Active energy ray-curable resin composition, coating film, and laminated film

Abstract

The invention relates to an active energy ray-curable resin composition, a coating film, and a laminated film. Provided are an active energy ray-curable resin composition, a cured coating film, and a laminated film, which have high hardness and good appearance when formed into a cured product layer, excellent scratch resistance, flexibility, curl resistance, long-term stability, and adhesion, and also excellent recoatability. This active energy ray-curable resin composition contains the following components (A)-(D), the ratio of component (A) being 30% by mass or more of the total solid content, and the ratio of component (B) being 1-20% by mass of the total solid content. It is preferable that a photopolymerization initiator is contained as component (E). Component (A): a trifunctional or higher polyfunctional urethane (meth) acrylate; component (B): an alkylene oxide-modified bifunctional or higher (meth) acrylate having a homopolymer Tg of 10 DEG C or less; component (C): an antistatic agent; component (D): a solvent.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable resin composition, a coating film obtained by curing the composition, and a laminated film including the coating film. Background Art

[0002] In recent years, for display applications such as smartphones, development of displays that can be deformed such as bent and rolled up has been underway. However, glass that is commonly used to prevent scratches on the display surface is hard and breaks when bent, so it is not suitable for use in foldable displays. Therefore, instead of glass, in order to prevent scratches, a plastic film having a hard coat with abrasion resistance is being studied as a surface protective layer for foldable displays.

[0003] In the plastic film as described above, in order to impart abrasion resistance to the hard coat that is a cured product of a photocurable composition, it is generally necessary to increase the crosslink density in the hard coat, and a polyfunctional acrylate-based material is often used. On the other hand, it is well known that if the crosslink density in the hard coat is increased, the flexibility and elongation of the film deteriorate. Thus, there is a trade-off relationship between the abrasion resistance and flexibility of the hard coat, and it has been a problem to balance both physical properties.

[0004] To solve the above problems, for example, in Patent Document 1 below, a perfluoropolyether containing a poly(oxyperfluoroalkylene) group and silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton-donating functional group are blended with an ethylene oxide-modified or lactone-modified active energy ray-curable polyfunctional monomer. In Patent Document 1, a certain degree of flexibility is exhibited by a specific polyfunctional monomer, and silica and a fluorine-based additive are blended to thereby improve the sliding property of the coating film surface, and abrasion resistance is imparted without reducing flexibility.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2020 / 162323

[0008] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2023-70690

[0009] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2021-56512

[0010] Patent Document 4: Japanese Unexamined Patent Application Publication No. 2017-171794

[0011] Patent Document 5: Japanese Unexamined Patent Application Publication No. 2014-122987 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] Furthermore, in the hard coat films used in foldable displays in recent years, a functional layer such as an antireflection layer is sometimes laminated on the hard coat as a top coat. In the case of such a laminated coating film, for the hard coat, not only the adhesion to the bottom coat as the base material is important, but also the adhesion to the top coat, that is, the recoatability, is important.

[0014] The inventors of the present invention conducted research on the above-mentioned recoatability based on the above-mentioned prior art documents, and as a result, it was found that, particularly in Patent Document 1, by using a fluorine-based additive to improve the surface slidability, the surface wettability was significantly reduced, and thus problems occurred in terms of recoatability. In addition, it was found that the use of silica was a concern for the deterioration of the compatibility with antistatic agents such as quaternary ammonium salts and the reduction of the long-term stability of the coating material.

[0015] The problem to be solved by the present invention is to provide an active energy ray-curable resin composition, a cured coating film, and a laminated film that have high hardness, good appearance, excellent abrasion resistance, flexibility, curl resistance, long-term stability, and adhesion when formed into a cured product layer, and further excellent recoatability.

[0016] Means for Solving the Problem

[0017] The inventors of the present invention conducted in-depth research to solve the above problems, and as a result, it was found that by mainly using a hard polyfunctional urethane acrylate, abrasion resistance can be exhibited, and by adding a small amount of a specific acrylate having a short EO chain length and a low Tg, flexibility can be imparted without reducing abrasion resistance. In addition, it was found that a combination use with an antistatic agent such as a quaternary ammonium salt can be achieved, transparency and other appearances can be maintained, high antistatic properties can be imparted, and use in recoating applications can also be achieved.

[0018] As the mechanism of the present invention, it is speculated as follows.

[0019] The hard polyfunctional urethane acrylate and the acrylate having a low Tg containing an EO chain are phase-separated in the film to form an island structure, thereby improving flexibility without reducing abrasion resistance. The soft component having a low Tg exists in a state close to a homopolymer without copolymerizing with the hard urethane acrylate in the coating film, thereby alleviating the stress applied during the bending and tensile tests and suppressing the generation of cracks. In addition, since it is not necessary to use components that affect the surface slidability such as fluorine-based additives, the recoatability is also excellent.

[0020] That is, the present invention provides the following technical means.

