JP6180077B2 - Active energy ray-curable composition and coated film - Google Patents

Description

  The present invention provides an active energy ray-curable composition and a coating that can form an uncured coating film with no tackiness on a film substrate and that can form a cured film excellent in scratch resistance, chemical resistance, transparency, and the like. Related to film.

The active energy ray-curable composition is applied to the surface of various articles, and is easily cured by irradiation with active energy rays such as ultraviolet rays. The cured film (hard coat with high hardness, excellent scratch resistance, transparency, etc.) Since a protective layer that is a film) can be formed, it is widely used as a protective material such as a plastic material.

  In recent years, as seen in various electrical products, cosmetic containers and automotive interior / exterior parts, etc., a painting layer (printing layer, metal-deposited layer) is formed on the surface of a plastic substrate to provide decorativeness and design. A hard coat process is also performed on the film.

  However, a conventional protective layer made of an active energy ray-curable composition satisfies all of adhesion to a film base material or lower layer film, hard coat properties (high hardness, scratch resistance, etc.) and chemical resistance. It wasn't. Further, there is a problem that curing shrinkage occurs due to the components in the cured composition, causing warpage (so-called curl) of the coated film including the film base to the protective layer side.

  In contrast, for example, Patent Document 1 discloses a reaction product obtained by adding a carboxyl group-containing (meth) acrylic compound to a polymer having an epoxy group in the molecule, a phosphate compound containing a vinyl group, colloidal silica. In addition, it is disclosed that an active energy ray-curable composition containing a polyfunctional (meth) acrylic compound provides a molded article having excellent scratch resistance. Patent Document 2 includes a compound having two or more ethylenically unsaturated groups and an isocyanurate ring, a copolymer having a (meth) acryloyl group in the side chain, inorganic fine particles such as silica, and a photopolymerization initiator. It is disclosed that a photo-curable decorative laminated film composition provides a decorative laminated film that is excellent in workability even after being cured and excellent in scratch resistance of a cured film. However, when a large amount of the reaction product or copolymer as described above is blended, the internal stress of the resulting film increases and the adhesion decreases, and when a large amount of colloidal silica is blended, hardness and scratch resistance are increased. Improved, but the transparency sometimes decreased.

  Patent Document 3 discloses reactive particles obtained by chemically modifying colloidal silica with a radically polymerizable silane compound, poly (meth) acryloyloxyalkyl isocyanurate, at least two (meth) acryloyloxy groups and fat in one molecule. It is disclosed that a molded article having excellent scratch resistance is obtained by using a urethane (meth) acrylate having a cyclic skeleton and a wear-resistant coating forming composition containing a photopolymerization initiator. However, in this composition, the tacky surface remains on the surface of the uncured coating film, which may be inferior in workability in the subsequent process, and when trying to increase the amount of reactive particles to increase the scratch resistance. Adhesion may be reduced.

JP 2009-286972 A JP2011-225679A International Publication 97/011129 Brochure

  An object of the present invention is to provide an active energy ray-curable composition capable of forming an uncured coating film without a tackiness on a film substrate, and capable of forming a cured film excellent in scratch resistance, chemical resistance, transparency and the like. And providing a painted film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific acrylic resin (A), silica fine particles (b-1), and a hydrolyzable silane having a (meth) acryloyl group in the molecule. Active energy ray curing containing reactive particles (B) obtained by reacting (b-2), specific (meth) acryloyl group-containing compound (C) and photopolymerization initiator (D) in a specific ratio The present inventors have found that the above-mentioned problems can be solved by using a composition, and have completed the present invention.

  That is, the present invention relates to an acrylic resin (A) having a (meth) acryloyl group and a weight average molecular weight of 10,000 to 100,000, silica fine particles (b-1), and a (meth) acryloyl group in the molecule. Reactive particles (B) obtained by reacting with hydrolyzable silane (b-2) having a hydroxyl group in the molecule, a weight average molecular weight of 100 to 1,000 and a solubility parameter value of 10 An active energy ray-curable composition containing the (meth) acryloyl group-containing compound (C) and the photopolymerization initiator (D) as described above, wherein the component (A), the component (B), and the component (C) The solid content of the component (A) is 10 to 80 parts by mass, the solid content of the component (B) is 10 to 85 parts by mass, and the solid content of the component (C) with respect to 100 parts by mass of the total solid content of Content is 1-10 parts by mass and ingredients An active energy ray-curable composition characterized in that the content of D) is 0.1 to 5 parts by mass, and a coating film having a protective layer made of this active energy ray-curable composition on the film substrate surface About.

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray-curable composition which can form the uncured coating film without a tack feeling with respect to a film base material, and can form the cured film excellent in abrasion resistance, chemical resistance, transparency, etc. Can be obtained.

Active energy ray curable composition The active energy ray curable composition of the present invention has an acrylic resin (A) having a (meth) acryloyl group and a weight average molecular weight of 10,000 to 100,000, silica fine particles Reactive particles (B) obtained by reacting (b-1) with hydrolyzable silane (b-2) having a (meth) acryloyl group in the molecule, having a hydroxyl group in the molecule, and having a weight average A (meth) acryloyl group-containing compound (C) having a molecular weight of 100 to 1,000 and a solubility parameter value of 10 or more and a photopolymerization initiator (D) are contained.

Acrylic resin (A)
The acrylic resin (A) is an acrylic resin having a (meth) acryloyl group in the molecule. For example, 1) a method in which a carboxyl group-containing (meth) acrylate is added to an epoxy group-containing acrylic resin, and 2) a carboxyl group is contained. A method of adding an epoxy group-containing (meth) acrylate to an acrylic resin, 3) A method of adding an isocyanate group-containing (meth) acrylate to a hydroxyl group-containing acrylic resin, 4) A hydroxyl group-containing (meth) acrylate to an isocyanate group-containing acrylic resin Can be obtained by the addition reaction of

  Functional group-containing acrylic resin such as epoxy group-containing acrylic resin, carboxyl group-containing acrylic resin, hydroxyl group-containing acrylic resin, carboxyl group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, isocyanate group-containing (meta The addition reaction with acrylate, hydroxyl group-containing (meth) acrylate and the like can be usually carried out in an organic solvent at 40 to 160 ° C. using a catalyst as necessary. Although the addition reaction can be performed by melting the functional group-containing acrylic resin, it is preferable to perform the reaction in an organic solvent for ease of production.

