KR20220166708A - Inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate and article - Google Patents

Abstract

The present invention provides an inorganic fine particle dispersant, characterized in that the inorganic fine particle dispersant comprises: inorganic fine particles (A); a (meth)acrylate compound (B) having two or more (meth)acryloyl groups in one molecule; and a wetting and dispersing agent (C), wherein an average primary particle diameter of the inorganic fine particles (A) is in the range of 1-50 nm, the content of the inorganic fine particles (A) is in the range of 40-90 mass% of the total mass of the inorganic fine particles (A), the compound (B), and the wetting and dispersing agent (C), and the wetting and dispersing agent (C) has an acid value and/or an amine value. Accordingly, the inorganic fine particle dispersant having excellent adhesion and excellent scratch resistance in a cured product can be obtained.

Description

Inorganic fine particle dispersion, active energy ray curable composition, cured product, laminate and article

The present invention relates to an inorganic fine particle dispersion, an active energy ray-curable composition, a cured product, a laminate, and an article.

A resin material having a (meth)acryloyl group can be easily and instantaneously cured by ultraviolet irradiation or the like, and is widely used in the fields of paints and coating agents because the cured product has excellent transparency and hardness. It is being used. The objects to be coated cover a wide range of fields, such as optical films, plastic molded products, and woodworks, and since the required performance varies depending on the type of object to be coated, its use, etc., many resins designed according to the purpose have been proposed.

As a resin material having a (meth)acryloyl group, an active energy ray-curable resin composition containing a (meth)acryloyl group-containing acrylic resin, pentaerythritol tetraacrylate, and pentaerythritol triacrylate is known (eg For example, see Patent Document 1). Since the active energy ray-curable resin composition described in Patent Document 1 has an excellent balance between surface hardness and low curing shrinkage in a cured product, it is useful as a coating agent for coating a relatively thin plastic film. However, the adhesiveness to the film base material, especially after long-term storage under high-temperature wet conditions, was low, and peeling easily occurred.

Therefore, there has been a demand for a material having excellent adhesion and excellent scratch resistance that can be used as a coating agent.

Japanese Patent Laid-Open No. 2011-207947

The problem to be solved by the present invention is an inorganic fine particle dispersion, an active energy ray-curable composition, a cured product comprising the active energy ray-curable composition, and a laminate having excellent adhesion and excellent scratch resistance in a cured product. , and to provide goods.

As a result of intensive research to solve the above problems, the inventors of the present invention have found that specific inorganic fine particles, a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule, and a specific wetting and dispersing agent containing By using an inorganic fine particle dispersion, it was found that the above problems could be solved, and the present invention was completed.

That is, the present invention is an inorganic fine particle dispersion containing inorganic fine particles (A), a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule (B), and a wetting and dispersing agent (C) And, the average primary particle diameter of the inorganic fine particles (A) is in the range of 1 to 50 nm, and the content of the inorganic fine particles (A) is the inorganic fine particles (A), the compound (B), and the wetting and dispersing agent ( C) in the range of 40 to 90% by mass in the total mass, and the wetting and dispersing agent (C) has an acid value and / or an amine value, characterized in that the inorganic fine particle dispersion, active energy ray curable composition, cured product, laminate , and articles.

Since the inorganic fine particle dispersion of the present invention can form a cured product having excellent adhesion to a substrate and excellent scratch resistance, it can be used as a coating agent or adhesive, and can be particularly suitably used as a coating agent.

Characterized in that the inorganic fine particle dispersion of the present invention contains inorganic fine particles (A), a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule (B), and a wetting and dispersing agent (C) to be

In addition, in this invention, "(meth)acrylate" means an acrylate and/or methacrylate. In addition, "(meth)acryloyl" means acryloyl and/or methacryloyl. In addition, "(meth)acryl" means an acryl and/or methacryl.

As the inorganic fine particles (A), those having an average primary particle diameter in the range of 1 to 50 nm are used. The average primary particle diameter is obtained by measuring the diameters of a plurality of inorganic fine particles with a transmission electron microscope or a scanning electron microscope and calculating the average value thereof.

Examples of the inorganic fine particles (A) include zirconium oxide, silica, barium sulfate, zinc oxide, barium titanate, cerium oxide, alumina, titanium oxide, niobium oxide, zinc oxide, tin oxide, tungsten oxide, and antimony. can These inorganic fine particles may be used alone or in combination of two or more. Among these, silica is preferable, and silica particles obtained by hydrophobizing the particle surface are more preferable, from the viewpoint of obtaining an inorganic fine particle dispersion capable of forming a cured product having excellent adhesion to a substrate and excellent scratch resistance.

The content of the inorganic fine particles (A) is in the range of 40 to 90% by mass in the total mass of the inorganic fine particles (A), the (meth)acrylate compound (B), and the wetting and dispersing agent (C), and adhesion to the substrate And from the viewpoint of obtaining an inorganic fine particle dispersion capable of forming a cured product having excellent scratch resistance, the range of 45 to 70% by mass is more preferable.

As said (meth)acrylate compound (B), what has two or more (meth)acryloyl groups in one molecule is used.

