WO2016199717A1 - Curable resin composition including crosslinkable particles - Google Patents

Abstract

This curable resin composition includes: a resin component having ethylenically unsaturated groups; and crosslinkable particles obtained by bonding, to surfaces of base particles, polymer graft chains having ethylenically unsaturated groups. It is preferable that the density of the polymer graft chains on the surface of each of the base particles be 0.05-1.2 chains/nm².

Description

Curable resin composition containing crosslinkable particles

The present invention relates to a curable resin composition containing crosslinkable particles.
This application claims priority on June 12, 2015 based on Japanese Patent Application No. 2015-119208 for which it applied to Japan, and uses the content here.

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 the molecule, such as resin hardness, heat resistance, water resistance, solvent resistance, moisture resistance, etc. For the purpose of improving film physical properties, the resin composition may be cured using a crosslinking agent to be used as a coating agent, an adhesive, a fiber treatment agent, or the like.
As a crosslinking agent for resins having these functional groups, crosslinking agents capable of reacting with the functional groups are known. For example, when using resin which has a carboxy group as resin, the crosslinking agent which has a functional group which can react with a 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 properties. Up to now, attempts have been made to improve film properties by improving the structure of a resin having a reactive functional group or by polyfunctionalizing a crosslinking agent. For example, Patent Document 1 discloses an acrylic pressure-sensitive adhesive having a composition obtained by blending a base polymer with both a photo-crosslinking agent capable of UV crosslinking and a latent curing agent capable of heat crosslinking.
In patent document 1, since a characteristic cannot be fully expressed only by heat crosslinking of a reactive functional group, a crosslinking agent having a structure having a double bond is also used in combination.
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 a curable resin composition excellent in heat resistance and a cured product thereof.

In order to achieve the above object, the present invention provides the following means.
[1] A curable resin composition comprising a resin component having an ethylenically unsaturated group and crosslinkable particles in which a polymer graft chain having an ethylenically unsaturated group is bonded to the surface of the base particle.
[2] The curable resin composition according to [1], wherein the density of the polymer graft chains on the surface of the base particles is 0.05 to 1.2 strands / nm ² .
[3] The polymer graft chain is a single molecule 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. Curable resin composition as described in said [1] or [2] containing the monomer unit derived from a monomer (C).
[4] A reactive functional group in which 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 ( The reactive functional group (ii) of the compound (D) having ii) and an ethylenically unsaturated group is chemically bonded to the reactive functional group (i) of the monomer unit derived from the monomer (C). The curable resin composition according to [3], which has a structure.
[5] The 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, an isocyanato group, The curable resin composition according to [4], which is a combination of a hydroxyl group, a combination of an isocyanate group and a carboxyl group, or a combination of a carboxyl group and an isocyanato group.

[6] The polymer graft chain starts from a polymerization initiating 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 [1] to [5] above.
[7] The curable resin composition according to [6], wherein the compound (A) is a compound represented by the following formula (I).

[In the formula (I), R ¹ _, R ² and R ³ each independently represents 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. 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 the monomer (B) having no isocyanato group, carboxyl group, hydroxyl group, and epoxy group and having an ethylenically unsaturated group The curable resin composition according to any one of [1] to [7].
[9] The curable resin composition according to [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 the above [1] to [9], which contains at least one kind of 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 particle size distribution analyzer. Curable resin composition as described in any one of these.
[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 [1] to [13], wherein the curable resin composition is a resin particle selected from the group consisting of:
[15] The curable resin composition according to any one of [1] to [14], further including a photopolymerization initiator.
[16] A coating agent comprising the curable resin composition according to any one of [1] to [15].
[17] An 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, a curable resin composition having excellent heat resistance and a cured product thereof can be provided.

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 an 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. Particles 20 (FIG. 1).

<Resin component having an 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, a 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. 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. An acrylic resin acrylate is mentioned as an acrylic resin which has an ethylenically unsaturated group. Urethane acrylate is mentioned as a urethane resin which has an ethylenically unsaturated group.
Specific examples of the acrylic resin having an ethylenically unsaturated group include compounds having an isocyanate group and an ethylenically unsaturated group at the hydroxyl group of a copolymer of methyl methacrylate and hydroxyethacrylate, specifically 2-isocyanatoethyl. What reacted with methacrylate etc. is mentioned.

Specific examples of monomers having an ethylenically unsaturated group in the molecule include dienes such as butadiene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and 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 ( ) Acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl ( (Meth) acrylate, 5-ethylnorbornyl (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-dimethyl) (Meth) acrylic acid such as mino) propyl (meth) acrylate, glyceryl mono (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol mono (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate Esters; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic (Meth) acrylic amides such as acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride , Vinyl fluoride, vinylidide fluoride , N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene and other vinyl compounds; styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; diethyl citraconic acid, maleic acid Unsaturated dicarboxylic acid diesters such as diethyl, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; (meth) Unsaturated monobasic acids such as acrylic acid, crotonic acid, cinnamic acid; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having alicyclic epoxy and lactone adduct thereof [eg, Daicel Chemical Industries Cyclomer A2 manufactured by 00, M100], 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate mono (meth) acrylate, epoxidized dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meta ) Radical polymerizable monomers having an epoxy group such as epoxidized acrylate; unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride. These can 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 that one kind of resin is contained as a main component.
The acrylic resin is a resin having a monomer unit derived from an acrylic ester or a methacrylic 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, and more preferably 90 mol% or more of a monomer unit derived from an acrylic ester or methacrylic 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 that form urethane bonds, more preferably 80 mol% or more, and even more preferably 90 mol% or more.
“Containing resin as a main component” means containing at least one of the resins in an amount of 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more. More preferably, the content is 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 in the crosslinkable particle 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.

