Powders and granules and their uses

Abstract

A granular body for a thermosetting resin, the granular body comprising a polymer microparticle (A) that comprises a rubber-containing graft copolymer, the rubber-containing graft copolymer comprising an elastic body and grafted parts that are grafted to the elastic body. The polymer microparticle (A) has a volume average particle diameter of not less than 90 nm, and the polymer in the grafted part has a weight average molecular weight of not more than 200000.

Description

[Technical Field]

[0001] The present invention relates to a powder or granular material and its use. [Background technology]

[0002] In order to improve the toughness of thermosetting resins, a method of adding an elastomer, particularly crosslinked polymer fine particles, to the resin has been widely used (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2018-500440 [Patent Document 2] Japanese Patent Publication No. 2018-500441 [Patent Document 3] International Publication No. WO2011 / 046086 [Patent Document 4] International Publication No. WO2005 / 116155 Summary of the Invention [Problem to be solved by the invention]

[0004] In the above-mentioned technology, the present inventors have found that the use of polymer microparticles with a large particle size improves the dispersibility of the polymer microparticles blended into a thermosetting resin. However, the present inventors have independently discovered a technical problem: when polymer microparticles with a large particle size, each having a specific elastomer and a graft moiety grafted to the elastomer, are blended into a thermosetting resin matrix resin, the viscosity (blending viscosity) of the resulting thermosetting resin composition increases significantly, which can reduce workability.

[0005] One embodiment of the present invention has been made in consideration of the above-mentioned problems, and its object is to provide a novel powder or granular material that can suppress an increase in viscosity of the resulting resin composition when mixed with a thermosetting resin matrix resin, and a technology for using the same. [Means for solving the problem]

[0006] As a result of extensive research to solve the above-mentioned problems, the inventors independently discovered that when large-diameter polymer microparticles having a specific elastomer and a graft portion grafted to the elastomer are mixed with a thermosetting resin matrix resin, the increase in viscosity of the resulting resin composition is caused by the molecular weight of the graft portion of the polymer microparticles, which led to the completion of the present invention.

[0007] That is, one embodiment of the present invention includes the following configuration.

[0008] A powder containing polymer fine particles (A) to be blended with a thermosetting resin, the polymer fine particles (A) comprising a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer, the elastomer comprising, as a constituent unit, a constituent unit derived from butadiene, the graft portion comprising, as a constituent unit, a polymer comprising, as a constituent unit, a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer, the volume average particle diameter of the polymer fine particles (A) being 90 nm or more, and the weight average molecular weight of the polymer in the graft portion being 200,000 or less. [Effects of the Invention]

[0009] According to the powder / granule according to one embodiment of the present invention, even when added to a thermosetting resin, an increase in viscosity of the resin composition can be suppressed, thereby improving workability. DETAILED DESCRIPTION OF THE INVENTION

[0010] One embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the respective configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by appropriately combining the 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. All academic literature and patent documents described in this specification are incorporated herein by reference. Furthermore, unless otherwise specified in this specification, the term "A to B" representing a numerical range means "greater than or equal to A (including and greater than A) and less than or equal to B (including and less than B)."

[0011] [Embodiment 1] [1. Powder] One embodiment of the present invention provides a powder containing polymer fine particles (A) for incorporation into a thermosetting resin. The polymer fine particles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft portion grafted to the elastomer. The elastomer contains structural units derived from butadiene. The graft portion comprises a polymer containing structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. The volume-average particle diameter of the polymer fine particles (A) is 90 nm or greater, and the weight-average molecular weight of the polymer in the graft portion is 200,000 or less. Hereinafter, the powder for thermosetting resins according to one embodiment of the present invention will be referred to simply as the present powder. When the present powder is dispersed in a thermosetting resin (B), which is a matrix resin described below, a resin composition is formed. Note that the present invention does not include powders intended for thermoplastic resins.

[0012] As used herein, the term "granular material" refers to both powder and granules, and refers to an aggregate of powder, granules, etc. Furthermore, when specifically distinguishing between the two, "powder" refers to a material having a volume average particle diameter of 0.01 mm to 0.1 mm, and "granules" refers to a material having a volume average particle diameter of 0.1 mm to 10 mm. However, powder and granules may contain coarse particles of 10 mm or larger. Furthermore, "volume average particle diameters" in the range of less than 10 μm can be measured using a dynamic light scattering (DLS) particle size distribution analyzer Nanotrac Wave II-EX150 (manufactured by Microtrack Bell Co., Ltd.), and "volume average particle diameters" in the range of 10 μm or larger can be measured using a laser diffraction particle size distribution analyzer Microtrac MT3000 II (manufactured by Microtrack Bell Co., Ltd.).

[0013] The present inventors have conducted extensive research into the cause of an increase in viscosity (blending viscosity) of a resin composition obtained by mixing polymer microparticles having a specific particle size and a specific elastomer with a graft portion grafted to the elastomer with a thermosetting resin matrix resin. As a result, they have independently discovered that the viscosity of the resin composition increases significantly when the molecular weight of the polymer in the graft portion of the polymer microparticles is equal to or greater than a predetermined value. In one embodiment of the present invention, in a powder or granular material containing polymer microparticles (A), by setting the molecular weight of the polymer in the graft portion of the polymer microparticles (A) to a predetermined value or less, an increase in viscosity of the resin composition can be suppressed even when the polymer is added to a thermosetting resin.

[0014] (1-1. Polymer fine particles (A)) The polymer fine particles (A) contain a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer.

[0015] (1-1-1. Elastic body) The elastomer contains, as structural units, structural units derived from butadiene and structural units derived from one or more monomers copolymerizable with butadiene. The elastomer can also be referred to as butadiene-based rubber particles. When the elastomer has the above-mentioned structure, if the molecular weight of the molecular chain of the graft portion (described later) exceeds a predetermined value, the viscosity of the resin composition obtained by mixing the thermosetting resin and the powder or granule tends to increase significantly.

[0016] When the elastic material contains a butadiene-based rubber, the resulting resin composition containing the particulate material can provide a cured product that is excellent in toughness and impact resistance.

[0017] The butadiene-based rubber may be a polymer (polybutadiene rubber) composed only of structural units derived from butadiene, or may be a copolymer of structural units derived from butadiene and structural units derived from one or more monomers copolymerizable with butadiene.

[0018] Examples of butadienes include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2-chloro-1,3-butadiene, etc. These monomers may be used alone or in combination of two or more.

[0019] Examples of the structural units derived from one or more monomers copolymerizable with butadiene include structural units derived from vinyl monomers and / or structural units derived from (meth)acrylate monomers. In this specification, (meth)acrylate means acrylate and / or methacrylate.

[0020] The elastomer preferably contains, out of 100% by weight of constituent units, 30% by weight to 100% by weight of constituent units derived from butadiene and 0% by weight to 70% by weight of constituent units derived from one or more monomers copolymerizable with butadiene.More preferably, out of 100% by weight of constituent units, 50% by weight to 100% by weight of constituent units derived from butadiene and 0% by weight to 50% by weight of constituent units derived from one or more monomers copolymerizable with butadiene.

[0021] Examples of vinyl monomers include vinyl arenes such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; vinyl carboxylic 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; vinyl acetate; alkenes such as ethylene, propylene, butylene, and isobutylene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The above-mentioned vinyl monomers may be used alone or in combination of two or more. Among the above-mentioned vinyl monomers, styrene is particularly preferred.

[0022] The butadiene rubber is preferably a polybutadiene rubber consisting only of 1,3-butadiene, or a butadiene-styrene rubber (also referred to as polystyrene-butadiene) which is a copolymer of 1,3-butadiene and styrene. According to the above-mentioned configuration, the desired effects of the polymer fine particles (A) containing the butadiene rubber can be more effectively exhibited. Furthermore, the butadiene-styrene rubber is more preferable in that the transparency of the resulting cured product can be improved by adjusting the refractive index.

[0023] Examples of the (meth)acrylate monomer include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; Examples of suitable (meth)acrylate monomers include hydroxyalkyl (meth)acrylates such as acrylate; glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidyl alkyl (meth)acrylate; alkoxyalkyl (meth)acrylates; allyl alkyl (meth)acrylates such as allyl (meth)acrylate and allyl alkyl (meth)acrylate; and polyfunctional (meth)acrylates such as monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. 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 particularly preferred, with butyl (meth)acrylate being more preferred.

[0024] The elastomer may further contain a (meth)acrylate rubber or a polysiloxane rubber elastomer in addition to the butadiene rubber. Also, as an elastomer other than the butadiene rubber, (meth)acrylate rubber, and polysiloxane rubber elastomer, natural rubber may be included, for example.

[0025] (elastic cross-linked structure) From the viewpoint of maintaining the dispersion stability of the polymer microparticles (A) in the thermosetting resin, it is preferable that a crosslinked structure be introduced into the elastomer. A commonly used method can be used to introduce a crosslinked structure into the elastomer, and examples thereof include the following methods. Specifically, in the production of the elastomer, a method can be used in which a crosslinkable monomer such as a polyfunctional monomer and / or a mercapto group-containing compound is mixed with a monomer capable of constituting the elastomer, followed by polymerization. In this specification, the production of a polymer such as an elastomer is also referred to as polymerizing a polymer.

[0026] A polyfunctional monomer can also be said to be a monomer having two or more radically polymerizable reactive groups in the same molecule. The radically polymerizable reactive group is preferably a carbon-carbon double bond. Examples of polyfunctional monomers include (meth)acrylates having an ethylenically unsaturated double bond, such as allyl alkyl (meth)acrylates and allyloxy alkyl (meth)acrylates, and do not include butadiene. 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, cyclohexanedimethanol di(meth)acrylate, 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, and polyethylene glycol (600) di(meth)acrylate. Examples of monomers having three (meth)acrylate groups include alkoxylated trimethylolpropane tri(meth)acrylates, glycerol propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate. Examples of the alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate and trimethylolpropane triethoxy tri(meth)acrylate. Further, examples of monomers having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate.Further, examples of monomers having five (meth)acrylic groups include dipentaerythritol penta(meth)acrylate.Further, examples of monomers having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate.The polyfunctional monomers also include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like.

[0027] Examples of 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, acid group-substituted mercaptans, halo group-substituted mercaptans, and acyl group-substituted mercaptans. The alkyl group-substituted mercaptans are preferably alkyl group-substituted mercaptans having 1 to 20 carbon atoms, and more preferably alkyl group-substituted mercaptans having 1 to 10 carbon atoms. The aryl group-substituted mercaptans are preferably phenyl group-substituted mercaptans. The alkoxy group-substituted mercaptans are preferably alkoxy group-substituted mercaptans having 1 to 20 carbon atoms, and more preferably alkoxy group-substituted mercaptans having 1 to 10 carbon atoms. The acid group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having a carboxyl group and 1 to 10 carbon atoms, or an aryl group-substituted mercaptan having a carboxyl group and 1 to 12 carbon atoms.

[0028] (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, more preferably 20°C or lower, more preferably 10°C or lower, more preferably 0°C or lower, more preferably -20°C or lower, more preferably -40°C or lower, more preferably -45°C or lower, more preferably -50°C or lower, more 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, more preferably -85°C or lower, more preferably -90°C or lower, more preferably -95°C or lower, more preferably -100°C or lower, more preferably -105°C or lower, more preferably -110°C or lower, more preferably -115°C or lower, even more preferably -120°C or lower, and particularly preferably -125°C or lower. In this specification, "glass transition temperature" may also be referred to as "Tg." This configuration allows for the production of powders and granules with low Tg. As a result, resin compositions containing the resulting powder and granules can provide cured or molded articles with excellent toughness. The Tg of an elastomer can be determined by viscoelasticity measurements using a flat plate made of the elastomer. Specifically, Tg can be measured as follows: (1) Dynamic viscoelasticity measurements are performed under tensile conditions on a flat plate made of polymer microparticles using a dynamic viscoelasticity measuring device (e.g., DVA-200, manufactured by IT Measurement & Control Co., Ltd.) to obtain a tan δ graph; (2) The peak temperature of tan δ in the resulting tan δ graph is taken as the glass transition temperature. If multiple peaks are observed in the tan δ graph, the lowest peak temperature is taken as the glass transition temperature of the elastomer.

[0029] On the other hand, since this can suppress a decrease in the modulus of elasticity (rigidity) of the resulting cured product, i.e., a cured product with sufficient modulus of elasticity (rigidity) can be obtained, the Tg of the elastomer is preferably greater than 0°C, more preferably 20°C or greater, even more preferably 50°C or greater, particularly preferably 80°C or greater, and most preferably 120°C or greater.

[0030] The Tg of an elastomer can be determined by the composition of the structural units contained in the elastomer, etc. In other words, the Tg of the resulting elastomer can be adjusted by changing the composition of the monomers used when producing (polymerizing) the elastomer.

[0031] Here, when a homopolymer is prepared by polymerizing only one type of monomer, a group of monomers that provides a homopolymer having a Tg greater than 0°C is referred to as monomer group a. Furthermore, when a homopolymer is prepared by polymerizing only one type of monomer, a group of monomers that provides a homopolymer having a Tg less than 0°C is referred to as monomer group b. An elastomer containing 50 to 100 wt% (more preferably, 65 to 99 wt%) of structural units derived from at least one monomer selected from monomer group a and 0 to 50 wt% (more preferably, 1 to 35 wt%) of structural units derived from at least one monomer selected from monomer group b is referred to as elastomer X. Elastomer X has a Tg greater than 0°C. Furthermore, when the elastomer contains elastomer X, a resin composition containing the resulting powder or granule can provide a cured product with sufficient rigidity.