Examples of the compound (B) include 1,6-hexanedioldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,3-butylene glycoldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate, ethylene oxide-modified 1,6-hexanedioldi(meth)acrylate Rate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tri Ethylene glycol di(meth)acrylate, ethylene oxide-modified di(meth)acrylate of bisphenol A, propylene oxide-modified di(meth)acrylate of bisphenol A, ethylene oxide-modified di(meth)acrylate of bisphenol F, tricyclo Decane dimethanol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, propylene oxide-modified tri(meth)acrylate of glycerin , 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, ethylene oxide-modified di(meth)acrylate of bisphenoxyethanol fluorene, polytetramethylene glycol di(meth)acrylate, ethoxy Physocyanuric acid tri(meth)acrylate, phenoxyethylene glycol (meth)acrylate, stearyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, trifluoroethyl (meth)acryl Rate 3-methyl-1,5 pentanedioldi(meth)acrylate, 2,3-[(meth)acryloyloxymethyl]norbornane, 2,5-[(meth)acryloyloxymethyl]nor Bornane, 2,6-[(meth)acryloyloxymethyl]norbornane, 1,3-adamantyldi(meth)acrylate, 1,3-bis[(meth)acryloyloxymethyl]a Dantan, tris(hydroxyethyl)isocyanuric acid di(meth)acrylate, 3,9-bis[1,1-dimethyl-2-(meth)acryloyloxyethyl]-2,4,8,10 -Tetraoxospiro[5.5]undecane, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythyl bifunctional (meth)acrylates such as tritol di(meth)acrylate and ditrimethylolpropane di(meth)acrylate;

EO modified glycerol (meth)acrylate, PO modified glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO modified phosphate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, capro Lactone-modified trimethylolpropane tri(meth)acrylate, HPA-modified trimethylolpropane tri(meth)acrylate, (EO) or (PO)-modified trimethylolpropane tri(meth)acrylate, alkyl-modified dipentaerythritol tri( trifunctional (meth)acrylates such as meth)acrylate, tris(acryloxyethyl)isocyanurate, and tris(methacryloxyethyl)isocyanurate;

tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate;

pentafunctional (meth)acrylates such as dipentaerythritol hydroxypenta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate;

Six functional (meth)acrylates, such as dipentaerythritol hexa (meth)acrylate, etc. are mentioned.

The (meth)acrylate compound which has two or more (meth)acryloyl groups in these one molecule may be used independently and may use 2 or more types together. Among them, a (meth)acrylate compound having 2 to 4 (meth)acryloyl groups in one molecule is preferable from the viewpoint of obtaining an inorganic fine particle dispersion capable of forming a cured product having excellent adhesion to a substrate and excellent scratch resistance.

As said wetting and dispersing agent (C), it has an acid value and/or an amine value.

As the wetting and dispersing agent (C), for example, a urethane resin having a carboxy group, a phosphoric acid group and/or an amino group, an acrylic resin having a carboxy group, a phosphoric acid group and/or an amino group, a polyester resin having a carboxy group, a phosphoric acid group and/or an amino group, and a carboxyl group , an amide resin having a phosphoric acid group and/or an amino group, and the like. These wetting and dispersing agents may be used alone or in combination of two or more. Moreover, among these, a polyester resin having a carboxy group and an amide resin having an amino group are preferable because they have excellent dispersibility with respect to inorganic particles and maintain excellent stability.

Examples of commercially available products of the above wetting and dispersing agent (C) include "DISPERBYK-102", "DISPERBYK-106", "DISPERBYK-108", "DISPERBYK-109", "DISPERBYK-110/111" and "DISPERBYK" manufactured by BYK. -118”, “DISPERBYK-140”, “DISPERBYK-142”, “DISPERBYK-145”, “DISPERBYK-”, “DISPERBYK-161”, “DISPERBYK-162/163”, “DISPERBYK-164”, “DISPERBYK- 167”, “DISPERBYK-168”, “DISPERBYK-170”, “DISPERBYK-174”, “DISPERBYK-180”, “DISPERBYK-182”, “DISPERBYK-184”, “DISPERBYK-185”, “DISPERBYK-2000” , 「DISPERBYK-2001」, 「DISPERBYK-2008」, 「DISPERBYK-2009」, 「DISPERBYK-2013」, 「DISPERBYK-2022」, 「DISPERBYK-2023」, 「DISPERBYK-2025v2026」, 「DISPERBYK-2050」, 「 "DISPERBYK-2055", "DISPERBYK-2096", "DISPERBYK-2150", "DISPERBYK-2155", "DISPERBYK-2157", "DISPERBYK-2158", "DISPERBYK-2159", "DISPERBYK-2163", "DISPERBYK- 2164”, “BYK-9076”, “BYK-9077”, “BYK-220 S”, “ANTI-TERRA-U/U100”, “ANTI-TERRA-U/U204”, Kusumoto Chemical Co., Ltd. 「Disparon 1831」, 「Disparon 1850」, 「Disparon 1860」, 「Disparon DA-1401」, 「Disparon DA-1200」, 「Disparon PW36 Disparon DA- 703-50", "Disparon DA7301", "Disparon DA-325", "Disparon DA-375", and "Disparon DA234".

The acid value of the wetting and dispersing agent (C) is preferably in the range of 0.5 to 180 mgKOH/g, and more preferably in the range of 10 to 80 mgKOH/g, because it has excellent dispersibility to inorganic fine particles and maintains excellent stability. . In addition, the amine value of the wetting and dispersing agent (C) is preferably in the range of 0 to 150 mgKOH / g, and more preferably in the range of 20 to 50 mgKOH / g, because it has excellent dispersibility with respect to inorganic particles and maintains excellent stability. desirable. In the present invention, the acid value is a value measured based on the neutralization titration method of JIS K 0070 (1992). In addition, an amine value is a value calculated based on JIS K 2501 (2003).

In the inorganic fine particle dispersion of the present invention, other active energy ray-curable resin components other than the compound (B) may be used in combination within a range that does not impair the effects of the present invention.

Examples of the other active energy ray-curable resin component include other (meth)acrylate resins (D) other than the compound (B). Examples of the other (meth)acrylate resins (D) include dendrimer type (meth)acrylate resins (D1), acrylic (meth)acrylate resins (D2), and epoxy (meth)acrylate resins (D3). ) and the like. These other (meth)acrylate resins (D) may be used alone or in combination of two or more.

