JP2023057312A - Composition, polyvinyl chloride-based plastisol composition and method for producing the same - Google Patents

Abstract

To provide a composition that comprises a plasticizer and polymer particulates and is blended in a polyvinyl chloride-based plastisol composition, capable of providing a molding having excellent mechanical properties.SOLUTION: A composition comprises polymer particulates (A) and a specific amount of a plasticizer (B). The polymer particulates (A) each comprise a rubber-containing graft copolymer comprising a specific elastic body and a graft moiety being grafted to the elastic body, with the elastic body being crosslinked.SELECTED DRAWING: None

Description

The present invention relates to a composition, a vinyl chloride-based plastisol composition, and a method for producing the same.

A plastisol composition obtained by dispersing fine resin particles in a plasticizer is a paste-like composition (sol) at room temperature, and can be said to be a fluid liquid at room temperature. Such plastisol compositions are now widely used industrially as coating agents.

For example, in Patent Document 1, (i) an unsaturated monomer (m) having a solubility in water at 0° C. of 2.0 to 30% by mass is added in an aqueous dispersion medium (S) in the absence of an emulsifier micelle. 1.7 to 2.0 parts per 100 parts by mass of the acrylic unsaturated monomer (M) and the acrylic unsaturated monomer (M) in the dispersion liquid of the seed particles (A) obtained by polymerization. Add a part by mass of an emulsifier and perform the polymerization operation at least once, and the ratio of the volume average primary particle size (DvP) to the number average primary particle size (DnP) (DvP/DnP) is 1.3 to 3.5. A plastisol composition is disclosed that includes certain acrylic polymer microparticles and (ii) a plasticizer.

In addition, in Patent Document 2, an antiviral agent containing 0.1 to 7.5 parts by weight of a sulfonic acid-based surfactant and 10 to 100 parts by weight of a plasticizer is added to 100 parts by weight of a polyvinyl chloride resin for paste. Polyvinyl chloride-based sol compositions are disclosed.

Improvements in mechanical properties (eg, tensile strength, tensile elongation, and elastic modulus) are currently being sought for molded articles (sheets, etc.) obtained from the plastisol compositions described above.

By the way, in order to improve the mechanical properties of moldings (molded articles) of thermoplastic resins and cured products of thermosetting resins, methods of adding elastomers to thermoplastic resins and thermosetting resins are widely used. . Examples of the elastomer include polymer microparticles (for example, crosslinked polymer microparticles).

For example, Patent Document 3 contains 100 parts by weight of a vinyl monomer (A) and 0.1 to 45 parts by weight of polymer fine particles (B) having a volume average particle diameter of 0.05 to 1 μm, and the polymer fine particles ( B) is a curable composition dispersed in the form of primary particles in a continuous layer of the vinyl monomer (A), further comprising a nitroxy-based A curable composition is disclosed comprising 50 to 5000 ppm by weight of a polymerization inhibitor (C).

Further, Patent Document 4 includes a step of mixing a latex of polymer particles with an organic solvent, and then bringing the resulting mixture into contact with water to form aggregates of polymer particles in the aqueous phase. , disclose a method for producing purified polymer microparticles.

JP 2013-007052 A International Publication WO2015/005476 JP 2011-213952 A JP 2006-241404 A

However, a method of adding fine polymer particles to a plastisol composition to improve the mechanical properties of a molded plastisol composition has not yet been developed.

An object of one embodiment of the present invention is to provide (a) a vinyl chloride-based plastisol composition capable of providing a molded product having excellent mechanical properties, and (b) a plasticizer and An object of the present invention is to provide a composition containing polymer microparticles.

The present inventor has completed the present invention as a result of intensive studies in order to solve the above problems.

That is, one embodiment of the present invention includes the following configurations.
[1] Containing a polymer fine particle (A) and a plasticizer (B), the polymer fine particle (A) having an elastic body and a graft portion graft-bonded to the elastic body It contains a rubber-containing graft copolymer, the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber, and the elastic body is crosslinked. When the total of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight, and the plasticizer (B ) is from 50 to 99% by weight.
[2] The composition according to [1], wherein the polymer fine particles (A) have a dispersibility of 0 μm as measured according to JIS K5101 using a grind gauge.
[3] The plasticizer (B) includes a phthalate ester plasticizer, a trimellitate ester plasticizer, an adipate ester plasticizer, an azelaic ester plasticizer, a sebacate ester plasticizer, and a phosphate ester. [1] or [2], which contains one or more selected from the group consisting of plasticizers based on plasticizers, polyester plasticizers, epoxy plasticizers, fatty acid ester plasticizers, and pyromellitic ester plasticizers. Composition.
[4] The composition according to any one of [1] to [3], wherein the plasticizer (B) is a phthalate plasticizer.
[5] Any one of [1] to [4], wherein the elastic body is a diene-based rubber, a (meth)acrylate-based rubber, or a mixture of a diene-based rubber and a (meth)acrylate-based rubber. composition.
[6] A vinyl chloride plastisol composition containing the composition according to any one of [1] to [5] and a vinyl chloride resin.
[7] The vinyl chloride-based plastisol composition of [6], which further contains an inorganic filler.
[8] 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 remove the polymer containing the organic solvent. A first step of generating aggregates of coalesced fine particles (A) in an aqueous phase, after separating and recovering the aggregates from the aqueous phase, the aggregates are mixed with the organic solvent to obtain the polymer fine particles ( A second step of obtaining an organic solvent dispersion containing A), and a third step of mixing the organic solvent dispersion with the plasticizer (B) and then distilling off the organic solvent from the resulting mixture, in order. wherein the fine polymer particles (A) comprise a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body, the elastic body comprising a diene rubber, ( containing one or more selected from the group consisting of meth)acrylate-based rubbers and organosiloxane-based rubbers, wherein the elastic body is crosslinked, and in the third step, the polymer fine particles (A) and the plasticized When the total of the agent (B) and the agent (B) is 100% by weight, the polymer fine particle (A) is 1 to 50% by weight and the plasticizer (B) is 50 to 99% by weight. and a method for producing a composition, wherein the fine polymer particles (A) and the plasticizer (B) are mixed.

According to one embodiment of the present invention, (a) a vinyl chloride-based plastisol composition capable of providing molded articles having excellent mechanical properties, and (b) a plasticizer and The effect is that it is possible to provide a composition containing polymer microparticles.

An embodiment of the invention will be described below, but the invention is not limited thereto. 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)".

[1. Technical idea of the present invention]
A plastisol composition (for example, a vinyl chloride-based plastisol composition) obtained by blending fine resin particles with a plasticizer is a "sol" in which fine resin particles are dispersed in a plasticizer, and is a liquid having fluidity at room temperature. It can also be said. In addition, in the plastisol composition, the fine resin particles are melted (compatibility) with the plasticizer by heating, and the fine resin particles lose their particle shape.

It is easy to simply mix polymer fine particles and a plastisol composition that is a sol (liquid having fluidity). As a mixing method, for example, several polymer fine particles having a particle diameter of less than 1 μm are collected to prepare a powdery granule of polymer fine particles having a particle diameter of 1 µm or more, and then the powdery granule and the plastisol composition are mixed. and a method of mechanically mixing. In addition, the granules of polymer fine particles prepared by collecting several polymer fine particles in this way are called secondary particles, and the polymer fine particles themselves having a particle diameter of less than 1 μm before being turned into granules are referred to as secondary particles. Also called primary particles. It is possible to disperse the secondary particles of the fine polymer particles in the plastisol composition by the mixing method described above.

Here, in order to enjoy the effect of improving the mechanical properties of the polymer fine particles in the molded article of the plastisol composition, (i) it is essential that the polymer fine particles are present in the molded article while maintaining the shape of the particles. and (ii) it is preferable that the fine polymer particles are dispersed in the form of primary particles as much as possible in the molding. However, in a plastisol composition obtained by blending fine resin particles with a plasticizer, the fine resin particles are melted (compatibility) with the plasticizer by heating, and the fine resin particles lose their particle shape. As a result, no particulate resin fine particles are present in the molded article obtained, and the effect of improving mechanical properties, etc., due to the resin fine particles is not exerted. In addition, in order for the polymer fine particles to be dispersed in the state of primary particles as much as possible in the molded product, the polymer fine particles should It is important that the However, it is very difficult on an industrial level to disperse the primary particles of fine polymer particles having a particle diameter of less than 1 μm in a plastisol composition. For example, as described above, when the secondary particles (granules) of the polymer fine particles and the plastisol composition are mechanically mixed, the primary particles of the polymer fine particles aggregate in the resulting plastisol composition. remain. Therefore, the mechanical properties of the resulting plastisol composition moldings are equivalent to the mechanical properties of plastisol composition moldings containing no polymer fine particles, and are not satisfactory. Furthermore, there is also the problem that the molded article of the plastisol composition obtained by mechanically mixing the secondary particles of the fine polymer particles and the plastisol composition has a very poor surface appearance.

Therefore, the present inventors have made extensive studies to provide a vinyl chloride-based plastisol composition capable of providing moldings having excellent mechanical properties. As a result, the present inventors have found the following points and have completed the present invention: A composition in which specific polymer fine particles are dispersed in a plasticizer is prepared in advance, and the composition is treated with a resin ( For example, by mixing with vinyl chloride resin), a plastisol composition capable of providing molded articles having excellent mechanical properties can be obtained.

