JP4001180B2 - Active energy ray-curable resin composition for film protective layer and film using the same - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition for a film that can be used as a protective layer for a substrate such as a film or sheet and forms a hardened cured film. Furthermore, the present invention relates to a film having a protective layer made of a cured film of the composition and an optical sheet made of a cured product of the composition.

  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 that are damaged or deformed or internal changes that degrade the materials that make up the article Receive. In order to prevent such a change, a protective layer is provided on the surface of the article, or the article itself is strengthened.

  Plastics are used in various fields for reasons such as good processability, light weight, and low cost. However, the processability is good, but there are drawbacks such as softness and easy scratching on the surface. In order to improve this drawback, it is common to coat a hard coat material and provide a protective layer on the surface. Thermosetting resin compositions such as silicon-based resin compositions, acrylic resin compositions, and melamine-based resin compositions have been used as the hard coat material. However, there were drawbacks such as inapplicable.

  In recent years, the active energy ray-curable resin composition has advantages such as (1) fast curing, (2) low energy cost, and (3) curing at low temperature. It has been adopted rapidly as a coating material. Especially, it is hardened immediately by irradiation of active energy rays such as ultraviolet rays, so it forms a hard film, so the processing speed is fast, it has excellent hardness, scratch resistance, stain resistance, etc. It has become mainstream as a hard coat material.

  Display bodies such as a liquid crystal display, a plasma display, and a touch panel display, which are provided with a film having a hard coat material as a protective layer on the surface, are rapidly spreading. In particular, liquid crystal displays have become larger and are used by an unspecified number of consumers, so hard coat materials used for them have higher hardness, scratch resistance, and curling of the film when cured. It is requested. More recently, when a film or molded body having a hard coat layer is cut into a predetermined shape, the hard coat material has good cutting properties so that the cut surface will not be chipped or cracked, resulting in a defective product. Is required.

  As a method for providing a protective layer on an article, there is a method in which a protective layer laminated on a film-like transfer material is transferred so that it becomes the outermost layer of a molded article after transfer. This transfer method is used for articles in the fields of home appliances, automobiles, etc., and is also used for outer plates of refrigerators, mobile phone casings, and the like. The active energy ray-curable resin composition can also be used for the protective layer laminated on the transfer material, but since it is used by an unspecified number of consumers, higher hardness and scratch resistance are required, and transfer In order to improve the workability at the time of transfer, it is required that the transfer material has a small curl.

  Moreover, since the active energy ray resin composition is immediately cured by irradiation with active energy rays such as ultraviolet rays to form a hard film, when the active energy ray resin composition is cured while being in contact with the mold, the mold Can be transferred, and a molded body having a special shape can be produced. For example, an optical sheet such as a Fresnel lens sheet is manufactured by this method. Also in this production method, an active energy ray curable resin composition having a small curl of the cured film is required for higher hardness and scratch resistance and to improve workability.

  As such an active energy ray-curable resin composition, a polyfunctional product obtained by reacting a radiation curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups and a hydroxyl group in the molecule with a polyisocyanate. A radiation curable resin composition containing urethane acrylate has been proposed (for example, see Patent Document 1). However, the polyfunctional urethane acrylate obtained by addition reaction of pentaerythritol triacrylate and isophorone diisocyanate, which is disclosed as a specific example of this radiation curable resin composition, has a large curling shrinkage due to a large curing shrinkage. There was a problem that the defective product rate was high due to insufficient adhesion to the material and poor cutting properties.

Moreover, an active energy ray-curable resin composition containing a urethane acrylate obtained by reacting a compound having a (meth) acryloyl group and a hydroxyl group in the molecule with 1,4-cyclohexyl diisocyanate has been proposed (for example, (See Patent Document 2). Since this active energy ray-curable resin composition has a large cure shrinkage as in the composition described in Patent Document 1, the curl after curing is large, the adhesion to the film substrate is insufficient, and the cutting property is low. However, there was a problem that the defective product rate was high.
JP 2001-113648 A JP 2002-338628 A

  The problem to be solved by the present invention is that curling generated when an active energy ray-curable resin composition is applied to a substrate such as a film or sheet and then cured by irradiation with active energy rays such as ultraviolet rays is small and high. An active energy ray-curable resin composition for a film protective layer that has a hardness, high scratch resistance, and can obtain a cured film that is not cracked or cracked during cutting, a film having a protective layer comprising the cured film, and the film It is to provide an optical sheet comprising a cured product of the composition.

The present inventors have conducted intensive studies and as a result, and norbornane diisocyanate, bi scan (2- (meth) acryloyloxyethyl) urethane acrylate is an addition reaction product of hydroxyethyl isocyanurate wetting over preparative, 3 or more in one molecule It has a (meth) acryloyl group obtained by reacting a polyfunctional acrylate having a (meth) acryloyl group and / or a glycidyl (meth) acrylate polymer having an epoxy group in the side chain with an α, β-unsaturated carboxylic acid. When the active energy ray-curable resin composition containing a polymer is used, the above-described problems are solved, and the present invention has been completed.

