TW201819439A - Active energy ray-curable resin composition and laminated film - Google Patents

Abstract

Provided are an active energy ray-curable resin composition, the cured coating film of which is endowed with both surface hardness and flexibility, that does not tend to develop interference fringes in a laminated film, a coating containing the same, and a coating film and laminated film made from the coating. An active energy ray-curable resin composition containing barium sulfate microparticles (A) having an average particle size in the 60-250 nm range and a matrix resin (B) having (meth)acryloyl groups, a coating containing the same, and a coating film and laminated film made from the coating.

Description

   Active energy ray hardening resin composition and laminated film   

The present invention relates to an active energy ray-curable resin composition, a paint containing the same, a coating film and a laminated film formed from the above paint. The active energy ray-curable resin composition has both the surface hardness and the bending of the hardened coating film. It is difficult to generate interference fringes in the laminated film.

The inorganic microparticle-dispersed resin material obtained by dispersing inorganic microparticles in a resin component is formed to be able to impart "higher hardness of hardened coating film, improved scratch resistance, and New materials with high performance or new functions such as "barrier resistance" have attracted attention in recent years. Inorganic microparticle-dispersed resin materials are used in a variety of applications. For example, they are widely used as hard coating agents "to protect the surface of molded products or displays, and to protect various film materials from damage."

As the inorganic fine particles used in the inorganic fine particle-dispersed resin material, silica or alumina is widely used. For example, it is known to contain 214 g / eq of acryl fluorenyl equivalent, 262 mg KOH / g of hydroxyl number, and weight. A reactive dispersion of an acrylic polymer having an average molecular weight (Mw) of 40,000 and alumina fine particles or zirconia fine particles having an average particle size in the range of 55 to 90 nm (see Patent Document 1). The reactive dispersion described in Patent Document 1 has the characteristics of higher hardness of the surface of the hardened material and better scratch resistance than the hard coating agent composed only of an organic system, but has insufficient flexibility or warpage resistance, and In the case of coating on a plastic film to form a laminated film, interference fringes and the like are likely to be generated, and it is not a person that can fully correspond to the required performance on the market.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-289943

Therefore, the problem to be solved by the present invention is to provide an active energy ray-curable resin composition, a coating material containing the same, a coating film formed from the coating material, and a laminated film. The active energy ray-curable resin composition has both curing properties. The surface hardness and bendability of the coating film, and interference fringes in the laminated film are difficult to produce.

The present inventors conducted diligent research in order to solve the above-mentioned problems, and found that an active energy ray-curable resin composition containing barium sulfate fine particles having an average particle size in a range of 60 to 250 nm has both surface hardness and bendability of the hardened material. Further, it is difficult to generate interference fringes in the laminated film, thereby completing the present invention.

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

Furthermore, this invention relates to the coating material containing the said active-energy-ray-curable resin composition.

Furthermore, this invention relates to the coating film which consists of the said coating material.

Furthermore, this invention relates to the laminated film which has the layer which consists of the said coating film.

According to the present invention, it is possible to provide an active energy ray-curable resin composition, a coating material containing the same, a coating film formed from the coating material, and a laminated film. The active energy ray-curable resin composition has both the surface hardness of the hardened coating film. And bendability, and interference fringes in laminated films are difficult to produce.

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

The barium sulfate fine particles (A) are obtained by dispersing barium sulfate fine particles (a) as a raw material in a matrix resin (B) or a blend of the matrix resin (B) and an organic solvent. The average particle diameter of the said barium sulfate fine particle (A) means the value which measured the average particle diameter in the state dispersed in the active-energy-ray-curable resin composition by the following method. The average particle diameter of the above barium sulfate fine particles (A) is 60 to 250 nm. From the viewpoint that the balance between the surface hardness and the bendability of the hardened material is more excellent, the range is more preferably 70 to 200 nm, and particularly preferably 80 to 120 nm. Range.

[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: A product obtained by diluting an active energy ray-curable resin composition with methyl isobutyl ketone and adjusting the concentration of barium sulfate fine particles (A) to 0.2% by mass.

As the raw material of the barium sulfate fine particles (a), for example, any of the following can be suitably used, that is, those produced by using barium sulfide and sulfuric acid, or those produced by using barium chloride and sodium sulfate, and using the surfaces of the particles. Alumina, silicon dioxide, various silane coupling agents, etc. can be obtained as modified products, and can be obtained as commercially available products. Examples of commercially available products include barium sulfate manufactured by Hori Chemical Industry Co., Ltd., including the BARIFINE series or the surface of the barium sulfate fine particles modified with alumina or silicon dioxide, and the "BARIACE series," "Barium sulfate BB -02 "and other special product series. The average particle diameter of the barium sulfate fine particles (a) is preferably in the range of 0.001 to 0.15 μm.

As long as the matrix resin (B) having a (meth) acrylfluorene group has a (meth) acrylfluorene group which is polymerized by irradiating active energy rays, the specific structure is not particularly limited, and various types can be used. By. The matrix resin (B) can be classified into, for example, a (meth) acrylate resin (B1) and a (meth) acrylate monomer (B2).

Examples of the (meth) acrylate resin (B1) include (meth) acrylfluorene-containing acrylic resin (B1-1), dendrimer-type poly (meth) acrylate resin (B1-2), A (meth) acrylate resin (B1-3), an epoxy (meth) acrylate resin (B1-4), and the like. The (meth) acrylate resin (B1) preferably has a molecular weight distribution and a weight average molecular weight (Mw) of 1,000 to 50,000. These can be used individually or in combination of 2 or more types.

Examples of the (meth) acrylic acid group-containing acrylic resin (B1-1) include (meth) acrylic acid ester monomers having a reactive functional group such as a hydroxyl group or a carboxyl group, an isocyanate group, or a glycidyl group. The acrylic resin intermediate obtained by polymerizing the polymer (α) as an essential component and the (meth) acrylic acid ester monomer (β) having a reactive functional group capable of reacting with these functional groups are further reacted to introduce (form Based) Acrylofluorenyl.

