WO2022186248A1

WO2022186248A1 - Resin composition, method for producing polymer fine particles, and method for producing resin composition

Info

Publication number: WO2022186248A1
Application number: PCT/JP2022/008754
Authority: WO
Inventors: 展祥舞鶴
Original assignee: 株式会社カネカ
Priority date: 2021-03-05
Filing date: 2022-03-02
Publication date: 2022-09-09
Also published as: JPWO2022186248A1

Abstract

The present invention provides a curable resin composition which has excellent handling properties and excellent storage stability. A resin composition which contains a specific amount of polymer fine particles (A) and a specific amount of a matrix resin (B) that has two or more polymerizable unsaturated bonds in each molecule, wherein: each of the polymer fine particles (A) has an elastic body and a graft part; and the graft part is formed of a polymer that contains a specific amount of a specific first constituent unit and a specific amount of a second constituent unit that is derived from a multifunctional monomer which has two or more polymerizable unsaturated bonds in each molecule.

Description

Resin composition, method for producing fine polymer particles, and method for producing resin composition

The present invention relates to a resin composition, a method for producing polymer fine particles, and a method for producing a resin composition.

Radically curable resins such as unsaturated polyester resins and vinyl ester resins are widely used in various applications such as coating materials and molding compositions containing reinforcing materials such as glass fibers. .

These curable resins have the problem that they are accompanied by large curing shrinkage during curing, and cracks occur in the cured product due to internal stress within the cured product. Therefore, various attempts have been made to impart toughness to these curable resins, which are very brittle materials.

For example, a method of adding an elastomer to a curable resin is widely used in order to improve the toughness of the curable resin. Elastomers include polymer microparticles (eg, crosslinked polymer microparticles).

In Patent Document 1, a specific amount of polymer microparticles (polymer microparticles) as an elastomer are dispersed in a curable resin in the state of primary particles, and if necessary, a specific amount of an epoxy resin and at least one polymerizable non-polymeric polymer in the molecule. A curable resin composition containing a low molecular weight compound having a saturated bond and a molecular weight of less than 300 is disclosed. Then, the curable resin composition of Patent Document 1 has toughness and crack resistance without reducing the heat resistance (Tg), transparency, elastic modulus, surface tackiness, and weather resistance (yellowing) of the resulting cured product. It is disclosed that the adhesive properties can be significantly improved, the viscosity of the composition is low, and the adhesion to the substrate can be improved.

WO2014/115778

However, the above-mentioned conventional techniques are not sufficient from the viewpoint of handleability and storage stability, and there is room for further improvement.

One aspect of the present invention has been made in view of the above problems, and its object is to provide a resin composition that is excellent in handleability and storage stability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that by including a specific amount of a specific polyfunctional monomer as a cross-linking agent in the monomer constituting the graft portion of the polymer fine particles, The inventors have found new knowledge that a resin composition excellent in handleability and storage stability can be provided, and have completed the present invention.

That is, the resin composition according to one embodiment of the present invention contains polymer fine particles (A) and a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule, and The coalesced fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body, and the elastic body is a diene-based rubber, a (meth)acrylate-based One or more selected from the group consisting of rubber and organosiloxane rubber, wherein the graft portion is derived from a first structural unit derived from a first monomer and a second monomer second structural unit, wherein the first monomer is selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers One or more types, the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and the first structural unit in the graft portion and the When the total amount of the second structural unit and the second structural unit is 100% by weight, the second structural unit is more than 0.00% by weight and less than 2.00% by weight, and the polymer microparticles (A) and the The polymer fine particles (A) account for 1 to 50% by weight, and the matrix resin (B) accounts for 50 to 99% by weight, when the total with the matrix resin (B) is 100% by weight.

Further, the composition according to one embodiment of the present invention contains polymer fine particles (A) and a low molecular weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule. and the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body, and the elastic body is a diene rubber, ( One or more selected from the group consisting of meth)acrylate-based rubbers and organosiloxane-based rubbers, wherein the graft portion comprises a first structural unit derived from a first monomer and a second monomer the first monomer is an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer. is one or more selected from, the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and the first monomer in the graft portion When the total amount of the structural unit and the second structural unit is 100% by weight, the second structural unit is more than 0.00% by weight and less than 2.00% by weight, and the polymer fine particles ( When the total amount of A) and the low molecular compound (C) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the low molecular compound (C) is 50 to 99% by weight. %.

Further, in the method for producing polymer microparticles according to one embodiment of the present invention, at least one selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers and a graft portion preparation step of graft-polymerizing a first monomer and a second monomer onto the elastic body prepared by the elastic body preparation step. wherein the first monomer is one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers; The monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and in the graft part preparation step, the first monomer and the second monomer The second monomer is used in an amount of more than 0.00% by weight and less than 2.00% by weight when the total of the above is 100% by weight.

According to one aspect of the present invention, it is possible to provide a resin composition excellent in handleability and storage stability.

An embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each configuration described below, and various modifications are possible within the scope of the claims. Further, embodiments or examples obtained by appropriately combining technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the scientific literatures and patent documents described in this specification are used as references in this specification. In addition, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)".

[Embodiment 1]
[1. Technical idea of Embodiment 1 of the present invention]
In a resin composition containing polymer fine particles and a matrix resin having two or more polymerizable unsaturated bonds in the molecule, from the viewpoint of handling when using the resin composition, A low viscosity is preferred. Further, in conventional resin compositions, when the resin composition is stored for a long period of time, phase separation may occur between the polymer fine particles in the resin composition and the matrix resin, which improves the storage stability of the resin composition. There was room for In particular, when the content of the matrix resin having two or more polymerizable unsaturated bonds in the molecule is large in the resin composition (for example, the matrix resin is 90% by weight in 100% by weight of the resin composition). above), phase separation between the polymer fine particles and the matrix resin was remarkable during long-term storage of the resin composition. As a result of investigation by the present inventors, it was presumed that the phase separation between the polymer fine particles in the resin composition and the matrix resin was caused by aggregation of the polymer fine particles in the resin composition.

Therefore, the present inventors have made extensive studies to achieve both the handleability and the storage stability of the resin composition. In the process, the present inventor newly found the following findings:
(1) The viscosity of the resin composition can be reduced by using a specific polyfunctional monomer as a monomer in the formation (polymerization) of the graft portion of the polymer fine particles. Here, the specific polyfunctional monomer can function as a cross-linking agent.

(2) At the same time, however, when the amount of the specific polyfunctional monomer used is large, the dispersed state of the polymer fine particles in the resin composition becomes unstable, and the polymer fine particles tend to stick to each other and aggregate. to be easier.

Based on these new findings, the present inventors conducted further intensive studies in order to achieve both reduction in the viscosity of the resin composition and maintenance of the dispersed state of the polymer fine particles in the resin composition.

As a result, the present inventors have newly discovered the following knowledge and completed the present invention: in the formation (polymerization) of the graft portion of polymer fine particles, a specific polyfunctional monomer (crosslinking agent) By using a specific amount of, it is possible to reduce the viscosity of the resin composition and maintain the dispersion state of the polymer fine particles in the resin composition.

[2. Resin composition]
The resin composition according to Embodiment 1 of the present invention contains fine polymer particles (A) and a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule. The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body. The elastic body of the fine polymer particles (A) contains one or more selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers. The graft portion of the fine polymer particles (A) is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer, and The first monomer is one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers, and the second monomer is , is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule. When the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight, the second structural unit is 0.00%. % by weight and less than 2.00% by weight. When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight and the matrix resin (B) is 50 to 99% by weight. is.

In the resin composition according to Embodiment 1 of the present invention, the polymer constituting the graft portion of the polymer fine particles (A) contains the second structural unit derived from the second monomer, whereby the polymer The viscosity of the resin composition can be reduced as compared with the case where the grafted portion of the fine particles (A) does not contain the second structural unit. Therefore, the resin composition according to Embodiment 1 of the present invention has the advantage of being excellent in handleability.

Further, in the resin composition according to Embodiment 1 of the present invention, the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight. In this case, when the content of the second structural unit is more than 0.00% by weight and less than 2.00% by weight, the dispersed state of the polymer fine particles (A) in the resin composition can be maintained. Aggregation of the polymer fine particles (A) can be prevented. As a result, phase separation is less likely to occur when the resin composition is stored for a long period of time. Therefore, the resin composition according to Embodiment 1 of the present invention has an advantage of excellent storage stability.

As used herein, the term "polymerizable unsaturated bond" means a polymerizable unsaturated bond. In other words, the polymerizable unsaturated bond can be said to be a bond that initiates a polymerization reaction with the bond as a starting point. As used herein, "a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule" means "a polyfunctional monomer having two or more radically polymerizable reactive groups in the same molecule. ” can also be said. A "radical polymerizable reactive group" means a reactive group having radical polymerizability. In other words, the radically polymerizable reactive group can be said to be a reactive group that initiates a radical polymerization reaction with the reactive group as a starting point when a radical attacks the reactive group.

<1-1. Polymer microparticles (A)>
The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body.

(elastic body)
The elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber. The elastic body may contain natural rubber in addition to the rubbers described above. The elastic body can also be called an elastic portion or a rubber particle. (Meth)acrylate as used herein means acrylate and/or methacrylate.

The case where the elastic body contains diene rubber (Case A) will be described. In Case A, the resulting resin composition can provide a cured product with excellent toughness and impact resistance. A cured product having excellent toughness and/or impact resistance can also be said to be a cured product having excellent durability.

A diene-based rubber is an elastic body containing structural units derived from diene-based monomers. The diene-based monomer can also be called a conjugated diene-based monomer. In Case A, the diene-based rubber contains (i) 50% to 100% by weight of structural units derived from a diene-based monomer and a diene copolymerizable with the diene-based monomer, out of 100% by weight of the structural units. may contain 0% to 50% by weight of structural units derived from vinyl monomers other than system monomers, and (ii) 50% by weight of structural units derived from diene monomers; 100% by weight or less, and 0% by weight or more and less than 50% by weight of structural units derived from vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers, (iii) 60% to 100% by weight of structural units derived from diene-based monomers, and derived from vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers (iv) 70% to 100% by weight of structural units derived from a diene-based monomer, and copolymerized with a diene-based monomer It may contain 0% to 30% by weight of structural units derived from vinyl monomers other than diene monomers, and (v) 80 structural units derived from diene monomers. % to 100% by weight, and 0% to 20% by weight of constitutional units derived from a vinyl-based monomer other than a diene-based monomer copolymerizable with a diene-based monomer. , (vi) 90% to 100% by weight of structural units derived from a diene-based monomer, and a structure derived from a vinyl-based monomer other than a diene-based monomer copolymerizable with a diene-based monomer It may contain 0% by weight to 10% by weight of units, or (vii) may be composed only of structural units derived from diene-based monomers.

In Case A, the diene-based rubber may contain, as structural units, structural units derived from (meth)acrylate-based monomers in an amount smaller than the structural units derived from diene-based monomers.

Examples of diene-based monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), and 2-chloro-1,3-butadiene. These diene-based monomers may be used alone or in combination of two or more.

Vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers (hereinafter also referred to as vinyl-based monomers A) include, for example, styrene, α-methylstyrene, and monochlorostyrene. Vinylarenes such as , dichlorostyrene; Vinylcarboxylic acids such as acrylic acid and methacrylic acid; Vinyl cyanides such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; , propylene, butylene, and isobutylene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The vinyl-based monomer A described above may be used alone or in combination of two or more. Among the vinyl-based monomers A described above, styrene is particularly preferable. In addition, in the diene-based rubber in Case A, the structural unit derived from the vinyl-based monomer A is an optional component. In case A, the diene-based rubber may be composed only of structural units derived from diene-based monomers.

In Case A, the diene-based rubber may be butadiene rubber (also referred to as polybutadiene rubber) composed of structural units derived from 1,3-butadiene, or butadiene- Styrene rubber (also called polystyrene-butadiene) is preferred, and butadiene rubber is more preferred. According to the above configuration, the polymer fine particles (A) containing the diene rubber can more effectively exhibit the desired effects. In addition, butadiene-styrene rubber is more preferable in that the transparency of the resulting cured product can be enhanced by adjusting the refractive index.

The butadiene-styrene rubber contains (i) more than 50% by weight and 100% by weight or less of butadiene-derived structural units and 0% by weight or more and 50% by weight of styrene-derived structural units in 100% by weight of butadiene-styrene rubber. (ii) 60% to 100% by weight of structural units derived from butadiene and 0% to 40% by weight of structural units derived from styrene. , (iii) may contain 70% to 100% by weight of structural units derived from butadiene and 0% to 30% by weight of structural units derived from styrene, and (iv) a structure derived from butadiene It may contain 80% to 100% by weight of units and 0% to 20% by weight of structural units derived from styrene, and (v) 90% to 100% by weight of structural units derived from butadiene. , and 0% to 10% by weight of structural units derived from styrene. The butadiene-styrene rubber contains (vi) 70% to 90% by weight of butadiene-derived structural units and 10% to 30% by weight of styrene-derived structural units in 100% by weight of butadiene-styrene rubber. (vii) may contain 70% to 85% by weight of structural units derived from butadiene and 15% to 30% by weight of structural units derived from styrene, and (viii) It may contain 70% to 80% by weight of structural units derived from butadiene and 20% to 30% by weight of structural units derived from styrene, and (ix) 75% by weight of structural units derived from butadiene. % to 80% by weight, and 20% to 25% by weight of structural units derived from styrene.

A case (Case B) in which the elastic body contains (meth)acrylate rubber will be described. In case B, a wide variety of elastomeric polymer designs are possible by combining a wide variety of monomers.

(Meth)acrylate-based rubber is an elastic body containing, as a structural unit, a structural unit derived from a (meth)acrylate-based monomer. In case B, the (meth)acrylate rubber contains (i) 50% to 100% by weight of structural units derived from (meth)acrylate monomers in 100% by weight of structural units, and (meth)acrylate 0% to 50% by weight of a structural unit derived from a vinyl monomer other than a (meth)acrylate monomer copolymerizable with the monomer may be included, (ii) (meth ) More than 50% by weight but not more than 100% by weight of structural units derived from acrylate-based monomers, and vinyl units other than (meth)acrylate-based monomers copolymerizable with (meth)acrylate-based monomers It may contain 0% by weight or more and less than 50% by weight of structural units derived from a monomer, (iii) 60% to 100% by weight of structural units derived from a (meth)acrylate monomer, and It may contain 0% to 40% by weight of a structural unit derived from a vinyl-based monomer other than a (meth)acrylate-based monomer copolymerizable with a (meth)acrylate-based monomer, ( iv) 70% to 100% by weight of structural units derived from (meth)acrylate-based monomers, and vinyl-based monomers other than (meth)acrylate-based monomers copolymerizable with (meth)acrylate-based monomers It may contain 0% to 30% by weight of structural units derived from a monomer, and (v) 80% to 100% by weight of structural units derived from (meth)acrylate monomers, and It may contain 0% to 20% by weight of structural units derived from a vinyl-based monomer other than a (meth)acrylate-based monomer copolymerizable with a (meth)acrylate-based monomer, ( vi) 90% to 100% by weight of structural units derived from (meth)acrylate-based monomers, and vinyl-based monomers other than (meth)acrylate-based monomers copolymerizable with (meth)acrylate-based monomers It may contain 0% by weight to 10% by weight of structural units derived from monomers, or (vii) may be composed only of structural units derived from (meth)acrylate monomers.

In Case B, the (meth)acrylate-based rubber may contain structural units derived from a diene-based monomer in an amount smaller than the structural units derived from the (meth)acrylate-based monomer. good.

Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and dodecyl (meth)acrylate. , Alkyl (meth)acrylates such as stearyl (meth)acrylate and behenyl (meth)acrylate; Aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; ) acrylate, hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate; glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidylalkyl (meth)acrylate; alkoxyalkyl (meth)acrylates; Allylalkyl (meth)acrylates such as allyl (meth)acrylate and allylalkyl (meth)acrylate; monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc. Examples include polyfunctional (meth)acrylates. These (meth)acrylate monomers may be used alone or in combination of two or more. Among these (meth)acrylate monomers, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and butyl (meth)acrylate is more preferred.

In Case B, the (meth)acrylate rubber is preferably one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber and 2-ethylhexyl (meth)acrylate rubber. , butyl (meth)acrylate rubber is more preferred. Ethyl (meth)acrylate rubber is rubber composed of structural units derived from ethyl (meth)acrylate, butyl (meth)acrylate rubber is rubber composed of structural units derived from butyl (meth)acrylate, and 2-ethylhexyl ( A meth)acrylate rubber is a rubber composed of structural units derived from 2-ethylhexyl (meth)acrylate. According to this configuration, the glass transition temperature (Tg) of the elastic body is lowered, so that the polymer fine particles (A) and the resin composition having a low Tg can be obtained. As a result, (i) the obtained resin composition can provide a cured product having excellent toughness, and (ii) the viscosity of the resin composition can be made lower.

As the vinyl-based monomer other than the (meth)acrylate-based monomer copolymerizable with the (meth)acrylate-based monomer (hereinafter also referred to as vinyl-based monomer B), the vinyl-based monomer The monomers listed in Form A are included. Only one kind of the vinyl-based monomer B may be used, or two or more kinds thereof may be used in combination. Among the vinyl-based monomers B, styrene is particularly preferred. In addition, in the (meth)acrylate rubber in Case B, the structural unit derived from the vinyl monomer B is an optional component. In Case B, the (meth)acrylate rubber may be composed only of structural units derived from (meth)acrylate monomers.

The case where the elastic body contains organosiloxane rubber (Case C) will be described. In Case C, the resulting resin composition has sufficient heat resistance and can provide a cured product with excellent impact resistance at low temperatures.

Organosiloxane-based rubbers include, for example, (i) composed of alkyl- or aryl-disubstituted silyloxy units such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy. Organosiloxane polymers, (ii) organosiloxane polymers composed of alkyl- or aryl-monosubstituted silyloxy units such as organohydrogensilyloxy in which some of the alkyl side chains are substituted with hydrogen atoms. be done. These organosiloxane polymers may be used alone or in combination of two or more.

In this specification, a polymer composed of dimethylsilyloxy units is referred to as dimethylsilyloxy rubber, and a polymer composed of methylphenylsilyloxy units is referred to as methylphenylsilyloxy rubber. Polymers composed of oxy units are called dimethylsilyloxy-diphenylsilyloxy rubbers. In the case C, the organosiloxane rubber is (i) dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenyl, since the resulting resin composition can provide a cured product having excellent heat resistance. It is preferably one or more selected from the group consisting of silyloxy rubbers, and (ii) more preferably dimethylsilyloxy rubber because it is readily available and economical.

In case C, the fine polymer particles (A) preferably contain 80% by weight or more, more preferably 90% by weight or more, of the organosiloxane rubber in 100% by weight of the elastic material contained in the fine polymer particles (A). It is more preferable to have According to the configuration, the obtained resin composition can provide a cured product having excellent heat resistance.

The elastic body may further contain an elastic body other than diene rubber, (meth)acrylate rubber and organosiloxane rubber. Examples of elastic bodies other than diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers include natural rubbers.

In one embodiment of the present invention, the elastomer is butadiene rubber, butadiene-styrene rubber, butadiene-(meth)acrylate rubber, ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, 2-ethylhexyl (meth)acrylate rubber. , dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenylsilyloxy rubber, preferably one or more selected from the group consisting of butadiene rubber, butadiene-styrene rubber, butyl (meth)acrylate It is more preferably one or more selected from the group consisting of rubber and dimethylsilyloxy rubber.

(Crosslinked structure of elastic body)
From the viewpoint of maintaining the dispersion stability of the polymer fine particles (A) in the thermosetting resin, it is preferable that a crosslinked structure is introduced into the elastic body. As a method for introducing a crosslinked structure into the elastic body, a generally used method can be adopted, and examples thereof include the following methods. That is, in the production of the elastic body, a monomer capable of constituting the elastic body is mixed with a cross-linkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound, and then polymerized. . In this specification, manufacturing a polymer such as an elastomer is also referred to as polymerizing the polymer.

