JP6933315B1 - Active energy ray curable resin composition, coating agent kit, cured product and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition, a coating agent kit, a cured product and a laminate. The present disclosure includes a (meth) acryloyl group-containing silica particle, a poly (meth) acrylate, a 1-hydroxycyclohexyl group-containing photopolymerization initiator and a morpholino group-containing photopolymerization initiator, and the 1-hydroxycyclohexyl group. Active energy ray curing in which the mass ratio of the contained photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator) is 1.1 or more. A sex resin composition is provided. [Selection diagram] None

Description

The present disclosure relates to active energy ray-curable resin compositions, coating agent kits, cured products and laminates.

Active energy ray-curable resin compositions capable of forming a coating layer on the surface of various substrates by active energy rays have been developed. As such an active energy ray-curable resin composition, an active energy ray-curable resin composition containing colloidal silica has been proposed (Patent Document 1).

Special Publication No. 62-021815

The active energy ray-curable resin composition is required to have various physical properties depending on the application. An object to be solved by the present invention is to provide an active energy ray-curable resin composition capable of producing a cured product having good scratch resistance and pencil hardness.

As a result of diligent studies, the present inventors have found that the above-mentioned problems can be solved by an active energy ray-curable resin composition having a specific composition.

（式中、Ｘは、ＮＨ、Ｏ又はＳであり、Ｙは、Ｏ又はＳである。）
で表される基を含む、上記項目に記載の活性エネルギー線硬化性樹脂組成物。
（項目３）
上記項目に記載の活性エネルギー線硬化性樹脂組成物であるコーティング剤Ａ及び
コーティング剤Ｂを含む、コーティング剤キットであって、
前記コーティング剤Ｂは、１−ヒドロキシシクロヘキシル基含有光重合開始剤と前記モルホリノ基含有光重合開始剤との質量比（１−ヒドロキシシクロヘキシル基含有光重合開始剤／モルホリノ基含有光重合開始剤）が１．１未満であるか、又は
モルホリノ基含有光重合開始剤を含んでいない、コーティング剤キット。
（項目４）
上記項目のいずれか１項に記載の活性エネルギー線硬化性樹脂組成物及び／又は項目３に記載のコーティング剤キットの硬化物。
（項目５）
上記項目に記載の硬化物を含む、積層物。 The disclosure provides the following items:
(Item 1)
(Meta) acryloyl group-containing silica particles,
Poly (meth) acrylate,
Contains a 1-hydroxycyclohexyl group-containing photopolymerization initiator and a morpholino group-containing photopolymerization initiator.
The mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator) is 1.1 or more. An active energy ray-curable resin composition.
(Item 2)
The (meth) acryloyl group-containing silica particles

(In the formula, X is NH, O or S, and Y is O or S.)
The active energy ray-curable resin composition according to the above item, which comprises a group represented by.
(Item 3)
A coating agent kit containing the coating agent A and the coating agent B, which are the active energy ray-curable resin compositions according to the above items.
The coating agent B has a mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator). A coating agent kit that is less than 1.1 or does not contain a morpholino group-containing photopolymerization initiator.
(Item 4)
The active energy ray-curable resin composition according to any one of the above items and / or the cured product of the coating agent kit according to item 3.
(Item 5)
A laminate containing the cured product according to the above item.

In the present disclosure, the above-mentioned one or more features may be provided in addition to the specified combinations.

By using the active energy ray-curable resin composition according to the present disclosure, a cured product having good scratch resistance and pencil hardness can be produced.

Throughout the present disclosure, the range of numerical values such as each physical property value and content can be set as appropriate (for example, by selecting from the upper and lower limit values described in each of the following items). Specifically, for the numerical value α, when A4, A3, A2, A1 (A4> A3> A2> A1) and the like are exemplified as the upper and lower limits of the numerical value α, the range of the numerical value α is A4 or less. Examples thereof include A3 or less, A2 or less, A1 or more, A2 or more, A3 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, and A3 to A4.

[Active energy ray-curable resin composition]
The present disclosure describes (meth) acryloyl group-containing silica particles,
Poly (meth) acrylate,
Contains a 1-hydroxycyclohexyl group-containing photopolymerization initiator and a morpholino group-containing photopolymerization initiator.
The mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator) is 1.1 or more. Provided is an active energy ray-curable resin composition.

<(Meta) acryloyl group-containing silica particles>
The (meth) acryloyl group-containing silica particles can be used alone or in combination of two or more.

In the present disclosure, "(meth) acrylic" means "at least one selected from the group consisting of acrylic and methacryl". Similarly, "(meth) acrylate" means "at least one selected from the group consisting of acrylates and methacrylates". Further, "(meth) acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

The (meth) acryloyl group-containing silica particles are a reaction product of the silica particles and the (meth) acryloyl group-containing compound.

(Silica particles)
Silica particles can be used alone or in combination of two or more.

The upper and lower limits of the particle size of silica particles are 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 nm. Etc. are exemplified. In one embodiment, the particle size of the silica particles is preferably 5 to 100 nm.

Examples of the shape of the silica particles include a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fibrous shape, and an indefinite shape. In one embodiment, the shape of the silica particles is preferably spherical.

In one embodiment, the silica particles are preferably in the form of powder or solvent-dispersed sol.

When the silica particles are a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility and dispersibility with other components.

The organic solvent may be used alone or in combination of two or more.

Examples of the organic solvent include a ketone solvent, an aromatic solvent, an alcohol solvent, a glycol solvent, a glycol ether solvent, an ester solvent, a petroleum solvent, a haloalkane solvent, an amide solvent and the like.

Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like.

Examples of the aromatic solvent include toluene and xylene.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol and the like.

Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and the like.

Glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Examples thereof include ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-t-butyl ether.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and the like.

Examples of the petroleum-based solvent include Solbesso # 100 (manufactured by Exxon Co., Ltd.) and Solbesso # 150 (manufactured by Exxon Co., Ltd.).

Examples of the haloalkane solvent include chloroform and the like.

Examples of the amide solvent include dimethylformamide and the like.

Commercially available silica particles (coloidal silica) are manufactured by Nissan Chemical Co., Ltd. Product names: Methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP , ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, MeOH-ST-L, MIBK-TL and the like.

Commercially available silica particles (powdered silica) are manufactured by Nippon Aerosil Co., Ltd. Product names: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product names: Sildex H31, H32, H51, H52, H121, H122, manufactured by Nippon Silica Industry Co., Ltd. Product name: E220A, E220, manufactured by Fuji Silicia Co., Ltd. Product name: SYLYSIA470, manufactured by Nippon Plate Glass Co., Ltd. Product name: SG flakes, etc. are exemplified. NS.

((Meta) acryloyl group-containing compound)
The (meth) acryloyl group-containing compound may be used alone or in combination of two or more.

（式中、Ｘは、ＮＨ、Ｏ又はＳであり、Ｙは、Ｏ又はＳである。）
で表される基を含む。 In one embodiment, the (meth) acryloyl group-containing compound is of formula U.

(In the formula, X is NH, O or S, and Y is O or S.)
Includes groups represented by.

Specific groups represented by the above group [-X-C (= Y) -NH-] are [-OC (= O) -NH-] and [-OC (= S) -NH. -], [-SC (= O) -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-], [-SC (= S) -NH-]. These groups can be used alone or in combination of two or more. In one embodiment, from the viewpoint of thermal stability, the (meth) acryloyl group-containing silica particles are [-OC (= O) -NH-] and [-OC (= S) -NH-] and / Or it is preferable to have [-SC (= O) -NH-].

The above group [-X-C (= Y) -NH-] generates an appropriate cohesive force due to hydrogen bonds between molecules, and when it is made into a cured product, it has excellent mechanical strength, adhesion to a base material, and It is considered that properties such as heat resistance are imparted. The above is just one theory, and the present invention is not intended to be bound by the above theory.

