JP6958553B2 - Active energy ray-curable resin composition and laminated film - Google Patents

Description

The present invention has an active energy ray-curable resin composition that has both surface hardness and flexibility in a cured coating film and is unlikely to cause interference fringes in a laminated film, a coating material containing the same, a coating film made of the coating film, and a laminated film. Regarding.

The inorganic fine particle dispersion type resin material obtained by dispersing the inorganic fine particles in the resin component has higher hardness of the cured coating film, improved scratch resistance, and blocking resistance as compared with the resin material consisting only of the organic material. In recent years, it has been attracting attention as a new material that enables the addition of high performance and new functions. The inorganic fine particle dispersion type resin material has various uses. For example, it is widely used as a hard coating agent for protecting a molded product, a display surface, and various film materials from scratches.

Silica and alumina are relatively widely used as the inorganic fine particles used in the inorganic fine particle dispersion type resin material. For example, acrylic having an acryloyl group equivalent of 214 g / eq, a hydroxyl value of 262 mgKOH / g, and a weight average molecular weight (Mw) of 40,000. Reactive dispersions containing a polymer and alumina fine particles or zirconia fine particles having an average particle size in the range of 55 to 90 nm are known (see Patent Document 1). The reactive dispersion described in Patent Document 1 has a feature that the surface hardness of the cured product is higher and the scratch resistance is excellent as compared with the hard coating agent composed only of an organic type, but the flexibility and curl resistance are high. It was not sufficient, and interference fringes were likely to occur when it was applied on a plastic film to form a laminated film, and the performance required by the market could not be fully met.

Japanese Unexamined Patent Publication No. 2007-289943

Therefore, the problem to be solved by the present invention is an active energy ray-curable resin composition having both surface hardness and flexibility in a cured coating film and less likely to cause interference fringes in a laminated film, a coating material containing the same, and the like. It is an object of the present invention to provide a coating film and a laminated film made of a paint.

As a result of diligent studies to solve the above problems, the present inventor has determined that the active energy ray-curable resin composition containing barium sulfate fine particles having an average particle diameter in the range of 60 to 250 nm has a surface hardness in a cured product. It has been found that it has flexibility and that interference fringes are less likely to occur in the laminated film, and the present invention has been completed.

That is, the present invention relates to an active energy ray-curable resin composition containing barium sulfate fine particles (A) having an average particle diameter in the range of 60 to 250 nm and a matrix resin (B) having a (meth) acryloyl group.

The present invention further relates to a coating material containing the active energy ray-curable resin composition.

The present invention further relates to a coating film composed of the above-mentioned paint.

The present invention further relates to a laminated film having a layer composed of the coating film.

According to the present invention, an active energy ray-curable resin composition having both surface hardness and flexibility in a cured coating film and less likely to cause interference fringes in a laminated film, a coating material containing the same, a coating film composed of the coating film and the like. Laminated films can be provided.

The active energy ray-curable resin composition of the present invention contains barium sulfate fine particles (A) having an average particle diameter in the range of 60 to 250 nm and a matrix resin (B) having a (meth) acryloyl group.

The barium sulfate fine particles (A) can be obtained by dispersing the raw material barium sulfate fine particles (a) in a matrix resin (B) or a mixture of the matrix resin (B) and an organic solvent or the like. The average particle size of the barium sulfate fine particles (A) is a value obtained by measuring the average particle size in a state of being dispersed in the active energy ray-curable resin composition by the following method. The average particle size of the barium sulfate fine particles (A) is 60 to 250 nm, which is more excellent in the balance between surface hardness and flexibility in the cured product, and is more preferably in the range of 70 to 200 nm, preferably 80 to 120 nm. The range is particularly preferred.

[Method for measuring average particle size of barium sulfate fine particles (A)]
Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.
Particle size measurement sample: An active energy ray-curable resin composition diluted with methyl isobutyl ketone to adjust the concentration of barium sulfate fine particles (A) to 0.2% by mass.

The barium sulfate fine particles (a), which are raw materials, are, for example, those produced using barium sulfide and sulfuric acid, those produced using barium chloride and sodium sulfate, and the surface of these particles are alumina and silica. , Those modified with various silane coupling agents and the like, and those available as commercially available products can be preferably used. Examples of commercially available products include barium sulfate manufactured by Sakai Chemical Industry Co., Ltd., and special products such as the BARIFINE series, the BARIACE series in which the particle surface of barium sulfate fine particles is modified with alumina or silica, and "barium sulfate BB-02". Product series etc. can be mentioned. The average particle size of the barium sulfate fine particles (a) is preferably in the range of 0.001 to 0.15 μm.

The specific structure of the matrix resin (B) having a (meth) acryloyl group is not particularly limited as long as it has a (meth) acryloyl group that causes polymerization by irradiation with active energy rays, and a wide variety of the same can be used. Can be used. The matrix resin (B) can be classified into, for example, a (meth) acrylate resin (B1) and a (meth) acrylate monomer (B2).

The (meth) acrylate resin (B1) includes, for example, a (meth) acryloyl group-containing acrylic resin (B1-1), a dendrimer-type poly (meth) acrylate resin (B1-2), and a urethane (meth) acrylate resin (B1-). 3), epoxy (meth) acrylate resin (B1-4) and the like can be mentioned. Further, the (meth) acrylate resin (B1) preferably has a molecular weight distribution and a weight average molecular weight (Mw) of 1,000 to 50,000. Each of these may be used alone, or two or more types may be used in combination.

The acrylic resin (B1-1) having a (meth) acryloyl group contains, for example, a (meth) acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group as an essential component. It is obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate monomer (β) having a reactive functional group capable of reacting with these functional groups with an acrylic resin intermediate obtained by polymerization. Things can be mentioned.