The dendrimer type (meth)acrylate resin (D1) has a regular multi-branched structure and refers to a resin having a (meth)acryloyl group at the end of each branch chain, and in addition to the dendrimer type, hyperbranched type or They are called star polymers. Such compounds include, for example, those represented by the following structural formulas (1-1) to (1-8), but are not limited thereto, have a regular multi-branched structure, and each Any resin can be used as long as it has a (meth)acryloyl group at the end of the branch chain.

[In formulas (1-1) to (1-8), R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 1 to 4 carbon atoms]

As a commercial item of the said dendrimer type (meth)acrylate resin (D1), for example, Osaka Yuki Chemical Co., Ltd. "Viscot #1000" [weight average molecular weight (Mw) 1,500-2,000, average per molecule (meth)acryloyl group number 14], "Viscoat 1020" [weight average molecular weight (Mw) 1,000 to 3,000], "SIRIUS501" [weight average molecular weight (Mw) 15,000 to 23,000], MIWON's "SP-1106" [ Weight average molecular weight (Mw) 1,630, average number of (meth)acryloyl groups per molecule 18], SARTOMER company "CN2301", "CN2302" [average number of (meth)acryloyl groups per molecule 16], "CN2303" [ [average number of (meth)acryloyl groups per molecule: 6], "CN2304" [average number of (meth)acryloyl groups per molecule: 18]; "A-HBR-5" manufactured by Shin Nakamura Chemical Co., Ltd., "New Frontier R-1150" manufactured by Daiichi Kogyo Seiyaku Corporation, "Hypertec UR-101" manufactured by Nissan Chemical Industries, Ltd. can be heard

The weight average molecular weight (Mw) of the dendrimer type (meth)acrylate resin (D1) is preferably in the range of 1,000 to 30,000. Moreover, the average number of (meth)acryloyl groups per molecule is preferably in the range of 5 to 30.

As the acrylic (meth)acrylate resin (D2), for example, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group is polymerized as an essential component. What is obtained by introduce|transducing a (meth)acryloyl group by making an acrylic resin intermediate further react with the (meth)acrylate compound ((beta)) which has a reactive functional group which can react with these functional groups is mentioned.

Examples of the (meth)acrylate compound (α) having the reactive functional group include hydroxyl group-containing (meth)acrylate monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; Carboxy group-containing (meth)acrylate monomers such as (meth)acrylic acid; isocyanate group-containing (meth)acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; Glycidyl group containing (meth)acrylate monomers, such as glycidyl (meth)acrylate and 4-hydroxybutyl acrylate glycidyl ether, etc. are mentioned. These may be used independently or may use 2 or more types together.

The acrylic resin intermediate may be copolymerized with other polymerizable unsaturated group-containing compounds as necessary in addition to the (meth)acrylate compound (α). Examples of the other polymerizable unsaturated group-containing compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. (meth)acrylic acid alkyl esters such as acrylates; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isoboronyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; Styrene derivatives, such as styrene, (alpha)-methylstyrene, and chlorostyrene, etc. are mentioned. These may be used independently or may use 2 or more types together.

The said acrylic resin intermediate body can be manufactured by the method similar to a general acrylic resin. As an example of the production conditions, it can be produced by, for example, polymerizing various monomers in the presence of a polymerization initiator in a temperature range of 60°C to 150°C. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Moreover, as for the polymerization mode, a random copolymer, a block copolymer, a graft copolymer etc. are mentioned, for example. When carried out by solution polymerization, for example, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. A glycol ether solvent of can be preferably used.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but from the viewpoint of reactivity, the following combinations are preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxy group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The said (meth)acrylate compound ((beta)) may be used independently and may use 2 or more types together.

The reaction between the acrylic resin intermediate and the (meth)acrylate compound (β) is, for example, when the reaction is an esterification reaction, in a temperature range of 60 to 150°C, an esterification catalyst such as triphenylphosphine. Methods such as using appropriately can be cited. Moreover, when the said reaction is a urethanization reaction, the method of making it react, adding dropwise the compound ((beta)) to the acrylic resin intermediate body in the temperature range of 50-120 degreeC is mentioned. As for the reaction ratio of both, it is preferable to use the said (meth)acrylate compound ((beta)) in the range of 1.0-1.1 mol with respect to 1 mol of the number of functional groups in the said acrylic resin intermediate body.

As said epoxy (meth)acrylate resin (D3), what is obtained by making (meth)acrylic acid or its anhydride react with an epoxy resin is mentioned, for example. Examples of the epoxy resin include diglycidyl ethers of dihydric phenols such as hydroquinone and catechol; diglycidyl ethers of biphenol compounds such as 3,3'-biphenyldiol and 4,4'-biphenyldiol; bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, binaphthol, bis(2,7-dihydroxynaphthyl) Polyglycidyl ether of naphthol compounds, such as methane; Triglycidyl ethers such as 4,4',4"-methylidinetrisphenol; Novolac type epoxy resins such as phenol novolak type epoxy resins and cresol novolac resins; (Poly) in the molecular structure of the above various epoxy resins (Poly)oxyalkylene modified products having introduced (poly)oxyalkylene chains such as oxyethylene chain, (poly)oxypropylene chain, and (poly)oxytetramethylene chain; Lactone modified products etc. which introduce|transduced a lactone structure are mentioned.