The (meth) acryloyl group-containing compound is preferably a compound containing a silanol group (also referred to as a silanol group-containing compound) or a compound that produces a silanol group by hydrolysis (also referred to as a silanol group-producing compound).

Examples of the silanol group-forming compound include compounds having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen group and the like on a silicon atom. In one embodiment, the silanol group-forming compound is preferably a compound containing an alkoxy group or an aryloxy group.

The silanol group-forming site of a silanol group or a silanol group-forming compound is a structural unit that binds to silica particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

（式中、Ｒ^ｓ１、Ｒ^ｓ２はそれぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ^ｓ３はアルキレン基又はアリーレン基であり、Ｒ^ｓ４は２価の有機基であり、Ｒ^ｓ５は（ｓ’’＋１）価の有機基であり、Ｚは（メタ）アクリロイル基であり、ｓ’は１、２又は３であり、ｓ’’は１〜２０の整数である。）
で表される化合物が好ましい。 In one embodiment, the (meth) acryloyl group-containing compound is represented by the following formula S:

(In the formula, R ^s1 and R ^s2 are independently hydrogen atoms, alkyl groups or aryl groups, R ^s3 is an alkylene group or an arylene group, R ^s4 is a divalent organic group, and R ^s5 is a divalent organic group. (S'' + 1) valent organic group, Z is a (meth) acryloyl group, s'is 1, 2 or 3, and s'' is an integer of 1-20.)
The compound represented by is preferable.

Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

The linear alkyl group is _{represented by the general formula of −C n} H _{2n + 1} (n is an integer of 1 or more). The linear alkyl group includes methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl. Group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group, octadecyl group (stearyl group), nonadecil group, icosyl group, henicosyl group , Docosil group and the like are exemplified.

A branched alkyl group is a group in which at least one hydrogen atom of a linear alkyl group is substituted with an alkyl group. Examples of the branched alkyl group include an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, a trimethylhexyl group, and a 2-ethylhexyl group. ..

Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a crosslinked ring cycloalkyl group, and a condensed ring cycloalkyl group.

In the present disclosure, a single ring means a cyclic structure formed by covalent bonds of carbon and having no bridging structure inside. Further, a fused ring means a cyclic structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (condensed) with each other). A crosslinked ring means a cyclic structure in which two or more monocycles share three or more atoms.

Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group and the like.

Examples of the crosslinked ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, and a norbornyl group.

Examples of the fused ring cycloalkyl group include a bicyclodecyl group.

Examples of the aryl group include a monocyclic aryl group and a condensed ring aryl group. Further, the aryl group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.

Examples of the monocyclic aryl group include a phenyl group, a tolyl group, and a mesityl group.

Examples of the fused ring aryl group include a naphthyl group.

Wherein _{^{S, (R s1 O) s}} 'R s2 3-s' Si- in groups shown are trimethoxysilyl group, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group Is exemplified. Of these, a trimethoxysilyl group or a triethoxysilyl group is preferable.

Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

The linear alkylene group is represented by the general formula: _{− (CH 2} ) _n − (n is an integer of 1 or more). The linear alkylene group includes a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decamethylene group and the like. Is exemplified.

A branched alkylene group is a group in which at least one hydrogen atom of a linear alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group (trimethylhexamethylene group) and the like.

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a crosslinked ring cycloalkylene group, and a condensed ring cycloalkylene group. Further, the cycloalkylene group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.

Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group and the like.

Examples of the crosslinked ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornene group.

Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

Examples of the arylene group include a monocyclic arylene group and a condensed ring arylene group. Further, the arylene group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.

Examples of the monocyclic arylene group include a phenylene group, a trilene group, and a mesitylene group.

Examples of the fused ring aryl group include a naphthylene group.

In formula S, R ^s4 is a divalent organic group.

The molecular weight of R ^s4 is preferably 14 to 10,000, more preferably 76 to 500.

Examples of R ^s4 include an alkylene group and an arylene group. R ^s4 may contain elements other than carbon atoms and hydrogen atoms, and may also contain a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the above formula U.

In the formula S, R ^s5 is an organic group having a (s'' + 1) valence, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and an unsaturated hydrocarbon group.

（ｓ’’’は０〜２の整数である。）
等が例示される。 R ^s5 is

(S'''is an integer from 0 to 2.)
Etc. are exemplified.

In the formula S, s ″ is an integer of 1 to 20, preferably 1 to 10, and more preferably 1 to 5.

Examples of the method for synthesizing the (meth) acryloyl group-containing compound represented by the formula S include the methods described in JP-A-9-100111. That is, the method for synthesizing the (meth) acryloyl group-containing compound is as follows: (A) an addition reaction of mercaptoalkoxysilane, polyisocyanate and an active hydrogen group-containing (meth) acrylate, and (B) a compound having an alkoxysilyl group and an isocyanate group. Examples thereof include a reaction with an active hydrogen-containing (meth) acrylate, and an addition reaction between a compound having (C) (meth) acryloyl group and an isocyanate group and mercaptoalkoxysilane or aminosilane.

In one embodiment, the method (A) above is preferable as the method for synthesizing the (meth) acryloyl group-containing compound represented by the formula S. More specifically,
Method (A1): First, a step of forming an intermediate containing an alkoxysilyl group, a [-SC (= O) NH-] group and an isocyanate group by reacting a mercaptoalkoxysilane with a polyisocyanate, the intermediate step. Method (A2) method including a step of reacting a body with a hydroxyl group-containing (poly) (meth) acrylate to form a [-OC (= O) NH-] bond; first, polyisocyanate and a hydroxyl group-containing (poly) A step of forming an intermediate containing a (meth) acryloyl group, an [-OC (= O) NH-] group, and an isocyanate group by reacting with (meth) acrylate, and mercaptoalkoxysilane is added to the intermediate. Examples thereof include a method including a step of reacting to form a [-SC (= O) -NH-] bond. The method (A1) is preferable in that the polymerizable unsaturated group is not reduced by the Michael addition reaction.

The mercaptoalkoxysilane can be used alone or in combination of two or more.

Mercaptoalkoxysilanes include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysisilane, mercaptopropyltributoxysisilane, etc. Is exemplified.

In one embodiment, the mercaptoalkoxysilane is preferably mercaptopropyltrimethoxysilane or mercaptopropyltriethoxysilane.

Examples of commercially available mercaptoalkoxysilanes include Toray Dow Corning Co., Ltd. trade name: SH6062 and the like. Further, an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan, and an addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

Polyisocyanates can be used alone or in combination of two or more.

In the present disclosure, "polyisocyanate" is a compound having two or more isocyanate groups (-N = C = O).

Examples of the polyisocyanate include a linear aliphatic polyisocyanate, a branched aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and a biuret form, an isocyanurate form, an allophanate form, and an adduct form thereof.

Examples of the linear aliphatic polyisocyanis include methylene diisocyanis, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanis. NS.

Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked alicyclic polyisocyanates, and condensed alicyclic polyisocyanates.

The monocyclic alicyclic polyisocyanate includes hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane. Examples thereof include diisocyanate.

Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

Examples of the condensed alicyclic polyisocyanate include bicyclodecylene diisocyanate.

Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed ring aromatic polyisocyanate.

The monocyclic aromatic polyisocyanate includes dialkyldiphenylmethane diisocyanate such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4, Examples thereof include 4'-dibenzyl isocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

Examples of the fused ring aromatic polyisocyanate include 1,5-naphthylene diisocyanate.

The hydroxyl group-containing (poly) (meth) acrylate may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (poly) (meth) acrylate include a hydroxyl group-containing (meth) acrylate and a hydroxyl group-containing poly (meth) acrylate.

The hydroxyl group-containing (meth) acrylates are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth). ) Acrylate, 8-hydroxyoctyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate and the like are exemplified.

