JP6749325B2 - Adhesive composition, paper treatment agent or fiber treatment agent, coating composition and coating method - Google Patents

Description

The present invention relates to an adhesive composition, a paper or fiber treating agent, a coating composition and a coating method .
The present application claims priority based on Japanese Patent Application No. 2015-119208 filed in Japan on June 12, 2015, and the content thereof is incorporated herein.

Conventionally, a resin having a hydroxyl group, a carboxyl group, an isocyanato group, an epoxy group, a silanol group, a carbonyl group, an amino group, a methylol group, etc. in its molecule has a resin hardness, heat resistance, water resistance, solvent resistance, and moisture resistance. In order to improve the physical properties of the film, the resin composition may be cured with a crosslinking agent to be used as a coating agent, an adhesive agent, a fiber treatment agent, or the like.
As a cross-linking agent for resins having these functional groups, cross-linking agents capable of reacting with the functional groups are known. For example, when a resin having a carboxy group is used as the resin, a crosslinking agent having a functional group capable of reacting with the carboxy group is used. Examples of the functional group include an isocyanato group, a block isocyanato group, an epoxy group, a β-hydroxyalkylamide group, and a carbodiimide group.

However, there is still room for improvement in providing coating agents, adhesives, fiber treatment agents, molding materials and the like having excellent film physical properties. Until now, attempts have been made to improve the structure of a resin having a reactive functional group, or to make the cross-linking agent polyfunctional to improve the film properties. For example, Patent Document 1 discloses an acrylic pressure-sensitive adhesive characterized by a composition in which both an ultraviolet-crosslinkable photocrosslinking agent and a heat-crosslinkable latent curing agent are blended in a base polymer.
In Patent Document 1, since sufficient properties cannot be sufficiently expressed only by heat crosslinking of the reactive functional group, a crosslinking agent having a structure having a double bond is also used.
However, in these cross-linking agents, unreacted cross-linking agents may remain in the film, and as a result, problems such as deterioration of film physical properties may occur, and development of new cross-linking agents has been demanded. ..
On the other hand, Patent Document 2 discloses composite fine particles capable of constructing a colloidal crystal structure.

JP, 2006-335840, A International Publication No. 2005/108451

An object of the present invention is to provide an adhesive composition that has excellent heat resistance.
Another object of the present invention is to provide a coating agent composition which is excellent in adhesion to a substrate and water resistance, and a cured product having high hardness, and a paper treating agent or a fiber treating agent.

［式（Ｉ）中、Ｒ^１ _、Ｒ^２、Ｒ^３は、それぞれ独立して炭素数１〜３のアルキル基を表し、Ｒ^４、Ｒ^５はそれぞれ独立して炭素数１〜３のアルキル基を表し、Ｘはハロゲン原子を表し、ｎは３〜１０の整数である。］
［８］前記高分子グラフト鎖が、イソシアナト基、カルボキシル基、ヒドロキシル基、及びエポキシ基のいずれをも有さず且つエチレン性不飽和基を有する単量体（Ｂ）に由来するモノマー単位を含有する、前記［１］〜［７］のいずれか一つに記載の硬化性樹脂組成物。
［９］前記単量体（Ｂ）が（メタ）アクリロイルオキシ基を有する単量体である、前記［８］に記載の硬化性樹脂組成物。
［１０］前記エチレン性不飽和基を有する樹脂成分が、エチレン性不飽和基を有するアクリル樹脂、エチレン性不飽和基を有するウレタン樹脂、不飽和ポリエステル樹脂、及び不飽和ポリオレフィン樹脂からなる群から選択される少なくとも１種の樹脂を主成分として含む、前記［１］〜［９］のいずれか一つに記載の硬化性樹脂組成物。
［１１］前記ベース粒子の、レーザー回折式粒度分布測定装置を用いて測定される５０％体積累積径（Ｄ５０）である体積平均粒子径が１０ｎｍ〜１μｍである、前記［１］〜［１０］のいずれか一つに記載の硬化性樹脂組成物。
［１２］前記ベース粒子が、無機粒子である、前記［１］〜［１１］のいずれか一つに記載の硬化性樹脂組成物。
［１３］前記無機粒子が、シリカ粒子または金属酸化物の粒子である、前記［１２］に記載の硬化性樹脂組成物。
［１４］前記ベース粒子が、有機粒子であり、前記有機粒子はアクリル樹脂、ポリスチレン樹脂、スチレン−アクリル共重合樹脂、酢酸ビニル樹脂、ウレタン樹脂、メラミン樹脂、シリコーン樹脂、又はスチレンブタジエンゴムのいずれかから選択される樹脂の粒子である、前記［１］〜［１３］のいずれか一つに記載の硬化性樹脂組成物。
［１５］さらに、光重合開始剤を含む前記［１］〜［１４］のいずれか一つに記載の硬化性樹脂組成物。
［１６］前記［１］〜［１５］のいずれか一つに記載の硬化性樹脂組成物を含有するコーティング剤。
［１７］前記［１］〜［１５］のいずれか一つに記載の硬化性樹脂組成物を含有する粘接着剤。
［１８］前記［１］〜［１５］のいずれか一つに記載の硬化性樹脂組成物を含有する紙又は繊維処理剤。In order to achieve the above object, the present invention provides the following means.
[1] A curable resin composition containing a resin component having an ethylenically unsaturated group and crosslinkable particles having a polymer graft chain having an ethylenically unsaturated group bonded to the surface of a base particle.
[2] The curable resin composition according to the above [1], wherein the density of the polymer graft chains on the surface of the base particles is 0.05 to 1.2 main chains/nm ² .
[3] A single polymer graft chain having at least one reactive functional group (i) selected from the group consisting of an isocyanato group, a carboxyl group, a hydroxyl group, and an epoxy group, and an ethylenically unsaturated group. The curable resin composition according to the above [1] or [2], which contains a monomer unit derived from the monomer (C).
[4] A reactive functional group (wherein the polymer graft chain is capable of reacting with at least one reactive functional group (i) selected from the group consisting of an isocyanato group, a carboxyl group, a hydroxyl group, and an epoxy group ( ii) The reactive functional group (ii) of the compound (D) having an ethylenically unsaturated group and the reactive functional group (i) of the monomer unit derived from the monomer (C) are chemically bonded. The curable resin composition according to the above [3], which has a structure.
[5] A combination of the reactive functional group (i) in the monomer (C) and the reactive functional group (ii) in the compound (D) is a combination of a hydroxyl group and an isocyanato group, or an isocyanato group. The curable resin composition according to the above [4], which is a combination of hydroxyl groups, a combination of isocyanato groups and carboxyl groups, or a combination of carboxyl groups and isocyanato groups.

[6] The polymer graft chain has as a starting point a polymerization initiation group having a structure derived from the compound (A), in which the compound (A) having an alkoxysilyl group and a halogen group is bonded to the surface of the base particle. The curable resin composition according to any one of the above [1] to [5].
[7] The curable resin composition according to the above [6], wherein the compound (A) is a compound represented by the following formula (I).

[In formula (I), R ¹ _, R ² , and R ³ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ are each independently an alkyl group having 1 to 3 carbon atoms. Represents, X represents a halogen atom, and n is an integer of 3 to 10. ]
[8] The polymer graft chain contains a monomer unit derived from a monomer (B) having neither an isocyanato group, a carboxyl group, a hydroxyl group, nor an epoxy group and having an ethylenically unsaturated group. The curable resin composition according to any one of [1] to [7] above.
[9] The curable resin composition according to the above [8], wherein the monomer (B) is a monomer having a (meth)acryloyloxy group.
[10] The resin component having an ethylenically unsaturated group is selected from the group consisting of an acrylic resin having an ethylenically unsaturated group, a urethane resin having an ethylenically unsaturated group, an unsaturated polyester resin, and an unsaturated polyolefin resin. The curable resin composition according to any one of [1] to [9], which contains at least one resin as a main component.
[11] The above-mentioned [1] to [10], wherein the base particles have a volume average particle diameter of 10 nm to 1 μm, which is a 50% volume cumulative diameter (D50) measured using a laser diffraction type particle size distribution measuring device. The curable resin composition according to any one of 1.
[12] The curable resin composition according to any one of [1] to [11], wherein the base particles are inorganic particles.
[13] The curable resin composition according to [12], wherein the inorganic particles are silica particles or metal oxide particles.
[14] The base particles are organic particles, and the organic particles are any of acrylic resin, polystyrene resin, styrene-acrylic copolymer resin, vinyl acetate resin, urethane resin, melamine resin, silicone resin, or styrene-butadiene rubber. The curable resin composition according to any one of the above [1] to [13], which is a particle of a resin selected from.
[15] The curable resin composition according to any one of [1] to [14], further including a photopolymerization initiator.
[16] A coating agent containing the curable resin composition according to any one of [1] to [15].
[17] A tacky adhesive containing the curable resin composition according to any one of [1] to [15].
[18] A paper or fiber treatment agent containing the curable resin composition according to any one of [1] to [15].