[0032] It is also preferable that a crosslinked structure be introduced into the elastic body when the Tg of the elastic body is higher than 0° C. Methods for introducing a crosslinked structure include the methods described above.

[0033] Monomers that can be included in the monomer group a include, but are not limited to, unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; vinyl-substituted aromatic compounds such as α-methylstyrene; ring-alkylated vinyl aromatic compounds such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, and 2,4,6-trimethylstyrene; ring-alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; ring-halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; ring-ester-substituted vinyl aromatic compounds such as 4-acetoxystyrene; and ring-hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene. vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; aromatic monomers such as acenaphthalene and 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 such as methacrylonitrile; certain acrylic acid esters such as isobornyl acrylate and tert-butyl acrylate; acrylic monomers including acrylic acid derivatives such as acrylonitrile, and the like. Further, examples of 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-adamantyl acrylate, and 1-adamantyl methacrylate, which, when made into a homopolymer, can provide a homopolymer having a Tg of 120° C. or higher. These monomers a may be used alone or in combination of two or more.

[0034] Examples of the monomer b include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. These monomers b may be used alone or in combination of two or more. Among these monomers b, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are particularly preferred.

[0035] (Volume average particle size of elastic body) The volume average particle size of the elastomer is preferably 0.03 μm to 50.00 μm, more preferably 0.10 μm to 10.00 μm, more preferably 0.15 μm to 2.00 μm, even more preferably 0.15 μm to 1.00 μm, even more preferably 0.20 μm to 0.80 μm, and particularly preferably 0.20 μm to 0.50 μm. When the volume average particle size of the elastomer is (a) 0.03 μm or more, an elastomer having the desired volume average particle size can be stably obtained, and when (b) 50.00 μm or less, the heat resistance and impact resistance of the resulting cured product or molded article are excellent. The volume average particle size of the elastomer can be measured using a dynamic light scattering particle size distribution analyzer or the like, using an aqueous latex containing the elastomer as a sample. The method for measuring the volume average particle size of the elastomer is described in detail in the Examples below.

[0036] (elastic body ratio) The proportion of the elastomer in the polymer microparticles (A), based on 100% by weight of the entire polymer microparticles (A), is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, even more preferably 70 to 93% by weight, particularly preferably 75 to 90% by weight, and most preferably 80 to 89% by weight. When the proportion of the elastomer is (a) 40% by weight or more, the resulting resin composition containing the granules can provide a cured product with excellent toughness and impact resistance, and (b) when it is 97% by weight or less, the polymer microparticles (A) do not easily aggregate, so the resin composition does not become highly viscous, and as a result, the resulting resin composition containing the granules can be easy to handle.

[0037] In particular, if the proportion of the elastomer in the polymer microparticles (A) is 70% by weight or more, assuming the total polymer microparticles (A) to be 100% by weight, the increase in the blend viscosity of the resulting resin composition containing the powder particles can be more effectively suppressed, resulting in a low-viscosity resin composition. Furthermore, if the proportion of the elastomer is too high, aggregation begins, and the blend viscosity begins to increase again. Therefore, it is particularly preferable that the proportion of the elastomer in the polymer microparticles (A) be 89% by weight or less.

[0038] (gel content of elastic body) The elastomer is preferably one that can swell in a suitable solvent but is substantially insoluble in the solvent, and is preferably insoluble in the thermosetting resin used.

[0039] The elastomer 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 elastomer is within the above range, the resulting resin composition containing the granular material can provide a cured product with excellent toughness.

[0040] In this specification, the gel content is calculated as follows. First, an aqueous latex containing polymer microparticles (A) is obtained, and then a powder of polymer microparticles (A) is obtained from the aqueous latex. The method for obtaining a powder of polymer microparticles (A) from the aqueous latex is not particularly limited, but examples include (i) agglomerating the polymer microparticles (A) in the aqueous latex, (ii) dehydrating the resulting agglomerates, and (iii) further drying the agglomerates to obtain a powder of polymer microparticles (A). Next, 2.0 g of the powder of polymer microparticles (A) is dissolved in 50 mL of methyl ethyl ketone (MEK). The obtained MEK solution is then separated into a component soluble in MEK (MEK solubles) and a component insoluble in MEK (MEK insolubles). Specifically, the obtained MEK soluble matter is centrifuged using a centrifuge (Hitachi Koki Co., Ltd., CP60E) at a rotation speed of 30,000 rpm for 1 hour to separate the soluble matter into MEK-soluble matter and MEK-insoluble matter. A total of three sets of centrifugation are performed. The weights of the obtained MEK-soluble matter and MEK-insoluble matter are measured, and the gel content is calculated using 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.

[0041] (Modification of elastic body) In one embodiment of the present invention, the "elastic body" of the polymer microparticles (A) contains, as structural units, structural units derived from butadiene and structural units derived from one or more monomers copolymerizable with butadiene, and may consist of only one type of elastomer having structural units of the same composition. In one embodiment of the present invention, the elastomer may consist of multiple types of elastomers each having structural units of different compositions.

[0042] In one embodiment of the present invention, the case where the "elastic body" of the polymer fine particles (A) is composed of multiple types of elastomers will be described. In this case, the multiple types of elastomers will be referred to as elastomer 1, elastomer 2, ..., and elastomer 3. nHere, n is an integer equal to or greater than 2. The elastic bodies are composed of elastic body 1, elastic body 2, ..., and elastic body n The "elastic body" of the polymer fine particles (A) may include the elastic body 1, the elastic body 2, ..., and the elastic body n The polymer may contain a polymer obtained by sequentially polymerizing each of the above. Such sequential polymerization of a plurality of polymers (elastomers) is also called multistage polymerization. A polymer obtained by multistage polymerization of a plurality of types of elastomers is also called a multistage polymerized elastomer. The method for producing a multistage polymerized elastomer will be described in detail later.

[0043] Elastic body 1, Elastic body 2, ..., and Elastic body n In the multi-stage polymerized elastomer, the elastomer n is an elastic body n-1 or an elastic body n-1 In the multi-stage polymerized elastomer, n Part of the material is elastic n-1 Sometimes it penetrates inside the

[0044] In a multistage polymerized elastomer, each of the multiple elastomers may have a layer structure. For example, when a multistage polymerized elastomer is composed of elastomer 1, elastomer 2, and elastomer 3, one embodiment of the present invention is one in which elastomer 1 is the innermost layer, a layer of elastomer 2 exists outside elastomer 1, and a layer of elastomer 3 exists outside the layer of elastomer 2 as the outermost layer of the elastomer. In this way, a multistage polymerized elastomer in which each of the multiple elastomers has a layer structure can also be called a multilayer elastomer. That is, in one embodiment of the present invention, the elastomer may include a mixture of multiple types of elastomers, a multistage polymerized elastomer, and / or a multilayer elastomer.

[0045] (1-1-2. Graft area) In this specification, the polymer grafted to the elastomer is referred to as a graft moiety. The graft moiety is a polymer containing, as a structural unit, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. Because of its structure, the graft moiety can fulfill various roles. Examples of "various roles" include (a) improving the compatibility between the polymer microparticles (A) and the thermosetting resin, (b) improving the dispersibility of the polymer microparticles (A) in the thermosetting resin, which is the matrix resin to be mixed with the polymer microparticles, and (c) dispersing the polymer microparticles (A) in the form of primary particles in the resin composition or the cured product thereof.

[0046] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

[0047] Specific examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.

[0048] Specific examples of the (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

[0049] The one or more monomers selected from the group consisting of the aromatic vinyl monomer, the vinyl cyan monomer, and the (meth)acrylate monomer may be used alone or in combination of two or more.

[0050] The graft portion preferably contains, as structural units, structural units derived from aromatic vinyl monomers, structural units derived from vinyl cyan monomers, and structural units derived from (meth)acrylate monomers in a total amount of 10 to 95% by weight, more preferably 30 to 92% by weight, even more preferably 50 to 90% by weight, particularly preferably 60 to 87% by weight, and most preferably 70 to 85% by weight, based on 100% by weight of all structural units.

[0051] The graft moiety preferably contains a structural unit derived from a monomer having a reactive group. The reactive group-containing monomer is preferably a monomer containing one or more reactive groups selected from the group consisting of epoxy groups, oxetane groups, hydroxyl groups, amino groups, imide groups, carboxylic acid groups, carboxylic anhydride groups, cyclic esters, cyclic amides, benzoxazine groups, and cyanate ester groups, and more preferably a monomer containing one or more reactive groups selected from the group consisting of epoxy groups, hydroxyl groups, and carboxylic acid groups. This configuration allows the graft moiety of the polymer microparticles (A) to be chemically bonded to the thermosetting resin in the resin composition. This allows the polymer microparticles (A) to be maintained in a well-dispersed state in the resin composition or in a cured product thereof without agglomeration.

[0052] Specific examples of the monomer having an epoxy group include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether.

[0053] Specific examples of monomers having a hydroxyl group include hydroxy linear alkyl (meth)acrylates (particularly, hydroxy linear C1-6 alkyl (meth)acrylates) such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; caprolactone-modified hydroxy (meth)acrylates; hydroxy branched alkyl (meth)acrylates such as α-(hydroxymethyl)methyl acrylate and α-(hydroxymethyl)ethyl acrylate; and hydroxyl group-containing (meth)acrylates such as mono(meth)acrylates of polyester diols (particularly saturated polyester diols) obtained from divalent carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol).

[0054] Specific examples of the monomer having a carboxylic acid group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. The above-mentioned monocarboxylic acids are preferably used as the monomer having a carboxylic acid group.

[0055] The reactive group-containing monomers described above may be used alone or in combination of two or more.

[0056] The graft portion preferably contains 0.5 to 90 wt % of structural units derived from the reactive group-containing monomer, based on 100 wt % of the graft portion, more preferably 1 to 50 wt %, even more preferably 2 to 35 wt %, and particularly preferably 3 to 20 wt %. When the graft portion contains (a) 0.5 wt % or more of structural units derived from the reactive group-containing monomer, based on 100 wt % of the graft portion, the resulting resin composition containing the granular material can provide a cured product having sufficient impact resistance, and when (b) 90 wt % or less of the structural units are contained, the resulting resin composition containing the granular material can provide a cured product having sufficient impact resistance, and the storage stability of the resin composition is advantageously good.

[0057] The structural unit derived from the reactive group-containing monomer is preferably contained in the graft portion, and more preferably contained only in the graft portion.

[0058] The graft moiety may contain a structural unit derived from a polyfunctional monomer as a structural unit. When the graft moiety contains a structural unit derived from a polyfunctional monomer, it has the following advantages: (a) swelling of the polymer fine particles (A) in the resin composition can be prevented, (b) the viscosity of the resin composition is reduced, which tends to improve the handleability of the resin composition, and (c) the dispersibility of the polymer fine particles (A) in the thermosetting resin is improved.

[0059] When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the resin composition containing the resulting powder or granule can provide a cured product that is more excellent in toughness and impact resistance than when the graft portion contains a structural unit derived from a polyfunctional monomer.

[0060] Examples of polyfunctional monomers that can be used in the polymerization of the graft portion include the same monomers as the polyfunctional monomers described above. Among these polyfunctional monomers, polyfunctional monomers that can be preferably used in the polymerization of the graft portion include allyl methacrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. These polyfunctional monomers may be used alone or in combination of two or more.

[0061] The graft portion preferably contains 1 to 20% by weight, and more preferably 5 to 15% by weight, of structural units derived from polyfunctional monomers, based on 100% by weight of the graft portion.

[0062] In the polymerization of the graft portion, the above-mentioned monomers may be used alone or in combination of two or more.

[0063] The graft moiety may contain, as constituent units, constituent units derived from other monomers in addition to the constituent units derived from the above-mentioned monomers.

[0064] In particular, the graft portion preferably contains a polymer containing a structural unit derived from a (meth)acrylate monomer as a structural unit. This structure provides good compatibility with the butadiene-derived structural unit that constitutes the elastomer. This makes it possible to more effectively suppress an increase in the blend viscosity of the resin composition containing the resulting powder / granule, thereby producing a resin composition with a low viscosity.

[0065] (Glass transition temperature of the grafted 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, more preferably 60°C or lower, more preferably 50°C or lower, more preferably 40°C or lower, more preferably 30°C or lower, more preferably 20°C or lower, more preferably 10°C or lower, more preferably 0°C or lower, more preferably -20°C or lower, more preferably -40°C or lower, more preferably -45°C or lower, more preferably -50°C or lower. °C or lower, more 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, more preferably -85°C or lower, more preferably -90°C or lower, more preferably -95°C or lower, more preferably -100°C or lower, more preferably -105°C or lower, more preferably -110°C or lower, more preferably -115°C or lower, even more preferably -120°C or lower, and particularly preferably -125°C or lower.

[0066] The glass transition temperature of the grafted 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, even more preferably 90°C or higher, and particularly preferably 110°C or lower.

[0067] The Tg of the graft portion can be determined by the composition of the structural units contained in the graft portion, etc. In other words, the Tg of the resulting graft portion can be adjusted by changing the composition of the monomers used when producing (polymerizing) the graft portion.