[2. Composition〕
A composition according to one embodiment of the present invention contains a polymer fine particle (A) and a plasticizer (B), and the polymer fine particle (A) comprises an elastic body and a grafted polymer to the elastic body. and a rubber-containing graft copolymer having a bonded graft portion, wherein the elastic body comprises one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber. and the elastic body is crosslinked, and when the total amount of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight. %, and the plasticizer (B) is 50 to 99% by weight.

In this specification, the "composition according to one embodiment of the present invention" may be simply referred to as "the present composition".

Since the present composition has the structure described above, it is possible to provide a composition containing a plasticizer and fine polymer particles, in which the fine polymer particles (A) are dispersed in the plasticizer (B). In the present composition, the fine polymer particles (A) can preferably be dispersed in the plasticizer (B) in the form of primary particles. Further, by mixing the present composition with a vinyl chloride resin to be described later, a vinyl chloride plastisol composition in which polymer fine particles (A) are dispersed in a mixture of a vinyl chloride resin and a plasticizer (B) is obtained. Obtainable. In the vinyl chloride-based plastisol composition, the polymer fine particles (A) can preferably be dispersed in the form of primary particles. As a result, the vinyl chloride-based plastisol composition has the advantage of being able to provide moldings with excellent mechanical properties (eg, tensile strength, tensile elongation and elastic modulus).

<2-1. 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.

A case (Case A) in which the elastic body contains a diene rubber will be described. In Case A, the resulting composition can provide a vinyl chloride-based plastisol composition capable of providing moldings with excellent toughness and impact resistance. A molded article having excellent toughness and/or impact resistance can also be said to be a molded article having excellent durability.

A diene-based rubber is an elastic body containing, as a structural unit, a structural unit derived from a diene-based monomer. 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 structural units derived from (meth)acrylate-based monomers as structural units in an amount smaller than the structural units derived from diene-based monomers.

Examples of diene 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 preferred. 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 effect. In addition, butadiene-styrene rubber is more preferable in that the transparency of the obtained molding can be improved 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.

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.

A (meth)acrylate rubber is an elastic body containing, as a structural unit, a structural unit derived from a (meth)acrylate 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 fine polymer particles (A) and a composition having a low Tg can be obtained. As a result, (i) the resulting composition can provide a vinyl chloride-based plastisol composition capable of providing shapes having excellent toughness, and (ii) the viscosity of the composition and the vinyl chloride-based plastisol composition can be reduced to can be 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.

A case (Case C) in which the elastic body contains an organosiloxane rubber will be described. In Case C, the resulting composition can provide a vinyl chloride-based plastisol composition that has sufficient heat resistance and can provide moldings 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 case C, the organosiloxane rubber is (i) dimethylsilyloxy rubber, methylphenyl It is preferably one or more selected from the group consisting of silyloxy rubber and dimethylsilyloxy-diphenylsilyloxy rubber, and (ii) dimethylsilyloxy rubber because it is readily available and economical. is more preferred.

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 above configuration, the obtained composition can provide a vinyl chloride-based plastisol composition capable of providing molded articles 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, and one or more selected from the group consisting of butadiene rubber, butadiene-styrene rubber and butyl (meth)acrylate rubber. is more preferred.

The elastic body preferably contains one or more selected from the group consisting of diene-based rubbers and (meth)acrylate-based rubbers. More preferably, the elastic body contains 60 parts by weight or more, more preferably 70 parts by weight or more, of one or more elastic bodies selected from the group consisting of diene rubbers and (meth)acrylate rubbers in 100 parts by weight of the elastic body. It is more preferable to contain 80 parts by weight or more, and it is particularly preferable to contain 90 parts by weight or more. This configuration has the advantages of (a) easy cross-linking of the elastic body and (b) being economically excellent (in other words, the elastic body can be obtained at low production costs). Cross-linking of the elastic body will be described later. The elastic body may contain 100 parts by weight of one or more elastic bodies selected from the group consisting of diene-based rubbers and (meth)acrylate-based rubbers in 100 parts by weight of the elastic body. That is, the elastic body may be a diene-based rubber, a (meth)acrylate-based rubber, or a mixture of a diene-based rubber and a (meth)acrylate-based rubber.

(Crosslinked structure of elastic body)
The elastic body of the polymer microparticles (A) is crosslinked.

As described above, Patent Document 1 discloses a plastisol composition containing acrylic polymer fine particles and a plasticizer. However, the acrylic polymer microparticles of Patent Document 1 are neither a graft copolymer nor crosslinked. Therefore, in the plastisol composition described in Patent Document 1, the plasticizer and the acrylic polymer fine particles are compatible with each other by heating, and the acrylic polymer fine particles lose their particle shape. Therefore, in the molded product of the plastisol composition of Patent Document 1, the acrylic polymer compatible with the plasticizer is present, but the "fine particles" are not present. That is, the acrylic polymer fine particles in the plastisol composition of Patent Document 1 do not have the effect of imparting mechanical properties to the molded article of the plastisol composition.

On the other hand, the elastic body of the fine polymer particles (A) in the present composition is crosslinked. Therefore, even when the vinyl chloride-based plastisol composition obtained by mixing the composition and the vinyl chloride-based resin is heated, the fine polymer particles (A) can maintain the particle shape. That is, when the elastic body is crosslinked, there is an advantage that the fine polymer particles (A) can be dispersed while maintaining their particle shape in the molded article of the vinyl chloride-based plastisol composition described later. Therefore, molded articles of the vinyl chloride-based plastisol composition can enjoy the effect of improving mechanical properties due to the fine polymer particles (A). That is, the present composition can provide a vinyl chloride-based plastisol composition capable of providing moldings with excellent mechanical properties.

"The elastic body is crosslinked" can also be said to be "a crosslinked structure is introduced into the elastic body." When a crosslinked structure is introduced into the elastic body, there is also the advantage that the dispersion stability of the polymer fine particles (A) in the vinyl chloride plastisol composition is maintained. 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. The term "polymerizable unsaturated bond" can also be referred to as "polymerizable unsaturated bond", and intends an unsaturated bond that can become a starting point for a polymerization reaction by a radical or 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.

Here, the elastic body is a structural unit derived from a monomer having two or more polymerizable unsaturated bonds (e.g., carbon-carbon double bonds) in one molecule (e.g., a diene-based monomer, etc.) , is included (Case D). In case D, the structural unit derived from a monomer having two or more polymerizable unsaturated bonds in one molecule contained in the elastic body has one polymerizable unsaturated bond per structural unit. have more than Therefore, in case D, the elastic body has two or more polymerizable unsaturated bonds, and as a result, a crosslinked structure can be formed between the unsaturated bonds. That is, in Case D, the elastomer can be crosslinked even if the elastomer is produced without the use of a crosslinkable monomer. More specifically, when the elastic body contains a diene rubber, a crosslinked structure may be formed in the diene rubber even if the elastic body is produced without using a crosslinkable monomer. , ie the elastomer can be crosslinked.

(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 composition having a low Tg can be obtained. As a result, the resulting composition can provide a vinyl chloride-based plastisol composition capable of providing moldings having excellent toughness. Moreover, according to the said structure, the viscosity of the 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 molded product can be suppressed from decreasing, that is, a molded 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 resulting composition can provide a vinyl chloride-based plastisol composition capable of providing a molded article having sufficient rigidity.

Even when the Tg of the elastic body is higher than 0° C., it is preferable to introduce a crosslinked structure 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 b include ethyl acrylate, butyl acrylate (also known as butyl acrylate), 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and the like. is mentioned. These monomers b may be used alone or in combination of two or more. Among these monomers b, particularly preferred are ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

(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 molded product are improved. The volume average particle size of the elastic body can be measured by using an aqueous latex 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 fine particles (A) is preferably 40 to 97 wt%, more preferably 60 to 95 wt%, and 70 to 93 wt%, based on 100 wt% of the polymer fine particles (A) as a whole. is more preferred. When the proportion of the elastic body is (i) 40% by weight or more, the obtained composition can provide a vinyl chloride-based plastisol composition capable of providing molded articles having excellent toughness and impact resistance, (ii) When the content is 97% by weight or less, the fine polymer particles (A) do not easily aggregate, so that the composition does not become highly viscous, and as a result, the obtained composition has excellent handleability. can be.

(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 composition can provide a vinyl chloride-based plastisol composition capable of providing a molded article having excellent toughness.

In the present specification, the method for calculating the gel content is as follows. First, an aqueous latex containing the polymer microparticles (A) is obtained, and then powder particles of the polymer microparticles (A) are obtained from the aqueous latex. The method for obtaining powdery particles of the polymer microparticles (A) from the aqueous latex is not particularly limited. For example, (i) the polymer microparticles (A) in the aqueous latex are aggregated, A method of dehydrating the substance and (iii) further drying the agglomerate to obtain powdery particles of the polymer fine particles (A) can be mentioned. 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 30,000 rpm, and the lysate was Separation into MEK soluble matter and MEK insoluble matter. 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 each having a different composition 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 entirety of the 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 polymer elastic body, each of the plurality of elastic bodies may form a layered structure. For example, when the multi-stage polymerized elastic body is composed of elastic body ₁ , elastic body ₂ , and elastic body ₃ , the elastic body ₁ forms the innermost layer, the elastic body ₂ layer is formed on the outer side of the elastic body ₁ , and A mode in which _{the 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 polymer elastic body and/or (iii) a multi-layer elastic It may contain a body.