That is, the present invention includes a norbornane diisocyanate (a-1), bi scan (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate wetting over preparative (a-2) an addition reaction in which a urethane acrylate (A) Α, β-unsaturated carboxylic acid to polyfunctional acrylate (B) having 3 or more (meth) acryloyl groups in one molecule and / or glycidyl (meth) acrylate polymer having an epoxy group in the side chain providing a fill arm having a protective layer made of-reacted (meth) polymer (C) characterized as a film protective layer for the active energy ray curable resin composition and a cured film that contains an acryloyl group and To do.

  The active energy ray-curable resin composition of the present invention is small in curing shrinkage and has high hardness and high scratch resistance when cured by irradiation with active energy rays such as ultraviolet rays after being applied to a substrate such as a film or sheet. This is useful as a protective layer for a film. Moreover, since the curl which generate | occur | produces at the time of hardening is small, it can apply also to a large sized film. Furthermore, when the cured film of the active energy ray-curable resin composition of the present invention is cut into a predetermined shape and size together with the film, the cured film is not cracked or chipped, so the defective product rate can be reduced. Therefore, the active energy ray-curable resin composition of the present invention is suitable as a material for a protective layer for an optical film of a large screen display such as a liquid crystal display.

  The active energy ray-curable resin composition of the present invention can also be used as a protective layer for plastic molded 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 film-like transfer material and then transferred to become the outermost layer of the plastic molded body.

The present invention is described in detail below. Urethane acrylate (A) used in the present invention, the norbornane diisocyanate (a-1), bi scan (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate wetting over preparative (a-2) and a compound obtained by addition reaction It is . By using this urethane acrylate (A), after application to a substrate, small curl that occurs when cured by irradiation with active energy rays such as ultraviolet rays, the cured film of high hardness is obtained, the cured film It is possible to suppress cracks and chippings that occur when cutting and cutting the film or molded body . Contact name in the present invention, the term "(meth) acrylate" refers to either or both of methacrylates and acrylates also applies "(meth) acryloyl group" and "(meth) acrylic acid".

The urethane acrylate (A) is obtained by an addition reaction between norbornane diisocyanate (a-1) and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate (a-2). The ratio of bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate (a-2) to 1 equivalent of isocyanate in norbornane diisocyanate (a-1) used in this addition reaction is usually 0. It is the range of 1-50, Preferably, it is 0.1-10, Most preferably, it is 0.9-1.2. The reaction temperature between norbornane diisocyanate (a-1) and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate (a-2) is in the range of 30 to 150 ° C, preferably 50 to 100 ° C. It is. In addition, the end point of reaction can be confirmed by calculating | requiring an isocyanate group content rate by the loss | disappearance of the infrared absorption spectrum of 2,250cm < ^-1 > which shows an isocyanate group, or the method as described in JISK7301-1995, for example.

  Furthermore, a catalyst can be used for the purpose of shortening the reaction time of the addition reaction. Examples of such catalysts include basic catalysts (amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphifin) and acidic catalysts (copper naphthenate). And metal alkoxides such as cobalt naphthenate, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium, and tetrabutoxyzirconium, Lewis acids such as aluminum chloride, and tin compounds such as dibutyltin laurate and dibutyltin acetate). Among these, an acidic catalyst is preferable, and a tin compound is most preferable. A catalyst adds 0.1-1 mass part normally with respect to 100 mass parts of norbornane diisocyanate (a-1).

  In addition, a solvent such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or the like can be used as necessary during the addition reaction. Furthermore, a radically polymerizable compound having no site that reacts with isocyanate, for example, a polyfunctional acrylate (B) described later which does not have a hydroxyl group or amino group and has a relatively low viscosity may be used as a solvent. good. These solvents and radical polymerizable compounds can be used alone or in combination of two or more.

  In addition to the urethane acrylate (A), the active energy ray-curable resin composition of the present invention has a polyfunctional acrylate (B) having 3 or more (meth) acryloyl groups in one molecule and / or a side chain. A polymer (C) having a (meth) acryloyl group obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl (meth) acrylate polymer having an epoxy group is contained.

  Examples of the polyfunctional acrylate (B) include trimethylolpropane tri (meth) acrylate, triethylene oxide-modified trimethylolpropane tri (meth) acrylate, tripropylene oxide-modified glycerol tri (meth) acrylate, and triethylene oxide-modified glycerol tri ( (Meth) acrylate, triepichlorohydrin-modified glycerin tri (meth) acrylate, 1,3,5-triacroylhexahydro-s-triazine, tris (2-acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene oxide modified pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, diethylene oxide-modified ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate (for example, “Kayarad D-310” manufactured by Nippon Kayaku Co., Ltd.), alkyl-modified di Pentaerythritol tetraacrylate (for example, “Kayarad D-320” manufactured by Nippon Kayaku Co., Ltd.), ε-caprolactone-modified dipentaerythritol hexaacrylate (for example, “Kayarad DPCA-20” manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol Pentamethacrylate, dipentaerythritol hexa (meth) acrylate, hexaethylene oxide modified sorbitol hexa (meth) acrylate, hexakis (methacryloyl) And oxyethyl) cyclotriphosphazene (for example, “PPZ” manufactured by Kyoeisha Chemical Co., Ltd.). Among these polyfunctional acrylates, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and tris (2-acryloyloxyethyl) isocyanurate have the effect of increasing the hardness of the cured film. It is preferable because it is large. These polyfunctional acrylates can be used alone or in combination of two or more.

