisidine diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, etc.

[0020] As the above hydroxyl group-containing (meth)acrylate, a (meth)acrylate having at least one or more, preferably 1 to 5 hydroxyl groups can be used. Further, such a hydroxyl group-containing (meth)acrylate preferably desirably has a hydrocarbon moiety having 2 to 20 carbon atoms. Here, the hydrocarbon moiety refers to an organic group having a linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be saturated or unsaturated. In addition, a part of the hydrocarbon moiety may contain an ether bond (C—O—C bond).

[0021] Examples of the (meth)acrylate monomer having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, and their caprolactone adducts (Placcel FA1, FA2, etc. manufactured by Daicel Corporation), OH group-terminated polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, their ethylene oxide-modified products (AM-90G, AM-130G manufactured by Shin-Nakamura Chemical Co., Ltd., Light Acrylate EC-A, MTG-A, EHDG-AT, etc. manufactured by Kyoeisha Chemical Co., Ltd.), glycerin mono(meth)acrylate (Blemmer GLM, etc. manufactured by NOF Corporation), glycerin di(meth)acrylate (Aronix MT3560, etc. manufactured by Toagosei Co., Ltd.), isocyanuric acid EO-modified di(meth)acrylate (Aronix M-313, M-315, etc. manufactured by Toagosei Co., Ltd.), pentaerythritol tri / tetra(meth)acrylate (Biscoat 300 manufactured by Osaka Organic Chemical Industry Co., Ltd., Aronix M-305, M-306, M-450, MT-3548 manufactured by Toagosei Co., Ltd., Light Acrylate PE-3A manufactured by Kyoeisha Chemical Co., Ltd., NK Ester A-TMM-3L manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), dipentaerythritol penta(meth)acrylate (Aronix M-400, M-402, M-403, MT-3549 manufactured by Toagosei Co., Ltd., Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd., NK Ester A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd., etc.). Among these, from the viewpoints of the weather resistance, abrasion resistance, and scratch resistance of the cured film, it is preferable to use isocyanuric acid EO-modified diacrylate or pentaerythritol tri / tetraacrylate. Such hydroxyl group-containing (meth)acrylate may be used alone or in combination of two or more kinds.

[0022] As the polyol other than the above hydroxyl group-containing (meth)acrylate used as needed, known polyols such as polyether polyol, polyester polyol, and polyolefin polyol can be used. Specifically, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polycaprolactone polyol, alkylene diol, etc. can be mentioned. Such polyols may be used alone or in combination of two or more.

[0023] In the present invention, among the above urethane (meth)acrylates (A), at least a hexafunctional or higher urethane (meth)acrylate (a1) is used. The upper limit of the functional group number of the hexafunctional or higher urethane (meth)acrylate (a1) is not particularly limited, and for example, it may be 12-functional or less, or 10-functional or less. By using a hexafunctional or higher urethane (meth)acrylate (a1) instead of a urethane (meth)acrylate with a small number of functional groups (for example, 2-3 functional groups), the substrate adhesion and hardness of the cured film can be improved.

[0024] The content of the hexafunctional or higher urethane (meth)acrylate (a1) is 10% by mass or more and 40% by mass or less, preferably 12% by mass or more and 38% by mass or less, more preferably 15% by mass or more and 35% by mass or less, based on 100% by mass of the solid content of the photocurable resin composition, from the viewpoints of the substrate adhesion and hardness of the cured film.

[0025] ((Meth)acrylate monomer (B)) (Meth)acrylate monomer (B) is a monomer having at least one or more (meth)acryloyl groups, and forms a cured film together with the above urethane (meth)acrylate (A) when the photocurable resin composition is irradiated with ultraviolet rays.

[0026] The content of the (meth)acrylate monomer (B) is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 55% by mass or less, still more preferably 20% by mass or more and 52% by mass or less, and even more preferably 25% by mass or more and 50% by mass or less, from the viewpoints of the adhesion of the cured film to the substrate and the hardness, based on 100% by mass of the solid content of the photocurable resin composition.

[0027] ((Meth)acrylate monomer (b1) having 5 to 6 functional groups) (Meth)acrylate monomer (B) contains at least (meth)acrylate monomer (b1) having 5 to 6 functional groups. The (meth)acrylate monomer having 5 to 6 functional groups means a compound having 5 or 6 (meth)acryloyloxy groups as functional groups in the molecule. Examples of the (meth)acrylate monomer having 5 to 6 functional groups include dipentaerythritol penta(meth)acrylate, alkoxylated dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkoxylated dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. Among these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable. These (meth)acrylate monomers having 5 to 6 functional groups may be used alone or in combination of two or more.

[0028] The content of the (meth)acrylate monomer (b1) having 5 to 6 functional groups is 20% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, even more preferably 70% by mass or more, most preferably 75% by mass or more, and may be 100% by mass or 90% by mass or less, based on the total amount of the (meth)acrylate monomer (B), from the viewpoints of the adhesion of the cured film to the substrate and the hardness.