Examples of the hydroxyl group-containing poly (meth) acrylate include compounds having a hydrogen atom covalently bonded to an oxygen atom among the poly (meth) acrylates described below.

In one embodiment, the hydroxyl group-containing poly (meth) acrylate is trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth). Acrylate is preferred.

In one embodiment, the hydroxyl group-containing (poly) (meth) acrylate is preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or pentaerythritol tri (meth) acrylate.

（式中、Ｘは、ＮＨ、Ｏ又はＳであり、Ｙは、Ｏ又はＳである。）
で表される基を含まない。 In one embodiment, the (meth) acryloyl group-containing compound is of formula U.

(In the formula, X is NH, O or S, and Y is O or S.)
Does not include groups represented by.

（式中、Ｚ^ｕは（メタ）アクリロイル基であり、Ｒ^ｕ１はアルキレン基又はアリーレン基であり、Ｒ^ｕ２はアルキル基又はアリール基であり、ｕは、１〜３の整数である。）
等が例示される。 The group-free (meth) acryloyl group-containing compound represented by the formula U is represented by the formula U1.

(Wherein, ^{Z u} is the (meth) acryloyl ^{group, R u1} is an alkylene group or an arylene ^{group, R u2} is an alkyl group or an aryl group, u is an integer of 1 to 3.)
Etc. are exemplified.

The compounds represented by the formula U1 are tri (meth) acryloxyethyl monomethoxysilane, di (meth) acryloxyethyl dimethoxysilane, (meth) acryloxyethyltrimethoxysilane, and tri (meth) acryloxipropyl monomethoxysilane. , Di (meth) acryloxypropyl dimethoxysilane, (meth) acryloxipropyltrimethoxysilane, tri (meth) acryloxipropyl monoethoxysilane, di (meth) acryloxipropyldiethoxysilane, (meth) acryloxipropyltri Examples thereof include ethoxysilane, tri (meth) acryloxypropyl monophenoxysilane, di (meth) acryloxypropyl diphenoxysilane, and (meth) acryloxipropyltriphenoxysilane.

The method for producing (meth) acryloyl group-containing silica particles is a step of hydrolyzing alkoxysilane to obtain an alkoxysilane hydrolyzate, and mixing the alkoxysilane hydrolyzate with a powder silica particle or a solvent-dispersed sol of silica particles. Examples include a method including a step of heating and stirring, a method of hydrolyzing alkoxysilane in the presence of silica particles, and the like. In one embodiment, the method for producing the (meth) acryloyl group-containing silica particles is preferably a method in which the hydrolysis of alkoxysilane is carried out in the presence of the silica particles.

When producing (meth) acryloyl group-containing silica particles, the temperature thereof is preferably 0 to 150 ° C, more preferably 20 to 100 ° C. The reaction time is preferably 5 minutes to 24 hours.

In the production of (meth) acryloyl group-containing silica particles, an organic solvent that is uniformly compatible with water may be added for the purpose of allowing the reaction to proceed smoothly and uniformly. The amount of the organic solvent added is not particularly limited as long as it meets the purpose of making the reaction smooth and uniform.

During the production of (meth) acryloyl group-containing silica particles, an acid, salt or base may be added as a catalyst in order to promote the reaction.

A dehydrating agent may be added in order to promote the reaction during the production of (meth) acryloyl group-containing silica particles.

Examples of the dehydrating agent include inorganic dehydrating agents such as zeolite, anhydrous silica and anhydrous alumina, and organic dehydrating agents such as methyl orthoate, ethyl orthoate, tetraethoxymethane and tetrabutoxymethane. In one embodiment, the dehydrating agent is preferably an organic dehydrating agent, and more preferably orthoesters such as methyl orthoate and ethyl orthoate.

The amount of alkoxysilane bonded to the (meth) acryloyl group-containing silica particles is a constant value of% mass reduction when the dry powder is completely burned in the air, and heat from 110 ° C. to 800 ° C. in the air. Can be determined by thermogravimetric analysis.

The upper and lower limits of the particle size of the (meth) acryloyl group-containing silica particles are 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70. , 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 nm and the like. In one embodiment, the particle size of the (meth) acryloyl group-containing silica particles is preferably 5 to 150 nm.

In the present disclosure, the particle size is measured in accordance with JIS Z8828: 2013, and dynamic light scattering using a commercially available measuring machine (product name "DYNAMIC LIGHT SCATTERING NANOPARTICLE SIZE ANALYZER LB-550", HORIBA, Ltd.). It is carried out by measuring the particle size distribution by the method. In the present specification, the particle size is measured in accordance with JIS Z8828: 2013, and dynamic light using a commercially available measuring machine (product name "DYNAMIC LIGHT SCATTERING NANOPARTICLE SIZE ANALYZER LB-550", HORIBA, Ltd.) It is performed by measuring the particle size distribution by the scattering method. In the present specification, the particle size is measured in accordance with JIS Z8828: 2013, and dynamic light using a commercially available measuring machine (product name "DYNAMIC LIGHT SCATTERING NANOPARTICLE SIZE ANALYZER LB-550", HORIBA, Ltd.) It is performed by measuring the particle size distribution by the scattering method. In the present specification, the particle size is measured in accordance with JIS Z8828: 2013, and dynamic light using a commercially available measuring machine (product name "DYNAMIC LIGHT SCATTERING NANOPARTICLE SIZE ANALYZER LB-550", HORIBA, Ltd.) It is performed by measuring the particle size distribution by the scattering method.

（式中、Ｘは、ＮＨ、Ｏ又はＳであり、Ｙは、Ｏ又はＳである。）
で表される基を含む。 In one embodiment, the (meth) acryloyl group-containing silica particles are of formula U.

(In the formula, X is NH, O or S, and Y is O or S.)
Includes groups represented by.

（式中、Ｘは、ＮＨ、Ｏ又はＳであり、Ｙは、Ｏ又はＳである。）
で表される基を含まない。 In one embodiment, the (meth) acryloyl group-containing silica particles are of formula U.

(In the formula, X is NH, O or S, and Y is O or S.)
Does not include groups represented by.

The upper and lower limits of the content of (meth) acryloyl group-containing silica particles in 100% by mass of the solid content of the active energy ray-curable resin composition are 85, 80, 75, 70, 65, 60, 55, 50, 45, Examples include 40, 35, 30% by mass and the like. In one embodiment, the content is preferably 30% by mass or more, more preferably 30 to 85% by mass.

<Poly (meth) acrylate>
In the present disclosure, poly (meth) acrylate means a compound having two or more (meth) acryloyl groups. The poly (meth) acrylate can be used alone or in combination of two or more.

Poly (meth) acrylates are (poly) pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) trimethylpropanpoly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) glycerin. Poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, isocyanurate structure-containing poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate, Bisphenol A di (alkylene oxide-modified or epoxy-modified) (meth) acrylate and the like are exemplified.

The upper and lower limits of the number of (meth) acryloyl groups contained in the poly (meth) acrylate are 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3 and the like are exemplified. In one embodiment, the number is preferably 3 to 20.

［式中、ｎは０〜２の整数であり、Ｒ^ｂ１’〜Ｒ^{ｂ６ ’}は、それぞれ独立に水素原子、

｛式中、ｑはそれぞれ独立に０〜１６の整数であり、Ｒ^１’〜Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ４’、及びＲ^ｂ５’は各構成単位ごとに基が異なっていてもよく、
式（Ａ^’）中において

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］ <(Poly) Pentaerythritol Poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate>
(Poly) Pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate is a compound represented by the formula (A') or the like.

[In the formula, n is an integer of 0 to 2, and R ^b1'to R ^b6'are independent hydrogen atoms.