  The polymer (C) having the (meth) acryloyl group has a (meth) acryloyl group obtained by reacting a glycidyl (meth) acrylate polymer having an epoxy group on the side chain with an α, β-unsaturated carboxylic acid. It is a polymer having. The production method of the polymer (C) having the (meth) acryloyl group is not particularly limited, and can be produced by a conventionally known method. Examples thereof include the following production methods.

  The polymer (C) has a (meth) acrylic acid or carboxyl group and an acryloyl group on part or all of the epoxy group of a glycidyl (meth) acrylate polymer or copolymer having an epoxy group in the side chain. It can manufacture by the method of making the compound which has it react and introduce | transducing a (meth) acryloyl group.

  The glycidyl (meth) acrylate-based polymer having an epoxy group in the side chain is made of glycidyl (meth) acrylate or (meth) acrylate having an alicyclic epoxy group (for example, “CYCLOMER M100 manufactured by Daicel Chemical Industries, Ltd.”). ”,“ CYCLOMER A200 ”), and (meth) acrylate having an epoxy group such as 4-hydroxybutyl acrylate glycidyl ether, and obtained by homopolymerizing them.

  A glycidyl (meth) acrylate copolymer having an epoxy group in the side chain has a (meth) acrylate having the epoxy group and a carboxyl group such as (meth) acrylate, styrene, vinyl acetate, acrylonitrile. It can be obtained by copolymerizing two or more monomers using a raw α, β-unsaturated monomer. When an α, β-unsaturated monomer having a carboxyl group is used instead of the α, β-unsaturated monomer having no carboxyl group, the copolymerization reaction with glycidyl (meth) acrylate is carried out. At this time, it is not preferable because a crosslinking reaction is caused to increase the viscosity and gelation.

  Examples of the α, β-unsaturated carboxylic acid that reacts with the glycidyl (meth) acrylate polymer or copolymer having an epoxy group in the side chain include, for example, (meth) acrylic acid, a carboxyl group, and an acryloyl group. Examples thereof include compounds (for example, “Biscoat 2100” manufactured by Osaka Organic Chemical Co., Ltd.).

  The weight average molecular weight of the polymer (C) having a (meth) acryloyl group obtained by the above production method is preferably 5,000 to 80,000, more preferably 5,000 to 50,000, and 8,000 to 35,000 is more preferred. When the weight average molecular weight is 5,000 or more, the effect of reducing curing shrinkage is large, and when it is 80,000 or less, the hardness is sufficiently high.

  The (meth) acryloyl group equivalent of the polymer (C) having a (meth) acryloyl group is preferably from 100 to 400 g / eq, more preferably from 200 to 300 g / eq. When the (meth) acryloyl group equivalent of the polymer (C) having a (meth) acryloyl group is within this range, curing shrinkage can be reduced and the hardness can be sufficiently increased.

  When producing the polymer (C) having a (meth) acryloyl group by the above production method, the weight average molecular weight and (meth) acryloyl group equivalent of the polymer (C) having the (meth) acryloyl group are determined. It is preferable to appropriately select the types of monomers and polymers to be used, the amount of these used, and the like so as to satisfy the requirements.

  When dipentaerythritol pentaacrylate (pentafunctional acrylate) or dipentaerythritol hexaacrylate (hexafunctional acrylate) is used as the polyfunctional acrylate (B), the hardness of the cured film can be increased, but curing shrinkage is reduced. The curl tends to be slightly larger due to its large size. Therefore, when the polymer (C) having the (meth) acryloyl group is used in combination, the curing shrinkage is reduced, so that the hardness of the cured film can be increased while curling is suppressed.

  The blending ratio (mass basis) of the urethane acrylate (A) and the polyfunctional acrylate (B) and the polymer (C) is preferably (A) :( B + C) = 10: 90 to 90:10. More preferably, (A) :( B + C) = 15: 85 to 80:20. If the blending ratio is within this range, curing shrinkage can be reduced while curling is suppressed while maintaining high hardness, and good cutting properties can be obtained.

  The active energy ray-curable resin composition of the present invention includes other radical polymerizable compounds such as N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, N, N-dimethyl ( (Meth) acrylamide, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyl Octyl (meth) acrylate, acryloylmorpholine, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate Rate, tetrahydrofurfuryl (meth) acrylate, ethylenediethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. The monoacrylate may be added.

  Further, the active energy ray-curable resin composition of the present invention has a radical polymerizable compound having an acid group such as a carboxyl group, a phosphoric acid group or a sulfonic acid group, a radical polymerization having an amino group, an alkoxysilyl group or an alkoxy titanyl group. It is preferable to add a functional compound because the adhesion to the substrate can be improved. On the other hand, when a radically polymerizable compound having a fluorocarbon chain, a dimethylsiloxane chain, or a hydrocarbon chain having 12 or more carbon atoms is used, the surface properties of the protective layer such as surface slipperiness, stain resistance, and fingerprint resistance can be improved. Is preferable.