In the active energy ray-curable composition of the present invention, depending on the type of active energy ray to be used, it is preferable to use a photopolymerization initiator. Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl. ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2 ,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1- Radical polymerization initiators such as (4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, etc. can be heard

Examples of commercially available photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", and "Omnirad". 4265”, “Omnirad 1000”, “Omnirad 651”, “Omnirad TPO”, “Omnirad 819”, “Omnirad 2022”, “Omnirad 2100”, “Omnirad 754”, “Omnirad 784”, “Omnirad 500”, “Omnirad 81” (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (made by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (made by Ward Blenkinsop); "Runtecure 1104" (made by Runtec) etc. are mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds may be used in combination with the photopolymerization initiator.

The amount of the photopolymerization initiator used is preferably in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, based on 100 parts by mass of components excluding the organic solvent in the active energy ray-curable composition of the present invention. desirable.

The active energy ray-curable composition used in the present invention may further contain other components. Examples of the other components include silane coupling agents, phosphoric acid ester compounds, solvents, ultraviolet absorbers, antioxidants, silicone additives, fluorine additives, antistatic agents, organic beads, quantum dots (QD), rheology control agents, A foam agent, an antifogging agent, a coloring agent, etc. are mentioned.

Examples of the silane coupling agent include [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, and [(meth)acryloyloxyalkyl]alkyl (meth)acryloyloxy silane coupling agents such as dialkoxysilane and [(meth)acryloyloxyalkyl]trialkoxysilane; Vinyl silane coupling agents such as trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, and trialkoxyallylsilane. ; styrenic silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, and styryltrialkoxysilane; (glycidyloxyalkyl)trialkylsilane, (glycidyloxyalkyl)dialkylalkoxysilane, (glycidyloxyalkyl)alkyldialkoxysilane, (glycidyloxyalkyl)trialkoxysilane, [(3, 4-epoxycyclohexyl)alkyl]trimethoxysilane, [(3,4-epoxycyclohexyl)alkyl]trialkylsilane, [(3,4-epoxycyclohexyl)alkyl]dialkylalkoxysilane, [(3, Epoxy silane coupling agents, such as 4-epoxycyclohexyl) alkyl] alkyldialkoxysilane and [(3,4-epoxycyclohexyl) alkyl] trialkoxysilane; Isocyanate type silane coupling agents, such as (isocyanate alkyl) trialkylsilane, (isocyanate alkyl) dialkyl alkoxysilane, (isocyanate alkyl) alkyl dialkoxysilane, and (isocyanate alkyl) trialkoxysilane, etc. are mentioned. These silane coupling agents may be used independently, respectively, or may use 2 or more types together.

As a commercial item of the said phosphoric acid ester compound, Nippon Kayaku Co., Ltd. "Kayama PM-2" and "Kayama PM-21" which are phosphoric acid ester compounds which have a (meth)acryloyl group in molecular structure, for example. "Light Ester P-1M", "Light Ester P-2M", "Light Acrylate P-1A(N)" manufactured by Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100" manufactured by SOLVAY, "SIPOMER PAM 200" ", "SIPOMER PAM 300", "SIPOMER PAM 4000", "Biscott #3PA", "Biscott #3PMA" by Osaka Yuki Chemical Industry Co., Ltd., "New Frontier S-23A" by Daiichi Kogyo Seiyaku Co., Ltd.; and "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphoric acid ester compound having an allyl ether group in the molecular structure.

The said solvent is added according to the objective, such as adjusting the coating viscosity of an active energy ray-curable composition, and the kind and addition amount are adjusted suitably according to desired performance. Generally, it is used so that the non-volatile content of an active energy ray-curable composition may fall into the range of 10-90 mass %. Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; Ester, such as methyl acetate, ethyl acetate, and butyl acetate; Aromatic solvents, such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; and glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether. These solvents may be used alone or in combination of two or more.

As said ultraviolet absorber, for example, 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) )-1,3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4- Triazine derivatives such as dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5' -Methylphenyl) benzotriazole, 2-xanthencarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. are mentioned. These ultraviolet absorbers may be used alone or in combination of two or more.

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

Examples of the silicone-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, amino-modified dimethyl Polyorganosiloxane having an alkyl group or phenyl group such as a polysiloxane copolymer, polydimethylsiloxane having a polyether-modified acrylic group, and polydimethylsiloxane having a polyester-modified acrylic group. These silicone additives may be used alone or in combination of two or more.

As a commercial item of the said fluorine-type additive, the "Megaface" series by DIC Corporation etc. are mentioned, for example. These fluorine-type additives may be used independently or may use 2 or more types together.

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

Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylstyrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine-based resin beads, melamine-based resin beads, and polyolefins. based resin beads, polyester-based resin beads, polyamide resin beads, polyimide-based resin beads, polyfluorinated ethylene resin beads, polyethylene resin beads, and the like. These organic beads may be used alone or in combination of two or more. In addition, it is preferable that the average particle diameter of these organic beads is in the range of 1 to 10 μm.