The (meth) acrylate monomer (α) having a reactive functional group is, for example, a hydroxyl group-containing (meth) such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and dihydroxypropyl acrylate. Acrylate;

(Meta) acrylic acid, (acryloyloxy) acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 1- [2- (acryloyloxy) ethyl] succinate, -1- (2-acryloyloxy) phthalate Ethyl), carboxy group-containing (meth) acrylates such as 2- (acryloyloxy) ethyl hexahydrophthalate;

Isocyanate group-containing (meth) acrylates such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate;

Examples thereof include glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether. Each of these may be used alone, or two or more types may be used in combination.

Among these, since the production of the acrylic resin (B1-1) having the (meth) acryloyl group is simple, the (meth) acrylate monomer (α) having the reactive functional group contains a carboxy group (meth). It is preferable to use acrylate or glycidyl group-containing (meth) acrylate.

The acrylic resin intermediate may be obtained by copolymerizing the (meth) acrylate monomer (α) having a reactive functional group and other polymerizable unsaturated group-containing compounds according to the copolymerization. ..

The other polymerizable unsaturated group-containing compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and the like. Heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, (Meta) acrylic acid alkyl ester such as stearyl (meth) acrylate;

Cyclo ring-containing (meth) acrylates such as cyclohexyl (meth) acrylate, isobolonyl (meth) acrylate, and dicyclopentanyl (meth) acrylate;

Aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl acrylate;

A silyl group-containing (meth) acrylate such as 3-methacryloxypropyltrimethoxysilane;

N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate;

2,2,2-Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, A (per) fluoroalkyl (meth) acrylate having a (per) fluoroalkyl group having a carbon number in the range of 1 to 18 such as 2H-heptadecafluorodecyl (meth) acrylate and perfluoroethyloxyethyl (meth) acrylate;

A (per) fluoroalkyl group having a carbon number in the range of 1 to 18 such as trifluoromethyltrifluorovinyl ether, pentafluoroethyltrifluorovinyl ether, and heptafluoropropyltrifluorovinyl ether;

Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconic acid, dibutyl itaconic acid, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconic acid;

Styrene derivatives such as styrene, α-methylstyrene, chlorostyrene;

Diene compounds such as butadiene, isoprene, piperylene, and dimethyl butadiene;

Vinyl halides such as vinyl chloride and vinyl bromide or vinylidene halides;

Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;

Vinyl esters such as vinyl acetate and vinyl butyrate;

Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;

Vinyl cyanide such as acrylonitrile, methacrylonitrile, vinylidene cyanide;

Acrylamide or its alkyd substituted amide;

N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

Examples thereof include fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene and hexafluoropropylene. Each of these may be used alone, or two or more types may be used in combination.

Among these other polymerizable unsaturated group-containing compounds, the above-mentioned (meth) acrylic acid alkyl ester can be used because it is an active energy ray-curable resin composition having excellent surface hardness and flexibility in a cured coating film. preferable.

When the acrylic resin intermediate is obtained by copolymerizing the (meth) acrylate monomer (α) having the reactive functional group with the other polymerizable unsaturated group-containing compound, the reaction between the two. Since the ratio is the (meth) acryloyl group-containing acrylic resin (B1-1) having excellent curability, the ratio of the (meth) acrylate monomer (α) having the reactive functional group to the total of both is 30 to 90. The range is preferably in the range of parts by mass, more preferably in the range of 40 to 80 parts by mass, and particularly preferably in the range of 50 to 70 parts by mass.

The acrylic resin intermediate can be produced, for example, by polymerizing various monomers in a temperature range of 60 ° C. to 150 ° C. in the presence of a polymerization initiator. Examples of the polymerization method include a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. In addition, examples of the polymerization mode include random copolymers, block copolymers, graft copolymers, and the like. When the solution polymerization method is used, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone or a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether is preferably used. Can be done.

Next, the (meth) acrylate monomer (β) to be reacted with the obtained acrylic resin intermediate is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate monomer (α). , The following combinations are preferable from the viewpoint of reactivity. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the carboxy group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the glycidyl group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the hydroxyl group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the glycidyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the carboxy group-containing (meth) acrylate as the (meth) acrylate monomer (β).

The reaction between the acrylic resin intermediate and the (meth) acrylate monomer (β) is, for example, an esterification catalyst such as triphenylphosphine in a temperature range of 60 to 150 ° C. when the reaction is an esterification reaction. Can be mentioned as appropriate. When the reaction is a urethanization reaction, a method of reacting the compound (α) while dropping the compound (α) on the acrylic resin intermediate in a temperature range of 50 to 120 ° C. can be mentioned.

The weight average molecular weight (Mw) of the (meth) acryloyl group-containing acrylic resin (B1-1) is an active energy ray-curable resin composition having excellent surface hardness and flexibility in a cured coating film. The range is preferably in the range of 000 to 80,000, more preferably in the range of 10,000 to 50,000. The (meth) acryloyl group equivalent of the (meth) acryloyl group-containing acrylic resin (B1-1) is preferably in the range of 200 to 500 g / equivalent.

In the present invention, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mn / Mw) are values measured by a gel permeation chromatograph (GPC) under the following conditions.

