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

Abstract

To provide an inorganic particulate dispersion which has excellent adhesiveness and has excellent scratch resistance in a cured product and to provide an active energy curable composition, a cured product, a laminate and an article.SOLUTION: There is provided an inorganic particulate dispersion which contains inorganic particulates (A), a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule (B) and a wetting dispersant (C), wherein the average primary particle diameter of the inorganic particulates (A) is in the range of 1 to 50 nm, the content of the inorganic particulates (A) is in the range of 40 to 90 mass% in the total mass of the inorganic particulates (A), the compound (B) and the wetting dispersant (C) and the wetting dispersant (C) has an acid value or an amine value.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an inorganic fine particle dispersion, an active energy ray-curable composition, a cured product, a laminate, and an article. [Background technology]

[0002] Resin materials containing (meth)acryloyl groups can be easily and instantly cured by ultraviolet irradiation or the like, and the cured products have excellent transparency, hardness, etc., and are therefore widely used in the fields of paints, coating agents, etc. The objects to be coated are diverse, ranging from optical films and plastic molded products to woodworking products, and the required performance varies depending on the type and application of the object to be coated, so many resins designed for specific purposes have been proposed.

[0003] Known resin materials having (meth)acryloyl groups include active energy ray-curable resin compositions containing a (meth)acryloyl group-containing acrylic resin, pentaerythritol tetraacrylate, and pentaerythritol triacrylate (see, for example, Patent Document 1). The active energy ray-curable resin composition described in Patent Document 1 has an excellent balance between surface hardness and low cure shrinkage in the cured product, and is therefore useful as a coating agent for coating relatively thin plastic films. However, there is a problem in that the adhesion to the film substrate, particularly after long-term storage under high-temperature and humid conditions, is poor, and peeling easily occurs.

[0004] Therefore, there has been a demand for a material that has excellent adhesion and excellent scratch resistance and can be used as a coating agent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-207947 Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide an inorganic fine particle dispersion having excellent adhesion and excellent scratch resistance in a cured product, an active energy ray-curable composition, a cured product, a laminate, and an article made of the active energy ray-curable composition. [Means for solving the problem]

[0007] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an inorganic microparticle dispersion containing specific inorganic microparticles, a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule, and a specific wetting dispersant, and have thus completed the present invention.

[0008] That is, the present invention relates to an inorganic fine particle dispersion containing inorganic fine particles (A), a (meth)acrylate compound (B) having two or more (meth)acryloyl groups in one molecule, and a wetting dispersant (C), wherein the inorganic fine particles (A) have an average primary particle diameter 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 dispersant (C), and the wetting dispersant (C) has an acid value and / or an amine value, and the inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate, and article are also provided. [Effects of the Invention]

[0009] The inorganic fine particle dispersion of the present invention can form a cured product having excellent adhesion to substrates and scratch resistance, and can therefore be used as a coating agent or adhesive, and is particularly suitable for use as a coating agent. DETAILED DESCRIPTION OF THE INVENTION

[0010] The inorganic fine particle dispersion of the present invention is characterized by containing 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).

[0011] In the present invention, "(meth)acrylate" means acrylate and / or methacrylate. "(meth)acryloyl" means acryloyl and / or methacryloyl. "(meth)acrylic" means acrylic and / or methacrylic.

[0012] The inorganic fine particles (A) have an average primary particle diameter of 1 to 50 nm. The average primary particle diameter is obtained by measuring the diameters of a plurality of inorganic fine particles using a transmission electron microscope or a scanning electron microscope and calculating the average value.

[0013] 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. These inorganic fine particles can be used alone or in combination of two or more. Among these, silica is preferred because it can provide an inorganic fine particle dispersion that can form a cured product with excellent substrate adhesion and scratch resistance, and silica fine particles whose particle surfaces have been subjected to a hydrophobic treatment are more preferred.

[0014] 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 (meth)acrylate compound (B), and the wetting and dispersing agent (C), and a range of 45 to 70 mass % is more preferable because an inorganic fine particle dispersion capable of forming a cured product having excellent substrate adhesion and scratch resistance can be obtained.

[0015] As the (meth)acrylate compound (B), one having two or more (meth)acryloyl groups in one molecule is used.