As the quantum dot (QD), a group II-V semiconductor compound, a group II-VI semiconductor compound, a group III-IV semiconductor compound, a group III-V semiconductor compound, a group III-VI semiconductor compound, a group IV-VI semiconductor compound, A group I-III-VI semiconductor compound, a group II-IV-VI semiconductor compound, a group II-IV-V semiconductor compound, a group I-II-IV-VI semiconductor compound, a group IV element or a compound containing the same may be mentioned. there is. The II-VI group semiconductor compound may be, for example, a binary compound such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, or HgTe; ternary compounds such as ZnSeS, ZnSeTe, ZnSTe, CdZnS, CdZnSe, CdZnTe, CdSeS, CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, HgZnTe; and quaternary compounds such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, and HgZnSTe. Examples of the group III-IV semiconductor compound include B ₄ C ₃ , Al ₄ C ₃ , Ga ₄ C ₃ and the like. The group III-V semiconductor compound may be, for example, a binary compound such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb; ternary compounds such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and GaAlNP; quaternary compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb; and the like. The III-VI group semiconductor compound, for example, Al ₂ S ₃ , Al ₂ Se ₃ , Al ₂ Te ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , GaTe, In ₂ S ₃ , In ₂ Se ₃ , In ₂ Te ₃ , InTe and the like are exemplified. The group IV-VI semiconductor compound may be, for example, a binary compound such as SnS, SnSe, SnTe, PbS, PbSe, or PbTe; Ternary compounds, such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, and SnPbTe; Quaternary compounds, such as SnPbSSe, SnPbSeTe, and SnPbSTe, etc. are mentioned. The I-III-VI group semiconductor compound, for example, CuInS ₂ , CuInSe ₂ , CuInTe ₂ , CuGaS ₂ , CuGaSe ₂ , CuGaSe ₂ , AgInS ₂ , AgInSe ₂ , AgInTe ₂ , AgGaSe ₂ , AgGaS ₂ , AgGaTe ₂ etc. can be mentioned. Examples of the group IV element or the compound containing it include C, Si, Ge, SiC, and SiGe. The quantum dot may be made of a single semiconductor compound or may have a core-shell structure made of a plurality of semiconductor compounds. Moreover, what modified the surface with the organic compound may be used.

These various additives can be added in an arbitrary amount depending on the desired performance and the like, but it is usually preferably used in the range of 0.01 to 40 parts by mass out of 100 parts by mass of the total components excluding the solvent in the active energy ray-curable composition.

The active energy ray-curable composition used in the present invention is prepared by mixing the above-mentioned respective compounding components. The mixing method is not particularly limited, and a paint shaker, disper, roll mill, bead mill, ball mill, attritor, sand mill or the like may be used.

The cured product of the present invention can be obtained by irradiating the active energy ray-curable composition with an active energy ray. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Moreover, when using an ultraviolet-ray as said active energy ray, in performing hardening reaction by an ultraviolet-ray efficiently, you may irradiate under an inert gas atmosphere, such as nitrogen gas, and you may irradiate under an air atmosphere.

As an ultraviolet generation source, an ultraviolet lamp is generally used in view of practicality and economy. Specifically, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, LED, and the like are exemplified.

The amount of integrated light of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m 2 , and more preferably 0.5 to 10 kJ/m 2 . When the amount of integrated light is within the above range, it is preferable from the viewpoint of being able to prevent or suppress the occurrence of uncured portions.

Moreover, irradiation of the said active energy ray may be performed in one step, or may be divided into two or more steps.

The laminate of the present invention has a cured coating film of the active energy ray-curable composition on one or both surfaces of a substrate, by applying the active energy ray-curable composition on the substrate and curing by irradiation with active energy rays. You can get it.

As said base material, a cyclic olefin type base material, a linear olefin type base material, etc. are mentioned, for example. Moreover, the said base material may be in the form of a film.

Examples of the method for forming the cured coating film include a coating method, a transfer method, and a sheet bonding method.

The above coating method is a method in which the above coating is spray coated or coated as a top coat on a molded product using a printing machine such as a curtain coater, roll coater, or gravure coater, and then cured by irradiation with active energy rays.

The transfer method refers to applying the above-described active energy ray-curable composition on a base sheet having releasability, adhering a transfer material obtained to the surface of a molded article, peeling the base sheet, transferring the top coat to the surface of the molded article, and then activating the active energy ray-curable composition. A method of curing by irradiating energy rays, or a method of attaching the transfer material to the surface of a molded product, then curing by irradiating active energy rays, and then peeling off the base sheet to transfer the top coat to the surface of the molded product.

The above-described sheet bonding method refers to a protective sheet having a coating film made of the curable composition described above on a base sheet or a protective sheet having a coating film made of the curable composition and a decorative layer on a base sheet bonded to a plastic molded product, thereby forming a surface of the molded product. A method of forming a protective layer on

The above-described sheet bonding method is, specifically, a method in which a base sheet of a sheet for forming a protective layer prepared in advance and a molded product are bonded together, and then thermally cured by heating to cross-link and cure a resin layer that may be B-staged (after bonding method), or by inserting the sheet for forming a protective layer into a molding mold, injecting and filling the cavity with resin to obtain a resin molded product, bonding the surface of the sheet for forming a protective layer to the surface thereof, and then thermally curing by heating. and a method of cross-linking and curing the resin layer (molding in-mold bonding method).

Here, when a film-shaped cyclic olefin-based substrate or linear olefin-based substrate is used as the substrate, the amount of application when the active energy ray-curable composition of the present invention is applied onto the film-shaped cyclic olefin-based substrate or linear olefin-based substrate It is preferable to adjust so that the film thickness after hardening may fall into the range of 1-100 micrometers. In addition, as the coating method at this time, for example, bar coater coating, die coating coating, spray coating coating, curtain coating coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, A screen printing method etc. are mentioned. When the active energy ray-curable composition of the present invention contains an organic solvent, after application, the organic solvent is volatilized by heating under conditions of 80 to 150°C for several tens of seconds to several minutes, and then irradiated with active energy rays to obtain the active energy rays. It is preferred to cure the curable composition.

The layered product of the present invention may have other layer configurations in addition to the cured coating film composed of the active energy ray-curable composition. The method for forming these various layer configurations is not particularly limited, and for example, a resin raw material may be directly applied and formed, or sheets formed in advance may be bonded together with an adhesive.

As an article of this invention, it has the said laminated body on the surface. Examples of the article include plastic molded products such as mobile phones, home appliances, automotive interior and exterior materials, and OA equipment.

(Example)

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the Example given below.

In addition, in this Example, the weight average molecular weight (Mw) is a value measured under the following conditions using gel permeation chromatography (GPC).

measuring device; "HLC-8220" by Tosoh Corporation

column; "Guard Column H _XL -H" manufactured by Tosoh Corporation

+ "TSKgel G5000HXL" manufactured by Toso Co., Ltd.

