WO2006115085A1 - Actinic radiation curable resin composition and articles and moldings made by using the same - Google Patents

Abstract

An actinic radiation curable resin composition characterized by comprising a urethane acrylate (A) which is a product of addition reaction of a polyisocyanate (a1) with an acrylate (a2) having one hydroxyl group and two or more (meth)acryloyl groups in the molecule and a polymer (B) having a (meth)acryloyl group which is obtained by reacting a (meth)acrylate polymer (b1) having a reactive functional group in the side chain with an α,β-unsaturated compound (b2) having a functional group reactive with the reactive functional group. The composition can be cured by irradiation with an actinic radiation such as ultraviolet light to give a cured film having high hardness and high mar resistance with little cure shrinkage.

Description

 Specification

 Active energy ray-curable resin composition, articles and molded articles using the same

 The present invention relates to an active energy ray-curable resin composition that can be used as a protective layer of an article and forms a high-hardness cured film. Sarakuko relates to an article having a cured film of the composition and a molded article comprising a cured product of the resin composition.

 Background art

 [0002] An article is affected by the contact between the articles, contact with other articles, or the environment in which the article is placed, and external changes such as damage or deformation and the materials constituting the article deteriorate. Undergo internal changes. In order to prevent such changes, a protective layer is provided on the surface of the article or the article itself is strengthened.

 [0003] Plastics are used in various fields for reasons such as good workability, light weight, and low cost. However, while the processability is good, there is a problem that the soft surface is easily scratched. In order to solve this problem, a method of providing a protective layer by coating a hard coat material on the surface is generally used. Thermosetting resin compositions such as silicon-based resin compositions, acrylic resin compositions, and melamine-based resin compositions have been used as this hard coat material. Due to its long length, there was a problem that it could not be applied to articles such as plastic films that are vulnerable to heat.

 [0004] In recent years, active energy ray-curable resin compositions have advantages such as (1) fast curing, (2) low energy cost, and (3) curing at low temperatures. It is rapidly adopted as a hard coat material. In particular, as a hard coating material for film, it is hardened immediately upon irradiation with an active energy ray such as an ultraviolet ray to form a hard coating, so it has excellent hardness, scratch resistance, stain resistance, etc. Because it can be processed continuously, it has become mainstream.

[0005] Display physical strength such as a liquid crystal display, a plasma display, a touch panel display and the like provided with a film having a hard coat material as a protective layer on the surface is rapidly spreading. In particular, liquid crystal displays have become larger and used by an unspecified number of consumers. Therefore, a hard coating material used for the coating is required to have higher hardness, higher scratch resistance, less shrinkage at the time of curing, and smaller curl of the film.

 [0006] Further, as a method of providing a protective layer on an article, there is a transfer method in which a protective layer is used as a protective layer, and the protective layer becomes the outermost layer of the article after transfer. This transfer method is used for articles in the field of home appliances, automobiles, etc., and is used in the outer panel of refrigerators and mobile phone casings. The active energy ray-curable resin composition can also be used for the protective layer provided on this transfer material, but since it is used by an unspecified number of consumers, it requires higher hardness and higher scratch resistance, and In order to improve the workability at the time of transfer, the curl of the transfer material is required to be small.

 [0007] Further, since the active energy ray resin composition is immediately cured by irradiation with an active energy ray such as ultraviolet rays to form a hard film, the active energy ray resin composition is in contact with the mold. When cured, a molded body having a shape obtained by transferring the mold can be produced. For example, an optical sheet such as a Fresnel lens sheet is manufactured by this method. Even in this production method, higher hardness and higher scratch resistance are required, and in order to improve workability, there is a need for an active energy ray-curable resin composition that has a low curing shrinkage and curling of the cured coating. Yes.

 [0008] As an active energy ray-curable resin composition having high, hardness, high, and scratch resistance, radiation curable polyfunctional (meta) having at least two (meth) attaloyl groups and hydroxyl groups in one molecule. ) Radiation curable resin composition containing a polyfunctional urethane atreate obtained by reacting acrylate and polyisocyanate (see, for example, Patent Document 1), a polyol having a condensed polycyclic structure and a polyisothene. There has been proposed an active energy ray-curable coating composition (see, for example, Patent Document 2), which contains urethane acrylate resin consisting of cyanate and a compound having a hydroxyl group and a (meth) atalyloyl group as an essential component. . However, these active energy ray-curable resin compositions have small cure shrinkage but low hardness or increase hardness. Therefore, when polyfunctional acrylate dipentaerythritol is added to oxalate, etc., cure shrinkage is reduced. There was a problem of getting bigger.

[0009] In addition, an active energy ray containing a polymer having a (meth) acrylic equivalent of 100 to 300 gZeq, a hydroxyl value of 20 to 500, a weight average molecular weight of 5,000-50,000, and a polyfunctional isocyanate Curable榭脂compositions have been proposed (e.g., see Patent Document 3.) ₀ However, even low hardness active energy ray curable榭脂composition This scratch resistance has been made insufficient.

 Patent Document 1: Japanese Patent Laid-Open No. 2001-113648

 Patent Document 2: JP 2002-212500 A

 Patent Document 3: Japanese Patent Laid-Open No. 9-290491

 Disclosure of the invention

 Problems to be solved by the invention

[0010] The problem to be solved by the present invention is that an active film capable of obtaining a cured film having a small curing shrinkage force S, a high hardness, and a high scratch resistance when cured by irradiation with active energy rays such as ultraviolet rays. It is to provide an energy ray curable resin composition, an article having a protective layer made of the cured film, and a molded article made of a cured product of the resin composition.

 Means for solving the problem

 [0011] As a result of diligent research, the inventors of the present invention have found that urethane obtained by addition reaction of polyisocyanate with attalylate having one hydroxyl group and two or more (meth) atalyloyl groups in one molecule. It has been found that the above-mentioned problems can be solved by using an active energy ray-curable resin composition containing attalylate and a (meth) acrylate polymer having a (meth) attalyloyl group in the side chain. The present invention has been completed.

 [0012] That is, the present invention relates to a urethane alkoxide which is an addition reaction product of polyisocyanate (al) and acrylate (a2) having one hydroxyl group and two or more (meth) taroloyl groups in one molecule. Relate (A) and a (meth) atalylate polymer (bl) having a reactive functional group in the side chain have a functional group capable of reacting with the reactive functional group (X, β unsaturated compound ( an active energy one-line curable resin composition comprising a polymer (B) reacted with (2) and reacted with (2), and an article having a protective layer made of the cured film. Furthermore, the present invention provides a molded article made of a cured product of the resin composition.

 The invention's effect

[0013] The active energy ray-curable resin composition of the present invention has an active energy such as ultraviolet rays. When cured by irradiation with a wire, a cured film having a curing shrinkage, a high hardness, and a high scratch resistance can be obtained, which is useful as a protective layer for a film. Further, since the curing shrinkage is small, curling can be suppressed even in a large film, and it is suitable as a material for a protective layer for an optical film of a large screen display such as a liquid crystal display.