[0016] Examples of the compound (B) include 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 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, triethylene 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, tricyclodecane dimethanol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, propylene oxide-modified glycerin tri(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, ethylene oxide-modified di(meth)acrylate of bisphenoxyethanol fluorene, polytetramethylene glycol di(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, phenoxyethylene glycol (meth)acrylate, stearyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, trifluoroethyl ( 3-Methyl-1,5-pentanediol di(meth)acrylate, 2,3-[(meth)acryloyloxymethyl]norbornane, 2,5-[(meth)acryloyloxymethyl]norbornane, 2,6-[(meth)acryloyloxymethyl]norbornane, 1,3-adamantyl di(meth)acrylate, 1,3-bis[(meth)acryloyloxymethyl]adamantane, tris(hydroxyethyl)isocyanuric acid di(meth)acrylate, 3,9-bis[1,1-dimethyl-2-(meth)acryloyloxyethyl]-2,4,Bifunctional (meth)acrylates such as 8,10-tetraoxospiro[5.5]undecane, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, and ditrimethylolpropane di(meth)acrylate;

[0017] trifunctional (meth)acrylates such as 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, caprolactone-modified trimethylolpropane tri(meth)acrylate, HPA-modified trimethylolpropane tri(meth)acrylate, (EO) or (PO)-modified trimethylolpropane tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, and tris(methacryloxyethyl) isocyanurate;

[0018] tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate;

[0019] Pentafunctional (meth)acrylates such as dipentaerythritol hydroxypenta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate;

[0020] Examples include hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate.

[0021] These (meth)acrylate compounds having two or more (meth)acryloyl groups in one molecule can be used alone or in combination of two or more. Among them, (meth)acrylate compounds having 2 to 4 (meth)acryloyl groups in one molecule are preferred because they can provide an inorganic fine particle dispersion capable of forming a cured product having excellent substrate adhesion and scratch resistance.

[0022] The wetting and dispersing agent (C) has an acid value and / or an amine value.

[0023] Examples of the wetting and dispersing agent (C) include urethane resins having carboxyl groups, phosphate groups, and / or amino groups, acrylic resins having carboxyl groups, phosphate groups, and / or amino groups, polyester resins having carboxyl groups, phosphate groups, and / or amino groups, and amide resins having carboxyl groups, phosphate groups, and / or amino groups. These wetting and dispersing agents can be used alone or in combination of two or more. Among these, polyester resins having carboxyl groups and amide resins having amino groups are preferred because they have excellent dispersibility for inorganic particles and maintain excellent stability.

[0024] Commercially available wetting and dispersing agents (C) include, for example, "DISPERBYK-102", "DISPERBYK-106", "DISPERBYK-108", "DISPERBYK-109", "DISPERBYK-110 / 111", "DISPERBYK-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", and "DISPERBYK-186". ISPERBYK-185", "DISPERBYK-2000", "DISPERBYK-2001", "DISPERBYK-2008", "DISPERBYK-2009", "DISPE RBYK-2013”, “DISPERBYK-2022”, “DISPERBYK-2023”, “DISPERBYK-2025v2026”, “DISPERBYK-2050”, “DISP ERBYK-2055", "DISPERBYK-2096", "DISPERBYK-2150", "DISPERBYK-2155", "DISPERBYK-2157", "DISPERBY K-2158", "DISPERBYK-2159", "DISPERBYK-2163", "DISPERBYK-2164", "BYK-9076", "BYK-9077", "BYK-220 S," "ANTI-TERRA-U / U100," and "ANTI-TERRA-U / U204," and Kusumoto Chemicals Co., Ltd.'s "Disparlon 1831," "Disparlon 1850," "Disparlon 1860," "Disparlon DA-1401," "Disparlon DA-1200," "Disparlon PW36 Disparlon DA-703-50," "Disparlon DA7301," "Disparlon DA-325," "Disparlon DA-375," and "Disparlon DA234."

[0025] The acid value of the wetting and dispersing agent (C) is such that it has excellent dispersibility for inorganic fine particles and excellent stability. In order to maintain the quality, the range of 0.5 to 180 mgKOH / g is preferable, and 10 to 80 The amine value of the wetting and dispersing agent (C) is preferably in the range of mgKOH / g. It has excellent particle dispersibility and maintains excellent stability, so it can be used in a range of 0 to 150 mg. The range of KOH / g is preferred, and the range of 20 to 50 mgKOH / g is more preferred. In the present invention, the acid value is measured based on the neutralization titration method of JIS K 2501 (1992). The amine value is the value specified in JIS K 7237 ( 1995 ) calculated based on This is the value to be used.

[0026] The inorganic fine particle dispersion of the present invention may contain other active energy ray-curable resin components in addition to the compound (B) as long as the effects of the present invention are not impaired.

[0027] The other active energy ray-curable resin component may be (D) other than the compound (B). Examples of the other (meth)acrylate resin (D) include a dendrimer-type (meth)acrylate resin (D1), an acrylic (meth)acrylate resin (D2), and an epoxy (meth)acrylate resin (D3). These other (meth)acrylate resins (D) may be used alone or in combination of two or more.

[0028] The dendrimer-type (meth)acrylate resin (D1) refers to a resin having a regular multi-branched structure and having a (meth)acryloyl group at the end of each branched chain, and is also called a dendrimer-type, hyperbranched-type, star polymer, etc. Examples of such compounds include those represented by the following structural formulas (1-1) to (1-8), but are not limited thereto, and any resin having a regular multi-branched structure and having a (meth)acryloyl group at the end of each branched chain can be used.