Examples of the (meth) acrylate monomer (α) having a reactive functional group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and acrylic acid. (Meth) acrylic acid esters containing hydroxyl groups such as dihydroxypropyl ester; (meth) acrylic acid, (acryloxy) acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 1- [2- Carboxyl-containing groups such as (propenyloxy) ethyl] ester, phthalic acid-1- (2-propenyloxyethyl) phthalate, and 2- (propylenepropoxy) ethyl hexahydrophthalate (Meth) acrylates; 2-propenyloxyethyl isocyanate, 2-methacryloxyethyl isocyanate, 1,1-bis (propenyloxymethyl) isocyanate Isocyanate group-containing (meth) acrylates such as ethyl esters; glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether. These can be used individually or in combination of 2 or more types.

Among these, in terms of the simplicity of production of the (meth) acrylic acid group-containing acrylic resin (B1-1), it is preferable to use a carboxyl group-containing (meth) acrylate or a glycidyl group. The (meth) acrylate is used as the (meth) acrylate monomer (α) having a reactive functional group.

The acrylic resin intermediate may be any one of the following: in addition to the (meth) acrylate monomer (α) having a reactive functional group, other polymerizable unsaturated group-containing compounds may be copolymerized as needed, and Winner.

Examples of the other polymerizable unsaturated group-containing compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) Amyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (formyl) (Meth) acrylic acid alkyl groups such as decyl acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate Esters; ring-containing (meth) acrylates such as cyclohexyl (meth) acrylate, isofluorenyl (meth) acrylate, and dicyclopentyl (meth) acrylate; phenyl (meth) acrylate, ( (Meth) acrylates containing aromatic rings such as benzyl methacrylate and phenoxyethyl acrylate; (meth) acrylates containing silicon groups such as 3-methacryloxypropyltrimethoxysilane ; N, N- (meth) acrylate dimethylaminoethyl, N, N- (meth) acrylate diethylaminoethyl, N, N- (meth) acrylate diethylaminopropyl, etc. N , N- (meth) acrylate dialkylamine Alkyl esters; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H- (meth) acrylate Carbon number of (per) fluoroalkyl such as fluoropentyl ester, 1H, 1H, 2H, 2H-heptadecafluorodecyl ester, perfluoroethyloxyethyl (meth) acrylate, etc. is 1-18 (Per) fluoroalkyl (meth) acrylate; trifluoromethyl trifluoroethylene ether, pentafluoroethyl trifluoroethylene ether, heptafluoropropyl trifluoroethylene ether, etc. (Per) fluoroalkyl-perfluoroethylene ethers having a carbon number in the range of 1 to 18; dimethyl fumarate, diethyl fumarate, dibutyl fumarate, itaconic Unsaturated dicarboxylic acid esters such as dimethyl acid, dibutyl itaconate, ethyl fumarate ethyl ester, methyl fumarate butyl ester, methyl itaconate ethyl ester; styrene, α-methylstyrene, chlorostyrene and other styrene derivatives; butadiene, isoprene, pentadiene, dimethyl butadiene and other diene compounds; vinyl chloride, bromoethylene and other halogenated ethylene or Vinylidene halide; Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone; vinyl acetate, vinyl butyrate, etc. Alkenyl esters; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl cyanide such as acrylonitrile, methacrylonitrile, and vinylidene chloride; acrylamide or its alkyd substituted amidine; N-substituted cis-butene diimide, such as alkene diimide, N-cyclohexyl cis butene diimide; vinyl fluoride, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, trifluorobromoethylene , Α-olefins such as pentafluoropropylene, hexafluoropropylene, etc. These can be used individually or in combination of 2 or more types.

Among these other compounds containing a polymerizable unsaturated group, the above-mentioned (meth) acrylic acid is preferably used for the active energy ray-curable resin composition having excellent surface hardness and flexibility as a cured coating film. Alkyl esters.

When the acrylic resin intermediate is obtained by copolymerizing the (meth) acrylic acid ester monomer (α) having a reactive functional group with the other polymerizable unsaturated group-containing compound, The reaction ratio is preferably a (meth) acrylic acid group-containing acrylic resin (B1-1) having excellent curability, and it is preferred that the (meth) acrylic acid ester monomer (α) having a reactive functional group is relatively The total ratio of the two is in a range of 30 to 90 mass%, more preferably in a range of 40 to 80 mass%, and particularly preferably in a range of 50 to 70 mass%.

The acrylic resin intermediate can be produced, for example, by polymerizing various monomers in a temperature range of 60 ° C to 150 ° C due to the presence of a polymerization initiator. Examples of the polymerization method include a block polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Examples of the polymerization form include random copolymers, block copolymers, and graft copolymers. When using a solution polymerization method, for example, a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, or propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, or propylene glycol monomer can be preferably used. Glycol ether solvents such as butyl ether.

Then, as long as the (meth) acrylic acid ester monomer (β) that reacts with the obtained acrylic resin intermediate is reactive with a reactive functional group of the (meth) acrylic acid ester monomer (α), Although it does not specifically limit, From a viewpoint of reactivity, the following combination is preferable. That is, when using the said (meth) acrylate containing a hydroxyl group as said (meth) acrylate monomer ((alpha)), it is preferable to use the (meth) acrylate containing an isocyanate group as (meth) Acrylate monomer (β). When the carboxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the glycidyl group-containing (meth) acrylate as (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 (meth) acrylic acid. Ester monomer (β). In the case of using the glycidyl group-containing (meth) acrylate as the (meth) acrylate monomer (α), it is preferable to use the carboxyl group-containing (meth) acrylate as (meth) Acrylate monomer (β).

Regarding the reaction between the acrylic resin intermediate and the (meth) acrylate monomer (β), for example, when the reaction is an esterification reaction, triphenylphosphine may be appropriately used in a temperature range of 60 to 150 ° C. Esterification catalysts and other methods. In the case where the reaction is an amine esterification reaction, methods such as reacting the compound (α) by dropping the compound (α) on the acrylic resin intermediate in a temperature range of 50 to 120 ° C. may be mentioned.