[0021] [1]A radiation-curable resin composition containing the following components (A) to (D), wherein the ratio of component (A) is 30% by mass or more in all solid components, and the ratio of component (B) is 1 to 20% by mass in all solid components.

[0022] Component (A): A polyfunctional urethane (meth)acrylate having 3 or more functional groups

[0023] Component (B): An alkylene oxide-modified (meth)acrylate having 2 or more functional groups and a Tg of the homopolymer of 10°C or less

[0024] Component (C): An antistatic agent

[0025] Component (D): A solvent

[0026] [2]The radiation-curable resin composition according to [1], which contains a photopolymerization initiator as component (E).

[0027] [3]A coating film which is a cured product of the radiation-curable resin composition according to [1] or [2].

[0028] [4]A laminated film which contains the coating film according to [3] and a substrate.

[0029] Effects of the Invention

[0030] The radiation-curable resin composition of the present invention can form a cured coating film having good appearance, high hardness, and excellent abrasion resistance, flexibility, curl resistance, stability over time, antistatic property, adhesion, and recoatability. Therefore, it can be suitably used as a protective coating agent for the surfaces of various substrates. In addition, the laminated film having the cured coating film has excellent abrasion resistance, curl resistance, and adhesion, and high flexibility, and is not easily broken when bent or wound, and further has impact resistance such that it is not easily broken even when there are falling objects on the film. Detailed Description

[0031] In this specification, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate", and "(meth)acryloyl" and "acryloyl" are collectively referred to as "(meth)acryloyl". In addition, the radiation-curable resin composition may sometimes be abbreviated as "composition".

[0032] [Radiation-Curable Resin Composition]

[0033] The composition of the present invention contains the following components (A) to (D), wherein the ratio of component (A) is 30% by mass or more in all solid components, and the ratio of component (B) is 1 to 20% by mass in all solid components.

[0034] (A) Component: A polyfunctional urethane (meth)acrylate having three or more functional groups

[0035] (B) Component: An alkylene oxide-modified (meth)acrylate having two or more functional groups with a Tg of the homopolymer of 10°C or lower

[0036] (C) Component: An antistatic agent

[0037] (D) Component: A solvent

[0038] The composition of the present invention may contain components other than the above (A) to (D) components. Hereinafter, each component will be described in detail.

[0039] [(A) Component]

[0040] The polyfunctional urethane (meth)acrylate having three or more functional groups as the (A) component is a resin having a urethane bond and three or more acryloyl groups, and preferably has an aliphatic structure in terms of excellent flexibility. Examples of the aliphatic structure include a linear or branched alkyl group having 4 to 20 carbon atoms and an alicyclic structure having 6 to 12 carbon atoms such as cyclohexane. The (A) component may be used alone or in combination of two or more.

[0041] The number of acrylate functional groups of the (A) component is three or more, preferably 4 to 15, more preferably 5 to 12. By having three or more functional groups, the crosslinking density when forming a cured coating film can be increased, and high hardness can be achieved.

[0042] The (A) component can be obtained, for example, by reacting a polyisocyanate (a1) with a compound (a2) having a hydroxyl group and a (meth)acryloyl group. In addition, a compound (a3) having a hydroxyl group other than the above compound (a2) can be further used as a reaction raw material.

[0043] As the polyisocyanate (a1), as long as it can form the component (A) in which the content of the (meth)acryloyl group used in the present invention is a specific value, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as toluene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, o-tolidine diisocyanate; their isocyanurate-modified products, biuret-modified products, urethane-modified products, etc.

[0044] In addition, when the polyisocyanate (a1) is particularly an isocyanurate-modified product of isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or hexamethylene diisocyanate, it is more preferable in terms of forming a cured product having a soft touch and excellent tear strength and resilience.

[0045] As the compound (a2) having a hydroxyl group and a (meth)acryloyl group, as long as it can form the component (A), there is no particular limitation, and it can be appropriately selected according to the purpose. For example, (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, (meth)acrylic acid hydroxybutyl ester, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, bis(trimethylolpropane) (meth)acrylate, bis(trimethylolpropane) di(meth)acrylate, bis(trimethylolpropane) tri(meth)acrylate, etc. In addition, (poly)oxyalkylene-modified products obtained by introducing a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain into the molecular structure of the above various compounds having a hydroxyl group and a (meth)acryloyl group, and lactone-modified products obtained by introducing a (poly)lactone structure into the molecular structure of the above various compounds having a hydroxyl group and a (meth)acryloyl group can also be used.

[0046] In addition, when the compound (a2) having a hydroxyl group and a (meth)acryloyl group is particularly 2-hydroxyethyl (meth)acrylate or its lactone-modified product, it is more preferable in terms of forming a cured product having a soft touch, excellent tear strength and resilience.

[0047] As the compound (a3) having a hydroxyl group, there is no particular limitation as long as it is a compound having a hydroxyl group in the molecule and not having a (meth)acryloyl group, and it can be appropriately selected according to the purpose. For example, polyols having a linear alkyl structure such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol can be used; polyols having a branched alkyl structure such as 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol; polycarbonate polyols synthesized by the transesterification reaction of these polyols with carbonates; polyester polyols synthesized by the dehydration condensation reaction of the above polyols with dibasic acids; polyalkylene glycols such as polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, and copolymers of polyethylene glycol and polypropylene glycol can be used.