[0029] [ka]

[0030] [ka] [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.

[0031] Commercially available products of the dendrimer type (meth)acrylate resin (D1) include, for example, "Viscoat #1000" [weight average molecular weight (Mw) 1,500 to 2,000, average number of (meth)acryloyl groups per molecule: 14], "Viscoat 1020" [weight average molecular weight (Mw) 1,000 to 3,000], "SIRIUS501" [weight average molecular weight (Mw) 15,000 to 23,000], manufactured by Osaka Organic Chemical Co., Ltd., and "SP-1106" [weight average molecular weight (Mw) 1,630, average number of (meth)acryloyl groups per molecule: 0.01], manufactured by MIWON Co., Ltd. Examples of such acrylate copolymers include "CN2301" and "CN2302" (average number of (meth)acryloyl groups per molecule: 16), "CN2303" (average number of (meth)acryloyl groups per molecule: 6), and "CN2304" (average number of (meth)acryloyl groups per molecule: 18), manufactured by SARTOMER Co., Ltd.; "ESDRIMER HU-22" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "A-HBR-5" manufactured by Shin-Nakamura Chemical Co., Ltd.; "New Frontier R-1150" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; and "Hypertech UR-101" manufactured by Nissan Chemical Corporation.

[0032] 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. The average number of (meth)acryloyl groups per molecule is preferably in the range of 5 to 30.

[0033] Examples of the acrylic (meth)acrylate resin (D2) include those obtained by polymerizing, as an essential component, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, to obtain an acrylic resin intermediate, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group.

[0034] Examples of the (meth)acrylate compound (α) having a reactive functional group include hydroxyl group-containing (meth)acrylate monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; carboxyl 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; and glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate and 4-hydroxybutyl acrylate glycidyl ether. These can be used alone or in combination of two or more.

[0035] The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. Examples of the other polymerizable unsaturated group-containing compounds include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (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; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0036] The acrylic resin intermediate can be produced by the same method as that for general acrylic resins. For example, the acrylic resin intermediate can be produced by polymerizing various monomers in the presence of a polymerization initiator at a temperature range of 60°C to 150°C. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Examples of the polymerization mode include random copolymerization, block copolymerization, and graft copolymerization. When the solution polymerization method is used, for example, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether can be preferably used.

[0037] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred 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 preferred 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 (meth)acrylate compounds (β) can be used alone or in combination of two or more.

[0038] For example, when the reaction between the acrylic resin intermediate and the (meth)acrylate compound (β) is an esterification reaction, an esterification catalyst such as triphenylphosphine may be appropriately used at a temperature in the range of 60 to 150° C. When the reaction is a urethanization reaction, an example of the reaction is to dropwise add compound (β) to the acrylic resin intermediate at a temperature in the range of 50 to 120° C. The reaction ratio between the two is preferably such that 1.0 to 1.1 moles of the (meth)acrylate compound (β) are used per mole of functional groups in the acrylic resin intermediate.

[0039] The epoxy (meth)acrylate resin (D3) may be, for example, one obtained by reacting an epoxy resin with (meth)acrylic acid or its anhydride. 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 epoxy resin, bisphenol B epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, binaphthol, bis(2,7 triglycidyl ethers of 4,4',4"-methylidinetrisphenol and the like; novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac resins; (poly)oxyalkylene modified products in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various epoxy resins; and lactone modified products in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various epoxy resins.

[0040] In addition, depending on the type of active energy ray used, it is preferable to use a photopolymerization initiator in the active energy ray-curable composition of the present invention. Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 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-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0041] Examples of commercially available photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); and "Vicure 10" and "Vicure 55" (manufactured by Stoffa Examples of photopolymerization initiators include "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ), "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop), and "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more.

[0042] The photopolymerization initiator may also be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound.

[0043] 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, per 100 parts by mass of the components excluding the organic solvent in the active energy ray-curable composition of the present invention.

[0044] The active energy ray-curable composition used in the present invention may further contain other components, such as a silane coupling agent, a phosphate ester compound, a solvent, an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, an antistatic agent, organic beads, quantum dots (QDs), a rheology control agent, a defoaming agent, an antifogging agent, and a colorant.