Regarding the weight average molecular weight (Mw) of the (meth) acrylic acid group-containing acrylic resin (B1-1), in terms of an active energy ray-curable resin composition having excellent surface hardness and flexibility of a cured coating film, A range of 5,000 to 80,000 is preferable, and a range of 10,000 to 50,000 is more preferable. The (meth) acrylfluorenyl equivalent of the (meth) acrylfluorene-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), number average molecular weight (Mn), and molecular weight distribution (Mn / Mw) are values measured using a gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Co., Ltd.

Column: Protective Column H _XL -H made by Tosoh Co., Ltd.

+ 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 Co., Ltd.

Measurement conditions: column temperature 40 ℃

Tetrahydrofuran

Flow rate 1.0ml / min

Standard: Polystyrene

Sample: a solution obtained by filtering a tetrahydrofuran solution with a mass fraction of 0.4% by mass of a resin solid content through a microfilter (100 μl)

The so-called dendrimer type poly (meth) acrylate resin (B1-2) refers to a resin having a regular multi-branched structure and a (meth) acrylfluorene group at the end of each branch chain, except Other than the dendrimer type, it is also called a hyperbranch type or a star polymer. Such compounds include, for example, those represented by the following structural formulae (1-1) to (1-8), but are not limited to these, as long as they have a regular multi-branched structure and are at the ends of each branch chain Any resin having a (meth) acrylfluorenyl group can be used.

(Wherein 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 (B1-2) having such a molecular structure, "Viscoat # 1000" manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 ~ 2,000, average (meth) acryl group number per molecule 14], "Viscoat 1020" [weight average molecular weight (Mw) 1,000 to 3,000], "SIRIUS 501" [weight average molecular weight (Mw) 15,000 to 23,000], MIWON Corporation Manufactured "SP-1106" [weight-average molecular weight (Mw) 1,630, average (meth) acryl group number per molecule 18], "CN 2301", "CN 2302" [average per molecule (A) Base) acryl fluorene base number 16], "CN 2303" [average (meth) acryl fluorene base number per molecule 6], "CN 2304" [average (meth) acryl fluorene base number per molecule 18], Nippon Steel & Sumikin "ESDRIMER HU-22" manufactured by Chemical Co., Ltd., "A-HBR-5" manufactured by Shin Nakamura Chemical Co., Ltd., "NEW FRONTIER R-1150" manufactured by Dai-Industrial Pharmaceutical Co., Ltd., and Nissan Chemical Co., Ltd. Commercial products such as "HYPERTECH UR-101" manufactured by the company. These can be used individually or in combination of 2 or more types.

Among the above dendritic polymer type poly (meth) acrylates (B1-2), the balance between the surface hardness and the bendability of the cured coating film is also excellent, and it is preferably an average (meth) propylene per molecule醯 The base is in the range of 5 to 50, and 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.

Examples of the (meth) acrylic acid amine ester (B1-3) include various polyisocyanate compounds, monohydroxy (meth) acrylate compounds, and optionally dihydroxy (meth) acrylate compounds or various polyol compounds. Receiver of the response.

Examples of the polyisocyanate compound include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Aliphatic diisocyanate compounds such as isocyanate; cycloaliphatic diisocyanate, isophorone diisocyanate, hydrogenated diisocyanate, hydrogenated diphenylmethane diisocyanate, and other alicyclic diisocyanate compounds; toluene diisocyanate, stubble Aromatic diisocyanate compounds such as xylylene diisocyanate, tetramethyl stubyl diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthyl diisocyanate; have the following structural formula (2) Polymethylene polyphenyl polyisocyanate of the repeating structure shown; such as urea isocyanate modifier, biuret modifier, urethane modifier, and the like.

[In the formula, R ^{3 is} each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ^{4 is} each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point connected to a structural site represented by the structural formula (2) via a methylene group with an * symbol. m is an integer of 0 or 1 ~ 3, 1 is an integer of 1 or more]

Examples of the monohydroxy (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and neopentyl tetraol. (Meth) acrylates, dipentaerythritol penta (meth) acrylates, and polyoxyalkylene modified bodies, polylactone modified bodies, and the like.

Examples of the dihydroxy (meth) acrylate compound include trimethylolpropane mono (meth) acrylate, neopentaerythritol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylic acid. Esters, and such polyoxyalkylene modifiers, polylactone modifiers, and the like.

Examples of the polyhydric alcohol compound include ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, and neopentyl tetraol.

The weight average molecular weight (Mw) of the (meth) acrylic acid amine resin (B1-3) is preferably in the range of 1,000 to 5,000. The (meth) acrylfluorenyl equivalent is preferably in the range of 100 to 400 g / equivalent.

Examples of the epoxy (meth) acrylate resin (B1-4) include a bisphenol compound or a biphenol compound, ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyoxyethylene glycol, and polyoxypropylene glycol. Polyglycidyl ethers of polyhydric alcohol compounds such as glycerol, trimethylolpropane, neopentyl tetraol, etc., and (meth) acrylic acid are obtained by reaction.

That is, it is convenient for the (meth) acrylic acid ester resin (B1) to be excellent in dispersion stability of the above-mentioned barium sulfate fine particles (A). (B1-1), any one or more of the above-mentioned dendrimer-type poly (meth) acrylate resin (B1-2), and the above-mentioned (meth) acrylate resin (B1-3) are used as essential components .