(Surface cross-linked polymer)
The rubber-containing graft copolymer preferably further has a surface-crosslinked polymer in addition to the elastic body and the graft portion graft-bonded to the elastic body. In other words, the fine polymer particles (A) preferably further have a surface-crosslinked polymer in addition to the elastic body and the graft portion graft-bonded to the elastic body. An embodiment of the present invention will be described below, taking as an example the case where the polymer fine particles (A) (for example, a rubber-containing graft copolymer) further has a surface-crosslinked polymer. In this case, (a) blocking resistance can be improved in the production of the fine polymer particles (A), and (b) dispersibility of the fine polymer particles (A) in the thermosetting resin is improved. These reasons are not particularly limited, but can be presumed as follows: By covering at least a part of the elastic body with the surface cross-linked polymer, the exposure of the elastic part of the fine polymer particles (A) is reduced. 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 polymer microparticles (A) have a surface-crosslinked polymer, the following effects may also be obtained: (a) the effect of reducing the viscosity of the present composition, (b) the effect of increasing the crosslink density in the elastic body, and (c) The effect of increasing the graft efficiency of the graft portion. The crosslink density in the elastic means the degree of the number of crosslink structures in the whole 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.

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 polymer microparticles (A) may contain a surface-crosslinked polymer polymerized independently of the polymerization of the rubber-containing graft copolymer, or may contain a surface-crosslinked polymer polymerized together with the rubber-containing graft copolymer. May include coalescing. The fine polymer particles (A) may be a multi-stage polymer obtained by multi-stage polymerization of an elastic body, a surface-crosslinked polymer and a graft portion in this order. In any of these embodiments, the surface-crosslinked polymer can cover at least a portion of the elastic body.

Surface cross-linked polymers can also be considered part of the elastomer. In other words, the surface-crosslinked polymer can also be regarded as a part of the rubber-containing graft copolymer, and can also be said to be a surface-crosslinked polymer portion. When the polymer microparticles (A) contain a surface-crosslinked polymer, the graft portion may be (a) graft-bonded to an elastic body other than the surface-crosslinked polymer, and (b) to the surface-crosslinked polymer. (c) may be graft-bonded to both the elastic body other than the surface-crosslinked polymer and the surface-crosslinked polymer. When the polymer fine particles (A) contain a surface-crosslinked polymer, the volume-average particle diameter of the elastic body mentioned above means the volume-average particle diameter of the elastic body 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 contains, as structural units, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. It is preferably (including) a polymer. A graft section having the above configuration can serve a variety of purposes. "Various roles" are, for example, (a) to improve the compatibility of the polymer fine particles (A) with the plasticizer and/or the vinyl chloride resin described later, (b) in the plasticizer and/or (d) improving the dispersibility of the polymer fine particles (A) in the vinyl chloride resin described later; allowing to distribute in state, and so on.

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. By (meth)acrylate is intended herein acrylate and/or methacrylate.

One or more monomers selected from the group consisting of the above-mentioned aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers may be used alone, Two or more kinds may be used in combination.

In the graft portion, as structural units, a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a vinyl cyanide monomer, and a structural unit derived from a (meth)acrylate monomer are added to the graft portion. In 100% by weight of the polymer contained, it preferably contains 10 to 95% by weight, more preferably 30 to 92% by weight, more preferably 50 to 90% by weight, and 60 to 87% by weight. It is particularly preferred and most preferably contains 70 to 85% by weight.

The graft portion may further contain, as a structural unit, a structural unit derived from a monomer having a reactive group. 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. As a result, the fine polymer particles (A) can be maintained in a good dispersed state without agglomeration of the fine polymer particles (A) in the vinyl chloride-based plastisol composition or its molding.

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, (a) 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxy straight-chain alkyl (meth)acrylates; Acrylate (particularly preferably, hydroxy linear C1-6 alkyl (meth)acrylate); (b) caprolactone-modified hydroxy (meth)acrylate; (c) methyl α-(hydroxymethyl)acrylate, α-(hydroxymethyl)acryl hydroxy-branched alkyl (meth)acrylates such as ethyl acetate; (d) polyester diols (particularly preferably saturated polyester diols) obtained from dihydric carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol) ( and hydroxyl group-containing (meth)acrylates such as meth)acrylates. The term “straight-chain C1-6 alkyl” means straight-chain alkyl having 1 to 6 carbon atoms.

Specific examples of monomers having a carboxylic acid group include (a) monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and (b) dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. , and so on. 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 a structural unit derived from a monomer having a reactive group in 100% by weight of the polymer contained in 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 (a) 0.5% by weight or more of structural units derived from a monomer having a reactive group in 100% by weight of the polymer contained in the graft portion, the obtained composition has a sufficient It is possible to provide a vinyl chloride-based plastisol composition that can provide a molded article having good impact resistance. and the storage stability of the composition and/or the vinyl chloride plastisol composition is improved.

A 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.

The graft part may contain a structural unit derived from a polyfunctional monomer as a structural unit. When the graft portion contains a structural unit derived from a polyfunctional monomer, (a) to prevent swelling of the polymer fine particles (A) in the composition and/or in the vinyl chloride-based plastisol composition described later. (b) the viscosity of the composition and/or the vinyl chloride plastisol composition described later tends to be low, so that the composition and/or the vinyl chloride plastisol composition described later tends to be easier to handle; and (c) improved dispersibility of the fine polymer particles (A) in the composition and/or in the vinyl chloride plastisol composition described later.

When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the resulting composition exhibits improved toughness and resistance compared to the case where the graft portion contains a structural unit derived from a polyfunctional monomer. It is possible to provide a vinyl chloride-based plastisol composition capable of providing a molded article having excellent impact resistance.

Examples of the polyfunctional monomer 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 the polyfunctional monomers described above, polyfunctional monomers that can be preferably used for polymerization of the graft portion include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and 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.

The graft portion preferably contains 1 to 20% by weight, more preferably 5 to 15% by weight, of a structural unit derived from a polyfunctional monomer in 100% by weight of the polymer contained in the graft portion.

In the polymerization of the graft portion, the above monomers may be used alone or 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 portion can be determined by the composition of the constituent units contained in the graft portion. 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 part of the fine polymer particles (A) according to one embodiment 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 composition and/or the vinyl chloride-based plastisol composition described later does not become too high.

In the present specification, the method for calculating the graft ratio is as follows. First, an aqueous latex containing the polymer microparticles (A) is obtained, and then powder particles of the polymer microparticles (A) are obtained from the aqueous latex. Specifically, the method for obtaining the powdery particles of the polymer microparticles (A) from the aqueous latex includes (i) coagulating the polymer microparticles (A) in the aqueous latex, and (ii) obtaining the coagulation A method of dehydrating the substance and (iii) further drying the coagulate to obtain powdery particles of the polymer fine particles (A) 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 graft portion)×10,000.

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, 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 fine polymer particles (A) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous latex, or the like can be used.

(Modified example of 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 single 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 is composed of multiple types of graft portions, not all of these multiple types of graft portions may be graft-bonded to the elastic body. When the graft portion consists of a plurality of types of graft portions, it is sufficient that at least a portion of at least one type of graft portion is graft-bonded to the elastic body, and the graft portions of other types (a plurality of other types) are It may be grafted to a graft portion that is grafted to the elastic body. 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 multistage 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 (a) a composite of multiple types of graft portions, (b) a multi-stage polymerization graft portion and/or (c) 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 multistage polymers, the graft portion may cover at least a portion of the elastic body, or may 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.

A case (Case E) where the fine polymer particles (A) are a multi-stage polymer obtained by multi-stage polymerization of an elastic body, a surface-crosslinked polymer and a graft portion in this order will be described. In Case E, the surface cross-linked polymer may coat a portion of the elastomer or may coat the entire elastomer. In case E, part of the surface-crosslinked polymer may be inside the elastic body. In Case E, the graft portion may cover a portion of the surface cross-linked polymer or may cover the entire surface cross-linked polymer. In case E, part of the graft may be inside the surface-crosslinked polymer. In Case E, the elastic body, the surface-crosslinked polymer and the graft portion may have a layered structure. For example, the elastic body is the innermost layer (core layer), the surface-crosslinked polymer layer is present as an intermediate layer outside the elastic body, and the graft portion layer is the outermost layer (shell layer) outside the surface-crosslinked polymer. The present aspect is also an aspect of the invention.

(Volume average particle diameter (Mv) of polymer microparticles (A))
The volume-average particle diameter (Mv) of the fine polymer particles (A) is 0.0 because a highly stable composition having a desired viscosity and/or a vinyl chloride-based plastisol composition to be described later can be obtained. 03 μm to 50.00 μm is preferable, 0.05 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 more preferable, and 0.10 μm to 0.80 μm is more preferable. More preferably, 0.10 μm to 0.50 μm is particularly preferable. When the volume average particle diameter (Mv) of the polymer fine particles (A) is within the above range, the polymer fine particles (A) have good dispersibility in the composition and/or the vinyl chloride-based plastisol composition described below. It also has the advantage of In the present specification, the "volume average particle diameter (Mv) of the polymer microparticles (A)" is intended to be 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.