{Wherein, q are each independently 0 to 16 integer, R 1 ^'to R ^3' are each independently a hydrogen atom or an alkyl group, even if R 1 ^'is different groups for each unit good. }
And
R ^b4'and R ^b5' may have different groups for each structural unit.
In formula (A ^' )

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
Is included in two or more. ]

Ｒ^ｂ４ＡとＲ^ｂ４Ｂとは異なる基であってよく、Ｒ^ｂ５ＡとＲ^ｂ５Ｂとは異なる基であってよいことを意味する。 In the present disclosure, "the group may be different for each structural unit" means, for example, when n is 2 in the formula (A').

It ^means that R b4A and R ^b4B may be different groups, and R ^b5A and R ^{b5B may be different groups.}

In the present disclosure, "(poly) pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "pentaerythritol poly (meth) acrylate, pentaerythritol polyalkylene oxide-modified (meth) acrylate, pentaerythritol polyepoxy-modified". Means "at least one selected from the group consisting of (meth) acrylate, polypentaerythritol poly (meth) acrylate, polypentaerythritol polyalkylene oxide modified (meth) acrylate, and polypentaerythritol polyepoxy modified (meth) acrylate". do.

Examples of the pentaerythritol poly (meth) acrylate include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

Pentaerythritol polyalkylene oxide-modified (meth) acrylate includes pentaerythritol di (ethylene oxide-modified (meth) acrylate), pentaerythritol tri (ethylene oxide-modified (meth) acrylate), and pentaerythritol tetra (ethylene oxide-modified (meth) acrylate). , Pentaerythritol di (propylene oxide-modified (meth) acrylate), pentaerythritol tri (propylene oxide-modified (meth) acrylate), pentaerythritol tetra (propylene oxide-modified (meth) acrylate) and the like are exemplified.

Examples of the pentaerythritol polyepoxy-modified (meth) acrylate include pentaerythritol diepoxy (meth) acrylate, pentaerythritol triepoxy (meth) acrylate, and pentaerythritol tetraepoxy (meth) acrylate.

Polypentaerythritol poly (meth) acrylate is dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa. (Meta) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, Examples thereof include trypentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate.

Polypentaerythritol polyalkylene oxide-modified (meth) acrylate includes dipentaerythritol di (ethylene oxide-modified (meth) acrylate), dipentaerythritol tri (ethylene oxide-modified (meth) acrylate), and dipentaerythritol tetra (ethylene oxide-modified (ethylene oxide-modified)). Meta) acrylate), dipentaerythritol penta (ethylene oxide-modified (meth) acrylate), dipentaerythritol hexa (ethylene oxide-modified (meth) acrylate), dipentaerythritol di (propylene oxide-modified (meth) acrylate), dipentaerythritol Tri (propylene oxide modified (meth) acrylate), dipentaerythritol tetra (propylene oxide modified (meth) acrylate), dipentaerythritol penta (propylene oxide modified (meth) acrylate), dipentaerythritol hexa (propylene oxide modified (meth) acrylate) Acrylate), tripentaerythritol di (ethylene oxide-modified (meth) acrylate), tripentaerythritol tri (ethylene oxide-modified (meth) acrylate), tripentaerythritol tetra (ethylene oxide-modified (meth) acrylate), tripentaerythritol penta ( Ethylene oxide-modified (meth) acrylate), tripentaerythritol hexa (ethylene oxide-modified (meth) acrylate), tripentaerythritol hepta (ethylene oxide-modified (meth) acrylate), tripentaerythritol octa (ethylene oxide-modified (meth) acrylate) , Tripenta erythritol di (propylene oxide modified (meth) acrylate), tripenta erythritol tri (propylene oxide modified (meth) acrylate), tripenta erythritol tetra (propylene oxide modified (meth) acrylate), tripenta erythritol penta (propylene oxide) Modified (meth) acrylate), tripentaerythritol hexa (propylene oxide-modified (meth) acrylate), tripentaerythritol hepta (propylene oxide-modified (meth) acrylate), tripentaerythritol octa (propylene oxide-modified (meth) acrylate), etc. Illustrated.

Polypentaerythritol polyepoxy-modified (meth) acrylate is dipentaerythritol diepoxy (meth) acrylate, dipentaerythritol triepoxy (meth) acrylate, dipentaerythritol tetraepoxy (meth) acrylate, dipentaerythritol pentaepoxy (meth) acrylate. Acrylate, dipentaerythritol hexaepoxy (meth) acrylate, tripentaerythritol diepoxy (meth) acrylate, tripentaerythritol triepoxy (meth) acrylate, tripentaerythritol tetraepoxy (meth) acrylate, tripentaerythritol pentaepoxy (meth) Examples thereof include acrylates, tripentaerythritol hexaepoxy (meth) acrylates, tripentaerythritol heptaepoxy (meth) acrylates, and tripentaerythritol octaepoxy (meth) acrylates.

［式中、ｍは０〜２の整数であり、Ｒ^ｂ７’〜Ｒ^{ｂ１０ ’}は、それぞれ独立に水素原子、

｛式中、ｑはそれぞれ独立に０〜１６の整数であり、Ｒ^１’〜Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ９’は各構成単位ごとに基が異なっていてもよく、
式（Ｂ^’）中において

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］ <(Poly) trimethylolpropane poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate>
(Poly) Trimethylolpropane Poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate is a compound represented by the formula (B') or the like.

[In the formula, m is an integer of 0 to 2, and R ^b7'to R ^b10'are independent hydrogen atoms.

{Wherein, q are each independently 0 to 16 integer, R 1 ^'to R ^3' are each independently a hydrogen atom or an alkyl group, even if R 1 ^'is different groups for each unit good. }
And
R ^b9'may have a different base for each structural unit.
In formula (B ^' )

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
Is included in two or more. ]

In the present disclosure, "(poly) trimethylolpropane poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "trimethylolpropane poly (meth) acrylate, trimethylolpropane polyalkylene oxide-modified (meth) acrylate, trimethylol". Selected from the group consisting of propanepolyepoxy-modified (meth) acrylates, polytrimethylolpropane poly (meth) acrylates, polytrimethylolpropane polyalkylene oxide-modified (meth) acrylates, and polytrimethylolpropane polyepoxy-modified (meth) acrylates. Means at least one.

Examples of the trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

The trimethylolpropane polyalkylene oxide-modified (meth) acrylate includes trimethylolpropane di (ethylene oxide-modified (meth) acrylate), trimethylolpropane tri (ethylene oxide-modified (meth) acrylate), and trimethylolpropane di (propylene oxide-modified (propylene oxide-modified)). Meta) acrylate), trimethylolpropane tri (propylene oxide-modified (meth) acrylate) and the like are exemplified.

Examples of the trimethylolpropane polyepoxy-modified (meth) acrylate include trimethylolpropane diepoxy (meth) acrylate and trimethylolpropane triepoxy (meth) acrylate.

Examples of the polytrimethylolpropane poly (meth) acrylate include ditrimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.

Polytrimethylolpropane Polyalkylene oxide-modified (meth) acrylate includes ditrimethylolpropane di (ethyleneoxide-modified (meth) acrylate), ditrimethylolpropane tri (ethyleneoxide-modified (meth) acrylate), and ditrimethylolpropane tetra (ethyleneoxide-modified). (Meta) acrylate), ditrimethylolpropane di (propylene oxide-modified (meth) acrylate), ditrimethylolpropane tri (propylene oxide-modified (meth) acrylate), ditrimethylolpropane tetra (propylene oxide-modified (meth) acrylate), etc. are exemplified. Will be done.

Examples of the polytrimethylolpropane polyepoxy-modified (meth) acrylate include ditrimethylolpropane diepoxy (meth) acrylate, ditrimethylolpropane triepoxy (meth) acrylate, and ditrimethylolpropane tetraepoxy (meth) acrylate.

［式中、ｐは０〜７の整数であり、Ｒ^ｂ１１’〜Ｒ^{ｂ１４ ’}は、それぞれ独立に水素原子、

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ１３’は各構成単位ごとに基が異なっていてもよく、
式（Ｃ^’）中において

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］ <(Poly) glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate>
(Poly) Glycerin Poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate is a compound represented by the formula (C') or the like.