  Examples of the carboxyl group-containing (meth) acrylate include (meth) acrylic acid. Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4- (meth) acrylic acid 3,4- Examples thereof include epoxy cyclohexyl methyl and 3,4-epoxy cyclohexyl ethyl (meth) acrylate. Examples of the isocyanate group-containing (meth) acrylate include isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate, isocyanate octyl (meth) acrylate, and p-methacryloxy-α, α′-dimethyl. Examples include benzyl isocyanate and m-acryloxy-α, α′-dimethylbenzyl isocyanate. Moreover, what made some isocyanate of a polyisocyanate compound react with a hydroxyl-containing (meth) acrylate is mentioned. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxy Examples thereof include butyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropyne glycol mono (meth) acrylate, a ring-opening reaction product of a (meth) acrylate compound and an ε-caprolactone compound. Further, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and the like can be mentioned.

  Next, functional group-containing acrylic resins such as the carboxyl group-containing acrylic resin, epoxy group-containing acrylic resin, and hydroxyl group-containing acrylic resin will be described.

  Various methods can be applied to prepare the functional group-containing acrylic resin. The above-mentioned carboxyl group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, isocyanate group-containing (meth) acrylate and hydroxyl group-containing (meth) A method of copolymerizing a polymerizable unsaturated monomer selected for obtaining a desired functional group-containing acrylic resin from an acrylate and the like and, if necessary, another polymerizable unsaturated monomer in an organic solvent. The simplest and preferred.

  Various polymerization initiators and organic solvents can be used. In preparing the epoxy group-containing acrylic resin, a carboxyl group-containing polymerizable unsaturated monomer, an isocyanate group-containing polymerizable unsaturated monomer, and a hydroxyl group-containing polymerizable unsaturated monomer are used in preparing the carboxyl group-containing acrylic resin. A group-containing polymerizable unsaturated monomer, an isocyanate group-containing polymerizable unsaturated monomer, and a hydroxyl group-containing polymerizable unsaturated monomer are used in preparing a hydroxyl group-containing acrylic resin. In the preparation of the isocyanate group-containing acrylic resin, a saturated monomer and an isocyanate group-containing polymerizable unsaturated monomer are used, and a carboxyl group-containing polymerizable unsaturated monomer, an epoxy group-containing polymerizable unsaturated monomer, and a hydroxyl group-containing polymerizable unsaturated monomer are used. , Both Of treated as other polymerizable unsaturated monomer.

Examples of the other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2- (Meth) acrylic acid alkyl esters such as ethyloctyl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Alkyl carbitol (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate; isobornyl (meth) acrylate , Other (meth) acrylic acid esters such as dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate;
hydrolyzable silyl group-containing polymerizable unsaturated monomers such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane;
Fluorine-containing α-olefin compounds such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene and hexafluoropropylene;
Perfluoroalkyl / perfluorovinyl ether such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, heptafluoropropyl trifluorovinyl ether or (per) fluoroalkyl vinyl ether (wherein the alkyl group has 1 to 18 carbon atoms) )) Fluorine-containing vinyl polymerizable unsaturated monomers such as
Mono- or diester compounds of various polyvalent carboxyl group-containing polymerizable unsaturated monomers represented by fumaric acid, maleic acid, itaconic acid, etc., and monoalkyl alcohols having 1 to 18 carbon atoms; styrene, Aromatic vinyl compounds such as vinyltoluene, α-methylstyrene, p-tert-butylstyrene;
Amino group-containing amide polymerizable unsaturated monomers such as (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, diacetone (meth) acrylamide;
Dimethylaminoalkyl (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; tert-butylaminoethyl (meth) acrylate, tert-butylaminopropyl (meth) acrylate, aziridinyl Ethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate, (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyloxazoline, Nitrogen-containing polymerizable unsaturated monomers such as (meth) acrylonitrile;
Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched (branched) vinyl aliphatic carboxylate having 9 carbon atoms, carbon number 10 A branched (branched) aliphatic carboxylate, an aliphatic vinyl carboxylate such as a branched (branched) aliphatic carboxylate having 11 carbon atoms, and vinyl stearate;
Vinyl ester compounds of carboxylic acids having a cyclic structure such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, vinyl p-tert-butylbenzoate;
Alkyl vinyl ether compounds such as ethyl vinyl ether, hydroxyethyl vinyl ether, hydroxy n-butyl vinyl ether, hydroxyisobutyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether;
Halogenated olefin compounds other than the above-mentioned fluoroolefin compounds such as vinyl chloride and vinylidene chloride; α-olefin compounds such as ethylene, propylene, and butene-1.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. “(Meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylamide” means acrylamide or methacrylamide.

  Examples of radical polymerization initiators used for the preparation of functional group-containing acrylic resins such as carboxyl group-containing acrylic resins, epoxy group-containing acrylic resins, hydroxyl group-containing acrylic resins, and isocyanate group-containing acrylic resins include 2,2′-azo. Bisisobutyronitrile, 2,2'-azobis-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis-cyclohexanecarbonitrile, dimethyl-2,2 ' -Azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropene) dihydrochloride, 2-tert-butylazo-2-cyanopropane, 2, 2'-azobis (2-methyl-propionamide) dihydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propene], Azo compounds such as 2,2'-azobis (2,2,4-trimethylpentane); benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, potassium persulfate, tert-butylperoxyneodecanoate, tert-butyl Peroxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, 1,1-bis-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert- Ketone peroxides such as butyl peroxy-laurate, tert-butyl peroxyisophthalate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dicumyl peroxide, di-tert-butyl peroxide Peroxyketal compounds; hydroperoxide compounds; dialkyl peroxide compounds; diacyl peroxide compounds; peroxyester compounds; peroxydicarbonate compounds; hydrogen peroxide and the like.

  Examples of the organic solvent used in the preparation of the functional group-containing acrylic resin include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, Alkyl alcohol solvents such as isopentanol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether Glycol ether solvents such as benzene, toluene, xylene, ethylbenzene and other aromatics Hydrocarbon solvents; Exxon Aromatic Naphtha No. Mixed hydrocarbon solvent containing aromatic hydrocarbon such as 2 (manufactured by Exxon USA); aliphatic hydrocarbon solvent such as n-pentane, n-hexane and n-octane; Isopar C, Isopar E, Exol DSP100 / 140, Exol D30 (all manufactured by Exxon USA), mixed solvent containing aliphatic hydrocarbon such as IP Solvent 1016 (Idemitsu Petrochemical Co., Ltd.); cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. Alicyclic hydrocarbon solvents such as: tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether and other ether solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketone solvents; methyl acetate, ethyl acetate, n-propyl acetate , Isopropyl acetate, n acetate Butyl, isobutyl acetate, n- amyl, isoamyl acetate, hexyl acetate, ethyl propionate, and ester solvents such as butyl propionate. A small amount of water can be used in combination with these organic solvents.

  Furthermore, in preparing the acrylic resin, a chain transfer agent can be used as necessary. Examples of the chain transfer agent include dodecyl mercaptan, lauryl mercaptan, thioglycolic acid ester, mercaptoethanol, α-methylstyrene dimer, and the like.