<2-2. 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.

Polymer microparticles (A) can be produced by known methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Specifically, the polymerization of the elastic body, the polymerization of the graft portion (graft polymerization), and the polymerization of the surface-crosslinked polymer in the fine polymer particles (A) are performed by known methods such as emulsion polymerization, suspension polymerization, It can be carried out by a method such as a microsuspension polymerization method. Among these, the emulsion polymerization method is particularly preferable as the method for producing the polymer fine particles (A). According to the emulsion polymerization method, (i) composition design of the polymer microparticles (A) is easy, (ii) industrial production of the polymer microparticles (A) is easy, and (iii) the present production method described later It has the advantage that an aqueous latex suitable for use is readily available. 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.

(Manufacturing method of elastic body)
The elastic body can be produced by 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, the elastic body can be produced by polymerizing one or more monomers selected from the group consisting of diene-based monomers and (meth)acrylate-based monomers. 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.

Consider the case where the elastic body contains an organosiloxane rubber. In this case, the elastic body can be produced by polymerizing organosiloxane monomers. 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. Alternatively, elastic body _{1 1} , elastic _{body 2 2} , .

A specific description will be given of the multi-stage polymerization of the elastic body. For example, a multi-stage polymerized elastic body can be obtained by sequentially performing the following steps (1) to (4): (1) elastic body ₁ is polymerized to obtain elastic body ₁ ; (3) Polymerize elastic ₃ in the presence of elastic 1 _{+2 to} obtain three-step elastic _{1 +2+3 ;} ( 4) Thereafter, following the same procedure, the elastic body _n is polymerized in the presence of the elastic body _{1+2+...+(n-1)} to obtain the multi-stage polymerized elastic body _1+2+...+n .

(Manufacturing method of graft portion)
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 latex, polymerization of the graft portion is carried out by an emulsion polymerization method. is preferred. 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. Alternatively, the graft portion _{1 1} , the graft portion _{2 2 ,} .

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

When the graft portion is composed of a plurality of types of graft portions, the polymer microparticles (A) may be produced by polymerizing the graft portions having a plurality of types of graft portions and then graft-polymerizing the graft portions onto the elastic body. . The polymer microparticles (A) may be produced by sequentially carrying out multistage graft polymerization of a plurality of types of polymers constituting the graft portion to the elastic body in the presence of the elastic body.

(Method for producing surface-crosslinked polymer)
The surface-crosslinked polymer can be formed by polymerizing a monomer used for forming the surface-crosslinked polymer by known radical polymerization in the presence of an elastic body. When the elastic body is obtained as an aqueous latex, the polymerization of the surface-crosslinked polymer is preferably carried out by an emulsion polymerization method.

When an emulsion polymerization method is employed as the method for producing the polymer fine particles (A), a known emulsifier (dispersant) can be used as an emulsifier (dispersant) in 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 (abbreviated as SDBS). Phosphorus-based emulsifiers include sodium polyoxyethylene lauryl ether phosphate and the like.

When an emulsion polymerization method is employed 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 the polymer microparticles (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 initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox initiator is used, can be used within a known range.

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 for 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 the polymerization conditions such as polymerization temperature, pressure, and deoxidization.

An aqueous latex containing the polymer microparticles (A) can be obtained by the method for producing the polymer microparticles (A) described above. That is, <1-2. Method for producing fine polymer particles (A)> can be used as the description of the method for preparing the aqueous latex in the method for producing the present composition.

<2-3. Plasticizer (B)>
The plasticizer (B) is not particularly limited, and known plasticizers can be used as appropriate. Examples of the plasticizer (B) include phthalate ester plasticizers, trimellitate ester plasticizers, adipate ester plasticizers, azelate plasticizers, sebacate ester plasticizers, and phosphate ester plasticizers. Plasticizers, polyester plasticizers, epoxy plasticizers, fatty acid ester plasticizers, pyromellitic ester plasticizers, benzoic ester plasticizers, citric ester plasticizers, glycolic ester plasticizers, chlorinated Examples include paraffin-based plasticizers, chlorinated fatty acid ester-based plasticizers, and texanol isobutyrate.

Examples of phthalate plasticizers include di-2-ethylhexyl phthalate, dioctyl phthalate (DOP), dibutyl phthalate, and diisononyl phthalate (DINP).

Examples of trimellitate plasticizers include tri-2-ethylhexyl trimellitate.

Examples of the adipate plasticizer include di-2-ethylhexyl adipate.

Examples of the azelaic acid ester plasticizer include di-2-ethylhexyl azelate.

Sebacate plasticizers include, for example, di-2-ethylhexyl sebacate.

Phosphate ester plasticizers include tricresyl phosphate (TCP), triphenyl phosphate (TPP), trixylenyl phosphate (TXP), 2-ethylhexyldiphenyl phosphate and the like.

Polycondensates of aliphatic dibasic acids and diols are suitable examples of polyester plasticizers. Examples of the aliphatic dibasic acid include succinic acid, maleic acid, fumaric acid, glutamic acid, adipic acid, azelaic acid, sebacic acid, and dodecane dicarboxylic acid. Examples of the diol include 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5 -pentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl -1,3-propanediol, 2-methyl-1,8-octanediol, 1,12-octadecanediol and the like. As the polyester plasticizer, an adipic acid polyester plasticizer, which is a polycondensate of adipic acid and diol, is preferably used.

Epoxy plasticizers generally include epoxy triglycerides composed of alkyl epoxystearate and soybean oil. In addition, so-called epoxy resins made mainly from bisphenol A and epichlorohydrin can also be used as epoxy plasticizers.

Fatty acid ester plasticizers include (a) esters of fatty acids and alkyl alcohols, and (b) esters of fatty acids and polyhydric alcohols. Examples of the fatty acid include phthalic acid, maleic acid, adipic acid, stearic acid, and the like. Moreover, ethylene glycol, glycerin, etc. are mentioned as the said polyhydric alcohol. Specific examples of fatty acid ester plasticizers include esters of fatty acids and alkyl alcohols (monohydric alcohols) such as dibutyl phthalate, di-2-ethylhexyl phthalate, dibutyl adipate, di-2-ethylhexyl sebacate, and dibutyl maleate. , ethyl myriphosphate, isopropyl myristate, isopropyl palmitate, butyl stearate, isopropyl isostearate, hexyl laurate, cetyl lactate, myristyl lactate, diethyl phthalate, bis(2-ethylhexyl) phthalate, octyldodecyl myristate, olein octyldodecyl acid, hexyldecyl dimethyloctanoate, cetyl 2-ethylhexanoate, isocetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, dioctyl succinate and the like. Specific examples of fatty acid ester plasticizers include esters of fatty acids and polyhydric alcohols (dihydric or higher alcohols) such as propylene glycol dicaprylate, propylene glycol dicaprate, propylene glycol diisostearate, glyceryl monocaprylate, and tricaprylic acid. Glyceryl, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, glyceryl trilaurate, glyceryl triisostearate, glyceryl trioleate, trimethylolpropane tri-2-ethylhexanoate and the like.

Examples of pyromellitic acid ester plasticizers include tetraoctyl pyromellitic acid and tetraisodecyl pyromellitic acid.

Benzoic acid ester plasticizers include di-2-ethylhexyl benzoate, diethylene glycol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol isobutyrate benzoate and the like.

Citric acid ester plasticizers include acetyltributyl citrate and the like.

The plasticizer (B) mentioned above may be used individually by 1 type, and may be used in combination of 2 or more types.

Because of their excellent compatibility with vinyl chloride resins, plasticizers (B) include phthalate ester plasticizers, trimellitate ester plasticizers, adipate ester plasticizers, azelate ester plasticizers, and sebatine. At least one selected from the group consisting of an acid ester plasticizer, a phosphate ester plasticizer, a polyester plasticizer, an epoxy plasticizer, a fatty acid ester plasticizer, and a pyromellitic ester plasticizer. More preferably, it contains a phthalate plasticizer.

Because of its excellent compatibility with vinyl chloride resins, the plasticizer (B) includes, in 100% by weight of the plasticizer (B), a phthalate ester plasticizer, a trimellitate ester plasticizer, an adipate ester plasticizer, The group consisting of a plasticizer, an azelate plasticizer, a sebate plasticizer, a phosphate ester plasticizer, a polyester plasticizer, an epoxy plasticizer, a fatty acid ester plasticizer, and a pyromellitic ester plasticizer One or more selected plasticizers are preferably contained in an amount of 60% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and particularly preferably 90% by weight or more. Since the compatibility with the vinyl chloride resin is further excellent, the plasticizer (B) contains, in 100% by weight of the plasticizer (B), a phthalate plasticizer, a trimellitic ester plasticizer, and an adipate ester. plasticizer, azelate plasticizer, sebate plasticizer, phosphate ester plasticizer, polyester plasticizer, epoxy plasticizer, fatty acid ester plasticizer, and pyromellitic ester plasticizer. It may contain 100% by weight of one or more plasticizers selected from the group. In other words, the plasticizer (B) contained in the present composition includes a phthalate ester plasticizer, a trimellitate ester plasticizer, an adipate ester plasticizer, an azelate ester plasticizer, and a sebate ester plasticizer. It may be one or more selected from the group consisting of plasticizers, phosphate ester plasticizers, polyester plasticizers, epoxy plasticizers, fatty acid ester plasticizers, and pyromellitic ester plasticizers.