According to the present invention, an adhesive composition having excellent heat resistance can be provided.
Further, according to the present invention, it is possible to provide a coating agent composition and a paper treatment agent or a fiber treatment agent which are excellent in adhesiveness to a substrate and water resistance and can obtain a cured product having high hardness.

It is a schematic diagram which shows an example of the curable resin composition of this invention.

<<Curable resin composition>>
The curable resin composition 1 according to one embodiment of the present invention has a crosslinkability in which a resin component 10 having an ethylenically unsaturated group and a polymer graft chain 21 having an ethylenically unsaturated group are bonded to the surface of a base particle 22. And particles 20 (FIG. 1).

<Resin component having ethylenically unsaturated group>
In the present invention, the resin component having an ethylenically unsaturated group is a polymer or monomer having an ethylenically unsaturated group in the molecule. In the present invention, the monomer constituting the resin may be included in the resin component. Examples of the resin component include an acrylic resin having an ethylenically unsaturated group, a urethane resin having an ethylenically unsaturated group, an unsaturated polyester resin, an unsaturated polyolefin resin, and the like, and among them, high curability and used. From the viewpoint of adhesion to a substrate or the like, an acrylic resin having an ethylenically unsaturated group and a urethane resin having an ethylenically unsaturated group are preferable. Examples of the acrylic resin having an ethylenically unsaturated group include acrylic resin acrylate. Examples of the urethane resin having an ethylenically unsaturated group include urethane acrylate.
Specific examples of the acrylic resin having an ethylenically unsaturated group include a compound having an isocyanato group and an ethylenically unsaturated group at a hydroxyl group of a copolymer of methyl methacrylate and hydroxyethacrylate, specifically 2-isocyanatoethyl. The thing which made methacrylate etc. react is mentioned.

Specific examples of the monomer having an ethylenically unsaturated group in the molecule include dienes such as butadiene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate. , N-butyl (meth)acrylate, sec-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth) ) Acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl ( (Meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethyl Norbornyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (Meth)acrylate, perfluoro-iso-propyl(meth)acrylate, triphenylmethyl(meth)acrylate, cumyl(meth)acrylate, 3-(N,N-dimethylamino)propyl(meth)acrylate, glyceryl mono( (Meth)acrylic acid esters such as (meth)acrylate, butanetriol mono(meth)acrylate, pentanetriol mono(meth)acrylate, naphthalene(meth)acrylate, anthracene(meth)acrylate; (meth)acrylic acid amide, (meth) ) Acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-iso-propylamide, (Meth)acrylic acid amides such as (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride , Vinyl compounds such as N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene; styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; diethyl citracone, diethyl maleate Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconic acid; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide; (meth)acrylic Unsaturated monobasic acids such as acids, crotonic acid, cinnamic acid; glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy and lactone adducts thereof [eg, Daicel Chemical Industries ( Cyclomer A200, M100], 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate mono(meth)acrylic acid ester, dicyclopentenyl(meth)acrylate epoxidized product, dicyclo. Radical polymerizable monomers having an epoxy group such as an epoxidized product of pentenyloxyethyl (meth)acrylate; unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride. These may be used alone or in combination of two or more.

The resin component having an ethylenically unsaturated group is at least selected from the group consisting of an acrylic resin having an ethylenically unsaturated group, a urethane resin having an ethylenically unsaturated group, an unsaturated polyester resin, and an unsaturated polyolefin resin. It is preferable to contain one kind of resin as a main component.
The acrylic resin is a resin having a monomer unit derived from an acrylic acid ester or a methacrylic acid ester as a main component, and may be a copolymer with another monomer. In the case of a copolymer, the acrylic resin preferably contains 50 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more of a monomer unit derived from an acrylic acid ester or a methacrylic acid ester. preferable.
The urethane resin is a resin having a urethane bond, and may be a copolymer with another monomer. In the case of a copolymer, the urethane resin preferably contains 50 mol% or more of monomer units forming a urethane bond, more preferably 80 mol% or more, and further preferably 90 mol% or more.
"Containing a resin as a main component" means that at least one kind of the resin is contained in 50% by mass or more of the resin component, preferably 70% by mass or more, more preferably 80% by mass or more, It is more preferable to contain 90% by mass or more.

When the resin component has an ethylenically unsaturated group, the ethylenically unsaturated group in the resin component and the ethylenically unsaturated group in the polymer graft chain of the crosslinkable particles can be polymerized.

<Base particles>
Examples of the base particles that are the basis of the crosslinkable particles in the present invention include inorganic particles and/or organic particles.

As the inorganic particles, silicon oxide particles such as silica particles, precious metal particles such as Au particles, Ag particles, Pt particles, and Pd particles, Ti particles, Zr particles, Ta particles, Sn particles, Zn particles, Cu particles, Transition metal particles such as V particles, Sb particles, In particles, Hf particles, Y particles, Ce particles, Sc particles, La particles, Eu particles, Ni particles, Co particles, and Fe particles, and oxide particles or nitriding thereof. Examples include particles of the object. Of these, silica particles or metal oxide particles are preferable as the inorganic particles, and colloidal silica particles are most preferable.
Examples of the organic particles include acrylic resin, polystyrene resin, styrene-acrylic copolymer resin, vinyl acetate resin, urethane resin, melamine resin, silicone resin, and styrene-butadiene rubber (SBR). Among them, acrylic resin, polystyrene resin, styrene-acrylic copolymer resin, urethane resin, vinyl acetate resin and the like resin particles, among them, acrylic resin, styrene-acrylic copolymer resin, or urethane resin particles preferable.

Inorganic particles are more preferable from the viewpoint that the manufacturing process is simpler than that of organic particles.

Further, the density of the polymer graft chains on the surface of the base particles is preferably in the numerical range of 0.05 to 1.2 single chains/nm ² from the viewpoint of excellent dispersibility of particles and crosslinking efficiency, and 0 It is more preferable that the numerical range is 0.1 to 1.0 strand/nm ² , and it is further preferable that the numerical range is 0.3 to 0.7 strand/nm ² .
The density of the polymer graft chains on the surface of the base particles can be determined by the measuring method described in Examples below.

The average particle diameter of the base particles is preferably in the numerical range of 10 nm to 1 μm, more preferably in the numerical range of 10 nm to 700 nm, and more preferably 10 nm to 300 nm, from the viewpoint of excellent dispersibility of particles and crosslinking efficiency. The numerical range is more preferable, and the numerical range of 10 nm to 80 nm is particularly preferable.
When the average particle diameter of the base particles is 10 nm or more, it is less likely to be affected by the curvature of the particles when the particles are graft-polymerized from the particle surface, so that the density of the graft chains is increased, and when used in the resin composition, the crosslinking density is increased. Is preferable and the film physical properties such as hardness of the resin tend to be good, which is preferable. When the particle size is 1 μm or less, when used in a resin composition, the risk of lowering the transparency of the coating film tends to be reduced, which is preferable. The average particle diameter of the base particles refers to the 50% volume cumulative diameter (D50) measured using a laser diffraction type particle size distribution measuring device.

The weight average molecular weight of the entire polymer graft chain per one particle of the crosslinkable particles is preferably 1,000 to 500,000, more preferably 10,000 to 400,000, from the viewpoint of excellent dispersibility and crosslinking efficiency. 40,000 to 300,000 is more preferable. When the weight average molecular weight is 1,000 or more, the stability of the crosslinkable particles tends to be improved. When it is 500,000 or less, the risk that the viscosity of the dispersion liquid becomes extremely high in the organic solvent is reduced, and the handling tends to be good.
The weight average molecular weight of the entire polymer graft chain per one particle of the crosslinkable particles can be determined by the measuring method described in Examples below.

<Polymer graft chain having ethylenically unsaturated group>
The crosslinkable particles in the present invention have a polymer graft chain having an ethylenically unsaturated group on the surface of the base particles. The polymer graft chain is a polymer chain (polymer) and can be formed by extending from the surface of the base particles by a polymerization reaction.
The ethylenically unsaturated group in the polymer graft chain acts as a cross-linking agent by cross-linking the resin components having the ethylenically unsaturated group.

The polymer graft chain is preferably one produced by living radical polymerization. In this case, the length of the polymer chains becomes relatively uniform, and the crosslinking efficiency tends to improve.