  The acrylic resin (A) is a (meth) acryloyl group-containing acrylic resin obtained by addition reaction of a carboxyl group-containing (meth) acrylate to an epoxy group-containing acrylic resin from the viewpoint of tackiness of the curable and uncured coating film. A (meth) acryloyl group-containing acrylic resin obtained by addition reaction of an epoxy group-containing (meth) acrylate with a carboxyl group-containing acrylic resin is preferred.

  The acrylic resin (A) has a weight average molecular weight of 10,000 to 100,000, preferably 12,000 to 80,000. Outside this range, it is not preferable in terms of control of tackiness of the uncured coating film, flexibility of the uncured coating film, gelation during production, and the like.

  In addition, in this specification, a weight average molecular weight is the value which converted the weight average molecular weight measured using the gel permeation chromatograph (GPC) on the basis of the molecular weight of a standard polystyrene. Specifically, as a gel permeation chromatograph, one “TSKgel G4000HXL”, two “TSKgel G3000HXL”, and one “TSKgel G2000HXL” (trade names, all manufactured by Tosoh Corporation), a total of 4 The book can be used for measurement under the conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, and detector RI. As the “standard polystyrene”, commercially available products such as “TSK standard polystyrene” manufactured by Tosoh Corporation can be used.

  Content of the acrylic resin (A) in the active energy ray-curable composition of the present invention is 10 to 80 mass with respect to 100 mass parts of the total solid content of the component (A), the component (B) and the component (C). Part, preferably 15 to 77 parts by mass. Outside this range, it becomes difficult to control the scratch resistance of the cured coating film, which is not preferable.

Reactive particles (B)
The reactive particles (B) are obtained by reacting silica fine particles (b-1) with hydrolyzable silane (b-2) having a (meth) acryloyl group in the molecule.

  Examples of the silica fine particles (b-1) include colloidal silica and powdered fine particle silica.

  Colloidal silica is obtained by dispersing ultrafine silica particles in a dispersion medium. As a dispersion medium, water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. Polyhydric alcohol derivatives; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol; and monomer compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and tetrahydrofurfuryl acrylate. Of these, water, methanol, ethanol, isopropanol and the like are preferable from the viewpoint of ease of production.

  As colloidal silica, methanol silica sol, IPA-ST, IPA-ST-ZL, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, PGM-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL (all manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.

  As the fine powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 (all manufactured by Nippon Aerosil), Sildex H31, H32, H51, H52, H121, H122 (all manufactured by Asahi Glass) , E220A, E220 (all manufactured by Nippon Silica Kogyo Co., Ltd.), SYLYSIA470 (manufactured by Fuji Silysia Chemical Ltd.), and the like.

  The silica fine particles (b-1) are colloidal silica having an average primary particle diameter of 1 to 200 nm, preferably 10 to 150 nm, and the reaction operability with the compound (b-2) is obtained. It is desirable from the point of transparency of the cured coating film.

  Further, the silica fine particle (b-1) is a cured coating film that is a mixture of colloidal silica having an average primary particle diameter of 1 to 30 nm and colloidal silica having an average primary particle diameter of 60 to 200 nm. This is preferable from the viewpoint of scratch resistance. The mixing ratio of colloidal silica having an average primary particle diameter in the range of 1 to 30 nm and colloidal silica having an average primary particle diameter in the range of 60 to 200 nm is solid from the viewpoint of transparency of the cured coating film and scratch resistance. The mass ratio is 90:10 to 30:70, preferably 80:20 to 40:60.

  The average primary particle diameter in the present invention is a median diameter (d50) of a volume-based particle size distribution measured by a dynamic light scattering method, and can be measured using, for example, a nanotrack particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd. it can.

  Hydrolyzable silane (b-2) having a (meth) acryloyloxy group in the molecule [hereinafter sometimes referred to as “compound (b-2)”. ] Has a hydrolyzable silyl group. The hydrolyzable silyl group is a silanol group or a group that generates a silanol group by hydrolysis. Examples of the group that forms a silanol group include groups in which an alkoxy group, an aryloxy group, an acetoxy group, a halogen atom, or the like is bonded to a silicon atom. Here, the alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and the aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms. A halogen atom includes chlorine.

  The compound (b-2) is not particularly limited as long as it is a compound having a (meth) acryloyloxy group and a hydrolyzable silyl group in the molecule.

  As the compound (b-2), for example, the following general formula (BI)

[In formula (BI), Z represents a (meth) acryloyloxy group. R ¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms. At least one of R ^a , R ^b and R ^c represents a halogen atom, a hydroxy group, an alkoxy group or an aryloxy group, and the remainder represents a hydrogen atom, an alkyl group or an aryl group. ]
The compound represented by these is mentioned.

R ¹ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group, octylene group and the like can be mentioned. It is done.

Examples of the alkoxy group represented by R ^a , R ^b and R ^c include those having 1 to 8 carbon atoms, and a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octyloxy group and the like are preferable.

Examples of the alkyl group represented by R ^a , R ^b and R ^c include those having 1 to 8 carbon atoms, and a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like are preferable.

Examples of the aryloxy group represented by R ^a , R ^b and R ^c include those having 6 to 18 carbon atoms, and a phenoxy group, a xylyloxy group and the like are preferable.

Examples of the aryl group represented by R ^a , R ^b and R ^c include those having 6 to 18 carbon atoms, and a phenyl group, a xylyl group and the like are preferable.

Examples of the group represented by R ^a (R ^b ) (R ^c ) Si— include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. it can. Of these groups, a trimethoxysilyl group, a triethoxysilyl group, and the like are preferable.

  As the compound (b-2), specifically, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyl Examples thereof include at least one compound selected from methyldimethoxysilane and the like. As the compound (b-2), the compounds exemplified above may be used alone or in combination of two or more kinds.

  In addition to the compound (b-2), when obtaining the reactive particles (B), an alkoxysilane having an alkyl group having 1 or more carbon atoms and silica fine particles (b-) together with the compound (b-2) as necessary. You may make it react with 1). By reacting the alkoxysilane having an alkyl group having 1 or more carbon atoms, the water resistance of the coating film obtained using the obtained reactive particles (B) may be improved. Examples of the alkoxysilane having an alkyl group having 1 or more carbon atoms include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and dodecyltrimethoxy. Silane etc. are mentioned, The compound (for example, methyltriethoxysilane etc.) which substituted the methoxy group in these illustrated compounds by the ethoxy group is also mentioned.

