TW201736133A - Multilayer film - Google Patents

Abstract

The purpose of the present invention is to provide a multilayer film which exhibits high surface hardness and scratch resistance and exhibits excellent flexibility. Provided is a multilayer film which has a plastic film layer (X), a primer layer (Y) and a hard coat layer (Z), and which is characterized in that the primer layer (Y) is a cured product of a primer-forming composition (y) that contains inorganic fine particles (A) and a (meth)acryloyl group-containing resin (B) having a weight average molecular weight (Mw) of 1000 or more as essential components, and the hard coat layer (Z) is a cured product of a hard coat-forming composition (z) that contains a (meth)acrylate compound (C) as an essential component.

Description

Laminated film

The present invention relates to a laminated film having high surface hardness and scratch resistance and excellent flexibility.

Plastic films such as a triacetyl cellulose film, a polyester film, an acrylic film, and a cycloolefin polymer film are often used for industrial applications such as a polarizing plate protective film incorporated in a flat panel display or a surface protective film of a touch panel. These plastic films are often provided with a coating composed of an active energy ray-curable resin or the like because the surface thereof is easily damaged by the use thereof, and the workability is low and cracking or cracking is likely to occur. A laminated film is formed to compensate for these properties.

As a laminated film excellent in scratch resistance on the surface, for example, an intermediate layer composed of an organic-inorganic fine particle-mixed resin is provided on a PET film, and a carbon-containing cerium oxide layer is deposited thereon by a plasma CDV method. Further, a vapor-deposited layer of a fluorine-containing acrylate is further provided thereon (see Patent Document 1). The laminated film described in Patent Document 1 has a fluorine-containing acrylate layer on its surface, and therefore has excellent surface scratch resistance. However, the surface hardness is not high and the flexibility is also inferior.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2015-3510

In view of the above circumstances, the problem to be solved by the present invention is to provide a laminated film which is obtained by providing a coating on various plastic substrates, and which has high surface hardness and scratch resistance and excellent flexibility.

The present inventors have made an effort to solve the above problems, and as a result, it has been found that a laminate film obtained by using a curable composition containing inorganic fine particles as a primer layer when a hard coat layer is provided on a plastic film substrate has a surface hardness and The present invention has been completed in terms of scratch resistance and flexibility.

That is, the present invention relates to a laminated film having a plastic film layer (X), an undercoat layer (Y), and a hard coat layer (Z), characterized in that the undercoat layer (Y) contains inorganic fine particles ( A) and a cured product of the undercoating composition (y) containing the (meth)acrylonitrile group-containing resin (B) as an essential component, and the weight of the (meth)acrylonitrile-containing resin (B) The average molecular weight (Mw) is 1,000 or more; and the hard coat layer (Z) is a cured product of the hard coating composition (z) containing the (meth) acrylate compound (C) as an essential component.

According to the present invention, it is possible to provide a laminated film having high surface hardness and scratch resistance and excellent flexibility.

The laminated film of the present invention has a plastic film layer (X), an undercoat layer (Y), and a hard coat layer (Z), characterized in that the undercoat layer (Y) contains inorganic fine particles (A) and the following The (meth)acrylonitrile-based resin (B) is a cured product of the primer composition (y) as an essential component, and the weight average molecular weight (Mw) of the (meth)acrylonitrile-containing resin (B) is 1,000 or more; the hard coat layer (Z) is a cured product of the hard coat composition (z) containing the (meth) acrylate compound (C) as an essential component.

Examples of the plastic film layer (X) include various plastic films which are generally referred to as a base film. In particular, it is preferable to exhibit the characteristics of the laminated film of the present invention which is excellent in surface hardness and scratch resistance, and which is excellent in flexibility, and is also used as a high-performance trimethyl cellulose film or polyester film for an optical film for a display. Any one of an acrylic film, a cycloolefin polymer film, a polyamide film, a polyimide film, a polystyrene film, a polycarbonate film, and a polypropylene film.

The undercoat layer (Y) is a cured product of the undercoating composition (y) containing inorganic fine particles (A) and the following (meth)acrylonitrile-based resin (B) as an essential component; The weight average molecular weight (Mw) of the acryl resin (B) is 1,000 or more.

The inorganic fine particles (A) are obtained by dispersing the inorganic particles (a) to be a raw material in a matrix component such as a (meth)acrylonitrile-containing resin (B) or another curable component or an organic solvent. Examples of the inorganic particles (a) include cerium oxide, aluminum oxide, and oxidation. Microparticles such as zirconium, titanium dioxide, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more.

Among the inorganic particles (a), cerium oxide fine particles are preferred because they are easy to obtain and easy to handle. Examples of the cerium oxide fine particles include various cerium oxide fine particles such as cerium oxide, or wet cerium oxide such as precipitated cerium oxide, gel cerium oxide, or sol-gel cerium oxide. Any one can be used.

The inorganic particles (a) may be those having a functional group introduced on the surface of the fine particles by various decane coupling agents. By introducing a functional group on the surface of the inorganic particles (a), the mixing property with the organic component such as the (meth)acrylonitrile-containing resin (B) is improved, and the storage stability is improved.

Examples of the above decane coupling agent include vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and 3- Glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane , 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl Salt of trimethoxy decane Acid salt, special amino decane, 3-ureidopropyltriethoxy decane, 3-chloropropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxy Base decane, bis(triethoxymethyl propyl) tetrasulfide, 3-isocyanate propyl triethoxy decane, allyl trichloro decane, allyl triethoxy decane, allyl trimethyl Oxy decane, diethoxymethyl vinyl decane, trichlorovinyl decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-methoxy) Vinyl decane coupling agent such as ethoxy) decane; diethoxy (glycidoxypropyl) methyl decane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxy decane, 3-shrinkage Epoxy decane coupling agent such as glyceryloxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane; Styrene-based decane coupling agent such as trimethoxy decane; 3-methacryloxypropylmethyldimethoxydecane, 3-propenyloxypropyltrimethoxydecane 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, etc. Methyl) propylene methoxy decane coupling agent; N-2 (aminoethyl) 3-aminopropyl methyl dimethoxy decane, N-2 (aminoethyl) 3-aminopropyl Trimethoxydecane, N-2 (aminoethyl) 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 - an amine-based decane coupling agent such as triethoxyindenyl-N-(1,3-dimethyl-butylene)propylamine or N-phenyl-3-aminopropyltrimethoxydecane; a urea-based decane coupling agent such as ureidopropyltriethoxy decane; a chloropropyl decane coupling agent such as 3-chloropropyltrimethoxydecane; a mercapto decane coupling agent such as 3-mercaptopropylmethyldimethoxydecane or 3-mercaptopropyltrimethoxydecane; a thioether decane coupling agent such as bis(triethoxydecylpropyl)tetrasulfide An isocyanate-based decane coupling agent such as 3-isocyanatepropyltriethoxydecane. These decane coupling agents may be used alone or in combination of two or more. Among these, the primer composition (y) which is excellent in the miscibility of the organic component such as the (meth)acryl fluorenyl group-containing acrylic resin (B) and which is excellent in curability is The (meth)acryloxy methoxy decane coupling agent is more preferably 3-propenyloxypropyltrimethoxydecane or 3-methylpropenyloxypropyltrimethoxydecane.