In the polymer graft chain, the monomer constituting the polymer graft chain is not particularly limited as long as it has an ethylenically unsaturated group in the molecule of the polymer graft chain. The chain preferably contains a structure derived from the compound (D) having an ethylenically unsaturated group and a reactive functional group (ii) described later. More preferably, by containing a monomer unit derived from a monomer (C) having a reactive functional group (i) capable of reacting with the reactive functional group (ii) of the compound (D) and an ethylenically unsaturated group. is there. More preferably, it contains a monomer unit derived from the monomer (B). More preferably, it contains a structure derived from the compound (A).
As used herein, “derived from” means that the monomer or compound has undergone a structural change necessary for polymerization.
When the polymer graft chain includes all the reaction products of the compound (A), the monomer (B), the monomer (C), and the compound (D), the polymer graft chain is formed from the base particle side, A polymer containing a structure derived from the compound (A), a monomer unit derived from the monomer (B), and a monomer unit derived from the monomer (C) in this order, and further a monomer (C). It is preferable that the compound (D) is bound via the reactive functional group (i). The polymer graft chain is obtained by reacting the base particles of the crosslinkable particles with the compound (A), the monomer (B), the monomer (C) and the compound (D) in this order. The structure derived from the compound (A), the monomer unit derived from the monomer (B), the monomer unit derived from the monomer (C), and the structure derived from the compound (D) are, from the base particle side, In the polymer graft chain constructed in this order, the units or structures of the same kind may be continuous and any other structure may be added, as long as the order is maintained. It may be one.

<Compound (A)>
The polymer graft chain has a compound (A) having an alkoxysilyl group and a halogen group as a starting point, which is a polymerization initiation group having a structure derived from the compound (A), which is bonded to the surface of the base particle. It is preferable. The compound (A) preferably has no ethylenically unsaturated group in the molecule.
In the crosslinkable particles, the compound (A) is preferably contained in a form in which an alkoxysilyl group is directly bonded to the surface of the base particles.

When the compound (A) polymerized as a constituent unit of the polymer graft chain does not have an ethylenically unsaturated group in the molecule, the compound (A) is directly bonded to the surface of the base particle, and An appropriate distance from the surface of the particle to the ethylenically unsaturated group can be secured, which is preferable because the dispersibility of the crosslinkable particle is good.

Examples of the compound (A) having an alkoxysilyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane. , 3-acryloxypropyltrimethoxysilane and other terminal double bonds to which halogen such as bromine, chlorine and iodine is added. Among them, 3-methacryloxypropyltrimethoxysilane is preferable, and bromine is preferable as the halogen.

As the compound (A), only one kind may be used, or two or more kinds may be mixed and used.

As the compound (A) having an alkoxysilyl group and a halogen, a compound represented by the following formula (I) is preferable from the viewpoint that the step of supporting it on the inorganic particles is simple.

In formula (I), R ¹ _, R ² and R ³ each independently represent an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. R ^{4, R 5} each independently represents an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. X represents a halogen atom, and Br is particularly preferable. n is an integer of 3 to 10.

In the present specification, the “alkyl group” refers to a monovalent group generated by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane and propane, and is generally represented by CnH _2n+1 −. (Where n is a positive integer). Alkyl groups can be straight or branched. Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, propyl group and isopropyl group.

In formula (I), n represents the number of —CH ₂ —, n is an integer of 3 to 10, an integer of 4 to 8 is preferable, and 6 is most preferable. In formula (I), the (CH ₂ )n portion has a role as a spacer.

The compound represented by the above formula (I) can be synthesized based on general organic chemistry. Examples of the compound represented by the formula (I) include (2-bromo-2-methyl)propionyloxyhexyltriethoxysilane (BHE).

<Monomer (B)>
The polymer graft chain according to the present invention has a monomer unit derived from a monomer (B) having neither an isocyanato group, a carboxyl group, a hydroxyl group, nor an epoxy group and having an ethylenically unsaturated group. It is preferable to contain.
It is preferable that the monomer (B) undergoes living radical polymerization of the ethylenically unsaturated group of the monomer (B) starting from the halogen terminal of the compound (A) bound to the surface of the base particle.
Since the monomer (B) does not have any of an isocyanato group, a carboxyl group, a hydroxyl group, and an epoxy group, it should have an appropriate distance from the structure derived from the compound (D) described later on the surface of the base particle. Therefore, the dispersibility of the crosslinkable particles is good, which is preferable.

The monomer (B) is preferably a monomer having a (meth)acryloyloxy group.

Specific examples of the monomer (B) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth). It is possible to use acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, acrylonitrile, styrene, styrene derivative, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, ethylene, propylene, butylene, isobutylene, etc. Of these, methyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferred. Among them, 2-ethylhexyl acrylate or butyl acrylate is preferable, and butyl acrylate is preferable. As the monomer (B), one type may be used, or two or more types may be mixed and used.

<Monomer (C), Compound (D)>
The polymer graft chain according to the present invention has a monofunctional group having at least one reactive functional group (i) selected from the group consisting of an isocyanato group, a carboxyl group, a hydroxyl group, and an epoxy group, and an ethylenically unsaturated group. It is preferable to contain a monomer unit derived from the monomer (C).
The monomer unit derived from the monomer (C) is preferably present in the polymer graft chain in a form bound to the monomer unit derived from the monomer (B). In the monomer unit derived from the monomer (C), the ethylenically unsaturated group contained in the monomer (C) is present in the graft chain in a form of polymerizing with the monomer (B). preferable. For example, the ethylenically unsaturated group of the monomer (C) is added to the ethylenically unsaturated group of the polymer graft chain whose terminal is an ethylenically unsaturated group due to the ethylenically unsaturated group of the monomer (B). Examples include a form in which a saturated group is bonded.

The polymer graft chain according to the present invention is capable of reacting with at least one reactive functional group (i) selected from the group consisting of an isocyanato group, a carboxyl group, a hydroxyl group, and an epoxy group ( ii) The reactive functional group (ii) of the compound (D) having an ethylenically unsaturated group and the reactive functional group (i) of the monomer unit derived from the monomer (C) are chemically bonded. It is preferable to have a structure.
The compound (D) has the above-mentioned reactive functional group (i) of the polymer graft chain whose terminal is a reactive functional group (i) due to the reactive functional group (i) of the monomer (C), The form in which the reactive functional group (ii) of the compound (D) is bonded is preferable.
The ethylenically unsaturated group contained in the compound (D) may be the ethylenically unsaturated group contained in the polymer graft chain.

As the monomer (C) or compound (D) having an isocyanato group as the reactive functional group (i) or (ii), 2-isocyanatoethyl (meth)acrylate or 3-isocyanatopropyl (meth)acrylate is used. And these are preferable in that the reaction conditions for binding the compound (D) and the monomer (C) can be carried out at a low temperature and in a short time. As the monomer (C), only one kind of the isocyanato group-containing ethylenically unsaturated monomer may be contained in the polymer graft chain, or a plurality of kinds thereof may be contained. Similarly, as the compound (D), the isocyanato group-containing ethylenically unsaturated monomer may be contained in the polymer graft chain in only one kind or in plural kinds.

Examples of the monomer (C) or compound (D) having a carboxyl group as the reactive functional group (i) or (ii) include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, Examples thereof include 2-methylmaleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, their metal salts and ammonium salts. From the viewpoint of polymerization stability, the monomer (C) and the compound (D) are preferably acrylic acid, methacrylic acid, maleic acid or maleic anhydride. As such a carboxyl group-containing ethylenically unsaturated monomer, as the monomer (C), only one type may be contained in the polymer graft chain, or a plurality of types may be contained. Similarly, as the compound (D), the carboxyl group-containing ethylenically unsaturated monomer may be contained in the polymer graft chain in only one kind or in plural kinds.

Examples of the monomer (C) or compound (D) having a hydroxyl group as the reactive functional group (i) or (ii) include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol. Monoacrylate, polytetramethylene glycol monoacrylate, polyethylene glycol polytetramethylene glycol monoacrylate, polypropylene glycol polytetramethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, Examples thereof include polytetramethylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, and the like. From the viewpoint of polymerization stability, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferable as the monomer (C) and the compound (D). As the monomer (C), only one kind of such a hydroxyl group-containing ethylenically unsaturated monomer may be contained in the polymer graft chain, or a plurality of kinds thereof may be contained. Similarly, as the compound (D), the hydroxyl group-containing ethylenically unsaturated monomer may be contained in the polymer graft chain in only one kind or in plural kinds.

Examples of the monomer (C) or compound (D) having an epoxy group as the reactive functional group (i) or (ii) include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methylglycidyl acrylate, methylglycidyl methacrylate, 3 , 4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate and the like. From the viewpoint of polymerization stability, the monomer (C) and the compound (D) are preferably glycidyl methacrylate. As such a glycidyl group-containing ethylenically unsaturated monomer, as the monomer (C), only one type may be contained in the polymer graft chain, or a plurality of types may be contained. Similarly, as for the glycidyl group-containing ethylenically unsaturated monomer, only one kind may be contained in the polymer graft chain as the compound (D), or plural kinds thereof may be contained.

<Combination of reactive functional group (i) or (ii)>
In the present invention, when the polymer graft chain contains both the monomer (C) and (D), the reactive functional group (i) in the monomer (C) and the reactive functional group (in the compound (D) ( As the combination of ii), the following combinations are preferable.