[0048] In addition, when the compound (a3) having a hydroxyl group is polypropylene glycol or polytetramethylene ether glycol, a curable resin composition capable of forming a cured product having a soft touch, excellent tear strength and resilience can be obtained, and thus it is more preferable.

[0049] Furthermore, the number average molecular weight of polypropylene glycol and polytetramethylene ether glycol is preferably in the range of 200 to 5000, more preferably in the range of 400 to 3500, and particularly preferably in the range of 500 to 3000. By setting the number average molecular weight within the above range, a curable resin composition capable of forming a cured product having a soft touch, excellent tear strength and resilience can be obtained.

[0050] As the manufacturing method, there is no particular limitation, and it can be manufactured by any method. For example, it can be manufactured by reacting the reaction raw materials containing the above-mentioned polyisocyanate (a1) and the above-mentioned compound (a2) having a hydroxyl group and a (meth)acryloyl group together, or by reacting the reaction raw materials separately and sequentially. In addition, a compound (a3) having a hydroxyl group can be used as a reaction raw material, or it can be not used.

[0051] In the manufacturing process, as a catalyst, for example, dibutyltin dilaurate, dibutyltin diacetate, etc. can be used, and it can be manufactured under the conditions of a normal urethanization reaction. In addition, if necessary, solvents such as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, etc. can be used, or a radical polymerizable monomer containing no moiety that reacts with isocyanate and containing no hydroxyl group or amino group can be used as a solvent.

[0052] (A) The component as described above can be obtained by synthesizing from polyisocyanate (a1) and a compound (a2) having a hydroxyl group and a (meth)acryloyl group, or a commercially available product can be directly used. As commercially available products, for example, Miramer PU-320, Miramer PU-330, Miramer PU-340, Miramer PU-370, Miramer PU-3000, Miramer PU-3200, Miramer PU-3210, Miramer PU-3410, Miramer PU-3420, Miramer PU-3450, Miramer PU-460, Miramer PU-5000, Miramer PU-610, Miramer PU-620, Miramer PU-6510, Miramer PU-640, Miramer MU-9500, Miramer MU-9800, Miramer SC-2152 (the above are manufactured by MIWON Co., Ltd.), UA-306H, UA-306T, UA-306I, UA-510H (the above are manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL 4220, EBECRYL 4513, EBECRYL 4738, EBECRYL 4740, EBECRYL 4820, EBECRYL 8311, KRM 8667, KRM 8296, EBECRYL 4265, EBECRYL 4587, EBECRYL 8465, EBECRYL 9260, EBECRYL 8701, EBECRYL 4666, EBECRYL 4680, EBECRYL 8210, EBECRYL 8405, EBECRYL 8606, KRM 8528, EBECRYL 1290, EBECRYL 5129, EBECRYL 8301R, KRM 8200, KRM 8200AE, KRM 8530, KRM 8904, KRM 8531BA, KRM 8452, EBECRYL 220 (the above are from DAICEL-ALLNEX LTD.Manufactured by Negami Kogyo Co., Ltd.: ART RESIN UN-3320HA, ART RESIN UN-3320HC, ART RESIN UN-3320HS, ART RESIN UN-904, ART RESIN UN-901T, ART RESIN UN-952, ART RESIN UN-954, ART RESIN UN-905; Manufactured by DIC Corporation: LUXYDIR V-4260, LUXYDIR V-4263, LUXYDIR 17-806, LUXYDIR 17-813, LUXYDIR EPS-1306, LUXYDIR ENS-836, LUXYDIR ESS-620.

[0053] The weight average molecular weight (Mw) of component (A) is preferably in the range of 1,000 to 150,000, more preferably in the range of 1,200 to 120,000, and particularly preferably in the range of 1,500 to 100,000. In addition, the (meth)acryloyl equivalent is preferably in the range of 200 to 1,500 g / equivalent, more preferably in the range of 250 to 1,200 g / equivalent, and preferably in the range of 280 to 1,000 g / equivalent.

[0054] The content of component (A) in the composition of the present invention is 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more in all solid components. By setting it within the above range, a composition capable of forming a cured coating film with high hardness, excellent abrasion resistance, flexibility, and curl resistance can be obtained. It should be noted that the "solid components" in this specification refer to all the solid components contained in the composition.

[0055] [Component (B)]

[0056] The Tg (glass transition point) of the homopolymer of the bifunctional or higher (meth)acrylate of component (B) is 10°C or lower, preferably 0°C or lower, and more preferably -10°C or lower. When Tg is in this range, it becomes soft and exists in a state close to a homopolymer without copolymerizing with the hard urethane acrylate in the coating film, thereby being able to relieve stress and inhibit the generation of cracks. Tg can be measured using TG / DTA (thermogravimetric analyzer), DSC (differential scanning calorimeter), etc. Component (B) can be used alone or in combination of two or more. It should be noted that the compound corresponding to component (A) is not included in component (B).