[0068] The Tg of the grafted portion can be determined by viscoelasticity measurements using a flat plate made of polymer microparticles. Specifically, Tg can be measured as follows: (1) Dynamic viscoelasticity measurements are performed under tensile conditions on the flat plate made of polymer microparticles using a dynamic viscoelasticity measuring device (e.g., DVA-200, manufactured by IT Measurement & Control Co., Ltd.) to obtain a tan δ graph; (2) The peak temperature of tan δ in the obtained tan δ graph is taken as the glass transition temperature. Here, if multiple peaks are obtained in the tan δ graph, the highest peak temperature is taken as the glass transition temperature of the grafted portion.

[0069] (Graft ratio of grafted part) In one embodiment of the present invention, the polymer microparticles (A) may comprise a polymer having the same structure as the graft moiety but not grafted to the elastomer. In this specification, a polymer having the same structure as the graft moiety but not grafted to the elastomer is also referred to as a non-graft polymer. This non-graft polymer corresponds to the free polymer (FP) described below. The non-graft polymer can also be said to be a polymer produced in the polymerization of the graft moiety but not grafted to the elastomer.

[0070] In this specification, the proportion of the polymer grafted to the elastomer, i.e., the proportion of the grafted portion, among the polymers produced in the polymerization of the grafted portion, is referred to as the graft ratio. The graft ratio can also be expressed as the value expressed by (weight of the grafted portion) / {(weight of the grafted portion)+(weight of the non-grafted polymer)}×100.

[0071] The graft ratio of the grafted portion is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. A graft ratio of 80% or more has the advantage that the viscosity of the resin composition does not become too high.

[0072] In this specification, the graft ratio is calculated as follows. First, an aqueous latex containing polymer microparticles (A) is obtained, and then a powder of polymer microparticles (A) is obtained from the aqueous latex. Specific methods for obtaining a powder of polymer microparticles (A) from an aqueous latex include (i) coagulating the polymer microparticles (A) in the aqueous latex, (ii) dehydrating the obtained coagulated material, and (iii) further drying the coagulated material to obtain a powder of polymer microparticles (A). Next, 2 g of the powder of polymer microparticles (A) is dissolved in 50 mL of methyl ethyl ketone (MEK). Thereafter, the obtained MEK solution is separated into a component soluble in MEK (MEK solubles) and a component insoluble in MEK (MEK insolubles). Specifically, the obtained MEK solution was centrifuged using a centrifuge (Hitachi Koki Co., Ltd., CP60E) at 30,000 rpm for 1 hour, and the solution was separated into MEK-soluble and MEK-insoluble fractions. Three sets of centrifugation were performed. Next, 20 ml of the concentrated MEK-soluble fraction was mixed with 200 ml of methanol, and an aqueous calcium chloride solution prepared by dissolving 0.01 g of calcium chloride in water was added, followed by stirring for 1 hour. The mixture was then separated into methanol-soluble and methanol-insoluble fractions, and the amount of the methanol-insoluble fraction was taken as the amount of free polymer (FP). The graft rate is calculated by the following formula. Graft rate (%) = 100 - [(FP amount) / {(FP amount) + (MEK insoluble matter)}] / (weight of polymer in grafted portion) × 10,000 The weight of the polymer other than the graft portion is the amount of monomers charged that constitute the polymer up to the graft portion. The polymer other than the graft portion is, for example, an elastomer. When the polymer microparticles (A) contain a surface-crosslinked polymer described below, the polymer other than the graft portion includes both the elastomer and the surface-crosslinked polymer. The weight of the polymer in the graft portion is the amount of monomers charged that constitute the polymer in the graft portion. In calculating the graft ratio, the method for coagulating the polymer microparticles (A) is not particularly limited, and methods such as using a solvent, using a coagulant, and spraying an aqueous latex can be used.

[0073] (Modification of the graft part) In one embodiment of the present invention, the graft portion may consist of only one type of graft portion having structural units of the same composition, or may consist of multiple types of graft portions each having a structural unit of a different composition.

[0074] 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 will be referred to as graft portion 1, graft portion 2, ..., graft portion n (n is an integer of 2 or more). The graft portion is composed of graft portion 1, graft portion 2, ..., and graft portion n The graft portion may include a composite of graft portion 1, graft portion 2, ..., and graft portion n The polymer may contain one polymer obtained by multistage polymerization of a plurality of types of graft moieties. A polymer obtained by multistage polymerization of a plurality of types of graft moieties is also called a multistage polymerization graft moiety. The method for producing the multistage polymerization graft moiety will be described in detail later.

[0075] When the graft portion is composed of multiple types of graft portions, not all of these multiple types of graft portions need to be graft-bonded to the elastomer. It is sufficient that at least a portion of at least one type of graft portion is graft-bonded to the elastomer, and other types (multiple other types) of graft portions may be graft-bonded to graft portions that are graft-bonded to the elastomer. Furthermore, when the graft portion is composed of multiple types of graft portions, it may also contain multiple types of polymers (multiple types of non-graft polymers) that have the same structure as the multiple types of graft portions and are not graft-bonded to the elastomer.

[0076] Graft part 1, graft part 2, ..., and graft part n In the multi-stage polymerization graft portion, n is the graft area n-1 or a graft portion. n-1 In the multi-stage polymerization graft portion, n Part of the graft n-1 Sometimes it penetrates inside the

[0077] In a multi-stage polymerization graft portion, each of the multiple graft portions may have a layer structure. For example, when a multi-stage polymerization graft portion consists of graft portion 1, graft portion 2, and graft portion 3, one embodiment of the present invention is one in which graft portion 1 is the innermost layer of the graft portion, a layer of graft portion 2 exists outside graft portion 1, and a layer of graft portion 3 exists outside graft portion 2 as the outermost layer. In this way, a multi-stage polymerization graft portion in which each of the multiple graft portions has a layer structure can also be referred to as a multi-layered graft portion. That is, in one embodiment of the present invention, the graft portion may include a mixture of multiple types of graft portions, a multi-stage polymerization graft portion, and / or a multi-layered graft portion.

[0078] When the elastomer and the graft moiety are polymerized in this order in the production of polymer microparticles (A), at least a portion of the graft moiety can cover at least a portion of the elastomer in the resulting polymer microparticles (A). Polymerization of the elastomer and the graft moiety in this order can be said to be multistage polymerization of the elastomer and the graft moiety. The polymer microparticles (A) obtained by multistage polymerization of the elastomer and the graft moiety can also be said to be multistage polymers.

[0079] When the polymer fine particles (A) are multistage polymers, the graft moieties may cover at least a portion of the elastomer or may cover the entire elastomer. When the polymer fine particles (A) are multistage polymers, the graft moieties may partially penetrate into the elastomer.

[0080] When the polymer microparticles (A) are multistage polymers, the elastomer and the graft moiety may have a layer structure. For example, one embodiment of the present invention is one in which the elastomer is the innermost layer (also referred to as the core layer) and the graft moiety is present as the outermost layer (also referred to as the shell layer) outside the elastomer. A structure in which the elastomer is the core layer and the graft moiety is the shell layer can also be referred to as a core-shell structure. Thus, polymer microparticles (A) in which the elastomer and the graft moiety have a layer structure (core-shell structure) can also be referred to as a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer microparticles (A) may be multistage polymers and / or multilayer polymers or core-shell polymers. However, as long as the graft moiety is graft-bonded to the elastomer, the polymer microparticles (A) are not limited to the above structure.

[0081] At least a portion of the graft portion preferably covers at least a portion of the elastomer, in other words, at least a portion of the graft portion preferably exists on the outermost side of the polymer fine particles (A).

[0082] (1-1-3.Surface crosslinked polymer) The polymer microparticles (A) preferably contain a surface-crosslinked polymer in addition to the elastomer and the graft portion grafted to the elastomer. This configuration (a) improves the blocking resistance during the production of the polymer microparticles (A), and (b) improves the dispersibility of the polymer microparticles (A) in the thermosetting resin. The reasons for this are not particularly limited, but are presumed to be as follows: By coating at least a portion of the elastomer with the surface-crosslinked polymer, the exposed elastomer portion of the polymer microparticles (A) is reduced, and as a result, the elastomers are less likely to stick to each other, improving the dispersibility of the polymer microparticles (A).

[0083] When the polymer microparticles (A) contain a surface-crosslinked polymer, they can also have the following effects: (a) reducing the viscosity of the resin composition, (b) increasing the crosslink density in the elastomer, and (c) increasing the graft efficiency of the grafted portion. The crosslink density in the elastomer refers to the number of crosslinked structures in the entire elastomer.

[0084] The surface cross-linked polymer is composed of a polymer containing, as structural units, 30 to 100% by weight of structural units derived from polyfunctional monomers and 0 to 70% by weight of structural units derived from other vinyl monomers, totaling 100% by weight.

[0085] Examples of polyfunctional monomers that can be used in the polymerization of surface-crosslinked polymers include the same monomers as the polyfunctional monomers described above. Among these polyfunctional monomers, polyfunctional monomers that can be preferably used in the polymerization of surface-crosslinked polymers 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. These polyfunctional monomers may be used alone or in combination of two or more.

[0086] 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. The polymer microparticles (A) may be a multistage polymer obtained by multistage polymerization of an elastomer, a surface-crosslinked polymer, and a graft moiety in this order. In either of these embodiments, the surface-crosslinked polymer can cover at least a portion of the elastomer.

[0087] The surface-crosslinked polymer can also be considered as part of the elastomer. When the polymer microparticles (A) contain a surface-crosslinked polymer, the graft moiety may be (a) graft-bonded to an elastomer other than the surface-crosslinked polymer, (b) graft-bonded to a surface-crosslinked polymer, or (c) graft-bonded to both an elastomer other than the surface-crosslinked polymer and the surface-crosslinked polymer. When the polymer microparticles (A) contain a surface-crosslinked polymer, the volume-average particle diameter of the elastomer mentioned above refers to the volume-average particle diameter of the elastomer containing the surface-crosslinked polymer.

[0088] The case where the polymer microparticles (A) are a multistage polymer obtained by multistage polymerization of an elastomer, a surface-crosslinked polymer, and a graft moiety in this order (Case D) will be described. In Case D, the surface-crosslinked polymer may cover a part of the elastomer, or may cover the entire elastomer. In Case D, a part of the surface-crosslinked polymer may penetrate into the inside of the elastomer. In Case D, the graft moiety may cover a part of the surface-crosslinked polymer, or may cover the entire surface-crosslinked polymer. In Case D, a part of the graft moiety may penetrate into the surface-crosslinked polymer. In Case D, the elastomer, the surface-crosslinked polymer, and the graft moiety may have a layer structure. For example, one embodiment of the present invention is one in which the elastomer is the innermost layer (core layer), a layer of surface-crosslinked polymer exists outside the elastomer as an intermediate layer, and a layer of graft moiety exists outside the surface-crosslinked polymer as an outermost layer (shell layer).

[0089] (1-2. Method for producing polymer microparticles (A)) The polymer fine particles (A) can be produced by polymerizing an elastomer, and then graft-polymerizing a polymer that will form a graft moiety onto the elastomer in the presence of the elastomer.

[0090] The polymer microparticles (A) can be produced by known methods, such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Specifically, the polymerization of the elastomer, the polymerization of the graft moiety (graft polymerization), and the polymerization of the surface-crosslinked polymer in the polymer microparticles (A) can be produced by known methods, such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Among these, emulsion polymerization is particularly preferred as a method for producing the polymer microparticles (A), because it is easy to design the composition of the polymer microparticles (A), is easy to produce industrially, and an aqueous latex of the polymer microparticles (A) that can be suitably used in the production of the present resin composition can be easily obtained. Below, we will explain the methods for producing the elastomer, graft moiety, and optional surface-crosslinked polymer that can be contained in the polymer microparticles (A).

[0091] (Method of manufacturing elastic body) The elastic body can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, or the like, and the production method can be, for example, the method described in WO2005 / 028546.

[0092] If the elastic body is made of multiple types of elastic bodies (e.g., elastic body 1, elastic body 2, ..., elastic body n ) is made up of elastic body 1, elastic body 2, ..., elastic body n may be polymerized separately by the above-mentioned method and then mixed to produce an elastomer having a plurality of types of elastomers. n may be sequentially polymerized in multiple stages to produce an elastomer having a plurality of types of elastomers.

[0093] The multi-stage polymerization of elastomers will be specifically described. For example, (1) elastomer 1 is polymerized to obtain elastomer 1; (2) elastomer 2 is then polymerized in the presence of elastomer 1 to obtain a two-stage elastomer. 1+2 (3) Then, the elastic body 1+2 In the presence of 1+2+3 (4) After the same procedure, the elastic body 1+2+···+(n-1) In the presence of elastic n Multi-stage polymerized elastomer 1+2+···+n get.

[0094] (Method for manufacturing the graft portion) The graft portion can be formed, for example, by polymerizing the monomer used to form the graft portion by known radical polymerization. When (a) the elastomer or (b) the polymer microparticle precursor containing the elastomer and the surface-crosslinked polymer is obtained as an aqueous latex, the polymerization of the graft portion is preferably carried out by emulsion polymerization. The graft portion can be produced, for example, according to the method described in WO2005 / 028546.