The average particle diameter of the inorganic fine particles (A) in the primer composition (y) is preferably in the range of 80 to 250 nm in terms of the balance between the surface hardness and the flexibility of the laminated film. Preferably, it is in the range of 90 to 180 nm, and particularly preferably in the range of 100 to 150 nm.

Furthermore, in the invention, the average particle diameter of the inorganic fine particles (A) is a value obtained by measuring the particle diameter in the undercoat composition (y) under the following conditions.

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

Particle size measurement sample: The primer composition (y) was obtained by preparing a methyl isobutyl ketone solution having a nonvolatile content of 1% by mass.

The content of the inorganic fine particles (A) in the primer composition (y) is preferably in comparison with the primer composition in terms of the balance between the surface hardness and the flexibility of the laminate film ( The total of the inorganic fine particles (A) and the resin component in the above y) is in the range of 5 to 85% by mass, more preferably in the range of 10 to 75% by mass, still more preferably in the range of 20 to 65 parts by mass. In addition, the above-mentioned resin component means the following (meth) acrylonitrile-containing resin (B), And a resin component other than the (meth)acrylonitrile-based resin (B).

The weight average molecular weight (Mw) of the (meth)acrylonitrile group-containing resin (B) having a weight average molecular weight (Mw) of 1,000 or more is 1,000 or more, as long as it has a plurality of (meth)acrylonitrile groups in the resin structure. However, the specific structure is not particularly limited.

The weight average molecular weight (Mw) of the (meth)acrylonitrile group-containing resin (B) is excellent in adhesion to the plastic film layer (X), and the laminated film is excellent in the primer composition (y). The softness is preferably in the range of 1,000 to 80,000, more preferably in the range of 1,200 to 50,000, and particularly preferably in the range of 1,500 to 30,000.

Further, in the present invention, the weight average molecular weight (Mw) is a value measured by a gel permeation chromatography (GPC) by the following conditions.

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

Pipe column: Protection column H _XL -H manufactured by Tosoh Co., Ltd.

+TSKgel G5000H _XL manufactured by Tosoh Co., Ltd.

+TSKgel G4000H _XL manufactured by Tosoh Co., Ltd.

+TSKgel G3000H _XL manufactured by Tosoh Co., Ltd.

+TSKgel G2000H _XL manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data Processing: SC-8010 manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: Polystyrene

Sample: A tetrahydrofuran solution of 0.4% by mass in terms of resin solid content was filtered through a microfilter to obtain (100 μl)

Specific examples of the (meth)acrylonitrile group-containing resin (B) include a (meth)acrylonitrile-based acrylic resin (B1) and a dendrimer-type poly(meth)acrylate. (B2), (meth) acrylate (B3), epoxy (meth) acrylate (B4), and the like. These may be used alone or in combination of two or more.

The (meth)acrylate monomer (B1) containing the (meth) acrylonitrile group may, for example, be a (meth) acrylate monomer having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group ( (α) an acrylic resin intermediate obtained by polymerization as an essential component, further reacted with a (meth) acrylate monomer (β) having a reactive functional group reactive with the functional groups, and introduced (methyl) Acetylene based and obtained.

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. Hydroxy (meth) acrylate such as dihydroxypropyl ester; (meth)acrylic acid, (acryloxy)acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 1-[2-( a carboxyl group (such as acryloxy)ethyl]ester, -1-(2-propenyloxyethyl) phthalate, 2-(propylene decyloxy) hexahydrophthalate Methyl) acrylate; 2-propenyloxyethyl isocyanate, 2-methylpropenyloxyethyl isocyanate, 1,1-bis(acryloxymethyl)ethyl isocyanate Isocyanate group-containing (meth) acrylate; (meth) acrylate glycidyl ester, 4-hydroxybutyl acrylate glycidyl A glycidyl group-containing (meth) acrylate or the like such as oleyl ether. These may be used alone or in combination of two or more.

Among these, it is preferred to use a carboxyl group-containing (meth) acrylate or a shrinkage-containing product in terms of production of the (meth) acrylonitrile-based acrylic resin (B1) which can be produced in a simple and stable manner. A glyceryl (meth) acrylate is used as the above-mentioned (meth) acrylate monomer (α) having a reactive functional group.

The acrylic resin intermediate may be obtained by copolymerizing other polymerizable unsaturated group-containing compound, if necessary, in addition to the above-mentioned (meth) acrylate monomer (α) having a reactive functional group. By.

Examples of the other polymerizable unsaturated group-containing compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, and (methyl). Amyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (A) Ethyl acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, etc. a ring-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isodecyl (meth) acrylate or dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate; An aromatic ring-containing (meth) acrylate such as benzyl acrylate or phenoxyethyl acrylate; or a fluorenyl (meth) acrylate such as 3-methacryloxypropyltrimethoxydecane; N-(meth)acrylic acid dimethylaminoethyl ester, N,N-(methyl) propylene N,N-(meth)acrylic acid dialkylaminoalkyl ester such as diethylaminoethyl acetate or diethylaminopropyl N,N-(meth)acrylate; (meth)acrylic acid 2,2, 2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H, (meth)acrylic acid, (meth)acrylic acid (per) fluoroalkane having a carbon number of from 1 to 18, such as 2H, 2H-heptadecafluorodecyl ester, (per) fluoroethyloxyethyl (meth) acrylate a (per)fluorine having a carbon number of from 1 to 18, such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluoroethylene ether, heptafluoropropyl trifluorovinyl ether or the like. Alkyl-perfluorovinyl ether; dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, anti Unsaturated dicarboxylates such as methyl butyrate, butyl fumarate, methyl ethyl itaconate; styrene such as styrene, α-methylstyrene or chlorostyrene Derivatives; diene compounds such as butadiene, isoprene, pentadiene, dimethyl butadiene; halogenated ethylene or vinylidene halide such as vinyl chloride or vinyl bromide An unsaturated ketone such as methyl vinyl ketone or butyl vinyl ketone; a vinyl ester such as vinyl acetate or vinyl butyrate; a vinyl ether such as methyl vinyl ether or butyl vinyl ether; acrylonitrile or methacrylonitrile; Ethylene cyanide such as metacyanylene dichloride; acrylamide or its alkyd substituted decylamine; N-substituted maleimide such as N-phenyl maleimide and N-cyclohexyl maleimide Diimine Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, trifluorobromoethylene, pentafluoropropylene, and hexafluoropropylene. These may be used alone or in combination of two or more.

Among these other compounds containing a polymerizable unsaturated group, it is preferable to use the above (meth) in terms of the undercoating composition (y) excellent in adhesion to the plastic film layer (X). Alkyl acrylate.

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

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

Then, the (meth) acrylate monomer (β) which reacts with the obtained acrylic resin intermediate is a member which can react with the reactive functional group of the above (meth) acrylate monomer (α), and It is not particularly limited, and from the viewpoint of reactivity, the following combinations are preferred. That is, in the case where the above-mentioned hydroxyl group-containing (meth) acrylate is used as the above (meth) acrylate monomer (α), it is preferred to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate. Monomer (β). When the above carboxyl group-containing (meth) acrylate is used as the above (meth) acrylate monomer (α), it is preferred to use the above glycidyl group-containing (meth) acrylate as the (meth) acrylate. Monomer (β). When the above-mentioned (meth) acrylate-containing (meth) acrylate monomer (α) is used, it is preferred to use the above-mentioned hydroxy group-containing (meth) acrylate as the (meth) acrylate single. Body (β). When the above glycidyl group-containing (meth) acrylate is used as the above (meth) acrylate monomer (α), it is preferred to use the above carboxyl group-containing (meth) acrylate as the (meth) acrylate. Monomer (β).