Methods for introducing a crosslinked structure into an organosiloxane rubber include the following methods: (A) when polymerizing an organosiloxane rubber, a polyfunctional alkoxysilane compound and another material are combined; (B) introducing a reactive group (e.g., (i) a mercapto group and (ii) a reactive vinyl group, etc.) into an organosiloxane-based rubber, and then to the resulting reaction product, (i) a method of radical reaction by adding an organic peroxide or (ii) a polymerizable vinyl monomer or the like, or (C) a polyfunctional monomer when polymerizing an organosiloxane rubber; and/or a method of mixing a crosslinkable monomer such as a mercapto group-containing compound with other materials, followed by polymerization, and the like.

A polyfunctional monomer is a monomer having two or more polymerizable unsaturated bonds in the molecule. Said polymerizable unsaturated bond is preferably a carbon-carbon double bond. Examples of polyfunctional monomers include (meth)acrylates having an ethylenically unsaturated double bond, such as allylalkyl (meth)acrylates and allyloxyalkyl (meth)acrylates, butadiene is not included. be done. Examples of monomers having two (meth)acrylic groups include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and cyclohexanedimethanol. Di(meth)acrylates, and polyethylene glycol di(meth)acrylates. Examples of the polyethylene glycol di(meth)acrylates include triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, and the like. are exemplified. Further, as monomers having three (meth)acrylic groups, alkoxylated trimethylolpropane tri(meth)acrylates, glycerolpropoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxy Ethyl)isocyanurate tri(meth)acrylate and the like are exemplified. Alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate and trimethylolpropane triethoxy tri(meth)acrylate. Furthermore, examples of monomers having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Furthermore, dipentaerythritol penta(meth)acrylate etc. are illustrated as a monomer which has five (meth)acrylic groups. Furthermore, examples of monomers having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate. Polyfunctional monomers also include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like.

Among the polyfunctional monomers described above, polyfunctional monomers that can be preferably used in the polymerization of the elastic body include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol. Di(meth)acrylates, hexanediol di(meth)acrylates, cyclohexanedimethanol di(meth)acrylates, and polyethylene glycol di(meth)acrylates. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.

Mercapto group-containing compounds include alkyl group-substituted mercaptans, allyl group-substituted mercaptans, aryl group-substituted mercaptans, hydroxy group-substituted mercaptans, alkoxy group-substituted mercaptans, cyano group-substituted mercaptans, amino group-substituted mercaptans, silyl group-substituted mercaptans, and acid group-substituted mercaptans. mercaptans, halo group-substituted mercaptans, acyl group-substituted mercaptans, and the like. As the alkyl-substituted mercaptan, an alkyl-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkyl-substituted mercaptan having 1 to 10 carbon atoms is more preferable. As the aryl group-substituted mercaptan, a phenyl group-substituted mercaptan is preferred. As the alkoxy-substituted mercaptan, an alkoxy-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkoxy-substituted mercaptan having 1 to 10 carbon atoms is more preferable. The acid group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having a carboxyl group and having 1 to 10 carbon atoms or an aryl group-substituted mercaptan having a carboxyl group and having 1 to 12 carbon atoms.

(Glass transition temperature of elastic body)
The glass transition temperature of the elastic body is preferably 80° C. or lower, more preferably 70° C. or lower, more preferably 60° C. or lower, more preferably 50° C. or lower, more preferably 40° C. or lower, more preferably 30° C. or lower. ° C. or lower is more preferred, 10 ° C. or lower is more preferred, 0 ° C. or lower is more preferred, -20 ° C. or lower is more preferred, -40 ° C. or lower is more preferred, -45 ° C. or lower is more preferred, and -50 ° C. or lower is more preferred. preferably -55°C or lower, more preferably -60°C or lower, more preferably -65°C or lower, more preferably -70°C or lower, more preferably -75°C or lower, more preferably -80°C or lower, -85°C or lower is more preferred, -90°C or lower is more preferred, -95°C or lower is more preferred, -100°C or lower is more preferred, -105°C or lower is more preferred, -110°C or lower is more preferred, -115 °C or lower is more preferred, -120°C or lower is even more preferred, and -125°C or lower is particularly preferred. In this specification, "glass transition temperature" may be referred to as "Tg". According to this configuration, polymer fine particles (A) having a low Tg and a resin composition having a low Tg can be obtained. As a result, the obtained resin composition can provide a cured product having excellent toughness. Moreover, according to the said structure, the viscosity of the resin composition obtained can be made lower. The Tg of the elastic body can be obtained by performing viscoelasticity measurement using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) For a flat plate made of polymer fine particles (A), a dynamic viscoelasticity measuring device (eg, DVA-200 manufactured by IT Keisoku Co., Ltd.) ) is used to perform dynamic viscoelasticity measurement under tensile conditions to obtain a tan δ graph; (2) Regarding the obtained tan δ graph, the tan δ peak temperature is taken as the glass transition temperature. Here, in the graph of tan δ, when a plurality of peaks are obtained, the lowest peak temperature is taken as the glass transition temperature of the elastic body.

On the other hand, the elastic modulus (rigidity) of the resulting cured product can be suppressed from decreasing, that is, a cured product having a sufficient elastic modulus (rigidity) can be obtained. 20° C. or higher is more preferred, 50° C. or higher is even more preferred, 80° C. or higher is particularly preferred, and 120° C. or higher is most preferred.

The Tg of the elastic body can be determined by the composition of the constituent units contained in the elastic body. In other words, the Tg of the resulting elastic body can be adjusted by changing the composition of the monomers used when manufacturing (polymerizing) the elastic body.

Here, when a homopolymer obtained by polymerizing only one type of monomer, a group of monomers that provide a homopolymer having a Tg greater than 0 ° C. is referred to as a monomer group a. . A group of monomers that provide a homopolymer having a Tg of less than 0° C. when only one type of monomer is polymerized is referred to as a monomer group b. 50 to 100% by weight (more preferably 65 to 99% by weight) of structural units derived from at least one monomer selected from monomer group a, and at least selected from monomer group b An elastic body G is defined as an elastic body containing 0 to 50% by weight (more preferably 1 to 35% by weight) of structural units derived from one type of monomer. The elastic body G has a Tg greater than 0°C. Moreover, when the elastic body contains the elastic body G, the obtained resin composition can provide a cured product having sufficient rigidity.

Also when the Tg of the elastic body is higher than 0°C, it is preferable that a crosslinked structure is introduced into the elastic body. Methods for introducing the crosslinked structure include the methods described above.

Examples of monomers that can be included in the monomer group a include, but are not limited to, styrene, unsubstituted vinyl aromatic compounds such as 2-vinylnaphthalene; vinyl-substituted compounds such as α-methylstyrene; Aromatic compounds; ring-alkylated vinyls such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene and 2,4,6-trimethylstyrene Aromatic compounds; Ring alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; Ring halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; 4-acetoxystyrene and the like ring-ester-substituted vinyl aromatic compounds; ring hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; , indene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and isopropyl methacrylate; aromatic methacrylates such as phenyl methacrylate; methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; methacrylic monomers including methacrylic acid derivatives; certain acrylic acid esters such as isobornyl acrylate and tert-butyl acrylate; acrylic monomers including acrylic acid derivatives such as acrylonitrile; Further, monomers that can be included in the monomer group a include acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1- Monomers such as adamantyl acrylate and 1-adamantyl methacrylate that can provide a homopolymer having a Tg of 120° C. or higher when converted to a homopolymer are included. These monomers a may be used alone or in combination of two or more.

Examples of the monomer group b include ethyl acrylate, butyl acrylate (also known as butyl acrylate), 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. etc. Only one type of these monomer group b may be used, or two or more types may be used in combination. Among these monomer groups b, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.

(Volume average particle size of elastic body)
The volume average particle diameter of the elastic body is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, more preferably 0.08 μm to 2.00 μm, and further preferably 0.10 μm to 1.00 μm. It is preferably 0.10 μm to 0.80 μm, and particularly preferably 0.10 μm to 0.50 μm. When the volume average particle diameter of the elastic body is (i) 0.03 μm or more, an elastic body having a desired volume average particle diameter can be stably obtained, and (ii) when it is 50.00 μm or less, it can be obtained. The heat resistance and impact resistance of the resulting cured product are improved. The volume-average particle size of the elastic body can be measured by using an aqueous suspension containing the elastic body as a sample and using a dynamic light scattering particle size distribution analyzer or the like.

(Proportion of elastic body)
The proportion of the elastic body in the polymer microparticles (A) is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, more preferably 60 to 93% by weight, based on 100% by weight of the entire polymer microparticles (A). is more preferable, 70 to 93% by weight is more preferable, 70 to 90% by weight is more preferable, 70 to 87% by weight is more preferable, and 70 to 85% by weight is even more preferable. When the proportion of the elastic body is (i) 40% by weight or more, the resulting resin composition can provide a cured product having excellent toughness and impact resistance, and (ii) is 97% by weight or less. In this case, since the polymer fine particles (A) do not easily aggregate, the resin composition does not become highly viscous, and as a result, the obtained resin composition can be excellent in handleability.

The following reasons can be considered for this. First, with regard to the ratio of the elastic material in the fine polymer particles (A), when the ratio of the elastic material in the fine polymer particles (A) increases and the ratio of the graft portion decreases, the elastic material is absorbed by the graft portion. It is exposed as an elastic body without being fully covered, and tends to aggregate. This is because aggregation of the fine polymer particles (A) is prevented by the steric repulsion effect of the graft portion. This aggregation increases the viscosity of the resin composition. This aggregation occurs during production of the resin composition containing the polymer fine particles (A) or over time.

Next, the cross-linking of the graft part fixes the graft chain to some extent, suppressing entanglement and reducing the viscosity. However, the fixation of the grafted chains suppresses the steric repulsion effect, making aggregation more likely to occur over time.

(Gel content of elastic body)
Preferably, the elastomer is swellable in a suitable solvent, but substantially insoluble. The elastic body is preferably insoluble in the thermosetting resin used.

The elastic body preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more. When the gel content of the elastic body is within the above range, the obtained resin composition can provide a cured product having excellent toughness.

In the present specification, the method for calculating the gel content is as follows. First, an aqueous suspension containing the polymer fine particles (A) is obtained, and then powder particles of the polymer fine particles (A) are obtained from the aqueous suspension. The method for obtaining powdery particles of the polymer microparticles (A) from the aqueous suspension is not particularly limited. For example, (i) aggregate the polymer microparticles (A) in the aqueous suspension, ) dehydrating the obtained aggregates, and (iii) further drying the aggregates to obtain powder particles of the polymer fine particles (A). Next, 2.0 g of powder particles of polymer fine particles (A) are dissolved in 50 mL of methyl ethyl ketone (MEK). After that, the obtained MEK melt is separated into a component soluble in MEK (MEK soluble matter) and a component insoluble in MEK (MEK insoluble matter). Specifically, using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E), the obtained MEK lysate was subjected to centrifugation for 1 hour at a rotation speed of 30000 rpm, and the lysate was subjected to MEK soluble. It is separated into a soluble portion and an MEK insoluble portion. Here, a total of 3 sets of centrifugation operations are carried out. The weights of the obtained MEK soluble matter and MEK insoluble matter are measured, and the gel content is calculated from the following formula.
Gel content (%)=(weight of methyl ethyl ketone-insoluble matter)/{(weight of methyl ethyl ketone-insoluble matter)+(weight of methyl ethyl ketone-soluble matter)}×100.

(Modified example of elastic body)
In one embodiment of the present invention, the "elastic body" of the fine polymer particles (A) may consist of only one type of elastic body having the same composition of structural units. In this case, the "elastic body" of the fine polymer particles (A) is one selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers.

In one embodiment of the present invention, the "elastic body" of the fine polymer particles (A) may consist of a plurality of types of elastic bodies having different compositions of structural units. In this case, the "elastic body" of the fine polymer particles (A) may be two or more selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers. In this case, the "elastic body" of the fine polymer particles (A) may be one selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers. In other words, the "elastic body" of the fine polymer particles (A) may be a plurality of types of diene-based rubbers, (meth)acrylate-based rubbers, or organosiloxane-based rubbers each having a different composition of structural units.

In one embodiment of the present invention, the case where the "elastic body" of the fine polymer particles (A) is composed of a plurality of types of elastic bodies having different compositions of structural units will be described. In this case, each of the plurality of types of elastic bodies is defined as elastic body ₁ , elastic body ₂ , . . . , and elastic body _n . Here, n is an integer of 2 or more. The "elastic body" of the fine polymer particles (A) may include a composite of separately polymerized elastic bodies ₁ , ₂ , . . . , and elastic body _n . The "elastic body" of the fine polymer particles (A) may include one elastic body obtained by polymerizing the elastic body ₁ , the elastic body ₂ , . . . and the elastic body _n in order. Such polymerization of a plurality of elastic bodies (polymers) in order is also called multistage polymerization. A single elastic body obtained by multi-stage polymerization of a plurality of types of elastic bodies is also referred to as a multi-stage polymerized elastic body. A method for producing the multi-stage polymer elastic body will be described in detail later.

A multistage polymerized elastic body composed of elastic body ₁ , elastic body ₂ , . . . , and elastic body _n will be described. In the multi-stage polymer elastic body, the elastic body _n may cover at least a portion of the elastic body n _- _{1 or may cover the entire elastic body n-1} . In the multi-stage polymerized elastic body, part of the elastic body _n may be inside the elastic body _n-1 .

In the multi-stage polymerized elastic body, each of the plurality of elastic bodies may form a layered structure. For example, when the multi-stage polymer elastic body is composed of elastic body ₁ , elastic body ₂ , and elastic body ₃ , elastic body ₁ forms the innermost layer, elastic body ₂ is formed outside elastic body ₁ , and elastic body 2 is formed on the outer side of elastic body 1. A mode in which a layer of the elastic body ₃ is formed as the outermost layer of the elastic body outside the layer of the elastic body ₂ is also one mode of the present invention. Thus, a multi-stage polymerized elastic body in which each of a plurality of elastic bodies forms a layered structure can also be called a multi-layered elastic body. That is, in one embodiment of the present invention, the “elastic body” of the fine polymer particles (A) is (i) a composite of multiple types of elastic bodies, (ii) a multi-stage polymerized elastic body and/or (iii) a multi-layered elastic It may contain a body.

(Surface cross-linked polymer)
The elastic body may further contain a surface-crosslinked polymer in addition to one or more rubbers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers and organosiloxane-based rubbers. In the following description, for the purpose of distinguishing from the surface-crosslinked polymer contained in the elastic body, the portion of the elastic body containing the above-mentioned rubber as a main component may be referred to as the "elastic core of the elastic body". In other words, the elastic body has an elastic core formed by polymerizing at least one monomer selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber, and organosiloxane-based rubber. , and a surface-crosslinked polymer obtained by polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer. is preferred. An embodiment of the present invention will be described below, taking as an example the case where the elastic body further has a surface-crosslinked polymer in addition to the elastic core of the elastic body. In this case, (i) blocking resistance can be improved in the production of the polymer fine particles (A), and (ii) dispersibility of the polymer fine particles (A) in the thermosetting resin becomes better. These reasons are not particularly limited, but can be presumed as follows: The surface cross-linked polymer covers at least a part of the elastic core of the elastic body, thereby increasing the elasticity of the elastic body of the fine polymer particles (A). The exposure of the core is reduced, and as a result, the elastic bodies are less likely to stick to each other, thereby improving the dispersibility of the fine polymer particles (A).

When the elastic body has a surface-crosslinked polymer, it may also have the following effects: (i) the effect of lowering the viscosity of the present resin composition, (ii) the effect of increasing the crosslink density of the elastic body as a whole, and ( iii) The effect of increasing the grafting efficiency of the grafted part. The crosslink density in the elastic core of the elastic means the degree of the number of crosslinked structures in the entire elastic core of the elastic.

The surface-crosslinked polymer contains, as structural units, 30 to 100% by weight of structural units derived from a polyfunctional monomer and 0 to 70% by weight of structural units derived from other vinyl monomers, a total of 100 % by weight of the polymer.

Examples of polyfunctional monomers that can be used for polymerization of the surface-crosslinked polymer include the polyfunctional monomers exemplified in the above section "Crosslinked structure of elastic body". Among these polyfunctional monomers, polyfunctional monomers that can be preferably used for polymerization of the surface-crosslinked polymer include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate (e.g. 1,3-butylene glycol dimethacrylate), butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.

The elastomer may comprise a surface cross-linked polymer polymerized independently of the polymerisation of the elastic core of the elastomer, or it may comprise a surface cross-linked polymer polymerized with the elastic core of the elastomer. good. In other words, the fine polymer particles (A) may be a multistage polymer obtained by polymerizing the elastic core of the elastic body and the surface-crosslinked polymer together, and then polymerizing the graft portion. Further, the polymer fine particles (A) may be a multi-stage polymer obtained by multi-stage polymerization of an elastic core of an elastic body, a surface-crosslinked polymer and a graft portion in this order. In any of these embodiments, the surface cross-linked polymer may coat at least a portion of the elastic core of the elastomer.

The surface cross-linked polymer can be regarded as a part of the elastic body, and the surface cross-linked polymer can be said to be the surface cross-linked part of the elastic body, as opposed to the elastic core of the elastic body. When the elastic body contains a surface-crosslinked polymer, the graft portion may be (i) graft-bonded to an elastic body other than the surface-crosslinked polymer (that is, the elastic core of the elastic body); It may be grafted to the crosslinked polymer, or (iii) grafted to both the elastic body other than the surface crosslinked polymer (that is, the elastic core of the elastic body) and the surface crosslinked polymer. good. When the elastic contains a surface-crosslinked polymer, the volume-average particle size of the elastic means the volume-average particle size of the elastic containing the surface-crosslinked polymer.

(graft part)
In this specification, the polymer graft-bonded to the elastic body is referred to as a graft portion. The graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer.

(First structural unit)
The first structural unit (hereinafter, “first structural unit”) is the first monomer (hereinafter, “first monomer”) among the structural units constituting the polymer contained in the graft portion. refers to the part derived from A 1st monomer is 1 or more types selected from the group which consists of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer.

The graft part has the first structural unit derived from the first monomer, so that (i) the compatibility between the polymer fine particles (A) and the matrix resin (B) is improved, and (ii) the matrix resin. The dispersibility of the polymer fine particles (A) in (B) is improved, and (iii) the polymer fine particles (A) can be dispersed in the state of primary particles in the resin composition or its cured product. has the advantage of

Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

Specific examples of vinyl cyan monomers include acrylonitrile and methacrylonitrile.

Specific examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxybutyl (meth)acrylate. (Meth)acrylate as used herein means acrylate and/or methacrylate.

Of the one or more monomers selected from the group consisting of the above-mentioned aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers, only one type is used as the first monomer. may be used, or two or more may be used in combination as the first monomer.

(Second structural unit)
The second structural unit (hereinafter, “second structural unit”) is the second monomer (hereinafter, “second monomer”) among the structural units constituting the polymer contained in the graft portion. refers to the part derived from The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in its molecule.

The graft portion having the second structural unit derived from the second monomer can be produced by using the second monomer in addition to the first monomer in the production (polymerization) of the graft portion. The second monomer can crosslink the polymer obtained by polymerizing the first monomer in the production of the graft. Therefore, the second monomer can be said to be a "crosslinking agent", and the second structural unit can be said to be a "structural unit derived from the crosslinking agent".

The graft part has the second structural unit derived from the second monomer, so that (i) the polymer fine particles (A) can be prevented from swelling in the resin composition, (ii) the resin composition (iii) the dispersibility of the fine polymer particles (A) in the matrix resin (B) is improved.