[0029] ((Meth)acrylate monomer (b2) with a functional group number of 2 or less) (Meth)acrylate monomer (B) may further contain a (meth)acrylate monomer (b2) having a functionality of 2 or less in a specific amount or less. The (meth)acrylate monomer having a functionality of 2 or less means a compound having 2 or less (meth)acryloyloxy groups as functional groups in the molecule. Examples of the (meth)acrylate monomer having a functionality of 2 or less include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate; polyoxyalkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate; di(meth)acrylates of halogen-substituted alkylene glycols such as tetrafluoroethylene glycol di(meth)acrylate; di(meth)acrylates of aliphatic polyols such as trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, and polycarbonate diol di(meth)acrylate; di(meth)acrylates of hydrogenated dicyclopentadiene or tricyclodecane dialkanol such as hydrogenated dicyclopentadienyl di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; di(meth)acrylates of dioxane glycol or dioxane dialkanol such as 1,3-dioxane-2,5-diyl di(meth)acrylate [alias: dioxane glycol di(meth)acrylate];Di(meth)acrylates of alkylene oxide adducts of bisphenol A or bisphenol F, such as bisphenol A ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate; epoxy di(meth)acrylates of bisphenol A or bisphenol F, such as acrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of bisphenol F diglycidyl ether; silicone di(meth)acrylate; di(meth)acrylate of neopentyl glycol hydroxypivalate; 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane; 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane; di(meth)acrylate of 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane; tris(hydroxyethyl)isocyanurate di(meth)acrylate; lower alkyl mono(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate; higher alkyl mono(meth)acrylates such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate; cyclic alkyl mono(meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate; cyclic ether mono(meth)acrylates such as tetrahydrofurfuryl (meth)acrylate; aromatic alkyl mono(meth)acrylates such as phenoxyethyl (meth)acrylate; (alkoxy)alkylene glycol mono(meth)acrylates such as (methoxy)polyethylene glycol (meth)acrylate, (methoxy)polypropylene glycol (meth)acrylate, (ethoxy)polyethylene glycol (meth)acrylate, (ethoxy)polypropylene glycol (meth)acrylate;Aromatic (alkoxy) alkylene glycol mono (meth) acrylates such as phenoxy diethylene glycol (meth) acrylate and phenoxy polyethylene glycol (meth) acrylate; hydroxyl group-containing mono (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, etc.; etc. are mentioned. Among these (meth) acrylate monomers with a functional group number of 2 or less, alkylene glycol di (meth) acrylate, polyoxyalkylene glycol di (meth) acrylate, di (meth) acrylate of halogen-substituted alkylene glycol, di (meth) acrylate of aliphatic polyol, di (meth) acrylate of hydrogenated dicyclopentadiene or tricyclodecane dialkanol, di (meth) acrylate of dioxane glycol or dioxane dialkanol, silicone di (meth) acrylate, di (meth) acrylate of neopentyl glycol hydroxypivalate, 2,2-bis [4-(meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2-bis [4-(meth) acryloyloxyethoxyethoxycyclohexyl] propane, di (meth) acrylate of 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane, tris (hydroxyethyl) isocyanurate di (meth) acrylate are preferred, alkylene glycol di (meth) acrylate is more preferred, and 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are particularly preferred. These (meth) acrylate monomers with a functional group number of 2 or less may be used alone or in combination of two or more.;

[0030] The content of the (meth)acrylate monomer (b2) having a functional group number of 2 or less is less than 20% by mass, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, even more preferably 1% by mass or less, and may be 0% by mass, from the viewpoints of the substrate adhesion and hardness of the cured film, based on the total amount of the (meth)acrylate monomer (B).

[0031] ((meth)acrylate monomer (b3) having a functional group number of 3 or more and 4 or less) (Meth)acrylate monomer (B) may further contain a (meth)acrylate monomer (b3) having a functional group number of 3 or more and 4 or less. The (meth)acrylate monomer having a functional group number of 3 or more and 4 or less means a compound having 3 or 4 (meth)acryloyloxy groups as functional groups in the molecule. Examples of the (meth)acrylate monomer having a functional group number of 3 or more and 4 or less include poly(meth)acrylates of aliphatic polyols such as tris(2-acryloyloxyethyl) isocyanurate, alkylene oxide-modified tris(2-acryloyloxyethyl) isocyanurate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc. Among these, pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate are preferable. These (meth)acrylate monomers having a functional group number of 3 or more and 4 or less may be used alone or in combination of two or more.

[0032] The content of the (meth)acrylate monomer (b3) having a functional group number of 3 or more and 4 or less is preferably 5% by mass or more and 80% by mass or less, more preferably 6% by mass or more and 75% by mass or less, still more preferably 7% by mass or more and 65% by mass or less, even more preferably 8% by mass or more and 55% by mass or less, particularly preferably 9% by mass or more and 45% by mass or less, and most preferably 10% by mass or more and 35% by mass or less, from the viewpoints of the substrate adhesion and hardness of the cured film, based on the total amount of the (meth)acrylate monomer (B).

[0033] (Photoinitiator (C)) The photoinitiator is not particularly limited, and a conventionally known photoinitiator for a photocurable resin composition can be used. Examples of the photoinitiator include acylphosphine oxide-based polymerization initiators, acetophenone-based polymerization initiators, benzoylformate-based polymerization initiators, thioxanthone-based polymerization initiators, oxime ester-based polymerization initiators, hydroxybenzoyl-based polymerization initiators, benzophenone-based polymerization initiators, α-aminoalkylphenone-based polymerization initiators, and the like.

[0034] Examples of the acylphosphine oxide-based polymerization initiator include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Examples of the acetophenone-based polymerization initiator include acetophenone, 3-methylacetophenone, benzyldimethylketal, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one, and the like. Examples of the benzoyl formate-based polymerization initiator include methyl benzoyl formate and the like. Examples of the thioxanthone-based polymerization initiator include isopropyl thioxanthone and the like. Examples of the oxime ester-based polymerization initiator include 2-[(benzoyloxy)imino]-1-[4-(phenylthio)phenyl]octan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]-3-(cyclopentyl)propan-1-one O-acyloxime, and the like. Examples of the hydroxybenzoyl-based polymerization initiator include benzoin alkyl ether and the like. Examples of the benzophenone-based polymerization initiator include benzophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, and the like. Examples of the α-aminoalkylphenone-based polymerization initiator include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like. These polymerization initiators may be used alone or in combination of two or more.

[0035] From the viewpoints of the curability of the photocurable resin composition and the transparency of the cured film, the content of the photoinitiator (C) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and 9.0% by mass or less, and still more preferably 2.0% by mass or more and 8.0% by mass or less, based on 100% by mass of the solid content of the photocurable resin composition.

[0036] (Infrared Absorbing Agent (D)) Examples of the infrared absorbing agent (D) include the general formula M x W y O z(In the formula, M is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb; W is tungsten; O is oxygen; 0.001 ≦ x / y ≦ 1; 2.0 < z / y ≦ 3.0). It is preferable to use a composite tungsten oxide represented by the formula. The composite tungsten oxide is preferably composite tungsten oxide fine particles. If the value of x / y is 0.001 or more, it becomes easier to obtain near-infrared absorption characteristics. If the value of x / y is 1 or less, it is possible to avoid the formation of an impurity phase in the composite tungsten fine particles. Further, when the value of z / y exceeds 2.0, it becomes easier to avoid the appearance of the crystal phase of WO2, which is a compound other than the target, in the composite tungsten oxide, and it becomes easier to obtain chemical stability as a material, so it can be applied as an effective infrared absorber. On the other hand, if the value of z / y is 3.0 or less, the required amount of free electrons is generated in the tungsten oxide, and it becomes an infrared absorber with good efficiency.