 Furthermore, it can also be used as a protective layer for plastic articles such as home appliances and mobile phone casings. In this case, the protective layer can also be applied to a method of forming by a transfer method in which the protective layer is prepared as a transfer material and then transferred to become the outermost layer of the plastic article.

 [0015] On the other hand, a molded article comprising the cured product of the active energy ray-curable resin composition of the present invention by curing the active energy beam-curable resin composition of the present invention while being in contact with the mold. Can also be made. This molded body can be used as an optical sheet such as a Fresnel lens.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The present invention is described in detail below. Examples of the polyisocyanate (al) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4, 4 , 1-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4, 4-diphenylmethane diisocyanate, etc .; dicyclohexylmethane diisocyanate, isophorone diisocyanate Isocyanate groups bonded to alicyclic hydrocarbons such as cyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene bisphenol diisocyanate, 1,4-cyclohexane diisocyanate, etc. Compound having two (hereinafter abbreviated as alicyclic diisocyanate); trimethylene diisocyanate, hexamethylene diisocyanate Aliphatic compound having two Isoshianeto groups combined binding hydrocarbon (hereinafter, referred to as aliphatic Jiisoshianeto.) And the like. These polyisocyanates can be used alone or in combination of two or more.

[0017] Among these polyisocyanates (al), isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, among which aliphatic diisocyanate or alicyclic diisocyanate are preferred. Hydrogenated methylene bisphenol diisocyanate and hexamethylene diisocyanate are preferred. In particular, norbornane diisocyanate Nate is most preferred.

 [0018] Examples of the attalylate (a2) having one hydroxyl group and two or more (meth) atalyloyl groups in one molecule used in the present invention include, for example, trimethylolpropane di (meth) acrylate and pentaerythritol tris. And polyatalylates of polyhydric hydroxyl group-containing compounds such as (meth) acrylate and dipentaerythritol penta (meth) acrylate, and adducts of these poly acrylates with ε-force prolatatone, Examples include adducts of these polyacrylates and alkylene oxides, and epoxy acrylates. These talates (a2) can be used alone or in combination of two or more. In the present invention, “(meth) acrylate” refers to one or both of metatalylate and acrylate, and the same applies to “(meth) atalyloyl group” and “(meth) acrylic acid”. is there.

 [0019] Of these acrylates (a2), acrylates having one hydroxyl group and three to five (meth) taroloyl groups in one molecule are preferred. Examples of such acrylates include pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and these are particularly preferred because a hard coating film can be obtained.

[0020] The urethane acrylate (A) used in the present invention can be obtained by subjecting two components of the polyisocyanate (al) and the acrylate (a2) to an addition reaction. The ratio of the acrylate (a2) to 1 equivalent of isocyanate in the polyisocyanate (al) is usually preferably 0.1 to 50 force, more preferably 0.1 to 10 as the hydroxyl equivalent. 2 is more preferred. The reaction temperature between the polyisocyanate (al) and the attalylate (a2) is preferably 30 to 150 ° C, more preferably 50 to 100 ° C. Incidentally, the end point of the reaction, for example, can be confirmed by determining loss and the infrared absorption spectrum of 2250 cm ^_1 showing a Isoshiane one bets group, a Isoshianeto group content by the method described in JIS K 7301- 1995.

Furthermore, in the above addition reaction, a catalyst can be used for the purpose of shortening the reaction time. Examples of the catalyst include basic catalysts (amines such as pyridine, pyrrole, triethylamine, jetyramine, dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine) and acidic catalysts (copper naphthenate, cobalt naphthenate). , Naphthenic acid dumbbell, tributoxyaluminum, tetrabutoxytrititanium, tetrabutoxyzirconium and other metal alkoxides, aluminum chloride and other Lewis acids, dibutyl Tin compounds such as tin dilaurate and dibutyltin diacetate). Among these, an acidic catalyst is preferred, and a tin compound is most preferred. Catalyst is polyisocyanate

Usually, 0.1 to 1 part by mass is added to 100 parts by mass. Toluene, xylene as required

, Ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other solvents, or radical polymerizable monomers that do not have a site to react with isocyanate, such as the radical polymerizable monomer described below. Substances (C) having no hydroxyl group or amino group may be used as a solvent. These solvents and monomers can be used alone or in combination of two or more.

 [0022] The molecular weight of the urethane acrylate (A) is preferably in the range of 500 to 1,500. When the molecular weight is within this range, a cured film having a sufficiently high hardness can be obtained and the curing shrinkage can be reduced, so that the curl of the film having the cured film can also be reduced.

 [0023] The blending amount of the urethane acrylate (A) in 100 parts by weight of the total amount of the resin components in the resin composition is preferably 5 to 90 parts by weight, and more preferably 10 to 70 parts by weight. 10 to 60 parts by mass Force S is more preferable. If the blending amount of urethane acrylate (A) is within this range, a cured film having a sufficiently high hardness can be obtained, and curing shrinkage can be reduced, so that the curl of the film having the cured film can also be reduced. .

 [0024] The reactive functional group of the (meth) acrylate polymer (bl) having a reactive functional group in the side chain used in the present invention is preferably a hydroxyl group, a carboxyl group, an epoxy group or the like. In addition, the functional groups that can react with these reactive functional groups (X, β unsaturated compounds (b2) include isocyanate groups, carboxyl groups, acid halide groups, hydroxyl groups, epoxy groups, etc. In addition, a (β) unsaturated compound (b2) having a functional group capable of reacting with the reactive functional group is added to the (meth) acrylate polymer (bl) having a reactive functional group in the side chain. The method for producing the polymer (B) having a reacted (meth) atallyloyl group can be produced by any conventional known method without any particular limitation. For example, the following production methods (1) to (3 ).

 [0025] Manufacturing method (1)

As the (meth) acrylate polymer (bl), a (meth) acrylate polymer or copolymer having a hydroxyl group as a reactive functional group in the side chain is used, and a part of the hydroxyl group is used. In all, a, j8-unsaturated compound (b2) is reacted with (meth) acryloylethyl isocyanate, (meth) acrylic acid, (meth) acrylic acid chloride, etc. How to introduce.

 [0026] Manufacturing method (2)

 As the (meth) acrylate polymer (bl), a (meth) acrylate polymer or copolymer having a carboxyl group as a reactive functional group in the side chain is used. All, a, j8-unsaturated compound (b2) is reacted with an acrylate containing a hydroxyl group and a (meth) acryloyl group, or an atelate containing an epoxy group and a (meth) acryloyl group, ) A method for introducing an attailoyl group.