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column H _XL- H manufactured by Tosoh Corporation
_{+ TSKgel G5000H XL} manufactured by Tosoh Corporation
_{+ TSKgel G4000H XL} manufactured by Tosoh Corporation
_{+ TSKgel G3000H XL} manufactured by Tosoh Corporation
_{+ TSKgel G2000H XL} manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard; Polystyrene sample; 0.4 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

The dendrimer-type poly (meth) acrylate resin (B1-2) refers to a resin having a regular multi-branched structure and a (meth) acryloyl group at the end of each branched chain, and is a dendrimer-type poly (meth) acrylate resin. In addition, it is called hyperbranched type or star polymer. Examples of such a compound include those represented by the following structural formulas (1-1) to (1-8), but are not limited thereto, and have a regular multi-branched structure. Any resin having a (meth) acryloyl group at the end of each branched chain can be used.

（式中Ｒ^１は水素原子又はメチル基を表し、Ｒ^２は炭素原子数１〜４の炭化水素基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 4 carbon atoms.)

As a dendrimer type poly (meth) acrylate resin (B1-2) having such a molecular structure, "Viscoat # 1000" manufactured by Osaka Organic Chemical Co., Ltd. [Weight average molecular weight (Mw) 1,500 to 2,000, one molecule Average (meth) acryloyl group number 14], "Viscort 1020" [weight average molecular weight (Mw) 1,000 to 3,000], "SIRIUS501" [weight average molecular weight (Mw) 15,000 to 23,000], MIWON "SP-1106" [weight average molecular weight (Mw) 1,630, average (meth) acryloyl group number 18 per molecule], SARTOMER "CN2301", "CN2302" [average per molecule (meth) ) Acryloyl group number 16], "CN2303" [average (meth) acryloyl group number 6 per molecule], "CN2304" [average (meth) acryloyl group number 18 per molecule], "Esdrimer HU-" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation 22 ”,“ A-HBR-5 ”manufactured by Shin-Nakamura Chemical Co., Ltd.,“ New Frontier R-1150 ”manufactured by Daiichi Kogyo Seiyaku Co., Ltd.,“ Hypertech UR-101 ”manufactured by Nissan Chemical Co., Ltd. You may. Each of these may be used alone, or two or more types may be used in combination.

Among the dendrimer-type poly (meth) acrylate resins (B1-2), the average number of (meth) acryloyl groups per molecule is 5 to 50 because the cured coating film has an excellent balance between surface hardness and flexibility. It is preferably in the range, particularly preferably in the range of 10 to 30. The weight average molecular weight (Mw) is preferably in the range of 1,000 to 30,000.

The urethane (meth) acrylate resin (B1-3) is prepared by reacting, for example, various polyisocyanate compounds, monohydroxy (meth) acrylate compounds, and if necessary, dihydroxy (meth) acrylate compounds and various polyol compounds. What can be obtained is mentioned.

The polyisocyanate compound is an aliphatic diisocyanate compound such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate, isophorone diisocyanate, water. Alicyclic diisocyanate compounds such as supplemented xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalenedi isocyanate; Polymethylene polyphenyl polyisocyanate having a repeating structure represented by (2); examples thereof include isocyanurate-modified products, biuret-modified products, and allophanate-modified products.

［式中、Ｒ^３はそれぞれ独立に水素原子、炭素原子数１〜６の炭化水素基の何れかである。Ｒ^４はそれぞれ独立に炭素原子数１〜４のアルキル基、又は構造式（２）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｍは０又は１〜３の整数であり、ｌは１以上の整数である。］

[In the formula, R ³ is independently either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁴ is either an alkyl group having 1 to 4 carbon atoms independently, or a bond point connected to a structural site represented by the structural formula (2) via a methylene group marked with *. m is an integer of 0 or 1-3, and l is an integer of 1 or more. ]

The monohydroxy (meth) acrylate compound is, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth). Examples thereof include acrylates and their polyoxyalkylene modified products and polylactone modified products.

The dihydroxy (meth) acrylate compound includes, for example, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and polyoxyalkylene modified products and polylactone modified products thereof. Can be mentioned.

Examples of the polyol compound include ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (B1-3) is preferably in the range of 1,000 to 5,000. The (meth) acryloyl group equivalent is preferably in the range of 100 to 400 g / equivalent.

The epoxy (meth) acrylate resin (B1-4) is a bisphenol compound, a biphenol compound, ethylene glycol, proprene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, penta. Examples thereof include those obtained by reacting polyglycidyl ether of a polyol compound such as erythritol with (meth) acrylic acid and the like.

Among these (meth) acrylate resins (B1), the (meth) acryloyl group-containing acrylic resin (B1-1) and the dendrimer-type poly (meth) are excellent in dispersion stability of the barium sulfate fine particles (A). It is preferable to use any one or more of the acrylate resin (B1-2) and the urethane (meth) acrylate resin (B1-3) as essential components.

The (meth) acrylate monomer (B2) is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( Meta) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydroflufreele acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3- Methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide-modified phenoxy (meth) acrylate, propylene oxide-modified Phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolythylene glycol (meth) acrylate, methoxypropylene glycol ( Meta) Acrylate, 2- (Meta) Acryloyloxyethyl-2-hydroxypropylphthalate, 2-Hydroxy-3-phenoxypropyl (Meta) Acrylate, 2- (Meta) Acryloyloxyethyl Hydrogenphthalate, 2- (Meta) Acryloyloxy Propylhydrogenphthalate, 2- (meth) acryloyloxypropylhexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyltetrahydrohydrogenphthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) ) Acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, a Mono (meth) acrylates such as damantyl mono (meth) acrylates;

Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, di (meth) acrylate such as neopentyl glycol di (meth) acrylate of hydroxypivalate;

Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris2-hydroxyethylisocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate Etc. Tri (meth) acrylate;

Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tetra (meth) Tetrafunctional or higher (meth) acrylates such as acrylates, dipentaerythritol penta (meth) acrylates, ditrimethylolpropanpenta (meth) acrylates, dipentaerythritol hexa (meth) acrylates, and ditrimethylolpropanehexa (meth) acrylates;

Examples thereof include a modified (meth) acrylate monomer in which a (poly) oxyalkylene chain or a (poly) lactone structure is introduced into the molecular structure of the various (meth) acrylate monomers. Each of these may be used alone, or two or more types may be used in combination.