[0037] The composite tungsten oxide transmits visible light and absorbs near-infrared light, making it easier to shield. Therefore, as the M element, Cs, Rb, K, Tl, Ba, Cu, Al, Mn, In are preferable, Cs and Rb are more preferable, and Cs is even more preferable. Regarding the value of x / y, 0.01 ≦ x / y ≦ 0.7 is more preferable, 0.1 ≦ x / y ≦ 0.5 is more preferable, 0.2 ≦ x / y ≦ 0.4 is even more preferable, and 0.3 ≦ x / y ≦ 0.35 is most preferable. Further, regarding the value of z / y, 2.2 ≦ z / y ≦ 3.0 is preferable, 2.6 ≦ z / y ≦ 3.0 is more preferable, and 2.7 ≦ z / y ≦ 3.0 is even more preferable.

[0038] Infrared absorbers other than those described above can also be used. For example, organic infrared absorbers such as porphyrin-based dyes, porphycene-based dyes, phthalocyanine-based dyes, naphthalocyanine-based dyes, squarylium-based dyes, cyanine-based dyes, perylene-based dyes, coronene-based dyes, diketopyrrolopyrrole-based dyes, dithiol metal complex-based dyes, triarylmethane-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, quinacridone dyes, nitroso compounds and their metal complexes, imonium-based dyes, diimonium-based dyes, copper phosphate ester complexes and other organometallic complexes, polycyclic aromatic hydrocarbons, aromatic heterocyclic compounds, etc.; inorganic infrared absorbers such as titanium oxide, tungsten oxide, tantalum oxide, niobium oxide, zinc oxide, indium oxide, tin-doped indium oxide, antimony-doped tin oxide, aluminum zinc composite oxide, gallium-doped zinc oxide, indium zinc composite oxide, zinc antimonate, cesium oxide, LaB6, CeB6, PrB6, NdB6, GdB6, TbB6, DyB6, HoB6, YB6, SmB6, EuB6, ErB6, TmB6, YbB6, LuB6, SrB6, CaB6, (La, Ce)B6 and other hexaborides. Such infrared absorbers may be used alone or in combination of two or more.

[0039] As the infrared absorber, commercially available infrared absorbers can be used. For example, products named EXCALAR IX-2-IR-14, IX-2-IR-28, IR-10, 12, 14, HA-1, 14, etc. manufactured by Nippon Shokubai Co., Ltd., products named YKR-2016, 2100, 2900, 2081, 2200, 2090, 3070, 3080, etc. manufactured by Yamamoto Chemical Co., Ltd., products named TAP-2, TAP-HTB, FDG-007, FDR-001, 002, 003, 004, 005, etc. manufactured by Yamada Chemical Industry Co., Ltd., products named NIR700A, 714A, 728A, 733A, 757A, 762A, 775B, 783C, 790B, 795A, 800A, 805B, 811A, 819C, 828B, 836C, 844A, 856A, 864A, 868A, 880C, 886A, 902A, 910C, 912C, 935A, 949C, 956A, 960A, 979C, 980B, 983A, 989A, 1003A, 1021A, 1031M, 1035A, 1047A, 1072C, etc. manufactured by QCR Solutions Corp, products named SDO-4, SDO-5, SDO-7, SDO-2, SDO-3, etc. manufactured by Arimoto Chemical Industry Co., Ltd., products named Optogen NIR-840S, 760S, etc. manufactured by Sumika Color Co., Ltd., products named Calenz IRT, etc. manufactured by Resonac Co., Ltd., products named Lumogen IR-765, 788, etc. manufactured by BASF, products named Kayasorb IRG-022, 023, CY-40MC(F), etc. manufactured by Nippon Kayaku Co., Ltd., products named CIR-960, 1081, 1083, 1085, RL, FS265, etc. manufactured by Nippon Carlit Co., Ltd. can be mentioned.

[0040] From the viewpoints of the visible light transmittance and infrared absorption property of the cured film, the content of the infrared absorber (D) is preferably 2% by mass or more and 40% by mass or less, more preferably 4% by mass or more and 35% by mass or less, still more preferably 6% by mass or more and 30% by mass or less, even more preferably 8% by mass or more and 25% by mass or less, and particularly preferably 10% by mass or more and 20% by mass or less with respect to 100% by mass of the solid content of the photocurable resin composition.

[0041] (Inorganic particles (E)) In film production, good lubricity (blocking resistance) in the processing step is required. Especially when the film after production is wound and stored in a roll form, if the surface of the cured film is smooth, blocking may occur due to contact between the coated surface and the substrate or between the coated surfaces during winding. In order to improve the winding property by suppressing blocking, it is preferable that the cured film has lubricity. In the present invention, in order to impart lubricity to the cured film, it is preferable to blend inorganic particles (E) into the photocurable resin composition to provide an uneven shape on the surface of the cured film.

[0042] The inorganic particles (E) are not particularly limited, and conventionally known inorganic particles can be used. The inorganic particles can be those dispersed in a colloidal state in a dispersion medium such as water or an organic solvent.

[0043] Examples of the inorganic particles include particles of aluminum, silicon, calcium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, gallium, germanium, strontium, zirconium, niobium, molybdenum, rhodium, palladium, silver, indium, tin, antimony, barium, tantalum, tungsten, iridium, platinum, gold, lead, bismuth, cerium, and alloys composed of two or more of these, or oxides, fluorides, nitrides, sulfides, carbides, borides, carbonates, other clay minerals, and composites thereof. Among the inorganic particles, silica particles, alumina particles, and zirconia particles are preferable from the viewpoint of the hardness of the resulting cured film, and silica particles are more preferable.

[0044] The inorganic particles may be reactive inorganic particles having functional groups such as hydroxyl groups, mercapto groups, isocyanate groups, amino groups, epoxy groups, and (meth)acryloyl groups on the surface. As the functional group, a (meth)acryloyl group is preferable.

[0045] The content of the inorganic particles (E) is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 45% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less, based on 100 mass of the solid content of the photocurable resin composition, from the viewpoints of the storage stability of the photocurable resin composition and the lubricity and recoatability of the cured film.

[0046] (silica particles (e)) As the silica particles, powdery or colloidal silica particles can be used. The shape of the silica is not particularly limited and may be any shape such as spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, etc., but a spherical shape is preferred.

[0047] As the silica particles, it is preferable to use both nanosilica (e1) having an average primary particle diameter of 5 nm or more and less than 70 nm and nanosilica (e2) having an average primary particle diameter of 70 nm or more and less than 300 nm. The average primary particle diameter of the nanosilica (e1) is preferably 7 nm or more and 50 nm or less, more preferably 9 nm or more and 30 nm or less, and even more preferably 10 nm or more and 20 nm or less. The average primary particle diameter of the nanosilica (e2) is preferably 80 nm or more and 250 nm or less, more preferably 90 nm or more and 220 nm or less, and even more preferably 100 nm or more and 200 nm or less. By using both two types of nanosilica (e1) and (e2) having different average particle diameters, the storage stability of the photocurable resin composition and the lubricity of the cured film can be improved. The average primary particle diameter of the silica particles can be measured by the laser diffraction method using a commercially available particle size distribution measuring instrument.