Regarding the reaction of the above-mentioned acrylic resin intermediate with the (meth) acrylate monomer (β), for example, when the reaction is an esterification reaction, triphenylphosphine is suitably used in the temperature range of 60 to 150 ° C. And other methods such as esterification catalyst. Further, when the reaction is an amine esterification reaction, a method in which a compound (α) is added dropwise to an acrylic resin intermediate in a temperature range of 50 to 120 ° C, and the like may be mentioned.

The weight average molecular weight (Mw) of the (meth)acrylonitrile group-containing acrylic resin (B1) is excellent in adhesion to the layer adjacent to the laminated film, and the primer composition (y) is excellent in adhesion to the layer adjacent to the laminated film. The aspect of the laminated film excellent in flexibility is preferably in the range of 5,000 to 80,000, more preferably in the range of 10,000 to 50,000. Further, the (meth)acryl oxime group equivalent of the (meth)acryl fluorenyl group-containing acrylic resin (B1) is preferably in the range of 200 to 300 g/eq.

The above-mentioned dendrimer-type poly(meth)acrylate (B2) refers to a tree having a regular multi-branched structure and having a (meth)acryl fluorenyl group at the end of each branch. The fat, in addition to the dendrimer type, is also referred to as a hyperbranch type or a star polymer. Examples of such a compound include those represented by the following structural formulae (B2-1) to (B2-8), but are not limited thereto, and are plural branches having a regular structure and are at the ends of each branch. Any resin having a (meth) acrylonitrile 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 the dendrimer-type poly(meth)acrylate (B2) having such a molecular structure, "Viscoat #1000" manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 to 2,000 can also be used. Average number of (meth)acrylonitrile groups per molecule 14], "Viscoat 1020" [weight average molecular weight (Mw) 1,000 to 3,000], "SIRIUS501" [weight average molecular weight (Mw) 15,000 to 23,000], "SP manufactured by MIWON" -1106" [weight average molecular weight (Mw) 1,630, average (methyl) acrylonitrile group per molecule 18], "CN2301" and "CN2302" manufactured by SARTOMER Co., Ltd. [average (methyl) acrylonitrile group per molecule 16 ], "CN2303" [average (methyl) acrylonitrile group per molecule 6], "CN2304" [average (meth) acrylonitrile group per molecule 18], "ESDRIMER" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "A-HBR-5" manufactured by Shin-Nakamura Chemical Co., Ltd., "NEW FRONTIER R-1150" manufactured by Daiichi Kogyo Co., Ltd., Nissan Chemical Co., Ltd. Commercial products such as "HYPERTECH UR-101" manufactured by the company. These may be used alone or in combination of two or more.

Among the dendrimer-type poly(meth)acrylates (B2), the primer composition (y) is excellent in adhesion to a layer adjacent to the laminate film, and the flexibility of the laminate film is also obtained. In terms of excellent balance with surface hardness, the average number of (meth)acrylonitrile groups per molecule is preferably in the range of 5 to 50, particularly preferably in the range of 10 to 30. Further, the weight average molecular weight (Mw) thereof is preferably in the range of 1,000 to 30,000.

The (meth)acrylic acid amine ester (B3) may, for example, be reacted with various polyisocyanate compounds, monohydroxy (meth) acrylate compounds, and optionally dihydroxy (meth) acrylate compounds or various polyol compounds. Winner. Examples of the polyisocyanate compound include diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, benzodimethyl diisocyanate, and 4,4′-diphenylmethane diisocyanate, or uronic acid thereof. Ester modified body, adduct modified body, biuret modified body. Examples of the monohydroxy (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di(meth) acrylate, and neopentyl alcohol. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, and such polyoxyalkylene modified bases, polylactone modified bodies, and the like. Examples of the above dihydroxy (meth) acrylate compound include trimethylolpropane mono (meth) acrylate, neopentyl alcohol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. An ester, and the like, a polyoxyalkylene modified body, a polylactone modified body, and the like. Examples of the above polyol compound include ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, and neopentyl alcohol.

The above epoxy (meth) acrylate (B4) may, for example, be a bisphenol compound Or a polyglycidyl ether of a polyhydric alcohol compound such as a biphenol compound, ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane or pentaerythritol. Obtained by reaction with (meth)acrylic acid or the like.

Among the (meth)acrylonitrile-containing resins (B), it is preferred to use the primer composition (y) which is excellent in adhesion to a layer adjacent to the laminate film. The (meth)acrylonitrile-containing acrylic resin (B1) or the dendrimer-type poly(meth)acrylate (B2) is an essential component.

In addition to the (meth)acrylonitrile-containing resin (B) having a weight average molecular weight (Mw) of 1,000 or more, the primer composition (y) may contain other resin components, and the present invention is sufficiently exhibited. In terms of the effect, it is preferable that the ratio of the (meth)acrylonitrile-containing resin (B) in the resin component in the primer composition (y) is in the range of 5 to 80% by mass, Preferably, it is in the range of 10 to 50% by mass, and particularly preferably in the range of 15 to 40% by mass.

Other resin components other than the (meth)acrylonitrile group-containing resin (B) having a weight average molecular weight (Mw) of 1,000 or more include other curable resin components (B') or non-curable resin components. (B"), etc. Examples of the other curable resin component (B') include various (meth) acrylate monomers, or (meth) acrylate having a weight average molecular weight (Mw) of less than 1,000, and weight. An epoxy (meth) acrylate compound having an average molecular weight (Mw) of less than 1,000.

Examples of the above various (meth) acrylate monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (methyl). ) n-butyl acrylate, isobutyl (meth)acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, propylene oxime Porphyrin, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (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, epoxy B Alkyl modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate Ester, nonylphenol (meth) acrylate, ethylene oxide modified nonyl phenol (meth) acrylate, propylene oxide modified nonyl phenol (meth) acrylate, methoxy diethylene glycol (Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, 2-(methyl) propylene methoxyethyl phthalate 2- Hydroxypropyl ester, (meth)acrylic acid 2- Hydroxy-3-phenoxypropyl ester, hydrogen 2-(methyl)propenyloxyethyl phthalate, 2-(methyl)propenyl propyl phthalate, hexahydroortylene 2-(methyl)propenyl propyl propyl dicarboxylate, 2-(methyl) propylene methoxy propyl tetrahydrophthalate, dimethylaminoethyl (meth) acrylate, (A) Trifluoroethyl acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, single Mono(meth)acrylate such as adamantyl methyl methacrylate; butanediol di(meth)acrylate, hexanediol di(meth)acrylate, hexylene glycol bis(meth)acrylate Ester, propane hexylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, new Di(meth) acrylate such as pentanediol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate; Hydroxymethylpropane tri(meth)acrylate, ethoxylated Hydroxymethylpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethylisocyanurate)tri(meth)acrylate, glycerin Tris(meth)acrylate such as tris(meth)acrylate; pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, di-trimethylolpropane tri Methyl) acrylate, neopentyl alcohol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol Alcohol penta (meth) acrylate, di-trimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane hexa(meth) acrylate a tetrafunctional or higher (meth) acrylate such as an ester; a modified (poly)oxyalkylene chain or (poly)lactone structure introduced into the molecular structure of the above various (meth) acrylate monomers (A Base) acrylate monomer and the like.