Among these (meth) acrylate monomers (B2), the di (meth) acrylate and the tri (meth) acrylate are the active energy ray-curable resin compositions having excellent surface hardness and flexibility in the cured coating film. , The tetrafunctional or higher functional (meth) acrylate, and a modified (meth) acrylate monomer in which a (poly) oxyalkylene chain or a (poly) lactone structure is introduced into the molecular structure thereof are preferable, and the tri (meth) acrylate, the above. More preferably, a tetrafunctional or higher functional (meth) acrylate and a modified (meth) acrylate monomer in which a (poly) oxyalkylene chain or a (poly) lactone structure is introduced into the molecular structure thereof are preferable. Further, the molecular weight of the (meth) acrylate monomer (B2) is preferably less than 1000.

The matrix resin (B) having a (meth) acryloyl group may be used alone or in combination of two or more, but has excellent activity in surface hardness and flexibility in a cured coating film. Since the energy ray-curable resin composition is obtained, it is preferable to use the (meth) acrylate resin (B1) in combination with the (meth) acrylate monomer (B2). At this time, the mass ratio [(B1) / (B2)] of the two is preferably in the range of 10/90 to 90/10, and more preferably in the range of 30/70 to 70/30.

Further, the mass ratio [(A) / (B)] of the barium sulfate fine particles (A) and the matrix resin (B) is excellent in the balance between the surface hardness and the flexibility of the cured coating film, and interferes with the laminated film. Since the active energy ray-curable resin composition is less likely to cause fringes, it is preferably in the range of 30/70 to 70/30.

The active energy ray-curable resin composition of the present invention may contain various additive components in addition to the barium sulfate fine particles (A) and the matrix resin (B) depending on desired performance. Additive components include, for example, photopolymerization initiators, photosensitizers, organic solvents, UV absorbers, antioxidants, silicon-based additives, fluorine-based additives, antistatic agents, silane coupling agents, organic beads, etc. Examples thereof include a rheology control agent, a defoaming agent, an antifogging agent, and a coloring agent.

Examples of the photopolymerization initiator include benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, and 4,4'-dichlorobenzophenone. Various benzophenones such as Michler's ketone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Xanthones, thioxanthones such as xanthones, thioxanthones, 2-methylthioxanthones, 2-chlorothioxanthones, 2,4-diethylthioxanthones; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;

Α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyldisulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

3,3'-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexylphenylketone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-hydroxy-2-methyl-1-one Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethylketal, benzyl-β-methoxyethylacetal, methyl o-benzoylbenzoate, bis (4-Dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyluni amount Body, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (4-ethoxy) phenyl-S-triazine , 2,4-Bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazine anthraquinone, 2-t-butyl anthraquinone, 2-amyl anthraquinone, β-chloroanthraquinone and the like. Each of these may be used alone, or two or more types may be used in combination.

Among the photopolymerization initiators, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-Methyl-1-propane-1-one, thioxanthone and thioxanthone derivative, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2) , 4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino) It is preferable to use one kind or a mixed system of two or more kinds selected from the group of phenyl) -butane-1-one because it exhibits activity against light of a wider range of wavelengths and a highly curable coating material can be obtained. ..

Commercially available products of the photopolymerization initiator include, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", and "Irgacure-" manufactured by Ciba Specialty Chemicals. 651, "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800" , "Irgacure-1850", "Irgacure-2959", "Irgacure-4043", "DaroCure-1173"; "Lucillin TPO" manufactured by BASF; "Kayacure-DETX", "Kayacure-MBP" manufactured by Nippon Kayaku Co., Ltd. , "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA"; "BiCure-10", "BiCure-55" manufactured by Stofa Chemical Co., Ltd .; 1000 ”;“ Deep ”manufactured by Apjon;“ Quantacure-PDO ”,“ Quantacure-ITX ”,“ Quantacure-EPD ”manufactured by Ward Brenkinsop, and the like.

The amount of the photopolymerization initiator used is preferably an amount that can sufficiently exert the function as the photopolymerization initiator and does not cause crystal precipitation or deterioration of the physical properties of the coating film. It is preferably used in the range of 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin composition.

Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

The organic solvent is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone (ketone solvent such as); cyclic ether solvent such as tetrahydrofuran, dioxolane; ester such as methyl acetate, ethyl acetate, butyl acetate; aromatic solvent such as toluene, xylene; Alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol mono Examples thereof include glycol ether solvents such as propyl ether. These may be used alone or in combination of two or more.

The organic solvent is mainly used for the purpose of adjusting the viscosity of the active energy ray-curable resin composition, but it is usually preferable to adjust the non-volatile content in the range of 10 to 60% by mass.

The ultraviolet absorber is, for example, 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, 2- [4-{(2-Hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-Triazine derivatives such as triazine, 2- (2'-xanthencarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Examples thereof include xanthencarboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. Each of these may be used alone, or two or more types may be used in combination.

Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, phosphoric acid ester-based antioxidants, and the like. Each of these may be used alone, or two or more types may be used in combination.

The silicon-based additive includes, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl. Examples include polyorganosiloxane having an alkyl group or a phenyl group such as a polysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxane having a polyether-modified acrylic group, and polydimethylsiloxane having a polyester-modified acrylic group. Be done. Each of these may be used alone, or two or more types may be used in combination.