  The reactive particles (B) are obtained by reacting the silica fine particles (b-1) with the compound (b-2). The method for reacting the silica fine particles (b-1) with the compound (b-2) is not particularly limited. For example, [i] a method in which silica fine particles (b-1) and a compound (b-2) are mixed in the presence of an organic solvent containing water and hydrolytic condensation is performed; [ii] in the presence of an organic solvent containing water. A method of condensing the hydrolyzate of the compound (b-2) with the silica fine particles (b-1) after hydrolyzing the compound (b-2) with [iii] the silica fine particles (b-1) and the compound ( b-2) may be mixed in the presence of other components such as water, an organic solvent and a polymerizable unsaturated compound, and hydrolysis condensation may be performed at once. Here, the water used in these production methods may be water contained in the raw material, for example, water that is a dispersion medium of colloidal silica.

  The method for producing the reactive particles (B) will be described more specifically. The reactive particles (B) are, for example, in the presence of colloidal silica that is silica fine particles (b-1), a compound (b-2), optionally a lower alcohol, and optionally a polymerizable unsaturated compound, Dispersion medium in colloidal silica and lower alcohol [including lower alcohol produced by hydrolyzing compound (b-2). ] Is azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium is replaced with the solvent, followed by a dehydration condensation reaction under heating. In the present invention, in particular, the reaction between the silica fine particles (b-1) and the compound (b-2) is carried out in the presence of the (meth) acryloyl group-containing compound (C) described later. This is preferable from the viewpoint of scratch resistance.

  In this production method, if necessary, a hydrolysis catalyst is added to a mixture of colloidal silica which is silica fine particles (b-1), compound (b-2), optionally a lower alcohol, and optionally a polymerizable unsaturated compound. In addition, the compound (b-2) is hydrolyzed by a conventional method such as stirring at room temperature or under heating. Subsequently, the dispersion medium in the colloidal silica and the lower alcohol are azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium is replaced with the solvent. The reaction is preferably carried out at a temperature of 80 to 130 ° C. with stirring for 0.5 to 10 hours while maintaining the nonvolatile content concentration in the range of 30 to 90% by mass, preferably in the range of 50 to 80% by mass. After the reaction, it is preferable to azeotropically distill water and lower alcohol generated by condensation reaction or hydrolysis together with a solvent having a boiling point higher than that of the lower alcohol.

  Examples of the solvent used in the above reaction include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and cyclohexane; halogenated hydrocarbon solvents such as trichloroethylene and tetrachloroethylene; 1,4-dioxane, dibutyl ether Ether solvents such as methyl isobutyl ketone; ester solvents such as n-butyl acetate, isobutyl acetate, ethyl acetate and ethyl propionate; polyhydric alcohol derivatives such as ethylene glycol monobutyl ether.

  By these production methods, the silicon atom on the surface of the silica fine particle (b-1) and the silicon atom in the compound (b-2) molecule are bonded via an oxygen atom, whereby the silica fine particle (b-1) and the compound ( Reactive particles (B) chemically bonded to b-2) are obtained.

  The compounding ratio of the compound (b-2) when obtaining the reactive particles (B) is preferably 1 part by mass or more, more preferably 2 parts by mass with respect to 100 parts by mass of the silica fine particles (b-1). As described above, it is particularly preferably 5 parts by mass or more. When the amount of the compound (b-2) bonded to the silica fine particles (b-1) is less than 5 parts by mass, the dispersibility of the reactive particles (B) in the active energy ray-curable composition is not sufficient, The cured film obtained may not have sufficient transparency. Moreover, the compounding ratio of the silica fine particles (b-1) in the raw material during the production of the reactive particles (B) is preferably 5 to 99 parts by mass with respect to 100 parts by mass of the obtained reactive particles (B). More preferably, it is 10 to 98 parts by mass.

  Moreover, when using the alkoxysilane which has a C1-C1 or more alkyl group, the mixture ratio is 2.5-100 mass% with respect to a compound (b-2), Preferably it is 25-50 mass%. It is preferable from the point of the water resistance improvement of the coating film obtained.

  The content of the reactive particles (B) in the active energy ray-curable composition of the present invention is 10 to 85 with respect to 100 parts by mass of the total solid content of the component (A), the component (B) and the component (C). It is a mass part, More preferably, it is 15-80 mass parts. Outside this range, it is not preferred because the scratch resistance of the cured film is lowered or the transparency is impaired.

(Meth) acryloyl group-containing compound (C)
The (meth) acryloyl group-containing compound (C) used in the present invention has a hydroxyl group in the molecule, has a weight average molecular weight of 100 to 1,000, preferably 150 to 900, and a solubility parameter value of 10. As mentioned above, Preferably it is a (meth) acryloyl group containing compound which is 10-13. If the weight average molecular weight of the (meth) acryloyl group-containing compound (C) is outside this range, it is not preferable in terms of tackiness of the uncured film and compatibility with other components, and if the solubility parameter value is less than 10, other It is not preferable in terms of compatibility with the other components.

In this specification, the solubility parameter value (sp value) is a value measured by a cloud point titration method. In the cloud point titration, 0.5 g of a sample is dissolved in 10 ml of acetone, and n-hexane is added to the cloud point. Read the titration amount H (ml) of the solution, and similarly read the titration amount D (ml) at the cloud point when deionized water was added to the acetone solution, and applied these to the following formula to obtain Vml, Vmh, δH, δD. Is calculated. The molecular volume (mol / ml) of each solvent is acetone: 74.4, n-hexane: 130.3, deionized water: 18, and SP of each solvent is acetone: 9.75, n- Hexane: 7.24, deionized water: 23.43.
Vml = 74.4 × 130.3 / ((1−VH) × 130.3 + VH × 74.4)
Vmh = 74.4 × 18 / ((1-VD) × 18 + VD × 74.4)
VH = H / (10 + H)
VD = D / (10 + D)
δH = 9.75 × 10 / (10 + H) + 7.24 × H / (10 + H)
δD = 9.75 × 10 / (10 + D) + 23.43 × D / (10 + D).

  The (meth) acryloyl group-containing compound (C) has one or more (preferably two or more) (meth) acryloyl groups in the molecule. For example, 2-hydroxyethyl acrylate, polypropylene glycol monomethacrylate Polycaprolactone-modified ethyl acrylate (average number of repeating caprolactone units is 5 or less), glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, trimethylolpropane diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Examples include isocyanuric acid ethylene oxide-modified di (meth) acrylate and isocyanuric acid propylene oxide-modified di (meth) acrylate. You may use these individually or in combination of 2 or more types.

  Commercially available products that can be used as the (meth) acryloyl group-containing compound (C) include “Aronix M-215” (sp value: 11.8) and “Aronix M-303” (sp value: Toagosei Co., Ltd.). 10.9), “Aronix M-313” (sp value: 11.2), “Aronix M-315” (sp value: 10.9), “Aronix M-305” (sp value: 11.0), “Aronix M-306” (sp value: 11.1); “NK ester 701” (sp value: 11.5), “NK ester 701A” (sp value: 12.2) manufactured by Shin-Nakamura Chemical Co., Ltd. NK ester 702A "(sp value: 10.7).