Examples of inorganic particles include silicon oxide particles such as silica particles, noble 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, Fe particles, oxide particles or nitriding thereof Examples include particles of objects. Among 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). In particular, resin particles such as acrylic resin, polystyrene resin, styrene-acrylic copolymer resin, urethane resin, and vinyl acetate resin can be cited. Among them, particles of acrylic resin, styrene-acrylic copolymer resin, or urethane resin are used. preferable.

From the viewpoint that the production process is simple compared to organic particles, inorganic particles are more preferable.

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 strands / nm ² from the viewpoint of excellent dispersibility and crosslinking efficiency of the particles. More preferably, the numerical range is from 1 to 1.0 strands / nm ² , and further preferably from 0.3 to 0.7 strands / nm ² .
The density of the polymer graft chains on the surface of the base particles can be determined by the measurement method described in the examples described later.

The average particle diameter of the base particles is preferably in a numerical range of 10 nm to 1 μm, more preferably in a numerical range of 10 nm to 700 nm, from the viewpoint of excellent particle dispersibility and crosslinking efficiency. A numerical range is more preferable, and a 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, the graft chain density is increased when the graft polymerization is performed from the particle surface, so that the density of the graft chain is increased. Is preferable because the film properties such as the hardness of the resin tend to be good. When the particle diameter is 1 μm or less, when used in a resin composition, there is a tendency that 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 particle size distribution measuring device.

The weight average molecular weight of the entire polymer graft chain per crosslinkable particle is preferably 1,000 to 500,000, more preferably 10,000 to 400,000, from the viewpoint of excellent dispersibility and crosslinking efficiency. More preferably, 40,000 to 300,000. When the weight average molecular weight is 1,000 or more, the stability of the crosslinkable particles tends to be improved. In the case of 500,000 or less, the possibility that the viscosity of the dispersion becomes extremely high in the organic solvent is reduced, and the handling tends to be good.
In addition, the weight average molecular weight of the whole polymer graft chain per one crosslinkable particle can be determined by the measurement method described in the examples described later.

<Polymer graft chain having an ethylenically unsaturated group>
The crosslinkable particle in the present invention has a polymer graft chain having an ethylenically unsaturated group on the surface of the base particle. The polymer graft chain is a polymer chain (polymer) and can be formed by extending from the surface of the base particle by a polymerization reaction.
The ethylenically unsaturated group in the polymer graft chain has a function of acting as a crosslinking agent by crosslinking the resin components having an ethylenically unsaturated group.

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

As long as the polymer graft chain has an ethylenically unsaturated group in the polymer graft chain, the monomer constituting the polymer graft chain is not particularly limited. The chain preferably includes a structure derived from the compound (D) having an ethylenically unsaturated group and a reactive functional group (ii) described later. More preferably, by including a monomer unit derived from the 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 includes a monomer unit derived from the monomer (B). More preferably, it includes a structure derived from the compound (A).
In the present specification, “derived” means that the monomer or compound has undergone a structural change necessary for polymerization.
When the polymer graft chain includes all reactants of the compound (A), the monomer (B), the monomer (C), and the compound (D), the polymer graft chain is from the base particle side, In addition to the structure derived from the compound (A), the monomer unit derived from the monomer (B), and the monomer unit derived from the monomer (C) in this order, the monomer (C) It is preferable that the compound (D) is bonded via the reactive functional group (i). The polymer graft chain is obtained by reacting the base particles of the crosslinkable particles in the order of the compound (A), the monomer (B), the monomer (C), and the compound (D). 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 constituted in this order, the same kind of units or structures may be continuous as long as the order is maintained, and any other structure is added. It may be a thing.

<Compound (A)>
The polymer graft chain starts from a polymerization initiating 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. It is preferable. In addition, it is preferable that a compound (A) does not have an ethylenically unsaturated group in a molecule | numerator.
In the crosslinkable particle, the compound (A) is preferably contained in a form in which an alkoxysilyl group is directly bonded to the surface of the base particle.

When the compound (A) polymerized as a structural 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. Since the space between the particle surface and the ethylenically unsaturated group can be appropriately set, the dispersibility of the crosslinkable particles becomes good, which is preferable.

Examples of the compound (A) having an alkoxysilyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. And a terminal double bond such as 3-acryloxypropyltrimethoxysilane to which a halogen such as bromine, chlorine or iodine is added. Of these, 3-methacryloxypropyltrimethoxysilane is preferable, and bromine is preferable as the halogen.

Compound (A) may be used alone or in combination of two or more.

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 inorganic particles is simple.

In the formula (I), R ¹ _, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. R ⁴ and 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 among them, Br is preferable. n is an integer of 3 to 10.