[0095] The graft portion is a plurality of types of graft portions (e.g., graft portion 1, graft portion 2, ..., graft portion n In this case, the graft portion 1, the graft portion 2, ..., the graft portion n may be polymerized separately by the above-mentioned method and then mixed to produce a graft portion having multiple types of graft portions. Alternatively, graft portion 1, graft portion 2, ..., graft portion n may be sequentially polymerized in multiple stages to produce a graft moiety having a plurality of types of graft moieties.

[0096] The multi-stage polymerization of the graft portion will be specifically explained. For example, (1) the graft portion 1 is polymerized to obtain the graft portion 1; (2) the graft portion 2 is then polymerized in the presence of the graft portion 1 to obtain a two-stage graft portion. 1+2 (3) Then, the graft portion is obtained. 1+2 The graft portion 3 is polymerized in the presence of1+2+3 (4) After the same procedure, the grafted part is obtained. 1+2+···+(n-1) In the presence of n is polymerized to form a multi-stage grafted portion. 1+2+···+n get.

[0097] When the graft moiety is composed of multiple types of graft moieties, the graft moieties having multiple types of graft moieties may be polymerized and then graft polymerized onto an elastomer to produce polymer microparticles (A).The polymer microparticles (A) may also be produced by sequentially graft polymerizing multiple types of polymers constituting the multiple types of graft moieties onto the elastomer in the presence of the elastomer.

[0098] (Method of producing surface cross-linked polymer) The surface cross-linked polymer can be formed by polymerizing a monomer used for forming the surface cross-linked polymer by known radical polymerization. When the elastomer is obtained as an aqueous latex, the polymerization of the surface cross-linked polymer is preferably carried out by emulsion polymerization.

[0099] When emulsion polymerization is employed as the method for producing the polymer fine particles (A), a known emulsifier (dispersant) can be used for producing the polymer fine particles (A).

[0100] When emulsion polymerization is used as the method for producing the polymer microparticles (A), a thermally decomposable initiator can be used to produce the polymer microparticles (A). Examples of the thermally decomposable initiator include known initiators such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate.

[0101] Redox initiators can also be used to produce polymer microparticles (A). The redox initiator is an initiator containing (a) a peroxide, such as an organic peroxide or an inorganic peroxide, and (b) optionally a reducing agent, such as sodium formaldehyde sulfoxylate or glucose, and optionally a transition metal salt, such as iron (II) sulfate, and optionally a chelating agent, such as disodium ethylenediaminetetraacetate, and optionally a phosphorus-containing compound, such as sodium pyrophosphate. Examples of organic peroxides include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide. Examples of inorganic peroxides include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

[0102] When a redox initiator is used, polymerization can be carried out even at a low temperature where the peroxide does not substantially decompose thermally, allowing the polymerization temperature to be set over a wide range. Therefore, it is preferable to use a redox initiator. Among redox initiators, organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide, and t-butyl hydroperoxide are preferably used as redox initiators. The amounts of the initiator used, and, when a redox initiator is used, the amounts of the reducing agent, transition metal salt, chelating agent, etc., can be within known ranges.

[0103] When a polyfunctional monomer is used in the polymerization of the elastomer, graft portion, or surface-crosslinked polymer for the purpose of introducing a crosslinked structure into the elastomer, graft portion, or surface-crosslinked polymer, a known chain transfer agent can be used in a known amount range. By using the chain transfer agent, the molecular weight and / or degree of crosslinking of the resulting elastomer, graft portion, or surface-crosslinked polymer can be easily adjusted.

[0104] In addition to the above-mentioned components, a surfactant may be used in the production of the polymer microparticles (A). The type and amount of the surfactant used are within known ranges.

[0105] In the production of the polymer fine particles (A), known conditions such as polymerization temperature, pressure, and deoxidation can be applied.

[0106] (1-3. Volume average particle size (Mv) of polymer microparticles (A)) The volume average particle diameter (Mv) of the polymer microparticles (A) is 90 nm or more, since this allows the production of a resin composition having the desired viscosity and high stability. Furthermore, it is preferably 0.09 μm (90 nm) to 50.00 μm, more preferably 0.10 μm to 10.00 μm, more preferably 0.15 μm to 2.00 μm, even more preferably 0.15 μm to 1.00 μm, even more preferably 0.20 μm to 0.80 μm, and particularly preferably 0.20 μm to 0.50 μm. When the volume average particle diameter (Mv) of the polymer microparticles (A) is within the above range, it also has the advantage of improving the dispersibility of the polymer microparticles (A) in the matrix resin. In this specification, the term "volume average particle diameter (Mv) of the polymer microparticles (A)" refers to the volume average particle diameter of the primary particles of the polymer microparticles (A), unless otherwise specified. The volume average particle diameter of the polymer microparticles (A) can be measured using a dynamic light scattering particle size distribution analyzer or the like, using an aqueous latex containing the polymer microparticles (A) as a sample. The volume average particle diameter of the polymer microparticles (A) will be described in detail in the Examples below. The volume average particle diameter of the polymer microparticles (A) can also be measured by cutting a cured product or molded product of the resin composition, photographing the cut surface using an electron microscope or the like, and using the resulting photographed data (photographed image). Note that the particle diameter of the elastomer and the particle diameter of the polymer microparticles containing the graft moiety may be the same.

[0107] The particle size number distribution of the polymer fine particles (A) in the thermosetting resin preferably has a half-value width of 0.5 to 1 times the volume average particle size, since this results in a resin composition that is low in viscosity and easy to handle.

[0108] Furthermore, in the course of research, the present inventors have found that the larger the particle size of the polymer microparticles (A), the larger the molecular weight of the grafted portion tends to be. The mechanism behind this is presumed to be as follows: As the particle size of the polymer microparticles (A) increases, the number of polymer microparticles (A) decreases. As a result, the reaction rate during polymerization of the grafted portion slows down. Therefore, the molecular weight of the grafted portion increases.

[0109] (1-4. Weight-average molecular weight of polymer in graft portion) The weight-average molecular weight of the polymer in the graft portion is not more than 200,000. In addition, it is preferably not more than 180,000, more preferably not more than 160,000, and even more preferably not more than 140,000. If it is within this range, an increase in the compounding viscosity of the resin composition can be suppressed.

[0110] The weight-average molecular weight of the polymer in the graft portion can be calculated from the weight-average molecular weight of a polymer (non-graft polymer) that has the same structure as the graft portion and is not graft-bonded to the elastomer, i.e., a free polymer (FP) as described below. A specific calculation method will be described in detail in the Examples below.

[0111] The method for controlling the weight-average molecular weight of the graft polymer within the above-mentioned range is not particularly limited. For example, the above-mentioned (method for producing the graft polymer) can be adjusted to a predetermined molecular weight. Examples include a method of polymerizing the graft polymer at an optimal temperature, a method of adding monomers at an optimal rate, a method of polymerizing at an optimal solids concentration, a method of polymerizing with an optimal initiator type and amount, and a method of polymerizing with an optimal reducing agent type and amount. As an example, the optimal temperature is 50°C to 90°C. The optimal rate is 40 parts per hour or less. The optimal solids concentration is 25% to 50%. The optimal initiator type and amount are an initiator with a solubility of 2 wt% or more at 20°C and 0.01 parts or more per 100 parts of monomer. The optimal reducing agent type and amount are a molar ratio of 0.5 to 1.2 times the amount of sodium formaldehyde sulfoxylate and initiator.

[0112] (1-5. Free Polymer (FP)) It is preferable that the present powder further contains, as a constituent unit, a free polymer (FP) containing a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer.

[0113] Here, the term "free polymer (FP)" refers to a polymer that is not bonded to the polymer microparticles (A) as a graft moiety. The free polymer (FP) can be mixed in mainly during the process of producing the polymer microparticles (A). Specifically, during the process of producing the polymer microparticles (A), when preparing the graft moiety, a polymer that is not bonded to the elastomer is generated (non-graft polymer). Such a polymer that is not graft-bonded to the elastomer can be the free polymer (FP). Note that the free polymer (FP) is not limited to those that are mixed in during the process of producing the polymer microparticles (A) described above, but also includes polymers that are added separately.

[0114] In the process of producing the graft portion of the polymer microparticles (A), in addition to the graft portion and the free polymer (FP), soluble components are also present. These soluble components are intended to be unpolymerized monomers and auxiliary materials such as initiators.

[0115] As a method for determining whether a polymer is a grafted portion polymer, a free polymer (FP), or a soluble component, for example, as shown in the examples described below, there can be mentioned a method in which (i) if it is insoluble in both MEK and methanol, it is determined to be a grafted portion polymer, (ii) if it is soluble in MEK but insoluble in methanol, it is determined to be a free polymer (FP), or (iii) if it is soluble in methanol, it is determined to be a soluble component.

[0116] The content of the free polymer (FP) in 100% by weight of the powder or granule is preferably 8% by weight or less. It is more preferably 6% by weight or less, even more preferably 4% by weight or less, and particularly preferably 2% by weight or less. Within this range, when the powder or granule is added to a thermosetting resin, a significant increase in viscosity can be suppressed. The lower limit of the free polymer (FP) content is not particularly limited, but may be, for example, 0.1% by weight or more.

[0117] Furthermore, the free polymer (FP) preferably contains a polymer containing a structural unit derived from a (meth)acrylate monomer as a structural unit. This structure provides good compatibility with the butadiene-derived structural unit constituting the elastomer. This effectively prevents an increase in the blending viscosity of the resin composition containing the resulting powder / particle, thereby enabling the production of a low-viscosity resin composition.

[0118] The free polymer (FP) is the same as that explained in the section (1-1-2. Graft portion) of the polymer fine particles (A) except for the above-mentioned configuration, and therefore the explanation therefor is omitted here by citing the explanation therein.

[0119] (1-4.Resin (D)) The powder preferably further contains a resin (D). The resin (D) may be the same type of resin as the thermosetting resin (B) that is the matrix resin to be mixed, which will be described later, or may be a resin different from the thermosetting resin (B). In the resin composition, it is preferable that the thermosetting resin (B) and the resin (D) are not phase-separated. The resin (D) is preferably a resin that is compatible with the thermosetting resin (B).

[0120] As an example, consider a case where resin (D) is used in a resin composition production method and resin (D) is the same type of resin as thermosetting resin (B). In this case, it is impossible to distinguish between thermosetting resin (B) and resin (D) in the resulting resin composition containing powder particles. Therefore, from the outside, the resulting resin composition containing powder particles appears to contain only thermosetting resin (B) in addition to polymer microparticles (A). Next, consider a case where resin (D) is used in a resin composition production method and resin (D) is a different type of resin from thermosetting resin (B). In this case, the resulting resin composition containing powder particles can distinguish between thermosetting resin (B) and resin (D). In this case, the finally obtained resin composition containing powder particles may contain resin (D) as a resin other than thermosetting resin (B) in addition to polymer microparticles (A). The present invention also includes a case where resin (D) is the same as the free polymer (FP) described above.

[0121] Resin (D) may be, for example, a thermoplastic resin, a thermosetting resin, or any combination of a thermosetting resin and a thermoplastic resin. When the powder or granule contains resin (D), resin (D) can have the effect of increasing the dispersibility of polymer fine particles (A) in the thermosetting resin.

[0122] Examples of the thermosetting resin in resin (D) include various thermosetting resins described in the section on thermosetting resin (B) below. In resin (D), only one type of thermosetting resin may be used, or two or more types may be used in combination.

[0123] When the matrix resin to be mixed is a thermosetting resin, it is preferable that resin (D) be of the same type as the thermosetting resin (B) of the matrix resin, since there is no risk of affecting various physical properties. In other words, when the thermosetting resin (B) of the matrix resin is an epoxy resin, resin (D) is also preferably an epoxy resin. When resin (D) is of a different type from the thermosetting resin (B) of the matrix resin, it is preferable that resin (D) be compatible with the thermosetting resin (B) of the matrix resin.

[0124] Examples of the thermoplastic resin in resin (D) include polymers containing, as structural units, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. In resin (D), only one type of thermoplastic resin may be used, or two or more types may be used in combination.

[0125] Further, usable thermoplastic resins include acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes, and polyvinyl acetates, etc. These may be used alone or in combination of two or more.

[0126] The acrylic polymer is mainly composed of a structural unit made of an acrylic acid ester monomer. The acrylic acid ester monomer preferably has an ester moiety having 1 to 20 carbon atoms. Examples of the acrylic polymer include (a) a homopolymer of an acrylic acid ester monomer, and (b) a copolymer of an acrylic acid ester monomer with a monomer such as an unsaturated fatty acid, an acrylamide monomer, a maleimide monomer, or vinyl acetate, or a vinyl copolymer (hereinafter also referred to as an acrylic copolymer).

[0127] Examples of acrylic acid ester monomers include methyl acrylate (MA), ethyl acrylate (EA), 2-ethylhexyl acrylate (2EHA), acrylic acid (AA), methacrylic acid (MAA), 2-hydroxyethyl acrylate (2HEA), 2-hydroxyethyl methacrylate (2HEMA), butyl acrylate (BA), methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (nBMA), isobutyl methacrylate (iBMA), propyl acrylate, isopropyl acrylate, and isobutyl acrylate. acrylate, t-butyl acrylate, neopentyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, tricyclodecyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, 2-methoxyethyl acrylate, dimethylaminoethyl acrylate, chloroethyl acrylate, trifluoroethyl acrylate, tetrahydrofurfuryl acrylate, etc. These may be used alone or in combination of two or more.