The plasticizer (B) is preferably a phthalate ester plasticizer because of its particularly excellent compatibility with vinyl chloride resins.

In the present composition, when the total of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the plasticizer (B) is 50 to 99% by weight. This configuration has the advantage that the present composition can be used as a high-concentration masterbatch in the production of a plastisol composition containing fine polymer particles.

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

<2-4. Other Ingredients>
If necessary, the present composition may contain, for example, coloring agents such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, anti-mold agents, stabilizers (e.g., anti-gelling agents), and cell regulators. , leveling agent, antifoaming agent, silane coupling agent, antistatic agent, flame retardant, lubricant, thickener, viscosity reducer, diluent, low shrinkage agent, adhesion agent, thixotropic agent, fiber reinforcement, inorganic substance It may further contain fillers, organic fillers, internal release agents, wetting agents, polymerization modifiers, thermoplastic resins, desiccants, dispersants, radical polymerization initiators, curing accelerators, co-catalysts, and the like.

In the present composition, the dispersibility of the fine polymer particles (A) is preferably 0 μm as measured according to JIS K5101 using a grind gauge. In the present composition, when the dispersibility of the polymer fine particles (A) measured according to JIS K5101 using a grind gauge is 0 μm, in the present composition, specifically in the plasticizer (B), the polymer The fine particles (A) can be considered to be dispersed in the state of primary particles. A method for measuring the dispersibility of the polymer fine particles (A) will be described in detail in [Examples] below.

[3. Method for manufacturing the composition]
The present composition is a composition in which fine polymer particles (A) are dispersed (preferably in the form of primary particles) in a plasticizer (B). As a method for obtaining the present composition, any known method for obtaining a composition in which the polymer fine particles (A) are dispersed in the plasticizer (B) (preferably in the form of primary particles) can be used. can be done. Examples of such a method include, for example, a method of contacting polymer fine particles (A) obtained as an aqueous latex with a plasticizer (B) and then removing unnecessary components such as water, and a method of removing polymer fine particles (A). A method of once extracting with an organic solvent and then mixing with the plasticizer (B) and then removing the organic solvent may be mentioned. As a method for producing the present composition, it is preferable to use the method described in WO 2005/28546.

A method for producing a composition according to one embodiment of the present invention comprises mixing an aqueous latex containing polymer fine particles (A) with an organic solvent that exhibits partial solubility in water, and then adding water to the resulting mixture. A first step of contacting to form aggregates of the polymer fine particles (A) containing the organic solvent in an aqueous phase, separating and recovering the aggregates from the aqueous phase, and then removing the aggregates from the A second step of mixing with an organic solvent to obtain an organic solvent dispersion containing the polymer fine particles (A), and after mixing the organic solvent dispersion with the plasticizer (B), the resulting mixture a third step of distilling off the organic solvent, wherein the polymer fine particles (A) are a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body; wherein the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber; the elastic body is crosslinked; Then, when the total of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight, and the plasticizer (B) The fine polymer particles (A) and the plasticizer (B) may be mixed at a compounding ratio of 50 to 99% by weight.

In this specification, the "method for producing a composition according to one embodiment of the present invention" is also simply referred to as "the present production method". In addition, a "mixture obtained by mixing an aqueous latex containing polymer fine particles (A) with an organic solvent exhibiting partial solubility in water" may be referred to as "mixture X", and "organic solvent dispersion A "mixture obtained by mixing the liquid with the plasticizer (B)" may be referred to as "mixture Y".

The manufacturing method described above will be described below. Composition] section is incorporated.

Since the present production method has the configuration described above, it is possible to provide a composition in which the polymer fine particles (A) are dispersed in the plasticizer (B). In the composition obtained by this production method, the fine polymer particles (A) can be dispersed in the state of primary particles in the plasticizer (B).

A method for producing a composition according to an embodiment of the present invention includes [2. composition] can be suitably used for producing the composition described in the section. Therefore, the polymer microparticles (A) and the plasticizer (B) in the method for producing a composition according to one embodiment of the present invention are described in [2. Composition] can be used as appropriate.

<3-1. Aqueous latex>
"Aqueous latex containing fine polymer particles (A)" is described in <2-2. Aqueous latex containing polymer microparticles (A), which is produced by the production method described in the above section, can be used. The fine polymer particles (A) are preferably produced by emulsion polymerization and obtained as an aqueous latex.

<3-2. Organic solvent>
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 smoothly mixed in the first step without coagulation. operation can be performed. Further, when the solubility in water at 20° C. of the organic solvent partially soluble in water is 5% by weight or more, the polymer particles (A) can be sufficiently mixed with the aqueous latex, and A mixing operation of the first step 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 (mixture) containing 50% by weight or more of methyl ethyl ketone is used as an organic solvent exhibiting partial solubility in water in terms of compatibility with a reactive polymerizable organic compound and availability. An organic solvent (mixture) containing more than 75% by weight is particularly preferably used.

<3-3. First step>
The amount of the organic solvent that exhibits partial solubility in water in the first step is not particularly limited. ) may be set as appropriate depending on the concentration of ). The amount of the organic solvent partially soluble in water in the first step may be, for example, 50 to 400 parts by weight with respect to 100 parts by weight of the aqueous latex containing the fine polymer particles (A). It may be up to 300 parts by weight.

No special equipment or method is required for the mixing operation when the aqueous latex containing the polymer fine particles (A) is mixed with the organic solvent partially soluble in water. In the mixing operation, any known device or method may be used as long as a good mixing state can be obtained. A typical apparatus includes a stirring vessel equipped with stirring blades.

In the first step, a mixture X is obtained by mixing an aqueous latex containing fine polymer particles (A) with an organic solvent partially soluble in water. In the first step, mixture X is further brought into contact with water. By such contact, part of the organic solvent contained in the mixture X may be dissolved in water to produce an aqueous phase. At the same time, water from the aqueous latex contained in mixture X can also be expelled to the aqueous phase. Therefore, in the mixture obtained by contacting the mixture X with water, the polymer fine particles (A) are concentrated in the organic solvent containing a small amount of water, resulting in the aggregation of the polymer fine particles (A) in the aqueous phase. Aggregates are generated. That is, the aggregate of polymer fine particles (A) obtained in the first step may contain an organic solvent and may contain a small amount of water.

In the first step, the amount of water to be brought into contact with the mixture X is not particularly limited. , the type of the organic solvent partially soluble in water, the amount of the organic solvent partially soluble in water, and the like. The amount of water used in contact with the mixture X may be, for example, 40 to 350 parts by weight, or 60 to 250 parts by weight, with respect to 100 parts by weight of the organic solvent partially soluble in water. may

In the first step, from the viewpoint of preventing the generation of partial unagglomerates, the contact between the mixture X and water should be carried out under stirring or under a fluid state that can impart fluidity equivalent to stirring. is preferred. In the first step, an aqueous latex containing polymer fine particles (A) and an organic solvent exhibiting partial solubility in water are mixed in an apparatus equipped with a stirring function (for example, a stirring tank equipped with stirring blades). Subsequently, it is more preferable to add water to the mixture X obtained in the apparatus and bring the mixture X and water into contact with the apparatus.

<3-4. Second step>
In the second step, by separating the aggregates from the aqueous phase, water contained in the organic solvent that may accompany the aggregates can be removed. Such moisture may include emulsifiers and electrolytes from the manufacturing process of the aqueous latex of polymer microparticles (A). Therefore, by separating the aggregates from the aqueous phase, the emulsifier and electrolyte derived from the production process of the aqueous latex of the polymer fine particles (A), which are contained in the aggregates, are separated from the polymer fine particles (A) together with the aqueous phase. can be removed.

In the second step, the apparatus used for separating and recovering the aggregates from the aqueous phase and the method for separating and recovering the aggregates from the aqueous phase are not particularly limited, and known apparatuses and methods are appropriately used. Available. Separability between the aggregates and the aqueous phase is good, and specific embodiments for separating and recovering the aggregates from the aqueous phase include filtering operations using filter paper, filter cloth, and metal screens with relatively large openings. mentioned.

In the second step, in order to obtain aggregates of fine polymer particles (A) containing fewer impurities such as emulsifiers and electrolytes, the following operations may be repeated: (1) separating and recovering aggregates; Additional water is added to the resulting agglomerates, and the agglomerates are separated and recovered from the resulting mixture.

In the second step, the aggregates separated and recovered from the aqueous phase are mixed with an organic solvent. By such an operation, the first organic solvent dispersion can be obtained in which the polymer fine particles (A) are dispersed in the organic solvent (preferably in the form of substantially primary particles).

In the second step, the amount of the organic solvent to be mixed with the aggregates is not particularly limited, and may be appropriately set depending on the type of polymer fine particles (A), the type of organic solvent used, and the like. The amount of the organic solvent to be mixed with the aggregate may be, for example, 40 to 1,400 parts by weight or 200 to 1,000 parts by weight with respect to 100 parts by weight of the polymer fine particles (A). .