  The active energy ray-curable resin composition of the present invention refers to a composition that cures when irradiated with active energy rays. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy ray, a photopolymerization initiator (D) is added to the active energy ray-curable resin composition. If necessary, a photosensitizer is further added. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no.

  The photopolymerization initiator (D) can be roughly classified into an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Methylphenyl) propan-1-one, oligo 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy Acetophenone compounds such as 2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin Benzoins such as benzoin methyl ether and benzoin isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl, And methylphenylglyoxyester.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, phenyl glyoxylic acid methyl ester, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl- And a mixture of acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester. These photopolymerization initiators (D) can be used alone or in combination of two or more.

  Further, among the photopolymerization initiators (D) listed above, it is preferable to use a photopolymerization initiator having a hydroxyl group because the hardness and scratch resistance of the cured film are improved. Examples of such a photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one and oligo 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl. ] Propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy 2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1-hydroxycyclohexyl-phenyl ketone and the like.

  Furthermore, when an acylphosphine oxide photopolymerization initiator is used as the photopolymerization initiator (D) in addition to the photopolymerization initiator having a hydroxyl group, adhesion with the film substrate is improved and curling of the film is suppressed. It is preferable because it is possible. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoin diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  On the other hand, examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. And the like.

  The amount of these photopolymerization initiators and photosensitizers used is preferably 0.1 to 20% by weight, preferably 0.5 to 10%, based on 100 parts by weight of the resin component in the active energy ray-curable resin composition. The mass% is more preferable.

  Moreover, you may add various additives to the active energy ray hardening-type resin composition of this invention as needed. Examples of such additives include polymerization inhibitors, antioxidants, leveling agents, antifoaming agents, coating surface improvers (such as wettability and slip property improvers), plasticizers, and colorants.

  Furthermore, a diluting solvent for viscosity adjustment may be added to the active energy ray-curable resin composition of the present invention in order to impart applicability to the film substrate. Examples of the diluent solvent include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate and ethyl sorbacetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Etc. These solvents can be used alone or in combination of two or more.

  The cured coating of the active energy ray-curable resin composition of the present invention has a small curing shrinkage and is excellent in high hardness and high scratch resistance, so that it can protect without affecting the film base material due to curling. . Furthermore, since the cut surface is not cracked or chipped when the film having the cured film is cut, the defective product rate at the time of cutting can be reduced. For this reason, the cured film of the active energy ray-curable resin composition of the present invention is effective as a protective layer for various film substrates. As this film base material, a pattern or an easily adhesive layer may be provided. In order to exhibit high hardness and high scratch resistance, the thickness of the cured coating is usually preferably 0.5 to 500 μm, more preferably 3 to 50 μm, and particularly preferably 4 to 30 μm.

The film having a cured coating of the active energy ray-curable resin composition of the present invention is usually 0.5% as the mass of the active energy ray-curable resin composition on the film substrate after drying the resin composition. ˜500 g / m ² (coat thickness 0.5 to 500 μm), preferably 3 to 50 g / m ² (coat thickness 3 to 50 μm), particularly preferably 4 to 30 g / m ² (coat thickness 4 to 30 μm) It can apply | coat, and after drying, it can obtain by irradiating an active energy ray and forming a cured film. In addition, when the mass after drying of the resin composition is less than 0.5 g / m ² , the hardness is not increased due to the influence of the substrate, and when it is 500 g / m ² or more, the deformation of the substrate is caused by the polymerization heat at the time of curing. Therefore, when forming a film thickness of 500 g / m ² or more, a device such as cooling is required.

  Examples of the material for the film substrate include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; and cellulose resins such as triacetyl cellulose. Polystyrene resin, polyamide resin, polycarbonate resin, norbornene resin (for example, “Zeonor” manufactured by Nippon Zeon Co., Ltd.), modified norbornene resin (for example, “Arton” manufactured by JSR Corporation), cyclic olefin copolymer (for example, And “Apel” manufactured by Mitsui Chemicals, Inc.) Among these materials, triacetyl cellulose exhibits excellent adhesion with the cured film of the active energy ray-curable resin composition of the present invention. So preferable Further, a substrate made of these resins may be used by laminating two or more. These film substrate may be a sheet, the thickness of the film substrate, 20 to 500 [mu] m is preferred.

  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, transfer coating, dip coating, and spinner coating. Wheeler coat, brush coating, solid coating with silk screen, wire bar coat, flow coat 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.

  Further, as a method of protecting the plastic molded body with the cured film of the active energy ray-curable resin composition of the present invention, the cured film is formed on the outermost surface before molding the plastic. There is also a method of pasting on the surface of the plastic so that the plastic is molded together 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. Moreover, you may affix on the molded object which shape | molded the plastics what carried out the secondary shaping | molding of the film in which the cured film was formed according to the external shape of this molded object.

  Further, as a method of providing a protective layer on an article formed of a material such as plastic or metal, there is a method of using a transfer film provided with a protective layer made of a cured coating of the active energy ray-curable resin composition of the present invention in advance. . 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, it is possible to impart design properties to the article and at the same time impart high hardness and high scratch resistance to the surface. Moreover, since the active energy ray-curable resin composition of the present invention has a small cure shrinkage, the curl of the transfer film using the resin composition is small, and the workability at the time of transfer is high.