Examples of the fluorine-based additive include DIC Corporation's "Megaface" series. Each of these may be used alone, or two or more types may be used in combination.

Examples of the antistatic agent include pyridinium, imidazolium, phosphonium, ammonium, and lithium salts of bis (trifluoromethanesulfonyl) imide or bis (fluorosulfonyl) imide. Each of these may be used alone, or two or more types may be used in combination.

The silane coupling agent includes, for example, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-. Glycydoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-Dimethyl butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-ureido Propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyandiapropyltriethoxysilane, allyltrichlorosilane , Allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltricrolsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and other vinyl-based silane coupling agents. ;

Diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-bricidoxypropyl Epoxy-based silane coupling agents such as triethoxysilane;

Styrene-based silane coupling agents such as p-styryltrimethoxysilane;

3-Methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (meth) Acryloxy-based silane coupling agent;

N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltri Amino-based silane couplings such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane Agent;

3-Ureido-based silane coupling agents such as ureidopropyltriethoxysilane;

3-Chloropropyltrimethoxysilane, a chloropropyl-based silane coupling agent;

3-mercaptopropyl methyldimethoxysilane, 3-mercaptopropyl trimetkinsilane, and other mercapro-based silane coupling agents;

Sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide;

Examples thereof include isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane. Each of these may be used alone, or two or more types may be used in combination.

The organic beads include, for example, polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, and polyolefin resin beads. Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads. Each of these may be used alone, or two or more types may be used in combination. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

These various additives can be added in an arbitrary amount depending on the desired performance and the like, but are usually used in the range of 0.01 to 40 parts by mass in 100 parts by mass of the active energy ray-curable resin composition. Is preferable.

The method for producing the active energy ray-curable resin composition is not particularly limited, and any method may be used. As an example of the manufacturing method, for example, a disperser having a stirring blade such as a dispenser or a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill or the like is used, and the barium sulfate fine particles (a) are produced. It can be produced by a method of mixing and dispersing in a matrix component such as a matrix resin (B) having a (meth) acryloyl group and an organic solvent. Above all, it is preferable to use a ball mill or a bead mill because a uniform and stable dispersion can be obtained. The method of mixing and dispersing the barium sulfate fine particles (a) in the matrix component may be, for example, a method of collectively producing an active energy ray-curable resin composition by dispersing the barium sulfate fine particles (a) in the entire matrix component. Then, a method may be used in which barium sulfate fine particles (a) are dispersed in a part of the matrix component to produce a pre-dispersion, and then the remaining matrix component is blended. Further, various additives may be added in the dispersion step, or barium sulfate fine particles (a) may be added after being dispersed in the matrix component.

Since the active energy ray-curable resin composition of the present invention has a feature of high surface hardness in a cured coating film, it is suitably used for coating applications for protecting molded products, display members, and various film materials from scratches. be able to. Further, it has high flexibility in a cured product and is less likely to cause interference fringes when used in a laminated film application, and can be particularly suitably used as a coating material for a plastic film.

The paint containing the active energy ray-curable resin composition can be applied onto various substrates and cured by irradiating the active energy rays to form a coating film that protects the surface of the substrate. The coating material of the present invention may be used by directly applying it to the surface protection member, or may be applied on a plastic film and used as a protective film. Alternatively, the coating film of the present invention may be applied onto a plastic film to form a coating film, which may be used as an optical film such as an antireflection film, a diffusion film, and a prism sheet.

Examples of the plastic film include triacetyl cellulose film, polyester film, acrylic film, cycloolefin polymer film, polyamide film, polyimide film, polystyrene film, polycarbonate film, polypropylene film and the like.

Of the above plastic films, the triacetyl cellulose film is a film that is particularly preferably used for polarizing plates of liquid crystal displays, but since it is generally as thin as 40 to 100 μm, it has a surface even when a hard coat layer is installed. It is difficult to increase the hardness sufficiently, and it is easy to curl large. The coating film made of the resin composition of the present invention has the effects of high surface hardness, excellent curl resistance, toughness, and transparency even when a triacetyl cellulose film is used as a base material, and is preferably used. Can be done. When the triacetyl cellulose film is used as a base material, the coating amount when applying the coating material of the present invention is such that the film thickness after drying is in the range of 4 to 20 μm, preferably in the range of 6 to 15 μm. Is preferable. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method and the like.

Among the above plastic films, the polyester film includes, for example, polyethylene terephthalate, and the thickness thereof is generally about 100 to 300 μm. It is a film used for various purposes such as touch panel displays because it is inexpensive and easy to process, but it is very soft and it is difficult to sufficiently increase the surface hardness even when a hard coat layer is installed. When the polyethylene film is used as a base material, the coating amount when applying the coating material of the present invention is in the range of 5 to 100 μm, preferably in the range of 7 to 80 μm after drying, depending on the application. It is preferable to apply as such. Generally, when a paint is applied with a film thickness of more than 30 μm, it tends to curl more easily than when it is applied with a relatively thin film thickness, but the paint of the present invention has excellent curl resistance. Since it has a characteristic, curling is unlikely to occur even when it is applied with a relatively high film thickness exceeding 30 μm, and it can be preferably used. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method and the like.