[0128] In the acrylic copolymer, the ratio of (a) a structural unit derived from an acrylic acid ester monomer (structural unit (a)) to (b) a structural unit derived from a monomer such as an unsaturated fatty acid, an acrylamide monomer, a maleimide monomer, or vinyl acetate, or a vinyl copolymer (structural unit (b)) is preferably 50% by weight to 100% by weight for the structural unit (a) and 0% by weight to 50% by weight for the structural unit (b).

[0129] The acrylic polymer preferably contains 50% by weight or more of structural units derived from butyl acrylate (BA), more preferably 60% by weight or more, even more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

[0130] The vinyl copolymer is obtained by copolymerizing a mixture of vinyl monomers containing one or more selected from the group consisting of aromatic vinyl monomers, cyanide vinyl monomers, and unsaturated carboxylic acid alkyl ester monomers. The vinyl monomer mixture may further contain another monomer (hereinafter also referred to as "monomer C") copolymerizable with the above-mentioned monomers.

[0131] Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and vinyltoluene. These vinyl monomers may be used alone or in combination of two or more. Among these, aromatic vinyl monomers are preferred, and styrene is more preferred, from the viewpoint of easily increasing the refractive index.

[0132] The unsaturated carboxylic acid alkyl ester monomer is not particularly limited. For example, an ester of an alcohol having 1 to 6 carbon atoms with acrylic acid or methacrylic acid is preferred. The ester of an alcohol having 1 to 6 carbon atoms with acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group.

[0133] Examples of esters of alcohols having 1 to 6 carbon atoms with acrylic acid or methacrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, chloromethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate, 2,3,4,5-tetrahydroxypentyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0134] Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. These may be used alone or in combination of two or more. Monomer C is a vinyl monomer other than the above-mentioned aromatic vinyl monomers, unsaturated carboxylic acid alkyl ester monomers, and vinyl cyanide monomers, and is not particularly limited as long as it does not impair the effects of the present invention. Specific examples of monomer C include unsaturated fatty acids, acrylamide monomers, maleimide monomers, vinyl acetate, and acrylic ester monomers. These may be used alone or in combination of two or more.

[0135] The unsaturated fatty acid may be selected from, for example, itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, methacrylic acid, and the like.

[0136] The acrylamide monomer may be selected from, for example, acrylamide, methacrylamide, and N-methylacrylamide.

[0137] The maleimide monomer may be selected from, for example, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide.

[0138] The method for producing the vinyl copolymer is not particularly limited, but examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.

[0139] Furthermore, in the method for producing a vinyl copolymer, a polymerization initiator may be used if necessary. The polymerization initiator may be, for example, one or more members selected appropriately from the group consisting of peroxides, azo compounds, potassium persulfate, etc. The amount of the polymerization initiator added is not particularly limited.

[0140] Examples of peroxides include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl isopropyl carbonate, di-t-butyl peroxide, t-butyl peroctate, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and t-butylperoxy-2-ethylhexanoate. Of these, cumene hydroperoxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)cyclohexane are particularly preferred.

[0141] Examples of azo compounds include azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t-butylazo-2-cyanobutane, and 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane. Among these, 1,1'-azobiscyclohexane-1-carbonitrile is particularly preferred.

[0142] The amount of the polymerization initiator to be added is not particularly limited.

[0143] Specific examples of vinyl copolymers include polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-acrylonitrile copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, etc. These may be used alone or in combination of two or more.

[0144] Examples of polyester include polyethylene terephthalate and polybutylene terephthalate.

[0145] (others) In this specification, fats and oils and fatty acid esters are also included in resin (D). Examples of fats and oils that can be suitably used as resin (D) include epoxidized fats and oils such as epoxidized soybean oil and epoxidized linseed oil. Commercially available epoxidized soybean oils can also be used, such as Adekaiser O-130P manufactured by ADEKA Corporation. Examples of fatty acid esters that can be suitably used as resin (D) include epoxidized fatty acid esters such as epoxidized fatty acid butyl esters, epoxidized fatty acid 2-ethylhexyl esters, epoxidized fatty acid octyl esters, and epoxidized fatty acid alkyl esters.

[0146] Epoxidized fats and oils and epoxidized fatty acid esters are sometimes referred to as epoxy plasticizers. In other words, in this specification, epoxy plasticizers are also included in resin (D). Epoxy plasticizers other than epoxidized fats and oils and epoxidized fatty acid esters include diepoxystearyl epoxyhexahydrophthalate and di-2-ethylhexyl epoxyhexahydrophthalate.

[0147] The above-mentioned thermosetting resins, thermoplastic resins, mixtures of thermosetting and thermoplastic resins, fats and oils, and fatty acid esters can each be used in combination with an antioxidant. In this specification, the antioxidant is considered to be part of resin (D) only when it is used in combination with each of the above-mentioned substances. When the antioxidant is used alone, it is not considered to be resin (D).

[0148] The antioxidant is not particularly limited and examples thereof include (a) primary antioxidants such as phenol-based antioxidants, amine-based antioxidants, lactone-based antioxidants, and hydroxylamine-based antioxidants, and (b) secondary antioxidants such as sulfur-based antioxidants and phosphorus-based antioxidants.

[0149] The phenolic antioxidant may be a hindered phenolic antioxidant. Examples of the hindered phenolic antioxidant include compounds having a hindered phenol structure or a mono-hindered phenol structure in the molecule. Commercially available phenolic antioxidants may also be used, such as Irganox 245 manufactured by BASF Japan Ltd.

[0150] The amine-based antioxidant is not particularly limited, and a wide variety of conventionally known antioxidants can be used. Specific examples of the amine-ketone compounds include 2,2,4-trimethyl-1,2-dihydroquinoline polymers, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and reaction products of diphenylamine and acetone.

[0151] The amine antioxidants also include aromatic amine compounds, such as naphthylamine antioxidants, diphenylamine antioxidants, and p-phenylenediamine antioxidants.

[0152] The lactone-based antioxidant, the hydroxylamine-based antioxidant, and the sulfur-based antioxidant are not particularly limited, and a wide variety of conventionally known antioxidants can be used.

[0153] The phosphorus-based antioxidant is not particularly limited, and a wide variety of conventionally known antioxidants can be used. Phosphoric acid and phosphate esters containing active hydrogen can adversely affect the storage stability of the resin composition containing the resulting powder or granule, and the heat resistance of the cured product or molded article provided by the resin composition. Therefore, preferred phosphorus-based antioxidants are alkyl phosphites, aryl phosphites, alkylaryl phosphite compounds, etc., which do not contain phosphoric acid or phosphate esters in the molecule.

[0154] Other conventionally known substances may also be used as the antioxidant, including various substances described in "Antioxidant Handbook" published by Taiseisha (first edition published on October 25, 1976) and "Polymer Additives Handbook" published by CMC Publishing (edited by Haruna Toru, first edition published on November 7, 2010).

[0155] Resin (D) is preferably one or more selected from the group consisting of thermosetting resins, mixtures of thermosetting resins and antioxidants, thermoplastic resins, mixtures of thermoplastic resins and antioxidants, oils and fats, mixtures of oils and antioxidants, fatty acid esters, mixtures of fatty acid esters and antioxidants, epoxy curing agents, and mixtures of epoxy curing agents and antioxidants, more preferably one or more selected from the group consisting of epoxy resins, acrylic polymers, mixtures of epoxy resins and antioxidants, mixtures of acrylic polymers and antioxidants, and mixtures of epoxy plasticizers and antioxidants, still more preferably one or more selected from the group consisting of mixtures of epoxy resins and antioxidants, mixtures of acrylic polymers and antioxidants, and mixtures of epoxy plasticizers and antioxidants, and particularly preferably a mixture of epoxy plasticizers and antioxidants. This configuration has the advantages of (a) providing a resin composition containing the resulting powder / granules with excellent heat resistance and (b) improving the dispersibility of polymer microparticles (A) in the matrix resin.

[0156] (Physical properties of resin (D)) Resin (D) is not particularly limited in terms of other properties, so long as it is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C. Note that "resin (D) has a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C" means "resin (D) at 25°C has a viscosity of 100 mPa·s to 1,000,000 mPa·s."

[0157] When resin (D) is a liquid, the viscosity of resin (D) at 25°C is preferably 750,000 mPa·s or less, more preferably 700,000 mPa·s or less, more preferably 500,000 mPa·s or less, more preferably 350,000 mPa·s or less, more preferably 300,000 mPa·s or less, more preferably 250,000 mPa·s or less, more preferably 100,000 mPa·s or less, more preferably 75,000 mPa·s or less, more preferably 50,000 mPa·s or less, more preferably 30,000 mPa·s or less, more preferably 25,000 mPa·s or less, even more preferably 20,000 mPa·s or less, and particularly preferably 15,000 mPa·s or less. According to the above configuration, resin (D) has the advantage of excellent fluidity.

[0158] Furthermore, the viscosity of resin (D) at 25°C is more preferably 200 mPa·s or more, more preferably 300 mPa·s or more, more preferably 400 mPa·s or more, more preferably 500 mPa·s or more, even more preferably 750 mPa·s or more, even more preferably 1000 mPa·s or more, and particularly preferably 1500 mPa·s or more. According to this configuration, resin (D) does not impregnate the polymer microparticles (A). Therefore, resin (D) can prevent the polymer microparticles (A) from fusing together.

[0159] The viscosity of resin (D) at 25°C is more preferably 100 mPa·s to 750,000 mPa·s, more preferably 100 mPa·s to 700,000 mPa·s, more preferably 100 mPa·s to 350,000 mPa·s, more preferably 100 mPa·s to 300,000 mPa·s, more preferably 100 mPa·s to 50,000 mPa·s, even more preferably 100 mPa·s to 30,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s.

[0160] When resin (D) is semi-solid, it can also be said that resin (D) is semi-liquid, and that resin (D) has a viscosity of greater than 1,000,000 mPa s. When resin (D) is semi-solid or solid, the resulting resin composition containing the powder or granule has the advantage of being less sticky and easier to handle.

[0161] The viscosity of the resin (D) can be measured using a viscometer. The method for measuring the viscosity of the resin (D) will be described in detail in the examples below.

[0162] The weight average molecular weight of the resin (D) is preferably not more than 200,000, more preferably not more than 180,000, even more preferably not more than 160,000, and particularly preferably not more than 140,000. Within this range, an increase in the compounding viscosity of the resin composition can be suppressed.

[0163] Resin (D) is preferably a resin having an endothermic peak of 25°C or less in a differential scanning calorimetry (DSC) thermogram, more preferably a resin having an endothermic peak of 0°C or less.

[0164] The content of resin (D) in the powder / granule is 50 to 99% by weight of the polymer microparticles (A) and 1 to 50% by weight of the resin (D), assuming the total of the polymer microparticles (A) and the resin (D) to be 100% by weight. The content of resin (D) can be appropriately set within the above-mentioned range and within a range in which a powder / granule can be obtained, depending on the type of resin (D) and its physical properties (solid, semi-solid, liquid, viscosity, etc.). If resin (D) is liquid at 25°C and the content of resin (D) in the powder / granule is high, the powder / granule may not be obtained. If resin (D) is liquid at 25°C and the content of resin (D) in the powder / granule is high, the fluidity (smoothness) of the powder / granule may be impaired.

[0165] The content of resin (D) in the present powder / granule will be explained from the viewpoint of excellent blocking resistance. When the total of the polymer fine particles (A) and the resin (D) is 100% by weight, the polymer fine particles (A) are 50 to 99% by weight and the resin (D) is 1 to 50% by weight. From the viewpoint of excellent blocking resistance, it is more preferable that the polymer fine particles (A) are 55 to 99% by weight and the resin (D) is 1 to 45% by weight, it is more preferable that the polymer fine particles (A) are 60 to 99% by weight and the resin (D) is 1 to 40% by weight, it is still more preferable that the polymer fine particles (A) are 65 to 99% by weight and the resin (D) is 1 to 35% by weight, it is still more preferable that the polymer fine particles (A) are 70 to 99% by weight and the resin (D) is 1 to 30% by weight, it is still more preferable that the polymer fine particles (A) are 75 to 99% by weight. % by weight and resin (D) is 1 to 25% by weight, more preferably 80 to 99% by weight of polymer microparticles (A) and 1 to 20% by weight of resin (D), even more preferably 85 to 99% by weight of polymer microparticles (A) and 1 to 15% by weight of resin (D), even more preferably 90 to 99% by weight of polymer microparticles (A) and 1 to 10% by weight of resin (D), and particularly preferably 95 to 99% by weight of polymer microparticles (A) and 1 to 5% by weight of resin (D).

[0166] The content of resin (D) in the present powder / granule will be explained from the viewpoint of improving the dispersibility of polymer fine particles (A) in the matrix resin. When the total of polymer fine particles (A) and resin (D) is 100% by weight, the polymer fine particles (A) are preferably 50 to 97% by weight and resin (D) is 3 to 50% by weight, more preferably 50 to 95% by weight and resin (D) is 5 to 50% by weight, still more preferably 50 to 92% by weight and resin (D) is 8 to 50% by weight, still more preferably 50 to 90% by weight and resin (D) is 10 to 50% by weight, and still more preferably 50 to 92% by weight and resin (D) is 8 to 50% by weight. It is more preferable that the polymer microparticles (A) are 0 to 87% by weight and the resin (D) is 13 to 50% by weight, it is more preferable that the polymer microparticles (A) are 50 to 85% by weight and the resin (D) is 15 to 50% by weight, it is even more preferable that the polymer microparticles (A) are 50 to 82% by weight and the resin (D) is 18 to 50% by weight, it is even more preferable that the polymer microparticles (A) are 50 to 80% by weight and the resin (D) is 20 to 50% by weight, it is particularly preferable that the polymer microparticles (A) are 60 to 80% by weight and the resin (D) is 20 to 40% by weight.