In the present specification, the “alkyl group” means a monovalent group generated by losing one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and is generally represented by CnH _{2n + 1} —. Where n is a positive integer. The alkyl group can be linear or branched. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

In the 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 the formula (I), the (CH ₂ ) n moiety has a role as a spacer.

The compound represented by the 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 comprises monomer units derived from a monomer (B) having no isocyanato group, carboxyl group, hydroxyl group, and epoxy group and having an ethylenically unsaturated group. It is preferable to contain.
In the monomer (B), the ethylenically unsaturated group of the monomer (B) is preferably living radically polymerized starting from the halogen terminal of the compound (A) bonded 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, the distance from the structure derived from the compound (D) described later on the surface of the base particle should be appropriately set. Therefore, the dispersibility of the crosslinkable particles becomes 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 derivatives, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, ethylene, propylene, butylene, isobutylene, etc. Among them, methyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferable. Of these, 2-ethylhexyl acrylate or butyl acrylate is preferable, and butyl acrylate is preferable. One type of monomer (B) 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 is a single molecule 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 combined with the monomer unit derived from the monomer (B). The monomer unit derived from the monomer (C) is such that the ethylenically unsaturated group of 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 end is an ethylenically unsaturated group due to the ethylenically unsaturated group of the monomer (B). The form which the saturated group has couple | bonded is mentioned.

The polymer graft chain according to the present invention is a reactive functional group (i) 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. The reactive functional group (ii) of the compound (D) having ii) and an ethylenically unsaturated group is chemically bonded to the reactive functional group (i) of the monomer unit derived from the monomer (C). It preferably has a structure.
Compound (D) is a 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). A form in which the reactive functional group (ii) of the compound (D) is bonded is preferred.
In addition, the ethylenically unsaturated group which a compound (D) has may be an ethylenically unsaturated group which a polymer graft chain has.

As the reactive functional group (i) or (ii), the monomer (C) or compound (D) having an isocyanato group includes 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate. These are preferable in that the reaction conditions for bonding the compound (D) and the monomer (C) can be carried out at a low temperature and in a short time. As such an isocyanato group-containing ethylenically unsaturated monomer, only one type or a plurality of types may be included in the polymer graft chain as the monomer (C). Similarly, only one type of isocyanate group-containing ethylenically unsaturated monomer may be contained in the polymer graft chain as the compound (D), or a plurality of types may be contained.

As the reactive functional group (i) or (ii), the monomer (C) or compound (D) having a carboxyl group includes 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, metal salts thereof, and ammonium salts. From the viewpoint of polymerization stability, the monomer (C) and the compound (D) are preferably acrylic acid, methacrylic acid, maleic acid, and maleic anhydride. Such a carboxyl group-containing ethylenically unsaturated monomer may contain only one type or a plurality of types as the monomer (C) in the polymer graft chain. Similarly, only one type of carboxyl group-containing ethylenically unsaturated monomer may be included in the polymer graft chain as the compound (D), or a plurality of types may be included.

As the reactive functional group (i) or (ii), the hydroxyl group-containing monomer (C) or compound (D) includes 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, Polytetramethylene glycol Bruno methacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, and the like. As the monomer (C) and the compound (D), hydroxyethyl acrylate and hydroxyethyl methacrylate are preferable from the viewpoint of polymerization stability. As such a hydroxyl group-containing ethylenically unsaturated monomer, only one type or a plurality of types may be contained in the polymer graft chain as the monomer (C). Similarly, only one kind of hydroxyl group-containing ethylenically unsaturated monomer may be contained in the polymer graft chain as the compound (D), or a plurality of kinds may be contained.

As the reactive functional group (i) or (ii), the monomer (C) or compound (D) having an epoxy group includes glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3 , 4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like. The monomer (C) and the compound (D) are preferably glycidyl methacrylate from the viewpoint of polymerization stability. As such a glycidyl group-containing ethylenically unsaturated monomer, only one type or a plurality of types may be contained in the polymer graft chain as the monomer (C). Similarly, only one type of glycidyl group-containing ethylenically unsaturated monomer may be included in the polymer graft chain as the compound (D), or a plurality of types may be included.

<Combination of reactive functional group (i) or (ii)>
In the present invention, when the polymer graft chain contains both of the monomers (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 “2” carboxyl group / epoxy group combination is more preferable because the time required for the reaction is shorter than the “3” carboxyl group / isocyanato group combination. The “1” hydroxyl / isocyanato group combination is most likely to proceed among the “2” to “4” combinations, and the reaction proceeds at a lower temperature than the “2” to “4” combinations. In addition, it is particularly preferable in that the time required for the reaction is short and the bonding step is easy.

The curable resin composition of the present invention preferably contains 0.1 to 100 parts by mass of crosslinkable particles 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 still more 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 range of 0.1 to 50% by mass, and in the range of 0.2 to 40% by mass in the curable resin composition. The content is more preferably in the range of 0.5 to 30% by mass, still more preferably 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 the crosslinkable particles can be efficiently crosslinked.