+ "TSKgel G4000HXL" manufactured by Toso Co., Ltd.

+ "TSKgel G3000HXL" manufactured by Toso Co., Ltd.

+ "TSKgel G2000HXL" manufactured by Toso Co., Ltd.

detector; RI (differential refractometer)

data processing; "SC-8010" made by Tosoh Corporation

Measuring conditions; Column temperature 40°C

solvent tetrahydrofuran

Flow rate 1.0ml/min

standard; polystyrene

sample; A 0.4% by mass tetrahydrofuran solution filtered through a microfilter in terms of resin solid content (100 μl)

(Example 1: Preparation of inorganic fine particle dispersion (1))

208.8 parts by mass of silica fine particles (“Aerosil 8200” manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix M manufactured by Toagosei Corporation”) -309") 25.2 parts by mass, 1,9-nonanediol diacrylate (Osaka Yuki Chemical Industry "Viscott #260") 72 parts by mass, and a wetting and dispersing agent ("ANTI-TERRA-" manufactured by Big Chemie Japan) U100") 18 parts by mass, and a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) 36 mass Part and 840 parts by mass of methyl ethyl ketone were blended to obtain a slurry of 30% by mass of non-volatile matter, mixed and dispersed using a wet ball mill (“Star Mill LMZ015” manufactured by Ashizawa Co., Ltd.), and non-volatile matter A 30% by mass inorganic fine particle dispersion (1) was obtained. The average particle diameter of the obtained dispersion was measured using a particle diameter measuring device ("ELSZ-2" manufactured by Ozuka Denshi Co., Ltd.). The average particle diameter (D50) was 105 nm. In addition, in the present invention, each condition for dispersion by the wet ball mill is as follows.

Media: Zirconia beads with a median diameter of 100 μm

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

Circumferential speed of the tip of the stirring blade: 11 m/sec

Flow rate of resin composition: 200ml/min

Dispersion time: 50 minutes

(Example 2: Preparation of inorganic fine particle dispersion (2))

208.8 parts by mass of silica fine particles (“Aerosil 9200” manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix M manufactured by Toagosei Corporation”) -309") 25.2 parts by mass, 1,9-nonanediol diacrylate (Osaka Yuki Chemical Industry "Viscott #260") 72 parts by mass, and a wetting and dispersing agent ("ANTI-TERRA-" manufactured by Big Chemie Japan) U100”) 18 parts by mass, and a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 (“Lumicure DPA-600” manufactured by Toagosei Co., Ltd.) 36 parts by mass , Mixing 840 parts by mass of methyl ethyl ketone to obtain a slurry of 30% by mass of non-volatile matter was mixed and dispersed using a wet ball mill (“Star Mill LMZ015” manufactured by Ashizawa Co., Ltd.), and 30% by weight of non-volatile matter % of inorganic fine particle dispersion (2) was obtained. The average particle diameter of the obtained dispersion was measured using a particle diameter measuring device ("ELSZ-2" manufactured by Ozuka Denshi Co., Ltd.). The average particle diameter (D50) was 124 nm.

(Example 3: Preparation of inorganic fine particle dispersion (3))

208.8 parts by mass of silica fine particles (“Aerosil #200” manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix manufactured by Toagosei Corporation”) M-309") 25.2 parts by mass, 1,9-nonanediol diacrylate (Osaka Yuki Chemical Industry "Viscot #260") 72 parts by mass, and a wetting and dispersing agent ("ANTI-TERRA" manufactured by Big Chemie Japan) -U100") 18 parts by mass, and a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) 36 parts by mass and 840 parts by mass of methyl ethyl ketone were blended to obtain a slurry containing 30% by mass of the non-volatile content, and mixed and dispersed using a wet ball mill (“Star Mill LMZ015” manufactured by Ashizawa Co., Ltd.) to obtain a non-volatile content of 30 A mass % inorganic fine particle dispersion (3) was obtained. The average particle diameter of the obtained dispersion was measured using a particle diameter measuring device ("ELSZ-2" manufactured by Ozuka Denshi Co., Ltd.). The average particle diameter (D50) was 132 nm.

(Example 4: Preparation of inorganic fine particle dispersion (4))

50 parts by mass of silica fine particles (“PGM-ST” manufactured by Nissan Chemical Industries, Ltd.; sol-gel silica, primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix M-ST” manufactured by Toagosei Corporation) 309”) 13.5 parts by mass, 1.5 parts by mass of a wetting and dispersing agent (“ANTI-TERRA-U100” manufactured by Big Chemie Japan), and 35 parts by mass of methyl ethyl ketone, an inorganic fine particle dispersion having 30% by mass of non-volatile content (4 ) was obtained.

(Example 5: Preparation of inorganic fine particle dispersion (5))

37.5 parts by mass of silica fine particles ("MEK-ST-40" manufactured by Nissan Chemical Industries, Ltd.; sol-gel silica, primary average particle diameter: 12 nm), and trimethylolpropane triacrylate ("Aronix" manufactured by Toagosei Corporation) M-309") 13.5 parts by mass, 1.5 parts by mass of a wetting and dispersing agent ("ANTI-TERRA-U100" manufactured by Big Chemie Japan), and 47.5 parts by mass of methyl ethyl ketone, inorganic fine particle dispersion having a non-volatile content of 30% by mass (5) was obtained.