In Table 1, the combination of “3” carboxyl group/isocyanato group is preferable because the reaction proceeds at a lower temperature and the time required for the reaction is shorter than the combination of “4” isocyanato group/epoxy group. The combination of the carboxyl group/epoxy group of "2" is more preferable because the reaction time is shorter than that of the combination of the carboxyl group/isocyanato group of "3". With the combination of the hydroxyl group/isocyanato group of "1", the reaction proceeds most easily among the combinations of "2" to "4", and the reaction proceeds at a lower temperature than the combination of "2" to "4". In addition, the reaction time is short, and the binding step is easy, which is particularly preferable.

The curable resin composition of the present invention preferably contains the crosslinkable particles in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin component in the curable resin composition. The content is more preferably in the range of 50 parts by mass, more preferably in the range of 0.3 to 20 parts by mass, and further preferably in the range of 0.3 to 10 parts by mass.

The curable resin composition of the present invention preferably contains the crosslinkable particles in the curable resin composition in the range of 0.1 to 50% by mass, and in the range of 0.2 to 40% by mass. More preferably, it is more preferably contained in the range of 0.5 to 30% by mass, and particularly preferably contained in the range of 1 to 10% by mass. By containing the content of the crosslinkable particles within the above numerical range, the dispersibility of the crosslinkable particles in the curable resin composition is good and efficient crosslinking can be achieved.

The curable resin composition of the present invention preferably contains the resin component in the curable resin composition in the range of 10 to 99.9% by mass, more preferably in the range of 20 to 80% by mass. , 30 to 70 mass% is more preferable. By containing the content of the resin component in the above numerical range, the adhesion, tackiness and water resistance of the resin component to the substrate can be improved.

In the curable resin composition of the present invention, the number of moles of the ethylenically unsaturated group of the crosslinkable particles in the curable resin composition is 0.5 to the number of moles of the ethylenically unsaturated group of the resin component. The molar amount is preferably 50 times, more preferably 1 to 30 times, and further preferably 2 to 20 times. By containing the number of moles of the ethylenically unsaturated group of the crosslinkable particles within the above numerical range, it is possible to crosslink efficiently.
When the polymer graft chain is a polymer containing a compound (A), a monomer (B), a monomer (C), and a compound or a monomer unit or structure derived from the compound (D). As the ratio of each unit or structure in the polymer graft chain to the number X of moles of the compound (A), the following can be exemplified.
Monomer (B): The molar amount is preferably 1 to 5000 times, more preferably 100 to 4500 times, and still more preferably 500 to 4000 times.
Monomer (C): 1 to 1000 times molar amount is preferable, 10 to 800 times molar amount is more preferable, and 50 to 500 times molar amount is further preferable.
The compound (D) is preferably 1 to 1000 times by mole, more preferably 10 to 800 times by mole, and even more preferably 50 to 500 times by mole.

<Reactive monomer>
The curable resin composition of the present invention may contain a so-called reactive monomer as a reactive and polymerizable diluent. The reactive monomer is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and preferably has a plurality of polymerizable functional groups. Such a reactive monomer is not always an essential component of the polymerizable composition, but by using it in combination with curability, it is possible to improve the film strength of the coating film formed and the adhesion to the substrate. ..
Examples of monofunctional monomers used as reactive monomers include (meth)acrylamide, methylol(meth)acrylamide, methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth). Acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4- Hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (Meth)acrylate such as (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of phthalic acid derivative Compounds; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. Moreover, these can be used individually or in combination of 2 or more types.
On the other hand, as the polyfunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth) Acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2 -Bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di( (Meth)acrylate, diglycidyl phthalate di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (that is, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate Etc. with 2-vidroxyethyl (meth)acrylate, (meth)acrylate compounds such as tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallylphthalate, diallylbenzenephosphonate A dicarboxylic acid ester compound such as divinyl adipate; triallyl cyanurate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, a condensation product of a polyhydric alcohol and N-methylol(meth)acrylamide, and the like. Moreover, these can be used individually or in combination of 2 or more types.

<Polymerization initiator>
The curable resin composition of the present invention may further contain a polymerization initiator.
The polymerization initiator contributes to the curing of the curable resin composition. Examples of the polymerization initiator include photopolymerization initiators and/or thermal polymerization initiators that generate radicals.
Examples of the photopolymerization initiator include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxy-phenylphenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, diphenyl-(2,4,6- Trimethylbenzoyl)phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, oligomers of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzophenone and the like. These photopolymerization initiators may be used alone or in combination of two or more.
Examples of the polymerization initiator containing two or more photopolymerization initiators include an oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one and 2,4,6-trimethyl. Examples thereof include a mixture of benzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzophenone.

Examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxy carbonate, t-butyl peroxy(2-ethylhexanoate), t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbo , Dilauroyl peroxide, diisopropyl peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane Can be mentioned. These thermal polymerization initiators may be used alone or in combination of two or more kinds.

The content of the polymerization initiator in the curable resin composition may be an amount that allows the curable resin composition to be appropriately cured. The content of the polymerization initiator in the curable resin composition is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, and further preferably 0.1 to 2% by mass. %.
When the content of the polymerization initiator is too large, the storage stability of the curable resin composition may be deteriorated and the curable resin composition may be colored. Further, if the content of the polymerization initiator is too large, the crosslinking during the production of the cured product may proceed rapidly, and problems such as cracking may occur. Further, if the addition amount of the polymerization initiator is too small, the curable resin composition is hard to cure.

<Other ingredients>
The curable resin composition of the present invention contains, in addition to the above components, a polymerization inhibitor and a leveling agent, if necessary, within a range that does not impair the viscosity of the composition and properties such as transparency and heat resistance of the cured product. , Antioxidants, ultraviolet absorbers, infrared absorbers, light stabilizers, pigments, fillers such as other inorganic fillers, and other modifiers may be contained. The curable resin composition of the present invention may contain a crosslinking agent having no particle structure, if necessary, in addition to the above components. The particle structure is the base particles. In the curable resin composition of the present invention, a solvent usually used for resin compositions can be used.
The content of the solvent in the curable resin composition may be appropriately determined in consideration of the viscosity of the curable resin composition and the like. The content of the solvent in the curable resin composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass.
The curable resin composition of the embodiment includes, as an example, a resin component, crosslinkable particles, a polymerization initiator, and a solvent. The curable resin composition contains, for example, one or more components described above such that the total content (% by mass) does not exceed 100% by mass.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, 2,6-di-t-butyl-4-methylphenol and the like. These can be used alone or in combination of two or more.

Examples of the leveling agent include polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, and polyether-modified Methyl alkyl polysiloxane copolymer etc. are mentioned. These can be used alone or in combination of two or more.

Examples of the filler or pigment include calcium carbonate, talc, mica, clay, Aerosil (registered trademark), barium sulfate, aluminum hydroxide, zinc stearate, zinc white, red iron oxide, azo pigment and the like. These can be used alone or in combination of two or more.

<Method for preparing curable resin composition>
(Crosslinkable particles)
The crosslinkable particles in which the polymer graft chains according to the present invention are bonded to the surface of the base particles can be produced, for example, through the following steps.
a) step of reacting the base particles with the compound (A) to bond a chain having a halogen group at the terminal to the surface of the base particle b) step c of living radical polymerization of the terminal halogen and the monomer (B) ) Step of further subjecting the monomer (C) to living polymerization from the polymerization end of the radical polymerization of the monomer (B) d) Polymer graft having the reactive functional group (i) of the monomer (C) as the end Step of reacting the reactive functional group (ii) of the compound (D) with the chain to introduce an ethylenically unsaturated group at the end of the polymer graft chain

<<Process a>>
As a method for producing a polymer graft chain, it is preferable to first bond the compound (A) to the surface of the base particle so that the terminal has a halogen atom, and then grow the polymer graft chain starting from that. In this case, the crosslinkable particles having a high density of polymer graft chains on the particle surface are prepared as compared with the production method in which a polymer chain is first prepared from the compound (A) and another monomer and then directly bonded to the base particles. The advantage is that

As the base particles to be reacted with the compound (A), it is preferable to use a dispersion prepared by dispersing the base particles in an organic solvent. Examples of the organic solvent in which the base particles are dispersed include ethanol, benzene, xylene, toluene and the like. By using such a dispersion, the base particles can be easily dispersed in the compound (A).

The method for mixing the compound (A) and the base particles is not particularly limited. For example, there may be mentioned a method of mixing the compound (A) with the base particles at room temperature using a mixer, a ball mill, a three-roll mixer or the like. Alternatively, a method may be used in which the compound (A) is placed in a reaction vessel, the base particles are added and mixed while continuously stirring the compound (A) in the reaction vessel, and a dispersion is prepared.
A catalyst and, if necessary, other components are added to the dispersion and mixed, and a condensation reaction is performed. The temperature of the mixed solution is preferably 100° C. or lower, more preferably 70° C. or lower, and further preferably 50° C. or lower in order to efficiently proceed the condensation reaction. The temperature of the mixed solution is preferably 20° C. or higher, and more preferably 30° C. or higher in order to carry out the step of removing alcohol or water generated by the reaction in a short time.