The curable resin composition of the present invention preferably contains a resin component in the range of 10 to 99.9% by mass in the curable resin composition, and more preferably in the range of 20 to 80% by mass. More preferably, it is contained in the range of 30 to 70% by mass. By containing the content of the resin component in the above numerical range, the adhesion, adhesiveness, 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 ethylenically unsaturated groups of the crosslinkable particles in the curable resin composition is from 0.5 to the number of moles of ethylenically unsaturated groups of the resin component. The molar amount is preferably 50 times, more preferably 1 to 30 times, and even more preferably 2 to 20 times. By containing the number of moles of the ethylenically unsaturated group of the crosslinkable particle within the above numerical range, it is possible to efficiently crosslink.
When the polymer graft chain is a polymer containing a monomer unit or structure derived from a compound or monomer of the compound (A), the monomer (B), the monomer (C), and the compound (D) Examples of the ratio of each unit or structure in the polymer graft chain to the number of moles X of the compound (A) include the following.
Monomer (B): The molar amount is preferably 1 to 5000 times, more preferably 100 to 4500 times, and even more preferably 500 to 4000 times.
Monomer (C): The molar amount is preferably 1 to 1000 times, more preferably 10 to 800 times, and even more preferably 50 to 500 times.
The molar amount of the compound (D) is preferably 1 to 1000 times, more preferably 10 to 800 times, and even more preferably 50 to 500 times.

<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 necessarily an essential component of the polymerizable composition, but by using this in combination with the curability, the film strength of the formed coating film and the adhesion to the substrate can be improved. .
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, glycerol mono (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid (Meth) acrylate compounds such as half (meth) acrylates of derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene; carboxylic acid esters such as vinyl acetate and vinyl propionate Can be mentioned. 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-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 (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. and 2-bidoxyethyl (meth) acrylate (Meth) acrylate compounds such as tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallylphthalate and diallylbenzenephosphonate; dicarboxylic acid ester compounds such as divinyl adipate; Examples include allyl cyanurate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, and a condensate of polyhydric alcohol and N-methylol (meth) acrylamide. 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 a photopolymerization initiator that generates radicals and / or a thermal polymerization initiator.
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 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 kinds of photopolymerization initiators include oligomers of 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one and 2,4,6-trimethyl. And a mixture of benzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzophenone.

Examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbo Nate, 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.

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 there is too much content of a polymerization initiator, the storage stability of curable resin composition may fall or it may color. Moreover, when there is too much content of a polymerization initiator, the bridge | crosslinking at the time of obtaining hardened | cured material will advance rapidly, and problems, such as a crack, may generate | occur | produce. Moreover, when there are too few addition amounts of a polymerization initiator, it will become difficult to harden | cure the curable resin composition.

<Other ingredients>
In addition to the above components, the curable resin composition of the present invention includes a polymerization inhibitor and a leveling agent as necessary, as long as the viscosity of the composition and the properties of the cured product, such as transparency and heat resistance, are not impaired. , Antioxidants, ultraviolet absorbers, infrared absorbers, light stabilizers, pigments, fillers such as other inorganic fillers, other modifiers, and the like. The curable resin composition of this invention may contain the crosslinking agent which does not have a particle structure as needed other than the said component. The particle structure is the base particle. In the curable resin composition of this invention, the solvent normally used for the resin composition 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. 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, the above-described one or more components so 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 leveling agents include polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, and polyether-modified. Examples thereof include methylalkylpolysiloxane copolymer. 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, bengara, 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 particle in which the polymer graft chain according to the present invention is bonded to the surface of the base particle can be produced, for example, through the following steps.
a) a step of reacting the base particle with the compound (A) to bond a chain having a terminal halogen group to the surface of the base particle b) a step of living radical polymerization of the terminal halogen and the monomer (B) c ) Step of living polymerizing monomer (C) from the polymerization terminal of radical polymerization of monomer (B) d) Polymer graft having reactive functional group (i) of monomer (C) as terminal A step of reacting a reactive functional group (ii) of the compound (D) with a chain and introducing an ethylenically unsaturated group into the terminal of the polymer graft chain

<< Step a >>
As a method for producing a polymer graft chain, it is preferable that the compound (A) is first bonded to the surface of the base particle so that the terminal is in a halogen state, and then the polymer graft chain is grown from that point. In this case, a crosslinkable particle having a higher density of polymer graft chains on the particle surface than a production method in which a polymer chain is first prepared with the compound (A) and another monomer and directly bonded to the base particle. There is a feature that can be obtained.

As the base particles to be reacted with the compound (A), it is preferable to use a dispersion obtained 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).

There is no restriction | limiting in particular as a method of mixing a compound (A) and base particle. For example, the method of mixing a compound (A) and base particles at room temperature using mixers, such as a mixer, a ball mill, and 3 rolls, is mentioned. Alternatively, a method may be used in which the compound (A) is placed in a reaction vessel, and base particles are added and mixed while the compound (A) is continuously stirred in the reaction vessel to prepare a dispersion.
A catalyst and, if necessary, other components are added to the dispersion and mixed to perform a condensation reaction. 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 condensation reaction to proceed efficiently. The temperature of the liquid mixture is preferably 20 ° C. or higher, and more preferably 30 ° C. or higher, in order to perform the step of removing alcohol or water generated by the reaction in a short time.