Examples of the (meth) acrylate monomer (B2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( N-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, glycidyl (meth) acrylate, acrylic acid Porphyrin, N-vinyl pyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, (methyl ) Isodecyl acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate , 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide Alkane modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylic acid Ester, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acrylic acid ethoxylate 2- Hydroxypropyl, (meth) acrylic acid 2- Hydroxy-3-phenoxypropyl, 2- (meth) acryloxyethyl hydrogen phthalate, 2- (meth) acryloxypropyl hydrogen phthalate, hexahydrophthalic acid 2- (meth) acryloxypropyl hydrogen diformate, 2- (meth) acryloxypropyl hydrogen tetrahydrophthalate, dimethylaminoethyl (meth) acrylate, (methyl Base) trifluoroethyl acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, mono ( Mono (meth) acrylates such as adamantyl methacrylate; butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate Ester, hexamethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, new Di (meth) acrylates such as pentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate; three Methylolpropane tri (meth) acrylate, ethoxylate Methylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl isocyanurate) tri (meth) acrylate, glycerol Tris (meth) acrylates such as tris (meth) acrylates; neopentaerythritol tris (meth) acrylates, dinepentaerythritol tris (meth) acrylates, di-trimethylolpropane tris ( (Meth) acrylate, neopentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dinepentaerythritol tetra (meth) acrylate, dinepentaerythr Alcohol penta (meth) acrylate, di-trimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane hexa (meth) acrylate (Meth) acrylic acid esters with more than 4 functions such as esters; the modification of the (poly) oxyalkylene chain or (poly) lactone structure introduced into the molecular structure of the above-mentioned various (meth) acrylate monomers Group) acrylate monomers and the like. These can be used individually or in combination of 2 or more types.

Among these (meth) acrylate monomers (B2), the active energy ray-curable resin composition having excellent surface hardness and flexibility of the cured coating film is preferably the above-mentioned di (methyl) Acrylic esters, the above-mentioned tri (meth) acrylates, the above-mentioned four-functional (meth) acrylates, and those having a (poly) oxyalkylene chain or (poly) lactone structure introduced into the molecular structure thereof The modified (meth) acrylate monomer is more preferably the above-mentioned tri (meth) acrylate, the above-mentioned 4-functional (meth) acrylate, and the introduction of (poly) oxygen into the molecular structure thereof Modified (meth) acrylate monomer of alkyl chain or (poly) lactone structure. The molecular weight of the (meth) acrylate monomer (B2) is preferably less than 1,000.

The matrix resin (B) having a (meth) acrylfluorene group may be used alone or in combination of two or more to form an active energy ray-curable resin composition having excellent surface hardness and flexibility of a cured coating film. In other words, it is preferable to use the (meth) acrylate resin (B1) and the (meth) acrylate monomer (B2) in combination. 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.

In addition, the active energy ray-curable resin composition having excellent balance between surface hardness and bendability formed as a hardened coating film and having difficulty in generating interference fringes in a laminated film, the barium sulfate fine particles (A) and the matrix resin The mass ratio ((A) / (B)] of (B) is preferably in the range of 30/70 to 70/30.

In addition to the barium sulfate fine particles (A) and the matrix resin (B), the active energy ray-curable resin composition of the present invention may contain various additive components according to desired properties. Examples of the additive component include a photopolymerization initiator, a photosensitizer, an organic solvent, an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, an antistatic agent, a silane coupling agent, an organic particle, a rheology control agent, and a consumer. Foaming agent, anti-fog agent, colorant, etc.

Examples of the photopolymerization initiator include benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, and 4,4'-bis (dimethylamino) benzophenone. Ketones, 4,4'-bis (diethylamino) benzophenone, 4,4'-dichlorobenzophenone, Michelin, 3,3 ', 4,4'-tetrakis Oxidation of various benzophenones such as tert-butylcarbonyl) benzophenone; Ketone, 9-oxysulfur 2-methyl 9-oxysulfur , 2-chloro9-oxysulfur , 2,4-diethyl 9-oxysulfur Wait Ketone, 9-oxysulfur Classes; acyloin ethers such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether; α-diones such as benzoin, diethylfluorene; tetramethylthiuram disulfide, p-toluene Thioethers such as methyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoic acid; 3,3'-carbonyl-bis (7-diethylamine ) Coumarin, 1-hydroxycyclohexylphenyl ketone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methyl Thio) phenyl] -2- Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4- (Phenylphenyl) -butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzylidene diphenylphosphine oxide , Bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1- Propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropane-1-one, 4-benzylidene-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzophenone dimethyl ketal, benzyl -Β-methoxyethyl acetal, methyl orthobenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-di Chloro-4-phenoxyacetophenone, 4-dimethylaminoamyl benzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis -Trichloromethyl-6- [bis (ethoxycarbonylmethyl) amino] phenyl-symmetric tris , 2,4-bis-trichloromethyl-6- (4-ethoxy) phenyl-symmetric tris , 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-symmetric tris Anthraquinone, 2-tert-butylanthraquinone, 2-pentylanthraquinone, β-chloroanthraquinone, and the like. These can be used individually or in combination of two or more.

Among the above-mentioned photopolymerization initiators, one selected from 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2- Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 9-oxysulfur And 9-oxysulfur Derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2,4 , 6-trimethylbenzylidene) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- Phenyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4- One or two or more mixed systems in the group of phosphonophenyl) -butane-1-one can exhibit activity to light in a wider range of wavelengths, thereby obtaining a coating with higher hardenability. good.

Examples of the commercially available photopolymerization initiators include "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", "Irgacure-500", manufactured by Ciba Specialty Chemicals. "Irgacure-651", "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure -1800 "," 1rgacure-1850 "," Irgacure-2959 "," Irgacure-4043 "," Darocure-1173 ";" Lucirin TPO "manufactured by BASF;" kayacure-DETX "manufactured by Nippon Kayaku Co., Ltd. , "Kayacure-MBP", "kayacure-DMBI", "kayacure-EPA", "kayacure-OA"; "Vicure-10" and "Vicure-55" manufactured by Stauffer Chemical; "Trigonal P1" manufactured by Akzo "Sandoray 1000" manufactured by Sandoz; "DEEP" manufactured by Upjohn; "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD", etc. manufactured by Ward Blenkinsop.

The amount of the photopolymerization initiator used is preferably in a range capable of sufficiently exerting its function as a photopolymerization initiator without causing crystal precipitation or deterioration of coating film physical properties. Specifically, it is preferably in a range relative to activity. 100 parts by mass of the energy ray-curable resin composition is used in a range of 0.05 to 20 parts by mass, and more preferably used in a range of 0.1 to 10 parts by mass.

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

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; methyl acetate, ethyl acetate, and butyl acetate Ester and other esters; aromatic solvents such as toluene and xylene; cycloaliphatic solvents such as cyclohexane and methylcyclohexane; carbitol, cyperidine, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohols Solvents; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether. These can be used individually or in combination of 2 or more types.