The (meth)acrylic acid amide compound may, for example, be obtained by reacting various polyisocyanate compounds, monohydroxy (meth) acrylate compounds, and optionally dihydroxy (meth) acrylate compounds or various polyol compounds. . Examples of the polyisocyanate compound include diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, benzodimethyl diisocyanate, and 4,4′-diphenylmethane diisocyanate, or uronic acid thereof. Ester modified body, adduct modified body, biuret modified body. Examples of the monohydroxy (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di(meth) acrylate, and neopentyl alcohol. (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the polyoxyalkylene alkyl plastomers, polyene Ester modified body and the like. Examples of the above dihydroxy (meth) acrylate compound include trimethylolpropane mono (meth) acrylate, neopentyl alcohol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. An ester, and the like, a polyoxyalkylene modified body, a polylactone modified body, and the like. Examples of the above polyol compound include ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, and neopentyl alcohol.

The epoxy (meth) acrylate compound may, for example, be a bisphenol type epoxy resin or a (meth) acrylate of an epoxy group-containing compound such as trimethylolpropane triglycidyl ether.

These other curable resin components (B') may be used alone or in combination of two or more. In particular, the di(meth)acrylate, the tris(meth)acrylate, and the above tetrafunctional (meth) are preferable in terms of excellent balance between surface hardness and flexibility of the laminated film. An acrylate, and a modified (meth) acrylate monomer having a (poly)oxyalkylene chain or a (poly)lactone structure introduced into the molecular structure, more preferably the above tri(meth)acrylic acid An ester, the above-mentioned tetrafunctional or higher (meth) acrylate, and a modified (meth) acrylate monomer having a (poly)oxyalkylene chain or a (poly)lactone structure introduced into the molecular structure .

When the (meth)acrylonitrile-containing resin (B) is contained in the primer composition (y) and the other curable resin component (B') is contained together, the blend ratio of the two is In view of the excellent balance between the surface hardness and the flexibility of the laminated film, the ratio of the (meth)acrylonitrile-containing resin (B) to the total of the two is preferably from 5 to 80% by mass. The range is more preferably in the range of 10 to 50% by mass, and particularly preferably in the range of 15 to 40% by mass. In addition, the content of the inorganic fine particles (A) in the primer composition (y) is preferably the inorganic fine particles (A) in terms of the balance between the surface hardness and the flexibility of the laminated film. The ratio of the total of the inorganic fine particles (A), the (meth)acrylonitrile-containing resin (B), and other curable resin component (B') to be used as needed is in the range of 5 to 85% by mass. More preferably, it is in the range of 10 to 75 mass%, and particularly preferably in the range of 20 to 65 mass parts.

The non-curable resin component (B") may, for example, be an acrylic resin, an amine ester resin, a polyester resin, a petroleum resin or the like which does not have a reactive group such as a (meth)acryl fluorenyl group. In the case of the resin component (B"), the resin component in the primer composition (y) is preferably the (meth)acrylonitrile-containing resin (B) and other curable resin component ( The total of B') is used in the range of 80% by mass, and more preferably in the range of 90% by mass.

The primer composition (y) may contain various additive components depending on the desired properties. Examples of the additive component include a photopolymerization initiator, a photosensitizer, an organic solvent, an ultraviolet absorber, an antioxidant, a lanthanide additive, a fluorine-based additive, an antistatic agent, a decane coupling agent, a adhesion aid, an organic granule, and a rheology. Control agent, antifoaming agent, antifogging agent, coloring agent, and the like.

Examples of the photopolymerization initiator include benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, and 4,4'-bis(dimethylamino)benzol. Ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, michelitone, 3,3',4,4'-tetra (over Various benzophenones such as tributyl carbonyl carbonyl benzophenone; Ketone, 9-oxosulfur 2-methyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-diethyl 9-oxosulfur Wait Ketone, 9-oxosulfur Category; benzoin, benzoin ether, benzoin ethyl ether, benzoin isopropyl ether and other acyloin ether; benzophenone, diethyl hydrazine and other α-diketones; tetramethylthiuram disulfide, p-toluene Sulfides such as thiodiether; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate; 3,3'-carbonyl-bis(7-diethylamine) Coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(A Thio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide , bis(2,4,6-trimethylbenzylidene)phenylphosphine 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-benzylidene-4'-methyldimethyl sulfide, 2,2'-diethoxyacetophenone, benzoin dimethyl ketal, benzyl Benzyl-β-methoxyethyl acetal, methyl phthalic acid benzoate, bis(4-dimethylaminophenyl) ketone, p-dimethylamino acetophenone, α, α-di Chloro-4-phenoxyacetophenone, amyl 4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2,4-double -trichloromethyl-6-[bis(ethoxycarbonylmethyl)amino]phenyl-symmetric three 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl-symmetric three 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-symmetric three 蒽醌, 2-tertiary butyl hydrazine, 2-pentyl hydrazine, β-chloropurine, and the like. These may be used alone or in combination of two or more.

Among the above photopolymerization initiators, by using 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2- Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 9-oxosulfur And 9-oxosulfur Derivative, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, double (2,4 ,6-trimethylbenzylidene)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4- One or a mixture of two or more of the group of morphylphenyl)-butan-1-one can exhibit activity over a wider range of wavelengths, thereby obtaining a coating having higher hardenability, and thus good.

The commercial product of the photopolymerization initiator is, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500" manufactured by Ciba Specialty Chemicals Co., Ltd. "Irgacure-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"; "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 Company; "Trigonal P1" manufactured by Akzo "Sandoray 1000" manufactured by Sandoz; "DEEP" manufactured by Upjohn; "Quantacure-PDO", "Quantacure-ITX" and "Quantacure-EPD" manufactured by Ward Blenkinsop.

The amount of the photopolymerization initiator to be used is preferably such a range that the function as a photopolymerization initiator can be sufficiently exhibited without causing crystal precipitation or deterioration of the physical properties of the coating film. Specifically, it is preferably in the opposite phase to the bottom. The coating composition (y) is used in an amount of from 0.05 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, based on 100 parts by mass.

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

Examples of the organic solvent include a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a cyclic ether solvent such as tetrahydrofuran or dioxolane; methyl acetate, ethyl acetate and butyl acetate; Equivalent esters; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohols such as carbitol, celecoxime, methanol, isopropanol, butanol, propylene glycol monomethyl ether Solvent; glycol ether solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether or propylene glycol monopropyl ether. These may be used alone or in combination of two or more.

The organic solvent is mainly used for adjusting the viscosity of the undercoat composition (y), and is usually preferably adjusted so that the nonvolatile content is in the range of 10 to 80% by mass.

Examples of the above ultraviolet absorber include 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4- Dimethylphenyl)-1,3,5-three ,2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-upylphenyl)- 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 may be used alone or in combination of two or more.

Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, and a phosphate-based antioxidant. These may be used alone or in combination of two or more.

Examples of the above lanthanide-based additives include, for example, dimethyl polyoxy siloxane, methyl phenyl polyoxy siloxane, cyclic dimethyl polyoxy siloxane, methyl hydrogen polyoxy siloxane, polyether modified dimethyl a polyoxyalkylene copolymer, a polyester modified dimethyl polyoxyalkylene copolymer, a fluorine modified dimethyl polyoxyalkylene copolymer, an amine modified dimethyl polyoxyalkylene copolymer, etc. Alkyl or phenyl polyorganooxygen The alkane and the polyether are modified to have an acryl-based polydimethyl siloxane, a polyester modified polydimethyl methoxy hydride having an acrylic group, and the like. These may be used alone or in combination of two or more.