Among the above plastic films, the polymethyl methacrylate film is generally relatively thick and durable with a thickness of about 100 to 2,000 μm, and is therefore suitable for applications requiring particularly high surface hardness such as front plate applications for liquid crystal displays. It is a film used for. When the polymethylmethacrylate film is used as a base material, the coating amount when applying the coating material of the present invention is in the range of 5 to 100 μm, preferably in the range of 7 to 80 μm after drying, depending on the application. It is preferable to apply so as to. Generally, when a paint is applied on a relatively thick film such as a polymethylmethacrylate film with a film thickness of more than 30 μm, the laminated film has a high surface hardness, but the transparency tends to decrease. However, since the paint of the present invention has extremely high transparency as compared with the conventional paint, a laminated film having both high surface hardness and transparency can be obtained. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method and the like.

Examples of the active energy rays irradiated when the coating film of the present invention is cured to form a coating film include ultraviolet rays and electron beams. When curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp is used as a light source, and the amount of light, the arrangement of the light source, and the like are adjusted as necessary. When a high-pressure mercury lamp is used, it is preferable to cure one lamp having a light amount usually in the range of 80 to 160 W / cm at a transport speed of 5 to 50 m / min. On the other hand, when curing with an electron beam, it is preferable to cure with an electron beam accelerator having an acceleration voltage usually in the range of 10 to 300 kV at a transport speed of 5 to 50 m / min.

Further, the base material to which the paint of the present invention is applied can be suitably used not only as a plastic film but also as a surface coating agent for various plastic molded products such as mobile phones, electric appliances, bumpers of automobiles and the like. .. In this case, examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.

The coating method is a method in which the paint is spray-coated, or a molded product is coated as a top coat using a printing device such as a curtain coater, a roll coater, or a gravure coater, and then irradiated with active energy rays to cure. be.

In the transfer method, the transfer material obtained by applying the coating material of the present invention on a base sheet having mold releasability is adhered to the surface of a molded product, and then the base sheet is peeled off to top coat the surface of the molded product. Is transferred and then cured by irradiating with active energy rays, or by adhering the transfer material to the surface of the molded product and then irradiating with active energy rays to cure, and then peeling off the substrate sheet to cure the molded product. A method of transferring the top coat to the surface can be mentioned.

On the other hand, in the sheet bonding method, a protective sheet having a coating film made of the paint of the present invention on a base sheet or a protective sheet having a coating film made of the paint and a decorative layer on the base sheet is plastically molded. This is a method of forming a protective layer on the surface of a molded product by adhering it to the product.

Among these, the coating material of the present invention can be preferably used for transfer methods and sheet bonding methods.

In the transfer method, a transfer material is first prepared. The transfer material can be produced, for example, by applying the coating material alone or a mixture with a polyisocyanate compound onto a base sheet and heating the coating film to be semi-cured (B-staged). ..

Here, when the matrix resin (B) having the (meth) acryloyl group contained in the active energy ray-curable compound of the present invention is a compound having a hydroxyl group in the molecular structure, the B-stageization step is more efficient. It may be used in combination with a polyisocyanate compound for the purpose of performing the above.

In order to produce the transfer material, first, the paint of the present invention described above is coated on the base material sheet. Examples of the method of applying the paint include a coating method such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method and a comma coating method, a printing method such as a gravure printing method and a screen printing method. The film thickness at the time of coating is preferably 1 to 6 μm so that the thickness of the coating film after curing is 0.5 to 30 μm because the wear resistance and chemical resistance are good. It is more preferable to paint so as to be.

After the coating material is applied onto the base material sheet by the method, the coating film is semi-cured (B-staged) by heating and drying. The heating is usually 55 to 160 ° C, preferably 100 to 140 ° C. The heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes.

The surface protective layer of the molded product using the transfer material is formed, for example, by adhering the B-staged resin layer of the transfer material to the molded product and then irradiating the molded product with active energy rays to cure the resin layer. Let me do it. Specifically, for example, the B-staged resin layer of the transfer material is adhered to the surface of the molded product, and then the base sheet of the transfer material is peeled off to obtain the B-staged resin layer of the transfer material. A method (transfer method) in which the resin layer is crosslinked and cured by being transferred onto the surface of the molded product and then subjected to energy ray curing by irradiation with active energy rays, or the transfer material is sandwiched in a molding mold and the resin is placed in the cavity. The injection is filled to obtain a resin molded product, and at the same time, a transfer material is adhered to the surface thereof, the substrate sheet is peeled off and transferred onto the molded product, and then the resin layer is crosslinked and cured by irradiation with active energy rays. (Simultaneous molding transfer method) and the like.

Next, in the sheet bonding method, specifically, a resin layer formed by adhering a base sheet of a protective layer forming sheet prepared in advance and a molded product and then heat-curing by heating to form a B-stage. (Post-adhesion method), or the protective layer forming sheet is sandwiched in a molding mold, and resin is injected and filled into the cavity to obtain a resin molded product, and at the same time, the surface and protective layer are formed. Examples thereof include a method (simultaneous molding bonding method) in which the resin layer is crosslinked and cured by heat-curing the resin layer after adhering the sheets.

Next, the coating film of the present invention is a coating film formed by applying and curing the coating film of the present invention on the plastic film described above, or coating and curing the coating film of the present invention as a surface protective agent for a plastic molded product. The film of the present invention is a film in which a coating film is formed on a plastic film.

Among the various uses of the film, as described above, a film obtained by applying the coating material of the present invention on a plastic film and irradiating it with active energy rays is a protective film for a polarizing plate used for a liquid crystal display, a touch panel display, or the like. It is preferable to use it as a coating film because it has excellent coating hardness. Specifically, when the coating material of the present invention is applied on a protective film of a polarizing plate used for a liquid crystal display, a touch panel display, etc., and the film is formed by irradiating and curing active energy rays, the cured coating film has high hardness. It is a protective film that has both high transparency. In the use of a protective film for a polarizing plate, an adhesive layer may be formed on the surface opposite to the coating layer coated with the coating material of the present invention.