<< Process b >>
In the step of living radical polymerization of the monomer (B) with the terminal halogen as the starting point, the monomer (B) is added to a liquid containing base particles to which a chain having a halogen group at the terminal is obtained. B), a catalyst, and other components as necessary 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 in which a graft chain in which the terminal obtained in the step b is a polymerization terminal of radical polymerization is bonded. Subsequently, the monomer (C) is added to and mixed with the liquid containing the monomer, and the monomer (C) is polymerized starting from the polymerization terminal of the radical polymerization. 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.

<< Step 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 reactive functional group (i) and the compound are mixed by adding and mixing the compound (D) and other components as necessary to the liquid containing the base particles to which the chain as the functional group (i) is bonded. (D) is reacted to obtain crosslinkable particles.
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)
A curable resin composition can be obtained by mixing the crosslinkable particles obtained in the step d, a resin component having an ethylenically unsaturated group, and, if necessary, other optional components.

You may filter with respect to curable resin composition. This filtration is performed in order to remove foreign substances such as dust contained in the curable resin composition. There is no restriction | limiting in particular in the filtration method. As a filtration method, it is preferable to use a pressure filtration method using, for example, a membrane type or cartridge type filter.
The curable resin composition of the present invention is obtained through the above steps.

≪Hardened product≫
The cured product of the present invention is obtained by curing the curable resin composition of the present invention.

[Method for producing cured product]
The manufacturing method of the hardened | cured material of this invention has the process of hardening the curable resin composition of this invention.

When the curable resin composition is cured by irradiation with active energy rays such as ultraviolet rays, a photopolymerization initiator is added as a polymerization initiator to the composition containing the crosslinkable particles obtained in the above step d. Moreover, when hardening a curable resin composition by heat processing, a thermal polymerization initiator is added as a polymerization initiator to the composition containing the crosslinkable particle obtained in said process d.

In order to form the cured product of the present invention, for example, the curable resin composition of the present invention is applied to a substrate such as a glass plate, a plastic plate, a metal plate or a silicon wafer to form a coating film or the like. A method such as injection into a mold or the like can be used. Thereafter, for example, the coating film is obtained by irradiating the coating film with active energy rays and / or heating and curing the coating film.

Examples of the application method of the curable resin composition include application by a bar coater, applicator, die coater, spin coater, spray coater, curtain coater or roll coater, application by screen printing, and application by 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 film thickness of the coating film obtained after the curing treatment by irradiation with active energy rays and / or heating is 1 μm to 10 mm, and 10 to 1000 μm. The amount is more preferred.

As the active energy ray used for curing the curable resin composition, an electron beam or light in the ultraviolet to infrared wavelength range is preferable. As the light source, for example, an ultra-high pressure mercury light source or a metal halide light source can be used in the case of ultraviolet rays. Moreover, as a light source, if it is visible light, a metal halide light source or a halogen light source can be used, for example. As the light source, for example, a halogen light source can be used in the case of infrared rays. In addition, for example, a light source such as a laser or an LED can be used.

The irradiation amount of the active energy ray is appropriately set according to the type of light source, the film thickness of the coating film, and the like.
Moreover, after irradiating an active energy ray and hardening a curable resin composition, you may heat-process (annealing) as needed, and may further harden | 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., 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 lengthen the heating time, and the economy tends to be lacking. If the heating temperature exceeds the above range, energy costs are required, and further, the heating temperature rise time and the temperature drop time are required. The heating time is appropriately set according to the heating temperature, the film thickness of the coating film, and the like.

After curing the curable resin composition by thermal polymerization, 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 is obtained through the above steps.

Since the curable resin composition of this embodiment contains multifunctional crosslinkable particles, the cured product of the curable resin composition of this embodiment has excellent hardness, heat resistance, and water resistance. ing. Therefore, the curable resin composition of this embodiment can be preferably used as, for example, a coating agent such as a film, plastic, or metal, an adhesive, a paper treatment agent, or 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 the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

(Average molecular weight)
The weight average molecular weight and number average molecular weight of the polymer graft chain in the present invention and in the present specification are determined by gel permeation after separating the polymer graft chain from the base particle by treating the crosslinkable particles with hydrogen fluoride. Using a chromatography (Shodex GPC System-11 manufactured by Showa Denko KK), measurement is performed at room temperature under the following conditions, and a standard polystyrene calibration curve can be used.
Column: Showa Denko KF-806L
Column temperature: 40 ° C
Sample: 0.2 mass% tetrahydrofuran solution of a reactive functional group-containing styrene elastomer 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 measuring device TGDTA (manufactured by SII, TG / DTA6200). The measurement was performed by raising the temperature of the crosslinkable particles from 30 ° C. to 700 ° C. at a rate of 20 ° C./min under atmospheric conditions. Thus, the weight of the polymer grafted on the surface of the base particle was determined, and the weight was calculated using the specific surface area of the base particle and the number average molecular weight of the graft polymer.
[Density of graft chain (main chain / nm ² )] =
((Polymer weight per gram of base particle [g] / number average molecular weight of graft polymer) × 6.02 × 10 ²³ ) / (specific surface area of base particle [m ² / g] × 10 ^{^} 18)

<Production Example 1-1> Production of crosslinkable particles (1) [Modification of halogen group-containing surface modifier 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) is ice-cooled, and 2-bromoisobutyryl bromide (63 ml) is added dropwise thereto. did. Thereafter, the reaction solution was stirred at 0 ° C. for 3 hours, and further stirred at room temperature for 10 hours. The reaction solution was filtered, and the filtrate was concentrated. The obtained solution was diluted with chloroform (500 ml), and 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) in a yield. Obtained at 90%. As the second stage, BPH (40 g), toluene (500 ml), triethoxysilane (500 ml), and karsted catalyst (450 ml) were put into a two-necked flask in that order, and the mixture was kept under argon atmosphere at room temperature for 12 hours. Stir. Toluene and unreacted triethoxysilane were removed under reduced pressure, and BHE was synthesized almost quantitatively.