Examples of polyfunctional monomers having two or more polymerizable unsaturated bonds in the molecule include the polyfunctional monomers exemplified in the above section "Crosslinked structure of elastic body".

Among polyfunctional monomers having two or more polymerizable unsaturated bonds in the molecule, polyfunctional monomers that can be preferably used as the second monomer for polymerization of the graft portion include allyl methacrylate. , ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylate types are mentioned. Only one type of these polyfunctional monomers may be used as the second monomer, or two or more types may be combined and used as the second monomer.

(Contents of first structural unit and second structural unit)
The graft portion preferably contains 10 to 95% by weight, more preferably 30 to 92% by weight, more preferably 50 to 90% by weight of the first structural unit in 100% by weight of the polymer constituting the graft portion. more preferably, 60 to 87% by weight is particularly preferable, and 70 to 85% by weight is most preferable.

The content of the second constitutional unit in the polymer constituting the graft portion is 0.00% when the total of the first constitutional unit and the second constitutional unit in the polymer constituting the graft portion is 100% by weight. 00% by weight and less than 2.00% by weight. When the content of the second structural unit in the polymer constituting the graft portion is within the above range, the viscosity of the resin composition is reduced and the state of dispersion of the polymer fine particles (A) in the resin composition is maintained. It has the advantage that it is possible to make both

(Preferred Content of Second Structural Unit)
As described above, in the resin composition according to Embodiment 1 of the present invention, the content of the second structural unit in the polymer that constitutes the graft portion is the same as that of the first structural unit in the polymer that constitutes the graft portion. When the total of the two structural units is 100% by weight, by exceeding 0.00% by weight and less than 2.00% by weight, the viscosity of the resin composition is reduced and the polymer in the resin composition It is compatible with maintenance of the dispersed state of the fine particles (A). Among the numerical ranges of the content of the second structural unit, from the viewpoint of reducing the viscosity of the resin composition, the content of the second structural unit in the polymer constituting the graft portion is When the total amount of the first structural unit and the second structural unit is 100% by weight, it is preferably 0.10% by weight or more, more preferably 0.20% by weight or more, and 0.20% by weight or more. It is more preferably 30% by weight or more, more preferably 0.40% by weight or more, more preferably 0.50% by weight or more, and even more preferably 0.55% by weight or more.

In addition, from the viewpoint of maintaining the dispersed state of the polymer fine particles (A) in the resin composition, the content of the second structural unit in the polymer constituting the graft portion is When the total of one structural unit and the second structural unit is 100% by weight, it is preferably 1.80% by weight or less, more preferably 1.70% by weight or less, and 1.60% by weight. is more preferably 1.40% by weight or less, more preferably 1.20% by weight or less, even more preferably 1.00% by weight or less, and 0.80 % by weight or less is even more preferable, and 0.60% by weight or less is particularly preferable.

(Other structural units)
The graft portion may further contain a structural unit derived from a monomer having a reactive group, in addition to the above-described first structural unit and second structural unit. The monomer having a reactive group includes an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group. It is preferably a monomer having one or more reactive groups selected from the group consisting of epoxy groups, hydroxyl groups, and having one or more reactive groups selected from the group consisting of carboxylic acid groups A monomer is more preferable, and a monomer having an epoxy group is most preferable. According to the above configuration, the grafted portion of the fine polymer particles (A) and the matrix resin (B) (for example, thermosetting resin) can be chemically bonded in the resin composition. Thereby, the fine polymer particles (A) can be maintained in a good dispersed state without agglomeration of the fine polymer particles (A) in the resin composition or the cured product thereof.

Specific examples of epoxy group-containing monomers include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether.

Specific examples of monomers having a hydroxyl group include, for example, (i) 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxy straight-chain alkyl (meth)acrylates; Acrylates (especially hydroxy linear C1-6 alkyl (meth)acrylates); (ii) caprolactone-modified hydroxy (meth)acrylates; (iii) α-(hydroxymethyl)methyl acrylate, α-(hydroxymethyl)ethyl acrylate hydroxy-branched alkyl (meth)acrylates such as; (iv) mono(meth)acrylates of polyester diols (particularly saturated polyester diols) obtained from dihydric carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol); hydroxyl group-containing (meth)acrylates, and the like.

Specific examples of monomers having a carboxylic acid group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. As the monomer having a carboxylic acid group, the monocarboxylic acid is preferably used.

Only one type of the above-described monomer having a reactive group may be used, or two or more types may be used in combination.

The graft portion preferably contains 0.5 to 90% by weight, and preferably 1 to 50% by weight, of structural units derived from a monomer having a reactive group in 100% by weight of the polymer constituting the graft portion. is more preferable, more preferably 2 to 35% by weight, and particularly preferably 3 to 20% by weight. When the graft portion contains (i) 0.5% by weight or more of structural units derived from a monomer having a reactive group in 100% by weight of the polymer constituting the graft portion, the resulting resin composition is A cured product having sufficient impact resistance can be provided, and (ii) when the content is 90% by weight or less, the resulting resin composition can provide a cured product having sufficient impact resistance, and , has the advantage that the storage stability of the resin composition is improved.

The structural unit derived from a monomer having a reactive group is preferably contained in the graft portion, and more preferably contained only in the graft portion.

In the polymerization of the graft portion, only one type of each of the above-described monomers may be used as the "first monomer", the "second monomer", or the "monomer having a reactive group". , may be used in combination of two or more. In addition, the graft portion may contain, as structural units, structural units derived from other monomers in addition to the structural units derived from the monomers described above.

(Glass transition temperature of graft portion)
The glass transition temperature of the graft portion is preferably 190°C or lower, more preferably 160°C or lower, more preferably 140°C or lower, more preferably 120°C or lower, preferably 80°C or lower, more preferably 70°C or lower, and 60°C. The following is more preferable, 50° C. or less is more preferable, 40° C. or less is more preferable, 30° C. or less is more preferable, 20° C. or less is more preferable, 10° C. or less is more preferable, 0° C. or less is more preferable, and −20° C. The following is more preferable, -40°C or less is more preferable, -45°C or less is more preferable, -50°C or less is more preferable, -55°C or less is more preferable, -60°C or less is more preferable, -65°C or less is More preferably -70°C or less, more preferably -75°C or less, more preferably -80°C or less, more preferably -85°C or less, more preferably -90°C or less, more preferably -95°C or less , -100°C or lower is more preferred, -105°C or lower is more preferred, -110°C or lower is more preferred, -115°C or lower is more preferred, -120°C or lower is even more preferred, and -125°C or lower is particularly preferred.

The glass transition temperature of the graft portion is preferably 0° C. or higher, more preferably 30° C. or higher, more preferably 50° C. or higher, more preferably 70° C. or higher, still more preferably 90° C. or higher, and particularly preferably 110° C. or lower. preferable.

The Tg of the graft part can be determined by the composition of the constituent units contained in the graft part. In other words, the Tg of the obtained graft portion can be adjusted by changing the composition of the monomers used when manufacturing (polymerizing) the graft portion.

The Tg of the graft portion can be obtained by performing viscoelasticity measurement using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) For a flat plate made of polymer fine particles (A), a dynamic viscoelasticity measuring device (eg, DVA-200 manufactured by IT Keisoku Co., Ltd.) ) is used to perform dynamic viscoelasticity measurement under tensile conditions to obtain a tan δ graph; (2) Regarding the obtained tan δ graph, the tan δ peak temperature is taken as the glass transition temperature. Here, in the graph of tan δ, when a plurality of peaks are obtained, the highest peak temperature is taken as the glass transition temperature of the graft portion.

(Graft ratio of graft part)
In one embodiment of the present invention, the fine polymer particles (A) may be a polymer having the same structure as the graft portion and may have a polymer that is not graft-bonded to the elastic body. In the present specification, "a polymer having the same structure as the graft portion and not graft-bonded to the elastic body" is also referred to as a non-grafted polymer. The non-grafted polymer also constitutes a part of the fine polymer particles (A) according to Embodiment 1 of the present invention. The non-graft polymer can also be said to be a polymer that is not graft-bonded to the elastic body, among the polymers produced in the polymerization of the graft portion.

In the present specification, the ratio of the polymer graft-bonded to the elastic body, that is, the graft portion, out of the polymer produced in the polymerization of the graft portion is referred to as the graft ratio. The graft ratio can also be said to be a value represented by (weight of grafted portion)/{(weight of grafted portion)+(weight of non-grafted polymer)}×100.

The graft ratio of the graft portion is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When the graft ratio is 70% or more, there is an advantage that the viscosity of the resin composition does not become too high.

In this specification, the method for calculating the graft ratio is as follows. First, an aqueous suspension containing the polymer fine particles (A) is obtained, and then powder particles of the polymer fine particles (A) are obtained from the aqueous suspension. Specifically, the method for obtaining powdery particles of the polymer microparticles (A) from the aqueous suspension includes (i) coagulating the polymer microparticles (A) in the aqueous suspension, and (ii) A method of obtaining powder particles of polymer fine particles (A) by dehydrating the obtained coagulate and (iii) further drying the coagulate can be mentioned. Next, 2 g of powder particles of polymer fine particles (A) are dissolved in 50 mL of methyl ethyl ketone (hereinafter also referred to as MEK). After that, the obtained MEK melt is separated into a component soluble in MEK (MEK soluble matter) and a component insoluble in MEK (MEK insoluble matter). Specifically, the following (1) to (3) are performed: (1) Using a centrifuge (CP60E, manufactured by Hitachi Koki Co., Ltd.), the obtained MEK is dissolved at a rotation speed of 30000 rpm for 1 hour. (2) mixing the obtained MEK soluble matter and MEK, and subjecting the obtained MEK mixture to the above-mentioned Using a centrifuge, centrifugation is performed at a rotation speed of 30000 rpm for 1 hour to separate the MEK mixture into MEK soluble matter and MEK insoluble matter; (3) Repeat the operation of (2) once ( That is, the centrifugation operation is performed a total of 3 times). A concentrated MEK soluble matter is obtained by such an operation. 20 ml of the concentrated MEK solubles are then mixed with 200 ml of methanol. An aqueous calcium chloride solution of 0.01 g of calcium chloride dissolved in water is added to the resulting mixture and the resulting mixture is stirred for 1 hour. Thereafter, the resulting mixture is separated into a methanol-soluble portion and a methanol-insoluble portion, and the weight of the methanol-insoluble portion is defined as the free polymer (FP) amount.

The graft ratio is calculated from the following formula.
Graft rate (%)=100−[(FP amount)/{(FP amount)+(MEK insoluble weight)}]/(weight of polymer in grafted portion)×10000.

The weight of the polymer other than the graft portion is the charged amount of the monomer constituting the polymer other than the graft portion. A polymer other than the graft portion is, for example, an elastic body. Moreover, when the fine polymer particles (A) contain a surface-crosslinked polymer, which will be described later, the polymer other than the graft portion contains both the elastic body and the surface-crosslinked polymer. The weight of the polymer of the graft portion is the charged amount of the monomers constituting the polymer of the graft portion. In calculating the graft ratio, the method of coagulating the polymer microparticles (A) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous suspension, or the like can be used. .

(Modified example of the graft part)
In one embodiment of the present invention, the graft portion may consist of only one type of graft portion having structural units of the same composition. In one embodiment of the present invention, the graft portion may consist of a plurality of types of graft portions each having a different composition of structural units.

In one embodiment of the present invention, a case where the graft portion is composed of a plurality of types of graft portions will be described. In this case, each of the plurality of types of graft portions is designated as graft portion ₁ , graft portion ₂ , . . . , graft portion _n (n is an integer of 2 or more). The graft portion may comprise a composite of graft portion _{1 1} , graft portion _{2 2} , . . . , and graft portion _n , each polymerized separately. The graft portion may contain one polymer obtained by sequentially polymerizing graft portion _{1 1} , graft portion _{2 2} , . . . , and graft portion _n . Such polymerization of a plurality of polymerized portions (graft portions) in order is also referred to as multi-stage polymerization. A polymer obtained by multistage polymerization of a plurality of types of graft portions is also referred to as a multistage polymerization graft portion. A method for producing the multistage polymerized graft portion will be described in detail later.

When the graft portion consists of multiple types of graft portions, not all of these multiple types of graft portions may be graft-bonded to the elastic body. At least a part of at least one type of graft portion may be graft-bonded to the elastic body, and other types (a plurality of other types) of graft portions are graft portions that are graft-bonded to the elastic body. may be grafted to. Further, when the graft portion is composed of a plurality of types of graft portions, a plurality of types of polymers that are polymers having the same configuration as the plurality of types of graft portions and are not graft-bonded to the elastic body graft polymer).

A multi-stage polymerized graft portion composed of graft portion ₁ , graft portion ₂ , . . . , and graft portion _n will be described. In the multi-stage polymerized graft portion, the graft portion _n may cover at least a portion of the graft portion _n−1 , or may cover the entirety of the graft portion _n−1 . In the multi-stage polymerized graft portion, a part of the graft portion _n may be inside the graft portion _n−1 .

In the multi-stage polymerized graft portion, each of the plurality of graft portions may form a layered structure. For example, when the multistage polymerized graft portion is composed of graft portion ₁ , graft portion ₂ , and graft portion ₃ , graft portion ₁ forms the innermost layer in the graft portion, and graft portion ₂ is formed on the outer side of graft portion ₁ . Further, an aspect in which the layer of the graft portion ₃ is formed as the outermost layer outside the layer of the graft portion ₂ is also an aspect of the present invention. Thus, a multi-stage polymerized graft portion in which each of a plurality of graft portions forms a layered structure can also be called a multi-layer graft portion. That is, in one embodiment of the present invention, the graft portion may include (i) a composite of multiple types of graft portions, (ii) a multi-stage polymerization graft portion and/or (iii) a multi-layer graft portion.

When the elastic body and the graft portion are polymerized in this order in the production of the polymer microparticles (A), at least a portion of the graft portion may cover at least a portion of the elastic body in the resulting polymer microparticles (A). . In other words, the elastic body and the graft portion are polymerized in this order, which means that the elastic body and the graft portion are polymerized in multiple stages. The polymer microparticles (A) obtained by multi-stage polymerization of the elastic body and the graft portion can be said to be a multi-stage polymer.

When the polymer microparticles (A) are a multistage polymer, the graft part can cover at least a part of the elastic body, or can cover the entire elastic body. When the fine polymer particles (A) are a multi-stage polymer, part of the graft portion may enter the inside of the elastic body. At least a portion of the graft portion preferably covers at least a portion of the elastic body. In other words, at least part of the graft portion is preferably present on the outermost side of the fine polymer particles (A).

When the fine polymer particles (A) are multistage polymers, the elastic body and the graft portion may form a layered structure. For example, an embodiment in which the elastic body forms the innermost layer (also referred to as a core layer) and the layer of the graft portion is formed as the outermost layer (also referred to as a shell layer) on the outside of the elastic body is also an aspect of the present invention. be. A structure in which an elastic body is used as a core layer and a graft portion is used as a shell layer can be called a core-shell structure. Thus, the polymer fine particles (A) in which the elastic body and the graft part form a layered structure (core-shell structure) can be called a multi-layered polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particle (A) may be a multi-stage polymer and/or a multi-layer polymer or core-shell polymer. However, as long as it has an elastic body and a graft portion, the fine polymer particles (A) are not limited to the above configuration.

The case (Case D) where the polymer fine particles (A) is a multi-stage polymer obtained by multi-stage polymerization of the elastic core of the elastic body, the surface-crosslinked polymer, and the graft portion in this order will be described. In Case D, the surface-crosslinked polymer impregnates (incorporates) a portion of the surface of the elastic core of the elastic, or impregnates the entire surface of the elastic core of the elastic ( inside). In Case D, the graft portion may cover a portion of the surface cross-linked polymer or may cover the entire surface cross-linked polymer. In case D, the graft part may form a layer of the graft part on the outside of the surface cross-linked polymer while partially impregnating the surface of the surface cross-linked polymer (entering inside). Further, in case D, part of the graft part may impregnate the surface of the elastic core of the elastic body (entering inside) to form a layer of the graft part on the outside of the elastic core of the elastic body. . In Case D, the elastic core of the elastic body, the surface-crosslinked polymer and the graft portion may have a layered structure. For example, the elastic core of the elastic body is the innermost layer (core layer), the layer of the surface-crosslinked polymer is present as the intermediate layer outside the elastic core of the elastic body, and the layer of the graft portion is the outermost layer of the surface-crosslinked polymer. An aspect in which it exists as an outer layer (shell layer) is also an aspect of the present invention.

(Volume average particle diameter (Mv) of polymer microparticles (A))
The volume average particle diameter (Mv) of the fine polymer particles (A) is preferably from 0.03 μm to 50.00 μm, since a highly stable resin composition having a desired viscosity can be obtained. 05 μm to 10.00 μm is more preferable, 0.08 μm to 2.00 μm is more preferable, 0.10 μm to 1.00 μm is still more preferable, 0.10 μm to 0.80 μm is even more preferable, 0.10 μm to 0.50 μm is particularly preferred. When the volume average particle diameter (Mv) of the polymer fine particles (A) is within the above range, the polymer fine particles (A) are said to have good dispersibility in the matrix resin (B) (for example, thermosetting resin). It also has advantages. In the present specification, the "volume average particle diameter (Mv) of the polymer microparticles (A)" means the volume average particle diameter of the primary particles of the polymer microparticles (A), unless otherwise specified. do. The volume average particle size of the polymer fine particles (A) can be measured using a dynamic light scattering particle size distribution analyzer or the like using an aqueous latex containing the polymer fine particles (A) as a sample.

<1-2. Method for producing polymer microparticles (A)>
An example of the method for producing the polymer microparticles (A) will be described below. The fine polymer particles (A) can be produced, for example, by polymerizing an elastic body and then graft-polymerizing a polymer forming a graft portion to the elastic body in the presence of the elastic body. The method for producing such polymer microparticles (A) is also included in the scope of the present invention. That is, the method for producing polymer microparticles according to one aspect of the present invention is a method for producing polymer microparticles (A), in which a diene-based monomer, a (meth)acrylate-based monomer, and an organosiloxane-based monomer an elastic body preparing step of polymerizing one or more monomers selected from the group consisting of a first monomer and a second monomer to the elastic body prepared by the elastic body preparing step; and the first monomer is selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer. There are one or more types, the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and in the graft part preparation step, the first monomer When the total of the monomer and the second monomer is 100% by weight, the second monomer is used in an amount of more than 0.00% by weight and less than 2.00% by weight. .

Each step that can be included in the method for producing polymer microparticles will be described below.

(Elastic body preparation step)
The elastic body preparation step is a step of polymerizing one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers. Consider the case where the elastic body contains at least one selected from the group consisting of diene-based rubbers and (meth)acrylate-based rubbers. In this case, in the elastic body preparation step, one or more monomers selected from the group consisting of diene-based monomers and (meth)acrylate-based monomers may be polymerized. Polymerization of the monomers in this case can be carried out, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. can.

Consider the case where the elastic body contains organosiloxane rubber. In this case, the organosiloxane-based monomer may be polymerized in the elastic body preparation step. Polymerization of the monomers in this case can be carried out, for example, by methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. can.

A case where the "elastic body" of the fine polymer particles (A) consists of a plurality of types of elastic bodies (eg, elastic body ₁ , elastic body ₂ , . . . , elastic body _n ) will be described. In this case, the elastic _bodies _{1 1} , _{2 2} , . may be manufactured. That is, in this case, the elastic body preparation process includes a preparation process for elastic body ₁ , _a preparation process for _elastic body ₂ , _. _, . Alternatively, in the elastic body _preparation step, elastic body ₁ , elastic body ₂ , . good too.