  When the active energy ray-curable resin composition of the present invention is irradiated with ultraviolet rays as an active energy ray, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, black is used as a light generation source. Examples thereof include a light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, sunlight, and an LED. Use of a flashing xenon-flash lamp is effective because the influence of heat on the film substrate is reduced.

  When irradiating an electron beam as an active energy ray, it is preferable to use an electron beam accelerator having an acceleration voltage of 30 to 300 kV. In addition, when the resin of the film base has an aromatic skeleton that is easily yellowed by an electron beam or when the resin is easily deteriorated by an electron beam, for example, a cellulose-based resin, a polyester-based resin, a polystyrene-based resin, a polyamide is used as the film base. In the case of using a system resin, a polycarbonate system resin, or the like, when the acceleration voltage is set to 30 to 150 kV, yellowing or deterioration of the film base material can be prevented.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following examples, “%” and “part” are based on mass.

Synthesis Example 1 Synthesis of Urethane Acrylate (1) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 250 parts of butyl acetate, 206 parts of norbornane diisocyanate (hereinafter referred to as “NBDI”), and methoxy. After adding 0.5 part of hydroquinone and 0.5 part of dibutyltin diacetate and raising the temperature to 70 ° C. while blowing air, pentaerythritol triacrylate (hereinafter referred to as “PE3A”) / pentaerythritol tetraacrylate (hereinafter referred to as “PE3A”) , "PE4A") 795 parts of a mixture (a mixture with a mass ratio of 75/25) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ indicating an isocyanate group disappeared, and then a urethane acrylate (1) / PE4A mixture (a mixture with a mass ratio of 80/20, non-volatile). 80% butyl acetate solution).

Synthesis Example 2 Synthesis of Urethane Acrylate (2) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 576 parts of butyl acetate, NBDI 206, 1.2 parts of methoxyhydroquinone, dibutyltin diacetate After charging 2 parts and heating to 70 ° C., a dipentaerythritol pentaacrylate (hereinafter referred to as “DPPA”) / dipentaerythritol hexaacrylate (hereinafter referred to as “DPHA”) mixture (with a mass ratio of 50/50) 2096 parts of the mixture 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 an isocyanate group disappears, and then a urethane acrylate (2) / DPHA mixture (a mixture with a mass ratio of 54/46, non-volatile). 80% butyl acetate solution).

Synthesis Example 3 Synthesis of Urethane Acrylate (3) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 252 parts of butyl acetate, 206 parts of NBDI, 0.5 part of methoxyhydroquinone, dibutyltin diacetate 0 .5 parts was charged and heated to 70 ° C. while blowing air, and then bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate (hereinafter referred to as “BAHIC”) / tris (2-acryloyloxyethyl) isocyanate. 1318 parts of a nurate (hereinafter referred to as “TAIC”) mixture (mixture having a mass ratio of 56/44) 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, and then urethane acrylate (3) / TAIC mixture (mixture of mass ratio 62/38, non-volatile) 80% butyl acetate solution).

Synthesis Example 4 Synthesis of Urethane Acrylate (4) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 254 parts of butyl acetate, 222 parts of isophorone diisocyanate (hereinafter referred to as “IPDI”), methoxy After adding 0.5 part of hydroquinone and 0.5 part of dibutyltin diacetate and heating to 70 ° C., 795 parts of a PE3A / PE4A mixture (mixture having 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 an isocyanate group disappears, and then a urethane acrylate (4) / PE4A mixture (a mixture with a mass ratio of 80/20, non-volatile). 80% butyl acetate solution).

Synthesis Example 5 Synthesis of Urethane Acrylate (5) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 566 parts of butyl acetate, 168 parts of hexamethylene diisocyanate (hereinafter referred to as “HDI”), After adding 0.5 part of methoxyhydroquinone and 0.5 part of dibutyltin diacetate and raising the temperature to 70 ° C., 2096 parts of a DPPA / DPHA mixture (mixture having a mass ratio of 50/50) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ indicating the isocyanate group disappeared, and then a urethane acrylate (5) / DPHA mixture (a mixture with a mass ratio of 54/46, non-volatile). 80%).

(Synthesis Example 6) Synthesis of Urethane Acrylate (6) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 264 parts of butyl acetate, methylenebis (4-cyclohexylisocyanate) (hereinafter “hydrogenated MDI”) 262 parts, methoxyhydroquinone 0.5 parts and dibutyltin diacetate 0.5 parts were charged and the temperature was raised to 70 ° C., then 795 parts of a PE3A / PE4A mixture (a mixture with a mass ratio of 75/25) was added for 1 hour. It was dripped over. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ indicating an isocyanate group disappeared, and a urethane acrylate (6) / PE4A mixture (a mixture of mass ratio 81/19, nonvolatile) 80% butyl acetate solution).