[0167] The powder containing the polymer fine particles (A) and the resin (D) before or after drying may be converted into granules such as pellets using an extruder or other device. If necessary, other resins may be mixed during pelletization.

[0168] In a transmission electron microscope (TEM) image of this powder or granule, in order to prevent fusion of the polymer microparticles (A) with each other, the number of domains in which the major axis of the resin (D) is 1.5 times or more the average particle size of the polymer microparticles (A) is preferably 5 or less, more preferably 3 or less, even more preferably 1 or less, and most preferably 0 or less. "The number of domains in which the major axis of the resin (D) is 1.5 times or more the average particle size of the polymer microparticles (A) in a transmission electron microscope (TEM) image is 0 or less" means that there are no domains in which the major axis of the resin (D) is 1.5 times or more the average particle size of the polymer microparticles (A) in a transmission electron microscope (TEM) image.

[0169] The major axis of the resin (D) refers to the maximum length (the length of the longest straight line among the lines connecting two points on the periphery) in a TEM image. The average particle diameter of the polymer microparticles (A) refers to the average value of the diameters of circles (area-equivalent diameters) having an area equal to the projected area of ​​each of 30 randomly selected polymer microparticles (A) in a TEM image.

[0170] The volume average particle diameter (Mv) of the powder or granule is preferably 30 μm to 500 μm, more preferably 30 μm to 300 μm, even more preferably 50 μm to 300 μm, and particularly preferably 100 μm to 300 μm. According to this configuration, the powder or granule exhibits excellent dispersibility of the polymer fine particles (A) in the matrix resin. Furthermore, according to this configuration, the powder or granule has the polymer fine particles (A) uniformly dispersed in the matrix resin, and a highly stable resin composition having a desired viscosity can be provided. In this specification, the volume average particle diameter of the powder or granule is a value obtained by measurement using a laser diffraction particle size distribution analyzer (Microtrac MT3000II) manufactured by Microtrac Bell Corporation.

[0171] Since the resulting powder or granule has the advantage of being less likely to contain fine powders that may cause dust explosions and coarse particles that are poorly dispersible, it is preferable that the number distribution of the volume average particle diameter of the powder or granule has a half-value width of 0.5 to 1 times the volume average particle diameter.

[0172] The powder preferably further contains an anti-blocking agent to improve blocking resistance and dispersibility in the thermosetting resin (B), which is the matrix resin. The anti-blocking agent is not particularly limited as long as it achieves the effects of one embodiment of the present invention. Examples of anti-blocking agents include: (i) anti-blocking agents composed of inorganic fine particles such as silicon dioxide, titanium oxide, aluminum oxide, zirconium oxide, aluminum silicate, diatomaceous earth, zeolite, kaolin, talc, calcium carbonate, calcium phosphate, barium sulfate, and magnesium hydrosilicate; (ii) anti-blocking agents composed of organic fine particles; and (iii) oil-based anti-blocking agents such as polyethylene wax, higher fatty acid amides, metal soaps, and silicone oils. Among these, anti-blocking agents composed of fine particles (inorganic or organic fine particles) are preferred, and anti-blocking agents composed of organic fine particles are more preferred. As the antiblocking agent, a particularly preferred antiblocking agent is an antiblocking agent composed of organic fine particles of a polymer containing, as a constituent unit, a constituent unit derived from one or more monomers selected from an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer.

[0173] Antiblocking agents consisting of fine particles are generally in the form of fine particles dispersed in a liquid or in a colloidal state. The fine particles in the antiblocking agent usually have a volume average particle diameter (Mv) of 10 μm or less, preferably 0.05 to 10 μm. The content of the antiblocking agent is preferably 0.01 to 5.0 wt %, more preferably 0.5 to 3.0 wt %, based on the total weight of the powder or granule.

[0174] The antiblocking agent and other optional components described later can be added as appropriate in any step in the production process for the powder or granule. For example, the antiblocking agent and other optional components can be added to the aqueous suspension of the polymer fine particles (A) before or after coagulation, or can be added by directly mixing with the polymer fine particles (A) or the powder or granule.

[0175] The powder or granular material has excellent blocking resistance. In this specification, the blocking resistance of the powder or granular material can be evaluated by the force required to break the block of the powder or granular material. It is preferable that the force required to break the block of the powder or granular material is 30,000 Pa or less. Here, the block is obtained by placing a 6.3 kg weight on 30 g of the powder or granular material contained in a cylindrical container with a diameter of 50 mm, and leaving the powder or granular material to stand at 60°C for 2 hours, and then applying a load of 6.3 kg to the powder or granular material. The force (the force required to break the block of the powder or granular material) is a value obtained by measurement using a rheometer.

[0176] 2. Powder and granular material manufacturing method The method for producing the powder or granule according to one embodiment of the present invention is not particularly limited, and various methods can be used. The method for producing the polymer fine particles (A) is as described above.

[0177] The method for controlling the amount of free polymer (FP) within the above-mentioned range is not particularly limited. Examples include a method of polymerizing the graft portion at an optimal temperature, a method of adding monomers at an optimal rate, a method of polymerizing at an optimal solids concentration, a method of polymerizing with an optimal initiator type and amount, and a method of polymerizing with an optimal reducing agent type and amount. For example, the optimal temperature is 50°C to 90°C. The optimal rate is 40 parts per hour or less. The optimal solids concentration is 25% to 50%. The optimal initiator type and amount are an initiator with a solubility of 2 wt% or more at 20°C and 0.01 parts or more per 100 parts of monomer. The optimal reducing agent type and amount are a molar ratio of 0.5 to 1.2 times the amount of sodium formaldehyde sulfoxylate and initiator.

[0178] Other methods for producing a powder or granular material containing polymer microparticles (A) include (i) a method in which an aqueous latex containing polymer microparticles (A) is salted out to coagulate the polymer microparticles (A), followed by dehydration and drying, and (ii) a method in which an aqueous latex containing polymer microparticles (A) is spray-dried.

[0179] The present production method preferably further comprises a step of mixing the polymer microparticles (A) with the resin (D). Various methods can be used to mix the polymer microparticles (A) with the resin (D). Examples of methods for mixing the polymer microparticles (A) with the resin (D) include: (1) adding the resin (D) directly, in an aqueous emulsion state, or in a solution state during the polymerization process of the polymer microparticles (A); (2) adding the resin (D) directly, in an aqueous emulsion state, or in a solution state to the aqueous latex of the polymer microparticles (A); and (3) polymerizing the resin (D) in the presence of the polymer microparticles (A). The method of adding the resin (D) in an aqueous emulsion state to the aqueous latex of the polymer microparticles (A) is preferred.

[0180] For details of other production methods, the above section (1-2. Production method of polymer fine particles (A)) can be appropriately cited.

[0181] It is preferable that the aggregates and granules containing polymer microparticles (A) and resin (D) are handled (manipulated) in a temperature environment below the glass transition temperature of the grafted portion of the polymer microparticles (A) throughout the production process. In other words, the shorter the time that the aggregates and granules containing polymer microparticles (A) and resin (D) are exposed to a temperature environment equal to or higher than the glass transition temperature of the grafted portion of the polymer microparticles (A), the better. This configuration results in the obtained granules having superior dispersibility of the polymer microparticles (A) in the matrix resin. As a result, the obtained granules can provide a resin composition in which the polymer microparticles (A) are more uniformly dispersed in the matrix resin.

[0182] In this production method, the time (period) during which the aggregates and powder containing polymer microparticles (A) and resin (D) are exposed to a temperature environment equal to or higher than the glass transition temperature of the grafted portion of polymer microparticles (A) can be shortened by adjusting the following temperatures: the temperature of the aqueous latex containing polymer microparticles (A), the temperature of the aqueous latex containing polymer microparticles (A) and resin (D) (aqueous latex before the addition of the coagulant), the temperature of the aqueous solution of the coagulant, the temperature of the aqueous latex containing polymer microparticles (A), resin (D) and the coagulant, the heating temperature in the heating step, the drying temperature in the drying step, the temperature of the washing water in the washing step, etc.

[0183] The temperature below the glass transition temperature of the graft portion of the polymer microparticles (A) varies depending on the composition of the graft portion and is appropriately set depending on the composition of the graft portion. The aggregates and granules containing the polymer microparticles (A) and the resin (D) are preferably handled in an environment below 90°C, more preferably below 80°C, and even more preferably below 70°C throughout the production method. That is, the above-mentioned temperatures are preferably below 90°C, more preferably below 80°C, more preferably below 70°C, more preferably below 60°C, more preferably below 50°C, and even more preferably below 40°C.

[0184] [3. Resin composition] A resin composition according to one embodiment of the present invention contains the above-mentioned powder and a thermosetting resin (B). Here, the thermosetting resin (B) is a so-called matrix resin. Hereinafter, the resin composition according to one embodiment of the present invention may be simply referred to as the present resin composition.

[0185] (3-1. Thermosetting resin (B)) The thermosetting resin (B) preferably contains at least one thermosetting resin selected from the group consisting of resins containing polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenolic resins, polyol resins, and amino-formaldehyde resins. Thermosetting resins also include resins containing polymers obtained by polymerizing aromatic polyester raw materials. Examples of aromatic polyester raw materials include radically polymerizable monomers such as aromatic vinyl compounds, (meth)acrylic acid derivatives, vinyl cyanide compounds, and maleimide compounds, as well as dimethyl terephthalate and alkylene glycol. These thermosetting resins may be used alone or in combination of two or more.

[0186] (ethylenically unsaturated monomer) The ethylenically unsaturated monomer is not particularly limited as long as it has at least one ethylenically unsaturated bond in the molecule.

[0187] Examples of ethylenically unsaturated monomers include acrylic acid, α-alkylacrylic acid, α-alkylacrylic acid esters, β-alkylacrylic acid, β-alkylacrylic acid esters, methacrylic acid, acrylic acid esters, methacrylic acid esters, vinyl acetate, vinyl esters, unsaturated esters, polyunsaturated carboxylic acids, polyunsaturated esters, maleic acid, maleic acid esters, maleic anhydride, and acetoxystyrene. These may be used alone or in combination of two or more.

[0188] (epoxy resin) The epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule.

[0189] Specific examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol S type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, novolac type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, hydrogenated bisphenol A (or F) type epoxy resins, fluorinated epoxy resins, rubber-modified epoxy resins containing polybutadiene or NBR, flame-retardant epoxy resins such as glycidyl ether of tetrabromobisphenol A, p-oxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane-based epoxy resins, urethane-modified epoxy resins having a urethane bond, various alicyclic epoxy resins, glycidyl ethers of polyhydric alcohols, hydantoin type epoxy resins, epoxidized products of unsaturated polymers such as petroleum resins, and amino-containing glycidyl ether resins. Examples of the polyhydric alcohol include N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, and glycerin. Examples of the epoxy resin include epoxy compounds obtained by subjecting the above-mentioned epoxy resins to an addition reaction with bisphenol A (or F), polybasic acids, or the like. The epoxy resin is not limited to these, and commonly used epoxy resins can be used. These epoxy resins may be used alone or in combination.

[0190] Among the above-mentioned epoxy resins, those having at least two epoxy groups per molecule are preferred because they have high reactivity during curing of the resin composition and the resulting cured product easily forms a three-dimensional network. Furthermore, among epoxy resins having at least two epoxy groups per molecule, those containing bisphenol-type epoxy resin as the main component are preferred because of their excellent economical efficiency and ease of availability.

[0191] (phenolic resin) The phenolic resin is not particularly limited as long as it is a compound obtained by reacting a phenol with an aldehyde. The phenol is not particularly limited, but examples thereof include phenol, orthocresol, meta-cresol, para-cresol, xylenol, para-tertiarybutylphenol, para-octylphenol, paraphenylphenol, bisphenol A, bisphenol F, and resorcinol. Particularly preferred phenols include phenol and cresol.

[0192] The aldehydes are not particularly limited, but examples thereof include formaldehyde, acetaldehyde, butylaldehyde, acrolein, and mixtures thereof. As the aldehydes, the above-mentioned substances that are sources of aldehydes or solutions of these aldehydes can also be used. As the aldehydes, formaldehyde is preferred because the operation when reacting phenols with aldehydes is easy.

[0193] When reacting phenols with aldehydes, the molar ratio (F / P) of the phenols (P) to the aldehydes (F) (hereinafter also referred to as the reaction molar ratio) is not particularly limited. When an acid catalyst is used in the reaction, the reaction molar ratio (F / P) is preferably 0.4 to 1.0, more preferably 0.5 to 0.8. When an alkali catalyst is used in the reaction, the reaction molar ratio (F / P) is preferably 0.4 to 4.0, more preferably 0.8 to 2.5. When the reaction molar ratio is equal to or greater than the lower limit, the yield does not become too low, and there is no risk of the molecular weight of the resulting phenolic resin becoming small. On the other hand, when the reaction molar ratio is equal to or less than the upper limit, the molecular weight of the phenolic resin does not become too large, and the softening point does not become too high, so sufficient fluidity can be obtained when heated. Furthermore, when the reaction molar ratio is equal to or less than the upper limit, molecular weight control is easy, and there is no risk of gelation or partial gelation occurring due to the reaction conditions.