[0045] Examples of the silane coupling agent include (meth)acryloyloxy-based silane coupling agents such as [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, [(meth)acryloyloxyalkyl]alkyldialkoxysilane, and [(meth)acryloyloxyalkyl]trialkoxysilane; vinyl-based silane coupling agents such as trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, and trialkoxyallylsilane; styrene-based silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, and styryltrialkoxysilane; and (glycidyloxyalkyl)trialkoxysilane. Examples of the silane coupling agent include epoxy-based silane coupling agents such as alkyl silane, (glycidyloxyalkyl)dialkylalkoxysilane, (glycidyloxyalkyl)alkyldialkoxysilane, (glycidyloxyalkyl)trialkoxysilane, [(3,4-epoxycyclohexyl)alkyl]trimethoxysilane, [(3,4-epoxycyclohexyl)alkyl]trialkylsilane, [(3,4-epoxycyclohexyl)alkyl]dialkylalkoxysilane, [(3,4-epoxycyclohexyl)alkyl]alkyldialkoxysilane, and [(3,4-epoxycyclohexyl)alkyl]trialkoxysilane; and isocyanate-based silane coupling agents such as (isocyanate alkyl)trialkylsilane, (isocyanate alkyl)dialkylalkoxysilane, (isocyanate alkyl)alkyldialkoxysilane, and (isocyanate alkyl)trialkoxysilane. These silane coupling agents can be used alone or in combination of two or more.

[0046] Commercially available examples of the phosphate ester compound include phosphate ester compounds having a (meth)acryloyl group in their molecular structure, such as "Kayamar PM-2" and "Kayamar PM-21" manufactured by Nippon Kayaku Co., Ltd.; "Light Ester P-1M," "Light Ester P-2M," and "Light Acrylate P-1A(N)" manufactured by Kyoeisha Chemical Co., Ltd.; "SIPOMER PAM 100," "SIPOMER PAM 200," "SIPOMER PAM 300," and "SIPOMER PAM 4000" manufactured by Solvay; "Viscoat #3PA" and "Viscoat #3PMA" manufactured by Osaka Organic Chemical Industry Ltd.; and "New Frontier S-23A" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; and "SIPOMER PAM 5000" manufactured by Solvay, a phosphate ester compound having an allyl ether group in its molecular structure.

[0047] The solvent is added for purposes such as adjusting the coating viscosity of the active energy ray-curable composition, and the type and amount thereof are appropriately adjusted depending on the desired performance. Generally, the solvent is used so that the non-volatile content of the active energy ray-curable composition is in the range of 10 to 90% by 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; esters 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 can be used alone or in combination of two or more.

[0048] Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more.

[0049] Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, phosphate ester-based antioxidants, etc. These antioxidants can be used alone or in combination of two or more.

[0050] Examples of the silicon-based additives include polyorganosiloxanes having an alkyl group or a phenyl group, such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, and amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxanes having a polyether-modified acrylic group, and polydimethylsiloxanes having a polyester-modified acrylic group. These silicon-based additives can be used alone or in combination of two or more.

[0051] Examples of commercially available fluorine-based additives include the "Megaface" series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.

[0052] Examples of the antistatic agent include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis(trifluoromethanesulfonyl)imide or bis(fluorosulfonyl)imide. These antistatic agents can be used alone or in combination of two or more.

[0053] Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyethylene fluoride resin beads, and polyethylene resin beads. These organic beads can be used alone or in combination of two or more. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

[0054] Examples of the quantum dots (QDs) include II-V group semiconductor compounds, II-VI group semiconductor compounds, III-IV group semiconductor compounds, III-V group semiconductor compounds, III-VI group semiconductor compounds, IV-VI group semiconductor compounds, I-III-VI group semiconductor compounds, II-IV-VI group semiconductor compounds, II-IV-V group semiconductor compounds, I-II-IV-VI group semiconductor compounds, Group IV elements, and compounds containing the same. Examples of the II-VI group semiconductor compound include binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, and HgTe; ternary compounds such as ZnSeS, ZnSeTe, ZnSTe, CdZnS, CdZnSe, CdZnTe, CdSeS, CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, and HgZnTe; and quaternary compounds such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, and HgZnSTe. Examples of the III-IV group semiconductor compounds include B4C3, Al4C3, Ga4C3, etc. Examples of the III-V group semiconductor compounds include binary compounds such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb; ternary compounds such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and GaAlNP; and quaternary compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. Examples of the III-VI group semiconductor compounds include Al2S3, Al2Se3, Al2Te3, Ga2S3, Ga2Se3, Ga2Te3, GaTe, In2S3, In2Se3, In2Te3, and InTe.Examples of the IV-VI group semiconductor compounds include binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, and PbTe; ternary compounds such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, and SnPbTe; and quaternary compounds such as SnPbSSe, SnPbSeTe, and SnPbSTe. Examples of the I-III-VI group semiconductor compounds include CuInS, CuInSe, CuInTe, CuGaS, CuGaSe, CuGaSe, AgInS, AgInSe, AgInTe, AgGaSe, AgGaS, and AgGaTe. Examples of the IV group elements or compounds containing them include C, Si, Ge, SiC, and SiGe. The quantum dots may be made of a single semiconductor compound, or may have a core-shell structure made of multiple semiconductor compounds, and may have their surfaces modified with organic compounds.

[0055] These various additives can be added in any amount depending on the desired performance, etc., but it is usually preferable to use them in a range of 0.01 to 40 parts by mass per 100 parts by mass of the total of the components excluding the solvent in the active energy ray-curable composition.