A specific description will be given of the multi-stage polymerization of the elastic body. For example, in the elastic body preparation step, the following steps (1) to (4) can be performed in order to obtain a multi-stage polymerized elastic body: (1) Polymerize the elastic body ₁ to obtain the elastic body ₁ . (2) then elastic ₂ is polymerized in the presence of elastic ₁ to obtain a two-step elastic ₁₊₂ ; (3) elastic ₃ is then polymerized in the presence of elastic ₁₊₂ to give a three-step elastic; (4) After the same procedure, the elastic body _n is polymerized in the presence of the elastic body 1+ ₂ _+...+(n-1) to obtain the multistage polymerized elastic body _1+2+...+n . obtain.

Further, a case where the "elastic body" of the fine polymer particles (A) further contains a surface-crosslinked polymer will be described. In this case, the elastic body preparation step may include the following steps (a) and (b):
(a) polymerizing one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers;
(b) one or more monomers selected from the group consisting of polyfunctional monomers having two or more polymerizable unsaturated bonds in the molecule and vinyl monomers other than the polyfunctional monomers A step of polymerizing the monomer.

An elastic core of an elastic body can be prepared by step (a). In addition, the step (b) can prepare a surface-crosslinked polymer of an elastic body.

The surface-crosslinked polymer can be formed by polymerizing the monomers used for forming the surface-crosslinked polymer by known radical polymerization in the presence of any polymer (eg, elastic core). When the elastic body is obtained as an aqueous suspension, the polymerization of the surface-crosslinked polymer is preferably carried out by an emulsion polymerization method.

When the elastic body preparation step includes step (a) and step (b), said step (b) may be performed simultaneously with said (a), or may be performed after said (a). In other words, in the elastic body preparation step, (i) one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers; , a polyfunctional monomer and a vinyl monomer other than the polyfunctional monomer may be used together to prepare the elastic core and the surface crosslinked polymer at the same time, (ii ) After the use of one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers, polyfunctional monomers and the polyfunctional It is also possible to use a vinyl-based monomer other than the organic monomer and prepare (polymerize) the surface-crosslinked polymer after completing the preparation (polymerization) of the elastic core. When the steps (a) and (b) are performed at the same time, the cross-linking of the elastic core of the elastic body and the covering of the elastic core can be performed at the same time.

(Graft portion preparation step)
The graft portion preparation step is a step of graft-polymerizing the first monomer and the second monomer onto the elastic body prepared in the elastic body preparation step. The graft portion can be formed, for example, by polymerizing a monomer used for forming the graft portion by known radical polymerization in the presence of an elastic body. When (i) an elastic body comprising an elastic core or (ii) an elastic body comprising an elastic core and a surface-crosslinked polymer is obtained as an aqueous suspension, the graft portion is polymerized by emulsion polymerization. It is preferable to carry out by The graft portion can be manufactured, for example, according to the method described in WO2005/028546.

A method of manufacturing a graft portion when the graft portion is composed of a plurality of types of graft portions (for example, graft portion _{1 1} , graft portion _{2 2} , . . . , graft portion _n 2 ) will be described. In this case, the graft portion _{1 1} , the _graft portion _{2 2} , . (composite) may be produced. That is, in this case, the graft portion preparation process includes a preparation step for graft portion ₁ , _a preparation step for _graft portion ₂ , _. _, . Alternatively, the graft portion preparation step is a step of sequentially polymerizing the _graft portion ₁ , the graft portion ₂ , . good too.

The multi-stage polymerization of the graft portion will be specifically described. For example, a multistage polymerized graft portion can be obtained by sequentially performing steps (1) to (4) in the graft portion preparation step: (1) Graft portion ₁ is polymerized to obtain graft portion ₁ . (2) then graft portion ₂ is polymerized in the presence of graft portion ₁ to obtain a two-step graft portion ₁₊₂ ; (3) graft portion ₃ is then polymerized in the presence of graft portion ₁ +2 to obtain a three-step graft; (4) After the same procedure, graft portion _n is polymerized in the presence of graft portion 1 ₊ ₂ ₊ . obtain.

When the graft portion is composed of a plurality of types of graft portions, the graft portions having a plurality of types of graft portions are polymerized, and then the graft portions are graft-polymerized to the elastic body prepared in the elastic body preparation step to obtain fine polymer particles. (A) may be produced. In the presence of the elastic body prepared in the elastic body preparation step, a plurality of types of polymers constituting the graft portion are sequentially subjected to multistage graft polymerization to the elastic body to produce the polymer microparticles (A). may

In one embodiment of the present invention, the production (polymerization) of the graft portion uses a first monomer and a second monomer. As noted above, the second monomer can crosslink the polymer obtained from the first monomer. Therefore, in the production of the graft portion, (i) the second monomer is used together with the first monomer, and the cross-linking reaction by the second monomer proceeds simultaneously with the polymerization of the first monomer; Alternatively, (ii) it is preferable to use the second monomer after using the first monomer and allow the cross-linking reaction by the second polymer to proceed after the completion of the polymerization of the first monomer.

Polymerization of the elastic body, polymerization of the graft portion (graft polymerization), and polymerization of the surface-crosslinked polymer in the fine polymer particles (A) are performed by known methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. It can be implemented by the method of Among these, the emulsion polymerization method is particularly preferable as the method for producing the polymer fine particles (A). The emulsion polymerization method has the advantages of (i) facilitating compositional design of the polymer microparticles (A) and (ii) facilitating industrial production of the polymer microparticles (A). Hereinafter, the method for producing the elastic body, the graft portion, and the surface-crosslinked polymer having any configuration that can be contained in the fine polymer particles (A) will be described.

When an emulsion polymerization method is adopted as the method for producing the polymer fine particles (A), a known emulsifier (dispersant) can be used as an emulsifier (dispersant) for the production of the polymer fine particles (A). Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives. Examples of anionic emulsifiers include sulfur-based emulsifiers, phosphorus-based emulsifiers, sarcosic acid-based emulsifiers, and carboxylic acid-based emulsifiers. Examples of sulfur-based emulsifiers include sodium dodecylbenzenesulfonate (abbreviation: SDBS). Phosphorus-based emulsifiers include sodium polyoxyethylene lauryl ether phosphate and the like.

When an emulsion polymerization method is adopted as the method for producing the polymer fine particles (A), a thermal decomposition initiator can be used for the production of the polymer fine particles (A). The thermal decomposition initiators include, for example, (i) 2,2′-azobisisobutyronitrile, and (ii) peroxides such as organic and inorganic peroxides, and other known initiators. agents can be mentioned. Examples of the organic peroxides include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t- and hexyl peroxide. Examples of the inorganic peroxides include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

A redox initiator can also be used for the production of polymer fine particles (A). The redox initiator includes (i) peroxides such as organic peroxides and inorganic peroxides, and (ii) transition metal salts such as iron (II) sulfate, sodium formaldehyde sulfoxylate, glucose and the like. It is an initiator used in combination with a reducing agent. Furthermore, if necessary, a chelating agent such as disodium ethylenediaminetetraacetate and, if necessary, a phosphorus-containing compound such as sodium pyrophosphate may be used in combination.

When a redox initiator is used, polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set in a wide range. Therefore, it is preferable to use a redox initiator. Among redox initiators, redox initiators using organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide, and t-butyl hydroperoxide as peroxides are preferred. The amount of the thermal decomposition type initiator used, the amount of the redox type initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when the redox type initiator is used are within a known range. can be used.

For the purpose of introducing a crosslinked structure into the elastic body, the graft part or the surface crosslinked polymer, when using a polyfunctional monomer in the polymerization of the elastic body, the graft part or the surface crosslinked polymer, a known chain transfer agent is used. can be used within the range of the amount used. By using a chain transfer agent, the molecular weight and/or the degree of cross-linking of the resulting elastomer, graft portion or surface-crosslinked polymer can be easily adjusted.

In addition to the components described above, a surfactant can be used in the production of the polymer microparticles (A). The types and amounts of the surfactants used are within known ranges.

In the production of the polymer microparticles (A), conditions within known numerical ranges can be appropriately applied to conditions such as polymerization temperature, pressure, and deoxidation in polymerization.

The polymer microparticles (A) produced by the method for producing polymer microparticles (A) described above are also included in the scope of the present invention.

The polymer microparticles (A) according to Embodiment 1 of the present invention may have the following configuration: from a diene-based monomer, a (meth)acrylate-based monomer, and an organosiloxane-based monomer an elastic body obtained by polymerizing one or more monomers selected from the group consisting of; a graft portion obtained by graft-polymerizing a first monomer and a second monomer to the elastic body; wherein the first monomer is one selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer Above, the second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule, and the first structural unit and the second The second structural unit is more than 0.00% by weight and less than 2.00% by weight, when the total amount of the second structural unit is 100% by weight.

<1-3. Matrix resin (B)>
The matrix resin (B) is a resin having two or more polymerizable unsaturated bonds in its molecule. Resins having two or more polymerizable unsaturated bonds in the molecule are not particularly limited, and examples thereof include curable resins having radically polymerizable reactive groups (eg, carbon-carbon double bonds). More specifically, the matrix resin (B) is a curable resin containing an ester bond in the repeating unit constituting the main chain, epoxy (meth)acrylate, urethane (meth)acrylate, polyether (meth)acrylate, acrylic (meth)acrylates, and the like. These curable resins may be used alone or in combination of two or more.

Epoxy (meth)acrylate is obtained by addition reaction of polyepoxide such as bisphenol A epoxy resin, unsaturated monobasic acid such as (meth)acrylic acid, and optionally polybasic acid in the presence of a catalyst. It is an addition reaction product obtained by The addition reaction product and, if necessary, a mixture of the addition reaction product and a vinyl monomer are generally referred to as a vinyl ester resin. This production method inevitably leaves a small amount of the raw material polyepoxide. If the polyepoxide does not have a polymerizable unsaturated bond in its molecule, it may remain uncured and adversely affect the physical properties of the cured product (heat resistance, etc.). From the viewpoint of reducing residual epoxide and from the viewpoint of economy, the content of epoxy (meth)acrylate in 100 parts by weight of the total amount of matrix resin (B) is preferably less than 99 parts by weight, preferably 95 parts by weight. Less than 90 parts by weight is more preferred, less than 80 parts by weight is even more preferred, less than 50 parts by weight is particularly preferred, and less than 30 parts by weight is most preferred. More preferably, the matrix resin (B) does not contain epoxy (meth)acrylate.

The "curable resin containing an ester bond in the repeating unit constituting the main chain" is particularly limited as long as it is a curable compound having an ester group and two or more polymerizable unsaturated bonds in the molecule. Examples include unsaturated polyesters and polyester (meth)acrylates.

The matrix resin (B) is selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and acrylated (meth)acrylates. More than one kind of curable resin is preferred.

Among these, the matrix resin (B) is one or more selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates from the viewpoint of economy. is preferred. Further, the matrix resin (B) is more preferably one or more selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, and urethane (meth)acrylates, since there is little residual epoxide. Further, from the viewpoint of heat resistance, the matrix resin (B) is more preferably unsaturated polyester or polyester (meth)acrylate. , and that the polymer fine particles (A) are easily dispersed, the matrix resin (B) is particularly preferably polyester (meth)acrylate. From the viewpoint of low viscosity and excellent workability, the matrix resin (B) preferably contains polyether (meth)acrylate or is polyether (meth)acrylate. From the viewpoint of low viscosity and excellent workability, the matrix resin (B) preferably contains an acrylated (meth)acrylate or is an acrylated (meth)acrylate.

(unsaturated polyester)
The unsaturated polyester is not particularly limited, and examples thereof include those obtained from a condensation reaction between a polyhydric alcohol and an unsaturated polycarboxylic acid or its anhydride.

Examples of polyhydric alcohols include those having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, and neopentyl glycol. dihydric alcohols, preferably dihydric alcohols having 2 to 6 carbon atoms, more preferably propylene glycol. Only one type of these dihydric alcohols may be used, or two or more types may be used in combination.

Examples of unsaturated polycarboxylic acids include divalent carboxylic acids having 3 to 12 carbon atoms, more preferably divalent carboxylic acids having 4 to 8 carbon atoms. Specific examples include fumaric acid and maleic acid. Only one type of these divalent carboxylic acids may be used, or two or more types may be used in combination.

Further, in the resin composition according to Embodiment 1 of the present invention, a saturated polycarboxylic acid or an anhydride thereof may be used in combination with the unsaturated polycarboxylic acid or anhydride thereof. It is preferable that the amount of the unsaturated polycarboxylic acid or its anhydride is at least 30 mol % or more based on the total amount (100 mol %) of the acid or its anhydride. Examples of saturated polycarboxylic acids or anhydrides thereof include phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid and glutaric acid. These saturated polycarboxylic acids or their anhydrides may be used alone or in combination of two or more.

The unsaturated polyester is prepared by combining the polyhydric alcohol and the unsaturated polycarboxylic acid or its anhydride in the presence of an esterification catalyst such as an organic titanate such as tetrabutyl titanate or an organic tin compound such as dibutyltin oxide. It can be obtained by condensation reaction below.

The curable unsaturated polyester compound is also commercially available, for example, from Ashland, Reichhold, AOC, and the like.

The number average molecular weight of the unsaturated polyester is not particularly limited, but is preferably 400-10,000, more preferably 450-5,000, and particularly preferably 500-3,000.

(polyester (meth)acrylate)
Polyester (meth)acrylate is not particularly limited, for example, polyvalent carboxylic acid or anhydride thereof having a valence of 2 or more, unsaturated monocarboxylic acid having a (meth)acryloyl group, and polyvalence of 2 or more Examples include those obtained by esterifying alcohol as an essential component. Further, the polyester (meth)acrylate is obtained, for example, by subjecting the hydroxyl group of the polyester obtained by the condensation reaction of a polyhydric carboxylic acid or its anhydride and a polyhydric alcohol to an esterification reaction with an unsaturated monocarboxylic acid. Obtainable. Furthermore, the polyester (meth)acrylate is obtained, for example, by subjecting the carboxyl group of the polyester obtained by the condensation reaction of a polyvalent carboxylic acid or its anhydride and a polyhydric alcohol to an esterification reaction with an unsaturated glycidyl ester compound. can be obtained by

Examples of polycarboxylic acids or anhydrides thereof include unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and citraconic acid, or anhydrides thereof. In addition, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, adipic acid, Azelaic acid, sebacic acid, 1,12-dodecanedioic acid, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride , 4,4′-biphenyldicarboxylic acid and other saturated carboxylic acids or their anhydrides.

Among these, the polyvalent carboxylic acid or its anhydride is preferably maleic anhydride, fumaric acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, adipic acid or sebacic acid, and phthalic anhydride. More preferred are acids, isophthalic acid and terephthalic acid. Isophthalic acid is particularly preferred from the viewpoint of the low viscosity of the resulting matrix resin (B) and the water resistance of the cured product.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methylpropane-1,3-diol, Examples include hydrogenated bisphenol A, adducts of bisphenol A and alkylene oxides such as propylene oxide and ethylene oxide, and trimethylolpropane.

Among these, polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and hydrogenated bisphenol. A, an adduct of bisphenol A and propylene oxide is preferred, and propylene glycol, neopentyl glycol, hydrogenated bisphenol A, and an adduct of bisphenol A and propylene oxide are more preferred. Neopentyl glycol is particularly preferable from the viewpoint of the resulting matrix resin (B) having a low viscosity and the water resistance and weather resistance of the cured product.

A known method can be used for the reaction method for the condensation reaction. Moreover, the mixing ratio of polyhydric carboxylic acids and polyhydric alcohols is not particularly limited. The presence or absence of additives such as other catalysts and antifoaming agents, and the amounts used are not particularly limited. Furthermore, the reaction temperature and reaction time in the condensation reaction may be appropriately set so that the reaction is completed.

The unsaturated monocarboxylic acid is a monobasic acid having at least one (meth)acryloyl group in the molecule. For example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, mono-2-(methacryloyloxy)ethyl maleate, mono-2-(acryloyloxy)ethyl maleate, mono-2-(methacryloyloxy)propyl maleate, mono -2-(Acryloyloxy)propyl maleate and the like.

The unsaturated glycidyl ester compound is a glycidyl ester compound having at least one (meth)acryloyl group in the molecule. Examples include glycidyl acrylate and glycidyl methacrylate.

At the time of the esterification reaction, it is preferable to add a polymerization inhibitor or molecular oxygen to prevent gelation due to polymerization.

The polymerization inhibitor is not particularly limited, and conventionally known compounds can be used. For example, hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, trihydroquinone, p-benzoquinone, naphthoquinone, methoxyhydroquinone, phenothiazine, hydroquinone monomethyl ether, trimethylhydroquinone, methylbenzoquinone, 2,6-dihydroquinone, -t-butyl-4-(dimethylaminomethyl)phenol, 2,5-di-t-butylhydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, copper naphthenate, etc. mentioned.

As molecular oxygen, for example, (i) air and (ii) mixed gas of air and inert gas such as nitrogen can be used. In this case, molecular oxygen may be blown into the reaction system (so-called bubbling). In order to sufficiently prevent gelation due to polymerization, it is preferable to use both a polymerization inhibitor and molecular oxygen.

The reaction conditions such as reaction temperature and reaction time in the esterification reaction may be appropriately set so as to complete the reaction, and are not particularly limited. In addition, it is preferable to use the above esterification catalyst in order to promote the esterification reaction. Moreover, you may use a solvent as needed in the case of an esterification reaction. Specific examples of the solvent include, but are not particularly limited to, aromatic hydrocarbons such as toluene. The amount of solvent used and the method for removing the solvent after the reaction are not particularly limited. Since water is produced as a by-product in the esterification reaction, it is preferable to remove water, which is a by-product, from the reaction system in order to promote the esterification reaction. A removal method is not particularly limited.

The number average molecular weight of the polyester (meth)acrylate is not particularly limited, and is preferably 400 to 10,000, more preferably 450 to 5,000, and particularly preferably 500 to 3,000. .

(epoxy (meth) acrylate)
Epoxy (meth)acrylate is not particularly limited, and for example, a polyfunctional epoxy compound having two or more epoxy groups in the molecule, an unsaturated monocarboxylic acid, and optionally a polyvalent carboxylic acid. It can be obtained by an esterification reaction in the presence of an esterification catalyst.

Examples of polyfunctional epoxy compounds include bisphenol-type epoxy compounds, novolac-type epoxy compounds, hydrogenated bisphenol-type epoxy compounds, hydrogenated novolak-type epoxy compounds, and one of the hydrogen atoms of the bisphenol-type epoxy compounds and novolak-type epoxy compounds. Examples include halogenated epoxy compounds obtained by substituting a portion with a halogen atom (eg, bromine atom, chlorine atom, etc.). These polyfunctional epoxy compounds may be used alone or in combination of two or more.

The bisphenol-type epoxy compound includes, for example, a glycidyl ether-type epoxy compound obtained by reacting epichlorohydrin or methyl epichlorohydrin with bisphenol A or bisphenol F, or a reaction of an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin. Epoxy compounds obtained by.

Hydrogenated bisphenol type epoxy compounds include, for example, glycidyl ether type epoxy compounds obtained by reacting epichlorohydrin or methyl epichlorohydrin with hydrogenated bisphenol A or hydrogenated bisphenol F, or alkylene oxide adducts of hydrogenated bisphenol A. and epichlorohydrin or methyl epichlorohydrin and epoxy compounds obtained by the reaction.

Examples of novolak-type epoxy compounds include epoxy compounds obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.

Examples of hydrogenated novolak-type epoxy compounds include epoxy compounds obtained by reacting hydrogenated phenol novolak or hydrogenated cresol novolac with epichlorohydrin or methyl epichlorohydrin.

The average epoxy equivalent of the polyfunctional epoxy compound is preferably in the range of 150-900, particularly preferably in the range of 150-400. Epoxy (meth)acrylates using polyfunctional epoxy compounds having an average epoxy equivalent of more than 900 are likely to lower reactivity and curability of the composition. When a polyfunctional epoxy compound having an average epoxy equivalent of less than 150 is used, the physical properties of the composition tend to deteriorate.