[0048] The silica particles may be reactive silica particles having functional groups such as hydroxyl groups, mercapto groups, isocyanate groups, amino groups, epoxy groups, and (meth)acryloyl groups on the surface. As the functional group, a (meth)acryloyl group is preferred. The reactive silica particles having a (meth)acryloyl group can be obtained, for example, by reacting silica particles with a hydrolyzable silane having a (meth)acryloyl group and a hydrolyzable group such as a methoxy group or an ethoxy group in the molecule.

[0049] From the viewpoints of the storage stability of the photocurable resin composition and the slipperiness of the cured film, the content of the nanosilica (e1) is preferably 5% by mass or more and 25% by mass or less, more preferably 7.5% by mass or more and 22.5% by mass or less, and still more preferably 10% by mass or more and 20% by mass or less with respect to 100 parts by mass of the solid content of the photocurable resin composition. From the viewpoints of the storage stability of the photocurable resin composition and the slipperiness of the cured film, the content of the nanosilica (e2) is preferably 5% by mass or more and 25% by mass or less, more preferably 7.5% by mass or more and 22.5% by mass or less, and still more preferably 10% by mass or more and 20% by mass or less with respect to 100 parts by mass of the solid content of the photocurable resin composition. From the viewpoint of the slipperiness of the cured film, the content ratio (e2 / e1) of the nanosilica (e2) to the nanosilica (e1) is preferably 0.1 or more and 1.8 or less, more preferably 0.3 or more and 1.7 or less, and still more preferably 0.5 or more and 1.6 or less.

[0050] (Leveling agent (F)) In recent years, in order to improve the added value of the heat ray shielding film, secondary processing (recoating) such as coating, printing, sputtering, vapor deposition, and adhesive coating may be performed on the cured film. Therefore, in addition to the slipperiness (blocking resistance), it is preferable that the cured film has good recoatability with the cured film formed by post-processing. In the present invention, in order to impart recoatability to the cured film, it is preferable to blend a leveling agent (F) into the photocurable resin composition to increase the surface free energy of the cured film.

[0051] The leveling agent (F) is one that adjusts the fluidity of the photocurable resin composition and has the function of flattening the applied film. Examples of the leveling agent include fluorine-based leveling agents, silicone-based leveling agents, acrylic polymer-based leveling agents, and the like.

[0052] Examples of the fluorine-based leveling agent include fluorine-based leveling agents having a perfluoroalkenyl group in the main chain or side chain, such as perfluoroalkenyl carboxylates, perfluoroalkenyl sulfonates, perfluoroalkenyl phosphoric acid esters, and perfluoroalkenyl betaines; fluorine-based leveling agents having a perfluoroalkyl group in the main chain or side chain, such as perfluoroalkyl polyoxyethylene ethers, perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphoric acid esters, and perfluoroalkyl betaines.

[0053] Examples of the silicone-based leveling agent include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, polyether-modified polydimethylsiloxane, polyether-modified polymethylphenylsiloxane, polyether-modified polymethylhydrogensiloxane, and the like.

[0054] As the acrylic polymer-based leveling agent, a polyether-modified (meth)acrylic compound represented by the following general formula (1) can be used.

Chemical formula

Chemical formula

[0055] As such a leveling agent, commercially available leveling agents can also be used. For example, as fluorine-based leveling agents, there are those with the trade name Fタージェント602A manufactured by Neo Corporation, and those with the trade name KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd. As silicone-based leveling agents, there are those with the trade name BYK-307, BYK-315N, BYK-325N, BYK-342, BYK-378, etc. manufactured by BYK, those with the trade name Polyflow KL-401 manufactured by Kyoeisha Chemical Co., Ltd., and those with the trade name Tego flow 425 manufactured by EVONIK. As acrylic polymer-based leveling agents, there are those with the trade name Polyflow No.75 manufactured by Kyoeisha Chemical Co., Ltd., and those with the trade name BYK-350, BYK-381, BYK-3560, etc. manufactured by BYK. As other leveling agents, there is those with the trade name BYK-399 manufactured by BYK.

[0056] From the viewpoint of the transparency of the cured film, the weight average molecular weight (Mw) of the leveling agent (F) is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and even more preferably 2,000 to 30,000. The weight average molecular weight (Mw) can be measured using gel permeation chromatography (GPC).

[0057] The content of the leveling agent (F) is preferably 0.01% by mass or more and 2.0% by mass or less, more preferably 0.05% by mass or more and 1.5% by mass or less, and still more preferably 0.1% by mass or more and 1.0% by mass or less with respect to 100% by mass of the solid content of the photocurable resin composition, from the viewpoints of the storage stability of the photocurable resin composition, the lubricity of the cured film, and recoatability.

[0058] (Dispersant (G)) In order to prevent aggregation of the inorganic particles when the near-infrared absorber (D) and the inorganic particles (E) are used in combination, it is preferable to blend a dispersant in the photocurable resin composition. The dispersant is not particularly limited, and a conventionally known dispersant for inorganic particles can be used. Examples of the dispersant include various dispersants such as copolymers and copolymers having an adsorption group such as carboxylic acid, phosphoric acid, and amine, and having a compatible chain such as fatty acid, polyamino, polyether, polyester, polyurethane, and polyacrylate.

[0059] As such a dispersant, commercially available dispersants can be used. For example, Disparon 2150, 1831, 1850, 1860, DA-1401, PW-36, DA-1200, DA-550, DA-703-50, DA-7301, DN-900, DA-325, DA-375, DA-234, etc. manufactured by Nambon Kasei Co., Ltd.; K-SPERSE 131, 152MS, etc. with the trade names of KING INDUSTRIES; Flowlen AF-1000, AF-1005, D-90, DOPA-15B, DOPA-15BHFS, DOPA-17HF, DOPA-22, DOPA-35, DOPA-100, G-700, G-820XF, GW-1500, KDG-2400, etc. manufactured by Kyoeisha Chemical Co., Ltd.; ANTI-TERRA-U100, 204, DISPERBYK-102, 103, 106, 108, 109, 110, 111, 118, 140, 142, 145, 161, 162, 163, 164, 167, 168, 170, 171, 174, 180, 182, 184, 185, 2000, 2001, 2008, 2009, 2013, 2022, 2025, 2050, 2055, 2096, 2150, 2152, 2155, 2163, 2164, 2200, BYK-P104, P104S, P105, 9076, 9077, 220S, etc. with the trade names of BYK; EFKA FA4609, FA4644, PU4061, PU4063, PX4701, PX4753, PX4780, DISPEX ULTRA FA4420, FA4431, etc. manufactured by BASF; SOLSPERSE 24000, 2600, 32000, 32500, 32600, 33000, 35000, 36000, 38500, 39000, 41000, 45000, 56000, 71000, 74000, 75000, 78000, 79000, 85000, 86000, 87000, 88000, J180, J200, 85000, X300, M385, M386, M387, M388, M389, W75, W150, etc. manufactured by Lubrizol Japan Co., Ltd. can be mentioned.