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

(Modification of monomers (B) to (D) on the surface of colloidal silica)
Butyl acrylate (20 g, monomer (B)), Cu (I) Cl (0.032 g), disulfide dispersed in a proportion of 2% by mass using colloidal silica having a polymerization initiating group prepared above as base particles. 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, each of the monomers (C) (1 g) shown in Table 2 below was added, degassed by nitrogen substitution, polymerized at 70 ° C. for 24 hours, and each having a different functional group at the polymer terminal. Particles were obtained. Next, air was introduced, the compound (D) shown in Table 2 below was added to the intermediate particles, and the reaction was performed under atmospheric conditions, so that crosslinkable particles (1 ) (Solid content concentration 10% by mass).
An example of the structural formula of the graft chains of the obtained component parts (B) to (D) is shown below (wherein, l, m and n each represents an arbitrary integer of 1 or more).

<Production Example 1-2> Production of crosslinkable particles (2) Monomer (C) and compound (D) used in Production Example 1-1 above are represented by monomers (C) shown in Table 2 below, respectively. In the same manner as in Production Example 1-1 except that the compound (D) was used, crosslinkable particles (2) (solid content concentration of 10% by mass) were obtained.

<Production Example 1-3> Production of crosslinkable particles (3) Monomer (C) and compound (D) used in Production Example 1-1 above are represented by monomers (C) shown in Table 2 below, respectively. In the same manner as in Production Example 1-1 except that the compound (D) was used, a crosslinkable particle (3) (solid content concentration of 10% by mass) was obtained.

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

<Production Example 1-5> Production of crosslinkable particles (5) Monomer (C) and compound (D) used in Production Example 1-1 above are represented by monomers (C) shown in Table 2 below, respectively. In the same manner as in Production Example 1-1 except that the compound (D) was used, crosslinkable particles (5) (solid content concentration of 10% by mass) were obtained.

<Production Example 1-6> Production of Crosslinkable Particle (6) Modification of the ethylenically unsaturated double bond on the surface of the colloidal silica particle was carried out by the following procedure. An ethanol dispersion (30 g) in which colloidal silica (manufactured by Nippon Shokubai Co., Ltd., average particle size 130 nm) is dispersed at a rate of 7.7 wt% is mixed into a mixed solution of 28% aqueous ammonia (13.9 g) and ethanol (200 ml). added. The mixture was stirred at 40 ° C. for 2 hours, and then an ethanol solution (10 ml) of 3-methacryloxypropyltrimethoxysilane (2 g) was added dropwise and stirred at 40 ° C. for 18 hours. Thereafter, the colloidal silica in which the ethylenically unsaturated double bond was modified was recovered by a centrifuge, washed with ethanol and toluene, and then stored in toluene.
In a reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer, the colloidal silica modified with the ethylenically unsaturated double bond prepared above is dispersed 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 to reflux, azobisisobutyro was used as a polymerization initiator. 0.2 g of nitrile was added and reacted at the reflux temperature of toluene for 8 hours. Thereafter, 2-isocyanatoethyl methacrylate (0.5 g, compound (D)) was added and an addition reaction was carried out to obtain crosslinkable particles (6) (solid content concentration 10% by mass).

The weight average molecular weight of the entire polymer graft chain per one of the 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 a 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. Thereafter, 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 charged with 280 g of methyl methacrylate, 73 g of 2-hydroxyethyl acrylate and 125 g of toluene. Then, 2.3 g of azobisisobutyronitrile was added as a polymerization initiator after the start of heating and refluxing, and the mixture was reacted at the reflux temperature of toluene for 8 hours. Thereafter, 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% by 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 (hydrogenated polybutadiene polyol manufactured by Nippon Soda), hydroquinone monomethyl ether (Wako Pure) 0.04 g of Yakuhin Kogyo Co., Ltd. 0.03 g of KS-1260 (dibutyltin dilaurate manufactured by Sakai Chemical Industry), 20 g of Desmodur W (Methylenebis (4-cyclohexylisocyanate) manufactured by Bayer), and 70 g of toluene. While stirring, the temperature was raised to 85 to 90 ° C. using an oil bath. Thereafter, the reaction was continued with stirring for 2.5 hours. Thereafter, the infrared absorption spectrum was measured, and it was confirmed that the absorption of the isocyanato group had disappeared. Then, the reaction was completed, 10 g of 2-isocyanatoethyl methacrylate was added, an addition reaction was performed, and 80 g of toluene was added. The mixture was dissolved by stirring to obtain a urethane resin for coating agent having a solid content of 50% by mass.