The above-mentioned organic solvent is mainly used for the purpose of adjusting the viscosity of the active energy ray-curable resin composition, and it is usually preferably adjusted so that the non-volatile component becomes a range of 10 to 60% by mass.

Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4- (Dimethylphenyl) -1,3,5-tri , 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-three Wait three Derivative, 2- (2'- Carboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These can be used individually or in combination of 2 or more types.

Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate-based antioxidants. These can be used individually or in combination of 2 or more types.

Examples of the above-mentioned silicon-based additives include, for example, dimethyl polysiloxane, methylphenyl polysiloxane, cyclic dimethyl polysiloxane, methyl hydrogen polysiloxane, and polyether modified dimethyl ether. Based polysiloxane copolymer, polyester modified dimethyl polysiloxane copolymer, fluorine modified dimethyl polysiloxane copolymer, amine modified dimethyl polysiloxane copolymer, etc. Alkyl or phenyl polyorganosiloxane, polyether modified polydimethylsiloxane with acrylic group, polyester modified polydimethylsiloxane with acrylic group, etc. These can be used individually or in combination of 2 or more types.

Examples of the fluorine-based additive include the "MEGAFAC" series of DIC Corporation. These can be used individually or in combination of 2 or more types.

Examples of the antistatic agent include pyridinium, imidazolium, sulfonium, ammonium, or lithium salts of bis (trifluoromethanesulfonyl) fluorenimide or bis (fluorosulfonyl) fluorenimide. These can be used individually or in combination of two or more.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3- Glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldi Methoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl Hydrochloride of trimethoxysilane, special aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, allyltrichlorosilane, allyltriethoxy Silyl, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Vinyl silane coupling agents such as tris (2-methoxyethoxy) silane; diethoxy (glycidyloxypropyl) methylsilane; 2- (3,4 epoxycyclohexyl) ethyltrimethyl Epoxy series such as oxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane Silane coupling agents; styrene-based silane coupling agents such as p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane; Propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl (Meth) acrylic alkoxy-based silane coupling agents such as triethoxysilane; N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl ) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and other amines Based silane coupling agents; urea based silane coupling agents such as 3-ureidopropyltriethoxysilane; chloropropyl based silane coupling agents such as 3-chloropropyltrimethoxysilane; 3-mercaptopropylmethyl Mercapto-based silane coupling agents such as dimethoxysilane, 3-mercaptopropyltrimethoxysilane; thioether-based silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide; 3-isocyanatepropyl Isocyanate-based silane coupling agents such as triethoxysilane. These can be used individually or in combination of 2 or more types.

Examples of the organic particles include polymethyl methacrylate particles, polycarbonate particles, polystyrene particles, polyacrylic styrene particles, polysiloxane particles, glass particles, acrylic resin particles, and benzoguanamine resin particles. , Melamine resin particles, polyolefin resin particles, polyester resin particles, polyamide resin particles, polyimide resin particles, polyvinyl fluoride resin particles, polyethylene resin particles, and the like. These can be used individually or in combination of 2 or more types. The average particle diameter of these organic particles is preferably in the range of 1 to 10 μm.

These various additives can be added in any amount according to the desired performance, etc., and it is usually preferably 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.

The method for producing the above-mentioned active energy ray-curable resin composition is not particularly limited, and it can be produced by any method. As an example of the manufacturing method, for example, manufacturing can be performed by using a disperser, a disperser having stirring blades such as a turbine blade, a paint mixer, a roll mill, a ball mill, an attritor, and sand. A disperser such as a mill or a bead mill mixes and disperses the barium sulfate fine particles (a) in a matrix component such as the (meth) acrylfluorene group-containing matrix resin (B) and an organic solvent. Among these, in order to obtain a uniform and stable dispersion, a ball mill or a bead mill is preferably used. The method of mixing and dispersing the barium sulfate fine particles (a) in the matrix component may be, for example, a method of dispersing the barium sulfate fine particles (a) in the total amount of the matrix component to produce the active energy ray-curable resin composition at once, A method of blending the remaining matrix components after the pre-dispersion is prepared by dispersing the barium sulfate fine particles (a) in a part of the matrix components. Various additives may be added in the dispersion step, or may be added after the barium sulfate fine particles (a) are dispersed in the matrix component.

Since the active energy ray-curable resin composition of the present invention has a feature of high surface hardness of the hardened coating film, it can be suitably used for coating applications for protecting molded articles, display members, and various film materials from damage. Furthermore, it has the characteristics of high flexibility of hardened materials and difficulty in generating interference fringes when used in laminated film applications, and is particularly suitable for coatings for plastic films.

The coating material containing the above-mentioned active energy ray-curable resin composition can be coated on various substrates and irradiated with active energy rays to harden it to form a coating film for protecting the surface of the substrate. The coating material of the present invention can be directly applied to a member protected by a surface, and can also be used as a protective film formed by coating on a plastic film. Alternatively, those who apply the coating material of the present invention to a plastic film to form a coating film can be used as an optical film such as an anti-reflection film, a diffusion film, and a cymbal.

Examples of the plastic film include triethyl cellulose film, polyester film, acrylic film, cycloolefin polymer film, polyimide film, polyimide film, polystyrene film, polycarbonate film, and polypropylene film. Wait.