[0060] Among these dispersants, it is preferable to use a compound having at least one or more acidic functional groups and having a molecular weight of 200 or more and 100,000 or less, or a salt thereof. The acidic functional group is a functional group having a proton donor, and examples thereof include a phosphate group, a phosphonic acid group, a sulfone group, a sulfate group, and a carboxyl group. As such a dispersant, a commercially available dispersant can also be used. For example, Disparon 2150, 1831, 1850, 1860, PW-36, DA-703-50, DA-325, DA-375, DA-234, etc. manufactured by Namboku Kasei Co., Ltd., AF-1000, AF-1005, DOPA-100, G-700, G-820XF, GW-1500, KDG-2400, etc. manufactured by Kyoeisha Chemical Co., Ltd., DISPERBYK-102, 106, 110, 111, 118, 140, 142, 145, 170, 171, 174, 180, 2001, 2013, 2025, 2096, ANTI-TERRA-U100 manufactured by BYK, Disparon 2150, 1831, 1850, 1860, PW-36, DA-703-50, DA-325, DA-375, DA-234, etc. manufactured by Namboku Kasei Co., Ltd., EFKA FA 4609, 4611, 4620, 4644, 4665, 4666, 4671, PU 4009, 4010, etc. manufactured by BASF, SOLSPERSE 26000, 36000, 41000, 45000, 79000, 85000, W150, etc. manufactured by Lubrizol Japan Co., Ltd.

[0061] From the viewpoints of the storage stability of the photocurable resin composition and the lubricity of the cured film, the content of the dispersant (G) is preferably 0.5% by mass or more and 5.0% by mass or less, more preferably 0.7% by mass or more and 4.5% by mass or less, and still more preferably 1.0% by mass or more and 4.0% by mass or less based on 100% by mass of the solid content of the photocurable resin composition.

[0062] (Ultraviolet absorber (H)) The ultraviolet absorber (H) is not particularly limited, and conventionally known ultraviolet absorbers can be used. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and the like. These ultraviolet absorbers may be used alone or in combination of two or more.

[0063] Examples of benzotriazole-based ultraviolet absorbers include 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl-3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, benzenepropanoic acid-3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, C7~9-branched linear alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, and the like.

[0064] Examples of the hydroxyphenyltriazine-based ultraviolet absorber include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2,2’,2’’-[1,3,5-triazine-2,4,6-triyltris(3-hydroxy-4,1-phenylene)oxy]-1,1’,1’’-trioctyl propionate, and the like.

[0065] Examples of the benzophenone-based ultraviolet absorber include 2,2’,4,4’-tetrahydroxybenzophenone, 2,2’-dihydroxy-4,4’-dimethoxybenzophenone, 2,2’-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2’-dihydroxy-4-methoxybenzophenone, 2,2’-dihydroxy-4,4’-dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2’-dihydroxy-4,4’-dimethoxy-5,5’-disulfobenzophenone disodium salt, and the like.

[0066] From the viewpoint of the weather resistance of the cured film, the content of the ultraviolet absorber (H) is preferably 0.5% by mass or more and 5% by mass or less, more preferably 0.6% by mass or more and 4% by mass or less, and still more preferably 0.7% by mass or more and 3% by mass or less, based on 100% by mass of the solid content of the photocurable resin composition.

[0067] (Light stabilizer (I)) The light stabilizer (I) is not particularly limited, and conventionally known light stabilizers can be used. It is preferable to use a hindered amine light stabilizer. Examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy]-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione, bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl malonate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl)-1,2,3,4-butanetetracarboxylate, Mixed{1,2,2,6,6-pentamethyl-4-piperidyl / β,β,β’,β’-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl}-1,2,3,4-butanetetracarboxylate, (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl)-1,2,3,4-butanetetracarboxylate, Mixed{2,2,6,6-tetramethyl-4-piperidyl / β,β,β’,β’-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl}-1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl)][(2,2,6,[(6-Tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino], the polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 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, the polycondensate of dibutylamine-1,3,5-triazine-N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethylpiperidyl)butylamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate, etc. may be mentioned.,

[0068] From the viewpoint of the weather resistance of the cured film, the content of the light stabilizer (I) is preferably 0.1% by mass or more and 4% by mass or less, more preferably 0.2% by mass or more and 3% by mass or less, and still more preferably 0.3% by mass or more and 2% by mass or less with respect to 100% by mass of the solid content of the photocurable resin composition.,

[0069] (Other components) The photocurable resin composition according to the present invention may contain other components other than the components (A) to (I) above as long as the object of the present invention is not impaired. Examples of other components include antioxidants, antistatic agents, polymerization inhibitors, non-reactive diluents, matting agents, defoaming agents, anti-settling agents, heat stabilizers, adhesion improvers, photosensitizers, antibacterial agents, fungicides, antiviral agents, silane coupling agents, plasticizers, etc., which can be blended as necessary.,

[0070] <Method for preparing the photocurable resin composition> The photocurable resin composition according to the present invention can be obtained by mixing and stirring the above components using a conventionally known apparatus such as a mixer, a disperser, a stirrer, etc. Examples of such an apparatus include a mixing and dispersing mill, a homodisper, a mortar mixer, a roll, a paint shaker, a homogenizer, etc.,

[0071] The photocurable resin composition according to the present invention may be a one-component composition. However, when the component (E) is contained, considering storage stability, ease of storage, etc., it is preferably a multi-component composition. The multi-component composition is, for example, a multi-component composition containing at least the component (A), preferably further containing the components (B), (C), (D), (F), and (G) as a first component, and a second component containing the component (E). Note that the multi-component composition may further include a third component containing additives and the like described later. These respective components are usually stored, preserved, transported, etc. in separate containers and mixed immediately before use.