<Manufacture example 2-3> Manufacture of acrylic resin for adhesives 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, 150 g of methyl methacrylate, 2 g of 2-hydroxyethyl acrylate and 195 g of toluene were charged, and after heating to reflux, 0.2 g of azobisisobutyronitrile was added as a polymerization initiator and 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 adhesive having a solid content of 50% by mass was obtained.

<Physical property evaluation>
The physical properties were evaluated by the following methods.
(Adhesion)
A cellophane (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

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

(Pencil hardness)
The measurement was performed based on JIS-K-5400 with a cured coating film applied to a PET film.

(Initial adhesive strength)
20 minutes after bonding the obtained adhesive sheet to a SUS304 polishing plate at 23 ° C. and 50% RH by reciprocating a 2 kg roller in accordance with the method for measuring the adhesive strength defined in JIS Z 0237 180 degree peel strength (N / cm) was measured.

(Heat resistant holding power)
The obtained pressure-sensitive adhesive sheet was affixed to a stainless steel plate so that the bonding area was 25 mm × 25 mm, applied with a load of 1 kg under a predetermined temperature condition, and in accordance with the measuring method for holding force defined in JIS Z 0237. The temperature at which the sample was not dropped for 1 hour or more was defined as the heat resistant holding force.

<Example 1> Production of coating agent composition and cured product thereof A crosslinkable particle (1) obtained in Production Example 1-1 was added to 100 g of the acrylic resin for coating agent obtained in Production Example 2-1. 12.5 g and 2 g of photopolymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., DAROCUR (registered trademark) 1173) were added to form a coating agent composition I got a thing.
The obtained coating agent composition was coated on a PET film (thickness 25 μm) so that the thickness after drying was 10 μm, and then dried at 105 ° C. for 3 minutes. After irradiating with 500 mJ / cm ² of ultraviolet rays, 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 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 physical properties were evaluated. The results are shown in Table 4.

<Example 7>
12.5 g of crosslinkable particles (1) and 2 g of photopolymerization initiator Irgacure were added to 100 g of acrylic resin for adhesives to obtain an adhesive composition. It coated so that the thickness after drying might be set to 10 micrometers on PET film (25 micrometers in thickness), and it dried at 105 degreeC after that for 3 minutes. Next, a release film was bonded to one side and pressure-bonded with a roll to obtain a PET film base material pressure-sensitive adhesive sheet. A release film was bonded to one side and irradiated with ultraviolet rays of 500 mJ / cm ² , and then physical properties of the initial adhesive strength and heat resistance were measured. The results are shown in Table 5.

<Example 8, Comparative Examples 3 to 4>
Except having changed the component as Table 5, the adhesive composition and the adhesive sheet were manufactured similarly to Example 7, and physical-property evaluation was performed. The results are shown in Table 5.

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

<Examples 9 and 10>
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 6 below, and the initial pressure-sensitive adhesive force and heat-resistant holding force were measured. The results are shown in Table 6.

---- Comparing the performance of different crosslinkable particle monomer (B) ----
<Production Example 1-9> Production of crosslinkable particles (9) Crosslinkable particles (9) were produced in the same manner as in Production Example 1-1 except that methyl methacrylate was used in place of butyl acrylate as the monomer (B). 9) A solid content concentration of 10% by mass was prepared.

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

<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 force and heat resistant holding force were measured. The results are shown in Table 7.

---- Comparison of performance due to differences in graft chain molecular weight ----
<Production Example 1-11> Production of crosslinkable particles (11) Methyl methacrylate (13.3 g) in which colloidal silica having a halogen group surface modifier prepared in Production Example 1-1 was dispersed in a proportion of 2 wt%. , Monomer (B)), Cu (I) Cl (0.32 g), dinonylbipyridine (2.68 g), ethyl 2-bromoisobutyrate (EBIB; 0.06 g) were placed in a flask and purged with nitrogen After deaeration by polymerization, polymerization was carried out at 70 ° C. for 24 hours. Next, 2-hydroxyethyl methacrylate (0.66 g) was added as 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 and subjected to an addition reaction to obtain crosslinkable particles (11) (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 one 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 colloidal silica having a halogen group surface modifier prepared in Production Example 1-1 was dispersed at a rate of 2 wt%. , Monomer (B)), Cu (I) Cl (0.0011 g), dinonylbipyridine (0.0095 g), ethyl 2-bromoisobutyrate (EBIB; 0.00021 g) were placed in a flask and purged with nitrogen After deaeration by polymerization, polymerization was carried out at 70 ° C. for 24 hours. Next, 2-hydroxyethyl methacrylate (1.03 g) was added as a monomer (C), degassed by nitrogen substitution, and polymerized at 70 ° C. for 24 hours to obtain intermediate particles. 2-isocyanatoethyl methacrylate (1.03 g) is added to the intermediate particles and subjected to 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 one particle of the crosslinkable particle (12) was about 300,000.

<Examples 13 and 14>
Except for using the crosslinkable particles (11) and (12) as the crosslinkable particles, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet were produced in the same manner as in Example 7, and the initial pressure-sensitive adhesive force and the heat-resistant holding force were measured. .
The results are shown in Table 8.