[0057] Examples of the bifunctional (meth)acrylate include bisphenol A EO-modified di(meth)acrylate, bisphenol AP O-modified di(meth)acrylate, bisphenol F EO-modified di(meth)acrylate, bisphenol F PO-modified di(meth)acrylate, hexanediol EO-modified di(meth)acrylate, triethylene glycol EO-modified di(meth)acrylate, polyethylene glycol EO-modified di(meth)acrylate, polypropylene glycol EO-modified di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and neopentyl glycol EO-modified di(meth)acrylate.

[0058] Examples of the trifunctional (meth)acrylate include trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, glycerol EO-modified tri(meth)acrylate, glycerol PO-modified tri(meth)acrylate, pentaerythritol EO-modified tri(meth)acrylate, and pentaerythritol PO-modified tri(meth)acrylate.

[0059] Examples of the tetrafunctional (meth)acrylate include bis(trimethylolpropane) tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Examples of the pentafunctional (meth)acrylate include dipentaerythritol hydroxypenta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate.

[0060] (Component (B) can be directly used as a commercially available product. Examples of commercially available products include Miramer M286, Miramer M284, Miramer M280, Miramer M202, Miramer M2040, Miramer M2070, Miramer M2100, Miramer M2200, Miramer M2300, Miramer M3150, Miramer M3160, Miramer M3190, Miramer M2301, Miramer M251, Miramer M281 (all manufactured by MIWON Co., Ltd.), NK Ester A-PTMG65, NK Ester A-400, NK Ester A-600, NK Ester A-1000, NK Ester APG-200, NK Ester APG-400, NK Ester APG-700, NK Ester A-BPE-10, NK Ester A-BPE-20, NK Ester A-BPE-30, NK Ester A-TMPT-9EO, NK Ester A-TMPT-6PO, NK Ester A-GLY-9E, NK Ester A-GLY-20E, NK Ester A-GLY-9P, NK Ester ATM-8EL, NK Ester ATM-35E, NK Ester A-DPH-24E, NK Ester A-DPH-48E (all manufactured by Shin-Nakamura Chemical Co., Ltd.), LIGHT ACRYLATE 9EG-A, LIGHT ACRYLATE 14EG-A, LIGHT ACRYLATE PTMGA-250 (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0061] The weight average molecular weight (Mw) of component (B) is preferably in the range of 200 to 4,000, more preferably in the range of 250 to 3,000, and particularly preferably in the range of 300 to 2,000. In addition, the (meth)acryloyl equivalent is preferably in the range of 100 to 2,000 g / equivalent, more preferably in the range of 125 to 1,500 g / equivalent, and preferably in the range of 150 to 1,000 g / equivalent.

[0062] The content of component (B) in the composition of the present invention is 1 to 20% by mass in all solid components, preferably 3 to 18% by mass, and more preferably 5 to 15% by mass. By setting it within the above range, flexibility, curl resistance, crack resistance, and stability over time are excellent.

[0063] [Component (C)]

[0064] Examples of the antistatic agent as the component (C) include anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, zwitterionic antistatic agents, metal oxide fine particles, conductive polymers, etc. The component (C) can be used alone or in combination of two or more.

[0065] Examples of the anionic antistatic agent include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, sulfates of aliphatic amines and aliphatic amides, aliphatic alcohol phosphates, sulfonates of dibasic fatty acid esters, aliphatic amide sulfonates, alkyl allyl sulfonates, formalin-condensed naphthalene sulfonates, etc. Examples of the cationic antistatic agent include aliphatic amine salts, quaternary ammonium salts, alkyl pyridinium salts, etc. Examples of the nonionic antistatic agent include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, etc. Examples of the zwitterionic antistatic agent include imidazoline derivatives, betaine-type higher alkyl amino derivatives, sulfate derivatives, phosphate derivatives, etc. Examples of the metal oxide fine particles include titanium oxide, zirconium oxide, cerium oxide, tin oxide, antimony tin oxide, indium tin oxide, phosphorus tin oxide, antimony oxide, aluminum zinc oxide, gallium zinc oxide. Examples of the conductive polymer include substituted or unsubstituted conductive polyaniline, poly(p-phenylene), polyparaphenylene vinylene, polythiophene, polyfuran, polypyrrole, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyacetylene, poly pyridyl vinylene, polyazine, or their derivatives, etc.

[0066] In the present invention, quaternary ammonium salts which are cationic antistatic agents are particularly preferred. Examples of commercially available products of such quaternary ammonium salts include 1SX-1090, 1SX-1055F (both are manufactured by TAISEI FINE CHEMICAL CO,.LTD.).

[0067] The content of the antistatic agent is preferably 1 to 15% by mass, more preferably 2 to 12% by mass in all solid components.