[0072] The viscosity of the photocurable resin composition (resin solution) at 25°C is preferably 0.5 to 500 mPa·s, more preferably 1 to 250 mPa·s, and even more preferably 5 to 100 mPa·s. A B-type viscometer can be used for measuring the viscosity. If the viscosity is within the above numerical range, it is easy to use as a paint and has excellent processability.

[0073] In the present invention, it can be diluted with a solvent as necessary, such as adjusting the photocurable resin composition to a viscosity suitable as a paint. The solvent is not particularly limited as long as it can dissolve the resin component in the photocurable resin composition. Specifically, aromatic hydrocarbons (e.g., toluene, xylene, and ethylbenzene), esters or ether esters (e.g., ethyl acetate, butyl acetate, and methoxybutyl acetate), ethers (e.g., diethyl ether, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and diethylene glycol monoethyl ether), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone), alcohols (e.g., methanol, ethanol, n- or i-propanol, n-, i-, sec- or t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (e.g., dimethyl sulfoxide), water, and mixed solvents of two or more of these can be mentioned.

[0074] (Cured film) When the cured film formed from the photocurable resin composition according to the present invention has a thickness of 3 μm to 10 μm, the haze measured in accordance with JIS K 7136 is preferably 3.0% or less, more preferably 2.0% or less, and even more preferably 1.0% or less. Further, for the cured film with a thickness of 3 μm to 10 μm, the total light transmittance measured in accordance with JIS K 7361-1 is preferably 70.0% or more, and more preferably 75.0% or more. If the haze and the total light transmittance are within the above ranges, the transparency is excellent.

[0075] When the cured film formed from the photocurable resin composition according to the present invention has a thickness of 3 μm to 10 μm, the transmittance at 500 nm is preferably 75% or more, more preferably 80% or more, and the transmittances at 1000 nm, 1500 nm, and 2000 nm are preferably 25% or less, more preferably 20% or less. If the transmittance at 500 nm is within the above range, it has excellent visible light transmittance, and if the transmittances at 1000 nm, 1500 nm, and 2000 nm are within the above range, it has excellent infrared absorption properties.

[0076] <Substrate with a cured film> The substrate with a cured film according to the present invention includes a cured film formed from the above photocurable resin composition on at least a part of the substrate surface. The substrate is not particularly limited, and various plastic films can be used. Examples of the plastic film include films of polyester resin, polycarbonate resin, polystyrene resin, polyolefin resin, polyethersulfone resin, acrylonitrile-styrene copolymer resin, polyamide resin, cellulose resin, polyarylate resin, polymethyl methacrylate resin, polymethacrylimide resin, etc. Since the photocurable resin composition of the present invention can form a transparent cured film with high total light transmittance and low haze, it is preferable to use a transparent plastic film. The cured film of the present invention has excellent adhesion to the substrate, particularly to PET resin, so it is more preferable to use a film of polyester resin, particularly PET resin, as the substrate.

[0077] The thickness of the substrate is not particularly limited, but is usually 10 μm or more and 500 μm or less, preferably 30 to 400 μm.

[0078] <Method for manufacturing a substrate with a cured film> The substrate with a cured film according to the present invention includes a coating step of applying the above photocurable resin composition to at least one surface of the substrate, a curing step of curing the above photocurable resin composition by ultraviolet irradiation to form a cured film after the coating step, It includes the following. Hereinafter, each step will be described in detail.

[0079] (Coating Step) The coating step is a step of coating one side of the substrate with the above-described photocurable resin composition by a conventionally known method. For coating, for example, coaters such as a bar coater, a gravure coater, a roll coater (natural roll coater, reverse roll coater, etc.), an air knife coater, a spin coater, and a blade coater can be used. Among these, from the viewpoints of workability and productivity, a coating method using a gravure coater is preferable.

[0080] The coating film thickness is not particularly limited and is appropriately selected depending on the type of the substrate. For example, the coating film thickness is preferably 0.5 to 25 μm as the film thickness after curing and drying. The more preferable upper limit is 15 μm from the viewpoints of drying property, curability, transparency, and curl resistance during curing, and the more preferable lower limit is 1 μm from the viewpoints of hardness and infrared absorbency.

[0081] When the resin composition is diluted with a solvent and used, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is preferably 10 to 200 °C, the more preferable upper limit is 150 °C from the viewpoints of the smoothness and appearance of the coating film, and the more preferable lower limit is 30 °C from the viewpoint of the drying rate.

[0082] (Curing Step) The curing step is a step of irradiating the coated surface of the substrate with ultraviolet rays to cure the coated photocurable resin composition to form a cured film. Examples of the method of curing with ultraviolet rays include a method of irradiating ultraviolet rays using a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a UV-LED, etc. that emit light in the wavelength range of 200 to 500 nm. The irradiation of ultraviolet rays can be performed in an inert gas atmosphere such as nitrogen or argon as necessary to suppress the curing inhibition by oxygen. The irradiation amount of ultraviolet rays is preferably 100 to 3,000 mJ / cm 2and more preferably 200 to 1,000 mJ / cm 2 is.