 [0027] Manufacturing method (3)

 As the (meth) acrylate polymer (bl), a (meth) acrylate polymer or copolymer having an epoxy group as a reactive functional group in the side chain is used, and a part or all of the epoxy group is used. And a, j8-unsaturated compound (b2) by reacting (meth) acrylic acid or an acrylate having a carboxyl group and an allyloyl group to introduce a (meth) attaroyl group.

 [0028] Using the production method (3) as an example, the production method of the polymer (B) will be described more specifically. In the production method (3), a polymer (Β) can be easily obtained by reacting an (meth) acrylate polymer or copolymer having an epoxy group with an α, β unsaturated carboxylic acid. it can. Here, the (meth) atalylate polymer having an epoxy group is, for example, a glycidyl (meth) acrylate or a (meth) acrylate having an alicyclic epoxy group (for example, Daicel Chemical Industries). (CYCLOMER M100 "," CYCLOMER A200 "manufactured by Co., Ltd.), and (meth) acrylate having an epoxy group such as 4-hydroxybutyl acrylate glycidyl ether can be obtained by homopolymerizing them.

[0029] In addition, the (meth) acrylate copolymer having an epoxy group is changed to the (meth) acrylate having the epoxy group, and (meth) acrylate, styrene, butyl acetate, atta It can be obtained by copolymerizing two or more types of monomers using _α , β unsaturated monomers having no carboxyl group such as mouth-tolyl as raw materials. In addition, α, j8-unsaturated monomer having a carboxyl group instead of α, j8-unsaturated monomer In the case of using a polymer, a cross-linking reaction is caused in the copolymerization reaction with glycidyl (meth) acrylate, which causes viscosity increase and gelling.

 [0030] Examples of ex and β-unsaturated carboxylic acids that react with the (meth) acrylate polymer or copolymer having an epoxy group include (meth) acrylic acid, carboxyl group, and attalyl group. (For example, “Biscoat 2100” manufactured by Osaka Organic Chemical Co., Ltd.) and the like.

 [0031] The polymer (重合) obtained by the above production method has a weight average molecular weight of 5,000 to 80,000 force S preferred <, 5,000 to 50,000 force preferred <, 8,000 ~ 35,000 power ^ more preferred! / ヽ. When the weight average molecular weight is 5,000 or more, the effect of reducing cure shrinkage is large. When the weight average molecular weight is 80,000 or less, the hardness is sufficiently high.

 [0032] Further, the equivalent of the (meth) atalyloyl group in the polymer (Β) is 100 to 300 gZeq, and more preferably 200 to 300 gZeq. When the (meth) atallyloyl group equivalent of the polymer (B) is within this range, curing shrinkage can be reduced and the hardness can be sufficiently increased.

 [0033] When the polymer (B) is produced by the production methods (1) to (3), the weight average molecular weight of the polymer (B) and the (meth) taroloyl group equivalent are satisfied. The type of monomer and polymer to be used, the amount of these used, etc. may be appropriately selected.

 [0034] The blending amount of the polymer (B) in 100 parts by mass of the total amount of the resin components in the composition is preferably 5 to 90 parts by mass, more preferably 10 to 70 parts by mass. 15 to 50 parts by mass Force S More preferable. If the blending amount of the polymer (B) is within this range, a cured film having a sufficiently high hardness can be obtained and curing shrinkage can be reduced. Can do.

 [0035] The blending ratio of the urethane acrylate (A) and the polymer (B) is preferably in the range of (A): (8) = 10:90 to 90:10 on a mass basis, (A): The range of (B) = 20: 80 to 80:20 is preferred, and the range of (A) :( B) = 25: 75 to 75:25 is more preferred. If the blending ratio force of the urethane acrylate (A) and the polymer (B) is within this range, a sufficiently high and hardened cured film can be obtained, and the curing shrinkage can be reduced. A film with a coating can be made into a barrel / J.

[0036] The active energy ray-curable resin composition of the present invention includes the urethane acrylate (A). In addition to the polymer (B), radically polymerizable monomers (C) may be added. Examples of the radically polymerizable monomers (C) include the following.

 [0037] N-Bielcaprolatatam, N-Buylpyrrolidone, N-Bulbcarbazole, Bulle pyridine, Acrylamide, N, N-Dimethyl (meth) acrylamide, Isobutoxymethyl (meth) acrylamide, toctyl (meth) acrylamide, diacetone (Meth) acrylamide, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, 7-amino 3,7-dimethyloctyl (meth) acrylate, attaroyl morpholine, lauryl (meth) acrylate , Dicyclopentagel (meth) atarylate, dicyclopente-loxychetyl (meth) atarylate, dicyclopentayl (meth) atacrylate, tetrahydrofurfuryl (meth) acrylate, ethylenediethylene glycol (meth) acrylate Butokishechiru (meth) Atari rate, mono Atari rate such as methyl triethylene diglycol (meth) Atari rate, Fuenokishechiru (meth) Atari rate;

 [0038] Trimethylol propane tri (meth) acrylate, triethylene oxide modified trimethylol propane tri (meth) acrylate, tripropylene oxide modified glycerol tri (meth) acrylate, triethylene oxide modified glycerol tri ( (Meth) attalylate, triechlorochlorohydrin-modified glycerol tri (meth) atalylate, 1, 3, 5-trichlorohexahydros-triazine

, Tris (atallyroyloxychetyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethyleneoxide modified bentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, diethylene oxide modified ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol pent acrylate (for example, “Charad” manufactured by Nippon Kayaku Co., Ltd. D-310 "), alkyl-modified dipentaerythritol tetraatalylate (for example," Carad D-320 "manufactured by Nippon Kayaku Co., Ltd.), epsilon prolatatone-modified dipentaerythritol hexaatalyle (For example, “Carad DPCA-20” manufactured by Nippon Shakuyaku Co., Ltd.), dipentaerythritol pentamethacrylate, dipentaerythritol hexa (meth) acrylate, hexaethylene oxide modified sorbitol hexa (meth) attaly Polyfunctional Atari, such as rate, hexakis (methacryloyloxychetyl) cyclotriphosphazene (for example, “ΡΡΖ” manufactured by Kyoeisha Chemical Co., Ltd.) There are rates.

 [0039] Among the radical polymerizable monomers (C), the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule has an effect of increasing hardness. Because there is, it is preferable. Examples of such polyfunctional (meth) acrylates include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexatarate. These may be used alone or in combination of two or more.

 [0040] Further, as the radical polymerizable monomers (C), monomers having an acid group such as a carboxyl group, a phosphoric acid group and a sulfonic acid group, a monomer having an amino group, an alkoxysilyl group It is preferable to use a monomer having an alkoxy titanyl group because the adhesion to the substrate can be improved. On the other hand, a monomer having a fluorocarbon chain, a dimethylsiloxane chain, or a hydride-opened carbon chain having 12 or more carbon atoms can improve the surface properties of the protective layer such as surface slipperiness, stain resistance, and fingerprint resistance. It is preferable because it is possible.