[0068] [(D) component]

[0069] As the solvent of component (D), for example, ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone can be cited; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, ethanol, isopropyl alcohol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate, etc. These solvents can be used alone or in combination of two or more. In addition, these organic solvents are mainly used for the purpose of adjusting the viscosity of the active energy ray-curable composition, and it is usually preferably adjusted so that the non-volatile component is in the range of 10 to 80% by mass.

[0070] [Photoinitiator]

[0071] The composition of the present invention preferably contains a photoinitiator. As photoinitiators, for example, various benzophenones such as benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, Michler's ketone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone; xanthones, thioxanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone; various benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; α-diketones such as benzil, butanedione; sulfides such as tetramethylthiuram disulfide, p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate; 3,3'-carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethyl sulfide, 2,2'-diethoxyacetophenone, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis(4-dimethylaminophenyl)ketone, p-dimethylaminoacetophenone, α,α-dichloro-4-phenoxyacetophenone, pentyl 4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6-[bis-(ethoxycarbonylmethyl)amino]phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-s-triazine, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, etc. These photoinitiators can be used alone or in combination of two or more kinds.

[0072] In addition, among photoinitiators, from the aspect of being able to exhibit activity with respect to light of a wider range of wavelengths and improving the curability of the cured coating film of the composition, it is preferable to use one or a mixture of two or more selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.

[0073] Examples of commercially available products of photoinitiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM Corporation), "KAYACURE-DETX", "KAYACURE-MBP", "KAYACURE-DMBI", "KAYACURE-EPA", "KAYACURE-OA" (manufactured by Nippon Kayaku Co., Ltd.), "VICURE-10", "VICURE-55" (manufactured by Stauffer Chemical Company), "TRIGONAL P1" (manufactured by Akzo Corporation), "SANDORAY 1000" (manufactured by SANDOZ Co., Ltd.), "DEAP" (manufactured by APJOHN Corporation), "QUANTACURE-PDO", "QUANTACURE-ITX", "QUANTACURE-EPD" (manufactured by WARD BLENKINSOP Co., Ltd.), "Runtecure-1104" (manufactured by Runtec Company), etc.

[0074] The addition amount of the photopolymerization initiator is an amount that can fully exhibit the function as a photopolymerization initiator, and preferably falls within a range where crystal precipitation does not occur and film physical properties do not deteriorate. Specifically, relative to 100 parts by mass of all solid components, a range of 0.05 to 20 parts by mass is preferred, and a range of 0.1 to 10 parts by mass is more preferred.

[0075] [Other components]

[0076] The composition of the present invention may contain other photocurable compounds, photosensitizers, ultraviolet absorbers, antioxidants, silicone-based additives, fluorine-based additives, silane coupling agents, phosphate compounds, organic beads, inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, antifogging agents, colorants, etc., in addition to the component (A) and the component (B).

[0077] Examples of other photocurable compounds include monofunctional (meth)acrylate compounds, polyfunctional (meth)acrylate compounds, urethane (meth)acrylates having 2 or less functional groups, polyester (meth)acrylates, epoxy (meth)acrylates, and acrylic (meth)acrylates.

[0078] Examples of monofunctional (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphate (meth)acrylate, ethylene oxide-modified phosphate (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide-modified phenoxy (meth)acrylate, propylene oxide-modified phenoxy (meth)acrylate, nonylphenol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, propylene oxide-modified nonylphenol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, 2-(meth)acryloyloxypropyl tetrahydrophthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, adamantyl mono(meth)acrylate and other mono(meth)acrylates.

[0079] Examples of polyfunctional (meth)acrylate compounds include glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, di(trimethylolpropane) tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and the like.

[0080] Examples of photosensitizers include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiouronium p-toluenesulfonate, and the like.

[0081] As ultraviolet absorbers, for example, there may be mentioned triazine derivatives such as 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(2,4-dimethylphenyl)-1,3,5-triazine, etc., benzotriazoles such as 2-(2'-xanthyl carboxyl-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, benzophenones such as 2-xanthyl carboxyl-4-dodecyloxydibenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxydibenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more kinds.

[0082] As antioxidants, for example, there may be mentioned hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, etc. These antioxidants can be used alone or in combination of two or more kinds.

[0083] As silicone-based additives, for example, there may be mentioned polyorganosiloxanes having alkyl or phenyl groups such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, amino-modified dimethylpolysiloxane copolymer, etc., polydimethylsiloxanes having polyether-modified acryloyl groups, polydimethylsiloxanes having polyester-modified acryloyl groups, etc. These silicone-based additives can be used alone or in combination of two or more kinds.

[0084] As fluorine-based additives, for example, there may be mentioned the "MEGAFACE" series manufactured by DIC Corporation, etc. These fluorine-based additives can be used alone or in combination of two or more kinds.