Among the above plastic films, triacetyl cellulose film is particularly suitable for use in polarizing plates of liquid crystal displays. However, since the thickness is usually as thin as 40 to 100 μm, even when a hard coating layer is provided, the surface hardness is difficult. It is increased to a sufficient hardness, and has a characteristic of being easily warped. The coating film formed from the resin composition of the present invention can achieve the effects of high surface hardness, warpage resistance, toughness, and transparency even when a triethylfluorene cellulose film is used as a substrate. Instead, it can be used appropriately. In the case of using the triethyl cellulose film as a substrate, the coating amount when coating the coating material of the present invention is preferably applied so that the film thickness after drying becomes in a range of 4 to 20 μm, and more preferably Coating was performed so that it might become the range of 6-15 micrometers. Examples of the coating method at this time include bar coater coating, Mel bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

Examples of the polyester film in the plastic film include polyethylene terephthalate, and the thickness is usually about 100 to 300 μm. Since it is inexpensive and easy to process, it is a film for various uses such as a touch panel display. However, it is very flexible, and even when a hard coat layer is provided, it is difficult to increase the surface hardness to a sufficient hardness. When the polyethylene film is used as a base material, it is preferable that the coating amount when coating the coating material of the present invention is applied in such a manner that the film thickness after drying becomes within a range of 5 to 100 μm according to the application. Coating is performed so that it may become the range of 7-80 micrometers. Generally, when the coating is applied with a film thickness exceeding 30 μm, compared with the case where the coating is performed with a relatively thin film thickness, there is a tendency that a large warpage tends to occur, but the coating of the present invention is Since it has a characteristic of being excellent in warpage resistance, even if it is applied at a thick film thickness exceeding 30 μm, warpage is difficult to occur, and it can be suitably used. Examples of the coating method at this time include bar coater coating, Mel bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

The polymethacrylate film in the above plastic film is relatively thick and generally strong because it is generally about 100 to 2,000 μm in thickness. Therefore, it is suitable for use in front panel applications such as liquid crystal displays, which require high surface hardness. When the polymethacrylate film is used as a base material, the coating amount when coating the coating material of the present invention is applied according to the application, and the coating is preferably performed so that the film thickness after drying becomes a range of 5 to 100 μm. It is preferable to perform coating so that it may become the range of 7-80 micrometers. Generally, when a coating is applied to a relatively thick film such as a polymethacrylate film with a thickness of more than 30 μm, although it is a laminated film with a high surface hardness, it is relatively transparent. It tends to decrease, but the paint of the present invention has a very high transparency compared with conventional paints, so a laminated film having both high surface hardness and transparency can be obtained. Examples of the coating method at this time include bar coater coating, Mel bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

Examples of the active energy rays irradiated when the coating material of the present invention is hardened to form a coating film include ultraviolet rays and electron beams. In the case of hardening by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp as a light source is used, and the amount of light and the configuration of the light source are adjusted as necessary. When a high-pressure mercury lamp is used, it is preferable to perform curing at a conveying speed in a range of 5 to 50 m / min. Relative to a 1-lamp with a light amount in a range of usually 80 to 160 W / cm. On the other hand, when it is hardened by an electron beam, it is preferable to harden by an electron beam acceleration device having an acceleration voltage in a range of usually 10 to 300 kV at a conveying speed of 5 to 50 m / min.

In addition, the base material on which the coating material 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, home appliances, and automobile bumpers. In this case, the method of forming the coating film includes, for example, a coating method, a transfer method, a sheet bonding method, and the like.

The coating method is to spray-coat the coating material described above, or use a curtain coater, roll coater, gravure coater or other printing equipment to form a top coat after forming the coated product, and then irradiate and harden the active energy rays. Method.

Examples of the transfer method include: transferring a transfer material obtained by applying the coating material of the present invention to a substrate sheet having mold release properties on the surface of a molded product, peeling the substrate sheet, and transferring the overcoat layer to the substrate. A method of hardening the surface of a molded product by irradiating active energy rays, or hardening the transfer material on the surface of the molded product, irradiating the active energy rays to harden the substrate, and then peeling off the base sheet to coat the top layer Method for transferring on the surface of the molded product.

On the other hand, the above-mentioned sheet bonding method is performed by applying a "protective sheet having a coating film made of the coating material of the present invention on the base sheet" or a "coating layer made of the above coating material on the base sheet". "Protective sheet of film and decorative layer" is a method of forming a protective layer on the surface of a molded product by forming it on a plastic molded product.

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

In the transfer method described above, a transfer material is first produced. The transfer material can be produced by, for example, coating the above-mentioned coating material alone or a mixture with a polyisocyanate compound on a base material sheet and heating it to semi-harden (B-stage) the coating film.

Here, when the matrix resin (B) having the (meth) acrylfluorenyl group contained in the active energy ray-curable compound of the present invention is a compound having a hydroxyl group in the molecular structure, it is performed more efficiently. For the purpose of the B-stage step, a polyisocyanate compound may be used in combination.

In order to manufacture a transfer material, the above-mentioned coating material of the present invention is first coated on a substrate sheet. Examples of the method for applying the above coating include gravure coating, roll coating, spray coating, lip coating, comma coat, and other coating methods; gravure printing and screen printing. Printing method, etc. In terms of abrasion resistance and chemical resistance, it is preferable that the film thickness at the time of coating is such that the thickness of the cured film becomes 0.5 to 30 μm, and more preferably 1 ~ 6μm.

After the coating material is coated on the base material sheet in the above-mentioned method, the coating film is semi-hardened (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, and more preferably 1 to 5 minutes.

The formation of the surface protective layer of a molded article using the transfer material is performed, for example, by bonding the B-staged resin layer of the transfer material to the molded article, and then curing the resin layer by irradiating active energy rays. Specifically, for example, there can be mentioned a method in which the B-staged resin layer of the transfer material is adhered to the surface of the molded article, and then the base material sheet of the transfer material is peeled off, and then the process of the transfer material is performed. After the B-staged resin layer is transferred onto the surface of the molded article, the energy rays are hardened by irradiation with active energy rays to cross-link and harden the resin layer (transfer method); or the transfer material described above It is sandwiched into a molding die, and the resin is injected to fill the mold groove. When a resin molded product is obtained, the transfer material is adhered to the surface, the base sheet is peeled off and transferred to the molded product, and then irradiated with active energy rays. A method of curing the energy ray to crosslink and harden the resin layer (simultaneous molding method) and the like.

Next, the sheet bonding method specifically includes a method in which a base sheet of a sheet for forming a protective layer formed in advance and a molded product are bonded, and then heat-cured by heating to perform "B-stage The method of “cross-linking and hardening the formed resin layer” (the subsequent method); or sandwiching the above-mentioned sheet for forming a protective layer into a molding die and injecting resin into the mold cavity to obtain a resin molded product. A method (simultaneous molding and continuous bonding method) of bonding the surface to a sheet for forming a protective layer and then thermally curing the resin layer by heating to perform cross-curing of the resin layer.