As the organic solvent to be mixed with the aggregates, in addition to the above-described organic solvents partially soluble in water, aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, ethylcyclohexane, and mixtures thereof are also used. can. From the viewpoint of ensuring the dispersibility of the polymer fine particles (A) in the aggregates, the same organic solvent that exhibits partial solubility in water used in the first step is used as the organic solvent to be mixed with the aggregates. It is preferred to use one organic solvent.

In the second step, the apparatus used for mixing the aggregate and the organic solvent and the method of the mixing operation are not particularly limited. In the second step, the agglomerate and the organic solvent can be mixed with a general apparatus having a stirring and mixing function (for example, a stirring vessel equipped with stirring blades).

<3-5. Third step>
In the third step, a mixture Y is obtained by mixing the organic solvent dispersion with the plasticizer (B).

In the third step, the amount of the plasticizer (B) mixed with the organic solvent dispersion can be set depending on the amount (concentration) of the polymer fine particles (A) in the first organic solvent dispersion. More specifically, in the third step, when the total amount of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) are 1 to 50% by weight, and the plasticizing The fine polymer particles (A) and the plasticizer (B) are mixed at a compounding ratio of 50 to 99% by weight of the agent (B).

In the third step, the device used for the mixing operation of the organic solvent dispersion and the plasticizer (B) and the method for the mixing operation are not particularly limited. In the third step, the organic solvent dispersion and the plasticizer (B) can be mixed using a general apparatus having a stirring and mixing function (for example, a stirring vessel equipped with stirring blades).

In the third step, the organic solvent is further distilled off from the mixture Y. By this operation (in other words, by this production method), when the polymer fine particles (A) and the plasticizer (B) are included, and the total of the polymer fine particles (A) and the plasticizer (B) is 100% by weight Furthermore, a composition containing 1 to 50% by weight of fine polymer particles (A) and 50 to 99% by weight of plasticizer (B) can be obtained. In the composition according to one preferred embodiment of the present invention, the fine polymer particles (A) are dispersed in the plasticizer (B) substantially in the form of primary particles.

In the third step, the device used for distilling off the organic solvent from the mixture Y and the method for distilling off the organic solvent from the mixture Y are not particularly limited, and known devices and methods can be used. Specific embodiments for distilling off the organic solvent from the mixture Y include (a) a method of charging the mixture in a tank and distilling off the organic solvent by heating under reduced pressure, and (b) countercurrent contact of the dry gas and the mixture in the tank. a continuous method using a thin-film evaporator; and a method using an extruder equipped with a devolatilization mechanism or a continuous stirring tank.

[4. Vinyl chloride plastisol composition]
[2. composition] and/or [3. Composition manufacturing method] and a vinyl chloride resin.

In this specification, "the vinyl chloride-based plastisol composition according to one embodiment of the present invention" may be referred to as "the present vinyl chloride-based plastisol composition".

Due to the above-described structure, the fine polymer particles (A) are dispersed in the present vinyl chloride plastisol composition, more specifically, in the mixture of the vinyl chloride resin and the plasticizer (B). In the present vinyl chloride-based plastisol composition, the polymer fine particles (A) can preferably be dispersed in the form of primary particles. As a result, the present vinyl chloride-based plastisol composition has the advantage of being able to provide moldings with excellent mechanical properties (eg, tensile strength, tensile elongation and elastic modulus).

The present vinyl chloride-based plastisol composition will be described below. Composition] and [3. Method for producing composition].

<4-1. Vinyl chloride resin>
The vinyl chloride-based resin in one embodiment of the present invention includes (a) a conventionally known homopolymer resin of vinyl chloride (vinyl chloride homopolymer), and/or (b) a conventionally known vinyl chloride and a copolymer resin (vinyl chloride copolymer) that is a copolymer of a conventionally known monomer other than vinyl chloride that can be copolymerized with vinyl chloride (hereinafter also referred to as "monomer C") and is not particularly limited.

(Monomer other than vinyl chloride copolymerizable with vinyl chloride (monomer C))
The monomer C is not particularly limited, but includes (a) olefins such as ethylene, propylene and butene, (b) vinyl esters such as vinyl acetate, vinyl propionate and vinyl stearate, ( c) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether and lauryl vinyl ether, (d) vinylidenes such as vinylidene chloride, (e) acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, Unsaturated carboxylic acids such as itaconic anhydride and acid anhydrides thereof, (f) unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate (g) aromatic vinyl compounds such as styrene, α-methylstyrene and divinylbenzene; (h) unsaturated nitriles such as acrylonitrile; (i) cross-linkable monomers such as diallyl phthalate; All known possible monomers can be used. The amount of these monomers C used in the preparation of copolymer resins is preferably less than 50% by weight in the monomer mixture with vinyl chloride.

(copolymer resin)
The copolymer resin is not particularly limited. Examples of the copolymer resin include (a) copolymer resins of vinyl chloride and vinyl esters (for example, vinyl chloride-vinyl acetate copolymer resins and vinyl chloride-vinyl propionate copolymer resins), (b) vinyl chloride and acrylic acid esters. (e.g. vinyl chloride-butyl acrylate copolymer resins and vinyl chloride-2-ethylhexyl acrylate copolymer resins), (c) copolymer resins of vinyl chloride and olefins (e.g. vinyl chloride-ethylene copolymer resins) and vinyl chloride-propylene copolymer resins, etc.), and (d) copolymer resins of vinyl chloride and unsaturated nitriles (eg, vinyl chloride-acrylonitrile copolymer resins, etc.).

Vinyl chloride homopolymer resins, vinyl chloride-ethylene copolymer resins and vinyl chloride-vinyl acetate copolymer resins are particularly preferred as vinyl chloride resins.

(Method for producing vinyl chloride resin)
A method for producing a vinyl chloride resin according to one embodiment of the present invention is not particularly limited. A vinyl chloride resin according to an embodiment of the present invention can be obtained, for example, by sequentially performing the following (1) and (2) ((2-a) or (2-b)):
(1) (a) a vinyl chloride monomer, or a mixture of a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer (monomer C), (b) an emulsifier, and if necessary optionally (c) adding dispersing aids such as higher alcohols, higher fatty acids, etc. to the aqueous medium;
(2) (2-a) further add an oil-soluble polymerization initiator to the aqueous medium, homogenize the resulting mixture, and then perform fine suspension polymerization, or (2-b) add the aqueous medium to Furthermore, after adding a water-soluble initiator, emulsion polymerization or seed emulsion polymerization is carried out.

The vinyl chloride-based resin obtained by the method described above can be dispersed in an aqueous medium. The aqueous homogenous dispersion (latex) of the vinyl chloride resin obtained by the above-described method is subjected to various known drying methods (e.g., spray drying and spray drying) to obtain powdery vinyl chloride resin products. can be obtained.

In the homogenization of the mixture in microsuspension polymerization of (2-a), one-stage or two-stage pressurization high pressure pump, colloid mill, centrifugal pump, homomixer, vibrating stirrer, high pressure jet from nozzle or orifice and super Known devices and methods such as sound waves can be used singly or in combination of two or more.

The emulsifier is not particularly limited. As the emulsifier, an anionic surfactant is usually used in an amount of about 0.1 to 3 parts by weight per 100 parts by weight of the monomer mixture. Examples of anionic surfactants include potassium, sodium and ammonium salts of fatty acids, alkyl sulfates, alkylbenzenesulfonic acids, alkylsulfosuccinic acids, α-olefinsulfonic acids, and alkyl ether phosphates.

The dispersing aid is not particularly limited. As dispersing aids, (a) higher alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol, and (b) higher fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid can be used. can. Other polymerization aids include aromatic hydrocarbons, polyvinyl alcohol, gelatin, particle size modifiers (such as sodium sulfate and sodium bicarbonate), chain transfer agents, antioxidants, and the like. These dispersing aids and polymerization aids may be used singly or in combination of two or more.

The oil-soluble initiator used in the fine suspension polymerization of (2-a) is not particularly limited. Examples of the oil-soluble initiator include (a) (a-1) diacyl peroxides such as dilauroyl peroxide and di-3,5,5, trimethylhexanoyl peroxide, and (a-2) diisopropyl peroxide. carbonates, peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate, (a-3) peroxyesters such as t-butyl peroxypivalate and t-butyl peroxyneodecanoate, etc. an organic peroxide initiator, and (b) 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy- 2,4-dimethylvaleronitrile) can be used.

The water-soluble initiator used in the emulsion polymerization of (2-b) is not particularly limited. Examples of the water-soluble initiator include ammonium persulfate, potassium persulfate, sodium persulfate, and aqueous hydrogen peroxide. As the water-soluble initiator, if necessary, the hydrogen peroxide solution and the reducing agent may be used in combination. Examples of the reducing agent include sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate dihydrate, ascorbic acid, sodium ascorbate and the like. These water-soluble initiators may be used singly or in combination of two or more.

<4-2. Inorganic filler>
The present vinyl chloride-based plastisol composition preferably further contains an inorganic filler. When the present vinyl chloride-based plastisol composition contains an inorganic filler, it has the advantage of being able to more strongly enjoy the effect of improving mechanical properties due to the fine polymer particles (B).