[0085] As silane coupling agents, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, special amino silane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane and other vinyl-based silane coupling agents; diethoxy(glycidoxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styrene-based silane coupling agents; 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and other (meth)acryloxy-based silane coupling agents; N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane and other amino-based silane coupling agents; 3-ureidopropyltriethoxysilane and other ureido-based silane coupling agents;Chloropropyl silane coupling agents such as 3-chloropropyltrimethoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane, etc. These silane coupling agents can be used alone or in combination of two or more kinds.

[0086] As the phosphate compound, for example, a compound having a (meth)acryloyl group in the molecular structure can be cited. As commercially available products, for example, "KAYAMER PM-2", "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd., "LIGHT ACRYLATE P-1M", "LIGHT ACRYLATE P-2M", "LIGHT ACRYLATE P-1A(N)" manufactured by Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100", "SIPOMER PAM 200", "SIPOMER PAM 300", "SIPOMER PAM 4000" manufactured by SOLVAY, "VISCOAT #3PA", "VISCOAT #3PMA" manufactured by Osaka Organic Chemical Industry Co., Ltd., "NEW FRONTIER S-23A" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can be cited; "SIPOMER PAM 5000" etc. manufactured by SOLVAY as the phosphate compound having an allyl ether group in the molecular structure.

[0087] As the organic beads, for example, polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, etc. can be cited. These organic beads can be used alone or in combination of two or more kinds. In addition, the average particle diameter of these organic beads is preferably in the range of 1 to 10 μm.

[0088] Inorganic fine particles such as silica, alumina, zirconia, titanium dioxide, barium titanate, antimony trioxide, etc. can be cited. These inorganic fine particles can be used alone or in combination of two or more kinds. In addition, the average particle diameter of these inorganic fine particles is preferably in the range of 10 to 300 nm, particularly more preferably in the range of 30 to 150 nm.

[0089] In the case of containing inorganic fine particles, a dispersion aid can be used. Examples of the dispersion aid include phosphate compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified dimethacrylate phosphate. These dispersion aids can be used alone or in combination of two or more. In addition, examples of commercially available products of the dispersion aid include "KAYAMER PM-21" and "KAYAMER PM-2" manufactured by Nippon Kayaku Co., Ltd., and "LIGHT ACRYLATE P-2M" manufactured by Kyoeisha Chemical Co., Ltd.

[0090] [Cured coating film]

[0091] The cured coating film of the present invention is obtained by curing the composition of the present invention. As the curing method of the composition, examples of the method include a method of heating and a method of irradiating active energy rays such as ultraviolet rays.

[0092] As the method of heating, curing can be carried out by heating in a temperature range of 60 to 200 °C for 0.5 minutes to 60 minutes. In addition, as the method of irradiating active energy rays, for example, in the case of ultraviolet rays, curing can be carried out by using an ultraviolet lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, or an LED as an ultraviolet ray generation source.

[0093] As the active energy rays, in addition to ultraviolet rays, for example, ionizing radiation rays such as electron beams, α rays, β rays, and γ rays can also be used. The irradiation amount of the active energy rays is preferably in the range of 0.05 to 5 J / cm 2 and more preferably in the range of 0.1 to 3 J / cm 2 and particularly preferably in the range of 0.1 to 1 J / cm 2 The above ultraviolet irradiation amount is based on the value measured in the wavelength range of 300 to 390 nm using a UV Checker UVR-N1 (manufactured by Nippon Denchi Co., Ltd.).

[0094] [Laminated film]

[0095] The laminated film of the present invention has the above cured coating film on a substrate. As the manufacturing method of the laminated film of the present invention, for example, a method of coating the above curable resin composition on at least one surface of the substrate and then irradiating active energy rays can be mentioned.

[0096] Examples of the substrate include a metal substrate, a plastic substrate, a glass substrate, a paper substrate, a wood substrate, and a fibrous substrate. Among these substrates, a plastic substrate is preferred from the viewpoint of excellent adhesion to the above curable resin composition.

[0097] As the material of the plastic substrate, examples include polyethylene terephthalate, polyester, acrylic resin (such as polymethyl methacrylate), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin, polyvinyl chloride, polyamide, polyolefin (such as polyethylene, polypropylene, polynorbornene (COP), etc.), triacetyl cellulose (TAC), polyimide, etc. As the plastic substrate, for example, plastic molded products such as mobile phones, household electrical appliances, interior and exterior automotive decoration materials, and OA equipment can be cited. In addition, a film substrate made of plastic as the raw material can also be used.

[0098] As the method of coating the composition, for example, coating methods using a gravure printing machine, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a flow coater, a spin coater, dipping, screen printing, spraying, brush coating, an applicator, a rod coater, etc. can be cited.

[0099] The film thickness of the coating film can be appropriately adjusted according to the intended use, and is usually preferably in the range of 0.01 to 50 μm.

[0100] In addition to the substrate and the layer formed by the cured product, the laminated film of the present invention may also have functional film layers such as an antireflection film, a diffusion film, and a polarizing film.

[0101] The laminated film of the present invention has a cured coating film with excellent abrasion resistance, flexibility, curl resistance, and impact resistance, and thus can be used as a surface coating for protecting the surface of the substrate. For example, it can be suitably used for the front panel applications of liquid crystal displays and organic EL displays.