The fluorine-based additive may, for example, be a "MEGAFAC" series of DIC Corporation. These may be used alone or in combination of two or more.

Examples of the antistatic agent include pyridinium, imidazolium, anthracene, ammonium, or a lithium salt of bis(trifluoromethanesulfonyl) quinone imine or bis(fluorosulfonyl) quinone imine. These may be used alone or in combination of two or more.

Examples of the above decane coupling agent include vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and 3- Glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane , 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl a hydrochloride of a trimethoxy decane, a special amino decane, a 3-ureidopropyl triethoxy decane, a 3-chloropropyltrimethoxy decane, a 3-mercaptopropylmethyldimethoxy decane, 3-mercaptopropyltrimethoxydecane, bis(triethoxymethylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane, allyltrichloro 矽, allyl triethoxy decane, allyl trimethoxy decane, diethoxymethyl vinyl decane, trichlorovinyl decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl Vinyl decane coupling agent such as triethoxy decane or vinyl tris(2-methoxyethoxy) decane; diethoxy (glycidoxypropyl) methyl decane, 2-(3, 4 Epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyl III Epoxy decane coupling agent such as ethoxy decane; styrene decane coupling agent such as p-styryl trimethoxy decane; 3-methyl propylene methoxy propyl methyl dimethoxy decane, 3-propene oxime Oxypropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxy (Meth) propylene methoxy decane coupling agent such as propyl triethoxy decane; N-2 (aminoethyl) 3-aminopropyl methyl dimethoxy decane, N-2 (amino group) B 3-aminopropyltrimethoxydecane, N-2 (aminoethyl) 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Amines such as triethoxydecane, 3-triethoxyindenyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane Base decane coupling agent; urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane; chloropropyl decane coupling agent such as 3-chloropropyltrimethoxydecane; 3-mercaptopropylmethyl a mercapto decane coupling agent such as dimethoxy decane or 3-mercaptopropyltrimethoxy decane; a thioether decane coupling agent such as bis(triethoxymethyl propyl) tetrasulfide; Isocyanate-based decane coupling agent such as 3-isocyanate propyl triethoxy decane. These may be used alone or in combination of two or more.

Examples of the adhesion aid include a phosphate compound such as acidic isopropyl phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These may be used alone or in combination of two or more. For example, "KAYAMER PM-21", "KAYAMER PM-2" manufactured by Nippon Kayaku Co., Ltd., and "LIGHT ESTER P-2M" manufactured by Kyoeisha Chemical Co., Ltd., etc., may be mentioned. .

Examples of the above organic particles include polymethyl methacrylate particles, polycarbonate particles, polystyrene particles, polyacrylic styrene particles, polyfluorene oxide particles, glass particles, acrylic resin particles, and benzoguanamine resin particles. The melamine resin particles, the polyolefin resin particles, the polyester resin particles, the polyamide resin particles, the polyamidylene resin particles, the polyvinyl fluoride resin particles, the polyethylene resin particles, and the like. These may be used alone or in combination of two or more. The average particle diameter of the organic particles is preferably in the range of 1 to 10 μm.

These various additives may be added in an arbitrary amount according to the desired properties and the like, and it is usually preferably used in the range of 0.01 to 40 parts by mass per 100 parts by mass of the primer composition (y).

The primer composition (y) can be produced, for example, by using a disperser, a disperser having a stirring blade such as a turbine blade, a paint agitator, a roll mill, a ball mill, an attritor, and sand. In the disperser such as a mill or a bead mill, the inorganic fine particles (a) are mixed and dispersed in the matrix component such as the (meth)acrylonitrile-containing acrylic resin (B) or other curable component or organic solvent. Among them, in terms of obtaining a uniform and stable dispersion, it is preferred to use a ball mill or a bead mill. The method of mixing and dispersing the above inorganic fine particles (a) in a matrix component can be produced once by dispersing the inorganic fine particles (a) in the total amount of the matrix component. The method of the primer composition (y) may be a method in which the inorganic fine particles (a) are dispersed in one part of the matrix component to prepare a pre-dispersion, and then the remaining matrix component is blended. Further, various additives may be added in the dispersion step, or may be added after the inorganic fine particles (a) are dispersed in the matrix component.

The hard coat layer (Z) is a cured product of the hard coat composition (z) containing the (meth) acrylate compound (C) as an essential component. The (meth) acrylate compound (C) is exemplified by the (meth) acrylonitrile-containing resin (B) or the other curable component (B') having a weight average molecular weight (Mw) of 1,000 or more. Various compounds are described. The (meth) acrylate compound (C) may be used alone or in combination of two or more. Among them, in terms of a laminated film excellent in the balance between scratch resistance and flexibility, it is preferred to use various (meth) acrylate monomers or (meth) acrylate amide compounds as essential components. For use in combination.

Further, among the various (meth) acrylate monomers, the di(meth) acrylate, the tri(meth) acrylate, the tetrafunctional or higher (meth) acrylate, and The modified (meth) acrylate monomer having a (poly)oxyalkylene chain or (poly)lactone structure introduced into the molecular structure, more preferably the above tri(meth) acrylate, the above 4-functional group The above (meth) acrylate, and a modified (meth) acrylate monomer having a (poly)oxyalkylene chain or a (poly)lactone structure introduced into the molecular structure.

Further, among the above (meth)acrylic acid amine ester compounds, the (meth)acrylonitrile group equivalent is preferably in the range of 100 to 150 g/eq. Further, it is preferably obtained by using neopentyl alcohol tri(meth)acrylate or dipentaerythritol penta (meth) acrylate as a monohydroxy (meth) acrylate compound, more preferably in a reaction raw material. Using dihydroxy (meth) acrylate Obtained by the compound.

The ratio of the above various (meth) acrylate monomers in the (meth) acrylate compound (C) is preferably a laminate film which is excellent in balance between scratch resistance and flexibility. The range of 20 to 80% by mass, more preferably 30 to 60% by mass.

The ratio of the above-mentioned (meth)acrylic acid amine ester compound in the (meth) acrylate compound (C) is preferably a laminate film which is excellent in balance between scratch resistance and flexibility. The range of ~80% by mass, more preferably 40% to 70% by mass.

When the above various (meth) acrylate monomers and the above (meth) acrylate amine compound are used in combination as the above (meth) acrylate compound (C), the above (meth) acrylate compound is preferred. The total of the two of (C) is 80% by mass or more, and more preferably 90% by mass or more. Further, the ratio of the above-mentioned various (meth) acrylate monomers to the above-mentioned (meth) acrylate urethane compound is preferably a laminate film which is excellent in balance between scratch resistance and flexibility. The total of the above (meth) acrylate monomers is in the range of 20 to 80% by mass, and more preferably in the range of 30 to 60% by mass.

The hard coating composition (z) may contain a non-curable resin component (C') in addition to the (meth) acrylate compound (C). The non-curable resin component (C') may, for example, be an acrylic resin, an amine ester resin, a polyester resin, a petroleum resin or the like which does not have a reactive group such as a (meth) acrylonitrile group. In the case of using the non-curable resin component (C'), it is preferred that the (meth) acrylate compound (C) is 80% in the resin component in the hard coating composition (z). It is used within the range of %, and is preferably used within a range of 90% by mass.