The inorganic filler is not particularly limited, and known inorganic fillers can be used. Examples of inorganic fillers include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, baryta, kaolin, talc, bentonite, silica (e.g., colloidal silica), mica powder, silica sand, diatomaceous earth clay, calcium silicate, and glass. powder, aluminum oxide, and the like. These inorganic fillers may be used singly or in combination of two or more.

The surface of the inorganic filler may be treated with a fatty acid, a modified fatty acid, or the like, from the viewpoint of enhancing affinity with the vinyl chloride resin. In other words, the inorganic filler may be a surface-treated inorganic filler.

<4-3. Content ratio of each component in the present vinyl chloride-based plastisol composition>
The content of the fine polymer particles (A) in the present vinyl chloride-based plastisol composition is not particularly limited. From the viewpoint of the mechanical properties of the molded article obtained from the vinyl chloride-based plastisol composition due to the polymer fine particles (A), the content of the polymer fine particles (A) in the present vinyl chloride-based plastisol composition is It is preferably 0.5 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin. is more preferred, and 0.5 to 5 parts by weight is particularly preferred.

The content of the plasticizer (B) in the present vinyl chloride plastisol composition is not particularly limited. From the viewpoint of the tensile strength of the molded article obtained from the vinyl chloride plastisol composition, the content of the plasticizer (B) in the present vinyl chloride plastisol composition is 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. It is preferably 200 parts by weight, more preferably 30 parts by weight to 150 parts by weight, even more preferably 30 parts by weight to 100 parts by weight, and particularly 30 parts by weight to 80 parts by weight. preferable.

The present vinyl chloride-based plastisol composition may further contain a plasticizer (B) in addition to the plasticizer (B) derived from the composition. In other words, the present vinyl chloride plastisol composition may contain the present composition, a vinyl chloride resin, and a plasticizer (B). In the present vinyl chloride-based plastisol composition, the plasticizer (B) derived from the composition and the plasticizer (B) further included may be of the same type or of different types.

The content of the inorganic filler in the present vinyl chloride plastisol composition is not particularly limited. The content of the inorganic filler in the present vinyl chloride plastisol composition includes (a) the effect of reducing the cost of the vinyl chloride plastisol composition by increasing the volume of the resulting vinyl chloride plastisol composition, and (b) fire prevention. Appropriately set from the viewpoint of passing the certification criteria, (c) hiding property, and (d) ease of expression of the mechanical property improvement effect by the polymer fine particles (A) in the molded article obtained from the vinyl chloride plastisol composition. do it. From these points of view, the content of the inorganic filler in the present vinyl chloride plastisol composition is, for example, preferably 30 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and 30 parts by weight. It is more preferably up to 150 parts by weight, even more preferably 30 parts by weight to 100 parts by weight, and particularly preferably 30 parts by weight to 80 parts by weight.

<4-4. Method for producing a vinyl chloride-based plastisol composition>
The method for producing the present vinyl chloride-based plastisol composition is not particularly limited. As a method for producing the present vinyl chloride-based plastisol composition, for example, there is a method of mixing and stirring the composition according to one embodiment of the present invention, a vinyl chloride-based resin, and, if necessary, a plasticizer (B). mentioned. A device for mixing and stirring raw materials is not particularly limited, and examples thereof include a dissolver type mixer (sometimes referred to as a dissolver type kneader), a butterfly mixer, a universal stirrer, and the like.

In the production of the present vinyl chloride plastisol composition, the mixing ratio of the present composition, the vinyl chloride resin, and the optionally used plasticizer (B) is not particularly limited. In the production of the present vinyl chloride-based plastisol composition, the content of each component in the obtained vinyl chloride-based plastisol composition is determined according to <4-3. Content ratio of each component in the present vinyl chloride plastisol composition>. Amount, mixing and stirring.

In the present vinyl chloride-based plastisol composition, the fine polymer particles (A) are preferably dispersed in the form of primary particles. By mixing and stirring a composition in which the polymer fine particles (A) are dispersed in the state of primary particles in the plasticizer (B) and the vinyl chloride resin, the polymer fine particles (A) are converted into primary particles. A vinyl chloride-based plastisol composition dispersed in the form of particles can be obtained.

[5. molding]
In the molded product obtained by molding the present vinyl chloride plastisol composition, the particulate polymer fine particles (A) can be uniformly dispersed, preferably the polymer fine particles (A) are uniformly in the state of primary particles. can be distributed in A molded article obtained by molding the present vinyl chloride-based plastisol composition is also an embodiment of the present invention. Since the molded article according to one embodiment of the present invention has the configuration described above, it has the advantage of being excellent in mechanical properties (for example, tensile strength, tensile elongation and elastic modulus).

[6. Application]
The present composition and vinyl chloride-based plastisol composition can be used for various uses, and their uses are not particularly limited. The composition and the vinyl chloride-based plastisol composition can be suitably used, for example, as coating materials and film materials. The present composition and the vinyl chloride plastisol composition are particularly suitable for outdoor advertising billboards, sign displays, film materials (sheets) for wall coverings, and the like.

The method of using the present composition and the vinyl chloride plastisol composition as a coating material or film material (also referred to as a coating method) is not particularly limited. For example, coating layers and films can be formed by casting the composition and the vinyl chloride plastisol composition. Cast molding methods include, for example, applying the present composition and the vinyl chloride plastisol composition to gravure coaters, roll coaters, knife coaters, blade coaters, curtain coaters, dip coaters, spray coaters, spin coaters, extrusion coaters and die coaters. and then drying with hot air to obtain a coating film.

EXAMPLES Hereinafter, one embodiment of the present invention will be described 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 aqueous latex containing fine polymer particles (A)>
1. Polymerization of elastic body Production Example 1-1; Preparation of aqueous latex (R-1) containing elastic body mainly composed of polybutadiene rubber In a pressure-resistant polymerization vessel, deionized water 200 parts by weight, tripotassium phosphate 0.03. 0.002 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by weight of ferrous sulfate heptahydrate, and 1.55 parts by weight of sodium dodecylbenzenesulfonate (SDBS) as an emulsifier. bottom. 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, 100 parts by weight of butadiene (Bd) was 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. After 15 hours from the start of the polymerization, devolatilization was performed under reduced pressure to remove residual monomers that were not used in the polymerization, thereby completing the polymerization. During the polymerization, each of PHP, EDTA and ferrous sulfate heptahydrate was added in an arbitrary amount and at an arbitrary timing into the pressure-resistant polymerization vessel. By the polymerization, an aqueous latex (R-1) containing an elastic body containing polybutadiene rubber as a main component was obtained. Using the obtained aqueous latex (R-1) as a sample, the volume average particle diameter of the elastic body contained in the aqueous latex (R-1) was measured with a dynamic light scattering particle size distribution measuring device. Met.

Production Example 1-2; Preparation of water-based latex (R-2) containing elastic body mainly composed of polybutadiene rubber Into a pressure-resistant polymerization vessel, 7 parts by weight of solid content of the water-based latex (R-1) obtained above was added. , 200 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of EDTA, and 0.001 parts by weight of ferrous sulfate heptahydrate were added. 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, 93 parts by weight of Bd was put into the pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C. After that, 0.02 parts by weight of PHP was charged into the pressure-resistant polymerization vessel, and then 0.10 parts by weight of SFS was charged into the pressure-resistant polymerization vessel to initiate polymerization. After 30 hours from the start of the polymerization, devolatilization was performed under reduced pressure to remove residual monomers that were not used in the polymerization, thereby completing the polymerization. During the polymerization, each of PHP, EDTA, ferrous sulfate heptahydrate and SDBS was added into the pressure-resistant polymerization vessel at arbitrary amounts and at arbitrary times. By the polymerization, a water-based latex (R-2) containing an elastic body composed mainly of polybutadiene rubber was obtained. Using the obtained aqueous latex (R-2) as a sample, the volume average particle diameter of the elastic body contained in the aqueous latex (R-2) was measured with a dynamic light scattering particle size distribution measuring device. Met.

2. Preparation of polymer microparticles (A) (polymerization of graft portion)
Production Example 2-1; Preparation of aqueous latex (L-1) containing fine polymer particles (A) In a glass reactor, 250 parts by weight of the aqueous latex (R-2) 87 parts by weight) and 50 parts by weight of deionized water were charged. 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 0.20 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. After that, a monomer for forming a graft portion (hereinafter also referred to as a graft monomer) (12.1 parts by weight of methyl methacrylate (MMA) and 0.9 parts by weight of butyl acrylate (BA)) and t-butyl hydroperoxide A mixture with 0.035 parts by weight of oxide (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 mixture in the glass reactor was stirred for another hour to complete the polymerization. By the above operation, an aqueous latex (L-1) containing fine polymer particles (A) and an emulsifier was obtained. The polymerization conversion rate of the monomer component was 96% by weight or more. Using the obtained aqueous latex (L-1) as a sample, the volume average particle diameter of the polymer fine particles (A) contained in the aqueous latex (L-1) is measured using a dynamic light scattering particle size distribution analyzer. As a result, it was 200 nm. The solid content concentration (concentration of the fine polymer particles (A)) in the resulting aqueous latex (L-1) was 30% by weight with respect to 100% by weight of the aqueous latex (L-1).