 [0041] When the radical polymerizable monomers (C) are blended in the resin composition, the total amount of the urethane acrylate (A) and the polymer (B) is 100 parts by mass. On the other hand, 10 to 300 parts by mass are preferable. Further, in order to reduce curing shrinkage and increase the surface hardness of the cured film, 20 to 200 parts by mass is more preferable. 20 to: LOO parts by mass is more preferable.

 [0042] Further, the active energy ray-curable resin composition of the present invention includes the urethane acrylate (A) and the polymer (B) as well as a urethane acrylate (other than the urethane acrylate (A)). D) may be accepted. As urethane acrylate (D), after addition reaction of a polyol and the polyisocyanate (al), acrylate having one hydroxyl group and two or more (meth) attalyloyl groups in one molecule. Examples thereof include those obtained by addition reaction of (a2). The blending amount of this urethane acrylate (D) in the resin composition is 5 to 5 parts by weight based on 100 parts by weight of the total amount of the urethane acrylate (A) and the polymer (B). LOO parts by mass are preferred. 10 to 50 parts by mass are more preferred.

[0043] The active energy ray-curable resin composition of the present invention refers to a resin composition that cures when irradiated with active energy rays. Active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, j8 rays, and γ rays. Active energy when using ultraviolet light A photopolymerization initiator is added to the linear curable resin composition. If necessary, further add a photosensitizer. On the other hand, when ionizing radiation such as electron beam, α-ray, j8-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no.

[0044] In the case of curing with ultraviolet rays, effective photopolymerization initiators can be broadly classified into intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy 2-methyl-1 ferrule 1-one, benzyl dimethyl ketal, 1- (4-isopropyl phenol). ) 2-Hydroxy-1-2-Methylpropane-1-one, 4-(2 Hydroxyethoxy) ferro- (2-Hydroxy-1-2-propyl) ketone, 1-Hydroxycyclohexylphenylketone, 2-Methyl-2-morpholino- ( 4-thiomethylphenol) propane 1one, 2benzil 2 dimethylamino 1- (4morpholinophenol) acetophenone compounds such as butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2, 4, 6 Trimethylbenzoyl diphosphine phosphine oxide, bis (2, 4, 6 trimethylbenzo Le) Single Hue - Ashiruho Sufuinokishido based compounds such as Le phosphine O sulfoxide; benzyl, Mechirufue - compounds such as caprylyl oxy esters.

 On the other hand, as the hydrogen abstraction type photopolymerization initiator, for example, benzophenone, ο-benzoyl methyl benzoate-4 phenol-penzophenone, 4, 4, dichroic benzophenone, hydroxybenzophenone, 4- Benzyl 4'-methyl-diphenyl sulfide, acrylylated benzophenone, 3, 3 ', 4, 4'-tetra (t-butylperoxycarbol) benzophenone, 3, 3, 1-dimethyl-4-methoxybenzophenone Benzophenone compounds such as 2 isopropylthioxanthone, 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, 2,4 dicyclothioxanthone and the like thixanthone compounds such as Michlerketone, 4,4, Aminobenzophenone compounds; 1 0 Butyl 2 Chlorotalidone, 2 Ethylanthraki Emissions, 9, 10 Fuenansuren quinone, include compounds such as camphor quinone.

[0046] The photosensitization suitably used for the active energy ray-curable resin composition of the present invention. Examples of the agent include, but are not limited to, amines such as aliphatic amines and aromatic amines, ureas such as O-tolylthiourea, sodium jetyl dithiophosphate, S-benzylisothiu-mu-P -Sulfur compounds such as toluene sulfonate.

[0047] The amount of the photopolymerization initiator and photosensitizer used is preferably 0.1 to 20% by mass with respect to 100 parts by mass of the resin component in the active energy ray-curable resin composition. 0.5 to 1

0% by mass is more preferable.

[0048] The active energy ray-curable resin composition of the present invention may be blended with various additives as necessary, and may be diluted with a solvent as desired. Examples of the additive include a polymerization inhibitor, an antioxidant, a leveling agent, an antifoaming agent, a coating surface improver (wetting property, slip property improving agent, etc.), a plasticizer, and a colorant. .

[0049] Solvents used for dilution include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate and ethyl solvate; methyl ethyl ketone, methyl isobutyl ketone, And ketones such as cyclohexanone. These solvents may be used alone or in combination of two or more.

 [0050] Since the cured coating of the active energy ray-curable resin composition of the present invention has a curing shrinkage force, a high hardness, and high scratch resistance, the article is affected by cure shrinkage. Can be protected without any problems. For this reason, the cured film of the active energy ray-curable resin composition of the present invention is useful as a hard coat material for forming a protective layer of various articles. Examples of this article include plastic, paper, and cellulose such as wood, ceramics such as glass, and articles having metal strength such as iron and aluminum, and are particularly useful for protecting articles made of plastic. When the active energy ray-curable resin composition of the present invention is used to protect the surface of a plastic film, a remarkable effect is exhibited because the curing shrinkage is small and the curling of the film is small. The surface of the article may be provided with a handle or an easy adhesion layer. The thickness of the cured coating is usually 0.5 to 500 / ζ πι, preferably 3 to 50 μm, particularly preferably 4 to 30 μm. When the thickness of the cured film is within this range, high hardness and high scratch resistance can be obtained.

[0051] A plastic film having a cured coating of the active energy ray-curable resin composition of the present invention. The film has the above active energy ray-curable resin composition on a film substrate, and the weight of the resin composition after drying is preferably 0.5 to 500 gZm ² , preferably 3 to 50 gZm ² . Alternatively, it is applied so as to be 4 to 30 g / m ² (in terms of film thickness, usually 0.5 to 500 / ζ πι, preferably 3 to 50 / ζ πι, particularly preferably 4 to 30 m). After drying, it can be obtained by irradiating active energy rays to form a cured film. If the amount of the cured film formed on the film substrate is less than 0.5 gZm ² , the film substrate itself may be affected by the hardness, and a sufficiently high hardness may not be obtained. In addition, if it is 500 gZm ² or more, there is a problem that the base material is deformed by the polymerization heat at the time of curing, so it is necessary to devise cooling or the like at the time of curing.

 [0052] Examples of the film substrate include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polypropylene, polyethylene, and polymethylpentene-11; and cellulose-based materials such as triacetyl cellulose. Film: polystyrene film, polyamide film, polycarbonate film, norbornene-based resin film (for example, “ZEONOR” manufactured by Nippon Zeon Co., Ltd.), modified norbornene-based resin film (for example, “ARTON” manufactured by CFSR Corporation), cyclic Examples include an olefin copolymer film (for example, “Abel” manufactured by Mitsui Engineering Co., Ltd.). Two or more of these films may be bonded together. These films may be in sheet form. The thickness of the film substrate is preferably 20 to 500 m force S. The film to be used may be one provided with a handle or an easy adhesion layer.