[0194] (Polyol resin) The polyol resin is a compound having two or more active hydrogen atoms at the terminals, and is a polyol having two or more functionalities and a molecular weight of about 50 to 20,000. Examples of the polyol resin include aliphatic alcohols, aromatic alcohols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols.

[0195] The aliphatic alcohol may be either a dihydric alcohol or a trihydric or higher alcohol (such as a trihydric alcohol or a tetrahydric alcohol). Examples of dihydric alcohols include alkylene glycols (particularly those having about 1 to 6 carbon atoms) such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and neopentyl glycol, as well as dehydration condensates of two or more molecules of the alkylene glycols (e.g., about 2 to 6 molecules) (diethylene glycol, dipropylene glycol, tripropylene glycol, etc.). Examples of trihydric alcohols include glycerin, trimethylolpropane, trimethylolethane, and 1,2,6-hexanetriol (particularly trihydric alcohols having about 3 to 10 carbon atoms). Examples of tetrahydric alcohols include pentaerythritol and diglycerin. Further examples include sugars such as monosaccharides, oligosaccharides, and polysaccharides.

[0196] Examples of aromatic alcohols include bisphenols such as bisphenol A and bisphenol F; biphenyls such as dihydroxybiphenyl; polyhydric phenols such as hydroquinone and phenol formaldehyde condensates; and naphthalenediol.

[0197] Examples of polyether polyols include random copolymers or block copolymers obtained by ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, or the like in the presence of one or more active hydrogen-containing initiators, and mixtures of these copolymers. Examples of active hydrogen-containing initiators used in the ring-opening polymerization of polyether polyols include diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and bisphenol A; triols such as trimethylolethane, trimethylolpropane, and glycerin; saccharides such as monosaccharides, oligosaccharides, and polysaccharides; sorbitol; and amines such as ammonia, ethylenediamine, urea, monomethyldiethanolamine, and monoethyldiethanolamine.

[0198] Examples of polyester polyols include polymers obtained by polycondensing (a) polybasic acids and / or acid anhydrides thereof, such as maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, dodecanedioic acid, isophthalic acid, and azelaic acid, with (b) polyhydric alcohols, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 3-methyl-1,5-pentanediol, in the presence of an esterification catalyst at a temperature ranging from 150 to 270° C. Further examples of (a) polyester polyols include ring-opening polymers of ε-caprolactone and valerolactone, and (b) active hydrogen compounds having two or more active hydrogen atoms, such as polycarbonate diol and castor oil.

[0199] Examples of polyolefin polyols include polybutadiene polyols, polyisoprene polyols, and hydrogenated products thereof.

[0200] Examples of acrylic polyols include (a) copolymers of hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, and vinylphenol with (b) general-purpose monomers such as n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, and mixtures of such copolymers.

[0201] Among these polyol resins, polyether-type polyols are preferred because the resulting resin composition containing the granules has low viscosity and excellent workability, and the resin composition can provide a cured product with an excellent balance between hardness and toughness.Furthermore, among these polyol resins, polyester-type polyols are preferred because the resulting resin composition containing the granules can provide a cured product with excellent adhesiveness.

[0202] (Amino-formaldehyde resin) The amino-formaldehyde resin is not particularly limited as long as it is a compound obtained by reacting an amino compound with an aldehyde in the presence of an alkaline catalyst. Examples of the amino compound include melamine; 6-substituted guanamines such as guanamine, acetoguanamine, and benzoguanamine; amine-substituted triazine compounds such as CTU guanamine (3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane) and CMTU guanamine (3,9-bis[(3,5-diamino-2,4,6-triazaphenyl)methyl]-2,4,8,10-tetraoxaspiro[5,5]undecane); and ureas such as urea, thiourea, and ethylene urea. Other examples of the amino compound that can be used include substituted melamine compounds in which the hydrogen atoms of the amino groups of melamine are substituted with alkyl groups, alkenyl groups, and / or phenyl groups (as described in U.S. Pat. No. 5,998,573 (corresponding Japanese Patent Publication No. JP-A-9-143238)), and substituted melamine compounds in which the hydrogen atoms of the amino groups of melamine are substituted with hydroxyalkyl groups, hydroxyalkyloxyalkyl groups, and / or aminoalkyl groups (as described in U.S. Pat. No. 5,322,915 (corresponding Japanese Patent Publication No. JP-A-5-202157)). Among the above-mentioned compounds, the polyfunctional amino compounds melamine, guanamine, acetoguanamine, and benzoguanamine are preferred, with melamine being particularly preferred, because they are industrially produced and inexpensive. The above-mentioned amino compounds may be used alone or in combination of two or more. In addition to these amino compounds, (a) phenols such as phenol, cresol, alkylphenol, resorcinol, hydroquinone, and pyrogallol, and (b) aniline may also be used.

[0203] Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and furfural. Formaldehyde and paraformaldehyde are preferred as the aldehydes because they are inexpensive and have good reactivity with the amino compounds listed above. In producing the amino-formaldehyde resin, the aldehydes are preferably used in an amount of 1.1 to 6.0 moles, and particularly preferably 1.2 to 4.0 moles, per mole of the amino compound, per available aldehyde group.

[0204] (aromatic polyester raw material) Examples of aromatic polyester raw materials include radically polymerizable monomers such as aromatic vinyl compounds, (meth)acrylic acid derivatives, vinyl cyanide compounds, and maleimide compounds, as well as dimethyl terephthalate and alkylene glycols. In this specification, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid.

[0205] (Physical properties of thermosetting resin (B)) The properties of the thermosetting resin (B) are not particularly limited. The thermosetting resin (B) preferably has a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C. The viscosity of the thermosetting resin (B) at 25°C is more preferably 50,000 mPa·s or less, even more preferably 30,000 mPa·s or less, and particularly preferably 15,000 mPa·s or less. According to the above configuration, the thermosetting resin (B) has the advantage of excellent fluidity. A thermosetting resin (B) having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C can also be said to be a liquid.

[0206] The greater the fluidity of the thermosetting resin (B), in other words, the lower the viscosity, the more difficult it becomes to disperse the polymer microparticles (A) in the form of primary particles in the thermosetting resin (B). Conventionally, it has been extremely difficult to disperse the polymer microparticles (A) in the form of primary particles in a thermosetting resin having a viscosity of 1,000,000 mPa·s or less at 25°C. However, the resin composition according to one embodiment of the present invention has the advantage that the polymer microparticles (A) having the above-described configuration are well dispersed in the thermosetting resin (B) having a viscosity of 1,000,000 mPa·s or less at 25°C.

[0207] Furthermore, the viscosity of the thermosetting resin (B) at 25°C is more preferably 100 mPa·s or more, even more preferably 500 mPa·s or more, even more preferably 1000 mPa·s or more, and particularly preferably 1500 mPa·s or more, because the thermosetting resin penetrates into the polymer microparticles (A) and thereby prevents the polymer microparticles (A) from fusing together.

[0208] The viscosity of the thermosetting resin (B) at 25°C is more preferably 100 mPa·s to 750,000 mPa·s, more preferably 100 mPa·s to 700,000 mPa·s, more preferably 100 mPa·s to 350,000 mPa·s, more preferably 100 mPa·s to 300,000 mPa·s, more preferably 100 mPa·s to 50,000 mPa·s, even more preferably 100 mPa·s to 30,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s.

[0209] The thermosetting resin (B) may have a viscosity of greater than 1,000,000 mPa·s. The thermosetting resin (B) may be semi-solid (semi-liquid) or solid. When the thermosetting resin has a viscosity of greater than 1,000,000 mPa·s, the resulting resin composition containing the powder or granule has the advantage of being less sticky and easier to handle.

[0210] The thermosetting resin (B) preferably has an endothermic peak of 25° C. or less in a thermogram obtained by differential scanning calorimetry (DSC), and more preferably has an endothermic peak of 0° C. or less. According to the above-mentioned configuration, the thermosetting resin (B) has the advantage of excellent fluidity.

[0211] (3-2. Mixing ratio of powder and thermosetting resin (B), etc.) The blending ratio of the powder or granules to the thermosetting resin (B), when the total of the powder or granules and the thermosetting resin (B) is taken as 100% by weight, is usually preferably 0.5 to 50% by weight of the powder or granules and 50 to 99.5% by weight of the thermosetting resin (B), more preferably 1 to 50% by weight of the powder or granules and 50 to 99% by weight of the thermosetting resin (B), more preferably 1 to 45% by weight of the powder or granules and 55 to 99% by weight of the thermosetting resin (B), still more preferably 1 to 40% by weight of the powder or granules and 60 to 99% by weight of the thermosetting resin (B), and still more preferably 1 to 35% by weight of the powder or granules and 60 to 99% by weight of the thermosetting resin (B). more preferably 65 to 99% by weight of the powder or granules, 1 to 30% by weight of the thermosetting resin (B) and 70 to 99% by weight of the thermosetting resin (B); more preferably 1 to 25% by weight of the powder or granules and 75 to 99% by weight of the thermosetting resin (B); more preferably 1.5 to 25% by weight of the powder or granules and 75 to 98.5% by weight of the thermosetting resin (B); even more preferably 1.5 to 20% by weight of the powder or granules and 80 to 98.5% by weight of the thermosetting resin (B); and particularly preferably 2.5 to 20% by weight of the powder or granules and 80 to 97.5% by weight of the thermosetting resin (B).

[0212] The temperature at which the powder or granule is mixed with the thermosetting resin (B) is generally set to a temperature at which the thermosetting resin (B) can flow. If the resin (D) can flow at a temperature at which the thermosetting resin (B) can flow, it becomes easy to uniformly mix the resin (D) and the thermosetting resin (B). Conversely, if the thermosetting resin (B) is liquid and the resin (D) (e.g., epoxy resin) in the powder or granule to be added to it is solid, it becomes difficult to uniformly mix the two. In this specification, if the thermosetting resin (B) is liquid at 25°C, it is interpreted that "the viscosity of the thermosetting resin (B) at 25°C is equal to or greater than the viscosity of the resin (D) at 25°C."

[0213] (3-3. Organic Solvents) The resin composition is preferably substantially free of organic solvents. When the above-mentioned powder or granules are substantially free of organic solvents, a resin composition substantially free of organic solvents can be obtained. "Substantially free of organic solvents" means that the amount of organic solvent in the resin composition is 100 ppm or less.

[0214] The amount of organic solvent (also referred to as solvent content) contained in the resin composition is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 25 ppm or less, and particularly preferably 10 ppm or less. The amount of organic solvent contained in the resin composition can also be considered the amount of volatile components (excluding water) contained in the resin composition. The amount of organic solvent (volatile components) contained in the resin composition can be determined, for example, by heating a predetermined amount of the resin composition using a hot air dryer or the like and measuring the weight of the resin composition before and after heating, thereby determining the weight loss. The amount of organic solvent (volatile components) contained in the resin composition can also be determined by gas chromatography. Furthermore, if no organic solvent is used in the production of the resin composition and the powder or granule contained in the resin composition, the amount of organic solvent contained in the resulting resin composition can be considered to be 0 ppm.

[0215] Examples of organic solvents that are substantially not contained in the present resin composition include: (a) esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; (b) ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; (c) alcohols such as ethanol, (iso)propanol, and butanol; (d) ethers such as tetrahydrofuran, tetrahydropyran, dioxane, and diethyl ether; (e) aromatic hydrocarbons such as benzene, toluene, and xylene; and (f) halogenated hydrocarbons such as methylene chloride and chloroform.

[0216] (3-4. Foreign matter level) The resin composition preferably has a foreign matter level of 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, even more preferably 40 μm or less, even more preferably 20 μm or less, and most preferably 0 μm, as evaluated using a grind gauge. If the foreign matter level is within the above range, no foreign matter is present in the resin composition. The foreign matter level can be determined by the method described in "(Dispersibility of polymer fine particles (A) in resin composition)" in the Examples.

[0217] (3-5. Other optional ingredients) The resin composition may contain optional components other than those described above, as needed, such as curing agents, colorants such as pigments and dyes, extender pigments, UV absorbers, antioxidants, heat stabilizers (antigelling agents), plasticizers, leveling agents, antifoaming agents, silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, shrinkage reducing agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, and dispersants.

[0218] The present resin composition may further contain a known thermosetting resin other than the thermosetting resin (B), or may further contain a known thermoplastic resin.

[0219] [4. Cured product] A cured product according to one embodiment of the present invention is obtained by curing the present resin composition described in Section 3. Resin Composition. Hereinafter, the cured product according to one embodiment of the present invention will also be simply referred to as the present cured product.

[0220] Because of the above-described structure, the present cured product has low viscosity and good workability. In addition, the present cured product (a) has a beautiful surface, (b) has high rigidity and high elastic modulus, and (c) has excellent toughness and adhesiveness.

[0221] [5. Adhesive] An adhesive according to one embodiment of the present invention may be a thermosetting structural adhesive containing the above-described powder and granule, a thermosetting resin (B), and an inorganic filler (C). Hereinafter, the adhesive according to one embodiment of the present invention may be simply referred to as the present adhesive. Because of the above-described configuration, the present adhesive has the advantages of being less likely to deteriorate in thixotropy (viscosity at low rotation speeds / viscosity at high rotation speeds) and less likely to deteriorate in stringiness.