  The content of the (meth) acryloyl group-containing compound (C) in the active energy ray-curable composition of the present invention is 100 parts by mass of the total solid content of the component (A), the component (B) and the component (C). 1 to 10 parts by mass, more preferably 1.5 to 8 parts by mass. Outside this range, it is not preferable in terms of tackiness of the uncured film and compatibility with other components. As described above, the (meth) acryloyl group-containing compound (C) may be included in the production of the reactive particles (B), and the amount charged is the content of the (meth) acryloyl group-containing compound (C). To be included.

Photopolymerization initiator (D)
The photopolymerization initiator (D) is not particularly limited as long as it is an initiator that absorbs active energy rays and generates radicals.

  Examples of the photopolymerization initiator (D) include α-diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, Thioxanthone compounds such as 4-diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Michler's ketone compound; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxyben Phenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- Acetophenone compounds such as (4-morpholinophenyl) -butan-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone; 2,4 Acylphosphine oxide compounds such as 1,6-trimethylbenzoyldiphenylphosphine oxide and bis (acyl) phosphine oxide; quinone compounds such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, trihalomethylphenylsulfone, tris ( Riharomechiru) -s-halogen compounds such as triazine; peroxides such as di -t- butyl peroxide and the like. These can be used as one or a mixture of two or more.

  Examples of commercially available photopolymerization initiators (D) include IRGACURE-184, IRGACURE-261, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907, IRGACURE-CGI-1700 (Ciba Specialty Chemicals, trade name, English notation IRGACURE), Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043 (Merck Japan, trade name, English notation Darocur), Kayacure (KAYACURE) -MBP, Kayacure-DETX-S, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (manufactured by Nippon Kayaku Co., Ltd., trade name English notation KAYACURE), Vicure-10, Vicure-55 [Stoufer (STAUFFER Co., L TD.), Product name], TRIGONAL P1 [manufactured by AKZO Co., LTD., Product name], SANDORAY 1000 [SANDOZ Co., LTD., Product Name], Deep (DEAP) (manufactured by APJOHN Co., LTD., Trade name), CANTACURE-PDO, CANTACURE-ITX, CANTACURE-EPD [WARD BLEKINSOP Co., LTD.), Product name] and the like.

  The usage-amount of a photoinitiator (D) is 0.5-5 mass parts with respect to 100 mass parts of total solids of the said component (A), a component (B), and a component (C), Preferably it is 1-4. .5 parts by mass.

  The active energy ray-curable composition of the present invention essentially comprises the component (A), the component (B), the component (C) and the component (D), and further contains the component (A) and A polymerizable unsaturated compound (E) other than the component (C) may be contained. The polymerizable unsaturated compound (E) is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond in its chemical structure, and is not limited to a monofunctional polymerizable unsaturated compound or a polyfunctional polymerizable unsaturated compound. Saturated compounds are mentioned.

  Examples of the monofunctional polymerizable unsaturated compound include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethylhexahydro Examples include phthalimide. Moreover, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, etc. Carboxyl group-containing (meth) acrylate; Glycidyl group-containing polymerizable unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether; Vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene; N , N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N- Me Chill (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include polymerizable amide compounds such as N, N-dimethylaminopropyl (meth) acrylamide and N, N-dimethylaminoethyl (meth) acrylamide.

  Examples of the polyfunctional polymerizable unsaturated compound include an esterified product of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricycloden Di (meth) acrylates such as candimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, hydrogenated hexafluorobisphenol A di (meth) acrylate, etc. Compound: glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, ε-caprolactone modified tris (acrylic) Examples include tri (meth) acrylate compounds such as (loxyethyl) isocyanurate; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexa (meth) acrylate; urethane acrylate and the like. These polymerizable unsaturated compounds can be used alone or in combination of two or more.

  When the polymerizable unsaturated compound (E) is used, its content is not particularly limited, and from the viewpoint of scratch resistance, transparency of the coating film and adhesion, the component (A), the component ( B) and 1 to 90 parts by mass or less, preferably 2 to 80 parts by mass with respect to 100 parts by mass of the total solid content of component (C).

  The active energy ray-curable composition of the present invention may further contain various additives as necessary, and may be diluted with a solvent if desired. Examples of additives include UV absorbers, antioxidants, rheology control agents, surfactants, lubricants, defoamers, mold release agents, silane coupling agents, antistatic agents, antifogging agents, and coloring agents. Can be used.

  Examples of the solvent used for dilution include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane Solvents: Glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, etc. Is mentioned. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment of coating property.

  The nonvolatile content of the active energy ray-curable composition of the present invention is not particularly limited. For example, Preferably it is 20-100 mass%, More preferably, it is 25-70 mass%.

Painted film The coated film of the present invention has a protective layer of the above-mentioned active energy ray-curable composition on the film substrate. Specifically, it is obtained by applying and drying an active energy ray-curable composition on at least one surface of various film substrates by a known method, and further curing by irradiating active energy rays as necessary. Obtained. The coating amount of the active energy ray-curable composition is, for example, such that the film thickness of the protective layer after drying is 1 to 50 μm, preferably 2 to 30 μm, more preferably 3 to 20 μm on various film substrates. It is preferable to apply to.

  Examples of the film base include polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyethylene terephthalate, polyethylene naphthalate, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, and norbornene resin. Can be mentioned. Among these film substrates, polyethylene terephthalate (PET) is preferable from the viewpoint of adhesion. The thickness of these film base materials is 10 to 250 μm, preferably 40 to 200 μm, and more preferably 50 to 190 μm. These film base materials may be appropriately subjected to a surface treatment, for example, may be subjected to a peeling treatment or an easy adhesion treatment.

  The application method of the active energy ray curable composition is not particularly limited and can employ a known method, for example, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, Examples include offset printing, flexographic printing, and screen printing.

  Examples of the active energy rays to be irradiated include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp as a light source is used, and the amount of light and the arrangement of the light sources are adjusted as necessary. For example, when a high-pressure mercury lamp is used, it is preferable to cure at 50 to 5000 mJ / cm 2 with respect to one lamp that usually has a light amount of 80 to 250 mW / cm 2. On the other hand, in the case of curing with an electron beam, it is preferably cured at 0.1 to 10 Mrad with an electron beam accelerator having an acceleration voltage of usually 10 to 300 kV.

The coated film of the present invention can be used as a hard coat film, and can be used by appropriately bonding to a molded product. The protective layer may be cured before being applied to the molded product body, or may be cured after being applied to the molded product body.
Moreover, the coating film may be a film in which a decorative layer and an adhesive layer are sequentially provided on the protective layer. The decorative layer is a layer on which a pattern or the like for obtaining design properties is formed, and the adhesive layer is a layer formed in order to improve the adhesion between the surface of the molded product, the decorative layer, and the protective layer.