The laminated film of the present invention has high surface hardness and flexibility, and is less likely to cause interference fringes. It is used for display members, automobile members, building materials, surface protective films for various electronic devices, home appliances, furniture, etc., and plating. It can be suitably used for various purposes such as substitution and painting substitution.

Hereinafter, the present invention will be described in more detail with reference to specific production examples and examples, but the present invention is not limited to these examples. All parts and% in the example are based on mass unless otherwise specified.

In the examples of the present invention, the values are measured under the following conditions using a weight average molecular weight (Mw) and a gel permeation chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column H _XL- H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard; Polystyrene sample; 0.4 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

In the examples of the present application, the average particle size of the barium sulfate fine particles (A) is a value obtained by measuring the particle size in the active energy ray-curable resin composition under the following conditions.
Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.
Particle size measurement sample: An active energy ray-curable resin composition diluted with methyl isobutyl ketone to adjust the concentration of barium sulfate fine particles (A) to 0.2% by mass.

Production Example 1 Production of Acryloyl Group-Containing Acrylate Resin (B-1) A reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube is charged with 453 parts by mass of methylisobutyl ketone, and the temperature inside the system rises while stirring. The temperature was raised to 110 ° C., then 720 parts by mass of glycidyl methacrylate, 480 parts by mass of methyl methacrylate and 48 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.). The mixed solution consisting of parts was added dropwise from the dropping funnel over 3 hours, and then the mixture was held at 110 ° C. for 15 hours. Then, after lowering the temperature to 90 ° C., 1.6 parts by mass of methquinone and 367 parts by mass of acrylic acid were charged, 7.8 parts by mass of triphenylphosphine was added, and then the temperature was further raised to 100 ° C. and held for 8 hours. , 3000 parts by mass (nonvolatile content 50.0% by mass) of a methyl isobutyl ketone solution of the acryloyl group-containing acrylic resin (B-1) was obtained. The weight average molecular weight (Mw) of the acryloyl group-containing acrylic resin (B-1) was 13,000, the theoretical acryloyl group equivalent in terms of solid content was 321 g / eq, and the hydroxyl value was 108 mgKOH / g.

Production Example 2 Production of Urethane Acrylate Resin (B-2) 166 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, 0.2 parts by mass of dibutyltin dilaurite and 0.2 parts by mass of methquinone were added to a reactor equipped with a stirring device. In addition, the temperature was raised to 60 ° C. with stirring. Next, 630 parts by mass of "Aronix M-305" (* 1) manufactured by Toagosei Co., Ltd. was charged in 10 batches every 10 minutes. The reaction was further carried out for 10 hours ^{, and it was confirmed in the infrared spectrum that the absorption of the isocyanate group of 22500 cm-1} had disappeared, and the reaction was terminated to obtain a urethane acrylate resin (B-2). The weight average molecular weight (Mw) of the urethane acrylate resin (B-2) was 1,400, and the theoretical acryloyl group equivalent was 120 g / eq.
(* 1) "Aronix M-305" manufactured by Toagosei Co., Ltd .: Pentaerythritol polyacrylate composition containing about 60% pentaerythritol triacrylate.

Production Example 3 Production of Urethane Acrylate Resin (B-3) 735 parts by mass of "Aronix M-403" (* 2) manufactured by Toa Synthetic Co., Ltd. was added to a reactor equipped with a stirring device, and the temperature was raised to 60 ° C. while stirring. bottom. Next, 79 parts by mass of hexamethylene diisocyanate, 0.2 parts by mass of dibutyltin dilaurite and 0.2 parts by mass of methquinone were charged in 10 portions every 10 minutes. The reaction was further carried out for 10 hours ^{, and it was confirmed in the infrared spectrum that the absorption of the isocyanate group of 22500 cm-1} had disappeared, and the reaction was terminated to obtain a urethane acrylate resin (B-3). The weight average molecular weight (Mw) of the urethane acrylate resin (B-3) was 4,500, and the theoretical acryloyl group equivalent was 350 g / eq.
(* 2) "Aronix M-403" manufactured by Toagosei Co., Ltd .: Dipentaerythritol polyacrylate composition containing about 55% dipentaerythritol pentaacrylate.

Example 1 Production and evaluation of an active energy ray-curable resin composition 40 parts by mass (resin solid content 20 parts by mass) of a methylisobutylketone solution of the (meth) acryloyl group-containing acrylic resin (B-1) obtained in Production Example 1 ), (Meta) acrylate monomer ("LumiCure DPA-600T" (* 3) manufactured by Toa Synthetic Co., Ltd.), 25 parts by mass, barium sulfate fine particles (a-1) ("BARIFINE BF-1" manufactured by Sakai Chemical Industry Co., Ltd.) average 50 parts by mass (particle size 0.05 μm) and 5 parts by mass of dispersion aid (“BYK-111” manufactured by Big Chemie) were blended, and an appropriate amount of methylisobutylketone (MIBK) was further added to prepare a slurry having a non-volatile content of 40% by mass. The mixture was mixed and dispersed using a wet ball mill (“Star Mill LMZ015” manufactured by Ashizawa Co., Ltd.) to obtain a dispersion.
(* 3) "LumiCure DPA-600T" manufactured by Toagosei Co., Ltd .: A composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40/60.