Next, the coating film of the present invention is a coating film formed by coating the coating material of the present invention on the plastic film and hardening it, or coating and curing the coating material of the present invention as a surface protective agent for plastic molded products The coating film of the present invention is a film having a coating film formed on a plastic film.

Among the various uses of the film, as described above, from the viewpoint of excellent coating film hardness, the film obtained by coating the coating material of the present invention on a plastic film and irradiating active energy rays is preferably used as a liquid crystal display or A protective film for a polarizing plate such as a touch panel display is used. Specifically, when the coating of the present invention is applied to a protective film of a polarizing plate used in a liquid crystal display, a touch panel display, or the like, and cured by irradiating with active energy rays, the coating film is cured. It will become a protective film with both high hardness and high transparency. In a protective film application of a polarizing plate, an adhesive layer may be formed on the other surface of the coating layer obtained by applying the coating material of the present invention.

The laminated film of the present invention can exhibit the characteristics of high surface hardness and flexibility, and difficult to generate interference fringes, and can be preferably used as a surface protection film for display components or automobile components, building materials, and various electronic devices, home appliances, furniture, etc. , Alternative plating, alternative coating, etc.

[Example]

Hereinafter, the present invention will be described more specifically with reference to specific manufacturing examples and examples, but the present invention is not limited to these examples. Unless otherwise stated, the parts and% in the examples are all based on quality.

In the examples of the present invention, the weight average molecular weight (Mw) is a value measured using a gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Co., Ltd.

Column: Protective Column H _XL -H made by Tosoh Co., Ltd.

+ 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 Co., Ltd.

Measurement conditions: column temperature 40 ℃

Tetrahydrofuran

Flow rate 1.0ml / min

Standard: Polystyrene

Sample: a solution obtained by filtering a tetrahydrofuran solution with a mass fraction of 0.4% by mass of a resin solid content through a microfilter (100 μl)

In the examples of this case, the average particle diameter of the barium sulfate fine particles (A) is a value obtained by measuring the particle diameter of the active energy ray-curable resin composition under the following conditions.

Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.

Particle diameter measurement sample: The active energy ray-curable resin composition was diluted with methyl isobutyl ketone, and the concentration of the barium sulfate fine particles (A) was adjusted to 0.2% by mass.

Production Example 1 Production of Acrylic Acrylic Group-Containing Acrylic Resin (B-1)

453 parts by mass of methyl isobutyl ketone was added to a reaction device equipped with a stirring device, a condensing tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised while stirring until the temperature in the system became 110 ° C; 720 parts by mass of glycidyl methacrylate, 480 parts by mass of methyl methacrylate, and third butyl peroxide (2-ethylhexanoate) ("PERBUTYL" O ″) 48 parts by mass of the mixed solution, and the mixture was kept at 110 ° C. for 15 hours. Subsequently, the temperature was lowered to 90 ° C, and then 1.6 parts by mass of p-methoxyphenol and 367 parts by mass of acrylic acid were added. After 7.8 parts by mass of triphenylphosphine was added, the temperature was further increased to 100 ° C and held for 8 hours to obtain 3000 parts by mass of a methyl isobutyl ketone solution of acryl-based acrylic resin (B-1) (nonvolatile content 50.0% by mass). The weight average molecular weight (Mw) of the acryl group-containing acrylic resin (B-1) was 13,000, the theoretical acryl group equivalent in terms of solid content was 321 g / eq, and the hydroxyl value was 108 mgKOH / g.

Production Example 2 Production of Acrylic Amide Resin (B-2)

166 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, 0.2 parts by mass of dibutyltin dilaurate, and 0.2 parts by mass of p-methoxyphenol were added to a reaction device equipped with a stirring device, and the temperature was raised while stirring 60 ° C. Then, 630 parts by mass of "Alonics M-305" (* 1) manufactured by Toa Kosei Co., Ltd. was added 10 times every 10 minutes. The reaction was allowed to wait for 10 hours, and the absorption of the isocyanate group at 22500 cm ^-1 disappeared by infrared spectroscopy, and the reaction was completed to obtain an acrylate amine resin (B-2). The weight average molecular weight (Mw) of the amine acrylate resin (B-2) was 1,400, and the theoretical propylene fluorene equivalent was 120 g / eq.

(* 1) "Alonics M-305" manufactured by Toa Synthesis Co., Ltd .: a neopentyltetraol polyacrylate composition containing approximately 60% of neopentyltetraol triacrylate

Production Example 3 Production of Acrylic Amide Resin (B-3)

735 parts by mass of "Alonics M-403" (* 2) manufactured by Toa Kosei Co., Ltd. was added to a reaction device equipped with a stirring device, and the temperature was raised to 60 ° C while stirring. Then, 79 parts by mass of hexamethylene diisocyanate, 0.2 parts by mass of dibutyltin dilaurate, and 0.2 parts by mass of p-methoxyphenol were added 10 times every 10 minutes. The reaction was allowed to wait for 10 hours, and the absorption of the isocyanate group at 22500 cm ^-1 disappeared by infrared spectroscopy, and the reaction was completed to obtain an acrylic amine resin (B-3). The weight average molecular weight (Mw) of the amine acrylate resin (B-3) was 4,500, and the theoretical propylene fluorene equivalent was 350 g / eq.

(* 2) "Alonics M-403" manufactured by Toa Synthesis Co., Ltd .: a dipentaerythritol polyacrylate composition containing about 55% of dipentaerythritol pentaacrylate

Example 1 Production and evaluation of active energy ray-curable resin composition

40 parts by mass of a methyl isobutyl ketone solution of the (meth) acrylfluorene-containing acrylic resin (B-1) obtained in Production Example 1 (20 parts by mass of the resin solid content), and (meth) 25 parts by mass of acrylic monomer ("Rumikyua DPA-600T" (* 3) manufactured by Toa Synthesis Co., Ltd.), barium sulfate fine particles (a-1) ("BARIFINE BF-1" manufactured by Sakai Chemical Industry Co., Ltd. , Average particle size: 0.05 μm), 50 parts by mass, 5 parts by mass of a dispersion aid ("BYK-111" manufactured by BYK), and an appropriate amount of methyl isobutyl ketone (MIBK) was further added to form a nonvolatile component of 40 The slurry in mass% was mixed and dispersed using a wet ball mill ("Starmill LMZ 015" manufactured by Ashizawa Co., Ltd.) to obtain a dispersion.