The decorative layer is made of a suitable color pigment using a resin such as polyvinyl resin, polyamide resin, polyester resin, acrylic resin, polyurethane resin, polyvinyl acetal resin, cellulose resin, alkyd resin, etc. as a binder. Or it can form by printing with the coloring ink etc. which contain dye as a coloring agent. Moreover, a decoration layer may consist of what consists of a metal vapor deposition layer, or a combination of a printing layer and a metal vapor deposition layer. For the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the material of the molded product is appropriately used. As the heat-sensitive adhesive resin, for example, an acrylic resin-based, rubber-based, or olefin-based one can be used.
Moreover, you may provide an anchor layer between a protective layer and a decoration layer. The anchor layer is a resin layer for improving the adhesion between the protective layer and the decorative layer and protecting the molded product and the decorative layer from chemicals, for example, a urethane-curing system, a melamine-curing system, an epoxy-curing system, etc. A thermoplastic resin such as a curable resin or a vinyl chloride resin can be used.

  In a specific embodiment of the coated film of the present invention, first, the active energy ray-curable composition is applied to one surface of a film substrate that has been subjected to a release treatment, and the formed protective layer surface is formed. In this case, a decorative layer and an adhesive layer are sequentially provided.

  Further, as another embodiment of the coated film of the present invention, a protective layer is formed by applying the active energy ray-curable composition to one surface of a film base that has been subjected to an easy adhesion treatment. A material obtained by sequentially providing a decorative layer and an adhesive layer on the other surface of the material may be mentioned.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples. Note that “part” and “%” indicate “part by mass” and “% by mass”, respectively, unless otherwise specified.

Manufacture example 1 of acrylic resin (A)
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and dropping device, 80 parts of xylene were charged and stirred at 100 ° C. while blowing nitrogen gas. In this, 10 parts of styrene, 40 parts of methyl methacrylate, glycidyl methacrylate A mixture of 50 parts and 5 parts of 2,2′-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours, and further aged at the same temperature for 2 hours. Thereafter, a mixture of 10 parts of xylene and 0.5 parts of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 1 hour, and the mixture was aged for 1 hour after completion of the addition, and an acrylic resin having a nonvolatile content of 55%. A solution was obtained. The weight average molecular weight was 12,000.

  To the acrylic resin solution 1055 parts (solid part 580 parts) obtained above, 170 parts of acrylic acid, 0.4 parts of hydroquinone monomethyl ether, 277 parts of butyl acetate and 0.2 parts of triphenylphosphine were charged, and air was introduced into the reaction vessel. The acrylic resin (A-1) having a non-volatile content of 55% was confirmed by cooling to 80 ° C. while maintaining the temperature for 5 hours, and confirming that all of the carboxyl groups and epoxy groups had reacted. A solution was obtained. The weight average molecular weight of this acrylic resin (A-1) was 14,000.

Production Example 2
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and dropping device, 80 parts of xylene were charged and stirred at 100 ° C. while blowing nitrogen gas. In this, 10 parts of styrene, 40 parts of methyl methacrylate, glycidyl methacrylate A mixture of 50 parts and 1.5 parts of 2,2′-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours and further aged at the same temperature for 2 hours. Thereafter, a mixture of 10 parts of xylene and 0.5 parts of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 1 hour, and the mixture was aged for 1 hour after completion of the addition, and an acrylic resin having a nonvolatile content of 55%. A solution was obtained. The weight average molecular weight was 35,000.

  To the acrylic resin solution 1055 parts (solid part 580 parts) obtained above, 170 parts of acrylic acid, 0.4 parts of hydroquinone monomethyl ether, 277 parts of butyl acetate and 0.2 parts of triphenylphosphine were charged, and air was introduced into the reaction vessel. The acrylic resin (A-2) having a nonvolatile content of 55% was cooled to 80 ° C. and kept at that temperature for 5 hours while confirming that all the carboxyl groups and epoxy groups had reacted. A solution was obtained. The weight average molecular weight of this acrylic resin (A-2) was 40,000.

Production Example 3
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and dropping device, 80 parts of xylene were charged and stirred at 100 ° C. while blowing nitrogen gas. In this, 10 parts of styrene, 40 parts of methyl methacrylate, glycidyl methacrylate A mixture of 50 parts and 8.0 parts of 2,2′-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours and further aged at the same temperature for 2 hours. Thereafter, a mixture of 10 parts of xylene and 0.5 parts of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 1 hour, and the mixture was aged for 1 hour after completion of the addition, and an acrylic resin having a nonvolatile content of 55%. A solution was obtained. The weight average molecular weight was 7,000.

  To the acrylic resin solution 1055 parts (solid part 580 parts) obtained above, 170 parts of acrylic acid, 0.4 parts of hydroquinone monomethyl ether, 277 parts of butyl acetate and 0.2 parts of triphenylphosphine were charged, and air was introduced into the reaction vessel. The acrylic resin (A-3) having a nonvolatile content of 55% was cooled to 80 ° C. and kept at that temperature for 5 hours while confirming that all the carboxyl groups and epoxy groups had reacted. A solution was obtained. The weight average molecular weight of this acrylic resin (A-3) was 8,000.

Production of reactive particles (B) Production Example 4
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) After mixing 333 parts (silica fine particle amount is 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.2 part and isopropanol 227 parts, the temperature was raised with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a dispersion P1 of reactive particles having a nonvolatile content of 40%.

Production Example 5
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 70-100 nm, trade name: IPA-ST-ZL, Nissan (Chemical Industry Co., Ltd.) 333 parts (silica fine particle amount 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.2 parts and isopropanol 227 parts, and then heated while stirring . When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a dispersion P2 of reactive particles having a nonvolatile content of 40%.

Production Example 6
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) 250 parts and colloidal silica (dispersion medium; isopropanol, silica concentration; 30% by mass, average primary particle size; 70 to 100 nm, trade name: IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd.) 100 parts in total), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.2 parts of p-methoxyphenol and 227 parts of isopropanol were added, and the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a dispersion P3 of reactive particles having a nonvolatile content of 40%.

Production Example 7
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) 333 parts (silica fine particle amount is 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, "Aronix M-305" (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, weight average molecular weight 300, solubility parameter) (11.0, manufactured by Toagosei Co., Ltd.) 10 parts, 0.2 parts of p-methoxyphenol and 227 parts of isopropanol were added, and the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation several times by adding propylene glycol monomethyl ether to obtain a mixed solution P4 having 40% nonvolatile content of reactive particles.