[0053] Examples of the method for applying the active energy ray-curable resin composition of the present invention to a film substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and transfer coating. Dip coat, spinner coat, wheeler coat, brush coating, solid coating with silk screen, wire bar coating, flow coating, and the like. Also, printing methods such as offset printing and letterpress printing may be used. Among these, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire-bar coating, and flow coating are preferable because a coating film having a more constant thickness can be obtained. In addition, also when apply | coating the active energy ray hardening-type resin composition of this invention to films other than the said film base material, or a sheet-like article, the same coating method as a film base material is used. Can do.

 [0054] The active energy ray-curable resin composition of the present invention can also be suitably used as a hard coating material for plastic molded articles. Since the cured film of the resin composition has small curing shrinkage, the cured film peels off from the substrate even when an impact is applied from the outside to the protective layer having good adhesion to the surface of the plastic molded body as the substrate. In addition, the protective layer has a high hardness and a high scratch resistance.

 [0055] The plastic molded article having a cured coating of the active energy ray-curable resin composition of the present invention is coated with the resin composition on the surface of the plastic molded article by, for example, spray coating or date coating, and then dried. Thereafter, it can be obtained by irradiating an active energy ray to form a cured film. Examples of the material of the plastic molded body include, but are not limited to, for example, polyacrylic resin, polyphenylene oxide 'polystyrene resin, polycarbonate resin, styrene copolymer resin, polystyrene resin, polyamide resin, ABS resin. Examples include fats. These plastic moldings may be provided with a handle, a thin metal layer, or an easy adhesion layer. In addition, when the active energy ray-curable resin composition of the present invention is applied to a molded article other than a plastic material, the same application method as that for a plastic molded body can be used.

 [0056] Further, as a method of protecting a plastic molded body with the cured coating of the active energy ray-curable resin composition of the present invention, the film on which the cured coating is formed is cured before the plastic is molded. There is also a method in which the film is attached to the surface of the plastic so that it becomes the outermost surface, and then the plastic is molded with the film. The film may be attached to the plastic surface by melting and bonding the film and the plastic at a high temperature or by using an adhesive. Further, a molded product formed with plastic may be pasted with a film formed with a cured film and secondarily molded in accordance with the outer shape of the molded product.

[0057] Further, as a method for providing a protective layer on a molded article made of plastic, metal or the like, a transfer material provided with a protective layer made of a cured coating of the active energy ray-curable resin composition of the present invention in advance. There is a method of using. In this case, the transfer material is attached to the surface of the article using a transfer method such as a hydraulic transfer method so that the protective layer of the transfer material becomes the outermost layer of the article after the transfer. When a pattern or a thin metal layer is provided on this transfer material, at the same time as imparting design properties to the article, High hardness and high scratch resistance can be imparted to the surface. Further, since the active energy one-line curable resin composition of the present invention has a small curing shrinkage, the curling force of a transfer material using the resin composition and the workability at the time of transfer are high.

 [0058] Examples of a method for producing a molded body made of a cured product of the active energy ray-curable resin composition of the present invention include the following methods.

[0059] An active energy ray-curable resin composition of the present invention is applied onto a substrate having a shape, and a cured product is formed by irradiating active energy rays. A method for producing a molded product by peeling.

[0060] The active energy ray-curable resin composition of the present invention is applied onto a base material that transmits active energy rays and has a shape. A method of forming a cured product by irradiating an active energy ray to form a cured product, and then removing the cured product from a mold and a substrate.

 [0061] The active energy ray-curable resin composition of the present invention is applied to the surface of a mold such as a mold, and further, an active energy ray is irradiated to form a cured product. A method of producing a molded product by peeling off a mold cover.

 [0062] Since the molded body made of the cured product of the active energy ray-curable resin composition of the present invention obtained by the above method has small curing shrinkage, high hardness, and high scratch resistance, There is no scratch on contact with the article. Therefore, it is very useful.

 [0063] When ultraviolet rays are used as a device for irradiating active energy rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, mercury Examples include xenon lamps, short arc lamps, helium-powered dominium lasers, argon lasers, sunlight, and LEDs. In addition, when the active energy ray-curable resin composition of the present invention is applied to a film substrate to form a cured coating, a flashing xenon flash lamp is used to form the cured substrate. It is preferable because it can reduce the effect of heat.

[0064] On the other hand, when an electron beam is used, an electron beam accelerator having an acceleration voltage of 30 to 300 kV is preferable. Note that the article forming the protective layer is a film substrate such as a cellulose film, a polyester film, a polystyrene film, a polyamide film, or a polycarbonate film. In this case, yellowing or deterioration occurs due to electron beam irradiation. Therefore, yellowing or deterioration of the film substrate can be prevented by setting the acceleration voltage to 30 to 150 kV.

 Example

 [0065] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

 [0066] (Synthesis Example 1) Synthesis of urethane acrylate (A1)

In a flask equipped with a stirrer, gas inlet tube, condenser tube, and thermometer, 250 parts by mass of butyl acetate, 206 parts by mass of norbornane diisocyanate (hereinafter referred to as “NBDI”), p-methoxyphenol 0.5 Part by weight, 0.5 parts by weight of dibutyltin diacetate were charged, the temperature was raised to 70 ° C. while blowing air, and then pentaerythritol tritalylate (hereinafter referred to as “PE3A”) Z pentaerythritol tetratalate (Hereinafter referred to as “PE4A”.) Mixture (mixture with a mass ratio of 75Z25) 795 parts by mass were added dropwise over 1 hour. After completion of the dropwise addition, it allowed to react for 3 hours at 70 ° C, further subjected to reaction until the infrared absorption spectrum of 2250 cm ^{_ 1} disappears indicating the Isoshianeto group, urethane Atari rate (A1) Z pentaerythritol tetra § click Relate mixture (weight ratio A mixture of 80Z20 and a butyl acetate solution having a nonvolatile content of 80% by mass was obtained. The molecular weight (calculated value) of urethane acrylate (A1) is 802.

 [Synthesis Example 2] Synthesis of Urethane Atylate (A2)

In a flask equipped with a stirrer, gas inlet tube, condenser tube, and thermometer, 568 parts by mass of butyl acetate, hexamethylene diisocyanate (hereinafter referred to as “HDI”) 168 parts by mass, p-methoxyphenol 1 2 parts by weight, dibutyltin diacetate 1. After charging 2 parts by weight and heating to 70 ° C, dipentaerythritol pentaatrate (hereinafter referred to as “DPPA”) Z dipentaerythritol hexaoxalate (Hereinafter referred to as “DPHA”) Mixture (mixture with a mass ratio of 50Z50) 2096 parts by mass were added dropwise over 1 hour. After completion of the dropwise addition, allowed to react for 3 hours at 70 ° C, the reaction was carried out further to the infrared absorption spectrum of 2250 cm ^{_ 1} showing the Isoshianeto group disappeared, urethane Atari rate (A2) ZDPHA mixture (a mixture of weight ratio 54Z56, nonvolatile butyl acetate min 80 mass _^0/0 solution) was obtained. The molecular weight (calculated value) of urethane acrylate (A2) is 1,216.