The hard coating composition (z) is also the same as the primer composition (y). Various additive components can be contained depending on the desired properties. Examples of the additive component include a photopolymerization initiator, a photosensitizer, an organic solvent, a UV absorber, an antioxidant, a lanthanide additive, a fluorine-based additive, an antistatic agent, a decane coupling agent, a adhesion aid, an organic granule, and a rheology. Control agent, antifoaming agent, antifogging agent, coloring agent, and the like. The specific examples, the blending amount, and the like may be the same as those of the specific additive component and the blending amount in the primer composition (y).

The hard coating composition (z) may further contain inorganic fine particles. Examples of the inorganic fine particles include fine particles such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more. The average particle diameter of the inorganic fine particles is preferably in the range of 5 to 300 nm, more preferably in the range of 95 to 250 nm. Further, in the case where the inorganic fine particles are contained, a dispersing aid may be further used, and examples of the dispersing aid include acidic isopropyl phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. Phosphate compounds such as lipids. These may be used alone or in combination of two or more. For the commercial products of the dispersing agent, for example, "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd., "KAYAMER PM-2", and "LIGHT ESTER P-2M" manufactured by Kyoeisha Chemical Co., Ltd. "Wait.

In the case where the hard coating composition (z) contains inorganic fine particles, the amount of the inorganic fine particles is preferably 20% by mass based on the total of the resin component and the inorganic fine particles in the hard coating composition (z). Hereinafter, it is preferably 10% by mass or less. In the case where the hard coating composition (z) contains inorganic fine particles, the primer composition (y) can be produced by using a disperser or a stirring blade such as a turbine blade. a dispersing machine, a paint mixer, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, etc., and the inorganic fine particle raw material is mixed and dispersed in a matrix such as a (meth) acrylate compound (C) or an organic solvent. to make In the middle.

The laminated film of the present invention has the above-described plastic film layer (X), the undercoat layer (Y), and the hard coat layer (Z) as essential structures, and may have other layer constitutions. The order of lamination of the respective layers of the laminated film of the present invention may be carried out by laminating the undercoat layer (Y) between the plastic film layer (X) and the hard coat layer (Z). Or the surface may have other layers. That is, between the plastic film layer (X) and the undercoat layer (Y), between the undercoat layer (Y) and the hard coat layer (Z), on the plastic film layer (X) or the above hard The outer surface of the coating (Z) may also have other layers.

Examples of the other layer configuration include an optical film such as a light-resistant reflective film, a light-diffusing film, a polarizing film, and a transparent electrode film, or an easy-adhesion layer, an adhesive layer, and a plastic film other than the plastic film layer (X).

As described above, in the laminated film of the present invention, various layer constitutions can be considered. Among them, the above-mentioned undercoat layer is preferable in terms of the effect of exhibiting high surface hardness and scratch resistance and excellent flexibility. One side of Y) is adjacent to the acrylic film layer (X), and the other side is adjacent to the hard coat layer (Z).

The method for producing the laminated film of the present invention is not particularly limited, and it can be produced by various methods depending on the desired properties. An example of the method for producing a laminated film is to apply a composition for coating a primer (y) to the plastic film layer (X), and then apply a hard coating composition (z). The method of hardening (method 1); or coating the primer composition (y) on the plastic film layer (X), if necessary, heating and drying the solvent to carry out B-stage, and then coating the hard coating thereon The composition (z) and the method (method 2) in which the primer composition (y) and the hard coat composition (z) are simultaneously cured.

The method 1 described above will be described as an example of a method for producing a laminated film. The coating amount when the primer composition (y) is applied to the plastic film layer (X) is preferably adjusted so that the film thickness after curing is in the range of 1 to 50 μm, more preferably The adjustment is performed so as to be in the range of 1 to 25 μm. Examples of the coating method include bar coater coating, die coating, spray coating, curtain coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, and offset printing. Printing, soft printing, screen printing, etc. When the primer composition (y) contains an organic solvent, it is heated at 80 to 150 ° C for several tens of seconds to several minutes to evaporate the organic solvent, and then irradiated with an active energy ray to make the bottom. The coating composition (y) is hardened to form an undercoat layer (Y).

The coating amount when the composition (z) for hard coating is applied is preferably adjusted so that the film thickness after curing is in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm. Make adjustments. Examples of the coating method include bar coater coating, die coating, spray coating, curtain coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, and sleeve coating. Printing, soft printing, screen printing, etc. When the hard coating composition (z) contains an organic solvent, it is heated at 80 to 150 ° C for several tens of seconds to several minutes to evaporate the organic solvent, and then irradiated with active energy rays to make the hard coating. The composition (z) is hardened to form a hard coat layer (Z).

The active energy ray to be irradiated to cure the primer composition (y) or the hard coat composition (z) is exemplified by ultraviolet rays or electron beams. In the case where it is hardened by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, or a metal halide lamp as a light source is used, and the amount of light, the arrangement of the light source, and the like are adjusted as needed. In the case of using a high-pressure mercury lamp, it is preferably 1 with respect to the amount of light having a range of usually 80 to 160 W/cm. The spreader is hardened in the range of 5 to 50 m/min. On the other hand, in the case of hardening by an electron beam, it is preferable to harden at a conveyance speed of 5 to 50 m/min by an electron beam acceleration device having an acceleration voltage in the range of usually 10 to 300 kV.

As described above, the laminated film of the present invention may have various layers other than the plastic film layer (X), the undercoat layer (Y), and the hard coat layer (Z) depending on the application. The method for forming the various layer constitutions is not particularly limited, and for example, it may be formed by directly applying a resin material, or may be formed into a sheet shape by bonding with an adhesive.

Since the undercoat layer (Y) and the hard coat layer (Z) of the laminated film of the present invention have characteristics of high transparency, when the layers other than the layers are all transparent, a multilayer structure can be obtained. And a laminated film with a high transparency. In the case where the laminated film of the present invention is a transparent film having a light transmissive property, it is preferable that the laminated film measured by "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd. has a haze value of 10 or less, more preferably It is 5 or less, and particularly preferably 0.5 or less. Further, the laminated film of the present invention may have a colored film in one of the layer constitutions. In this case, the undercoat layer (Y) and the hard coat layer (Z) of the laminated film of the present invention have high transparency, and thus have excellent color reproducibility or color development of the colored film. Laminated film.

The laminated film of the present invention is characterized in that it has high surface hardness and scratch resistance and is excellent in flexibility, and is preferably used for a display member, an automobile member, a building material, and various surface protective films for electronic appliances, home appliances, furniture, and the like. Various applications such as plating replacement and painting replacement.

[Examples]

Hereinafter, the present invention will be specifically described by way of specific production examples and examples, but the present invention is not limited to the examples. In the example, the share and % are all as long as there is no special record. The Department is a quality benchmark.

Further, in the examples of the present invention, the weight average molecular weight (Mw) is a value measured by a gel permeation chromatography (GPC) by the following conditions.

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

Pipe column: Protection column H _XL -H manufactured by Tosoh Co., Ltd.

+TSKgel G5000HXL manufactured by Tosoh Co., Ltd.

+TSKgel G4000HXL manufactured by Tosoh Co., Ltd.