Synthesis Example 7 Synthesis of Urethane Acrylate (7) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 240 parts of butyl acetate and 1,4-cyclohexyl diisocyanate (hereinafter referred to as “CHDI”). 166 parts, 0.5 part of methoxyhydroquinone and 0.5 part of dibutyltin diacetate were charged and the temperature was raised to 70 ° C., and then 795 parts of a PE3A / PE4A mixture (mixture with a mass ratio of 75/25) was added dropwise over 1 hour. did. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappeared, and a urethane acrylate (7) / PE4A mixture (mixture with a mass ratio of 79/21, non-volatile) 80% butyl acetate solution).

(Synthesis Example 8) Synthesis of polymer (1) having acryloyl group In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 250 parts of glycidyl methacrylate (hereinafter referred to as “GMA”), lauryl mercaptan 1.6 parts, 1000 parts of methyl isobutyl ketone (hereinafter referred to as “MIBK”) and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) were charged in a nitrogen stream. The mixture was heated to 90 ° C. over 1 hour while being stirred at 50 ° C. and reacted at 90 ° C. for 1 hour. Next, while stirring at 90 ° C., a mixed solution consisting of 750 parts of GMA, 4.4 parts of lauryl mercaptan, and 22.5 parts of AIBN was dropped over 2 hours, and then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts of AIBN was charged and further reacted at 100 ° C. for 1 hour, and then heated to around 120 ° C. and reacted for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube is replaced with an air inlet tube, 507 parts of acrylic acid (hereinafter referred to as “AA”), 2.0 parts of methoquinone, and 5.4 parts of triphenylphosphine are added and mixed. While bubbling the reaction solution with air, the temperature was raised to 110 ° C. and reacted for 8 hours. Thereafter, 1.4 parts of methoquinone was added, and after cooling to room temperature, MIBK was added so that the nonvolatile content was 50%, to obtain a polymer (1) having an acryloyl group (MIBK solution having a nonvolatile content of 50%). . In addition, the weight average molecular weight of the obtained polymer (1) having an acryloyl group was 11,000 (in terms of polystyrene by GPC), and the acryloyl group equivalent was 300 g / eq.

( Reference Example 1)
125 parts of urethane acrylate (1) / PE4A mixture obtained in Synthesis Example 1 (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80%), 1-hydroxycyclohexyl-phenylketone (Ciba Specialty Chemicals Co., Ltd.) "Irgacure 184" manufactured by company; hereinafter referred to as "HCPK") 5 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Lucirin TPO" manufactured by BASF Japan Ltd .; hereinafter referred to as "TPO") 2 parts Then, 33 parts of ethyl acetate and 42 parts of butyl acetate were mixed, heated to 40 ° C. and mixed to obtain a uniform active energy ray-curable resin composition.

( Reference Example 2)
100 parts of the urethane acrylate (2) / PE4A mixture obtained in Synthesis Example 1 (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80%), DPHA / DPPA mixture (mixture with a mass ratio of 70/30) 20 Part, HCPK 3 parts, TPO 4 parts, ethyl acetate 33 parts, and butyl acetate 47 parts were mixed, heated to 40 ° C. and mixed to obtain an active energy ray-curable resin composition.

( Reference Example 3)
50 parts of the urethane acrylate (1) / PE4A mixture obtained in Synthesis Example 1 (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80%), DPHA / DPPA mixture (mixture with a mass ratio of 70/30) 20 80 parts of the acryloyl group-containing polymer (1) obtained in Synthesis Example 8 (MIBK solution having a nonvolatile content of 50%), 2 parts of HCPK, 1.5 parts of TPO, 33 parts of ethyl acetate, and 17 parts of butyl acetate And heated to 40 ° C. and mixed to obtain an active energy ray-curable resin composition.

( Reference Example 4)
75 parts of urethane acrylate (2) / DPHA mixture obtained in Synthesis Example 2 (mixture with a mass ratio of 54/46, butyl acetate solution having a nonvolatile content of 80%), polymer having an acryloyl group obtained in Synthesis Example 8 ( 1) (MIBK solution having a nonvolatile content of 50%) 80 parts, TPO 2 parts, 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Ciba Specialty Chemicals Co., Ltd.); 4 parts, 33 parts of ethyl acetate, and 12 parts of butyl acetate were mixed, heated to 40 ° C. and mixed to obtain an active energy ray-curable resin composition.

(Example 1 )
Urethane acrylate (3) / TAIC mixture obtained in Synthesis Example 3 (mixture with a mass ratio of 62/38, butyl acetate solution with a nonvolatile content of 80%), 37.5 parts, DPHA / DPPA mixture (mixture with a mass ratio of 70/30) ) 70 parts, 2 parts HCPK, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure 819” manufactured by Ciba Specialty Chemicals Co., Ltd .; hereinafter referred to as “BAPO”) 1 part, ethyl acetate 33 And 59.5 parts of butyl acetate were mixed, heated to 40 ° C. and mixed to obtain a uniform active energy ray-curable resin composition.

( Reference Example 5 )
50 parts of the urethane acrylate (1) / PE4A mixture obtained in Synthesis Example 1 (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80%), DPHA / DPPA mixture (mixture with a mass ratio of 70/30) 10 Part, PE4A 20 parts, TAIC 30 parts, HCPK 4 parts, TPO 1 part, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty Chemicals) “Irgacure 2959” manufactured by Co., Ltd .; hereinafter referred to as “HHPO”) 1 part, 33 parts of ethyl acetate and 57 parts of butyl acetate are mixed, heated to 40 ° C. and mixed to obtain an active energy ray-curable resin. A composition was obtained.