[In the formula, p is an integer from 0 to 7, and R ^b11'to R ^b14'are independent hydrogen atoms.

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
And
R ^b13'may have a different base for each structural unit.
In equation (C ^' )

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
Is included in two or more. ]

In the present disclosure, "(poly) glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "glycerin poly (meth) acrylate, glycerin polyalkylene oxide-modified (meth) acrylate, glycerin polyepoxy-modified (meth) acrylate". , At least one selected from the group consisting of polyglycerin poly (meth) acrylate, polyglycerin polyalkylene oxide modified (meth) acrylate, and polyglycerin polyepoxy modified (meth) acrylate. "

Examples of the glycerin poly (meth) acrylate include glycerin di (meth) acrylate and glycerin tri (meth) acrylate.

Glycerin polyalkylene oxide-modified (meth) acrylate includes glycerindi (ethylene oxide-modified (meth) acrylate), glycerintri (ethylene oxide-modified (meth) acrylate), glycerindi (propylene oxide-modified (meth) acrylate), and glycerintri (glycerin tri). (Propylene oxide modified (meth) acrylate) and the like are exemplified.

Examples of the glycerin polyepoxy-modified (meth) acrylate include glycerin diepoxy (meth) acrylate and glycerin triepoxy (meth) acrylate.

Polyglycerin poly (meth) acrylate includes diglycerin di (meth) acrylate, diglycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, triglycerin di (meth) acrylate, triglycerin tri (meth) acrylate, and triglycerin tetra. Examples thereof include (meth) acrylate and triglycerin penta (meth) acrylate.

Polyglycerin Polyalkylene oxide-modified (meth) acrylate includes diglycerindi (ethylene oxide-modified (meth) acrylate), diglycerin tri (ethylene oxide-modified (meth) acrylate), diglycerin tetra (ethylene oxide-modified (meth) acrylate), and tri. Glycerindi (ethylene oxide modified (meth) acrylate), triglycerin tri (ethylene oxide modified (meth) acrylate), triglycerin tetra (ethylene oxide modified (meth) acrylate), triglycerin penta (ethylene oxide modified (meth) acrylate) Diglycerindi (propylene oxide modified (meth) acrylate), diglycerin tri (propylene oxide modified (meth) acrylate), diglycerin tetra (propylene oxide modified (meth) acrylate), triglycerindi (propylene oxide modified (meth) acrylate), Examples thereof include triglycerin tri (propylene oxide-modified (meth) acrylate), triglycerin tetra (propylene oxide-modified (meth) acrylate), and triglycerin penta (propylene oxide-modified (meth) acrylate).

Polyglycerin polyepoxy-modified (meth) acrylates include diglycerin diepoxy (meth) acrylate, diglycerin triepoxy (meth) acrylate, diglycerin tetraepoxy (meth) acrylate, triglycerin diepoxy (meth) acrylate, and triglycerin tri. Examples thereof include epoxy (meth) acrylate, triglycerin tetraepoxy (meth) acrylate, and triglycerin pentaepoxy (meth) acrylate.

［式中、Ｒ^ｂ１５’〜Ｒ^{ｂ１７ ’}は、それぞれ独立に水素原子、

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、式（Ｄ^’）中において

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］ <Isocyanurate structure-containing poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate>
The isocyanurate structure-containing poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate is a compound represented by the formula (D') or the like.

^{Wherein, R b15 '~R b17'} are independently a hydrogen atom,

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
And in the formula (D ^' )

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
Is included in two or more. ]

In the present disclosure, "isocyanurate structure-containing poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "isocyanurate structure-containing poly (meth) acrylate, isocyanurate structure-containing polyalkylene oxide-modified (meth) acrylate, and isocyanate. It means "at least one selected from the group consisting of a nurate structure-containing polyepoxy-modified (meth) acrylate".

Examples of the isocyanurate structure-containing poly (meth) acrylate include di (meth) acrylate of isocyanuric acid and tri (meth) acrylate of isocyanuric acid.

Examples of the isocyanurate structure-containing polyalkylene oxide-modified (meth) acrylate include isocyanuric acid di (ethylene oxide-modified (meth) acrylate) and isocyanuric acid tri (ethylene oxide-modified (meth) acrylate).

Examples of the isocyanurate structure-containing polyepoxy-modified (meth) acrylate include isocyanuric acid diepoxy-modified (meth) acrylate and isocyanuric acid triepoxy-modified (meth) acrylate.

［式中、Ｒ^ｂ１８’〜Ｒ^{ｂ１９ ’}は、それぞれ独立に

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ２０’は、アルキレン基であり、ｒは１以上の整数である。］ <(Poly) alkylenedi (alkylene oxide-modified or epoxy-modified) (meth) acrylate>
The (poly) alkylenedi (alkylene oxide-modified or epoxy-modified) (meth) acrylate is a compound represented by the formula (E') or the like.

[In the formula, R ^b18'to R ^b19'are independent of each other.

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
And
R ^b20'is an alkylene group, and r is an integer of 1 or more. ]

In the present disclosure, "(poly) alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "alkylene di (meth) acrylate, alkylene dialkylene oxide-modified (meth) acrylate, alkylene diepoxy-modified (meth) acrylate". , At least one selected from the group consisting of polyalkylene di (meth) acrylates, polyalkylene dialkylene oxide modified (meth) acrylates, and polyalkylene diepoxy modified (meth) acrylates. "

The alkylene di (meth) acrylate includes 1,2-ethylenediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol. Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di ( Examples thereof include meta) acrylate, 1,10-decanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.

The alkylenedialkylene oxide-modified (meth) acrylate includes 1,2-ethylenediol di (ethylene oxide-modified (meth) acrylate), 1,3-propanedioldi (ethylene oxide-modified (meth) acrylate), and 1,4-butane. Didioldi (ethylene oxide-modified (meth) acrylate), 1,5-pentanedioldi (ethyleneoxide-modified (meth) acrylate), 1,6-hexanedioldi (ethyleneoxide-modified (meth) acrylate), 1,7- Heptanedioldi (ethyleneoxide-modified (meth) acrylate), 1,8-octanedioldi (ethyleneoxide-modified (meth) acrylate), 1,9-nonanedioldi (ethyleneoxide-modified (meth) acrylate), 1,10 -Decandioldi (ethylene oxide-modified (meth) acrylate), neopentyl glycoldi (ethyleneoxide-modified (meth) acrylate), 1,2-ethylenedioldi (propylene oxide-modified (meth) acrylate), 1,3-propane Didiole (propylene oxide-modified (meth) acrylate), 1,4-butanedioldi (propylene oxide-modified (meth) acrylate), 1,5-pentanedioldi (propylene oxide-modified (meth) acrylate), 1,6- Hexanodioldi (propylene oxide-modified (meth) acrylate), 1,7-heptanedioldi (propylene oxide-modified (meth) acrylate), 1,8-octanedioldi (propylene oxide-modified (meth) acrylate), 1,9 Examples thereof include −nonanedioldi (propylene oxide-modified (meth) acrylate), 1,10-decanedioldi (propylene oxide-modified (meth) acrylate), and neopentyl glycoldi (propylene oxide-modified (meth) acrylate).

The alkylenediepoxy-modified (meth) acrylates are 1,2-ethylenediol diepoxy (meth) acrylate, 1,3-propanediol diepoxy (meth) acrylate, and 1,4-butanediol diepoxy (meth) acrylate, 1. , 5-Pentanediol diepoxy (meth) acrylate, 1,6-hexanediol diepoxy (meth) acrylate, 1,7-heptanediol diepoxy (meth) acrylate, 1,8-octanediol diepoxy (meth) acrylate , 1,9-Nonandiol diepoxy (meth) acrylate, 1,10-decanediol diepoxy (meth) acrylate, neopentyl glycol diepoxy (meth) acrylate and the like are exemplified.