The unsaturated monocarboxylic acid is a monobasic acid having at least one (meth)acryloyl group in the molecule. Examples include acrylic acid and methacrylic acid. Some of these unsaturated monocarboxylic acids can also be converted to cinnamic acid, crotonic acid, sorbic acid, and half esters of unsaturated dibasic acids (mono-2-(methacryloyloxy)ethyl maleate, mono-2-(acryloyloxy) ethyl maleate, mono-2-(methacryloyloxy)propyl maleate, mono-2-(acryloyloxy)propyl maleate, etc.).

Examples of the polyvalent carboxylic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, adipic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, anhydride trimellitic acid, hexahydrophthalic anhydride, 1,6-cyclohexanedicarboxylic acid, dodecanedioic acid, dimer acid and the like. The ratio of the unsaturated monocarboxylic acid and optionally used polyvalent carboxylic acid to the polyfunctional epoxy compound is the total carboxyl groups possessed by the unsaturated monocarboxylic acid and polyvalent carboxylic acid and the polyfunctional epoxy compound. It is preferable that the ratio with the epoxy group is in the range of 1:1.2 to 1.2:1.

As the esterification catalyst, conventionally known compounds can be used. Specific examples include tertiary amines such as triethylamine, N,N-dimethylbenzylamine, and N,N-dimethylaniline; trimethyl benzylammonium chloride, quaternary ammonium salts such as pyridinium chloride; phosphonium compounds such as triphenylphosphine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium idodide; sulfonic acids; and organic metal salts such as zinc octenoate.

The reaction method and reaction conditions for carrying out the above reaction are not particularly limited. Moreover, in the esterification reaction, it is more preferable to add a polymerization inhibitor or molecular oxygen to the reaction system in order to prevent gelation due to polymerization. As the polymerization inhibitor and molecular oxygen, those mentioned in the polyester (meth)acrylate can be used in the same manner.

The number average molecular weight of the epoxy (meth)acrylate is not particularly limited, and is preferably 300 to 10,000, more preferably 350 to 5,000, and particularly preferably 400 to 2,500. .

(Urethane (meth)acrylate)
Urethane (meth)acrylates are not particularly limited, and examples thereof include those obtained by a urethanization reaction of a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth)acrylate compound. Further, those obtained by the urethanization reaction between a polyol compound and a (meth)acryloyl group-containing isocyanate compound, and those obtained by a urethanization reaction between a hydroxyl group-containing (meth)acrylate compound and a polyisocyanate compound.

Specific examples of polyisocyanate compounds include 2,4-tolylene diisocyanate and its hydrides, 2,4-tolylene diisocyanate isomers and their hydrides, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and hexamethylene. Diisocyanate, trimer of hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate; or Millionate MR, Coronate L (Nippon Polyurethane Industry Co., Ltd. ), Barnock D-750, Crisbon NX (manufactured by Dainippon Ink and Chemicals, Inc.), Desmodur L (manufactured by Sumitomo Bayer Co., Ltd.), Takenate D102 (manufactured by Takeda Pharmaceutical Co., Ltd.), and the like.

Examples of polyol compounds include polyether polyols, polyester polyols, polybutadiene polyols, adducts of bisphenol A and alkylene oxides such as propylene oxide and ethylene oxide. The number average molecular weight of the polyether polyol is preferably in the range of 300-5,000, particularly preferably in the range of 500-3,000. Specific examples include polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol, and polyoxymethylene glycol. The polyester polyol preferably has a number average molecular weight in the range of 1,000 to 3,000.

A hydroxyl group-containing (meth)acrylate compound is a (meth)acrylate compound having at least one hydroxyl group in the molecule. Examples of the hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol. mono (meth) acrylate and the like.

A (meth)acryloyl group-containing isocyanate compound is a type of compound that shares at least one (meth)acryloyl group and an isocyanate group in the molecule. For example, 2-(meth)acryloyloxymethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate; or a compound obtained by urethanizing a hydroxyl group-containing (meth)acrylate compound and polyisocyanate at a molar ratio of 1:1. etc.

The reaction method in the urethanization reaction is not particularly limited, and reaction conditions such as reaction temperature and reaction time may be appropriately set so as to complete the reaction, and are not particularly limited. For example, when a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth)acrylate compound are subjected to a urethanization reaction, first, the ratio of the isocyanate groups possessed by the polyisocyanate compound to the hydroxyl groups possessed by the polyol compound (isocyanate group / hydroxyl group) is in the range of 3.0 to 2.0 to produce a prepolymer having an isocyanate group at the end, and then the hydroxyl group of the hydroxyl group-containing (meth) acrylate. and the isocyanate groups of the prepolymer are approximately equivalent to each other, so that the urethanization reaction can be carried out.

A urethanization catalyst is preferably used in the above reaction to promote the urethanization reaction. Examples of the urethanization catalyst include tertiary amines such as triethylamine and metal salts such as di-n-butyltin dilaurate, but any general urethanization catalyst can be used. Further, in the urethanization reaction, it is preferable to add a polymerization inhibitor or molecular oxygen to prevent gelation due to polymerization. As the polymerization inhibitor and molecular oxygen, those mentioned in the polyester (meth)acrylate can be used in the same manner.

The number average molecular weight of the urethane (meth)acrylate is not particularly limited, preferably 400 to 10,000, more preferably 800 to 8,000, particularly preferably 1,000 to 5,000. is.

(Polyether (meth)acrylate)
Polyether (meth)acrylate is not particularly limited, and examples thereof include those obtained by an esterification reaction of polyether polyol and (meth)acrylic acid, but can be obtained by other known techniques. Anything can be used.

The number average molecular weight of the polyether polyol is preferably within the range of 100 to 5,000, particularly preferably within the range of 100 to 3,000. Specific examples include polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol, and polyoxymethylene glycol.

The number average molecular weight of the polyether (meth)acrylate is not particularly limited, but is preferably 100-5000, more preferably 100-3000, and particularly preferably 100-1000.

(Acrylated (meth)acrylate)
The acrylated (meth)acrylate is not particularly limited, and includes, for example, those obtained by reacting an epoxy group-containing acrylic resin having two or more epoxy groups in the molecule with (meth)acrylic acid. However, those obtained by known techniques other than this can be arbitrarily used.

The number average molecular weight of the acrylated (meth)acrylate is not particularly limited, but is preferably 100-5000, more preferably 100-3000, and particularly preferably 100-1000.

(Physical properties of matrix resin (B))
The properties of the matrix resin (B) are not particularly limited. The matrix resin (B) preferably has a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C. The viscosity of the matrix resin (B) at 25° C. is more preferably 50,000 mPa·s or less, still more preferably 30,000 mPa·s or less, and particularly preferably 15,000 mPa·s or less. preferable. According to the above configuration, the matrix resin (B) has an advantage of excellent fluidity. The matrix resin (B) having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25° C. can also be said to be liquid.

Further, the viscosity of the matrix resin (B) is 100 mPa· at 25° C., since the matrix resin (B) enters the polymer fine particles (A) to prevent fusion between the polymer fine particles (A). s or more, more preferably 500 mPa·s or more, even more preferably 1000 mPa·s or more, and particularly preferably 1500 mPa·s or more.

The matrix resin (B) may have a viscosity of greater than 1,000,000 mPa·s. The matrix resin (B) may be semi-solid (semi-liquid) or solid. When the matrix resin (B) has a viscosity of more than 1,000,000 mPa·s, the obtained resin composition has the advantage of being less sticky and easier to handle.

The matrix resin (B) preferably has an endothermic peak at 25°C or lower, more preferably at 0°C or lower, in a differential scanning calorimetry (DSC) thermogram. According to the above configuration, the matrix resin (B) has an advantage of excellent fluidity.

(Blending ratio of fine polymer particles (A) and matrix resin (B))
In the resin composition according to Embodiment 1 of the present invention, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight. and the matrix resin (B) is 50 to 99% by weight.

In the resin composition according to Embodiment 1 of the present invention, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 10 to 50% by weight. and the matrix resin (B) may be 50 to 90% by weight. When the blending ratio of the polymer fine particles (A) and the matrix resin (B) in the resin composition is within the above range, there is an advantage that the resin composition can be used as a high-concentration masterbatch.

In the resin composition according to Embodiment 1 of the present invention, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 5% by weight to 50% by weight. %, the matrix resin (B) is preferably 50 wt % to 95 wt %, the fine polymer particles (A) are 6 wt % to 50 wt %, and the matrix resin (B) is 50 wt % to 94 wt %. It is more preferable that the polymer fine particles (A) are 7% by weight to 50% by weight, the matrix resin (B) is 50% by weight to 93% by weight, and the polymer fine particles (A) are 8% by weight. % to 50% by weight, the matrix resin (B) is more preferably 50% to 92% by weight, the fine polymer particles (A) are 9% to 50% by weight, and the matrix resin (B) is 50% by weight. It is more preferably 91% by weight, more preferably 10% by weight to 50% by weight of the polymer fine particles (A), and more preferably 50% by weight to 90% by weight of the matrix resin (B), and the polymer fine particles ( More preferably, A) is 15% by weight to 50% by weight, matrix resin (B) is 50% by weight to 85% by weight, polymer fine particles (A) is 20% by weight to 50% by weight, matrix resin (B ) is more preferably 50% to 80% by weight, the fine polymer particles (A) are more preferably 25% to 50% by weight, and the matrix resin (B) is more preferably 50% to 75% by weight. , More preferably, the polymer fine particles (A) are 30% by weight to 50% by weight, the matrix resin (B) is 50% by weight to 70% by weight, and the polymer fine particles (A) are 35% by weight to 50% by weight. , the matrix resin (B) is more preferably 50% by weight to 65% by weight. In the resin composition according to Embodiment 1 of the present invention, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 40% by weight to 50% by weight. %, the matrix resin (B) may be 50 wt % to 60 wt %, the fine polymer particles (A) may be 45 wt % to 50 wt %, and the matrix resin (B) may be 50 wt % to 55 wt %. There may be. When the blending ratio of the polymer fine particles (A) and the matrix resin (B) in the resin composition according to Embodiment 1 of the present invention is within the above range, the advantage is that the resin composition can be used as a masterbatch having a higher concentration. further has

<1-4. Low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond>
In the resin composition according to Embodiment 1 of the present invention, if necessary, a low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule (hereinafter simply referred to as "low-molecular-weight compound ( C)”) can be added.

Since the low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule has a low molecular weight, it reduces the viscosity of the resin composition according to Embodiment 1 of the present invention, and Improve handling. Further, when the resin composition according to Embodiment 1 of the present invention is cured, it is copolymerized with the matrix resin (B) and incorporated into the cross-linking points of the cured product. Furthermore, in the later-described step of dispersing the polymer fine particles (A) in the state of primary particles in the resin composition, the low-molecular-weight compound (C) can be used as a mixture with the matrix resin (B). It has the effect of facilitating the production process due to the viscosity-lowering effect of the molecular compound (C).

The mixing ratio (B/C) of the matrix resin (B) and the low-molecular-weight compound (C) is not particularly limited, but the weight ratio is preferably 9/1 to 3/7. A more preferable upper limit of B/C is 8/2, more preferably 7/3. When B/C exceeds 9/1, the viscosity of the resin composition according to Embodiment 1 of the present invention is high, and it may become difficult to handle. A more preferred lower limit for B/C is 4/6, more preferably 5/5. If B/C is less than 3/7, the cured product of the resin composition according to Embodiment 1 of the present invention may become thin due to the volatility of the low-molecular-weight compound (C), or the matrix resin (B) may be left behind. When added, the fine polymer particles (A) may aggregate to reduce the effect of improving toughness.

Examples of such low-molecular-weight compounds (C) include aromatic group-containing unsaturated monomers such as styrene and methylstyrene (vinyltoluene); nitrile group-containing unsaturated monomers such as acrylonitrile; (meth)acryloyl -COOCH=CH ₂ group-containing compounds such as vinyl versatate and vinyl acetate; polyvalent carboxylic acids such as phthalic acid, adipic acid, maleic acid, and malonic acid and unsaturated alcohols such as allyl alcohol Condensation reaction products; Polyfunctional ester monomers such as allyl cyanurate. Reaction speed between the (meth)acryloyl group-containing compound and the matrix resin (B) (reaction speed when the (meth)acryloyl group-containing compound is copolymerized with the matrix resin (B) and incorporated into the crosslink points of the cured product) is close to the reaction rate between matrix resins (B) (curing rate between matrix resins (B)). Therefore, the (meth)acryloyl group-containing compound is incorporated into the cross-linking points of the matrix resin (B) when the resin composition according to Embodiment 1 of the present invention containing the low-molecular-weight compound (C) is cured. It is easy to use, that is, it is preferable in terms of the physical properties of the cured product.

Specific examples of (meth)acryloyl group-containing compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, n-hexyl (meth)acrylate, ) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, allyl (meth) ) acrylate, phenyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, α-fluoromethyl acrylate, α-chloromethyl acrylate, α-benzylmethyl acrylate, α-cyanomethyl acrylate, α-acetoxyethyl acrylate , α-phenylmethyl acrylate, α-methoxymethyl acrylate, α-n-propylmethyl acrylate, α-fluoroethyl acrylate, α-chloroethyl acrylate, chloromethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxy ethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate , 2-cyanoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, m-chlorophenyl (meth)acrylate, p-chlorophenyl (meth)acrylate, p-tolyl (meth)acrylate, m-nitrophenyl (meth)acrylate , p-nitrophenyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, 2,2, 3,4,4,4-hexafluorobutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth) acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, etc. be Among these (meth)acryloyl group-containing compounds, a compound having a hydroxyl group improves the cured product by hybrid curing of radical crosslinking and urethane crosslinking by adding an isocyanate compound to the resin composition according to Embodiment 1 of the present invention. It is preferred because it allows quality. Only one type of the low-molecular compound (C) described above may be used, or two or more types may be used in combination. Examples of isocyanate compounds added to the resin composition according to Embodiment 1 of the present invention include diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI).

<1-5. Resin (D)>
The resin composition according to Embodiment 1 of the present invention may further contain a resin (D).

The resin (D) may be a resin of the same type (composition) as the matrix resin (B), or may be a resin of a different type from the matrix resin (B). Consider the case where the resin composition further comprises a resin (D), and the resin (D) is the same type of resin as the matrix resin (B). In this case, since the matrix resin (B) and the resin (D) cannot be distinguished from each other in the resin composition obtained, it appears that the resin composition obtained contains only the matrix resin (B). looks like Consider the case where the resin (D) is used in the method for producing the resin composition, and the resin (D) is a different type of resin from the matrix resin (B). In this case, the matrix resin (B) and the resin (D) can be distinguished from each other in the resulting resin composition. In this case, the finally obtained resin composition may contain the resin (D) as a resin other than the matrix resin (B).

The resin (D) is, for example, (i) a resin having two or more polymerizable unsaturated bonds in the molecule, (ii) a thermosetting resin, (iii) a thermoplastic resin, or (iv) these (i) Any combination of the resins of (iii).

For resins having two or more polymerizable unsaturated bonds in the molecule, the above <1-3. Matrix Resin (B)> section is incorporated. Resins having two or more polymerizable unsaturated bonds in the molecule that can be suitably used as the resin (D) include unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, One or more curable resins selected from the group consisting of polyether (meth)acrylates and acrylated (meth)acrylates.

Examples of thermosetting resins in the resin (D) include resins containing polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenol resins, polyol resins and amino-formaldehyde resins.

(Content when resin (D) is a resin other than epoxy resin)
The content of the resin (D) in the resin composition according to Embodiment 1 of the present invention is 10 parts by weight or more when the total of the fine polymer particles (A) and the matrix resin (B) is 100 parts by weight. is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, even more preferably 50 parts by weight or more, and particularly preferably 70 parts by weight or more. When the content of the resin (D) in the resin composition according to Embodiment 1 of the present invention is within the above range, there is an advantage that more of the desired effects of the resin (D) can be enjoyed.

The upper limit of the content of the resin (D) in the resin composition according to Embodiment 1 of the present invention is not particularly limited. When the total amount of the combined fine particles (A) and the matrix resin (B) is 100 parts by weight, it is preferably 10,000 parts by weight or less, more preferably 5,000 parts by weight or less. It is more preferably 000 parts by weight or less, more preferably 1,000 parts by weight or less, more preferably 750 parts by weight or less, more preferably 500 parts by weight or less, and 300 parts by weight or less. is more preferably 100 parts by weight or less, more preferably 90 parts by weight or less, even more preferably 80 parts by weight or less, and particularly preferably 70 parts by weight or less .

(When the resin (D) is an epoxy resin)
The resin composition according to Embodiment 1 of the present invention may further contain a known thermosetting resin other than the matrix resin (B), or may further contain a known thermoplastic resin.

For example, the resin composition according to Embodiment 1 of the present invention may further contain an epoxy resin as the resin (D). The content of the epoxy resin is preferably less than 0.5 parts by weight with respect to 100 parts by weight of the total amount of the matrix resin (B) and the low-molecular-weight compound (C). Since the epoxy resin is not incorporated into the cross-linking of the matrix resin (B), which is the main component, if the content is 0.5 parts by weight or more, the heat resistance (Tg) of the cured product may decrease, and the surface of the cured product may deteriorate. Stickiness (surface tackiness) may develop, and the solvent may be easily absorbed, resulting in a decrease in chemical resistance. The content of the epoxy resin is preferably less than 0.3 parts by weight and less than 0.2 parts by weight with respect to 100 parts by weight as the total amount of the matrix resin (B) and the low-molecular-weight compound (C). is more preferred, less than 0.1 part by weight is particularly preferred, and it is most preferred to contain no epoxy resin.

Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, hydrogenated bisphenol A (or F) type epoxy resin, glycidyl ether type epoxy resin, and aminoglycidyl ether-containing resin. Known epoxy resins such as resins and epoxy compounds obtained by subjecting these epoxy resins to addition reactions with bisphenol A (or F) compounds, polybasic acids and the like can be mentioned.

Other epoxy group-containing compounds (such as low-molecular-weight monomers) that do not have a polymerizable unsaturated bond may also adversely affect the physical properties of the cured product if they remain without being incorporated into the cross-linking of the matrix resin (B). It is preferable that the content in the composition is small because it has properties. Specifically, it is preferably 0.5 parts by weight or less, more preferably 0.1 parts by weight or less, relative to 100 parts by weight of the total amount of the matrix resin (B) and the low-molecular-weight compound (C).

The resin (D) is at least one thermosetting resin selected from the group consisting of resins containing polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenol resins, polyol resins and amino-formaldehyde resins. It may contain a flexible resin.

The thermoplastic resin in the resin (D) includes, for example, one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers as structural units. Examples thereof include polymers containing one or more structural units derived from a polymer. Examples of thermoplastic resins for resin (D) include acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes and polyvinyl acetates. In the resin (D), only one type of thermoplastic resin may be used, or two or more types may be used in combination.

<1-6. Other Ingredients>
(Radical polymerization initiator)
The resin composition according to Embodiment 1 of the present invention may further contain a radical polymerization initiator. The radical polymerization initiator is a curing agent for the matrix resin (B) and the low-molecular-weight compound (C), and is an initiator for cross-linking reaction of polymerizable unsaturated bonds (carbon-carbon double bonds, etc.) in this resin. . A radical polymerization initiator is used together with a curing accelerator and a co-catalyst, if necessary.

Such radical polymerization initiators include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t- organic peroxides such as butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy octanoate; and azo compounds such as azobisisobutyronitrile. From the viewpoint of curing the matrix resin (B) more effectively, one or more selected from the group consisting of benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, and methyl ethyl ketone peroxide are preferred, and cumene is more preferred. Hydroperoxide, methyl ethyl ketone peroxide. Only one type of the radical polymerization initiator described above may be used, or two or more types may be used in combination.