 [0068] (Synthesis Example 3) Synthesis of Urethane Atarylate (A3)

In a flask equipped with a stirrer, gas inlet tube, cooling tube, and thermometer, add butyl acetate. 1 part by weight, isophorone diisocyanate (hereinafter referred to as “IPDI”) 222 parts by mass, p-methoxyphenol 0.5 part by mass, dibutyltin diacetate 0.5 part by mass were heated to 70 ° C. After that, 795 parts by mass of PE3AZPE4A mixture (mixture with a mass ratio of 75/25) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture is reacted at 70 ° C for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm- ¹ indicating the isocyanate group disappears. Urethane acrylate (A3) ZPE4A mixture (mass ratio 80Z20 mixture, non-volatile 80% by weight butyl acetate solution) was obtained. The molecular weight (calculated value) of urethane acrylate (A3) is 818.

 [0069] (Synthesis Example 4) Synthesis of polymer (B1)

 In a flask equipped with a stirrer, gas introduction tube, cooling tube, and thermometer, 250 parts by mass of glycidyl methacrylate (hereinafter referred to as “GMA”), 1.6 parts by mass of lauryl mercaptan, methyl isobutyl ketone (hereinafter referred to as “ MIBK ") 1000 parts by mass and 2, 2, azobisisobuty-tolyl (hereinafter referred to as" AIBN ") 7. Charge 5 parts by mass and stir under a nitrogen stream over 1 hour. The temperature was raised to 90 ° C and reacted at 90 ° C for 1 hour. Next, while stirring at 90 ° C, a mixed solution consisting of 750 parts by weight of GMA, 4.4 parts by weight of lauryl mercaptan, and 22.5 parts by weight of AIBN was dropped over 2 hours, and then reacted at 100 ° C for 3 hours. . Thereafter, 10 parts by mass of AIBN was charged, and further reacted at 100 ° C for 1 hour, then heated to around 120 ° C and reacted for 2 hours. Cool to 60 ° C, replace the nitrogen inlet tube with the air inlet tube, 507 parts by weight of acrylic acid (hereinafter referred to as “AA”), 2 parts by weight of p-methoxyphenol, 5.4 parts by weight of triphenylphosphine Then, the temperature was raised to 110 ° C. and the reaction was continued for 8 hours while publishing the reaction solution with air. Then, add 1.4 parts by mass of p-methoxyphenol, cool to room temperature, add MIBK so that the nonvolatile content is 50% by mass, and add polymer (B1) (MIB solution with 50% by mass of non-volatiles). ) The obtained polymer (B1) had a weight average molecular weight of 11,000 (based on polystyrene by GPC), and the (meth) atallyloyl group equivalent was 300 gZeq.

 [Synthesis Example 5] Synthesis of polymer (B2)

In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, GMA 200 parts by mass, n-butyl methacrylate (hereinafter referred to as “nBMA”) 50 parts by mass, lauryl mercaptan 1.8 parts by mass, “ MIBK ”1000 parts by weight and AIBN 7.5 parts by weight While stirring, the temperature was raised to 90 ° C over 1 hour and reacted at 90 ° C for 1 hour. Next, while stirring at 90 ° C, a mixture of GMA 600 parts by mass, nBMA 150 parts by mass, lauryl mercaptan 4.8 parts by mass, AIBN 22.5 parts by mass was added dropwise over 2 hours, and then at 100 ° C for 3 hours. Reacted. Thereafter, 10 parts by weight of AIBN was charged, and further reacted at 100 ° C for 1 hour, then heated to around 120 ° C and reacted for 2 hours. Cool to 60 ° C, replace the nitrogen inlet tube with the air inlet tube, add 406 parts by mass of AA, 2 parts by mass of p-methoxyphenol, 5.4 parts by mass of triphenylphosphine, mix, and then react with air. While publishing, the temperature was raised to 110 ° C and reacted for 8 hours. Thereafter, 1.4 parts by mass of p-methoxyphenol was added, and after cooling to room temperature, MIBK was added so that the non-volatile content was 50% by mass, and the polymer (B 2) (non-volatile content 50 mass ° / (^ The polymer (B2) thus obtained had a weight average molecular weight of 8,800 (in terms of polystyrene by GPC) and a (meth) taroloyl group equivalent of 240 gZeq.

 [Synthesis Example 6] Synthesis of polymer (B3)

 In Synthesis Example 4, the same procedure was performed as in Synthesis Example 4 except that the first charged lauryl mercabtan was changed to 1.3 parts by mass, and the dripped lauryl mercabtan was then changed to 3.7 parts by mass. ) (Non-volatile content 50 mass ° / (^ MIBK solution) was obtained. The weight average molecular weight of the obtained polymer (B3) was 31 000 (in terms of polystyrene by GPC). The equivalent weight was 300 gZeq.

 [0072] Using the urethane acrylate (A1) to (A3) and the polymers (B1) to (B3) obtained above, the active energy ray-curable resin composition of the present invention was prepared as follows. did.

 [0073] (Example 1)

7.7 parts by mass of butyl acetate, 50 parts by mass of methyl ethyl ketone (hereinafter referred to as “MEK”), and the urethane acrylate (Al) ZPE4A mixture obtained in Synthesis Example 1 (a mixture with a mass ratio of 80Z20) Butyl acetate solution (non-volatile content 80 mass%) 42.5 mass parts, MIBK solution of polymer (B1) obtained in Synthesis Example 4 (non-volatile content 50 mass%) 74 mass parts, PE3AZPE4A mixture (mass ratio 75Z25 mixture) ) 29 parts by mass, silicon hexaatalylate (“Ebecryl 1360” manufactured by Daicel YUSHIB Co., Ltd .; hereinafter referred to as “SiA”) 0. 2 parts by mass and photopolymerization initiator (1-hydroxycyclohexylphenol- Luketone; hereinafter referred to as “HCPK”) 3 mass The parts were uniformly mixed to obtain a resin composition (1).

[Example 2]

 16.2 parts by mass of butyl acetate, 50 parts by mass of MEK, 70 parts by mass of a butyl acetate solution (non-volatile content 80% by mass) of the urethane atrelate (Al) ZPE4A mixture (mixture of 80Z20 in mass ratio) obtained in Synthesis Example 1 46 parts by mass of MIBK solution of polymer (B1) obtained in Synthesis Example 4 (non-volatile content 50 mass%), 21 parts by mass of PE3AZPE4A mixture (mixture of mass ratio 75Z25), 2 parts by mass of Si AO. And 3 parts by mass of HCPK Were uniformly mixed to obtain a resin composition (2).