Production Example 8
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) 333 parts (silica fine particle amount is 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, “NK ester 701A” (2-hydroxy-3-acryloyloxypropyl methacrylate, weight average molecular weight 214, solubility parameter 12. 2, 10 parts of Shin-Nakamura Chemical Co., Ltd.), 0.2 part of p-methoxyphenol and 227 parts of isopropanol were added, and the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed solution P5 having 40% nonvolatile content of reactive particles.

Production Example 9
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 70-100 nm, trade name: IPA-ST-ZL, Nissan (Made by Chemical Industry Co., Ltd.) 333 parts (silica fine particle amount is 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, “Aronix M-305” 10 parts, p-methoxyphenol 0.2 part and isopropanol 227 parts Then, the temperature was raised while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed solution P6 having a non-volatile content of 40% of the reactive particles.

Production Example 10
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 70-100 nm, trade name: IPA-ST-ZL, Nissan 333 parts (manufactured by Kagaku Kogyo Co., Ltd.) (the amount of silica fine particles is 100 parts), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 10 parts of “NK ester 701A”, 0.2 part of p-methoxyphenol and 227 parts of isopropanol were blended. Then, it heated up, stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed solution P7 having a non-volatile content of 40% of the reactive particles.

Production Example 11
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) 250 parts and colloidal silica (dispersion medium; isopropanol, silica concentration; 30% by mass, average primary particle size; 70 to 100 nm, trade name: IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd.) (total of silica fine particles) The amount was 100 parts), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 10 parts of “Aronix M-305”, 0.2 part of p-methoxyphenol and 227 parts of isopropanol, and then heated while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed solution P8 having 40% nonvolatile content of reactive particles.

Production Example 12
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) 250 parts and colloidal silica (dispersion medium; isopropanol, silica concentration; 30% by mass, average primary particle size; 70 to 100 nm, trade name: IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd.) (total of silica fine particles) The amount was 100 parts), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 10 parts of “NK ester 701A”, 0.2 part of p-methoxyphenol and 227 parts of isopropanol, and then heated while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed solution P9 having 40% nonvolatile content of reactive particles.

Production Example 13
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) 333 parts (silica fine particle amount is 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, "Aronix M-309" (trimethylolpropane triacrylate, weight average molecular weight 310, solubility parameter 10.2, Toagosei 10 parts), 0.2 parts of p-methoxyphenol and 227 parts of isopropanol were added, and the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed liquid P10 having 40% nonvolatile content of reactive particles.

Production Example 14
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) 333 parts (silica fine particle amount is 100 parts), 10 parts 3-methacryloyloxypropyltrimethoxysilane, “EBECRYL112” (aliphatic epoxy acrylate, weight average molecular weight 356, solubility parameter 9.0, manufactured by Daicel Cytec Co., Ltd.) 10 Part, p-methoxyphenol 0.2 part, and isopropanol 227 part were mixed, and then the temperature was raised with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed liquid P11 having a nonvolatile content of 40% of the reactive particles.

Production Example 15
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 70-100 nm, trade name: IPA-ST-ZL, Nissan (Made by Chemical Industry Co., Ltd.) 333 parts (silica fine particle amount is 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, "Aronix M-309" 10 parts, p-methoxyphenol 0.2 parts and isopropanol 227 parts Then, the temperature was raised while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed liquid P12 having 40% nonvolatile content of reactive particles.

Production Example 16
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 70-100 nm, trade name: IPA-ST-ZL, Nissan (Chemical Industry Co., Ltd.) 333 parts (silica fine particle amount 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, "EBECRYL112" 10 parts, p-methoxyphenol 0.2 parts and isopropanol 227 parts, The temperature was raised with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed solution P13 having a non-volatile content of reactive particles of 40%.

Production Example 17
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 250 parts and colloidal silica (dispersion medium; isopropanol, silica concentration; 30% by mass, average primary particle size; 70 to 100 nm, trade name: IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd.) The total amount was 100 parts), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 10 parts of “Aronix M-309”, 0.2 part of p-methoxyphenol and 227 parts of isopropanol, and then heated while stirring. . When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed solution P14 having a non-volatile content of reactive particles of 40%.

Production Example 18
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) 250 parts and colloidal silica (dispersion medium; isopropanol, silica concentration; 30% by mass, average primary particle size; 70 to 100 nm, trade name: IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd.) (total of silica fine particles) The amount was 100 parts), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 10 parts of “EBECRYL112”, 0.2 part of p-methoxyphenol and 227 parts of isopropanol, and then heated while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

  Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, and then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a mixed liquid P15 having a non-volatile content of 40% of the reactive particles.

Example 1 of making an active energy ray-curable composition
70 parts of the acrylic resin (A-1) solution obtained in Production Example 1 in solid amount, 30 parts of the reactive particle dispersion P1 obtained in Production Example 4 in solid content, and “Aronix M-305” 2.5 parts by solid content and 3.0 parts of “Darocur 1173” (trade name, photopolymerization initiator, manufactured by Merck Japan Co., Ltd.), diluted with ethyl acetate to a non-volatile content of 30%, stirred, and activated energy Line-curable composition No. 1 was obtained.

Examples 2 to 24 and Comparative Examples 1 to 15
In Example 1, the active energy ray-curable composition No. 1 in the same manner as in Example 1 except that the respective components and blending amounts were changed to the respective components and blending amounts described in Tables 1 and 2. 2-No. 39 was obtained.

In addition, the compounding quantity of Table 1 and Table 2 is solid content. (* 1) in the table is as follows.
(* 1) “Purple light UV-1700B”: Urethane acrylate, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

Production of painted film and decorative molded body Examples 25-48 and Comparative Examples 16-30
A biaxially stretched PET film having a thickness of 125 μm subjected to easy adhesion treatment is used as a base material, and each active energy ray-curable composition No. obtained in Examples 1 to 24 and Comparative Examples 1 to 15 is formed on one surface thereof. 1 to 39 are selected as shown in Tables 3 and 4 and applied to a dry film thickness of 5 μm, preheated at a drying temperature of 80 ° C. for 1 minute, and then coated with an active energy ray-curable composition. Acrylic ink as a decorative layer and an acrylic resin adhesive as an adhesive layer were sequentially applied to the substrate surface opposite to the above and dried at 80 ° C. for 2 minutes to prepare a coated film.

About the obtained coating films of Examples 25 to 48 and Comparative Examples 16 to 30, the results subjected to performance tests according to the following test methods are shown in Tables 3 and 4 together. In addition, each decorative molded body to be used for the test was prepared by matching the above-mentioned coating film adhesive layer to the surface of the ABS plate, and applying each coating film to the ABS plate at 60 ° C., 0.1 MPa, 1.0 m / min. After laminating, the active energy ray was irradiated at a dose of 500 mJ / cm ² using a high pressure mercury lamp to cure the protective layer made of the active energy ray curable composition.