Each condition of dispersion by the wet ball mill is as follows.
Media: Filling ratio of resin composition to internal volume of zirconia bead mill with media diameter of 100 μm: 70% by volume
Peripheral speed at the tip of the stirring blade: 12 m / sec
Flow rate of resin composition: 200 ml / min
Dispersion time: 60 minutes

To the obtained dispersion, 2 parts by mass of a photoinitiator (“Irgacure # 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) was added, and methyl isobutyl ketone and propylene glycol monomethyl ether were further added to adjust the non-volatile content to 40% by mass. Then, an active energy ray-curable resin composition was obtained. The obtained active energy ray-curable resin composition was evaluated by the following various tests. The results are shown in Table 1.

Evaluation of storage stability The active energy ray-curable resin composition was allowed to stand for one month under a temperature condition of 40 ° C., and the presence or absence of sediment at each elapsed time was evaluated.
A: No sediment is seen B: Sediment is seen after 3 weeks C: Sediment is seen after 1 week

Preparation of Laminated Film The active energy ray-curable resin composition is applied onto a polyethylene terephthalate film (thickness 125 μm) with a bar coater so that the cured film thickness is 5 μm, and dried at 70 ° C. for 1 minute. A laminated film was obtained by passing the film ^{under nitrogen at an irradiation amount of 250 mJ / cm 2} using a high-pressure mercury lamp and curing the film.

Evaluation of Transparency of Laminated Film The haze value of the laminated film was measured using "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd. The lower the haze value, the higher the transparency of the coating film.

Evaluation of interference fringes on the laminated film The occurrence of interference fringes on the surface of the laminated film was visually observed and evaluated according to the following criteria.
A: No interference fringes are observed.
B: Interference fringes are observed.

Pencil hardness test of laminated film The surface hardness of the laminated film on the resin coating film side was evaluated by a pencil scratch test with a load of 750 g according to JIS K 5400. The test was performed 5 times, and the hardness one below the hardness of the scratched film was defined as the pencil hardness of the coating film.

Curl resistance test of laminated film The laminated film was cut into 10 cm squares, and the floating of the four corners from the horizontal was measured and evaluated by the average value.

Flexibility test of laminated film A mandrel tester (“Bending tester” manufactured by TP Giken Co., Ltd.) was used to wind the laminated film around a test rod, and a test was conducted to visually confirm whether or not cracks were generated. The minimum diameter (mm) of the test rod that does not cause cracks was used as the evaluation result. The test rods used were those having a diameter of 2 mm to 13 mm in 1 mm increments.

Examples 2-14 Production and evaluation of active energy ray-curable resin composition The active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the composition of the dispersion was changed as shown in Tables 1 and 2. Obtained, and various tests were carried out in the same manner as in Example 1. The results are shown in Tables 1 and 2.
[Ingredients used]
-Barium sulfate fine particles (a-2): "BARIACE B-30" manufactured by Sakai Chemical Industry Co., Ltd.
-Barium sulfate fine particles (a-3): "BARIACE B-31" manufactured by Sakai Chemical Industry Co., Ltd.
-Barium sulfate fine particles (a-4): "BARIACE B-34" manufactured by Sakai Chemical Industry Co., Ltd.
-Barium sulfate fine particles (a-5): "Barium sulfate BB-02" manufactured by Sakai Chemical Industry Co., Ltd.
-MIWON "Miramer SP-1106": dendrimer type poly (meth) acrylate resin, weight average molecular weight (Mw) 1,630, average (meth) acryloyl group number per molecule 18
-KBM-503: Silane coupling agent, "KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd. 3-methacryloxypropyltrimethoxysilane-BYK-145: Dispersion aid, "BYK-145" manufactured by Big Chemie Co., Ltd.
-MEK: Methyl ethyl ketone-PGM: Propylene glycol monomethyl ether-MRK / PGM: Mass ratio of methyl ethyl ketone and propylene glycol monomethyl ether 50/50 mixed solvent

Comparative Example 1 Production and evaluation of an active energy ray-curable resin composition 40 parts by mass (resin solid content 20 parts by mass) of a methylisobutylketone solution of the (meth) acryloyl group-containing acrylic resin (B-1) obtained in Production Example 1 ), (Meta) acrylate monomer ("LumiCure DPA-600T" manufactured by Toa Synthetic Co., Ltd.) 30 parts by mass, silica sol (* 4) 167 parts by mass, photoinitiator ("Irgacure # 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) 2 parts by mass Methyl isobutyl ketone (MIBK) was added to adjust the non-volatile content to 40% by mass to obtain an active energy ray-curable resin composition. The obtained active energy ray-curable resin composition was subjected to various tests in the same manner as in Example 1. The results are shown in Table 2.
(* 4) Silica dispersion "MEK-ST" manufactured by Nissan Chemical Industries, Ltd .: Silica solid content 30% by mass, average particle size 10 to 15 nm

Claims (5)

The average particle diameter of barium sulfate particles in the range of 60～250Nm (A), an active energy ray curable resin composition comprising a matrix resin (B) having a (meth) acryloyl group, wherein the barium sulfate The mass ratio [(A) / (B)] of the fine particles (A) to the matrix resin (B) is in the range of 30/70 to 70/30.
The matrix resin (B) is a combination of a (meth) acrylate resin (B1) and a (meth) acrylate monomer (B2).
The (meth) acrylate resin (B1) is a (meth) acryloyl group-containing acrylic resin (B1-1), a dendrimer-type poly (meth) acrylate resin (B1-2), and a urethane (meth) acrylate resin (B1-3). ) Is an active energy ray-curable resin composition containing one or more selected from the group consisting of . The active energy ray-curable resin composition according to claim 1, wherein the (meth) acrylate monomer (B2) contains a tetrafunctional or higher functional (meth) acrylate. A coating material containing the active energy ray-curable resin composition according to claim 1 or 2. A coating film comprising the paint according to claim 3. A laminated film having a layer composed of the coating film according to claim 4.