[0056] The active energy ray-curable composition used in the present invention is produced by mixing the above-mentioned components. The mixing method is not particularly limited, and a paint shaker, disper, roll mill, bead mill, ball mill, attritor, sand mill, bead mill, etc. may be used.

[0057] The cured product of the present invention can be obtained by irradiating the active energy ray-curable composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be carried out in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

[0058] As a source of ultraviolet light, ultraviolet lamps are commonly used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0059] The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions.

[0060] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0061] The laminate of the present invention has a cured coating film of the active energy ray-curable composition on one or both sides of a substrate, and can be obtained by applying the active energy ray-curable composition to the substrate and curing it by irradiating it with active energy rays.

[0062] Examples of the substrate include a cyclic olefin substrate, a linear olefin substrate, etc. The substrate may also be in the form of a film.

[0063] Examples of methods for forming the cured coating film include a coating method, a transfer method, and a sheet adhesion method.

[0064] The coating method is a method in which the coating material is applied as a top coat to a molded product by spray coating or by using a printing machine such as a curtain coater, a roll coater, or a gravure coater, and then cured by irradiating with active energy rays.

[0065] The transfer method is a method in which a transfer material obtained by applying the active energy ray-curable composition described above onto a base sheet having releasability is adhered to the surface of a molded article, the base sheet is peeled off to transfer a top coat onto the surface of the molded article, and then the top coat is irradiated with active energy rays to cure it; or a method in which the transfer material is adhered to the surface of a molded article, the top coat is irradiated with active energy rays to cure it, and then the base sheet is peeled off to transfer the top coat onto the surface of the molded article.

[0066] The sheet adhesion method is a method of forming a protective layer on the surface of a plastic molded product by adhering a protective sheet having a coating film made of the curable composition 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, to the molded product.

[0067] Specifically, the sheet bonding method includes a method (post-bonding method) in which a base sheet of a protective layer forming sheet that has been prepared in advance is bonded to a molded product, and then the resin layer is crosslinked and hardened by heating to form a B-stage resin layer; and a method (simultaneous molding bonding method) in which the protective layer forming sheet is sandwiched between a molding die, resin is injected into the cavity to fill it, and the surface of the resin molded product is bonded to the protective layer forming sheet at the same time as the molded product is obtained, and then the resin layer is crosslinked and hardened by heating to form a B-stage resin layer.

[0068] When a film-like cyclic olefin substrate or linear olefin substrate is used as the substrate, the amount of coating of the active energy ray-curable composition of the present invention applied to the film-like cyclic olefin substrate or linear olefin substrate is preferably adjusted so that the film thickness after curing is in the range of 1 to 100 μm. Examples of coating methods include bar coater coating, die coating, spray coating, curtain coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. When the active energy ray-curable composition of the present invention contains an organic solvent, it is preferable to heat the applied composition at 80 to 150° C. for several tens of seconds to several minutes to volatilize the organic solvent, and then irradiate it with active energy rays to cure the active energy ray-curable composition.

[0069] The laminate of the present invention may have other layer structures in addition to the cured coating film made of the active energy ray-curable composition. The method for forming these various layer structures is not particularly limited, and for example, they may be formed by directly applying a resin raw material, or by laminating pre-formed sheets together with an adhesive.

[0070] The article of the present invention has the above-described laminate on the surface thereof, and examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior / exterior materials, and office automation equipment. [Example]

[0071] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

[0072] In the examples, the weight average molecular weight (Mw) is a value measured using gel permeation chromatography (GPC) under the following conditions.

[0073] Measuring device: Tosoh Corporation "HLC-8220" Column: Tosoh Guard Column H XL -H” +Tosoh Corporation's "TSKgel G5000HXL" +Tosoh Corporation's "TSKgel G4000HXL" +Tosoh Corporation's "TSKgel G3000HXL" +Tosoh Corporation's "TSKgel G2000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation "SC-8010" Measurement conditions: Column temperature 40℃ Solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: Polystyrene Sample: 100 μl of tetrahydrofuran solution containing 0.4% by mass of resin solids filtered through a microfilter

[0074] (Example 1: Production of inorganic fine particle dispersion (1)) Silica fine particles (Aerosil 8200 manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 12 nm) 208.8 parts by mass, trimethylolpropane triacrylate (Aronix M-309 manufactured by Toagosei Co., Ltd.) 25.2 parts by mass, 1,9-nonanediol diacrylate (Viscoat #260 manufactured by Osaka Organic Chemical Industry Co., Ltd.) 72 parts by mass, wetting and dispersing agent (Anti-terra-U100 manufactured by BYK Japan) 18 parts by mass, and 36 parts by weight of a composition containing pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40 / 60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) and 840 parts by weight of methyl ethyl ketone were blended to form a slurry with a nonvolatile content of 30% by weight. This slurry was mixed and dispersed using a wet ball mill ("Star Mill LMZ015" manufactured by Ashizawa Co., Ltd.) to obtain an inorganic fine particle dispersion (1) with a nonvolatile content of 30% by weight. The average particle size of the resulting dispersion was measured using a particle size measuring device ("ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.). The average particle size (D50) was 105 nm. In the present invention, the conditions for dispersion using a wet ball mill were as follows:

[0075] Media: Zirconia beads with a median diameter of 100 μm Filling rate of resin composition relative to the internal volume of the mill: 70% by volume Peripheral speed of the tip of the stirring blade: 11 m / sec Resin composition flow rate: 200 ml / min Dispersion time: 50 minutes

[0076] (Example 2: Production of inorganic fine particle dispersion (2)) Silica fine particles (Aerosil 9200 manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 12 nm) 208.8 parts by mass, trimethylolpropane triacrylate (Aronix M-309 manufactured by Toagosei Co., Ltd.) 25.2 parts by mass, 1,9-nonanediol diacrylate (Viscoat #260 manufactured by Osaka Organic Chemical Industry Co., Ltd.) 72 parts by mass, wetting and dispersing agent (Anti-terra-U100 manufactured by BYK Japan) 18 parts by mass, 36 parts by weight of a composition containing pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40 / 60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) and 840 parts by weight of methyl ethyl ketone were blended to form a slurry with a nonvolatile content of 30% by weight. This slurry was mixed and dispersed using a wet ball mill ("Starmill LMZ015" manufactured by Ashizawa Co., Ltd.) to obtain an inorganic fine particle dispersion (2) with a nonvolatile content of 30% by weight. The average particle size of the resulting dispersion was measured using a particle size measuring device ("ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.). The average particle size (D50) was 124 nm.

[0077] (Example 3: Production of inorganic fine particle dispersion (3)) 208.8 parts by mass of silica fine particles ("Aerosil #200" manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 12 nm), 25.2 parts by mass of trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.), 72 parts by mass of 1,9-nonanediol diacrylate ("Biscoat #260" manufactured by Osaka Organic Chemical Industry Co., Ltd.), 18 parts by mass of a wetting and dispersing agent ("ANTI-TERRA-U100" manufactured by BYK Japan), and 36 parts by weight of a composition containing pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40 / 60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) and 840 parts by weight of methyl ethyl ketone were blended to form a slurry with a nonvolatile content of 30% by weight. This slurry was mixed and dispersed using a wet ball mill ("Starmill LMZ015" manufactured by Ashizawa Co., Ltd.) to obtain an inorganic fine particle dispersion (3) with a nonvolatile content of 30% by weight. The average particle size of the resulting dispersion was measured using a particle size measuring device ("ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.). The average particle size (D50) was 132 nm.

[0078] (Example 4: Production of inorganic fine particle dispersion (4)) 50 parts by mass of silica microparticles ("PGM-ST" manufactured by Nissan Chemical Industries, Ltd.; sol-gel silica, primary average particle diameter: 12 nm), 13.5 parts by mass of trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.), 1.5 parts by mass of a wetting dispersant ("ANTI-TERRA-U100" manufactured by BYK Japan), and 35 parts by mass of methyl ethyl ketone were blended to obtain an inorganic microparticle dispersion (4) with a non-volatile content of 30% by mass.

[0079] (Example 5: Production of inorganic fine particle dispersion (5)) 37.5 parts by mass of silica microparticles ("MEK-ST-40" manufactured by Nissan Chemical Industries, Ltd.; sol-gel silica, average primary particle diameter: 12 nm), 13.5 parts by mass of trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.), 1.5 parts by mass of a wetting dispersant ("ANTI-TERRA-U100" manufactured by BYK Japan), and 47.5 parts by mass of methyl ethyl ketone were blended to obtain an inorganic microparticle dispersion (5) with a non-volatile content of 30% by mass.

[0080] (Example 6: Production of inorganic fine particle dispersion (6)) 37.5 parts by mass of silica microparticles ("TOL-ST" manufactured by Nissan Chemical Industries, Ltd.; sol-gel silica, primary average particle diameter: 12 nm), 13.5 parts by mass of trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.), 1.5 parts by mass of a wetting dispersant ("ANTI-TERRA-U100" manufactured by BYK Japan), and 47.5 parts by mass of methyl ethyl ketone were blended to obtain an inorganic microparticle dispersion (6) with a non-volatile content of 30% by mass.