+TSKgel G3000HXL manufactured by Tosoh Co., Ltd.

+TSKgel G2000HXL manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data Processing: SC-8010 manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: Polystyrene

Sample: A tetrahydrofuran solution of 0.4% by mass in terms of resin solid content was filtered through a microfilter to obtain (100 μl)

In the examples of the present invention, the average particle diameter of the inorganic fine particles (A) is a value obtained by measuring the particle diameter in the undercoating composition (y) under the following conditions.

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

Particle size measurement sample: The primer composition (y) was obtained by preparing a methyl isobutyl ketone solution having a nonvolatile content of 1% by mass.

Production Example 1 Production of (meth)acrylonitrile-based acrylic resin (B1-1)

184 parts by mass of methyl isobutyl ketone was added to a reaction apparatus equipped with a stirring device, a condenser, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised while stirring until the temperature in the system became 110 °C. Then, 221 parts by mass of glycidyl methacrylate, 52.5 parts by mass of methyl methacrylate, 2.8 parts by mass of ethyl acrylate, and (2-ethylhexanoic acid) peroxide were added dropwise by means of a dropping funnel over 3 hours. A mixed liquid of 16.6 parts by mass of butyl acrylate ("PERBUTYL O" manufactured by Nippon Emulsifier Co., Ltd.) was kept at 110 ° C for 15 hours. Then, the temperature was lowered to 90 ° C, and then 0.1 parts by mass of p-methoxyphenol and 76 parts by mass of acrylic acid were added, and 2.0 parts by mass of triphenylphosphine was added thereto, and the mixture was further reacted at 100 ° C for 8 hours or longer. After confirming that the acid value of the solution became 4.2 mgKOH/g or less, it was diluted with methyl isobutyl ketone to obtain a methyl isobutyl ketone solution 910 containing a (meth) enedifluorenyl group-containing acrylic resin (B1-1). Parts by mass (non-volatile content 50.0% by mass). The respective property values of the (meth)acrylonitrile-containing acrylic resin (B1-1) are as follows. Weight average molecular weight (Mw) 20,000, theoretical propylene sulfhydryl equivalent 250 g / equivalent, hydroxyl value 224 mg KOH / g

Production Example 2 Production of Primer Composition (y-1)

[Material used]

‧ "Aerosil R7200" [equivalent to inorganic fine particles (a)]: "Aerosil R7200" manufactured by Japan Aerosil Co., Ltd., having a primary particle diameter of 12 nm and having (meth)acrylonitrile-based cerium oxide microparticles on the surface of the particle

‧"DPA-600" [equivalent to other hardening component (B')]: "DBA-600" manufactured by Toagosei Co., Ltd., containing dipentaerythritol pentaacrylate and two in molar ratio 40/60 Composition of pentaerythritol hexaacrylate

[Production method]

Incorporation of 53 parts by mass of the above-mentioned "Aerosil R7200", 24 parts by mass of a (meth)acrylonitrile-containing acrylic resin (B1-1) solution obtained in Production Example 1 (12 parts by mass of the resin solid content), and the above "DPA" -600" 35 parts by mass and 188 parts by mass of methyl isobutyl ketone to prepare a slurry having a nonvolatile content of 50% by mass, and the obtained slurry was a wet ball mill ("Starmill LMZ015" manufactured by Ashizawa Co., Ltd." The mixture was dispersed to obtain a dispersion.

To the obtained dispersion, 2 parts by mass of a photopolymerization initiator ("Irgacure #184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added, and further methyl isobutyl ketone was added to adjust the nonvolatile content to 40% by mass. The composition for primer (y-1) was obtained. The average particle diameter of the cerium oxide microparticles in the primer composition (y-1) was 125 nm.

The respective conditions of the above dispersion by a wet ball mill are as follows.

Medium: zirconia particles with a median diameter of 100 μm

Resin composition filling ratio with respect to the inner volume of the grinder: 70% by volume

Peripheral speed of the front end of the mixing blade: 11m/sec

Flow rate of resin composition: 200ml/min

Dispersion time: 50 minutes

Production Example 3 Production of Primer Composition (y-2)

[Material used]

‧ "Aerosil R7200" [equivalent to inorganic fine particles (a)]: "Aerosil R7200" manufactured by Japan Aerosil Co., Ltd., having a primary particle diameter of 12 nm and having (meth)acrylonitrile-based cerium oxide microparticles on the surface of the particle

‧"Miramer SP-1106" [equivalent to dendrimer-type poly(meth)acrylate (B2)]: "Miramer SP-1106" manufactured by MIWON, weight average molecular weight (Mw) 1,630, average per molecule (Methyl) acrylonitrile group number 18

‧ "ARONIX M-404" [equivalent to other curable components (B')]: "ARONIX M-404" manufactured by Toagosei Co., Ltd., containing dinonpentaerythritol at a mass ratio of 30/70 to 40/60 a mixture of pentaacrylate and dipentaerythritol hexaacrylate

[Production method]

50 parts by mass of the above "Aerosil R7200", 20 parts by mass of the above "Miramer SP-1106", 30 parts by mass of the above "ARONIX M-404", 80 parts by mass of methyl isobutyl ketone, and 20 parts by mass of propylene glycol monomethyl ether. A slurry having a nonvolatile content of 50% by mass was prepared, and the resultant was mixed and dispersed using a wet ball mill ("Starmill LMZ015" manufactured by Ashizawa Co., Ltd.) to obtain a dispersion.

To the obtained dispersion, 2 parts by mass of a photopolymerization initiator ("Irgacure #184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added, and further methyl isobutyl ketone was added to adjust the nonvolatile content rate to 40% by mass. The primer composition (y-2) was obtained. The average particle diameter of the cerium oxide microparticles in the primer composition (y-2) was 120 nm.

The respective conditions of the above dispersion by a wet ball mill are as follows.

Medium: zirconia particles with a median diameter of 100 μm

Resin composition filling ratio with respect to the inner volume of the grinder: 70% by volume

Peripheral speed of the front end of the mixing blade: 11m/sec

Flow rate of resin composition: 200ml/min

Dispersion time: 50 minutes

Production Example 4 Production of (meth) acrylate compound (C-1)

[Material used]

‧ "Duranate 24A-100": "Duranate 24A-100" manufactured by Asahi Kasei Chemicals Co., Ltd., biuret modified by hexamethylene diisocyanate, isocyanate group content 23.5% by mass

‧"Alonics M-306": "Alonics M-306" manufactured by East Asia Synthetic Co., Ltd., containing neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, and new with a molar ratio of 5/70/25 Composition of pentaerythritol tetraacrylate

[Production method]

60 parts by mass of hexamethylene diisocyanate, 70 parts by mass of "Duranate 24A-100", 0.2 parts by mass of dibutyl dilaurate, and 0.2 parts by mass of p-methoxyphenol were added to a reaction apparatus equipped with a stirring device. The temperature was raised to 60 ° C while stirring. Then, 424 parts by mass of "Alonics M-306" was added 10 times every 10 minutes. Further, the reaction was allowed to proceed for 10 hours, and it was confirmed by infrared spectroscopy that the absorption of the isocyanate group of 2250 cm ^-1 disappeared, and the reaction was terminated to obtain a (meth) acrylate compound (C-1). The respective property values of the (meth) acrylate compound (C-1) are as follows. Weight average molecular weight (Mw) 9,980, theoretical propylene sulfhydryl equivalent 130 g / equivalent