<2. Production of composition>
(First step)
A mixing vessel (volume 1 L) equipped with a stirrer was used as an apparatus. In addition, methyl ethyl ketone (MEK) was used as an organic solvent exhibiting partial solubility in water. After the temperature in the mixing tank was adjusted to 30° C., 126 parts by weight of MEK was added to the mixing tank. Thereafter, while stirring the MEK in the mixing tank, 143 parts by weight of the aqueous latex (L-1) of the polymer particles (A) was introduced into the mixing tank. By uniformly mixing the charged raw materials, a mixture (mixture X) of an aqueous latex containing polymer fine particles (A) and an organic solvent exhibiting partial solubility in water was obtained. Next, while stirring the mixture X, 200 parts by weight of water (total of 469 parts by weight) was added to the mixing tank at a feed rate of 80 parts by weight/minute to bring the mixture X into contact with the water. After the supply of water was completed, the stirring was stopped immediately, and floating aggregates (aggregates of the polymer fine particles (A)) were generated in the aqueous phase to obtain a slurry liquid containing the aggregates.

(Second step)
Agglomerates were then separated and recovered from the aqueous phase. Specifically, while leaving the aggregates in the mixing tank, 350 parts by weight of the aqueous phase was discharged from the outlet at the bottom of the mixing tank to obtain the aggregates. 150 parts by weight of MEK was added to the resulting aggregates (also referred to as fine polymer particles (A) dope) and mixed to obtain an organic solvent solution containing fine polymer particles (A). The polymer microparticles (A) were dispersed in the organic solvent solution. The resulting organic solvent solution was 277 parts by weight (containing 42.9 parts by weight of the fine polymer particles (A)).

(Third step)
386.1 parts by weight of diisononyl phthalate (DINP) as the plasticizer (B) was added to 277 parts by weight of the resulting organic solvent solution (containing 42.9 parts by weight of the fine polymer particles (A)). After mixing the resulting mixture, MEK was distilled off from the mixture under reduced pressure to obtain a composition (A-1). In the third step, when the total amount of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) are 10% by weight and the plasticizer (B) is 90% by weight. The fine polymer particles (A) and the plasticizer (B) were mixed at a blending ratio of 1% by weight. That is, the resulting composition (A-1) contains 10% by weight of the fine polymer particles (A) and 10% by weight of the plasticizer (B) when the total of the fine polymer particles (A) and the plasticizer (B) is 100% by weight. It contained 90% by weight of agent (B).

The dispersibility of the fine polymer particles (A) in the composition (A-1) was evaluated using a grind gauge according to JIS K5101. A specific method is as follows. The composition (A-1) was placed on a grind meter (grind gauge), the fine polymer particles (A) on the gauge were scraped off with a metal scraper, and the state of dispersion was visually confirmed. Graduations were read at positions where 5 to 10 dots in a 3 mm wide band were produced by the motion of the scraper. As a result, no undispersed matter was found on the scale of 0 μm to 10 μm, so the result of dispersibility can be said to be 0 μm. From this result, it was confirmed that the fine polymer particles (A) were dispersed in the state of primary particles in the composition (A-1) (that is, in the plasticizer (B)).

<3. Production of vinyl chloride-based plastisol composition>
[Example 1]
Vinyl chloride resin (Kanevinyl (registered trademark) paste PSH-24 (polymerization degree 2800), manufactured by Kaneka Co., Ltd.) 100 parts by weight, composition (A-1) 54 parts by weight, DINP as a plasticizer (B) 36 parts by weight, 50 parts by weight of calcium carbonate (BF300, manufactured by Bihoku Funka Kogyo Co., Ltd., particle size 8 μm) as an inorganic filler, 3 parts by weight of a viscosity reducing agent (Oxazol S, manufactured by Oxalis Chemicals Co., Ltd.) and a stabilizer (Adekastab AC-322, manufactured by ADEKA Co., Ltd.) was added to obtain a mixture. The resulting mixture was kneaded using a dissolver type kneader [KIKA ROBO MICS/TOKU SHU] at 350 rpm for 1 minute once and 1000 rpm for 1 minute twice to obtain a vinyl chloride plastisol composition ( B-1) was obtained.

In the production of the vinyl chloride-based plastisol composition (B-1), the composition (A-1) in which the fine polymer particles (A) were dispersed in the form of primary particles was used. Therefore, even in the obtained vinyl chloride plastisol composition (B-1) (that is, in the mixture of the vinyl chloride resin and the plasticizer (B)), the fine polymer particles (A) are dispersed in the form of primary particles. Was.

[Comparative Example 1]
A vinyl chloride plastisol composition (B-2) was obtained in the same manner as in Example 1, except that the plasticizer (B) was increased to 80 parts by weight and the composition (A-1) was not used. rice field.

<4. Manufacture of moldings>
Each vinyl chloride-based plastisol composition obtained in Examples and Comparative Examples was applied to an OHP film with a roll coater so that the thickness of the molded product after drying was 200 μm. The OHP film coated with the vinyl chloride plastisol composition was baked at 200° C. for 5 minutes to obtain an OHP film laminated with the molding.

<5. Evaluation of molding>
(Measurement method of tensile strength, tensile elongation and elastic modulus)
The molded article was peeled off from the OHP film laminated with the molded article, and the molded article was punched out with a dumbbell-shaped No. 3 shape specified in JIS K6251 to prepare a test piece. After leaving the obtained test piece at 23° C. for 1 day or longer, the thickness of the test piece was measured.

Then, using an Autograph (manufactured by Shimadzu Corporation), a tensile test was performed at a tensile speed of 200 mm/min and at the temperature shown in Table 1 to measure tensile strength, tensile elongation and elastic modulus. Table 1 shows the results obtained.

In Table 1, "solid content" is the ratio (% by weight) of the total amount (parts by weight) of the vinyl chloride resin, the polymer fine particles (A) and the inorganic filler with respect to 100 weight of each vinyl chloride plastisol composition. Intend. From the results in Table 1, it can be seen that the molded article of Example 1 is superior to the molded article of Comparative Example 1 in mechanical properties due to the fine polymer particles (A). Therefore, it can be seen that in the molded product of Example 1, the fine polymer particles (A) are present while maintaining the shape of the particles. Further, as described above, in the composition (A-1) of Example 1 and the vinyl chloride-based plastisol composition (B-1), the polymer fine particles (A) are dispersed in the form of primary particles. was confirmed. Therefore, it can be considered that the polymer fine particles (A) are dispersed in the form of primary particles even in the molded product of Example 1.

One embodiment of the present invention is a composition in which particulate polymer fine particles (A) are dispersed in a plasticizer (B), and a particulate polymer in a mixture of a vinyl chloride resin and a plasticizer (B). It is possible to provide a vinyl chloride-based plastisol composition in which the polymer fine particles (A) are dispersed. The vinyl chloride-based plastisol composition can provide moldings with excellent mechanical properties. Therefore, the composition and vinyl chloride plastisol composition according to one embodiment of the present invention can be suitably used as coating materials and film materials. The composition and vinyl chloride-based plastisol composition according to one embodiment of the present invention are particularly suitable for outdoor advertising billboards, sign displays, film materials (sheets) for wall coverings, and the like.

Claims (8)

containing polymer fine particles (A) and a plasticizer (B),
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 elastic body is crosslinked,
When the total of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight, and the plasticizer (B) is 50% by weight. A composition that is -99% by weight. 2. The composition according to claim 1, wherein the polymer fine particles (A) have a dispersibility of 0 [mu]m as measured according to JIS K5101 using a grind gauge. The plasticizer (B) includes a phthalate ester plasticizer, a trimellitate ester plasticizer, an adipate ester plasticizer, an azelaic ester plasticizer, a sebate ester plasticizer, and a phosphate ester plasticizer. , a polyester plasticizer, an epoxy plasticizer, a fatty acid ester plasticizer and a pyromellitic ester plasticizer. The composition according to any one of claims 1 to 3, wherein the plasticizer (B) is a phthalate plasticizer. The composition according to any one of claims 1 to 4, wherein the elastic body is a diene-based rubber, a (meth)acrylate-based rubber, or a mixture of a diene-based rubber and a (meth)acrylate-based rubber. A vinyl chloride plastisol composition comprising the composition according to any one of claims 1 to 5 and a vinyl chloride resin. 7. The vinyl chloride-based plastisol composition of claim 6, further comprising an inorganic filler. After mixing an 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 the aggregates of A) in the aqueous phase,
After separating and recovering the aggregates from the aqueous phase, a second step of mixing the aggregates with the organic solvent to obtain an organic solvent dispersion containing the polymer fine particles (A), and the organic solvent dispersion a third step of distilling off the organic solvent from the resulting mixture after mixing the liquid with the plasticizer (B),
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 elastic body is crosslinked,
In the third step, when the total amount of the polymer fine particles (A) and the plasticizer (B) is 100% by weight, the polymer fine particles (A) is 1 to 50% by weight, and the plasticizing A method for producing a composition, wherein the fine polymer particles (A) and the plasticizer (B) are mixed at a mixing ratio in which the agent (B) is 50 to 99% by weight.