(Comparative Example 1)
100 parts of urethane acrylate (4) / PE4A mixture obtained in Synthesis Example 4 (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80%), DPHA / DPPA mixture (mixture with a mass ratio of 70/30) 20 Part, HCPK 3 parts, TPO 4 parts, ethyl acetate 33 parts, and butyl acetate 47 parts were mixed, heated to 40 ° C. and mixed to obtain an active energy ray-curable resin composition.

(Comparative Example 2)
75 parts of urethane acrylate (5) / DPHA mixture (mixture of mass ratio 54/46, nonvolatile content 80%) obtained in Synthesis Example 5, TAIC 40 parts, HCPK 1.5 parts, BAPO 1 part, ethyl acetate 33 parts, and acetic acid 52 parts of butyl was mixed, heated to 40 ° C. and mixed to obtain a uniform active energy ray-curable resin composition.

(Comparative Example 3)
Urethane acrylate (6) / PE4A mixture obtained in Synthesis Example 6 (mixture with a mass ratio of 81/19, butyl acetate solution with a nonvolatile content of 80%), 37.5 parts, DPHA / DPPA mixture (mixture with a mass ratio of 70/30) ) 70 parts, 2 parts of HCPK, 1 part of BAPO, 33 parts of ethyl acetate, and 59.5 parts of butyl acetate were mixed after heating to 40 ° C. to obtain an active energy ray-curable resin composition.

(Comparative Example 4)
62.5 parts of urethane acrylate (7) / PE4A mixture obtained in Synthesis Example 7 (mixture with a mass ratio of 79/21, butyl acetate solution with a nonvolatile content of 80%), DPHA / DPPA mixture (mixture with a mass ratio of 70/30) ) 50 parts, HCPK 2 parts, TPO 1.5 parts, ethyl acetate 33 parts, and butyl acetate 54.5 parts were mixed, heated to 40 ° C. and mixed to obtain an active energy ray-curable resin composition. .

(Comparative Example 5)
50 parts of the urethane acrylate (1) / PE4A mixture obtained in Synthesis Example 1 (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80%), DPHA / DPPA mixture (mixture with a mass ratio of 70/30) 10 Part, 20 parts of PE4A, 30 parts of TAIC, 6 parts of TPO, 33 parts of ethyl acetate, and 57 parts of butyl acetate were mixed after heating to 40 ° C. to obtain an active energy ray-curable resin composition.

Table 1 shows the composition of each component of the active energy ray-curable resin compositions obtained in Example 1 and Reference Examples 1 to 4 , and the active energy ray-curable resin compositions obtained in Comparative Examples 1 to 5 Table 2 shows the composition of each component of the product.

(Production of evaluation film)
The active energy ray-curable resin compositions obtained in Example 1 above , Reference Examples 1 to 4 and Comparative Examples 1 to 5 were converted into triacetyl cellulose (TAC) film ("TAC" manufactured by Fuji Photo Film Co., Ltd., thickness). : 80 μm) or polyethylene terephthalate (PET) film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd., thickness: 100 μm, coated on easy-adhesion treated surface) using a wire bar, and heated at 60 ° C. for 1 minute In an air atmosphere, an ultraviolet irradiation device (“Part S30 type UV irradiation device” manufactured by Nippon Battery Co., Ltd., lamp: 120 W / cm 2 metal halide lamps, lamp height: 20 cm, irradiation light quantity: 0.5 J / cm ² ) The film was irradiated with ultraviolet rays to obtain films having cured films with film thicknesses of 10 μm, 20 μm and 30 μm.

(Evaluation of surface hardness of evaluation film)
About the surface of the cured film of the film for evaluation (cured film thickness: 20 μm) obtained above, the pencil hardness is measured with a load of 500 g in accordance with JIS K5600-5-4: 1999, and the surface according to the following criteria. Hardness was evaluated.
◎: Pencil hardness is 4H or more ○: Pencil hardness is 3H
X: Pencil hardness is 2H or less

(Evaluation of scratch resistance of evaluation film)
Regarding the surface of the cured film of the evaluation film (cured film thickness: 10 μm) obtained above, in accordance with JIS K6404-16: 1999, a clock meter type friction tester, 2.8 cm diameter circular friction element, steel Evaluation was made under the conditions of wool # 0000, load 1.5 kg, 100 reciprocations, and the abrasion scratch resistance was visually determined according to the following criteria.
○: No scratch Δ: 1 to 4 scratches ×: 5 or more scratches

(Evaluation of curl of evaluation film)
A 100 mm × 100 mm test piece was cut out from the evaluation film (cured film thickness: 10 μm) obtained above, and left for 24 hours in an atmosphere of 23 ° C. and 65% RH, and then adjacent to the four ends of the test piece. The length between the two points is measured, the smallest length between the two adjacent points and the length between the other two points are measured, and the curl value is calculated by the following equation.
Curl value (mm) = 100− (minimum length between two adjacent points + length between two adjacent points) / 2