<<Process b>>
In the step of subjecting the monomer (B) to living radical polymerization with the terminal halogen as a starting point, the monomer (( B), the catalyst and, if necessary, other components are added and mixed, and the terminal halogen and the monomer (B) are radically polymerized. The temperature of the mixed solution is preferably 100° C. or lower, more preferably 70° C. or lower, and further preferably 50° C. or lower in order to allow the reaction to proceed efficiently. The temperature of the mixed solution is preferably 20° C. or higher, and more preferably 30° C. or higher in order to remove the solvent in a short time.

<<Process c>>
The step of further polymerizing the monomer (C) from the polymerization terminal of the living radical polymerization of the monomer (B) is a base particle having a graft chain bonded to the terminal obtained in step b, which is the polymerization terminal of the radical polymerization. The monomer (C) is continuously added to and mixed with the liquid containing the above, and the monomer (C) is polymerized with the polymerization terminal of the radical polymerization as a starting point. The temperature of the mixed solution is preferably 100° C. or lower, more preferably 70° C. or lower, and further preferably 50° C. or lower in order to allow the reaction to proceed efficiently. The temperature of the mixed solution is preferably 20° C. or higher, and more preferably 30° C. or higher in order to remove the solvent in a short time.

<<Process d>>
In the step of reacting the reactive functional group (ii) of the compound (D) with the polymer graft chain having the reactive functional group (i) of the monomer (C), the terminal obtained in the step c is reactive. The compound (D) and, if necessary, other components are added to and mixed with a liquid containing a base particle having a chain that is a functional group (i), and the reactive functional group (i) and the compound are mixed. By reacting with (D), crosslinkable particles are obtained.
The temperature of the mixed solution is preferably 100° C. or lower, more preferably 70° C. or lower, and further preferably 50° C. or lower in order to allow the addition reaction to proceed efficiently. The temperature of the mixed solution is preferably 20° C. or higher, and more preferably 30° C. or higher in order to remove the solvent in a short time.

(Curable resin composition)
The curable resin composition can be obtained by mixing the crosslinkable particles obtained in the step d, the resin component having an ethylenically unsaturated group, and optionally other optional components.

The curable resin composition may be filtered. This filtration is performed in order to remove foreign matter such as dust contained in the curable resin composition. The filtering method is not particularly limited. As a filtration method, it is preferable to use a method of pressure filtration using, for example, a membrane type or cartridge type filter.
The curable resin composition of the present invention can be obtained through the above steps.

<<Cured product>>
The cured product of the present invention is obtained by curing the curable resin composition of the present invention.

[Cured product manufacturing method]
The method for producing a cured product of the present invention has a step of curing the curable resin composition of the present invention.

When the curable resin composition is irradiated with active energy rays such as ultraviolet rays to be cured, a photopolymerization initiator is added as a polymerization initiator to the composition containing the crosslinkable particles obtained in the above step d. When the curable resin composition is cured by heat treatment, a thermal polymerization initiator is added as a polymerization initiator to the composition containing the crosslinkable particles obtained in the above step d.

To form the cured product of the present invention, for example, the curable resin composition of the present invention is applied onto a substrate such as a glass plate, a plastic plate, a metal plate or a silicon wafer to form a coating film, or A method of pouring into a mold or the like can be used. Then, for example, it is obtained by irradiating the coating film with an active energy ray and/or heating the coating film to cure it.

Examples of the coating method of the curable resin composition include coating with a bar coater, applicator, die coater, spin coater, spray coater, curtain coater or roll coater, screen printing, and dipping. ..
The coating amount of the curable resin composition of the present invention on the substrate is not particularly limited and can be appropriately adjusted according to the purpose. The coating amount of the curable resin composition on the substrate is preferably such that the thickness of the coating film obtained after the curing treatment by irradiation with active energy rays and/or heating is from 1 μm to 10 mm, and from 10 to 1000 μm. Amounts are more preferred.

The active energy ray used to cure the curable resin composition is preferably an electron beam or light in the ultraviolet to infrared wavelength range. As the light source, for example, if it is ultraviolet light, an ultrahigh pressure mercury light source or a metal halide light source can be used. As the light source, for example, a metal halide light source or a halogen light source can be used as long as it is visible light. As the light source, for example, a halogen light source can be used if it is infrared. Besides this, for example, a light source such as a laser or an LED can be used.

The irradiation amount of active energy rays is appropriately set according to the type of light source, the film thickness of the coating film, and the like.
Further, after curing the curable resin composition by irradiating with active energy rays, a heat treatment (annealing treatment) may be performed as necessary to further cure the curable resin composition. The heating temperature at that time is preferably in the range of 50 to 150°C. The heating time is preferably in the range of 5 minutes to 60 minutes.

When the curable resin composition is heated and cured by thermal polymerization, the heating temperature may be set according to the decomposition temperature of the thermal polymerization initiator, but is preferably in the range of 40 to 200°C, and more preferably It is in the range of 50 to 150°C. When the heating temperature is lower than the above range, it is necessary to prolong the heating time, and the economy tends to be poor. If the heating temperature exceeds the above range, energy cost is required, and further heating heating time and cooling time are required, so that there is a tendency to be economically disadvantageous. The heating time is appropriately set according to the heating temperature, the film thickness of the coating film, and the like.

After the curable resin composition is cured by thermal polymerization, a heat treatment (annealing treatment) may be performed as necessary to further cure the curable resin composition. The heating temperature at that time is preferably in the range of 50 to 150°C. The heating time is preferably in the range of 5 minutes to 60 minutes.
As an example, the cured product of the present invention can be obtained by undergoing the above steps.

Since the curable resin composition of the present embodiment contains polyfunctional crosslinkable particles, the cured product of the curable resin composition of the present embodiment has excellent hardness, heat resistance and water resistance. ing. Therefore, the curable resin composition of the present embodiment can be preferably used, for example, as a coating agent for films, plastics, metals, etc., an adhesive agent, a paper treatment agent, and a fiber treatment agent.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

(Average molecular weight)
The weight average molecular weight and the number average molecular weight of the polymer graft chain in the present invention and the present specification are the gel permeation after the polymer graft chain is separated from the base particles by treating the crosslinkable particles with hydrogen fluoride. Chromatography (Showa Denko Co., Ltd. Shodex GPC System-11) can be used to measure at room temperature under the following conditions, and can be determined using a standard polystyrene calibration curve.
Column: Showa Denko KF-806L
Column temperature: 40°C
Sample: 0.2 mass% tetrahydrofuran solution of styrenic elastomer containing reactive functional group Flow rate: 2 ml/min Eluent: Tetrahydrofuran Detector: Differential refractometer (RI)

(Density of graft chains on the base particle surface)
The density of the graft chain in the present invention and the present specification can be measured by the following method.
The graft density was measured using a thermogravimetric analyzer TGDTA (manufactured by SII, TG/DTA6200). The measurement method was carried out by raising the temperature of the crosslinkable particles from 30° C. to 700° C. at a rate of 20° C./min under atmospheric conditions. In this way, the weight of the polymer grafted on the surface of the base particles was determined, and calculated using the specific surface area of the base particles and the number average molecular weight of the graft polymer.
[Graft chain density (main chain/nm ² )]=
((Weight of polymer per 1 g of base particles [g]/number average molecular weight of graft polymer)×6.02×10 ²³ )/(specific surface area of base particles [m ² /g]×10 ^{^} 18)

<Production Example 1-1> Production of crosslinkable particles (1) [Modification of surface modification agent containing halogen group on colloidal silica surface]
(Synthesis of halogen group-containing surface modifier (2-bromo-2-methyl)propionyloxyhexyltriethoxysilane (BHE. Compound (A)))
BHE was synthesized by a two-step reaction. As a first step, a mixed solution of 5-hexen-1-ol (43 g), triethylamine (71 ml) and tetrahydrofuran (THF; 1000 ml) was ice-cooled, and 2-bromoisobutyryl bromide (63 ml) was added dropwise thereto. did. Then, the reaction solution was stirred at 0° C. for 3 hours and further at room temperature for 10 hours. The reaction solution was filtered, the filtrate was concentrated, and the obtained product was diluted with chloroform (500 ml), which was washed with a 1N hydrochloric acid aqueous solution, a saturated sodium hydrogen carbonate aqueous solution, and pure water in this order. The organic layer was dried and concentrated, and then purified by a silica gel column (eluent: hexane/ethyl acetate=15/1) to give 1-(2-bromo-2-methyl)propionyloxy-5-hexene (BPH). Obtained at 90%. As the second step, BPH (40 g), toluene (500 ml), triethoxysilane (500 ml) and Karstedt catalyst (450 ml) were sequentially charged into a two-necked flask, and the mixture was placed in an argon atmosphere at room temperature for 12 hours. It was stirred. Toluene and unreacted triethoxysilane were removed under reduced pressure to synthesize BHE almost quantitatively.