Example

[0083] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[0084] First, the following materials were prepared for the photocurable resin composition. · (A) Trifunctional urethane (meth) acrylate 1 (IPDI type, manufactured by Negami Kogyo Co., Ltd., trade name: Art Resin UCF-64) · (A) Trifunctional urethane (meth) acrylate 2 (HDI nurate type, manufactured by Daicel Ornex Co., Ltd., trade name: EBECRYL 8701) · (A) Hexafunctional urethane (meth) acrylate 1 (IPDI type, manufactured by Negami Kogyo Co., Ltd., trade name: Art Resin UN-CMP-1) · (A) Hexafunctional urethane (meth) acrylate 2 (HDI type, manufactured by Asia Industrial Co., Ltd., trade name: EXCELATE RUA-071VE) · (A) Nonafunctional urethane (meth) acrylate (IPDI type, manufactured by Negami Kogyo Co., Ltd., trade name: Art Resin UN-901T) · (A) Decafunctional urethane (meth) acrylate (manufactured by MIWON Co., trade name: MIRAMER MU9500H) · (A) Pentadecafunctional urethane (meth) acrylate (IPDI type, manufactured by Negami Kogyo Co., Ltd., trade name: Art Resin UN-3320HS) · (B) Difunctional (meth) acrylate monomer (1,6-hexanediol diacrylate (HDDA), manufactured by MIWON Co., trade name: MIRAMER M200) · (B) 3 / 4-functional (meth) acrylate monomer (pentaerythritol (tri / tetra) acrylate, manufactured by Daicel Ornex Co., Ltd., trade name: PETIA) · (B) Trifunctional (meth) acrylate monomer (trimethylolpropane triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: TMPTA) · (B) 5 / 6 functional (meth)acrylate monomer (dipentaerythritol (penta / hexa)acrylate (DPPA / DPHA), manufactured by Toagosei Co., Ltd., trade name: Aronix M-400) · (B) 6 functional (meth)acrylate monomer (manufactured by MIWON Co., Ltd., trade name: MIRAMER M600) · (C) Photoinitiator 1 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by IGM Resin, trade name: Omnirad 184) · (C) Photoinitiator 2 (methylbenzoyl formate, manufactured by IGM Resin, trade name: Omnirad MBF) · (C) Photoinitiator 3 (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by Chitec Technology, trade name: CHIVACURE TPO) · (D) Infrared absorber (cesium tungsten oxide (Cs 0.33 WO3) containing 18.5%, manufactured by Sumitomo Metal Mining Co., Ltd., trade name: YMF-02A) · (E) Inorganic particle 1 (silica dispersion, dispersion medium: propylene glycol monomethyl ether, average primary particle diameter 10 - 15 nm, manufactured by Nissan Chemical Industries, Ltd., trade name: PGM-AC-2140Y) · (E) Inorganic particle 2 (silica dispersion, dispersion medium: methyl ethyl ketone, average primary particle diameter 100 - 200 nm, manufactured by Mikuni Shikiso Co., Ltd., trade name: MHI filler #B929M) · (E) Inorganic particle 3 (silica dispersion, dispersion medium: propylene glycol monomethyl ether, average primary particle diameter 20 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: IX-3-CP-M-02-J) · (E) Inorganic particle 4 (silica dispersion, dispersion medium: methyl ethyl ketone, average primary particle diameter 100 nm, manufactured by CIK Nanotech Co., Ltd., trade name: AB-S03) · (F) Leveling agent 1 (silicone-based surface conditioner, manufactured by EVONIK, trade name: TEGO FLOW 425) · (F) Leveling agent 2 (fluorine-based surface conditioner, lipophilic, manufactured by Neos Co., Ltd., trade name: Ftergent 602A) ·(F) Levelling agent 3 (acrylic surface conditioner, manufactured by BYK, product name: BYK-3560) ·(G) Dispersant 1 (alkyloleammonium salt of copolymer having acid groups, acid value: 94 mg KOH / g, amine value: 94 mg KOH / g, manufactured by BYK, product name: DISPERBYK-180) ·(G) Dispersant 2 (polycaprolactone-based dispersant, amine value: 51 mg KOH / g, manufactured by Lubrizol Japan, product name: SOLSPERSE M86000) ·(G) Dispersant 3 (manufactured by Lubrizol Japan, product name: W75) ·(G) Dispersant 4 (acid value: 18 - 24 mg KOH / g, manufactured by Lubrizol Japan, product name: W150) ·(H) Ultraviolet absorber (manufactured by BASF, product name: TINUVIN 479) ·(I) Light stabilizer (manufactured by Rianlon, product name: RIASORB UV-123) · Solvent 1 (propylene glycol monomethyl ether) · Solvent 2 (butyl acetate)

[0085] [Examples 1 - 14, Comparative Examples 1 - 11] [Preparation 1 of photocurable resin composition] According to the formulations described in Tables 1 - 3, each component was mixed to obtain a photocurable resin composition.

[0086] [Manufacture 1 of substrate with cured film] On a substrate film (PET film, thickness 50 μm, 150 mm × 210 mm, manufactured by Toray Industries, Inc., product name: Lumirror U48), the photocurable resin composition prepared above was applied once with a bar coater so that the dry film thickness was 5 μm, and dried at 80°C for 1 minute. Subsequently, the coated surface of the substrate film was irradiated with ultraviolet rays (irradiation dose: 1000 mJ / cm 2 ) using a high-pressure mercury lamp to cure the coating film and form a cured film, thereby obtaining a substrate with a cured film.

[0087] [Evaluation 1 of substrate with cured film] The substrates with the cured film manufactured above were evaluated for transparency, substrate adhesion, hardness, and light transmittance. The evaluation results are shown in Tables 4 to 6.

[0088] (Transparency) For the substrates with the cured film manufactured above, using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number: NDH4000), the haze (HZ) was measured in accordance with JIS K 7136, and the total light transmittance (TT) was measured in accordance with JIS K 7361-1. If the haze value was 3.0% or less and the total light transmittance was 75.0% or more, it was considered excellent in transparency and passed the test.

[0089] (Substrate Adhesion) In accordance with the method of the cross-cut test described in JIS K 5600-5-6:1990, a test piece with a 1 mm wide and 100-square grid of scratches made with a cutter on the cured film of the substrate with the cured film manufactured above was prepared. Subsequently, after attaching cellophane tape (registered trademark) (product name, manufactured by Nichiban Co., Ltd.) to the test piece, the cellophane tape was quickly peeled off by pulling it in a direction 45 degrees obliquely upward with respect to the grid surface, and the number of cured film remaining on the remaining grid was counted, and this remaining number was used as an index of adhesion. If the number of cured film remaining on the grid was 95 / 100 or more, it was evaluated as excellent in adhesion.

[0090] (Hardness) The hardness of the coating film surface of the substrate with the cured film manufactured above was evaluated by scratch hardness (pencil method). The measurement of pencil hardness was performed using a scratch hardness tester (manufactured by Yasuda Seiki Co., Ltd., model number: 553-M) and pencils certified by the Japan Paint Inspection Association (manufactured by Mitsubishi Pencil Co., Ltd., Hi-uni). After attaching the pencil to press against the coating film at an angle of 45° and a load of 750 g, the scratch test was repeated 5 times with pencils of each hardness grade. If the number of times without observing breakage, depression, scratches, etc. of the coating film was 3 or more, it passed the test, and the hardness grade of the hardest pencil that passed the test was taken as the pencil hardness of the coating film. If the pencil hardness was F or higher, it was evaluated as having sufficient coating film surface hardness. For Examples 1 to 14, the number of times without observing breakage, depression, scratches, etc. of the coating film in the measurement of F and H pencil hardness was described in Tables 4 and 5.

[0091] (Light transmittance) The light transmittance of the substrate with the cured film manufactured above was evaluated by the light transmittance at wavelengths of 500 nm, 1000 nm, 1500 nm, and 2000 nm. The transmittance was measured in the wavelength range of 2000 nm to 300 nm using an ultraviolet-visible-infrared spectrophotometer (manufactured by Shimadzu Corporation, SolidSpec-3700). Regarding the transmittance, if it satisfied 75% or more at 500 nm and 25% or less at 1000 nm, 1500 nm, and 2000 nm, it was considered qualified because it had excellent visible light transmittance and excellent infrared absorption property.