Radical polymerization initiators can be classified according to their optimum use temperature. There are relatively high temperature acting initiators such as cumene hydroperoxide and dicumyl peroxide, and relatively low temperature acting initiators such as benzoyl peroxide and azobisisobutyronitrile. It is preferable to use a combination of two or more radical polymerization initiators having different decomposition temperatures because it is possible to obtain a resin composition having curing activity in a wide temperature range. By combining two or more radical polymerization initiators, for example, while controlling the curing start temperature relatively low, curing progresses and the composition has curing activity even in the late stage of curing when the temperature reaches a high temperature. The reaction rate of the polymerizable unsaturated bonds can be increased, and the physical properties of the cured product can be enhanced.

The combination of two or more radical polymerization initiators is not particularly limited, but specific examples include a combination of cumene hydroperoxide and methyl ethyl ketone peroxide, t-butyl peroxybenzoate and t-butyl peroxyoctanoate. A combination with, and the like.

　The 10-hour half-life temperature is an index of the decomposition temperature of the radical polymerization initiator. When two or more radical polymerization initiators are used in combination, the difference in 10-hour half-life temperature between the two or more radical polymerization initiators used is preferably 10°C or more, more preferably 20°C or more, and particularly preferably 20°C or more.

The curing accelerator is an additive that acts as a catalyst for the decomposition reaction (radical generation reaction) of the radical polymerization initiator, and includes metal salts of naphthenic acid and octenic acid (cobalt salts, tin salts, lead salts, etc.). Cobalt naphthenate is preferred from the viewpoint of improving toughness and appearance. When a curing accelerator is added, it should be added in an amount of 0.1 to 1 part by weight per 100 parts by weight of the matrix resin (B) immediately before the curing reaction in order to prevent the curing reaction from occurring rapidly. is preferred.

The co-catalyst is an additive for causing radical generation at low temperatures by decomposing the radical polymerization initiator even at low temperatures, and examples thereof include amine compounds such as N,N-dimethylaniline, triethylamine, and triethanolamine. However, N,N-dimethylaniline is preferred because efficient reaction is possible. When a co-catalyst is added, it is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the matrix resin (B) of the present invention, or 1 to 15 parts by weight with respect to 100 parts by weight of the radical polymerization initiator. is preferably added in the range of

The resin composition according to Embodiment 1 of the present invention may optionally include, for example, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (anti-gelling agents), plasticizers, agent, leveling agent, antifoaming agent, silane coupling agent, antistatic agent, flame retardant, lubricant, thickener, viscosity reducer, low shrinkage agent, fiber reinforcement, inorganic filler, organic filler, internal release agent agents, wetting agents, polymerization modifiers, thermoplastic resins, drying agents, dispersing agents, and the like.

Specific examples of fillers include calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, dry silica such as fumed silica, wet silica, crystalline silica, fused silica, bentonite, montmorillonite, silica. Calcium acid, wollastonite, rectorite, kaolin, halloysite, glass powder, alumina, clay, talc, milled fiber, silica sand, river sand, diatomaceous earth, mica powder, gypsum, cold water sand, asbestos powder, fly ash, powdered marble, Inorganic fillers such as carbon nanotubes and organic fillers such as polymer beads are included. Among the above fillers, at least one inorganic filler selected from the group consisting of calcium carbonate, aluminum hydroxide, dry silica, clay, talc and glass powder is particularly preferred. Only one filler may be used, or two or more fillers may be used in combination.

When a filler is used, it is preferably 5 to 400 parts by weight, more preferably 30 to 300 parts by weight, with respect to 100 parts by weight of the matrix resin (B) contained in the resin composition according to Embodiment 1 of the present invention. 100 to 200 parts by weight is particularly preferred. If the amount of the filler compounded is less than 5 parts by weight, the surface hardness and rigidity of the resulting cured product may not be sufficiently obtained. When the amount of the filler compounded exceeds 400 parts by weight, the viscosity of the resin composition tends to be too high, and workability during molding tends to deteriorate, and the fluidity of the resin composition in the mold decreases. However, the mechanical properties of the obtained molding may deteriorate.

The filler may be subjected to a coupling treatment in order to improve adhesion with the matrix resin (B). Thereby, physical properties such as impact resistance, strength and water resistance of the obtained cured product can be improved. These coupling agents are not particularly limited, but include silane-based coupling agents, chromium-based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, zirconium-based coupling agents, and the like. be done. Moreover, only one type of these may be used, or two or more types may be used in combination.

The thickener is not particularly limited, but inorganic thickeners such as oxides and hydroxides of alkaline earth metals are preferred. Specific examples include magnesium oxide, calcium oxide, magnesium hydroxide and calcium hydroxide. Thermoplastic polymers such as polymethyl methacrylate, which have swelling properties, can also be used as thickeners. Only one type of these thickeners may be used, or two or more types may be used in combination.

When a thickener is used, it is preferably 0.1 to 30 parts by weight, preferably 0.3 to 10 parts by weight is more preferred, and 1 to 3 parts by weight is particularly preferred. If the amount of the thickening agent is less than 0.1 parts by weight, sufficient thickening may not be obtained. If the amount of the filler compounded exceeds 30 parts by weight, the viscosity of the resin composition tends to be too high, resulting in poor workability during molding.

Specific examples of low shrinkage agents include polystyrene, polyethylene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polycaprolactam, saturated polyester, styrene-acrylonitrile copolymer, vinyl acetate-styrene copolymer, styrene. -Divinylbenzene copolymer, methyl methacrylate-polyfunctional methacrylate copolymer, polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and other rubber-like polymers are used. Moreover, these thermoplastic polymers may be partially introduced with a crosslinked structure. These low shrinkage agents may be used alone or in combination of two or more. When using a low shrinkage agent, it is preferably 2 to 20 parts by weight with respect to 100 parts by weight of the matrix resin (B) contained in the resin composition according to the first embodiment of the present invention. If the amount is less than 2 parts by weight, the shrinkage reduction effect may not be sufficient, and if the amount exceeds 20 parts by weight, the transparency of the molded product may be lowered and the cost may be increased.

Specific examples of fiber reinforcing materials include inorganic fibers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers; organic fibers such as aramid and polyester; natural fibers; not to be The form of the fiber includes roving, cloth, mat, woven fabric, chopped roving, chopped strand, etc., but is not particularly limited. Only one type of these fiber reinforcing materials may be used, or two or more types may be used in combination. When a fiber reinforcing material is used, it is preferably 1 to 400 parts by weight with respect to 100 parts by weight of the matrix resin (B) contained in the resin composition according to Embodiment 1 of the present invention. If it is less than 1 part by weight, the reinforcing effect may not be sufficient, and if it exceeds 400 parts by weight, the surface condition of the cured product may deteriorate.

Specific examples of internal release agents include stearic acid, zinc stearate, aluminum stearate, calcium stearate, barium stearate, stearamide, triphenyl phosphate, alkyl phosphate, commonly used waxes, silicone oil and the like.

As the wetting agent, commercially available products can be used as they are. For example, commercially available from BYK Chemie Co., Ltd. "W-995", "W-996", "W-9010", "W-960", "W-965", "W-990" and the like. However, these are appropriately selected and used depending on the purpose of use.

Examples of polymerization modifiers include polymerization inhibitors such as hydroquinone, methylhydroquinone, methoxyhydroquinone, and t-butylhydroquinone. These polymerization modifiers are preferably sufficiently dissolved in the thermosetting resin in advance. As antioxidants, hindered phenols such as 2,6-di-t-butylhydroxytoluene are preferably used.

Commercially available inorganic and organic pigments can be used as colorants, UV absorbers such as benzophenone, thixotropy imparting agents such as silica, and flame retardants such as phosphate esters can be used.

<1-7. Properties of Resin Composition>
(viscosity)
The resin composition according to Embodiment 1 of the present invention is excellent in handleability due to its low viscosity. For example, the resin composition according to Embodiment 1 of the present invention may have a viscosity of less than 6000 mPa·s at a shear rate (SR) of 10 s ⁻¹ . A method for measuring the viscosity of the resin composition will be described in detail in Examples described later.

(Storage stability)
Since the resin composition according to Embodiment 1 of the present invention can maintain the state of dispersion of the polymer fine particles (A) in the resin composition, aggregation of the polymer fine particles (A) can be prevented. As a result, phase separation is less likely to occur when the resin composition is stored for a long period of time. Therefore, the resin composition according to Embodiment 1 of the present invention has excellent storage stability. Conventionally, particularly when the content of a matrix resin having two or more polymerizable unsaturated bonds in the molecule in 100% by weight of the resin composition is large (for example, in 100% by weight of the resin composition, the matrix resin is 90% by weight or more), there is a problem that phase separation is more likely to occur during long-term storage of the resin composition. For example, in the resin composition according to Embodiment 1 of the present invention, even when the content of the matrix resin in the resin composition is 90% by weight or more, when stored for a long period of time, at 60 ° C. It can be stored for days without phase separation. A method for measuring the storage stability of the resin composition will be described in detail in Examples described later.

[Embodiment 2]
[Technical idea of Embodiment 2 of the present invention]
In a composition containing fine polymer particles and a low-molecular-weight compound having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule, from the viewpoint of handleability when using the composition, It is preferable that the viscosity of the material is low. In addition, a composition (resin composition), conventionally, when the resin composition is stored for a long period of time, the polymer fine particles in the resin composition and the resin may undergo phase separation, that is, there is room for improvement in the storage stability of the resin composition. there were. In particular, when the resin composition contains a large amount of resin having two or more polymerizable unsaturated bonds in the molecule (for example, the resin is 90% by weight or more in 100% by weight of the resin composition. In some cases, phase separation between the polymer fine particles and the resin was remarkable due to long-term storage of the resin composition. As a result of investigation by the present inventors, it was presumed that the phase separation between the polymer fine particles in the resin composition and the matrix resin was caused by aggregation of the polymer fine particles in the resin composition.

Therefore, the present inventors have found that a composition containing fine polymer particles and the low-molecular-weight compound has handleability and two or more polymerizable unsaturated bonds in the molecule of the fine polymer particles and the low-molecular-weight compound. In order to achieve compatibility between storage stability of a composition containing a resin (resin composition), the inventors conducted extensive studies. In the process, the present inventor newly found the following findings:
(1) A composition containing the polymer microparticles and the low-molecular-weight compound by using a specific polyfunctional monomer as a monomer in the formation (polymerization) of the graft portion of the polymer microparticles. Being able to reduce the viscosity of things. Here, the specific polyfunctional monomer can function as a cross-linking agent.

(2) At the same time, however, when the amount of the specific polyfunctional monomer used is large, the polymer microparticles, the low-molecular-weight compound, and a resin having two or more polymerizable unsaturated bonds in the molecule are included. The dispersed state of the polymer fine particles in the resin composition becomes unstable, and the polymer fine particles tend to stick to each other and aggregate easily.

Based on such new findings, the present inventors have found that the viscosity of a composition containing fine polymer particles and the low-molecular-weight compound is reduced, and that two or more molecules are present in the molecule of the fine polymer particles and the low-molecular-weight compound. In order to achieve compatibility with maintenance of the dispersed state of polymer fine particles in a composition (resin composition) containing a resin having a polymerizable unsaturated bond, further studies were conducted.

As a result, the present inventors have newly discovered the following knowledge and completed the present invention: in the formation (polymerization) of the graft portion of polymer fine particles, a specific polyfunctional monomer (crosslinking agent) By using a specific amount of, the viscosity of the composition containing the polymer fine particles and the low-molecular compound is reduced, and the polymer fine particles and the low-molecular-weight compound have two or more polymerizable heteroatoms in the molecule. It is possible to achieve both maintenance of the dispersed state of the polymer fine particles in the composition (resin composition) containing the resin having a saturated bond.

The second embodiment will be described below. The second composition according to Embodiment 2 of the present invention contains polymer fine particles (A) and a low molecular weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule. is doing. The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body. The elastic body of the fine polymer particles (A) contains one or more selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers. The graft portion of the fine polymer particles (A) is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer, and The first monomer is one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers, and the second monomer is , is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule. When the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight, the second structural unit is 0.00%. % by weight and less than 2.00% by weight. When the total amount of the polymer fine particles (A) and the low molecular weight compound (C) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight and the low molecular compound (C) is 50 to 99% by weight. % by weight.

In the second composition according to Embodiment 2 of the present invention, the polymer constituting the graft portion of the polymer fine particles (A) contains the second structural unit derived from the second monomer, thereby The viscosity of the second composition can be reduced as compared with the case where the graft portion of the coalesced fine particles (A) does not contain the second constitutional unit. Therefore, the second composition according to Embodiment 2 of the present invention has the advantage of being excellent in handleability.

In addition, the second composition may further contain a resin (D). In the second composition according to Embodiment 2 of the present invention, when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight Furthermore, since the content of the second structural unit is more than 0.00% by weight and less than 2.00% by weight, the dispersed state of the polymer fine particles (A) in the second composition can be maintained. Aggregation of the polymer fine particles (A) can be prevented. As a result, when the second composition further contains the resin (D), phase separation between the polymer fine particles (A) and the resin (D) in the second composition occurs when the second composition is stored for a long period of time. has the advantage of being less likely to occur. Therefore, the second composition according to Embodiment 2 of the present invention has the advantage of being excellent in storage stability.

<1-8. Polymer Fine Particles (A) and Low Molecular Compound (C)>
"Polymer fine particles (A)" and "low molecular weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond" are as described for the resin composition according to Embodiment 1. so I won't repeat it here.

(Blending ratio of fine polymer particles (A) and low-molecular compound (C))
In the second composition according to Embodiment 2 of the present invention, when the total amount of the polymer fine particles (A) and the low-molecular compound (C) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight. %, and the low molecular weight compound (C) is 50 to 99% by weight.

In the second composition according to Embodiment 2 of the present invention, when the total amount of the polymer fine particles (A) and the low-molecular compound (C) is 100% by weight, the polymer fine particles (A) is 10 to 50% by weight. %, and the low molecular weight compound (C) may be 50 to 90% by weight. When the mixing ratio of the polymer fine particles (A) and the low-molecular-weight compound (C) in the second composition is within the above range, there is an advantage that the second composition can be used as a high-concentration masterbatch.

In the second composition according to Embodiment 2 of the present invention, when the total amount of the polymer fine particles (A) and the low-molecular compound (C) is 100% by weight, the polymer fine particles (A) are 5% by weight to 50% by weight, preferably 50% to 95% by weight of the low molecular weight compound (C), 6% to 50% by weight of the fine polymer particles (A), and 50% to 50% by weight of the low molecular weight compound (C) It is more preferably 94% by weight, more preferably 7% to 50% by weight of the polymer fine particles (A) and 50% to 93% by weight of the low-molecular-weight compound (C), and the polymer fine particles ( More preferably, A) is 8% to 50% by weight, the low molecular weight compound (C) is 50% to 92% by weight, and the polymer fine particles (A) is 9% to 50% by weight, and the low molecular compound (C) is more preferably 50% to 91% by weight, the fine polymer particles (A) are 10% to 50% by weight, and the low molecular compound (C) is 50% to 90% by weight. More preferably, the polymer fine particles (A) are 15% by weight to 50% by weight, the low-molecular-weight compound (C) is 50% by weight to 85% by weight, and the polymer fine particles (A) are 20% by weight. It is more preferable that the content of the polymer fine particles (A) is 25% to 50% by weight and the low molecular weight compound (C) is 50% by weight. % to 75% by weight, more preferably 30% to 50% by weight of the fine polymer particles (A) and 50% to 70% by weight of the low-molecular-weight compound (C). More preferably, the fine particles (A) are 35% by weight to 50% by weight, and the low molecular weight compound (C) is 50% by weight to 65% by weight. In the second composition according to Embodiment 2 of the present invention, when the total amount of the polymer fine particles (A) and the low-molecular weight compound (C) is 100% by weight, the polymer fine particles (A) are 40% by weight to 50% by weight, the low molecular weight compound (C) may be 50% to 60% by weight, the polymer fine particle (A) is 45% to 50% by weight, and the low molecular weight compound (C) is 50% by weight to It may be 55% by weight. When the blending ratio of the polymer fine particles (A) and the low-molecular-weight compound (C) in the second composition according to Embodiment 2 of the present invention is within the above range, the second composition is used as a higher-concentration masterbatch. It has the further advantage of being able to

<1-9. Resin (D)>
The second composition according to Embodiment 2 of the present invention may further contain a resin (D). "Resin (D)" is as described for the resin composition according to Embodiment 1, and will not be repeated here.

(Content when resin (D) is a resin other than epoxy resin)
The content of the resin (D) in the second composition according to Embodiment 2 of the present invention is 10 parts by weight when the total of the fine polymer particles (A) and the low-molecular-weight compound (C) is 100 parts by weight. parts by weight or more, more preferably 20 parts by weight or more, more preferably 30 parts by weight or more, even more preferably 50 parts by weight or more, particularly 70 parts by weight or more preferable. When the content of the resin (D) in the second composition according to Embodiment 2 of the present invention is within the above range, there is an advantage that more of the desired effects of the resin (D) can be enjoyed.

The upper limit of the content of the resin (D) in the second composition according to Embodiment 2 of the present invention is not particularly limited, but from the viewpoint of maintaining excellent handleability and storage stability of the present second composition , When the total of the fine polymer particles (A) and the low-molecular-weight compound (C) is 100 parts by weight, it is preferably 10,000 parts by weight or less, more preferably 5,000 parts by weight or less. , more preferably 2,000 parts by weight or less, more preferably 1,000 parts by weight or less, more preferably 750 parts by weight or less, more preferably 500 parts by weight or less, It is more preferably 100 parts by weight or less, more preferably 90 parts by weight or less, even more preferably 80 parts by weight or less, and 70 parts by weight or less. is particularly preferred.

(When the resin (D) is an epoxy resin)
The second composition according to Embodiment 2 of the present invention may further contain a known thermosetting resin, or may further contain a known thermoplastic resin.

For example, the second composition according to Embodiment 2 of the present invention may further contain an epoxy resin as the resin (D). The content of the epoxy resin is preferably less than 0.5 parts by weight with respect to 100 parts by weight of the low molecular weight compound (C). When the content of the epoxy resin is 0.5 parts by weight or more, the heat resistance (Tg) of the cured product is lowered, the surface of the cured product is sticky (surface tackiness), and the solvent is easily absorbed. As a result, the chemical resistance may decrease. The content of the epoxy resin is preferably less than 0.3 parts by weight, more preferably less than 0.2 parts by weight, and 0.1 parts by weight with respect to 100 parts by weight of the low molecular weight compound (C). It is particularly preferred that the content is less than, and most preferred that it contains no epoxy resin.

<1-10. Other Ingredients>
Even if the second composition according to Embodiment 2 of the present invention further contains other components, they are as described for the resin composition according to Embodiment 1, and will not be repeated here. Regarding the amounts of other components to be added, the description of the resin composition according to Embodiment 1 is applied by replacing the “matrix resin (B)” with the “low molecular weight compound (C)”. are omitted.

<1-11. Properties of Second Composition>
(viscosity)
The second composition according to Embodiment 2 of the present invention has excellent handleability due to its low viscosity. For example, the second composition according to Embodiment 2 of the present invention may have a viscosity of less than 1600 mPa·s at a shear rate (SR) of 10 s ⁻¹ .

(Storage stability)
Since the second composition according to Embodiment 2 of the present invention can maintain the dispersion state of the polymer fine particles (A) in the composition, aggregation of the polymer fine particles (A) can be prevented. As a result, phase separation is less likely to occur when the second composition is stored for a long period of time. Therefore, the second composition according to Embodiment 2 of the present invention has excellent storage stability. Conventionally, particularly when the content of a matrix resin having two or more polymerizable unsaturated bonds in the molecule in 100% by weight of the composition is large (for example, in 100% by weight of the composition, the matrix resin is 90 % by weight or more), there is a problem that phase separation is more likely to occur during long-term storage of the composition. For example, in the second composition according to Embodiment 2 of the present invention, even when the content of the matrix resin in the composition is 90% by weight or more, when stored for a long period of time, at 60 ° C. It can be stored for days without phase separation.