(Halogen group-containing surface modifier on the surface of colloidal silica (modification of compound (A))
The surface of the silica fine particles was modified with the halogen-based surface modifier by the following procedure. An ethanol dispersion liquid (30 g) in which colloidal silica (manufactured by Nippon Shokubai Co., Ltd., average particle diameter 130 nm) is dispersed at a ratio of 7.7 wt% is mixed with a 28 mass% aqueous ammonia solution (13.9 g) and ethanol (200 ml). Added to. The mixture was stirred at 40° C. for 2 hours, then the ethanol solution (10 ml) of BHE (2 g) synthesized above was added dropwise, and the mixture was stirred at 40° C. for 18 hours. Then, the colloidal silica having a polymerization initiation group was recovered by a centrifuge, washed with ethanol and toluene, and then stored in toluene.

(Modification of Monomers (B) to (D) on Colloidal Silica Surface)
Using the colloidal silica having a polymerization initiation group prepared above as the base particles, butyl acrylate (20 g, monomer (B)), Cu(I)Cl (0.032 g), and di-dihydrate dispersed in a proportion of 2% by mass. Nonylbipyridine (0.268 g) and ethyl 2-bromoisobutyrate (EBIB; 0.006 g) were placed in a flask, degassed by nitrogen substitution, and then polymerized at 70° C. for 24 hours. Then, each of the monomers (C) (1 g) shown in Table 2 below was added, degassed by nitrogen substitution, and then polymerized at 70° C. for 24 hours to have different functional groups at the polymer terminals. The particles were obtained. Next, air is introduced, the compound (D) shown in Table 2 below is added to the intermediate particles, and the reaction is carried out under atmospheric conditions to obtain crosslinkable particles having an ethylenically unsaturated group at the polymer terminal (1 ) (Solid content concentration 10% by mass) was obtained.
Below, an example of the structural formula of the graft chain of the obtained component parts (B) to (D) is shown (wherein each of 1, m and n represents an arbitrary integer of 1 or more).

<Production Example 1-2> Production of crosslinkable particles (2) The monomer (C) and the compound (D) used in the above Production Example 1-1 are shown in Table 2 below. And crosslinked particles (2) (solid content concentration 10 mass%) were obtained in the same manner as in Production Example 1-1 except that the compound (D) was used instead.

<Production Example 1-3> Production of crosslinkable particles (3) Monomers (C) and compounds (D) used in the above Production Example 1-1 are shown in Table 2 below. Further, except that the compound (D) was used instead, the production was carried out in the same manner as in Production Example 1-1 to obtain crosslinkable particles (3) (solid content concentration 10% by mass).

<Production Example 1-4> Production of crosslinkable particles (4) The monomer (C) and the compound (D) used in the above Production Example 1-1 are shown in Table 2 below. And crosslinked particles (4) (solid content concentration 10 mass%) were obtained in the same manner as in Production Example 1-1 except that the compound (D) was used instead.

<Production Example 1-5> Production of crosslinkable particles (5) The monomer (C) and the compound (D) used in Production Example 1-1 above are shown in Table 2 below. And crosslinked particles (5) (solid content concentration 10 mass%) were obtained in the same manner as in Production Example 1-1 except that the compound (D) was used instead.

<Production Example 1-6> Production of crosslinkable particles (6) Modification of the ethylenically unsaturated double bond on the surface of the colloidal silica particles was performed by the following procedure. Colloidal silica (manufactured by Nippon Shokubai Co., Ltd., average particle size 130 nm) was dispersed at a ratio of 7.7 wt% in ethanol dispersion (30 g) into a mixture of 28% aqueous ammonia solution (13.9 g) and ethanol (200 ml). added. The mixture was stirred at 40° C. for 2 hours, then an ethanol solution (10 ml) of 3-methacryloxypropyltrimethoxysilane (2 g) was added dropwise, and the mixture was stirred at 40° C. for 18 hours. Then, the colloidal silica having the ethylenically unsaturated double bond modified was recovered by a centrifuge, washed with ethanol and toluene, and then stored in toluene.
The colloidal silica modified with the ethylenically unsaturated double bond prepared above was dispersed in a reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer at a ratio of 5 wt% (50 g). Methyl methacrylate (2 g, monomer (B)) and 2-hydroxyethyl acrylate (0.5 g, monomer (C)) were charged, and after heating under reflux, azobisisobutyro was used as a polymerization initiator. 0.2 g of nitrile was added, and the mixture was reacted at the reflux temperature of toluene for 8 hours. Then, 2-isocyanatoethylmethacrylate (0.5 g, compound (D)) was added and addition reaction was performed to obtain crosslinkable particles (6) (solid content concentration 10% by mass).

The weight average molecular weight of the entire polymer graft chain per one crosslinkable particle of the above crosslinkable particles (1) to (6) was about 100,000.

<Reference Production Example 1-1> Production of crosslinkable particles (C1) 2-hydroxyethyl methacrylate in which colloidal silica having the halogen group surface modifier prepared in Production Example 1-1 is dispersed at a ratio of 2 wt%. (20 g), Cu(I)Cl (0.032 g), dinonylbipyridine (0.268 g) and ethyl-2-bromoisobutyrate (EBIB:) 0.006 g were placed in a flask and degassed by nitrogen substitution. Then, polymerization was carried out at 70° C. for 24 hours. The obtained particles were gelled.

<Production Example 2-1> Production of acrylic resin for coating agent A reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer, was provided with 280 g of methyl methacrylate, 73 g of 2-hydroxyethyl acrylate, and 125 g of toluene. After the start of heating and reflux, 2.3 g of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was reacted at the reflux temperature of toluene for 8 hours. After that, 74 g of 2-isocyanatoethyl methacrylate was added to carry out an addition reaction. By diluting with toluene, an acrylic resin for coating agent having a solid content of 50 mass% was obtained.

<Production Example 2-2> Production of urethane resin for coating agent In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 120 g of GI-1000 (Nippon Soda hydrogenated polybutadiene polyol) and hydroquinone monomethyl ether (Wako Pure) (Yakuhin Kogyo) 0.04 g, KS-1260 (Sakai Chemical Industry dibutyltin dilaurate) 0.03 g, Desmodur W (Bayer methylenebis(4-cyclohexyl isocyanate)) 20 g, toluene 70 g, While stirring, the temperature was raised to 85 to 90°C using an oil bath. Then, the reaction was continued while stirring for 2.5 hours. After that, the infrared absorption spectrum was measured, the absorption of the isocyanato group was confirmed to have disappeared, the reaction was terminated, 10 g of 2-isocyanatoethylmethacrylate was further added, an addition reaction was carried out, and 80 g of toluene was added. The mixture was stirred and dissolved to obtain a urethane resin for a coating agent having a solid content of 50% by mass.

<Production Example 2-3> Production of Acrylic Resin for Adhesive Adhesive A reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer was charged with 34 g of n-butyl acrylate and 150 g of methyl methacrylate. 2-Hydroxyethyl acrylate (2 g) and toluene (195 g) were charged, and after heating under reflux, azobisisobutyronitrile (0.2 g) was added as a polymerization initiator, and the mixture was reacted at the reflux temperature of toluene for 8 hours. Thereafter, 2 g of 2-isocyanatoethyl methacrylate was added to carry out an addition reaction. By diluting with toluene, an acrylic resin for adhesives having a solid content of 50 mass% was obtained.

<Physical property evaluation>
The physical properties were evaluated by the following methods.
(Adhesion)
A cellotape (registered trademark) peel test was performed on the coating film. The surface after the test was visually observed and evaluated according to the following criteria.
○: No peeling △: Partial peeling ×: Most peeling

(Hot water whitening resistance)
A test piece similar to the adhesion test was immersed in warm water at 50° C. for 7 days, and the change in transmittance (430 nm) with respect to the glass plate was measured.

(Pencil hardness)
The cured coating film applied to the PET film was measured according to JIS-K-5400.

(Initial adhesion)
The obtained pressure-sensitive adhesive sheet was bonded to a SUS304 polishing plate at 23° C. and 50% RH by reciprocating a 2 kg roller once, and 20 minutes after the bonding, was performed according to the method for measuring the pressure-sensitive adhesive force specified in JIS Z 0237. The 180 degree peel strength (N/cm) was measured.

(Heat resistance retention)
The obtained pressure-sensitive adhesive sheet was attached to a stainless steel plate so that the attachment area was 25 mm×25 mm, and a load of 1 kg was applied under predetermined temperature conditions, according to the measuring method of holding force specified in JIS Z 0237. Then, the temperature was measured and the temperature at which it did not fall for one hour or more was defined as the heat resistant holding power.