Examples of the polyalkylene di (meth) acrylate include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate.

Polyalkylene dialkylene oxide-modified (meth) acrylate includes diethylene glycol di (ethylene oxide-modified (meth) acrylate), dipropylene glycol di (ethylene oxide-modified (meth) acrylate), and triethylene glycol (ethylene oxide-modified (meth) acrylate). , Tripropylene glycol (ethylene oxide-modified (meth) acrylate) and the like are exemplified.

Polyalkylene diepoxy-modified (meth) acrylates include diethylene glycol diepoxy (meth) acrylate, dipropylene glycol diepoxy (meth) acrylate, triethylene glycol diepoxy (meth) acrylate, and tripropylene glycol diepoxy (meth) acrylate. Illustrated.

［式中、Ｒ^ｂ２１’〜Ｒ^{ｂ２２ ’}は、それぞれ独立に

｛式中、ｑは０〜１６の整数であり、Ｒ^１’〜Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
である。］ <Bisphenol A di (alkylene oxide-modified or epoxy-modified) (meth) acrylate>
The bisphenol A di (alkylene oxide-modified or epoxy-modified) (meth) acrylate is a compound represented by the formula (F') or the like.

^{Wherein, R b21 '~R b22'} are each independently

{Wherein, q is an integer of 0~16, R 1 ^{'~R 3'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit. }
Is. ]

In the present disclosure, "bisphenol A di (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "bisphenol A di (meth) acrylate, bisphenol A dialkylene oxide-modified (meth) acrylate, and bisphenol A diepoxy-modified (meth) acrylate". It means "at least one selected from the group consisting of acrylates".

Examples of the bisphenol A dialkylene oxide-modified (meth) acrylate include bisphenol A di (ethylene oxide-modified (meth) acrylate) and bisphenol A di (propylene oxide-modified (meth) acrylate).

Examples of the poly (meth) acrylate other than the above include urethane poly (meth) acrylate, which is a reaction product of a compound group containing a hydroxyl group-containing poly (meth) acrylate and a polyisocyanate.

In one embodiment, the urethane poly (meth) acrylate is preferably a reaction product of a hydroxyl group-containing poly (meth) acrylate, a polyisocyanate, or an alkylenediol from the viewpoint of suppressing curling of the cured product.

Examples of the hydroxyl group-containing poly (meth) acrylate include those described above. In one embodiment, the hydroxyl group-containing poly (meth) acrylate is preferably a hydroxyl group-containing pentaerythritol poly (meth) acrylate.

Examples of the polyisocyanate include those described above. In one embodiment, the polyisocyanate is preferably an alicyclic polyisocyanate.

Examples of the alkylene diol include a linear aliphatic alkylene diol, a branched aliphatic alkylene diol, and an alicyclic alkylene diol.

Examples of the linear aliphatic alkylene diol include ethylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol.

The branched aliphatic alkylene diols are 1,2-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and neopentyl glycol. , 2-Butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,3-butanediol, 2-methyl-2,4- Examples thereof include pentanediol and the like.

Examples of the alicyclic diol include a monocyclic alicyclic diol, a crosslinked alicyclic diol, and a condensed alicyclic diol.

The monocyclic alicyclic diols are hydrogenated xylene diol, isophorone diol, cyclopentylene diol, cyclohexylene diol, cycloheptylene diol, cyclodecylene diol, 3,5,5-trimethylcyclohexylene diol, and dicyclohexylmethanediol. Etc. are exemplified.

Examples of the crosslinked alicyclic diol include tricyclodecylenediol, adamantanediol, and norbornenediol.

Examples of the condensed alicyclic diol include bicyclodecylenediol and the like.

In one embodiment, the alkylene diol is preferably a linear aliphatic alkylene diol.

The upper and lower limits of the content of poly (meth) acrylate in 100% by mass of the solid content of the active energy ray-curable resin composition are 69, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20. , 15, 14% by mass and the like. In one embodiment, the content is preferably 14 to 69% by mass.

<1-Hydroxycyclohexyl group-containing photopolymerization initiator>
The 1-hydroxycyclohexyl group-containing photopolymerization initiator may be used alone or in combination of two or more.

Examples of the 1-hydroxycyclohexyl group-containing photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone.

The upper and lower limits of the content of the 1-hydroxycyclohexyl group-containing photopolymerization initiator in 100% by mass of the solid content of the active energy ray-curable resin composition are 10, 9, 8, 7, 6, 5, 4, 3, and so on. 2, 1% by mass and the like are exemplified. In one embodiment, the content is preferably 1% by mass or more, more preferably 1 to 10% by mass.

<Mophorino group-containing photopolymerization initiator>
The morpholino group-containing photopolymerization initiator can be used alone or in combination of two or more.

The morpholino group-containing photopolymerization initiator is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, etc. Is exemplified.

The upper and lower limits of the content of the morpholino group-containing photopolymerization initiator in 100% by mass of the solid content of the active energy ray-curable resin composition are 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 Mass% and the like are exemplified. In one embodiment, the content is preferably 1% by mass or more, more preferably 1 to 10% by mass.

The upper and lower limits of the mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator) are 9. 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.9, 4.8, 4.7, 4.5, 4, 3.5, 3, 2. Examples include 5, 2.4, 2.3, 2.2, 2.1, 2, 1.5, 1.1 and the like. In one embodiment, the mass ratio is preferably 1.1 or more, more preferably 1.1 to 9.

<Organic solvent>
In one embodiment, the active energy raysetting resin composition may contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

Examples of the organic solvent include those described above.

In one embodiment, the organic solvent is preferably a ketone solvent from the viewpoint of increasing the hardness of the cured product.

The upper and lower limits of the content of the organic solvent in 100% by mass of the active energy ray-curable resin composition are 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0% by mass and the like are exemplified. In one embodiment, the content is preferably 0 to 90% by mass.

<Additives>
The active energy ray-curable resin composition includes any of (meth) acryloyl group-containing silica particles, poly (meth) acrylate, 1-hydroxycyclohexyl group-containing photopolymerization initiator, morpholino group-containing photopolymerization initiator, and organic solvent. It is possible to include an agent that does not correspond to the above as an additive.

Additives include metal oxide particles with a refractive index of 1.7 or more, binder resins (acrylic resin, urethane resin, polyester resin, epoxy resin, alkyd resin, etc.), polymerization inhibitors, antislip agents, slip agents, preservatives, etc. Examples thereof include rust preventives, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, defoaming agents, photosensitizers (amines, quinones, etc.).

In one embodiment, the content of the additive is less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 part by mass with respect to 100 parts by mass of the active energy ray-curable resin composition. The part and the like are exemplified. Further, 1 mass by mass with respect to 100 parts by mass of any of (meth) acryloyl group-containing silica particles, poly (meth) acrylate, 1-hydroxycyclohexyl group-containing photopolymerization initiator, morpholino group-containing photopolymerization initiator, and organic solvent. Examples thereof include less than parts, less than 0.1 parts by mass, less than 0.01 parts by mass, and 0 parts by mass.

The active energy ray-curable resin composition comprises (meth) acryloyl group-containing silica particles, poly (meth) acrylate, 1-hydroxycyclohexyl group-containing photopolymerization initiator, morpholino group-containing photopolymerization initiator, and, if necessary, a morpholino group-containing photopolymerization initiator. It can be produced by dispersing and mixing the organic solvent and the additive by various known means. The order of addition of each component is not particularly limited. Further, as the dispersion / mixing means, various known devices (emulsification disperser, ultrasonic disperser, etc.) can be used.

Upper limit of the mass ratio of (meth) acryloyl group-containing silica particles to poly (meth) acrylate (mass of (meth) acryloyl group-containing silica particles / mass of poly (meth) acrylate) in the above active energy ray-curable resin composition. And the lower limit is 6.1, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1.1, 1, 0.9, 0. 7, 0.5, 0.4 and the like are exemplified. In one embodiment, the mass ratio is preferably 0.4 to 6.1.