[0081] (Example 7: Production of inorganic fine particle dispersion (7)) 13.92 parts by mass of silica fine particles ("Aerosil 9200" manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 12 nm), 4.68 parts by mass of trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.), 4.8 parts by mass of 1,9-nonanediol diacrylate ("Biscoat #260" manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1.2 parts by mass of a wetting and dispersing agent ("ANTI-TERRA-U100" manufactured by BYK Japan), dipentaerythritol pentaacrylate and dipentaerythritol 2.4 parts by mass of a composition containing benzophenone and benzotriazol-2-acrylate in a molar ratio of 40 / 60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) was blended with 63 parts by mass of methyl ethyl ketone to form a slurry with a nonvolatile content of 30% by mass. This slurry was mixed and dispersed using a wet ball mill ("Star Mill LMZ015" manufactured by Ashizawa Co., Ltd.), and 10 parts by mass of silica microparticles ("MEK-ST-ZL" manufactured by Nissan Chemical Co., Ltd.; sol-gel silica, average primary particle diameter: 12 nm) were further blended to obtain an inorganic microparticle dispersion (7) with a nonvolatile content of 30% by mass.

[0082] (Example 8: Production of inorganic fine particle dispersion (8)) 146.2 parts by mass of silica fine particles ("Aerosil 8200" manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 12 nm), 125.6 parts by mass of trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.), 50.4 parts by mass of 1,9-nonanediol diacrylate ("Viscoat #260" manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 12.6 parts by mass of a wetting and dispersing agent ("ANTI-TERRA-U100" manufactured by BYK Japan), 25.2 parts by weight of a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40 / 60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.) and 840 parts by weight of methyl ethyl ketone were blended to form a slurry with a nonvolatile content of 30% by weight. This slurry was mixed and dispersed using a wet ball mill ("Star Mill LMZ015" manufactured by Ashizawa Co., Ltd.) to obtain an inorganic fine particle dispersion (8) with a nonvolatile content of 30% by weight. The average particle size of the resulting dispersion was measured using a particle size measuring device ("ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.). The average particle size (D50) was 105 nm.

[0083] (Comparative Production Example 1: Production of acrylic resin) A reactor equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen inlet tube was charged with 184 parts by mass of methyl isobutyl ketone, and the temperature was raised to 110 ° C. with stirring. Next, a mixture consisting of 221 parts by mass of glycidyl methacrylate, 52.5 parts by mass of methyl methacrylate, 2.8 parts by mass of ethyl acrylate, and 16.6 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Nyukazai Co., Ltd.) was added dropwise from the dropping funnel over 3 hours and maintained at 110 ° C. for 15 hours. Next, after cooling to 90 ° C., 0.1 parts by mass of methoquinone and 76 parts by mass of acrylic acid were charged, and 2.0 parts by mass of triphenylphosphine was added, followed by a reaction at 100 ° C. for 8 hours or more. After confirming that the solution acid value was 4.2 mg KOH / g or less, the solution was diluted with methyl isobutyl ketone to obtain 910 parts by mass of a methyl isobutyl ketone solution of acrylic resin (non-volatile content: 50.0 mass%). The weight-average molecular weight (Mw) of this acrylic resin was 20,000, the theoretical acryloyl group equivalent weight calculated as solids was 250 g / equivalent, and the hydroxyl value was 224 mg KOH / g.

[0084] (Comparative Example 1: Preparation of inorganic fine particle dispersion (R1)) 53 parts by mass of silica microparticles ("Aerosil R7200" manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter: 12 nm, silica microparticles having (meth)acryloyl groups on the particle surface), 12 parts by mass of the acrylic resin obtained in Comparative Synthesis Example 1 (12 parts by mass of resin solids), 35 parts by mass of a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40 / 60 ("Lumicure DPA-600" manufactured by Toagosei Co., Ltd.), and 188 parts by mass of methyl isobutyl ketone were blended to form a slurry with a nonvolatile content of 50% by mass. This slurry was mixed and dispersed using a wet ball mill ("Starmill LMZ015" manufactured by Ashizawa Co., Ltd.) to obtain an inorganic microparticle dispersion (R1) with a nonvolatile content of 50% by mass.

[0085] (Comparative Example 2: Preparation of inorganic fine particle dispersion (R2)) 37.5 parts by mass of silica microparticles ("MEK-AC 2140Z" manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter: 12 nm), 13.5 parts by mass of trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.), and 47.5 parts by mass of methyl ethyl ketone were blended to obtain an inorganic microparticle dispersion (R2) with a non-volatile content of 30% by mass.

[0086] The compositions of the inorganic fine particle dispersions (1) to (8), (R1) and (R2) obtained in Examples 1 to 8 and Comparative Examples 1 and 2 are shown in Table 1.

[0087] [Table 1]

[0088] (Example 9: Preparation of active energy ray-curable composition (1) and production of laminate (L1)) 100 parts by mass (30 parts by mass as solids) of the inorganic fine particle dispersion (1) having a nonvolatile content of 30% by mass obtained in Example 1 and 0.6 parts by mass of a photopolymerization initiator ("Omnirad-BP Flakes" manufactured by IGM Resins) were mixed to obtain an active energy ray-curable composition (1).