Production Example 5 Production of (meth) acrylate compound (C-2)

[Material used]

‧"Alonics MT-3533": "Alonics MT-3533" manufactured by East Asia Synthetic Co., Ltd., containing neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, and new with Mobi 22/52/27 Composition of pentaerythritol tetraacrylate

[Production method]

80 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane, 0.2 parts by mass of dibutyltin dilaurate, and 0.2 parts by mass of p-methoxyphenol were added to the reaction apparatus equipped with the stirring apparatus while stirring. Warm to 60 °C. Then, 245 parts by mass of "Alonics MT-3533" was added 10 times every 10 minutes. Further, the reaction was allowed to proceed for 10 hours, and it was confirmed by infrared spectroscopy that the absorption of the isocyanate group of 2250 cm ^-1 disappeared, and the reaction was terminated to obtain a (meth) acrylate compound (C-2). The respective property values of the (meth) acrylate compound (C-2) are as follows. Weight average molecular weight (Mw) 2,500, theoretical propylene thiol equivalent 135 g / equivalent

Production Example 6 Production of (meth) acrylate compound (C-3)

[Material used]

‧ "Alonics M-305": "Alonics M-305" manufactured by East Asia Synthetic Co., Ltd., containing a composition of neopentyl alcohol triacrylate and neopentyl alcohol tetraacrylate at a molar ratio of 60/40

[Production method]

80 parts by mass of hexamethylene diisocyanate, 0.2 parts by mass of dibutyl dilaurate, and 0.2 parts by mass of p-methoxyphenol were added to a reaction apparatus equipped with a stirring apparatus, and the temperature was raised to 60 ° C while stirring. Then, 520 parts by mass of "Alonics M-305" was added 10 times every 10 minutes. Further, the reaction was allowed to proceed for 10 hours, and it was confirmed by infrared spectroscopy that the absorption of the isocyanate group of 2250 cm ^-1 disappeared, and the reaction was terminated to obtain a (meth) acrylate compound (C-3). The respective property values of the (meth) acrylate compound (C-3) are as follows. Weight average molecular weight (Mw) 1,500, theoretical propylene sulfhydryl equivalent 118 g / equivalent

Production Example 7 to 10 Production of Hard Coating Composition (z-1) to (z-4)

[Material used]

‧"MT-3533" [equivalent to (meth) acrylate compound (C)]: "Alonics MT-3533" manufactured by Toagosei Co., Ltd., containing neopentyl alcohol 2 at a molar ratio of 22/52/27 Composition of acrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate

‧"DPA-600" [equivalent to (meth) acrylate compound (C)]: "DPA-600" manufactured by Toagosei Co., Ltd., containing dipentaerythritol pentaacrylate at a molar ratio of 40/60 And the composition of dipentaerythritol hexaacrylate

[Production method]

Each component was blended in a ratio shown in the following table, and a photopolymerization initiator ("Irgacure #184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added in an amount of 3% by mass based on the resin solid content component, and methyl isobutyl ketone was used. The non-volatile component was adjusted to 40% by mass to obtain a hard coating composition (z-1) to (z-4).

Example 1

The laminated film was produced by the following points, and various evaluations were performed. The results are shown in Table 2.

◆Manufacture of laminated film

A triacetonitrile cellulose film having a thickness of 60 μm was used as the plastic film layer (X), and the film thickness of the hardened film was 12 μm so that the film thickness of the cured film was 12 μm by a bar coater. The composition (y-1) was applied to the primer and dried at 70 ° C for 1 minute, and an ultraviolet ray of 250 mJ/cm ^{2 was} irradiated with a high-pressure mercury lamp under a nitrogen atmosphere to provide an undercoat layer (Y).

Then, the hard coating composition (z-1) obtained in Production Example 7 was applied to the undercoat layer (Y) so that the film thickness after curing was 3 μm, and dried at 70 ° C by a bar coater. For 1 minute, a high-pressure mercury lamp was used to irradiate ultraviolet rays of 250 mJ/cm ² under a nitrogen atmosphere, and a hard coat layer (Z) was set.

◆ Evaluation of curl resistance

The laminated film obtained previously was cut into 10 cm squares, and the ridges from the four corners of the horizontal were measured, and evaluated based on the total value.

◆Evaluation of transparency

The haze value of the laminated film was measured using "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd.

◆ Evaluation of scratch resistance

A disk-shaped indenter having a diameter of 2.4 cm was wrapped with steel wool ("BONSTAR #0000" manufactured by Nihon Steel Wool Co., Ltd.) 0.5 g, and a load of 1 kg was applied to the indenter to perform hard coating on the laminated film. The layer (Z) surface was subjected to a 1000-degree abrasion test. The haze value of the laminated film before and after the abrasion test was measured using "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd., and the scratch resistance was evaluated based on the difference (dH). Further, the surface of the hard coat layer (Z) after the abrasion test was visually evaluated by visual inspection.

◆Evaluation of surface hardness

The pencil hardness of the surface of the hard coat layer (Z) of the above laminated film was measured under a load of 750 g according to JIS K5600-5-4. 5 times for each hardness, there will be 4 or more uninjured The hardness measured was set to the surface hardness of the laminated film.

◆Evaluation of softness

The following experiment was carried out: the laminated film was wound around a test bar using a mandrel tester ("bending tester" manufactured by TP Technica Co., Ltd.), and it was visually confirmed whether or not cracks occurred, and the minimum diameter of the test bar which did not cause cracks was used as an evaluation result. . The test rods are used with a diameter of 5 mm to 19 mm and a 1 mm scale.

Examples 2 to 5, and Comparative Example 1

The types of the undercoat composition (y) and the hard coat composition (z) and the film thicknesses of the undercoat layer (Y) and the hard coat layer (Z) were changed as shown in Table 2, and the other examples were changed. A laminate film was produced in the same manner as in Example 1 and subjected to various evaluations. The results are shown in Table 2.

Claims (5)

A laminated film having a plastic film layer (X), an undercoat layer (Y), and a hard coat layer (Z), characterized in that the undercoat layer (Y) contains inorganic fine particles (A) and the following The (meth)acrylonitrile-based resin (B) is a cured product of the primer composition (y) as an essential component, and the weight average molecular weight (Mw) of the (meth)acrylonitrile-containing resin (B) is 1,000 or more; the hard coat layer (Z) is a cured product of the hard coat composition (z) containing the (meth) acrylate compound (C) as an essential component. The laminated film according to the first aspect of the invention, wherein the (meth)acrylonitrile-containing resin (B) is a (meth)acrylonitrile-based acrylic resin (B1) or a dendrimer-type poly( Methyl) acrylate (B2). The laminated film according to the first aspect of the patent application, in addition to the plastic film layer (X), the undercoat layer (Y), and the hard coat layer (Z), further comprises a light-resistant reflective film layer, a light diffusion film layer, and a polarizing film. Any of a film layer and a transparent electrode film layer. The laminated film of the first aspect of the invention, wherein the inorganic fine particles (A) in the primer composition (y) has an average particle diameter of 80 to 250 nm. The laminated film of the first aspect of the patent application, wherein the plastic film layer (X) is a triacetyl cellulose film, a polyester film, an acrylic film, a cycloolefin polymer film, a polyamide film, and a polyimine. Any of a film, a polystyrene film, a polycarbonate film, and a polypropylene film.