<Example 1> Production of coating agent composition and cured product thereof 100 g of the acrylic resin for coating agent obtained in the above Production Example 2-1 was crosslinked with the crosslinkable particles (1) obtained in the above Production Example 1-1. 12.5 g, and photopolymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., 2 g of DAROCUR (registered trademark) 1173 were added, and a coating agent composition was added. I got a thing.
The obtained coating agent composition was applied on a PET film (thickness 25 μm) so that the thickness after drying would be 10 μm, and then dried at 105° C. for 3 minutes. After irradiating with an ultraviolet ray of 500 mJ/cm ² , the obtained coating sheet was measured for physical properties such as adhesion, hot water resistance, and pencil height. The results are shown in Table 4.

<Examples 2-6, Comparative Examples 1-2>
A coating agent composition and a coating sheet were produced in the same manner as in Example 1 except that the components were changed as shown in Table 4, and the physical properties were evaluated. The results are shown in Table 4.

<Example 7>
12.5 g of the crosslinkable particles (1) and 2 g of the photopolymerization initiator Irgacure were added to 100 g of the acrylic resin for pressure-sensitive adhesive to obtain a pressure-sensitive adhesive composition. It was applied on a PET film (thickness 25 μm) so that the thickness after drying would be 10 μm, and then dried at 105° C. for 3 minutes. Then, a release film was attached to one surface and pressure-bonded with a roll to obtain a PET film-based pressure-sensitive adhesive sheet. A release film was attached to one surface, and after irradiating with ultraviolet rays of 500 mJ/cm ² , physical properties such as initial adhesive strength and heat resistance were measured. The results are shown in Table 5.

<Example 8, Comparative Examples 3 to 4>
An adhesive composition and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 7 except that the components were changed as shown in Table 5, and the physical properties were evaluated. The results are shown in Table 5.

---- Comparison of performance depending on particle size of crosslinkable particles ----
<Production Example 1-7> Production of crosslinkable particles (7) Crosslinkable particles (7) (solid) were produced in the same manner as in Production Example 1-1 except that colloidal silica having an average particle diameter of 15 nm was used. A concentration of 10% by mass was prepared.

<Production Example 1-8> Production of crosslinkable particles (8) Crosslinkable particles (8) (solid) were produced in the same manner as in Production Example 1-1 except that colloidal silica having an average particle diameter of 450 nm was used. A concentration of 10% by mass was prepared.

<Examples 9 and 10>
An adhesive composition and an adhesive sheet were produced in the same manner as in Example 7 except that the crosslinkable particles were changed as shown in Table 6 below, and the initial adhesive strength and heat resistance were measured. The results are shown in Table 6.

----Comparison of performance depending on the monomer (B) of crosslinkable particles ----
<Production Example 1-9> Production of crosslinkable particles (9) Crosslinkable particles (in the same manner as in Production Example 1-1 except that methyl methacrylate was used instead of butyl acrylate as the monomer (B) ( 9) (solid content concentration 10% by mass) was prepared.

<Production Example 1-10> Production of crosslinkable particles (10) Crosslinkability was the same as in Production Example 1-1 except that 2-ethylhexyl acrylate was used instead of butyl acrylate as the monomer (B). Particles (10) (solid content concentration 10% by mass) were produced.

<Examples 11 and 12>
An adhesive composition and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 7 except that the crosslinkable particles were changed as shown in Table 7 below, and the initial pressure-sensitive adhesive strength and heat resistance were measured. The results are shown in Table 7.

----Comparison of performance due to difference in graft chain molecular weight ----
<Production Example 1-11> Production of crosslinkable particles (11) Methyl methacrylate (13.3 g) in which the colloidal silica having the halogen group surface modifier prepared in Production Example 1-1 is dispersed at a ratio of 2 wt%. , Monomer (B)), Cu(I)Cl (0.32 g), dinonylbipyridine (2.68 g), and ethyl 2-bromoisobutyrate (EBIB; 0.06 g) were placed in a flask and replaced with nitrogen. After degassing by, the mixture was polymerized at 70° C. for 24 hours. Next, 2-hydroxyethyl methacrylate (0.66 g) was added as a monomer (C), degassed by nitrogen substitution, and then polymerized at 70°C for 24 hours to obtain intermediate particles. 2-Isocyanatoethyl methacrylate (0.66 g) is added to the intermediate particles to carry out an addition reaction to obtain crosslinkable particles (11) having an ethylenically unsaturated group at the polymer terminal (solid content concentration 10% by mass). It was The weight average molecular weight of the entire polymer graft chain per particle of the crosslinkable particle (11) was about 10,000.

<Production Example 1-12> Production of crosslinkable particles (12) Methyl methacrylate (20.8 g) in which the colloidal silica having the halogen group surface modifier prepared in Production Example 1-1 was dispersed at a ratio of 2 wt%. , Monomer (B)), Cu(I)Cl (0.0011 g), dinonylbipyridine (0.0095 g) and ethyl 2-bromoisobutyrate (EBIB; 0.00021 g) were placed in a flask and replaced with nitrogen. After degassing by, the mixture was polymerized at 70°C for 24 hours. Then, 2-hydroxyethyl methacrylate (1.03 g) was added as a monomer (C), degassed by nitrogen substitution, and then polymerized at 70° C. for 24 hours to obtain intermediate particles. 2-Isocyanatoethyl methacrylate (1.03 g) is added to the intermediate particles to carry out an addition reaction to obtain crosslinkable particles (12) (solid content concentration 10% by mass) having an ethylenically unsaturated group at the polymer terminal. It was The weight average molecular weight of the entire polymer graft chain per particle of the crosslinkable particle (12) was about 300,000.

<Examples 13 and 14>
An adhesive composition and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 7, except that the cross-linkable particles (11) and (12) were used as the cross-linkable particles, and the initial pressure-sensitive adhesive strength and heat resistance were measured. ..
The results are shown in Table 8.

----Comparison of performance depending on the density of graft chains ----
<Production Example 1-13> Production of crosslinkable particles (13) (modification of BHE on the surface of colloidal silica)
The surface of the silica fine particles was modified with the halogen-based surface modifier by the following procedure. An ethanol dispersion liquid (30 g) in which colloidal silica (manufactured by Nippon Shokubai Co., Ltd., average particle diameter 130 nm) was dispersed at a ratio of 7.7 wt% was added to a mixed liquid of 28% aqueous ammonia solution (25 g) and ethanol (200 ml). .. The mixture was stirred at 40° C. for 2 hours, then the ethanol solution (10 ml) of BHE (2 g) synthesized in Production Example 1-1 was added dropwise, and the mixture was stirred at 40° C. for 18 hours. Then, the colloidal silica having a starting group was recovered by a centrifuge, washed with ethanol and toluene, and then stored in toluene.

(Modification of Monomers (B) to (D) on Colloidal Silica Surface)
Methyl methacrylate (20 g, monomer (B)), Cu(I)Cl (0.032 g), and di-dihydrate, in which the colloidal silica having the halogen group-containing surface modifier prepared above is dispersed at a ratio of 2 wt %, Nonylbipyridine (0.268 g) and ethyl 2-bromoisobutyrate (EBIB; 0.006 g) were placed in a flask, degassed by nitrogen substitution, and then polymerized at 70° C. for 24 hours. Next, 2-hydroxymethyl methacrylate (1 g) was added as a monomer (C), degassed by nitrogen substitution, and then polymerized at 70° C. for 24 hours to obtain intermediate particles. 2-Isocyanatoethyl methacrylate (1 g, compound (D)) was added to the intermediate particles to carry out an addition reaction, and crosslinkable particles (13) having an ethylenically unsaturated group at the polymer terminal (solid content concentration 10% by mass). ) Got. The weight average molecular weight of the crosslinkable particles (13) per particle was about 100,000, and the graft density was 0.8 chains/nm ² .

<Production Example 1-14> Production of crosslinkable particles (14) (modification of BHE on the surface of colloidal silica)
The surface of the silica fine particles was modified with the halogen-based surface modifier by the following procedure. An ethanol dispersion liquid (30 g) in which colloidal silica (manufactured by Nippon Shokubai Co., Ltd., average particle diameter 130 nm) was dispersed at a ratio of 7.7 wt% was added to a mixed liquid of 28% aqueous ammonia solution (5 g) and ethanol (200 ml). .. The mixture was stirred at 40° C. for 2 hours, then the ethanol solution (10 ml) of BHE (2 g) synthesized in Production Example 1-1 was added dropwise, and the mixture was stirred at 40° C. for 18 hours. Then, the colloidal silica having a starting group was recovered by a centrifuge, washed with ethanol and toluene, and then stored in toluene.