[0075] (Example 3)

 Butyl acetate 9.4 parts by mass, MEK 50 parts by mass, urethane acrylate (A2) obtained in Synthesis Example 2 ZDPHA mixture (mixture with a mass ratio of 54Z46) in butyl acetate (non-volatile content 80% by mass) 28.8 parts by mass A MIBK solution of the polymer (B2) obtained in Synthesis Example 5 (non-volatile content 50% by mass) 76 parts by mass, DPHA 39 parts by mass, SiAO. 2 parts by mass and HCPK 3 parts by mass were uniformly mixed to obtain a resin composition. (3) was obtained.

[Example 4]

 Butyl acetate 15.2 parts by weight, MEK 50 parts by weight, urethane atrelate obtained in Synthesis Example 3 (A3) 60 parts by weight of butyl acetate solution (non-volatile content 80% by weight) of ZPE4A mixture (mixture of 80Z20 by weight) A MIBK solution of the polymer (B3) obtained in Synthesis Example 5 (non-volatile content 50 mass%) 52 parts by mass, DPHA 26 parts by mass, SiAO. 2 parts by mass and HCPK 3 parts by mass were mixed uniformly to obtain a resin composition. (4) was obtained.

[0077] (Example 5)

 Butyl acetate 14.4 parts by mass, MEK 50 parts by mass, urethane atrelate (Al) obtained in Synthesis Example 1 (Al) ZPE4A mixture (mixture with a mass ratio of 80Z20) in butyl acetate (non-volatile content 80% by mass) 53.8 masses Parts, MIBK solution of polymer (B1) obtained in Synthesis Example 4 (non-volatile content 50% by mass) 56 parts by mass, DPHA 29 parts by mass, SiAO. 2 parts by mass and HCPK 3 parts by mass to obtain a resin composition Things (5) were obtained.

[0078] (Example 6)

Butyl acetate 28.2 parts by mass, MEK 50 parts by mass, urethane atrelate (Al) ZPE4A mixture obtained in Synthesis Example 1 (mass ratio 80Z20 mixture) in butyl acetate (nonvolatile content 80 25 parts by mass) MIBK solution of polymer (B1) obtained in Synthesis Example 4 (non-volatile content 50% by mass) 40 parts by mass, DPHA 60 parts by mass, SiAO. 2 parts by mass and 3 parts by mass of HCPK The mixture was mixed to obtain a rosin composition (6).

[0079] (Example 7)

 23.2 parts by weight of butyl acetate, 50 parts by weight of MEK, 50 parts by weight of a butyl acetate solution (non-volatile content 80% by weight) of the urethane atrelate (Al) ZPE4A mixture obtained in Synthesis Example 1 (a mixture with a weight ratio of 80Z20), MIBK solution of polymer (B1) obtained in Synthesis Example 4 (non-volatile content 50 mass%) 40 parts by mass, PE3AZPE4A mixture (mixture of mass ratio 75Z25) 20 parts by mass, DP HA 20 parts by mass, SiAO. 2 parts by mass And 3 parts by mass of HCPK were uniformly mixed to obtain a rosin composition (7).

[0080] (Comparative Example 1)

 Butyl acetate 39.2 parts, MEK 50 parts, M IBK solution of polymer (B1) obtained in Synthesis Example 4 (non-volatile content 50% by weight) 28 parts, DPHA 86 parts, SiAO. 2 parts and HCPK3 The parts by mass were uniformly mixed to obtain a resin composition (C1).

[0081] (Comparative Example 2)

 40.7 parts by weight of butyl acetate, 50 parts by weight of MEK, urethane atrelate (Al) ZPE4A mixture obtained in Synthesis Example 1 (mixture with a weight ratio of 80Z20) in butyl acetate (non-volatile content 80% by weight) 62.5 parts by weight Part, DPHA 50 parts by mass, SiAO. 2 parts by mass and HCPK 3.0 parts by mass were mixed uniformly to obtain a resin composition (C2).

[0082] (Comparative Example 3)

 33.2 parts by mass of butyl acetate, 50 parts by mass of MEK, 100 parts by mass of a butyl acetate solution (non-volatile content of 80% by mass) of the urethane atrelate (Al) ZPE4A mixture (mass ratio of 80Z20) obtained in Synthesis Example 1 DPHA (20 parts by mass), SiAO. (2 parts by mass) and HCPK (3 parts by mass) were uniformly mixed to obtain a resin composition (C3).

[0083] (Comparative Example 4)

28.2 parts by mass of butyl acetate, 50 parts by mass of MEK, 125 parts by mass of a butyl acetate solution (non-volatile content 80% by mass) of urethane atrelate (Al) ZPE4A mixture (mass ratio 80Z20) obtained in Synthesis Example 1 SiAO. 2 parts by mass and 3 parts by mass of HCPK are mixed uniformly, The product (C4) was obtained.

[0084] (Comparative Example 5)

 MEK3. 2 parts by weight, MIBK solution of polymer (B1) obtained in Synthesis Example 4 (non-volatile content: 50% by weight) 200 parts by weight, SiAO. 2 parts by weight and HCPK3 parts by weight A composition (C5) was obtained.

 [0085] The composition ratios of the resin compositions (1) to (7) obtained in Examples 1 to 7 and the resin compositions (C1) to (C5) obtained in Comparative Examples 1 to 5 Shown in Tables 1 and 2.

 [0086] (Preparation of evaluation film)

The resin composition (1) to (7) and the resin composition (C1) to (C5) obtained above are made of polyethylene terephthalate (hereinafter referred to as “PET”) film base (Toyobo Co., Ltd.) “Cosmo Shine A4100 # 100” (thickness: 100 m), coated with a wire bar (# 4), heated at 60 ° C for 1 minute, and then irradiated with UV light in an air atmosphere (Japan Battery) "GS30 type UV irradiation device" manufactured by Co., Ltd., lamp: 120WZcm 2 metal halide lamps, lamp height: 20cm, irradiation light quantity: 0.5jZcm ² ), irradiated with ultraviolet rays, with a film thickness of 5-6 / ζ πι A film having a cured coating was obtained.

 [0087] (Evaluation of surface hardness of evaluation film)

 The surface of the cured film of the film for evaluation obtained above was measured in accordance with JIS Κ5600-5-4: 1999, pencil hardness was measured at a load of 500 g, and the surface hardness was evaluated according to the following criteria: 7 pieces.

 ○: Pencil hardness is 3H or more.

 X: Pencil hardness is 2H or less.