[0102] In addition, as the article having the laminated film of the present invention, for example, plastic molded products such as mobile phones, household electrical appliance casings, automotive bumpers, and OA equipment can be cited.

[0103] [Examples]

[0104] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples refers to "mass %", and "parts" refers to "mass parts".

[0105] [Example 1]

[0106] 92 parts of Miramer PU-610 (manufactured by MIWON), 8 parts of Miramer M286 (manufactured by MIWON) as component (B), 5 parts of Runtecure (registered trademark) 1104 (manufactured by Runtec Chemicals) as a photoinitiator, 6 parts of ACRIT1SX-1055U4 (manufactured by TAISEI FINE CHEMICAL CO., LTD.) as an antistatic agent, and a solution of methyl ethyl ketone (MEK) / methyl isobutyl ketone (MIBK) = 3 / 1 as a solvent were mixed to obtain a radiation-curable composition. Then, the obtained curable resin composition was coated on a polyethylene terephthalate film (PET film) with a thickness of 50 μm using a bar coater and dried at 60°C for 1 minute. Then, under a nitrogen atmosphere, ultraviolet rays were irradiated with a 120 W high-pressure mercury lamp at 150 mJ / cm 2 , and a laminated film having a cured coating film with a film thickness of 5 μm on the PET film was obtained.

[0107] [Examples 2 to 10, Comparative Examples 1 to 9]

[0108] The coating materials were changed as described in Tables 1 and 2 below, and otherwise, the same operations as in Example 1 were performed to obtain a curable resin composition and a laminated film.

[0109] [Table 1]

[0110]

[0111] [Table 2]

[0112]

[0113] The abbreviations in Tables 1 and 2 represent the following compounds.

[0114] Miramer PU-610: Aliphatic urethane acrylate (manufactured by MIWON)

[0115] Miramer MU-9500: Aliphatic urethane acrylate (manufactured by MIWON)

[0116] LUXYDIR (registered trademark) 17-806: Urethane acrylate (manufactured by DIC)

[0117] ARONIX M-450: Polyfunctional acrylate (manufactured by Toagosei Co., Ltd.)

[0118] EBECRYL 8402: Bifunctional urethane acrylate (manufactured by TAISEI HOLDINGS Corporation.)

[0119] Miramer M286: Polyethylene Glycol Diacrylate (manufactured by MIWON Co., Ltd.)

[0120] Miramer M284: Polyethylene Glycol Diacrylate (manufactured by MIWON Co., Ltd.)

[0121] Miramer M3150: Trimethylolpropane EO Modified Triacrylate (manufactured by MIWON Co., Ltd.)

[0122] Miramer M2040: Polypropylene Glycol Diacrylate (manufactured by MIWON Co., Ltd.)

[0123] Miramer M2100: EO Modified Bisphenol A Diacrylate (manufactured by MIWON Co., Ltd.)

[0124] NK Ester A-PTMG65: Polytetramethylene Glycol Diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0125] Miramer M282: Polyethylene Glycol Diacrylate (manufactured by MIWON Co., Ltd.)

[0126] Miramer M170: Ethoxydiglycol Acrylate (manufactured by MIWON Co., Ltd.)

[0127] Runtecure (registered trademark) 1104: Photoinitiator (manufactured by Runtec Chemicals Co., Ltd.)

[0128] 1SX-1055U4: Quaternary Ammonium Salt Type Antistatic Polymer (manufactured by TAISEI FINE CHEMICAL CO,.LTD.)

[0129] Using the laminated films obtained in the above Examples and Comparative Examples, the following evaluations were conducted.

[0130] [Coating Material and Coating Film Appearance]

[0131] For the laminated film, visual inspection was carried out to check for appearance defects such as fogging and cracking.

[0132] [Surface Resistance Value (Ω / □)]

[0133] For the surface of the laminated film, at a temperature of 23 degrees and a humidity of 50%, according to the JIS test method K6911-1995, using a high resistivity meter ( "Hiresta-UPMCP-HT450" manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the surface resistance value was measured with an applied voltage of 500V and a measurement time of 10 seconds. The 5.0×10 9Hereinafter, let it be A (qualified) if it is below 5.0×10 9 and 5.0×10 10 Hereinafter, let it be B (qualified) if it is above 5.0×10 10 and 5.0×10 11 Hereinafter, let it be C (unqualified) if it is above 5.0×10 11 and 5.0×10 12 Hereinafter, let it be D (unqualified) if it is above 5.0×10

[0134] [SW Test: Abrasion Resistance]

[0135] Conduct the following abrasion test: Wrap a 0.5 g steel wool ("BONSTAR #0000" manufactured by Nippon Steel Wool Co., Ltd.) around a disc-shaped indenter with a diameter of 2.4 cm, apply a load of 500 g to the indenter, and make 10 round trips on the surface of the laminated film obtained in the examples and comparative examples. After the test, visually check whether there are scratches on the surface.