The active energy ray-curable resin composition can be used as a coating agent, a surface coating agent, an antiglare coating agent, and the like.

[Coating agent kit]
The present disclosure is a coating agent kit containing a coating agent A and a coating agent B, which are active energy ray-curable resin compositions.
The coating agent B has a mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator). To provide a coating agent kit that is less than 1.1 or does not contain a morpholino group-containing photopolymerization initiator.

<Non-containing photopolymerization initiator that is neither a 1-hydroxycyclohexyl group-containing photopolymerization initiator nor a morpholino group-containing photopolymerization initiator: Also referred to as other photopolymerization initiators>
Other photopolymerization initiators may be used alone or in combination of two or more.

Other photopolymerization initiators include α-aminoalkylphenone, benzyl dimethyl ketal, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, oxime ester, α-hydroxy. Examples thereof include dimethylacetphenone.

Examples of α-aminoalkylphenone include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one.

Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one.

The unsubstituted or substituted alkylphenone is benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2. -(P-Toluenesulfonyloxy) acetophenone, benzoin, 2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, 2-methyl-4'-(methylthio) -2-morpholinopropiophenone, 2-iso Examples thereof include nitrosopropiophenone and 2,2-dimethoxy-1,2-diphenylethane-1-one.

Examples of the unsubstituted or substituted benzyl include unsubstituted or substituted benzyls such as benzyl and p-anisyl.

The unsubstituted or substituted benzophenone is benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2- Examples thereof include benzoyl benzoic acid, 4-benzoyl benzoic acid, and methyl 2-benzoyl benzoate.

Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.

Oxime esters are 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (ie 2-((benzoyloxy) imino) -1- (4- (phenylthio)). Phenyl) octane-1-one);
Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (ie 1-(((1- (9-ethyl-)- 6- (2-Methylbenzoyl) -9H-carbazole-3-yl) ethylidene) amino) oxy) ethane-1-one) and the like are exemplified.

α-Hydroxydimethylacetophenone is 2-hydroxy-2-methyl-1-phenylpropanone, 1- [4- (2-hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanol, 2-hydroxy-1- (4- (4- (2-Hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one and the like are exemplified.

The upper and lower limits of the content of the other photopolymerization initiator in the coating agent B solid content of 100% by mass are 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0% by mass and the like. Illustrated. In one embodiment, the content is more preferably 0 to 10% by mass.

Upper and lower limits of the mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator and the morpholino group-containing photopolymerization initiator in the coating agent B (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator). Is 1.09, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0 and the like. .. In one embodiment, the mass ratio is preferably less than 1.1.

<(Meta) acryloyl group-containing silica particles>
In one embodiment, the coating agent B may contain (meth) acryloyl group-containing silica particles. The (meth) acryloyl group-containing silica particles can be used alone or in combination of two or more.

Examples of the (meth) acryloyl group-containing silica particles include those described above.

The upper and lower limits of the content of (meth) acryloyl group-containing silica particles in the coating agent B solid content of 100% by mass are 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30. , 25, 20, 15, 10, 5, 1, 0% by mass and the like. In one embodiment, the content is preferably 0 to 85% by mass.

<Poly (meth) acrylate>
In one embodiment, the coating agent B may comprise a poly (meth) acrylate. The poly (meth) acrylate can be used alone or in combination of two or more.

Examples of the poly (meth) acrylate include those described above.

Coating agent B The upper and lower limits of the content of poly (meth) acrylate in 100% by mass of solid content are 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0% by mass and the like are exemplified.
In one embodiment, the content is preferably 0 to 99% by mass.

<Organic solvent>
In one embodiment, the coating agent B may contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

Examples of the organic solvent include those described above.

The upper and lower limits of the content of the organic solvent in 100% by mass of the coating agent B are 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0% by mass and the like are exemplified. In one embodiment, the content is preferably 0 to 90% by mass.

<Additives>
The coating agent B may contain as an additive an agent that does not correspond to any of other photopolymerization initiators, (meth) acryloyl group-containing silica particles, poly (meth) acrylate, and organic solvent.

Examples of the additive include those described above.

In one embodiment, the content of the additive is exemplified by less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. with respect to 100 parts by mass of the coating agent B. .. Further, less than 1 part by mass, less than 0.1 part by mass, and 0. Examples thereof include less than 01 parts by mass and 0 parts by mass.

In the coating agent B, other photopolymerization initiators and, if necessary, (meth) acryloyl group-containing silica particles, poly (meth) acrylate, organic solvent, additives and the like are dispersed and mixed by various known means. Can be manufactured by The order of addition of each component is not particularly limited. Further, as the dispersion / mixing means, the above-mentioned ones and the like are exemplified.

[Cured product]
The present disclosure provides a cured product of the active energy ray-curable resin composition and / or the coating agent kit.

Examples of the curing conditions are those described below.

[Laminate]
The present disclosure provides a laminate containing the cured product.

In one embodiment, a cured product layer made of the active energy ray-curable resin composition or the cured product of the coating agent kit is laminated on at least one surface of the base material. In one embodiment, a coating agent B (coating agent A) cured product layer composed of a cured product of the coating agent B (coating agent A) is laminated on at least one surface of the substrate, and the coating agent B (coating agent A) is cured. A cured product layer of coating agent A (coating agent B) composed of a cured product of coating agent A (coating agent B) is laminated on the material layer. In one embodiment, the coating agent A is used as a surface coating agent and the coating agent B is used as a non-surface coating agent. In another embodiment, the coating agent A is used as a non-surface coating agent, and the coating agent B is used as a surface coating agent.

The upper and lower limits of the thickness of the base material are 10000, 9000, 7500, 5000, 2500, 1000, 900, 750, 500, 250, 100, 90, 75, 50, 25, 10, 9, 5, 2, 1, 0.9, 0.5, 0.1 μm and the like are exemplified. In one embodiment, the thickness of the substrate is preferably 0.1 to 10,000 μm.

Examples of the upper and lower limits of the thickness of the coating agent A cured product layer are 100, 90, 75, 50, 25, 10, 9, 5, 2, 1, 0.9, 0.5, 0.1 μm and the like. .. In one embodiment, the thickness of the coating agent A cured product layer is preferably 0.1 to 100 μm.

Examples of the upper and lower limits of the thickness of the coating agent B cured product layer are 100, 90, 75, 50, 25, 10, 9, 5, 2, 1, 0.9, 0.5, 0.1 μm and the like. .. In one embodiment, the thickness of the coating agent B cured product layer is preferably 0.1 to 100 μm.

The laminate is produced by various known methods. In one embodiment, the method for producing the laminate is a step of coating the coating agent B on at least one surface of the base material (coating agent B coating step), and coating the coating agent A on the coating agent B coating layer. It includes a step of working (coating agent A coating step) and a step of forming a cured product layer by irradiating with active energy rays (active energy ray curing step).

The coating agent A coating process and the coating agent B coating process are collectively referred to as a coating process.

(Coating process)
Examples of coating methods include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coating coating, offset printing, flexographic printing, screen printing method, etc. Will be done.

The amount of coating is not particularly limited. The amount of coating is preferably 0.1 to 30 g / m ^{2 after drying.}

(Active energy ray curing process)
Examples of the active energy ray used for the active energy ray curing reaction include ultraviolet rays and electron beams. Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, an ultraviolet irradiation device having a metal halide lamp, and the like. The amount of light, the arrangement of the light source, the transport speed, and the like can be adjusted as needed. When a high-pressure mercury lamp is used, it is preferable to cure one lamp having a light amount of about 80 to 160 W / cm at a transport speed of about 2 to 50 m / min. On the other hand, in the case of an electron beam, it is preferable to cure it with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV under a condition of a transport speed of about 5 to 50 m / min.