From the curl value obtained above, the curl property was evaluated according to the following criteria.
A: Curl value is 10 mm or less B: Curl value exceeds 10 mm, 12 mm or less ×: Curl value exceeds 12 mm

(Evaluation of adhesion of cured film to substrate)
In accordance with JIS K5600-5-6: 1999, the film for evaluation obtained above (cured film thickness: 10 μm) is cut in 6 vertical and horizontal cuts at 1 mm intervals on the cured film surface of the film. Made 25 grids. Next, after the commercially available cellophane tape was brought into close contact with the surface and then peeled off at once, the number of cells remaining without being peeled was counted, and the adhesion was evaluated according to the following criteria.
○: Number of remaining squares is 25 Δ: Number of remaining squares is 24 ×: Number of remaining squares is less than 24

(Evaluation of cutting properties of evaluation film)
The film for evaluation (film thickness of the cured coating: 30 μm) obtained above was punched out using a dumbbell cutter made of Dumbbell Co., Ltd. Super Dumbbell (shape of No. 2 type test piece described in JIS K7113-1995). Next, the cutting part of the evaluation film punched out was confirmed with a microscope, and the cutting property was evaluated according to the following criteria.
○: Cracks, chips and cracks in the cut part are 0.1 mm or less and the cut part is smooth.
X: The cut part has cracks, chips and cracks where the size of the crack exceeds 0.1 mm, and the cut part is not smooth.

  The evaluation results are shown in Tables 1 and 2.

From the evaluation results of Example 1 shown in Table 1, the film having a cured coating of the active energy ray-curable resin composition for a film of the present invention has small curl, high surface hardness, scratch resistance, and cutting ability. I found it excellent. Moreover, it turned out that the cured film of the active energy ray hardening-type resin composition for films of this invention is excellent also in adhesiveness with a film base material.

  From the evaluation results of Comparative Examples 1 to 5 shown in Table 2, the following was found.

  Comparative Example 1 is an example using urethane acrylate (4) synthesized using isophorone diisocyanate instead of norbornane diisocyanate, but the film having a cured coating of this resin composition has a large curl (the film substrate is In the case of TAC), it was found that the scratch resistance and cutting properties were insufficient. Moreover, it turned out that the cured film of this resin composition is also insufficient in adhesiveness with a film base material.

  Comparative Example 2 is an example of an active energy ray-curable resin composition containing urethane acrylate (5) synthesized using hexamethylene diisocyanate instead of norbornane diisocyanate. A film having a cured coating of this resin composition Was found to have a large curl and insufficient scratch resistance and cutting properties. Moreover, it turned out that the cured film of this resin composition is also insufficient in adhesiveness with a film base material.

  Comparative Example 3 is an example of an active energy ray-curable resin composition containing urethane acrylate (6) synthesized using methylene bis (4-cyclohexyl isocyanate) instead of norbornane diisocyanate. It was found that a film having a coating film has large curl, low surface hardness, and insufficient scratch resistance. Moreover, it turned out that the cured film of this resin composition is also insufficient in adhesiveness with a film base material.

Comparative Example 4 is an example of an active energy ray-curable resin composition containing urethane acrylate (7) synthesized using 1,4-cyclohexyl diisocyanate instead of norbornane diisocyanate. The cured film of this resin composition It was found that the film having a large curl (when the film substrate is TAC), the surface hardness is low, and the scratch resistance and the cutting property are insufficient. Moreover, it turned out that the cured film of this resin composition is also insufficient in adhesiveness with a film base material.
Was found to have low surface hardness, large curl, and poor adhesion and cutting.

  Comparative Example 5 is an example of an active energy ray-curable resin composition containing urethane acrylate (4) synthesized using isophorone diisocyanate instead of norbornane diisocyanate. A film having a cured coating of this resin composition is It was found that the surface hardness was low and the scratch resistance was insufficient. Moreover, it turned out that the cured film of this resin composition is also insufficient in adhesiveness with a film base material.

Claims (5)

And norbornane diisocyanate (a-1), bi scan (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate wetting over preparative (a-2) an addition reaction in which a urethane acrylate (A), in one molecule 3 An α, β-unsaturated carboxylic acid was reacted with a polyfunctional acrylate (B) having at least one (meth) acryloyl group and / or a glycidyl (meth) acrylate polymer having an epoxy group on the side chain (meta ) An active energy ray-curable resin composition for a film protective layer, comprising a polymer (C) having an acryloyl group.   The polyfunctional acrylate (B) is at least one selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and tris (2-acryloyloxyethyl) isocyanurate. The active energy ray-curable resin composition for a film protective layer according to claim 1, which is a polyfunctional acrylate.   The active energy ray-curable resin composition for a film protective layer according to claim 1, comprising a photopolymerization initiator having a hydroxyl group as the photopolymerization initiator (D).   The active energy ray-curable resin composition for a film protective layer according to claim 1, comprising a photopolymerization initiator having a hydroxyl group and an acylphosphine oxide photopolymerization initiator as the photopolymerization initiator (D).   A film comprising a protective layer comprising a cured film of the active energy ray-curable resin composition for a film protective layer according to any one of claims 1 to 4.