(Example 6: Preparation of inorganic fine particle dispersion (6))

37.5 parts by mass of silica fine particles (“TOL-ST” manufactured by Nissan Chemical Industries, Ltd.; sol-gel silica, primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix M- 309”) 13.5 parts by mass, 1.5 parts by mass of a wetting and dispersing agent (“ANTI-TERRA-U100” manufactured by Big Chemie Japan), and 47.5 parts by mass of methyl ethyl ketone, an inorganic fine particle dispersion having 30% by mass of non-volatile content (6 ) was obtained.

(Example 7: Preparation of inorganic fine particle dispersion (7))

13.92 parts by mass of silica fine particles (“Aerosil 9200” manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix M manufactured by Toagosei Corporation”) -309") 4.68 parts by mass, 1,9-nonanediol diacrylate (Osaka Yuki Chemical Industry "Viscot #260") 4.8 parts by mass, and a wetting and dispersing agent ("ANTI-TERRA-" manufactured by Big Chemie Japan) U100”) 1.2 parts by mass, and a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 (“Lumicure DPA-600” manufactured by Toagosei Co., Ltd.) 2.4 parts by mass , 63 parts by mass of methyl ethyl ketone were blended to obtain a slurry containing 30% by mass of non-volatile content, and mixed and dispersed using a wet ball mill (“Star Mill LMZ015” manufactured by Ashizawa Co., Ltd.), and further silica fine particles ("MEK-ST-ZL" manufactured by Nissan Chemical Industries, Ltd.; sol-gel silica, primary average particle diameter: 12 nm) By blending 10 parts by mass, an inorganic fine particle dispersion (7) containing 30 mass% of non-volatile content was obtained.

(Example 8: Preparation of inorganic fine particle dispersion (8))

146.2 parts by mass of silica fine particles (“Aerosil 8200” manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix M manufactured by Toagosei Corporation”) -309") 125.6 parts by mass, 1,9-nonanediol diacrylate (Osaka Yuki Chemical Industry "Viscott #260") 50.4 parts by mass, and a wetting and dispersing agent ("ANTI-TERRA-" manufactured by Big Chemie Japan) U100") 12.6 parts by mass, and a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) 25.2 mass Part and 840 parts by mass of methyl ethyl ketone were blended to obtain a slurry of 30% by mass of non-volatile matter, mixed and dispersed using a wet ball mill (“Star Mill LMZ015” manufactured by Ashizawa Co., Ltd.), and non-volatile matter A 30% by mass inorganic fine particle dispersion (8) was obtained. The average particle diameter of the obtained dispersion was measured using a particle diameter measuring device ("ELSZ-2" manufactured by Ozuka Denshi Co., Ltd.). The average particle diameter (D50) was 105 nm.

(Comparative Preparation Example 1: Preparation of acrylic resin)

184 parts by mass of methyl isobutyl ketone was charged into a reactor equipped with a stirrer, a cooling pipe, a dropping funnel, and a nitrogen inlet pipe, and the temperature was raised while stirring until the temperature in the system reached 110°C. Next, 221 parts by mass of glycidyl methacrylate, 52.5 parts by mass of methyl methacrylate, 2.8 parts by mass of ethyl acrylate, and t-butylperoxy-2-ethylhexanoate (manufactured by Nippon Yukazai Co., Ltd. " Perbutyl O”) was added dropwise from a dropping funnel over 3 hours, and held at 110°C for 15 hours. Next, after the temperature fell to 90°C, 0.1 parts by mass of methoquinone and 76 parts by mass of acrylic acid were introduced, 2.0 parts by mass of triphenylphosphine was added, and the mixture was reacted at 100°C for 8 hours or more. After confirming that the solution acid value was 4.2 mgKOH/g or less, dilution was performed with methyl isobutyl ketone to obtain 910 parts by mass of a methyl isobutyl ketone solution of an acrylic resin (50.0% by mass of non-volatile content). The weight average molecular weight (Mw) of this acrylic resin was 20,000, the theoretical acryloyl group equivalent in terms of solid content was 250 g/equivalent, and the hydroxyl group was 224 mgKOH/g.

(Comparative Example 1: Preparation of inorganic fine particle dispersion (R1))

53 parts by mass of silica fine particles (“Aerosil R7200” manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm, silica fine particles having a (meth)acryloyl group on the particle surface) and Comparative Synthesis Example 1 A composition containing 12 parts by mass of an acrylic resin obtained from (12 parts by mass of resin solid content), dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 (manufactured by Toagosei Co., Ltd. "Lumicure DPA- 600”) 35 parts by mass and 188 parts by mass of methyl isobutyl ketone were blended to obtain a slurry containing 50% by mass of non-volatile content, and mixed using a wet ball mill (“Star Mill LMZ015” manufactured by Ashizawa Co., Ltd.) It dispersed, and the inorganic fine particle dispersion (R1) of 50 mass % of non-volatile matter was obtained.

(Comparative Example 2: Preparation of inorganic fine particle dispersion (R2))

37.5 parts by mass of silica fine particles (“MEK-AC 2140Z” manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm), and trimethylolpropane triacrylate (“Aronix M- 309”) 13.5 parts by mass and 47.5 parts by mass of methyl ethyl ketone were blended to obtain an inorganic fine particle dispersion (R2) having a non-volatile content of 30% by mass.

Table 1 shows the compositions of the inorganic fine particle dispersions (1) to (8), (R1) and (R2) obtained in Examples 1 to 8 and Comparative Example 1 and Comparative Example 2.

[Table 1]

(Example 9: Preparation of active energy ray-curable composition (1) and production of laminate (L1))

100 parts by mass (30 parts by mass as a solid content) of the inorganic fine particle dispersion (1) having a 30% by mass non-volatile content obtained in Example 1 and 0.6 parts by mass of a photopolymerization initiator ("Omnirad-BP Flakes" manufactured by IGM Resins) were mixed, and active energy A pre-curable composition (1) was obtained.