The laminate is produced by various known methods. In one embodiment, the method for producing a laminate is a step of applying an undercoating agent to at least one surface of a base material (coating step), or by irradiating an active energy ray with an active energy ray-curable resin cured product. It includes a step of forming a layer (active energy ray curing step).

(Coating process)
Examples of coating methods include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coating coating, offset printing, flexographic printing, screen printing method, etc. Will be done.

The amount of coating is not particularly limited. The amount of coating is preferably about 0.1 to 30 g / m ² after drying, and more preferably about 1 to ²⁰ g / m 2.

(Active energy ray curing process)
Examples of the active energy ray used for the active energy ray curing reaction include ultraviolet rays and electron beams. Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, an ultraviolet irradiation device having a metal halide lamp, and the like. The amount of light, the arrangement of the light source, the transport speed, and the like can be adjusted as needed. When a high-pressure mercury lamp is used, it is preferable to cure one lamp having a light amount of about 80 to 160 W / cm at a transport speed of about 2 to 50 m / min. On the other hand, in the case of an electron beam, it is preferable to cure it with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV under a condition of a transport speed of about 5 to 50 m / min.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the above description of the preferred embodiment and the following examples are provided only for the purpose of illustration, and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in the present specification, but is limited only by the claims. Further, in each Example and Comparative Example, unless otherwise specified, numerical values such as parts and% are based on mass.

<Manufacturing of silane coupling agent containing urethane (meth) acrylate structure>
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and air inlet, 20 parts of isophorone diisocyanate, 72 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name "KAYARAD PET-30", Japan) Chemicals Co., Ltd.), (3-mercaptopropyl) trimethoxysilane 8 parts, 2,6-di-tert-butyl-4-methylphenol 0.02 parts as a polymerization inhibitor, and dioctyltin dilaurate 0. The two parts were mixed and the reaction was carried out under the conditions of 70 ° C. for 5 hours. After completion of the reaction, a mixture containing urethane (meth) acrylate structure-containing trimethoxysilane, urethane (meth) acrylate, and pentaerythritol tetraacrylate, each containing about one-third by mass, was obtained. In the following examples, the urethane (meth) acrylate structure-containing silane coupling agent is the mixture obtained after the reaction is completed.

Production Example 1: (Meta) Acryloyl Group-Containing Silica Particles (A-1)
Silica dispersion (solid content: 30%, solution: 100 parts of methyl ethyl ketone and 10 parts of urethane (meth) acrylate structure-containing silane coupling in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and air inlet. The agents were mixed and reacted at 60 ° C. for 4 hours to obtain (meth) acryloyl group-containing silica particles.

Production Example 2: (Meta) Acryloyl Group-Containing Silica Particles (A-2)
Silica dispersion (solid content: 30%, solution: 100 parts of methyl ethyl ketone and 0.8 parts of triacryloxypropyl monomethoxysilane) was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and an air inlet. The mixture was mixed and reacted under the conditions of 60 ° C. for 4 hours to obtain (meth) acryloyl group-containing silica particles.

Example 1: Active energy ray-curable resin composition (meth) 30 parts of acryloyl group-containing silica particles (A-1), a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product name: "Aronix M-400" , 65 parts manufactured by Toa Synthetic Co., Ltd., 1-hydroxycyclohexyl-phenylketone (product name "OMNIRAD184", manufactured by IGM Resins), 4 parts, 2-methyl-1- [4- (methylthio) phenyl] -2 1 part of −morpholinopropane-1-one (product name “OMNIRAD907”, manufactured by IGM Resins) and 150 parts of methyl ethyl ketone were mixed to obtain an active energy ray-curable resin composition.

Unless otherwise specified, Examples and Comparative Examples other than Example 1 were carried out in the same manner as in Example 1 except that they were changed as shown in the table below.

<Explanation in the table>
Aronix M-400, M-321, M-315 A-DPH-12E manufactured by Toagosei Co., Ltd. Light acrylate A-DCP manufactured by Shin Nakamura Chemical Industry Co., Ltd. UA-306H manufactured by Kyoeisha Chemical Co., Ltd. Kyoeisha Chemical Co., Ltd. Made

Hereinafter, the photopolymerization initiator is manufactured by IGM Resins.
Omnirad 184: 1-Hydroxycyclohexyl-phenylketone Omnirad 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one Omnirad TPO: 2,4,6-trimethylbenzoil-diphenyl Phosphine oxide

<Manufacturing of laminate>
Using a bar coater (model number "No. 24", manufactured by Daiichi Rika Co., Ltd.) on the surface of the base material (TAC film (manufactured by Fujifilm, Fujitac TDY80ULM)), apply the active energy ray-curable resin composition to the thickness of the substrate. The film was applied at 5 μm, dried in a circulating air dryer at 80 ° C. for 1 minute, and cured under the conditions of an irradiation distance of 20 cm, a belt speed of 5 m / min, and an integrated irradiation amount of 200 mJ / cm ^{2 to form a laminate.}

<Scratch resistance>
Set on a commercially available measuring device (product name "flat wear tester", manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), and use steel wool (count "# 0000", grade "extra-fine", manufactured by Nippon Steel Wool Co., Ltd.). The surface of the cured product was reciprocally scratched 10 times with a load of 100 g. The scratches on the cured product were observed and evaluated according to the following criteria.
〇: No scratches △: 2-3 scratches ×: Many scratches

<Pencil hardness>
The pencil hardness of the cured product was measured according to JIS K5600-5-4.

<Manufacturing of laminate using coating agent kit>
The coating agent of Comparative Example 2 was applied as the coating agent B on the surface of the base material (TAC film (manufactured by Fujifilm, Fujitac TDY80ULM)) using a bar coater (model number "No. 24", manufactured by Daiichi Rika Co., Ltd.). , Dry for 1 minute in a circulation dryer at 80 ° C., and cure under the conditions of an irradiation distance of 20 cm, a belt speed of 5 m / min, and an integrated irradiation amount of 200 mJ / cm ² , to form a coating agent B cured product layer on the surface of the substrate. bottom.
Next, the coating agent A of Example 1 was applied to the surface of the coating agent B cured product layer, dried in a circulation dryer at 80 ° C. for 1 minute, and the irradiation distance was 20 cm, the belt speed was 5 m / min, and the cumulative irradiation amount was 200 mJ /. It ^{was cured under the condition of cm 2} , and a coating agent A cured product layer was formed on the surface of the coating agent B cured product layer to produce a laminate.
The obtained laminate is superior in hardness to the laminate produced using only one coating agent.

Claims (5)

Contains (meth) acryloyl group-containing silica particles, poly (meth) acrylate, 1-hydroxycyclohexyl group-containing photopolymerization initiator and morpholino group-containing photopolymerization initiator.
The mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator) is 1.1 or more. Oh it is,
As the poly (meth) acrylate, (poly) pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) trimethylpropanpoly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) Glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, isocyanurate structure-containing poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate A coating agent comprising only those selected from the group consisting of bisphenol A di (alkylene oxide-modified or epoxy-modified) (meth) acrylates . The (meth) acryloyl group-containing silica particles

(In the formula, X is NH, O or S, and Y is O or S.)
The coating agent according to claim 1, which comprises a group represented by. Coating a coating agent according to claim 1 or 2 including an A and a coating agent B, and a coating kit,
The coating agent B has a mass ratio of the 1-hydroxycyclohexyl group-containing photopolymerization initiator to the morpholino group-containing photopolymerization initiator (1-hydroxycyclohexyl group-containing photopolymerization initiator / morpholino group-containing photopolymerization initiator). A coating agent kit that is less than 1.1 or does not contain a morpholino group-containing photopolymerization initiator. A cured product of the coating agent according to claim 1 or 2 and / or the coating agent kit according to claim 3. A laminate containing the cured product according to claim 4.