(* 3) "Rumikyua DPA-600T" manufactured by Toa Synthesis Co., Ltd .: Composition containing dinepentaerythritol pentaacrylate and dinepentaerythritol hexaacrylate at a molar ratio of 40/60

Each condition of the dispersion by the wet ball mill is as follows.

Medium: Zirconia particles with a median diameter of 100 μm

Filling ratio of resin composition relative to the internal volume of the grinder: 70% by volume

The peripheral speed of the front end of the stirring blade: 12m / sec

Flow rate of resin composition: 200ml / min

Dispersion time: 60 minutes

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

Evaluation of storage stability

The above-mentioned active energy ray-curable resin composition was left to stand at a temperature of 40 ° C. for one month, and the presence or absence of precipitates was evaluated at each elapsed time.

A: No precipitate was found

B: Precipitation was found after 3 weeks

C: Precipitation was found after 1 week

Made of laminated film

The active energy ray-curable resin composition was applied to a polyethylene terephthalate film (film thickness 125 μm) with a bar coater so that the film thickness after curing became 5 μm, and dried at 70 ° C. for 1 minute. By using a high-pressure mercury lamp under nitrogen to harden it at an irradiation amount of 250 mJ / cm ² , a laminated film was obtained.

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 of laminated films

The occurrence of interference fringes on the surface of the laminated film was observed visually and evaluated using the following criteria.

A: No interference fringes were observed.

B: Interference fringes were confirmed.

Test of pencil hardness of laminated film

According to JIS K 5400, the surface hardness of the resin coating film side of the laminated film was evaluated by a pencil scratch test with a load of 750 g. The test was performed five times, and the hardness lower than the hardness with more than one scratch was set as the pencil hardness of the coating film.

Test of warpage resistance of laminated film

The laminated film was cut into 10 cm squares, and the bulges from the four corners of the level were measured and evaluated based on the average value.

Test of Flexibility of Laminated Film

The following experiment was performed: The laminated film was wound around a test rod using a mandrel tester ("bending tester" manufactured by TP Giken Co., Ltd.), and it was visually confirmed whether a crack occurred. The minimum diameter (mm) of the test rod without cracks was taken as the evaluation result. The test rods are those with a diameter of 2mm to 13mm and a scale of 1mm.

Examples 2 to 14 Production and evaluation of active energy ray-curable resin composition

Except that the blending of the dispersion was changed as shown in Tables 1 and 2, an active energy ray-curable resin composition was obtained in the same manner as in Example 1, and various methods were performed in the same manner as in Example 1. test. The results are shown in Tables 1 and 2.

[Used raw materials]

‧Barium sulfate fine particles (a-2): "BARIACE B-30" manufactured by Hikari Chemical Industry Co., Ltd.

‧Barium sulfate fine particles (a-3): "BARIACE B-31" manufactured by Hikari Chemical Industry Co., Ltd.

‧Barium sulfate fine particles (a-4): "BARIACE B-34" manufactured by Hikari Chemical Industry Co., Ltd.

‧Barium sulfate fine particles (a-5): "Barium sulfate BB-02" manufactured by Hikari Chemical Industry Co., Ltd.

‧ "Miramer SP-1106" manufactured by MIWON: dendritic polymer poly (meth) acrylate resin, weight average molecular weight (Mw) 1,630, average (meth) acrylic acid fluorene group number per molecule 18

‧KBM-503: Silane coupling agent, "KBM-503" 3-methacryloxypropyltrimethoxysilane produced by Shin-Etsu Chemical Industry Co., Ltd

‧BYK-145: Dispersion aid, "BYK-145" manufactured by BYK

‧MEK: methyl ethyl ketone

‧PGM: Propylene glycol monomethyl ether

‧MRK / PGM: 50/50 mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether

Comparative Example 1 Production and evaluation of active energy ray-curable resin composition

40 parts by mass of a methyl isobutyl ketone solution of the (meth) acrylfluorene-containing acrylic resin (B-1) obtained in Production Example 1 (20 parts by mass of the resin solid content), and (meth) 30 parts by mass of acrylate monomer ("Rumikyua DPA-600T" manufactured by Toa Synthesis Co., Ltd., 167 parts by mass of silica sol (* 4), photoinitiator ("Irgacure # 184" manufactured by Ciba Specialty Chemicals) ) 2 parts by mass, and methyl isobutyl ketone (MIBK) was further added to adjust the non-volatile content rate to 40% by mass to obtain an active energy ray-curable resin composition. Regarding the obtained active energy ray-curable resin composition, various tests were performed in the same manner as in Example 1. The results are shown in Table 2.

(* 4) Silicon dioxide dispersion "MEK-ST" manufactured by Nissan Chemical Co., Ltd .: solid content of silicon dioxide is 30% by mass, and average particle size is 10-15nm

Claims (6)

    An active energy ray-curable resin composition containing barium sulfate fine particles (A) having an average particle size in a range of 60 to 250 nm, and a matrix resin (B) having a (meth) acrylic acid fluorene group.         For example, the active energy ray-curable resin composition according to item 1 of the patent application range, wherein the mass ratio [(A) / (B)] of the barium sulfate fine particles (A) to the matrix resin (B) is 30/70 ~ 70/30 range.         For example, the active energy ray-curable resin composition according to item 1 of the patent application, wherein a (meth) acrylate resin (B1) and a (meth) acrylate monomer (B2) are used as the matrix resin (B). .         A coating material containing the active energy ray-curable resin composition according to any one of claims 1 to 3 of the application scope.         A coating film is composed of a coating material under the scope of patent application No. 4.         A laminated film having a layer composed of a coating film according to item 5 of the patent application.