Next, the obtained active energy ray curable composition (1) was applied onto a 23 μm-thick cycloolefin film (ZeonorFilm ZF-14, 23 μm manufactured by Nippon Zeon Co., Ltd.) by a bar coater, and at 90° C. dried for a minute. Next, ultraviolet rays were irradiated at 5 kJ/m 2 by an 80 W high-pressure mercury lamp in a nitrogen atmosphere to obtain a laminate (L1) having a cured coating film having a thickness of 5 μm on the cycloolefin film.

(Examples 10 to 17: Adjustment of active energy ray-curable compositions (2) to (9) and production of laminates (L2) to (L9))

Active energy ray-curable compositions (2) to (9) were obtained in the same manner as in Example 8 at the blending ratios shown in Table 2. Further, laminates (L2) to (L9) were obtained by the same method as for laminate (L1).

(Comparative Examples 3 and 4: Preparation of active energy ray-curable compositions (R1) and (R2), and production of laminates (L10) and (L11))

Active energy ray-curable compositions (R1) and (R2) were obtained in the same manner as in Example 8 at the blending ratios shown in Table 2. Further, laminates (L10) and (L11) were obtained by the same method as for laminate (L1).

The following evaluation was performed using the laminates (L1) to (L11) obtained in the above examples and comparative examples.

[Evaluation method of scratch resistance]

A disk-shaped indenter with a diameter of 2.4 cm was wrapped with 0.5 g of steel wool ("Bone Star #0000" manufactured by Nippon Steel Wool Co., Ltd.), and a heavy load of 500 g was applied to the indenter, and the obtained in Examples and Comparative Examples An abrasion test was conducted in which the painted surface of the laminate was reciprocated 10 times. The haze value of the laminated film before and after the abrasion test was measured using "Haze Computer HZ-2" manufactured by Sugashi Kenki Co., Ltd., and evaluated according to the following criteria using the difference value (dH) between them. In addition, the smaller the difference value (dH), the higher the scratch resistance.

A: dH was 1.0% or less

B: dH was greater than 1.0% and less than 3.0%

C: dH was greater than 3.0% and less than 5.0%

D: dH was greater than 5.0% and less than 10%

E: dH was greater than 10%

[Evaluation method of substrate adhesion (initial stage)]

A slit was made on the surface of the cured coating film of the laminate obtained in Examples and Comparative Examples with a cutter knife to prepare 100 1 mm × 1 mm base wood, and cellophane adhesive tape was attached therefrom. , Rapid stripping operation was performed, and the number of foundation lumber remaining without stripping was counted and evaluated according to the following criteria.

A: The remaining number of foundation trees was more than 80

B: The number of remaining foundation trees was more than 50 and less than 80

C: The number of remaining foundation trees was more than 30 and less than 50

D: Less than 30 remaining foundation trees

[Evaluation method of substrate adhesion (after light resistance test)]

The laminated body obtained by the Example and the comparative example was light-irradiated for 50 hours by the fade meter "U48AU" (63 degreeC, 50% of humidity) by Sugashi Kenki Co., Ltd.. After that, it was evaluated according to the following criteria by the same method as for the above-described adhesion to substrate (initial stage).

A: The remaining number of foundation trees was more than 80

B: The number of remaining foundation trees was more than 50 and less than 80

C: The number of remaining foundation trees was more than 30 and less than 50

D: Less than 30 remaining foundation trees

Compositions of active energy ray curable compositions (1) to (8), (R1) and (R2) prepared in Examples 9 to 17 and Comparative Examples 3 and 4, and Examples 9 to 17 and Comparative Examples 3 and 4 The evaluation results of the laminates (L1) to (L11) produced in Table 2 are shown.

[Table 2]

Examples 9 to 17 shown in Table 2 are examples of laminates using the active energy ray-curable composition containing the inorganic fine particle dispersion of the present invention. It was confirmed that this laminate had excellent scratch resistance and substrate adhesion.

On the other hand, Comparative Examples 3 and 4 shown in Table 2 are examples of laminates using an active energy ray-curable composition containing an inorganic fine particle dispersion having no wet dispersion. Although this laminate had excellent scratch resistance, it was confirmed that the adhesion to the substrate after the light resistance test was remarkably insufficient.

Claims (9)

Inorganic fine particles (A);
A (meth)acrylate compound (B) having two or more (meth)acryloyl groups in one molecule;
An inorganic fine particle dispersion containing a wetting and dispersing agent (C),
The average primary particle diameter of the inorganic fine particles (A) is in the range of 1 to 50 nm,
The content of the inorganic fine particles (A) is in the range of 40 to 90 mass% of the total mass of the inorganic fine particles (A), the compound (B), and the wetting and dispersing agent (C),
An inorganic fine particle dispersion characterized in that the wetting and dispersing agent (C) has an acid value and/or an amine value. According to claim 1,
The inorganic fine particle dispersion in which the compound (B) has 2 to 4 (meth)acryloyl groups in one molecule. According to claim 1 or 2,
The wetting and dispersing agent (C) is a resin having a carboxyl group, a phosphoric acid group and/or an amino group, and the resin is at least one selected from the group consisting of urethane resins, acrylic resins, polyester resins and amide resins. An active energy ray-curable composition comprising the inorganic fine particle dispersion according to claim 1 or 2 and a photopolymerization initiator. A cured product of the active energy ray-curable composition according to claim 4. A laminate characterized by having a cured coating film of the active energy ray-curable composition according to claim 4 on one side or both sides of a substrate. According to claim 6,
A layered product wherein the substrate is a cyclic olefin-based substrate or a linear olefin-based substrate. According to claim 6,
A layered product in which the base material is in the form of a film. An article characterized by having the laminate according to claim 6 on its surface.