[0088] (Evaluation of curling property of evaluation film)

 Cut out a 10cm x 10cm test piece from the evaluation film obtained above and leave it for 24 hours in an atmosphere of 23 ° C and 65% RH, then set the length between two adjacent points on the four ends of the test piece. Measured, measured the smallest length between two adjacent points and the length between the other two points, and calculated the curl value by the following formula.

 Curl value (mm) = 10— (minimum length between two adjacent points + length between two other adjacent points) Z2

[0089] From the curl value obtained above, the curl property was evaluated according to the following criteria. A: The curl value is less than 8 mm.

 ○: Curl value ¾ mm or more and 10 mm or less.

 X: The curl value exceeds 10mm.

[0090] (Transparency evaluation of evaluation film)

 The haze value of the evaluation film obtained above was measured with a haze meter NDH2000 (Nippon Denshoku Co., Ltd.). From the obtained haze value, transparency was evaluated according to the following criteria.

○: Haze value is 0.1% or less.

 X: The haze value exceeds 0.1%.

[0091] (Evaluation of adhesion of cured film to substrate)

 The base material obtained above is a PET evaluation film, and in the preparation of the evaluation film, the PET film base material is a triacetyl cellulose (hereinafter referred to as “TAC”) film base material (Fuji A film for evaluation was prepared in the same manner except that the film was replaced with “TAC” manufactured by Photographic Film Co., Ltd. (thickness: 80 m). These evaluation films were made in accordance with JIS K5400, and 100 grids were made by making 11 vertical and horizontal cuts at lmm intervals on the film surface. Next, after attaching a commercially available cellophane tape to the surface and then peeling it all at once, the number of cells remaining without peeling was counted, and the adhesion was evaluated according to the following criteria.

 ○: There are 100 squares left.

 X: Less than 100 squares remain.

[0092] The above evaluation results are shown in Tables 1 and 2.

[0093] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Urethane ¹ route (A1) 27.2 44.8 34.4 16 32

Component (A) Urethane seal ¹ route (A2) 12.4

 Urethane acrylate (A3) 38.4

Polymer (B1) 37 23 28 20 20 (B) Component Polymer (B2) 38

Assembly polymer (B3) 26

Completion

Ratio PE3A 21.8 15.8 15 Ratio (C) Component PE4A 14.1 16.5 9.6 8.6 4 13

 DPHA 49.6 26 29 60 20 Quality

Quantity SiA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Other

HCPK 3 3 3 3 3 3 3 Butyl oxalate 16.2 30.2 15.2 27.2 25.2 33.2 33.2 Solvent M Old K 37 23 38 26 28 20 20

MEK 50 50 50 50 50 50 50 f + 206.5 206.5 206.4 206.4 206.4 206.4 206.4 Pencil hardness 3H 3H 3H 3H 3H 3H 3H Surface hardness evaluation ○ ○ ○ o ○ ○ ○ Curl value (mm) 7.5 10 9 10 7.5 10 5

Evaluation ◎ OO ○ ◎ ○ ◎ Value haze value (%) 0.09 0.07 0.09 0.08 0.07 0.06 0.07 Transparency evaluation ○ O ○ ○ o O ○ Result Number of squares remaining in peel test (PET) 100 100 100 100 100 100 100 Adhesion evaluation (PET) ○ ○ ○ ○ oo ○ Number of cells remaining in peel test (TAC) 100 100 100 100 100 100 100 Adhesion evaluation (TAC) ○ ○ ○ ○ ○ ○ ○

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5

 Urethane acrylate (A1) 40 64 80

 Component (A) Urethane acrylate (A2)

 Urethane acrylate (A3)

 Group (B) Component Polymer (B1) 14 100 Component PE4A 10 16 20 Ratio (C) Component

 DPHA 86 50 20

 SiA 0.2 0.2 0.2 0.2 0.2 Other

 HCPK 3 3 3 3 3 Quantity Butyl acetate 39.2 53.2 53.2 53.2 parts

 Solvent MIBK 14 100

 MEK 50 50 50 50 3.2

 n e 206.4 206.4 206.4 206.4 206.4 Pencil hardness 3H 3H 3H 2H H Surface hardness evaluation O O ○ X X Curl value (mm) 20 19.3 13 5 0 Curl evaluation X X X

 Evaluation © © Value Haze value (%) 0.08 0.09 0.08 0.08 0.08 Result of transparency evaluation ○ ○ ○ O ○ Result

 Number of cells remaining in peel test (PET) 100 100 100 100 100 Adhesion evaluation (PET) 0 oo OO Number of cells remaining in peel test (TAG) 100 100 100 100 100 Adhesion evaluation (TAC) o ○ ○ ○ o

[0095] From the evaluation results shown in Table 1, the film having a cured coating of the active energy ray-curable resin composition of the present invention of Example 17 has a sufficiently high L, surface hardness, and transparency. It turned out that the curl of the film was small.

 [0096] From the evaluation results shown in Table 2, the film having a cured coating of the active energy ray-curable resin composition of Comparative Example 15 containing no urethane acrylate (A) or polymer (B) is: The surface hardness was insufficient or the curl was large.

 Industrial applicability

[0097] When the active energy ray-curable resin composition of the present invention is cured by irradiation with active energy rays such as ultraviolet rays, a cured film having small curl, high hardness, and high scratch resistance is obtained. Therefore, it is useful as a protective layer for a film.

Claims

The scope of the claims  [1] Urethane acrylate (A) which is an addition reaction product of polyisocyanate (al) and acrylate (a2) having one hydroxyl group and two or more (meth) attalyloyl groups in one molecule; An α, β unsaturated compound (b2) having a functional group capable of reacting with the reactive functional group was reacted with the (meth) acrylate polymer (bl) having a reactive functional group in the side chain (meta And) an active energy ray-curable resin composition comprising a polymer (B) having an attaylyl group.  2. The active energy ray-curable resin composition according to claim 1, wherein the polyisocyanate (al) force is an aliphatic diisocyanate and Z or an alicyclic diisocyanate. [3] The active energy ray-curable resin composition according to [1], wherein the attalylate (a2) force is an acrylate having one hydroxyl group and three to five (meth) attalyloyl groups in one molecule. [4] The active energy ray-curable resin according to claim 1, wherein the polymer (B) force is a reaction product obtained by reacting a glycidyl (meth) acrylate polymer with a, β-unsaturated carboxylic acid. Composition.  [5] The active energy ray-curable type according to [1], wherein the polymer (重量) has a weight average molecular weight of 5,000 to 80,000 and a (meth) aryl group equivalent of 100 to 300 gZeq.榭 Oil composition.  [6] An active energy ray-curable resin composition further comprising a radical polymerizable monomer (C) in addition to the active energy ray-curable resin composition according to claim 1.  [7] An article having a protective layer made of a cured film of the active energy ray-curable resin composition according to [1], wherein the composition is one of claims 1 to 6.  [8] A molded article comprising a cured product of the active energy ray-curable resin composition according to [1] or [1] of claim 1-6.