[3. Method for producing a resin composition]
The method for producing a resin composition according to Embodiment 1 of the present invention includes polymer fine particles (A) produced by the above-described method for producing polymer fine particles, and two or more polymerizable unsaturated bonds in the molecule. and a matrix resin (B), wherein in the mixing step, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles A configuration in which the polymer fine particles (A) and the matrix resin (B) are mixed at a mixing ratio of 1 to 50% by weight of (A) and 50 to 99% by weight of the matrix resin (B). is.

(Mixing process)
An example of the mixing step in the method for producing a resin composition according to Embodiment 1 of the present invention will be described below. The resin composition according to Embodiment 1 of the present invention is a composition in which polymer fine particles (A) are dispersed in the state of primary particles in a curable resin composition containing a matrix resin (B) as a main component. .

Various methods can be used for obtaining a composition in which the polymer fine particles (A) are dispersed in the state of primary particles. A method of removing unnecessary components such as water after bringing into contact with the matrix resin (B) and/or the low-molecular-weight compound (C), a method of extracting the polymer fine particles (A) once with an organic solvent, and then extracting the matrix resin (B) and / Or a method of removing the organic solvent after mixing with the low-molecular-weight compound (C), etc., but it is preferable to use the method described in International Publication No. 2005/28546.

That is, the mixing step in the method for producing the resin composition according to Embodiment 1 of the present invention may be configured to include the following first to third steps in this order: containing the fine polymer particles (A) After mixing the aqueous latex with an organic solvent that exhibits partial solubility in water, the resulting mixture is brought into contact with water to form aggregates of the polymer fine particles (A) containing the organic solvent in an aqueous phase. A first step of generating in the inside; after separating and recovering the aggregates of the polymer fine particles (A) from the aqueous phase, the aggregates are mixed with the organic solvent to form the polymer fine particles (A) A second step of obtaining an organic solvent dispersion; a third step of mixing the organic solvent dispersion with the matrix resin (B), and then distilling off the organic solvent from the obtained mixture.

The "organic solvent exhibiting partial solubility in water" means that when the aqueous latex of the polymer fine particles (A) is mixed with the organic solvent, the polymer fine particles (A) can be mixed without substantially solidifying and depositing. At least one or two or more organic solvents or organic solvent mixtures that can be achieved can be used without limitation. It is preferably 5% by weight or more and 30% by weight or less. When the solubility in water at 20° C. of the organic solvent partially soluble in water is 40% by weight or less, the aqueous latex of the polymer particles (A) is not coagulated, and the mixing operation can be performed smoothly. can. In addition, when the solubility in water at 20° C. of the organic solvent partially soluble in water is 5% by weight or more, it can be sufficiently mixed with the aqueous latex of the polymer particles (A), and can be smoothly mixed. operation can be performed.

Specific examples of the "organic solvent exhibiting partial solubility in water" include esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; ethanol , (iso)propanol, butanol and other alcohols; tetrahydrofuran, tetrahydropyran, dioxane, diethyl ether and other ethers; benzene, toluene, xylene and other aromatic hydrocarbons; methylene chloride, chloroform and other halogenated hydrocarbons or a mixture thereof, which satisfies the above range of solubility in water at 20°C. Among them, an organic solvent containing 50% by weight or more of methyl ethyl ketone is more preferably used as an organic solvent exhibiting partial solubility in water from the viewpoints of affinity with a reactive polymerizable organic compound and ease of availability. Furthermore, an organic solvent containing 75% by weight or more of methyl ethyl ketone is particularly preferably used.

Specifically, the composition (for example, the present resin composition) in which the polymer fine particles (A) are dispersed in the state of primary particles in a resin containing the matrix resin (B) as a main component is An aqueous latex containing the coalesced fine particles (A) (specifically, a reaction mixture after the production of the polymer fine particles (A) by emulsion polymerization) is added to an aqueous latex having a solubility in water at 20°C of 5% by weight or more and 40% by weight or less. After mixing with an organic solvent, the resulting mixture is further mixed with an excess amount of water to form a first step of aggregating the polymer fine particles (A), and separating and separating the aggregated polymer fine particles (A) from the liquid phase. After recovery, the obtained aggregates of polymer fine particles (A) are mixed again with an organic solvent to obtain an organic solvent dispersion of polymer fine particles (A) in a second step; and a third step of distilling off the organic solvent from the resulting mixture after mixing with the resin (B) and/or the low-molecular-weight compound (C).

When a large number of aggregates of primary particles (for example, powdery polymer fine particles (A)) are mixed with a liquid resin, the physical cohesive force of the particles is very strong. Even if a shearing force is applied, it is extremely difficult to disperse the fine polymer particles (A) in the resin without aggregation.

It is preferable that the matrix resin (B) or the mixture of the matrix resin (B) and the low-molecular-weight compound (C) is liquid at 23°C because the third step is facilitated. Furthermore, it is more preferable that the matrix resin (B) alone is liquid at 23°C. The term "liquid at 23°C" means that the softening point is 23°C or lower and that the material exhibits fluidity at 23°C.

The matrix resin (B), the low The resin composition according to Embodiment 1 of the present invention in which the polymer fine particles (A) are dispersed in the state of primary particles by further mixing the molecular compound (C) and the other compounding ingredients, if necessary. is obtained.

A resin composition produced by the method for producing a resin composition described above is also included in the scope of the present invention.

(Method for producing second composition)
In the method for producing the second composition according to Embodiment 2 of the present invention, in the description of the method for producing the resin composition according to Embodiment 1, "matrix resin (B)" is read as "low molecular weight compound (C)". The detailed description is omitted.

[4. Cured material]
A cured product obtained by curing the resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention, in other words, the resin composition according to Embodiment 1 of the present invention or the present invention In the cured product obtained by curing the second composition according to Embodiment 2, the fine polymer particles (A) can be uniformly dispersed in the state of primary particles. A cured product obtained by curing the resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention is also an embodiment of the present invention.

[5. Application]
The resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention can be used for various uses, and the uses are not particularly limited. The resin composition or the second composition is, for example, an adhesive, a coating material, a binder for reinforcing fibers, a composite material, a molding material for a 3D printer, a sealant, an electronic substrate, an ink binder, a wood chip binder, or a binder for rubber chips. , foam chip binders, binders for castings, bedrock consolidation materials for floor materials and ceramics, and urethane foams. Examples of urethane foam include automobile seats, automobile interior parts, sound absorbing materials, vibration damping materials, shock absorbers (shock absorbing materials), heat insulating materials, construction floor material cushions, and the like. Among the applications described above, the resin composition according to Embodiment 1 of the present invention or the second composition according to Embodiment 2 of the present invention is used as an adhesive, a coating material, a binder for reinforcing fibers, a composite material, and a molding of a 3D printer. It is more preferably used as materials, encapsulants, and electronic substrates.

An embodiment of the present invention may have the following configuration.

[1] Containing polymer fine particles (A) and a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule,
The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
The elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber,
The graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
The first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer,
The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit is more than 0.00% by weight and less than 2.00% by weight. and
When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the matrix resin (B) is 50% by weight. A resin composition that is ~99% by weight.

[2] When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 10 to 50% by weight, and the matrix resin (B ) is 50 to 90% by weight, the resin composition according to [1].

[3] The elastic body is
an elastic core of an elastic body obtained by polymerizing one or more monomers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers, and organosiloxane-based rubbers;
a surface-crosslinked polymer obtained by polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;
The resin composition according to [1] or [2], containing

[4] The resin composition according to any one of [1] to [3], further comprising a low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule. .

[5] The resin composition according to [4], wherein the low-molecular-weight compound (C) is a (meth)acryloyl group-containing compound.

[6] When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit exceeds 0.00% by weight and is 1.00% by weight. The resin composition according to any one of [1] to [5], which is less than % by weight.

[7] The matrix resin (B) is selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and acrylated (meth)acrylates. The resin composition according to any one of [1] to [6], which is one or more selected curable resins.

[8] The resin composition according to any one of [1] to [7], further comprising a resin (D).

[9] When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 5 to 50% by weight, and the matrix resin (B ) is 50 to 95% by weight, and the resin composition according to [1], which is for a masterbatch.

[10] Containing fine polymer particles (A) and a low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule,
The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
The elastic body includes one or more selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber, and organosiloxane-based rubber,
The graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
The first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer,
The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit is more than 0.00% by weight and less than 2.00% by weight. and
When the total amount of the polymer fine particles (A) and the low-molecular-weight compound (C) is 100% by weight, the polymer fine-particles (A) are 1 to 50% by weight, and the low-molecular-weight compound (C) is is 50 to 99% by weight.

[11] When the total amount of the polymer fine particles (A) and the low-molecular-weight compound (C) is 100% by weight, the polymer fine-particles (A) are 10 to 50% by weight, and the low-molecular-weight compound The composition according to [10], wherein (C) is 50 to 90% by weight.

[12] The elastic body is
an elastic core of an elastic body obtained by polymerizing one or more monomers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers, and organosiloxane-based rubbers;
a surface-crosslinked polymer obtained by polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;
The composition according to [10] or [11], containing

[13] The composition according to any one of [10] to [12], wherein the low-molecular weight compound (C) is a (meth)acryloyl group-containing compound.

[14] When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit exceeds 0.00% by weight and is 1.00% by weight. % by weight, the composition according to any one of [10] to [13].

[15] The composition according to any one of [10] to [14], further containing a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule.

[16] The matrix resin (B) is selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and acrylated (meth)acrylates. The composition according to any one of [10] to [15], which is one or more selected curable resins.

[17] The composition according to any one of [10] to [16], further comprising a resin (D).

[18] When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 5 to 50% by weight, and the matrix resin (B ) is 50 to 95% by weight and is for a masterbatch, the composition according to [10].

[19] an elastic body preparation step of polymerizing at least one monomer selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers;
a graft portion preparation step of graft-polymerizing the first monomer and the second monomer onto the elastic body prepared in the elastic body preparation step;
The first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer,
The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
In the graft portion preparation step, the second monomer exceeds 0.00% by weight when the total of the first monomer and the second monomer is 100% by weight. A method for producing polymer microparticles, using less than 2.00% by weight.

[20] The method for producing polymer microparticles according to [19], wherein the elastic body preparation step includes the following steps (a) and (b):
(a) polymerizing one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers;
(b) a step of polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;

[21] Polymer microparticles (A) produced by the method for producing polymer microparticles according to [19] or [20], and matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule including a mixing step of mixing with
In the mixing step, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the matrix resin A method for producing a resin composition, wherein the fine polymer particles (A) and the matrix resin (B) are mixed at a mixing ratio of 50 to 99% by weight of (B).

[22] The method for producing a resin composition according to [21], wherein the mixing step includes the following first to third steps in this order:
After mixing the aqueous latex containing the polymer fine particles (A) with an organic solvent that exhibits partial solubility in water, the resulting mixture is brought into contact with water to obtain the polymer fine particles containing the organic solvent. A first step of forming aggregates of (A) in an aqueous phase;
After separating and recovering the aggregates of the polymer fine particles (A) from the aqueous phase, the aggregates are mixed with the organic solvent to obtain an organic solvent dispersion of the polymer fine particles (A). process;
A third step of mixing the organic solvent dispersion with the matrix resin (B) and then distilling off the organic solvent from the resulting mixture.

[23] Polymer microparticles (A) produced by the method for producing polymer microparticles according to [19] or [20]; including a mixing step of mixing with the molecular compound (C),
In the mixing step, when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (C) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the low-molecular-weight compound (C) is A method for producing a composition, wherein the fine polymer particles (A) and the low-molecular-weight compound (C) are mixed at a compounding ratio in which the molecular compound (C) is 50 to 99% by weight.

[24] The method for producing a composition according to [23], wherein the mixing step includes the following first to third steps in this order:
After mixing the aqueous latex containing the polymer microparticles (A) with an organic solvent partially soluble in water, the resulting mixture is brought into contact with water to obtain the polymer microparticles containing the organic solvent. A first step of forming aggregates of (A) in an aqueous phase;
After separating and recovering the aggregates of the polymer fine particles (A) from the aqueous phase, the aggregates are mixed with the organic solvent to obtain an organic solvent dispersion of the polymer fine particles (A). process;
a third step of mixing the organic solvent dispersion with the low-molecular-weight compound (C), and then distilling off the organic solvent from the resulting mixture.

An embodiment of the present invention can also be expressed as follows.

[25] polymer microparticles (A);
(i) a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule, or (ii) a low molecular weight compound (C ), and
The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
The elastic body includes one or more selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber, and organosiloxane-based rubber,
The graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
The first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer,
The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit is more than 0.00% by weight and less than 2.00% by weight. and
(i) When the matrix resin (B) is included, the polymer fine particle (A) is 1 to 50% by weight when the total of the polymer fine particle (A) and the matrix resin (B) is 100% by weight. % by weight, and the matrix resin (B) is 50 to 99% by weight,
(ii) when the low-molecular-weight compound (C) is contained, the polymer fine-particles (A) is 1 ~50% by weight, and the low molecular weight compound (C) is 50-99% by weight.

[26] (i) Polymer fine particles (A) produced by the method for producing polymer fine particles according to [19] or [20], and a matrix resin having two or more polymerizable unsaturated bonds in the molecule (B), or (ii) polymer fine particles (A) produced by the method for producing polymer fine particles according to [19] or [20], and at least one in the molecule a second mixing step of mixing with a low molecular weight compound (C) having a polymerizable unsaturated bond of less than 300,
In the first mixing step, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and The polymer fine particles (A) and the matrix resin (B) are mixed at a blending ratio in which the matrix resin (B) is 50 to 99% by weight,
In the second mixing step, when the total amount of the polymer fine particles (A) and the low-molecular weight compound (C) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight, A method for producing a composition, comprising mixing the polymer fine particles (A) and the low-molecular-weight compound (C) at a mixing ratio of 50 to 99% by weight of the low-molecular-weight compound (C).
The first mixing step is the same as the mixing step in the method for producing the resin composition according to Embodiment 1, and the second mixing step is the same as the mixing step in the method for producing the second composition according to Embodiment 2. is.

An embodiment of the present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. One embodiment of the present invention can be modified and implemented as long as it conforms to the spirit of the above and later descriptions, and all of them are included in the technical scope of the present invention.

<1. Production of Latex Containing Polymer Microparticles (A)>
(Production Example 1-1: Step of preparing elastic body (preparation of water-based latex (R-1) containing elastic body mainly composed of polystyrene-butadiene rubber))
200 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of disodium ethylenediaminetetraacetate (EDTA), and 0.001 parts by weight of ferrous sulfate heptahydrate are placed in a pressure-resistant polymerization vessel. and 1.55 parts by weight of sodium dodecylbenzenesulfonate (SDBS) as an emulsifier. Next, oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the introduced raw materials. After that, 23.5 parts by weight of styrene (St) and 76.5 parts by weight of butadiene (Bd) were charged into the pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C. After that, 0.03 parts by weight of paramenthane hydroperoxide (PHP) was charged into the pressure-resistant polymerization vessel, and then 0.10 parts by weight of sodium formaldehyde sulfoxylate (SFS) was charged into the pressure-resistant polymerization vessel to initiate polymerization. started. 0.025 parts by weight of paramenthane hydroperoxide (PHP) was charged into the pressure-resistant polymerization vessel after 3, 5 and 7 hours from the start of the polymerization. Further, 0.0006 parts by weight of EDTA and 0.003 parts by weight of ferrous sulfate heptahydrate were charged into the pressure-resistant polymerization vessel 4 hours, 6 hours and 8 hours after the start of polymerization. After 15 hours from the initiation of the polymerization, devolatilization was performed under reduced pressure to remove residual monomers that were not used in the polymerization, thereby completing the polymerization. By the polymerization, a water-based latex (R-1) containing an elastic body (elastic body core) mainly composed of polystyrene-butadiene rubber was obtained. The volume-average particle size of the elastic body (core of the elastic body) contained in the obtained aqueous latex was 90 nm.

(Production Example 2-1; Graft portion preparation step (production of latex (L1) containing fine polymer particles (A))
A glass reactor was charged with 250 parts by weight of the aqueous latex (R-1) (containing 83 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 70 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Then 6.0 parts by weight methyl methacrylate (MMA), 10 parts by weight butyl acrylate (BA), 1.0 parts by weight 4-hydroxybutyl acrylate (4HBA), and 0.035 parts by weight t-butyl hydroperoxide (BHP). The mixture of parts was added continuously over 80 minutes into a glass reactor. After that, 0.013 parts by weight of BHP was added into the glass reactor, and stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L1) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L1) obtained was 30% by weight.

In L1, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 0.00% by weight when set to 100% by weight.

(Production Example 2-2; Graft portion preparation step (production of latex (L2) containing fine polymer particles (A))
A glass reactor was charged with 250 parts by weight of the aqueous latex (R-1) (containing 83 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 70 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Then, 5.9 parts by weight methyl methacrylate (MMA), 10 parts by weight butyl acrylate (BA), 1.0 parts by weight 4-hydroxybutyl acrylate (4HBA), 0.1 parts by weight allyl methacrylate (AMA), and t- A mixture of 0.035 parts by weight of butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes. After that, 0.013 parts by weight of BHP was added into the glass reactor, and stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L2) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L2) obtained was 30% by weight.

In L2, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 0.59% by weight when set to 100% by weight.

(Production Example 2-3; Graft portion preparation step (production of latex (L3) containing fine polymer particles (A))
A glass reactor was charged with 250 parts by weight of the aqueous latex (R-1) (containing 83 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 70 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Then, 5.7 parts by weight methyl methacrylate (MMA), 10 parts by weight butyl acrylate (BA), 1.0 parts by weight 4-hydroxybutyl acrylate (4HBA), 0.3 parts by weight allyl methacrylate (AMA), and t- A mixture of 0.035 parts by weight of butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes. After that, 0.013 parts by weight of BHP was added into the glass reactor, and stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L3) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L3) obtained was 30% by weight.

In L3, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.76% by weight when set to 100% by weight.

(Production Example 2-4; Graft portion preparation step (production of latex (L4) containing fine polymer particles (A))
A glass reactor was charged with 250 parts by weight of the aqueous latex (R-1) (containing 83 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 70 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Then, 5.4 parts by weight methyl methacrylate (MMA), 10 parts by weight butyl acrylate (BA), 1.0 parts by weight 4-hydroxybutyl acrylate (4HBA), 0.6 parts by weight allyl methacrylate (AMA), and t- A mixture of 0.035 parts by weight of butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes. After that, 0.013 parts by weight of BHP was added into the glass reactor, and stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L4) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L4) obtained was 30% by weight.

In L4, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 3.53% by weight when set to 100% by weight.

(Production Example 2-5; Graft portion preparation step (production of latex (L5) containing fine polymer particles (A))
A glass reactor was charged with 250 parts by weight of the aqueous latex (R-1) (containing 83 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 70 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Then, 5.0 parts by weight methyl methacrylate (MMA), 10 parts by weight butyl acrylate (BA), 1.0 parts by weight 4-hydroxybutyl acrylate (4HBA), 1.0 parts by weight allyl methacrylate (AMA), and t- A mixture of 0.035 parts by weight of butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes. After that, 0.013 parts by weight of BHP was added into the glass reactor, and stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L5) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L5) obtained was 30% by weight.

In L5, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 5.88% by weight when set to 100% by weight.