---- Comparison of performance due to graft chain density difference ----
<Production Example 1-13> Production of crosslinkable particles (13) (modification of BHE on colloidal silica surface)
Modification of the halogen group surface modifier on the surface of the silica fine particles was performed according to the following procedure. An ethanol dispersion (30 g) in which colloidal silica (manufactured by Nippon Shokubai, average particle size 130 nm) was dispersed at a rate of 7.7 wt% was added to a mixed solution of 28% aqueous ammonia (25 g) and ethanol (200 ml). . The mixture was stirred at 40 ° C. for 2 hours, and then an ethanol solution (10 ml) of BHE (2 g) synthesized in Production Example 1-1 was added dropwise and stirred at 40 ° C. for 18 hours. Thereafter, colloidal silica having an initiating group was recovered with a centrifuge, washed with ethanol and toluene, and then stored in toluene.

(Modification of monomers (B) to (D) on the surface of colloidal silica)
Methyl methacrylate (20 g, monomer (B)), Cu (I) Cl (0.032 g), disulfide having colloidal silica having a halogen group-containing surface modifier prepared as described above dispersed at a rate 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 monomer (C), degassed by nitrogen substitution, and polymerized at 70 ° C. for 24 hours to obtain intermediate particles. 2-isocyanatoethyl methacrylate (1 g, compound (D)) is added to the intermediate particles and subjected to an addition reaction to form crosslinkable particles (13) having an ethylenically unsaturated group at the polymer terminal (solid content concentration: 10% by mass) ) The weight average molecular weight per crosslinkable particle (13) was about 100,000, and the graft density was 0.8 strands / nm ² .

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

(Modification of monomers (B) to (D) on the surface of colloidal silica)
Methyl methacrylate (20 g, monomer (B)), Cu (I) Cl (0.032 g), disulfide having colloidal silica having a halogen group-containing surface modifier prepared as described above dispersed at a rate 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 monomer (C), degassed by nitrogen substitution, and polymerized at 70 ° C. for 24 hours to obtain intermediate particles.
2-isocyanatoethyl methacrylate (1 g, compound (D)) is added to the intermediate particles and subjected to an addition reaction to form crosslinkable particles (14) having an ethylenically unsaturated group at the polymer terminal (solid content concentration: 10% by mass) ) The weight average molecular weight per crosslinkable particle (14) was about 100,000, and the graft density was 0.2 strands / 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 force and heat-resistant holding force 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, add 13.6 g of pentaerythritol, 163 g of 2,2-bishydroxymethylpropionic acid, and 0.5 g of p-toluenesulfonic acid, and in a 145 ° C. oil bath while flowing nitrogen. For 2 hours to obtain a homogeneous solution. Then, it was made to react further under reduced pressure (50 mmHg or less, 145 degreeC) for 2 hours, and the dendrimer shown to following formula (II) was obtained.

Thereafter, 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 to the obtained dendrimer, and the mixture was reacted at 80 ° C. for 5 hours to obtain ethylenic acid. A dendrimer having an unsaturated group was obtained.

<Comparative Example 5>
The adhesive composition and the pressure-sensitive adhesive sheet were obtained 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 particle (1). Manufactured and measured for initial adhesion and heat retention. The results are shown in Table 10.

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

According to the present invention, a curable resin composition having excellent heat resistance and a cured product thereof can be provided.

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

Claims (15)

1. A curable resin composition comprising a resin component having an ethylenically unsaturated group and crosslinkable particles in which a polymer graft chain having an ethylenically unsaturated group is bonded to the surface of the base particle.
2. The curable resin composition according to claim 1, wherein the density of the polymer graft chains on the surface of the base particles is 0.05 to 1.2 strands / nm ² .
3. The polymer graft chain is a monomer 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 ( Curable resin composition of Claim 1 or 2 containing the monomer unit derived from C).
4. A reactive functional group (ii) in which 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; It has a structure in which 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 claim 3.
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 isocyanate group, an isocyanate group and a hydroxyl group. The curable resin composition according to claim 4, which is a combination, a combination of an isocyanate group and a carboxyl group, or a combination of a carboxyl group and an isocyanate group.
6. The polymer graft chain starts from a polymerization initiating group having a structure derived from the compound (A) in which a 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 claims 1 to 5.
7. The curable resin composition according to claim 6, wherein the compound (A) is a compound represented by the following formula (I).
   

   

   [In the formula (I), R ¹ _, R ² and R ³ each independently represents 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. 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 the monomer (B) having no isocyanato group, carboxyl group, hydroxyl group, and epoxy group and having an ethylenically unsaturated group. Item 8. The curable resin composition according to any one of Items 1 to 7.
9. The curable resin composition according to claim 8, wherein the monomer (B) is a monomer having a (meth) acryloyloxy group.
10. 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. The curable resin composition according to any one of claims 1 to 9, comprising one resin as a main component.
11. 11. The volume average particle diameter of the base particle, which is a 50% volume cumulative diameter (D50) measured using a laser diffraction particle size distribution measuring device, is 10 nm to 1 μm, according to any one of claims 1 to 10. The curable resin composition described.
12. The curable resin composition according to any one of Claims 1 to 11, wherein the base particles are inorganic particles.
13. The curable resin composition according to claim 12, wherein the inorganic particles are silica particles or metal oxide particles.
14. The base particles are organic particles, and the organic particles are selected from 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 claims 1 to 13, which is a resin particle.
15. The curable resin composition according to any one of claims 1 to 14, further comprising a photopolymerization initiator.

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