(Modification of Monomers (B) to (D) on Colloidal Silica Surface)
Methyl methacrylate (20 g, monomer (B)), Cu(I)Cl (0.032 g), and di-dihydrate, in which the colloidal silica having the halogen group-containing surface modifier prepared above is dispersed at a ratio of 2 wt %, Nonylbipyridine (0.268 g) and ethyl 2-bromoisobutyrate (EBIB; 0.006 g) were placed in a flask, degassed by nitrogen substitution, and then polymerized at 70° C. for 24 hours. Then, 2-hydroxymethyl methacrylate (1 g) was added as a monomer (C), degassed by nitrogen substitution, and then polymerized at 70° C. for 24 hours to obtain intermediate particles.
2-Isocyanatoethyl methacrylate (1 g, compound (D)) is added to the intermediate particles to carry out an addition reaction, and crosslinkable particles (14) having an ethylenically unsaturated group at the polymer terminal (solid content concentration 10% by mass). ) Got. The weight average molecular weight of each crosslinkable particle (14) was about 100,000, and the graft density was 0.2 chains/nm ² .

<Examples 15 and 16>
An adhesive composition and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 7, except that the cross-linkable particles (13) and (14) were used as the cross-linkable particles, and the initial pressure-sensitive adhesive strength and heat resistance were measured. ..
The results are shown in Table 9.

<Comparative Production Example 1-2>
To a three-necked flask equipped with a condenser and a stirrer, 13.6 g of pentaerythritol, 163 g of 2,2-bishydroxymethylpropionic acid, and 0.5 g of p-toluenesulfonic acid were added, and an 145° C. oil bath was added while flowing nitrogen. And reacted for 2 hours to form a homogeneous solution. Then, the mixture was further reacted under reduced pressure (50 mmHg or less, 145° C.) for 2 hours to obtain a dendrimer represented by the following formula (II).

Then, to the obtained dendrimer, 20 g of toluene, 202 g of 2-isocyanatoethyl methacrylate, 0.05 g of di-n-butyltin dilaurate and 0.07 g of hydroquinone were added, and the mixture was reacted at 80° C. for 5 hours to give an ethylenic compound. A dendrimer having unsaturated groups was obtained.

<Comparative Example 5>
An adhesive composition and a pressure-sensitive adhesive sheet were prepared in the same manner as in Example 7, except that the dendrimer having an unsaturated group obtained in Comparative Production Example 1-2 was used instead of the crosslinkable particles (1). It was manufactured, and the initial adhesive strength and heat resistance were measured. The results are shown in Table 10.

Each configuration and the combination thereof in each embodiment are examples, and addition, omission, replacement, and other changes of the configuration can be made without departing from the spirit of the present invention. The present invention is not limited to each embodiment, but is limited only by the scope of the claims.

According to the present invention, it is possible to provide a curable resin composition having excellent heat resistance and a cured product thereof.

DESCRIPTION OF SYMBOLS 1... Curable resin composition, 10... Resin component, 20... Crosslinkable particle, 21... Polymer graft chain, 22... Base particle

Claims (16)

It is seen containing a resin component having an ethylenically unsaturated group, and a crosslinkable particles polymer graft chain is bonded to the surface of a silica particle having an ethylenically unsaturated group, and
The resin component having an ethylenically unsaturated group contains an acrylic resin having an ethylenically unsaturated group as a main component,
The polymer graft chain,
A monomer unit derived from a monomer (B) having neither an isocyanato group, a carboxyl group, a hydroxyl group, nor an epoxy group and having a (meth)acryloyloxy group;
A monomer unit derived from a monomer (C) having a hydroxyl group and one (meth)acryloyl group,
The compound (D) having an isocyanato group and a (meth)acryloyl group has a structure in which an isocyanato group and a hydroxyl group of a monomer unit derived from the monomer (C) are chemically bonded,
The pressure-sensitive adhesive composition , wherein the weight average molecular weight of the entire polymer graft chain per one particle of the crosslinkable particles is 1,000 to 500,000 . The adhesive composition according to claim 1, wherein the density of the polymer graft chains on the surface of the silica particles is 0.05 to 1.2 chains/nm ² . The polymer graft chain uses as a starting point a polymerization initiation group having a structure derived from the compound (A), in which the compound (A) having an alkoxysilyl group and a halogen group is bonded to the surface of the silica particles. The adhesive composition according to claim 1 or 2 . The adhesive composition according to claim 3 , wherein the compound (A) is a compound represented by the following formula (I).

[In formula (I), R ¹ _, R ² , and R ³ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ are each independently an alkyl group having 1 to 3 carbon atoms. Represents, X represents a halogen atom, and n is an integer of 3 to 10. ] The silica particles, a volume average particle diameter is 50% volume cumulative diameter measured (D50) using a laser diffraction particle size distribution analyzer is 10 nm to 1 m, one of claims 1 to 4 one The adhesive composition according to item. The polymer graft chain has, from the silica particle side, a structure derived from the compound (A), a monomer unit derived from the monomer (B), and a monomer unit derived from the monomer (C). The pressure-sensitive adhesive composition according to claim 3, wherein the compound (D) is further bonded to the polymer contained in this order through the hydroxyl group of the monomer (C). The adhesive composition according to claim 6, wherein the monomer unit derived from the monomer (B) and the monomer unit derived from the monomer (C) are continuous. The pressure-sensitive adhesive composition according to claim 1, wherein the monomer (B) is any one selected from butyl acrylate, methyl acrylate, and 2-ethylhexyl acrylate. The monomer (C) is 2-hydroxyethyl methacrylate or 2-hydroxymethyl methacrylate,
The adhesive composition according to claim 1, wherein the compound (D) is 2-isocyanatoethyl methacrylate. The adhesive according to claim 1, wherein the acrylic resin is obtained by reacting a copolymer of n-butyl acrylate, methyl methacrylate and 2-hydroxyethyl acrylate with 2-isocyanatoethyl methacrylate. Agent composition. The pressure-sensitive adhesive composition according to claim 1 , further comprising a photopolymerization initiator. It is seen containing a resin component having an ethylenically unsaturated group, and a crosslinkable particles polymer graft chain is bonded to the surface of a silica particle having an ethylenically unsaturated group, and
The resin component having an ethylenically unsaturated group, as the main component, at least one resin selected from the group consisting of an acrylic resin having an ethylenically unsaturated group and a urethane resin having an ethylenically unsaturated group,
The polymer graft chain,
A monomer unit derived from a monomer (B) having neither an isocyanato group, a carboxyl group, a hydroxyl group, nor an epoxy group and having a (meth)acryloyloxy group;
Derived from a monomer (C) having at least one reactive functional group (i) selected from the group consisting of isocyanato group, carboxyl group, hydroxyl group, and epoxy group and one (meth)acryloyl group And a monomer unit,
The reactive functional group (ii) of the compound (D) having a reactive functional group (ii) capable of reacting with the reactive functional group (i) and a (meth)acryloyl group, and the monomer ( C) has a structure in which the reactive functional group (i) of the monomer unit derived from
A paper treating agent or a fiber treating agent in which the weight average molecular weight of the entire polymer graft chain per one particle of the crosslinkable particles is 1,000 to 500,000. The monomer (C) is any one selected from 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid, 2-isocyanatoethyl methacrylate, and 2-hydroxyethyl acrylate, and the monomer (D 13) is any one selected from 2-isocyanatoethyl methacrylate, methacrylic acid, glycidyl methacrylate and 2-hydroxyethyl methacrylate, The paper treating agent or fiber treating agent according to claim 12. It is seen containing a resin component having an ethylenically unsaturated group, and a crosslinkable particles polymer graft chain is bonded to the surface of a silica particle having an ethylenically unsaturated group, and
The resin component having an ethylenically unsaturated group, as the main component, at least one resin selected from the group consisting of an acrylic resin having an ethylenically unsaturated group and a urethane resin having an ethylenically unsaturated group,
The polymer graft chain,
A monomer unit derived from a monomer (B) having neither an isocyanato group, a carboxyl group, a hydroxyl group, nor an epoxy group and having a (meth)acryloyloxy group;
Derived from a monomer (C) having at least one reactive functional group (i) selected from the group consisting of isocyanato group, carboxyl group, hydroxyl group, and epoxy group and one (meth)acryloyl group And a monomer unit,
The reactive functional group (ii) of the compound (D) having a reactive functional group (ii) capable of reacting with the reactive functional group (i) and a (meth)acryloyl group, and the monomer ( C) has a structure in which the reactive functional group (i) of the monomer unit derived from
A coating agent composition in which the weight average molecular weight of the entire polymer graft chain per one particle of the crosslinkable particles is 1,000 to 500,000 . The monomer (C) is any one selected from 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid, 2-isocyanatoethyl methacrylate, and 2-hydroxyethyl acrylate, and the monomer (D 15. The coating agent composition according to claim 14, wherein) is any one selected from 2-isocyanatoethyl methacrylate, methacrylic acid, glycidyl methacrylate, and 2-hydroxyethyl methacrylate. A coating method comprising: a step of applying the coating agent composition according to claim 14 or 15 onto a substrate; and a step of curing the coating agent composition applied onto the substrate.

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