(Production Example 2-6; Graft portion preparation step (production of latex (L6) containing fine polymer particles (A))
A glass reactor was charged with 230 parts by weight of the aqueous latex (R-1) (containing 75 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 80 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. then 8.4 parts by weight methyl methacrylate (MMA), 14.7 parts by weight butyl acrylate (BA), 1.5 parts by weight 4-hydroxybutyl acrylate (4HBA), 0.4 parts by weight allyl methacrylate (AMA), and A mixture of 0.035 parts by weight of t-butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes. After that, 0.013 parts by weight of BHP was added into the glass reactor, and the stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L6) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the obtained aqueous latex (L6) was 30% by weight.

In L6, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.60% by weight when set to 100% by weight.

(Production Example 2-7; Graft portion preparation step (production of latex (L7) containing fine polymer particles (A))
A glass reactor was charged with 220 parts by weight of the aqueous latex (R-1) (containing 72 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 85 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. A mixture of 3.0 parts by weight of allyl methacrylate (AMA) and 0.03 parts by weight of t-butyl hydroperoxide (BHP) was then added into the glass reactor. Stirring of the mixture in the glass reactor was continued for an additional hour to complete the polymerization of the surface cross-linked polymer. then 8.4 parts by weight methyl methacrylate (MMA), 14.7 parts by weight butyl acrylate (BA), 1.5 parts by weight 4-hydroxybutyl acrylate (4HBA), 0.4 parts by weight allyl methacrylate (AMA), and A mixture of 0.035 parts by weight of t-butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes. After that, 0.013 parts by weight of BHP was added into the glass reactor, and stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L7) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L7) obtained was 30% by weight.

In L7, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.60% by weight when set to 100% by weight.

(Production Example 2-8; Graft portion preparation step (production of latex (L8) containing fine polymer particles (A))
A glass reactor was charged with 200 parts by weight of the aqueous latex (R-1) (including 67 parts by weight of an elastic body mainly composed of polystyrene-butadiene rubber) and 100 parts by weight of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.2 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. A mixture of 3.0 parts by weight of allyl methacrylate (AMA) and 0.03 parts by weight of t-butyl hydroperoxide (BHP) was then added into the glass reactor. Stirring of the mixture in the glass reactor was continued for an additional hour to complete the polymerization of the surface cross-linked polymer. then 10.1 parts by weight methyl methacrylate (MMA), 17.6 parts by weight butyl acrylate (BA), 1.8 parts by weight 4-hydroxybutyl acrylate (4HBA), 0.5 parts by weight allyl methacrylate (AMA), and A mixture of 0.035 parts by weight of t-butyl hydroperoxide (BHP) was continuously added into the glass reactor over 80 minutes. After that, 0.013 parts by weight of BHP was added into the glass reactor, and stirring of the mixture in the glass reactor was continued for 1 hour to complete the polymerization of the grafted portion. By the above operation, an aqueous latex (L8) containing polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 100 nm. The solid content concentration (concentration of fine polymer particles (A)) in 100% by weight of the aqueous latex (L8) obtained was 30% by weight.

In L8, the content of the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion. It was 1.67% by weight when set to 100% by weight.

Among the monomers used in the graft portion preparation steps of Production Examples 2-1 to 2-8, methyl methacrylate (MMA), butyl acrylate (BA) and 4-hydroxybutyl acrylate (4HBA) are the first monomers. monomer and allyl methacrylate (AMA) is the second monomer.

Table 1 summarizes the blending amounts of each component of the polymer microparticles (A). In addition, the "content of the second structural unit" described in Table 1 is the second structural unit when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion is 100% by weight. It is the content of the structural unit of No. 2.

<2. Production of Resin Composition>
[Example 1]
After the temperature inside the 1 L mixing tank was set to 30° C., 126 parts by weight of methyl ethyl ketone (MEK) as an organic solvent partially soluble in water was added to the mixing tank. After that, 143 parts by weight of the latex (L2) of the fine polymer particles (A) was added to the mixing tank while stirring the MEK in the mixing tank. After uniformly mixing the charged raw materials, 200 parts by weight of water (452 parts by weight in total) was added to the mixture (mixing vessel) at a feed rate of 80 parts by weight/minute while stirring the resulting mixture. After the supply of water was finished, the stirring of the mixture was quickly stopped, and aggregates of floating polymer fine particles (A) were formed in the water phase (first step). Through the first step, a slurry liquid containing aggregates of floating polymer fine particles (A) was obtained.

Next, leaving aggregates of polymer fine particles (A) in the mixing tank, 350 parts by weight of the liquid phase was discharged from the outlet at the bottom of the mixing tank. That is, aggregates of polymer fine particles (A) were separated and recovered from the aqueous phase. 150 parts by weight of MEK was added to the resulting aggregates of the polymer fine particles (A) (polymer fine particle (A) dope) and mixed to obtain an organic solvent dispersion in which the polymer fine particles (A) were dispersed. (Second step). To 277 parts by weight of this organic solvent dispersion (including 42.9 parts by weight of polymer fine particles (A)), 45 parts by weight of a liquid unsaturated polyester resin (manufactured by Eternal, Eterset 2010) as the matrix resin (B), and a low molecular After adding 19 parts by weight of 2-hydroxypropyl methacrylate (HPMA) which is the compound (C) and mixing the resulting mixture, MEK is distilled off from the mixture under reduced pressure to obtain a resin composition (A-1). was obtained (third step). The resin composition (A-1) contains 40% by weight of the fine polymer particles (A) when the total amount of the fine polymer particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

[Example 2]
A resin composition (A-2) was obtained in the same manner as in Example 1, except that the latex (L3) was used as the latex of the fine polymer particles (A). The resin composition (A-2) contains 40% by weight of the polymer particles (A) when the total of the polymer particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

[Comparative Example 1]
A resin composition (A-3) was obtained in the same manner as in Example 1, except that the latex (L1) was used as the latex of the polymer fine particles (A). The resin composition (A-3) contains 40% by weight of the fine polymer particles (A) when the total amount of the fine polymer particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

[Comparative Example 2]
A resin composition (A-4) was obtained in the same manner as in Example 1, except that the latex (L4) was used as the latex of the fine polymer particles (A). The resin composition (A-4) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

[Comparative Example 3]
A resin composition (A-5) was obtained in the same manner as in Example 1, except that the latex (L5) was used as the latex of the fine polymer particles (A). The resin composition (A-5) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

[Example 3]
A resin composition (A-6) was obtained in the same manner as in Example 1, except that the latex (L6) was used as the latex of the fine polymer particles (A). The resin composition (A-6) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

[Example 4]
A resin composition (A-7) was obtained in the same manner as in Example 1, except that the latex (L7) was used as the latex of the fine polymer particles (A). The resin composition (A-7) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

[Example 5]
A resin composition (A-8) was obtained in the same manner as in Example 1, except that the latex (L8) was used as the latex of the fine polymer particles (A). The resin composition (A-8) contains 40% by weight of the polymer fine particles (A) when the total of the polymer fine particles (A), the matrix resin (B) and the low-molecular weight compound (C) is 100% by weight. %, 42% by weight of the matrix resin (B), and 18% by weight of the low molecular weight compound (C).

<3. Evaluation of Resin Composition>
<Evaluation of handleability>
The handling properties of the resin compositions prepared in Examples and Comparative Examples were evaluated as follows based on the viscosity of the resin compositions at 25°C.
・ Especially excellent in handleability: the viscosity of the resin composition at 25 ° C. is 1000 mPa s or more and less than 3000 mPa s ・ Excellent handleability: the viscosity of the resin composition at 25 ° C. is 3000 mPa s or more and less than 6000 mPa s ・Poor handleability: Viscosity of resin composition at 25° C. of 6000 mPa·s or more A digital viscometer DV-II+Pro type manufactured by BROOKFIELD was used to measure the viscosity of the resin compositions prepared in Examples and Comparative Examples. In addition, the viscosity was measured at a measurement temperature of 25° C. and a shear rate (SR) of 10 s ⁻¹ using a spindle CPE-52 depending on the viscosity range.

<Evaluation of storage stability>
The storage stability of the resin compositions prepared in Examples and Comparative Examples was evaluated as follows based on the maintenance of the dispersed state of the polymer fine particles (A) in the resin composition.
- Excellent storage stability: the polymer fine particles (A) in the resin composition do not undergo phase separation at 60°C for at least 30 days.
- Poor storage stability: the polymer fine particles (A) in the resin composition undergo phase separation at 60°C within 30 days.

The storage stability of the resin compositions prepared in Examples and Comparative Examples was evaluated by mixing 10 g of the resin composition and 90 g of unsaturated polyester resin 2731-1 manufactured by Eternal Co., Ltd. as the resin (D) using a rotation and revolution mixer. After mixing, the mixture was placed in a transparent bottle, stored in an oven at 60° C., and visually checked for separation over time. The total content of the matrix resin (B) and the resin (D) in the resin composition after mixing the resin composition and the resin (D) (i.e., two or more polymerizable unsaturated bonds in the molecule The content of the matrix resin having ) was 94.2% by weight.

The results are shown in Table 1.

To explain the results of phase separation shown in Table 1, "Phase separation occurred on the X day" does not indicate that phase separation started on the X day of the start of the test, but on the X day of the start of the test. It means that phase separation was observed in at least a part of the resin composition as a result of observation. Therefore, "phase-separated on the X day" also includes an embodiment in which at least a part of the resin composition is phase-separated before the X day.

As shown in Table 1, in all of the resin compositions of Comparative Examples 2 and 3, phase separation was already observed on the 23rd day from the start of the test. On the other hand, both the resin compositions of Examples 1 to 5 and the resin composition of Comparative Example 1 showed phase separation when observed 65 days after the start of the test. For the resin compositions of Examples 1 to 5 and the resin composition of Comparative Example 1, the observation results on the 50th day from the start of the test are also shown in parentheses. Phase separation was observed in all of the resin compositions of Examples 2 to 5 when observed 50 days after the start of the test. On the other hand, no phase separation was observed in the resin compositions of Example 1 and Comparative Example 1 after 50 days from the start of the test.

From the above, regarding the storage stability, when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight, It has been found that when the structural unit of 2 is less than 2.00% by weight, the resin composition containing such fine polymer particles (A) has excellent storage stability. In particular, when the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight, the second structural unit is 1.00% by weight. %, the storage stability of the resin composition is particularly excellent.

As for handleability, the resin composition of Comparative Example 1 had a viscosity of 6000 mPa·s or more at a shear rate (SR) of 10 s ⁻¹ . On the other hand, the resin compositions of Examples 1 to 5 and Comparative Examples 2 to 3 all had low viscosities at a shear rate (SR) of 10 s ⁻¹ , well below 6000 mPa·s. rice field.

From the above, regarding the handleability, when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight, the second structural unit is more than 0.00% by weight, the resin composition containing the fine polymer particles (A) has excellent handleability.

To summarize the results of Examples and Comparative Examples, when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight, When the structural unit of 2 is more than 0.00% by weight and less than 2.00% by weight, the resin composition containing such polymer fine particles (A) is excellent in both handleability and storage stability. It became clear. In particular, when the total amount of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A) is 100% by weight, the second structural unit is 0.00% by weight. % and less than 1.00% by weight, the storage stability of the resin composition is particularly excellent.

Moreover, as shown in Examples 4 and 5, when the elastic body has a surface-crosslinked polymer, the polyfunctional monomer component contained in the surface-crosslinked polymer surprisingly affects the viscosity of the resin composition. can be further reduced, but the compatibility of the resin composition is not affected.

<4. Production of second composition>
[Example 6]
Instead of 45 parts by weight of a liquid unsaturated polyester resin (manufactured by Eternal, Eterset 2010) as the matrix resin (B) and 19 parts by weight of 2-hydroxypropyl methacrylate (HPMA) as the low-molecular compound (C), a low-molecular A composition (A-9) was obtained in the same manner as in Example 1, except that 64 parts by weight of 2-hydroxypropyl methacrylate (HPMA), which is the compound (C), was used. The composition (A-9) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.

[Example 7]
A composition (A-10) was obtained in the same manner as in Example 6, except that the latex (L3) was used as the latex of the fine polymer particles (A). The composition (A-10) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.

[Comparative Example 4]
A composition (A-11) was obtained in the same manner as in Example 6, except that the latex (L1) was used as the latex of the fine polymer particles (A). The composition (A-11) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.

[Comparative Example 5]
A composition (A-12) was obtained in the same manner as in Example 6, except that the latex (L5) was used as the latex of the fine polymer particles (A). The composition (A-12) contains 40% by weight of the polymer microparticles (A) and the low-molecular-weight compound (C ) in an amount of 60% by weight.

<5. Evaluation of Second Composition>
<Evaluation of handleability>
The viscosities of the compositions of Examples 6-7 and Comparative Examples 4-5 were measured by the same method as for the resin compositions of Examples 1-5 and Comparative Examples 1-3. The handleability of the compositions prepared in Examples 6 and 7 and Comparative Examples 4 and 5 was determined by the sum of the first structural unit and the second structural unit in the polymer constituting the graft portion of the fine polymer particles (A). was 100% by weight, the viscosity at 25° C. of the composition of Comparative Example 4 containing 0.00% by weight of the second structural unit was evaluated as follows.
・Handleability was further improved: Viscosity decreased by 30% or more relative to the viscosity at 25 ° C. of the composition of Comparative Example 4 ・Handleability was improved: Relative to the viscosity at 25 ° C. of the composition of Comparative Example 4 , Viscosity decreased by 10% or more ・Handleability decreased: Viscosity increased compared to the viscosity of the composition of Comparative Example 4 at 25°C.

<Evaluation of storage stability>
The storage stability of the compositions (resin compositions) of Examples 6-7 and Comparative Examples 4-5 was evaluated in the same manner as the resin compositions of Examples 1-5 and Comparative Examples 1-3.

The results are shown in Table 2.

As shown in Table 2, phase separation was already observed in the resin composition of Comparative Example 5 in observation on the 23rd day from the start of the test. On the other hand, both the resin compositions of Examples 6 and 7 and the resin composition of Comparative Example 4 were found to undergo phase separation when observed 65 days after the start of the test. For the resin compositions of Examples 6 and 7 and the resin composition of Comparative Example 4, the observation results on the 50th day from the start of the test are also shown in parentheses. The resin composition of Example 7 was found to undergo phase separation when observed 50 days after the start of the test. On the other hand, no phase separation was observed in the resin compositions of Example 6 and Comparative Example 4 after 50 days from the start of the test.

As for handleability, the composition of Comparative Example 4 had a viscosity of 1650 mPa·s at a shear rate (SR) of 10 s ⁻¹ . On the other hand, all of the compositions of Examples 6 to 7 and Comparative Example 5 had Shear Rate (SR, The viscosity at a shear rate of 10 s ^-1 was reduced by 10% or more, and the handleability was improved.

From the above, regarding the handleability, when the total of the first structural unit and the second structural unit in the polymer constituting the graft portion of the polymer fine particle (A) is 100% by weight, the second structural unit exceeds 0.00% by weight, the composition containing such fine polymer particles (A) has improved handleability.

From the results of Examples 6 and 7 and Comparative Examples 4 and 5, the second composition containing the polymer fine particles (A) and the low-molecular-weight compound (C) also constitutes the graft portion of the polymer fine particles (A). When the second structural unit is more than 0.00% by weight and less than 2.00% by weight, when the total of the first structural unit and the second structural unit in the polymer is 100% by weight , the second composition containing such polymer fine particles (A) was found to be excellent in both handleability and storage stability.

Claims

containing polymer fine particles (A) and a matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule,
The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
The elastic body includes one or more selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber, and organosiloxane-based rubber,
The graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
The first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer,
The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit is more than 0.00% by weight and less than 2.00% by weight. and
When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the matrix resin (B) is 50% by weight. A resin composition that is ~99% by weight.
When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 10 to 50% by weight, and the matrix resin (B) is 50% by weight. The resin composition of claim 1, which is ∼90% by weight.
The elastic body is
an elastic core of an elastic body obtained by polymerizing one or more monomers selected from the group consisting of diene-based rubbers, (meth)acrylate-based rubbers, and organosiloxane-based rubbers;
a surface-crosslinked polymer obtained by polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;
The resin composition according to claim 1 or 2, containing
The resin composition according to any one of claims 1 to 3, further comprising a low molecular weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule.
The resin composition according to claim 4, wherein the low-molecular-weight compound (C) is a (meth)acryloyl group-containing compound.
When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit is more than 0.00% by weight and less than 1.00% by weight. The resin composition according to any one of claims 1 to 5.
The matrix resin (B) is selected from the group consisting of unsaturated polyesters, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates and acrylated (meth)acrylates. The resin composition according to any one of claims 1 to 6, which is one or more curable resins.
The resin composition according to any one of claims 1 to 7, further comprising a resin (D).
When the total of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 5 to 50% by weight, and the matrix resin (B) is 50% by weight. ~95% by weight,
for masterbatches,
The resin composition according to claim 1.
Containing polymer fine particles (A) and a low-molecular-weight compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule,
The fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body,
The elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber,
The graft portion is made of a polymer containing a first structural unit derived from a first monomer and a second structural unit derived from a second monomer,
The first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer,
The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
When the total of the first structural unit and the second structural unit in the graft portion is 100% by weight, the second structural unit is more than 0.00% by weight and less than 2.00% by weight. and
When the total amount of the polymer fine particles (A) and the low-molecular-weight compound (C) is 100% by weight, the polymer fine-particles (A) are 1 to 50% by weight, and the low-molecular-weight compound (C) is is 50 to 99% by weight.
an elastic body preparation step of polymerizing at least one monomer selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers;
a graft portion preparation step of graft-polymerizing the first monomer and the second monomer onto the elastic body prepared in the elastic body preparation step;
The first monomer is one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth)acrylate monomer,
The second monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule,
In the graft portion preparation step, the second monomer exceeds 0.00% by weight when the total of the first monomer and the second monomer is 100% by weight. A method for producing polymer microparticles, using less than 2.00% by weight.
12. The method for producing polymer microparticles according to claim 11, wherein the elastic body preparation step includes the following steps (a) and (b):
(a) polymerizing one or more monomers selected from the group consisting of diene-based monomers, (meth)acrylate-based monomers, and organosiloxane-based monomers;
(b) a step of polymerizing one or more monomers selected from the group consisting of the polyfunctional monomer and vinyl-based monomers other than the polyfunctional monomer;
Mixing of polymer fine particles (A) produced by the method for producing polymer fine particles according to claim 11 or 12 and matrix resin (B) having two or more polymerizable unsaturated bonds in the molecule. including the process,
In the mixing step, when the total amount of the polymer fine particles (A) and the matrix resin (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the matrix resin A method for producing a resin composition, wherein the fine polymer particles (A) and the matrix resin (B) are mixed at a mixing ratio of 50 to 99% by weight of (B).
The method for producing a resin composition according to claim 13, wherein the mixing step includes the following first to third steps in this order:
After mixing the aqueous latex containing the polymer fine particles (A) with an organic solvent that exhibits partial solubility in water, the resulting mixture is brought into contact with water to obtain the polymer fine particles containing the organic solvent. A first step of forming aggregates of (A) in an aqueous phase;
After separating and recovering the aggregates of the polymer fine particles (A) from the aqueous phase, the aggregates are mixed with the organic solvent to obtain an organic solvent dispersion of the polymer fine particles (A). process;
A third step of mixing the organic solvent dispersion with the matrix resin (B) and then distilling off the organic solvent from the resulting mixture.
Polymer fine particles (A) produced by the method for producing polymer fine particles according to claim 11 or 12, and a low-molecular compound (C) having a molecular weight of less than 300 and having at least one polymerizable unsaturated bond in the molecule including a mixing step of mixing with
In the mixing step, when the total amount of the polymer fine particles (A) and the low-molecular-weight compound (C) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the low-molecular-weight compound (C) is A method for producing a composition, wherein the fine polymer particles (A) and the low-molecular-weight compound (C) are mixed at a compounding ratio in which the molecular compound (C) is 50 to 99% by weight.