Examples 49-72 and Comparative Examples 31-45
A biaxially stretched PET film having a thickness of 38 μm subjected to a release treatment was used as a base material, and each active energy ray-curable composition No. 1 obtained in Examples 1 to 24 and Comparative Examples 1 to 15 was formed on one surface thereof. 1 to 39 are selected as shown in Table 5 and Table 6 and applied to a dry film thickness of 5 μm, respectively, preheated at a drying temperature of 80 ° C. for 1 minute to form a protective layer, and then active energy ray curable. A urethane-based anchor agent as an anchor layer, an acrylic ink as a decorative layer, and an acrylic resin-based adhesive as an adhesive layer were sequentially applied onto the protective layer by the composition and dried at 80 ° C. for 2 minutes to prepare a coated film. .

  About the obtained coating film of Examples 49-72 and Comparative Examples 31-45, the result used for the performance test according to the following test method is combined with Table 5, and Table 6 is shown. In addition, each decorative molded body to be used for the test was prepared by matching the above-mentioned coating film adhesive layer to the surface of the ABS plate, and applying each coating film to the ABS plate at 60 ° C., 0.1 MPa, 1.0 m / min. After laminating in, the release-treated biaxially stretched PET film having a thickness of 38 μm is peeled off, and then the active energy ray is irradiated with an active energy ray at a dose of 500 mJ / cm 2 using a high-pressure mercury lamp. It was obtained by curing a protective layer made of material.

Performance test (Note 1) Transparency (compatibility):
Each active energy ray-curable composition was applied to a biaxially stretched PET film subjected to easy adhesion treatment or a biaxially stretched PET film subjected to mold release treatment, dried at 80 ° C. for 1 minute, and a haze meter (NDH5000 manufactured by Nippon Denshoku Co., Ltd.). The total light transmittance was evaluated using the following criteria.
A: Total light transmittance> 92.0%
○: Total light transmittance> 85.0%, ≦ 92.0%
Δ: Total light transmittance> 80.0%, ≦ 85.0%
×: Total light transmittance ≦ 80.0%

(Note 2) Tack feeling:
Each active energy ray-curable composition is applied to a biaxially stretched PET film that has been subjected to an easy adhesion treatment or a biaxially stretched PET film that has been subjected to a mold release treatment, and dried at 80 ° C. for 1 minute. Evaluated by criteria.
○: No stickiness △: Slightly sticky ×: Sticky

(Note 3) Each active energy ray-curable composition is applied to a biaxially stretched PET film that has been subjected to flexible and easy adhesion treatment or a biaxially stretched PET film that has been subjected to a mold release treatment, dried at 80 ° C. for 1 minute, and then folded. The flexibility of the uncured film was evaluated according to the following criteria.
○: No abnormality such as cracks in the coating film △: Slight cracking is observed in the coating film ×: Cracking or peeling is observed in the coating film

(Note 4) Solvent resistance:
Apply a pressure of about 1 kg / cm2 to the coating surface with gauze soaked in acetone on the protective layer surface of each decorative molded body, and reciprocate between about 5 cm length until a mark is made. The number of times was counted and the solvent resistance was evaluated according to the following criteria.

◎: No trace after 200 round trips ○: Trace after 100-200 round trips △: Trace after 50-99 round trips X: Trace after 49 round trips

(Note 5) Adhesion:
100 pieces of 2 mm x 2 mm gobangs were made on the surface of each decorative molded body in accordance with JIS K 5600-5-6 (1990), and adhesive tape was stuck on the surface, and then the remaining goban was removed. The following criteria evaluated from the number of eye coatings.

A: Remaining number / total number = 100/100, no missing edges ○: Remaining number / total number = 100/100, no edges missing Δ: Remaining number / total number = 99 to 90/100 X: Remaining number / total number = 89 or less / 100

(Note 6) Scratch resistance:
A Taber abrasion test (abrasion wheel CF-10P, load 500 g, 100 revolutions) was performed on the protective layer surface of each decorative molded body in accordance with ASTM D1044. About the protective layer surface before and behind a test, the glossiness of each coating surface was measured according to the mirror surface glossiness (60 degree | times) of JISK5600-4-7 (1999). The glossiness after the test with respect to the glossiness before the test was determined as a gloss retention (%) and evaluated according to the following criteria.

◎: Gloss retention 90% or more ○: Gloss retention 80% or more and less than 90% △: Gloss retention 60% or more and less than 80% ×: Gloss retention 60% or less

(Note 7) Acid resistance:
After 0.5 mL of 1% sulfuric acid aqueous solution is dropped on the protective layer surface of each decorative molded body and left in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65% for 24 hours, the protective layer film surface is wiped with gauze, The appearance was visually evaluated according to the following criteria:
◎: No abnormality on the coating film surface ○: Slight traces on the coating film surface, but disappears when washed with water △: Some discoloration or whitening is observed on the coating film surface ×: On the coating film surface Discoloration or whitening is remarkable

Claims (3)

Hydrolyzable having (meth) acryloyl group and acrylic resin (A) having a weight average molecular weight of 10,000 to 100,000, silica fine particles (b-1) and (meth) acryloyl group in the molecule Reactive particles (B), which are reactants with silane (b-2), have a hydroxyl group in the molecule, have a weight average molecular weight of 214 to 1,000 and a solubility parameter value of 10 or more (meth) A method for producing an active energy ray-curable composition containing an acryloyl group-containing compound (C) and a photopolymerization initiator (D),
The solid content of the component (A) is 10 to 80 parts by mass and the solid content of the component (B) is 100 parts by mass of the total solid content of the component (A), the component (B) and the component (C). 10 to 85 parts by mass, 1 to 10 parts by mass of the solid content of the component (C), and 0.1 to 5 parts by mass of the component (D),
The silica fine particles (b-1) are a mixture of colloidal silica having an average primary particle diameter of 1 to 30 nm and colloidal silica having an average primary particle diameter of 60 to 200 nm,
The reaction between the silica fine particles (b-1) and the hydrolyzable silane (b-2) having a (meth) acryloyl group in the molecule is carried out in the presence of the (meth) acryloyl group-containing compound (C). A method for producing an active energy ray-curable composition. The active energy ray-curable composition obtained by the production method according to claim 1 is applied to one surface of a film substrate that has been subjected to a release treatment, and a decorative layer and an adhesive layer are formed on the formed protective layer surface. A method for producing a coated film in which layers are sequentially provided. A protective layer is formed by applying the active energy ray-curable composition obtained by the production method according to claim 1 to one surface of the film base that has been subjected to the easy adhesion treatment. A method for producing a coated film, in which a decorative layer and an adhesive layer are sequentially provided on one surface.