[0092] [Table 1]

[0093] [Table 2]

[0094] [Table 3]

[0095] [Table 4]

[0096] [Table 5]

[0097] [Table 6]

[0098] [Examples 15 to 42, Comparative Example 12] [Preparation 2 of the photocurable resin composition] According to the formulations described in Tables 7 to 10, each component was mixed to obtain a photocurable resin composition.

[0099] [Evaluation of the photocurable resin composition] (Storage stability) The initial solution state of the photocurable resin composition prepared above was evaluated based on the following evaluation criteria. Furthermore, the solution state of the photocurable resin composition prepared above after being stored in a thermostat at 25°C for 7 days was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 11 to 14. [Evaluation criteria] ○: There were no abnormalities such as discoloration of the solution and formation of precipitate. ×: There were abnormalities such as discoloration of the solution and formation of precipitate.

[0100] [Manufacture of the substrate with a cured film 2] On a substrate film (PET film, thickness 50 μm, 150 mm × 210 mm, manufactured by Toray Industries, Inc., trade name: Lumirror U48), the photocurable resin composition prepared above was applied once with a bar coater so that the dry film thickness became 8 μm, and dried at 80°C for 1 minute. Subsequently, ultraviolet rays were irradiated (irradiation dose: 1000 mJ / cm 2 ) onto the coated surface of the substrate film to cure the coating film and form a cured film, thereby obtaining a substrate with a cured film.

[0101] [Evaluation of the substrate with a cured film 2] For the substrate with a cured film obtained above, evaluations of the coating film appearance, transparency, substrate adhesion, hardness, light transmittance, lubricity, and recoatability were performed. The evaluation results are shown in Tables 11 to 14. The evaluation methods for transparency, substrate adhesion, hardness, and light transmittance are as detailed in [Evaluation of the substrate with a cured film 1].

[0102] (Coating film appearance) The appearance of the substrate with a cured film manufactured above was visually evaluated based on the following evaluation criteria. If the evaluation was ○, it was considered qualified. [Evaluation criteria] ○: There were no abnormalities such as whitening, peeling, insufficient smoothness, and cracking in the cured film. ×: The cured film had abnormalities such as whitening, peeling, insufficient smoothness, and cracking.

[0103] (Slip property) Two substrates with cured films manufactured as described above were prepared, the cured film surfaces were overlapped, and the slip property when rubbed against each other with fingers was evaluated based on the following evaluation criteria. If the evaluation was ○, it was considered qualified. <Evaluation criteria> ○: It was in a state of smooth sliding with little resistance. △: There was a slight resistance but it was in a sliding state. ×: It was in a state of high resistance and did not slide.

[0104] (Wettability) According to the wetting tension test method described in JIS K 6788, several drops of the test mixture were dropped onto the cured film of the substrate with the cured film manufactured as described above, and a cotton swab was used to quickly spread it over an area of 6 cm 2 or more. When the liquid film did not break and the applied state was maintained for 2 seconds or more, it was evaluated as wet. Among the mixtures that maintained wetting for 2 seconds or more, the highest surface tension value was taken as the wetting tension of the cured film. If the wetting tension was 38 mN / m or more, it was determined that it had sufficient wettability and excellent recoatability.

[0105]

Table 7

[0106]

Table 8

[0107]

Table 9

[0108]

Table 10

[0109]

Table 11

[0110]

Table 12

[0111]

Table 13

[0112]

Table 14

Claims

1. A photocurable resin composition containing urethane (meth)acrylate (A), (meth)acrylate monomer (B), a photopolymerization initiator (C), and an infrared absorber (D), wherein the urethane (meth)acrylate (A) contains at least a urethane (meth)acrylate (a1) having 6 or more functional groups, and the content of the urethane (meth)acrylate (a1) having 6 or more functional groups is 10% by mass or more and 40% by mass or less based on 100% by mass of the solid content of the photocurable resin composition; the (meth)acrylate monomer (B) contains at least a (meth)acrylate monomer (b1) having 5 or more and 6 or less functional groups, and the content of the (meth)acrylate monomer (b1) having 5 or more and 6 or less functional groups is 20% by mass or more based on the total amount of the (meth)acrylate monomer (B); the (meth)acrylate monomer (B) may further contain a (meth)acrylate monomer (b2) having 2 or less functional groups, and the content of the (meth)acrylate monomer (b2) having 2 or less functional groups is less than 20% by mass based on the total amount of the (meth)acrylate monomer (B).

2. The photocurable resin composition according to claim 1, wherein the content of the (meth)acrylate monomer (B) is 10% by mass or more and 60% by mass or less based on 100% by mass of the solid content of the photocurable resin composition.

3. The photocurable resin composition according to claim 1, wherein the (meth)acrylate monomer (B) further contains a (meth)acrylate monomer (b3) having 3 or more and 4 or less functional groups.

4. The infrared absorber (D) has the general formula: M ｘ W ｙ O ｚ (wherein M is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb; W is tungsten; O is oxygen; 0.001 ≦ x / y ≦ 1; 2.0 < z / y ≦ 3.0), and is a composite tungsten oxide. The photocurable resin composition according to claim 1.

5. The photocurable resin composition according to claim 1, wherein the content of the infrared absorber (D) is 2% by mass or more and 40% by mass or less based on 100% by mass of the solid content of the photocurable resin composition.

6. The photocurable resin composition according to claim 1, further comprising inorganic particles (E).

7. The photocurable resin composition according to claim 6, wherein the inorganic particles (E) contain at least nanosilica (e1) having an average primary particle diameter of 5 nm or more and less than 70 nm and nanosilica (e2) having an average primary particle diameter of 70 nm or more and less than 300 nm.

8. The photocurable resin composition according to claim 1, further comprising a leveling agent (F).

9. The photocurable resin composition according to claim 1, further comprising a dispersant (G).

10. The photocurable resin composition according to claim 1, which is used as a coating material.

11. A cured film formed from the photocurable resin composition according to any one of claims 1 to 10.

12. A substrate with a cured film, having a cured film formed from the photocurable resin composition according to any one of claims 1 to 10 on at least a part of the surface of the substrate.

13. An application step of applying the photocurable resin composition according to any one of claims 1 to 10 to at least one surface of a substrate, and a curing step of curing the photocurable resin composition by ultraviolet irradiation to form a cured film after the application step. A method for manufacturing a substrate with a cured film, comprising:

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