[0136] [Mandrel Test: Flexibility]

[0137] Conduct the following test: Use a mandrel testing machine ("Bending Testing Machine" manufactured by TP Giken Co., Ltd.), wind the laminated film obtained in the examples and comparative examples around the test rod, visually check whether cracks occur, and take the minimum diameter of the test rod without cracks as the evaluation result. The test rods used are those with diameters from 2 mm to 12 mm at 1 mm intervals. Let it be qualified if it is 2 mm or less, and unqualified if it is 3 mm or more.

[0138] [Tensile Test: Elongation]

[0139] For the laminated film, evaluate the elongation at break under the following conditions in accordance with JIS K6251:2010. For the elongation at break, express the value obtained by subtracting the initial distance between the chucks from the distance between the chucks at the time of tensile fracture as a percentage. Let it be A (qualified) if the elongation at break is 10% or more, B (qualified) if it is less than 10% and 6% or more, C (unqualified) if it is less than 6% and 3% or more, and D (unqualified) if it is less than 3%.

[0140] Measuring Machine: Tensilon Universal Material Testing Machine (manufactured by ORIENTEC CORPORATION)

[0141] Sample Shape: Strip (10 mm×150 mm)

[0142] Initial Distance between Chucks: 100 mm

[0143] Tensile Speed: 10 mm / min

[0144] Measurement atmosphere: temperature 23°C, humidity 50%

[0145] According to Tables 1 and 2, for Examples 1 to 10 in which a polyfunctional (meth)acrylate having four or more functional groups as component (A) and an alkylene oxide-modified difunctional or trifunctional (meth)acrylate having a Tg of 10°C or lower as a homopolymer of component (B) are used in combination, the appearance is good, the surface resistance value is low, antistatic properties are exhibited, and furthermore, scratch resistance, flexibility, and curl resistance are excellent.

[0146] [Adhesion to substrate]

[0147] At 1 mm intervals, 11 longitudinal and 11 transverse slits were cut on the surface of the laminated film to make 100 grids. Then, the following operation was repeated twice: after a glass tape (“Cellotape (registered trademark) CT-18” manufactured by Nichiban Co., Ltd.) was adhered to the surface, it was peeled off all at once. The initial adhesion was evaluated according to the following criteria based on the residual area ratio of the non-peeled remaining area. Those evaluated as grade A or above were judged as qualified.

[0148] A: Residual area ratio is 100%.

[0149] B: Residual area ratio is 95% or more and less than 100%.

[0150] C: Residual area ratio is 10% or more and less than 95%.

[0151] D: Residual area ratio is less than 10%.

[0152] [SW test after surface coating: recoatability]

[0153] 76 parts of ARONIX M-305 (manufactured by Toagosei Co., Ltd.), 12 parts of Thrulya 4320 (manufactured by JGC Catalysts and Chemicals Ltd.), 12 parts of MEGAFACE RS-51 (manufactured by DIC Corporation), 4 parts of Runtecure (registered trademark) 1104 (manufactured by RuntecChemicals), and methyl isobutyl ketone (MIBK) as a solvent were mixed to obtain a radiation curable composition. Then, the obtained curable resin composition was coated on the films obtained in each example and comparative example using a bar coater and dried at 60°C for 1 minute. Then, under a nitrogen atmosphere, ultraviolet rays were irradiated with a 120 W high-pressure mercury lamp at 150 mJ / cm 2 , and a laminated film having a recoat layer with a film thickness of 0.5 μm on a PET film was obtained.

[0154] Perform the following abrasion test: Wrap a 0.5 g piece of steel wool ("BONSTAR #0000" manufactured by Nippon Steel Wool Co., Ltd.) around a disc-shaped indenter with a diameter of 2.4 cm, apply a load of 500 g to the indenter, and move it back and forth 10 times on the surface of the laminated film after surface coating. After the test, evaluate the degree of scratching and peeling of the surface coating according to the following criteria, and judge that it is qualified if it is rated B or above.

[0155] A: No scratches.

[0156] B: The peeling area of the surface coating is less than 10%.

[0157] C: The peeling area of the surface coating is 10% or more and less than 50%.

[0158] D: The peeling area of the surface coating is 50% or more.

Claims

1. A cationically curable resin composition comprising the following components (A) to (D), wherein the ratio of component (A) is 30% by mass or more in all solid components, and the ratio of component (B) is 1 to 20% by mass in all solid components. (A) Component: A polyfunctional urethane (meth)acrylate having 3 or more functional groups (B) Component: An alkylene oxide-modified (meth)acrylate having 2 or more functional groups with a Tg of the homopolymer of 10°C or lower (C) Component: An antistatic agent (D) Component: A solvent.

2. The cationically curable resin composition according to claim 1, which comprises a photopolymerization initiator as component (E).

3. A coating film which is a cured product of the cationically curable resin composition according to claim 1 or 2.

4. A laminated film comprising the coating film according to claim 3 and a substrate.

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