[0089] Next, the obtained active energy ray-curable composition (1) was applied to a 23 μm-thick cycloolefin film (Zeon Corporation's "ZeonorFilm ZF-14", 23 μm) using a bar coater and dried at 90° C. for 1 minute. Next, under a nitrogen atmosphere, ultraviolet light was applied at 5 kJ / m using an 80 W high-pressure mercury lamp. 2 The cycloolefin film was irradiated to obtain a laminate (L1) having a cured coating film with a thickness of 5 μm on the cycloolefin film.

[0090] (Examples 10 to 17: Preparation 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 using the blending ratios shown in Table 2 in the same manner as in Example 8. Furthermore, laminates (L2) to (L9) were obtained in the same manner as in the laminate (L1).

[0091] (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 using the blending ratios shown in Table 2 in the same manner as in Example 8. Furthermore, laminates (L10) and (L11) were obtained in the same manner as in the laminate (L1).

[0092] The laminates (L1) to (L11) obtained in the above examples and comparative examples were subjected to the following evaluations.

[0093] [Method for evaluating scratch resistance] An abrasion test was conducted in which a 2.4 cm diameter disk-shaped indenter was wrapped in 0.5 g of steel wool ("Bonstar #0000" manufactured by Nippon Steel Wool Co., Ltd.), and a load of 500 g was applied to the indenter, which was then moved back and forth 10 times over the coated surface of the laminate obtained in the Examples and Comparative Examples. The haze values of the laminate films before and after the abrasion test were measured using a "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd., and the difference between the measured values (dH) was used to evaluate the film according to the following criteria. The smaller the difference (dH), the higher the resistance to abrasion.

[0094] A: dH was 1.0% or less B:dH was greater than 1.0% and less than or equal to 3.0%. C:dH was greater than 3.0% and less than or equal to 5.0%. D:dH was greater than 5.0% and less than 10%. E:dH was greater than 10%.

[0095] [Evaluation method for substrate adhesion (initial)] The surface of the cured coating film of the laminate obtained in the Examples and Comparative Examples was scored with a cutter knife to create 100 1 mm x 1 mm grids. Cellophane adhesive tape was then applied over the grids and quickly peeled off. The number of grids remaining without peeling was counted and evaluated according to the following criteria.

[0096] A: There were 80 or more remaining grids. B: The number of remaining grids was 50 or more but less than 80. C: The number of remaining grids was 30 or more but less than 50. D: Fewer than 30 grids remained.

[0097] [Method for evaluating substrate adhesion (after light resistance test)] The laminates obtained in the examples and comparative examples were irradiated with light for 50 hours using a fade meter "U48AU" (63°C, 50% humidity) manufactured by Suga Test Instruments Co., Ltd. Thereafter, the same method as for the above-mentioned substrate adhesion (initial) was used and evaluated according to the following criteria.

[0098] A: There were 80 or more remaining grids. B: The number of remaining grids was 50 or more but less than 80. C: The number of remaining grids was 30 or more but less than 50. D: Fewer than 30 grids remained.

[0099] The compositions of the active energy ray-curable compositions (1) to (8), (R1) and (R2) prepared in Examples 9 to 17 and Comparative Examples 3 and 4, and the evaluation results of the laminates (L1) to (L11) prepared in Examples 9 to 17 and Comparative Examples 3 and 4 are shown in Table 2.

[0100] [Table 2]

[0101] 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 these laminates had excellent scratch resistance and substrate adhesion.

[0102] On the other hand, Comparative Examples 3 and 4 shown in Table 2 are examples of laminates using active energy ray-curable compositions containing an inorganic fine particle dispersion without a wet dispersion. Although these laminates have excellent scratch resistance, it was confirmed that the adhesion to the substrate after the light resistance test was significantly insufficient.

Claims

1. A laminate comprising a cyclic olefin-based substrate or a linear olefin-based substrate and a cured coating film of an active energy ray-curable composition on one or both sides thereof, the active energy ray-curable composition contains an inorganic fine particle dispersion and a photopolymerization initiator, the inorganic fine particle dispersion contains 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), the inorganic fine particles (A) are silica, the inorganic fine particles (A) have an average primary particle diameter 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% based on the total mass of the inorganic fine particles (A), the compound (B), and the wetting and dispersing agent (C); A laminate characterized in that the wetting and dispersing agent (C) has an acid value of 10 to 80 mgKOH / g and / or an amine value of 20 to 50 mgKOH / g.

2. The compound (B) has 2 to 4 (meth)acryloyl groups in one molecule. The laminate of claim 1.

3. 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 selected from the group consisting of urethane resin, acrylic resin, polyester resin and amide resin.

3. The laminate according to claim 1, wherein the laminate is one or more selected from the group consisting of:

4. The laminate according to any one of claims 1 to 3, wherein the substrate is in the form of a film.

5. An article having the laminate according to any one of claims 1 to 4 on its surface.

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