[0222] As the inorganic filler (C), known components blended in ordinary adhesive or pressure-sensitive adhesive compositions can be suitably used. For example, inorganic fillers can be added to impart heat resistance, thermal conductivity, flame retardancy, electrical conductivity, etc. Examples of the inorganic filler (C) include metal powders such as zinc oxide powder and titanium oxide powder, carbon blacks such as acetylene black, talc, glass powder, silica powder, conductive particles, and glass powder. These fillers can be used alone or in combination of two or more.

[0223] The blending ratio of each component is preferably 1 to 100 parts by mass of the powdery particle and 0.1 to 100 parts by mass of the inorganic filler (C) per 100 parts by mass of (i) the thermosetting resin (B).Within the above ranges, good adhesive strength can be achieved.

[0224] The adhesive can be suitably used for a variety of applications, such as automotive interior materials, general woodworking, furniture, interior decoration, wall materials, and food packaging.

[0225] This adhesive exhibits good adhesion to a variety of substrates, including cold-rolled steel, aluminum, fiberglass-reinforced polyester (FRP), cured thermosetting resin panels such as carbon fiber-reinforced epoxy resin, carbon fiber-reinforced thermoplastic resin sheet panels, sheet molding compound (SMC), acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride (PVC), polycarbonate, polypropylene, TPO, wood, and glass.

[0226] This adhesive has excellent adhesive properties and flexibility not only at low temperatures (around -20°C) to room temperature, but also at high temperatures (around 80°C), making it ideal for use as a structural adhesive.

[0227] Structural adhesives using this adhesive can be used, for example, as adhesives for structural members in automobiles and vehicles (such as bullet trains and trains), civil engineering, architecture, building materials, woodworking, electricity, electronics, aircraft, the space industry, etc. In particular, automotive-related applications include bonding interior materials such as ceilings, doors, and seats, and bonding exterior materials such as automotive lighting fixtures such as lamps and side moldings.

[0228] The adhesive can be produced using the powder or resin composition. There are no particular limitations on the method for producing the adhesive, and known methods can be used.

[0229] [6. Other uses] The powder or resin composition according to one embodiment of the present invention can be used in a variety of applications, and these applications are not particularly limited. The powder or resin composition is preferably used, for example, as a coating material, a binder for reinforcing fibers, a composite material, resin concrete, a 3D printer modeling material, a sealant, an electronic substrate, an ink binder, a wood chip binder, a rubber chip binder, a foam chip binder, a binder for castings, a rock consolidation material for flooring and ceramics, or as a urethane foam. Examples of urethane foam include automobile seats, automobile interior parts, sound-absorbing materials, vibration-damping materials, shock absorbers, heat insulation materials, and cushioning materials for construction flooring.

[0230] Among the uses mentioned above, the powder or resin composition is more preferably used as a coating material, a binder for reinforcing fibers, a composite material, a molding material for 3D printers, a sealant, and an electronic substrate.

[0231] (6-1. Coating materials) A coating material according to one embodiment of the present invention includes the powder or resin composition described above. Because the coating material according to one embodiment of the present invention has the above-described configuration, it can provide a coating film that is excellent in load-bearing capacity and abrasion resistance.

[0232] The coating material according to one embodiment of the present invention is also simply referred to as the coating material.

[0233] The present coating material contains, for example, an organic solvent and the present powder, and polymer fine particles (A) are dispersed in the organic solvent in the state of primary particles. The present coating material contains, for example, an organic solvent and the present resin composition, and polymer fine particles (A) are dispersed in the organic solvent in the state of primary particles. Conventionally, it has been very difficult to disperse polymer fine particles (A) in an organic solvent in the state of primary particles. However, the present powder has the advantage of being able to provide a coating material in which polymer fine particles (A) are more uniformly dispersed in the organic solvent. The present powder may be a powder for use in coating materials.

[0234] When applying this coating to, for example, a floor or corridor, commonly used application methods can be used. For example, after applying a primer to the prepared substrate, the coating is applied evenly using a trowel, roller, rake, spray gun, or other suitable tool depending on the application conditions. After application, the coating hardens, resulting in a high-performance paving film. The coating obtained by curing the coating can have excellent load-bearing and abrasion resistance.

[0235] The viscosity of the resin composition used in the coating material may be adjusted depending on the application method. For example, when applying the coating material using a trowel or rake, the viscosity of the resin composition used in the coating material is generally adjusted to about 500 to 9,000 cps / 25°C. When applying the coating material using a roller or spray, the viscosity of the resin composition used in the coating material is generally adjusted to about 100 to 3,000 cps / 25°C.

[0236] The substrate to which the coating material is applied (i.e., the material of the floor or hallway) is not particularly limited. Specific examples of the substrate include (a) inorganic substrates such as concrete walls, concrete plates, concrete blocks, CMU (Concrete Masonry Unit), mortar boards, ALC (Autoclaved Lightweight Concrete) boards, gypsum boards (Dens Glass Gold: manufactured by Georgia Pacific, etc.), and slate boards; (b) organic substrates such as wood-based substrates (wood, plywood, OSB (Oriented Strand Board), etc.), asphalt, modified bitumen waterproof sheets, ethylene-propylene-diene rubber (EPDM) waterproof sheets, TPO waterproof sheets, plastics, FRP, and urethane foam insulation; and (c) metal substrates such as metal panels.

[0237] The present coating material is applied to a metal substrate or a porous substrate. The laminate obtained by curing the coating material after application provides excellent corrosion protection to the substrate. Furthermore, the coating film obtained by curing the coating material after application can provide excellent crack resistance and load-bearing capacity to the substrate. Therefore, applying the present coating material to a metal substrate or a porous substrate is a particularly preferred embodiment.

[0238] The method for applying the coating material is not particularly limited, but it can be applied by any known application method such as with a trowel, rake, brush, roller, air spray, or airless spray.

[0239] Applications of the present coating material are not particularly limited, but include automobiles, electrical equipment, office machines, building materials, wood, painted floors, paving, heavy-duty corrosion protection, concrete corrosion protection, roof and roof waterproofing, corrosion resistance for roof and roof, coating waterproofing materials for underground waterproofing, automobile repair, can painting, top coats, intermediate coats, undercoats, primers, electrodeposition paints, highly weather-resistant paints, non-yellowing paints, etc. When used as a coating material for painted floors and paving coatings, it can be used in factories, laboratories, warehouses, clean rooms, etc.

[0240] The present coating material can be produced using the present powder or resin composition. The method for producing the present coating material is not particularly limited, and known methods can be used.

[0241] (6-1-1. Film) A film according to one embodiment of the present invention contains the powder or resin composition described above. Because the film according to one embodiment of the present invention has the above-described structure, it has excellent load-bearing capacity and abrasion resistance.

[0242] The film according to one embodiment of the present invention is also simply referred to as the present film.

[0243] The present film is obtained, for example, by volatilizing the organic solvent from a dope solution containing the organic solvent and the present powder / granule. The present film is obtained, for example, by volatilizing the organic solvent from a dope solution containing the organic solvent and the present resin composition. In these dope solutions, the polymer fine particles (A) are dispersed in the organic solvent in the state of primary particles. Conventionally, it has been very difficult to disperse the polymer fine particles (A) in the state of primary particles in an organic solvent. However, the present powder / granule can provide a dope solution in which the polymer fine particles (A) are more uniformly dispersed in the organic solvent, and therefore has the advantage of being able to provide a film in which the polymer fine particles (A) are more uniformly dispersed. The present powder / granule may be a powder / granule for film.

[0244] The applications of the present film are not particularly limited, but it can be used as an optical film such as a polarizer protective film, a decorative film, a conductive film, an electromagnetic wave absorbing sheet, an anti-reflection film, and the like.

[0245] The present film can be produced using the present powder or resin composition. The method for producing the present film is not particularly limited, and known methods can be used.

[0246] (6-2. Composite materials) A composite material according to one embodiment of the present invention contains the above-described powder or resin composition as a binder for reinforcing fibers. Because of the above-described configuration, the composite material according to one embodiment of the present invention has the advantages of excellent toughness and impact resistance.

[0247] The composite material according to one embodiment of the present invention may also be simply referred to as the present composite material.

[0248] The composite material may contain reinforcing fibers. Examples of the reinforcing fibers include, but are not limited to, glass fibers, long glass fibers, carbon fibers, natural fibers, metal fibers, thermoplastic resin fibers, boron fibers, aramid fibers, polyethylene fibers, and Zylon reinforcing fibers. Among these reinforcing fibers, glass fibers and carbon fibers are particularly preferred.

[0249] The manufacturing method (molding method) of this composite material is not particularly limited, but examples include autoclave molding using prepreg, filament winding molding, hand lay-up molding, vacuum bag molding, resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM), pultrusion molding, injection molding, sheet winding, spray-up, BMC (Bulk Molding Compound), and SMC (Sheet Molding Compound).

[0250] In particular, when carbon fiber is used as the reinforcing fiber, it is preferable to use an autoclave molding method using prepreg, a filament winding molding method, a hand lay-up molding method, a vacuum bag molding method, a resin transfer molding (RTM) method, a vacuum-assisted resin transfer molding (VARTM) method, or the like to manufacture the composite material.

[0251] Applications of the composite material include, but are not limited to, aircraft, spacecraft, automobiles, bicycles, ships, weapons, wind turbines, sporting goods, containers, building materials, waterproofing materials, printed circuit boards, and electrical insulating materials.

[0252] The composite material can be produced using the powder or resin composition. For more detailed information on the composite material, such as reinforcing fibers, production method (molding method), production conditions (molding conditions), compounding agents, and applications, see U.S. Patent Publication No. 2006 / 0173128, U.S. Patent Publication No. 2012 / 0245286, JP-A-2002-530445 (International Publication No. WO2000 / 029459), and JP-A-55-157620. Examples of such a method include those described in U.S. Patent Publication No. 4,251,428, JP 2013-504007 A (International Publication No. WO2011 / 028271), JP 2007-125889 A (U.S. Patent Publication No. 2007 / 0098997), and JP 2003-220661 A (U.S. Patent Publication No. 2003 / 0134085).

[0253] (6-3.3D printer modeling materials) A modeling material for a 3D printer according to one embodiment of the present invention contains the powder or resin composition described above. Because of the above-described configuration, the modeling material for a 3D printer according to one embodiment of the present invention has the advantages of excellent toughness and impact resistance.

[0254] The modeling material of the 3D printer according to one embodiment of the present invention is also simply referred to as the modeling material.

[0255] Applications of this molding material include, but are not limited to, prototypes for the purpose of verifying designs and functions before actually making the product, aircraft parts, building materials, and medical equipment parts.

[0256] The present modeling material can be produced using the present powder or resin composition. The method for producing the present modeling material is not particularly limited, and any known method can be used.

[0257] (6-4. Sealant) A sealant according to one embodiment of the present invention is made using the powder or resin composition described above. Because of the above-described configuration, the sealant according to one embodiment of the present invention has the advantages of excellent toughness and impact resistance.

[0258] The sealant according to one embodiment of the present invention may also be simply referred to as the sealant of the present invention.

[0259] The uses of the sealant of the present invention are not particularly limited, but include sealing of various electrical devices such as semiconductors and power devices.

[0260] The present sealant can be produced using the present powder or resin composition. The method for producing the present sealant is not particularly limited, and known methods can be used.

[0261] (6-5. Electronic board) An electronic substrate according to one embodiment of the present invention includes the powder or resin composition described above. Because of the above-described configuration, the electronic substrate according to one embodiment of the present invention has the advantages of excellent toughness and impact resistance.

[0262] The electronic substrate according to one embodiment of the present invention is also simply referred to as the present electronic substrate.

[0263] The applications of the electronic substrate are not particularly limited, but include printed circuits, printed wiring, printed circuit boards, printed circuit mounted products, printed wiring boards, and printed boards.

[0264] The present electronic substrate can be produced from the present resin composition using the present resin composition. The method for producing the present electronic substrate is not particularly limited, and known methods can be used.

[0265] [Embodiment 2] However, when organisms such as barnacles attach to underwater structures such as ships, it causes problems in terms of fuel efficiency and service life, so it is common to apply antifouling paint to underwater structures.

[0266] Various antifouling paints have been developed. For example, Patent Document 3 discloses an antifouling paint composition containing a hydrolyzable resin having a silicon-containing group and a metal atom-containing group containing a divalent metal atom M, and a thermoplastic resin and / or a plasticizer.

[0267] Furthermore, Patent Document 4 discloses a coating composition containing organic polymer particles having a solubility in artificial seawater at 23°C of 15 g / L or less, an artificial seawater water absorption of 0.01 mass% or more, and a particle size of 0.05 to 100 μm.

[0268] However, the above-mentioned conventional techniques are not sufficient from the viewpoint of durability, and there is room for further improvement.

[0269] The second embodiment of the present invention has been made in consideration of the above-mentioned problems, and its object is to provide a novel antifouling coating composition for underwater structures that can provide a coating film with excellent durability, and a technology for using the same.

[0270] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that an antifouling coating composition for underwater structures containing a binder resin and polymer microparticles can provide a coating film with excellent durability, and have thus completed the present invention.

[0271] That is, a second embodiment of the present invention includes the following configuration.

[0272] [1] A binder resin (E), polymer fine particles (A'), and a resin (D), wherein the polymer fine particles (A) contain a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer, the elastomer containing at least one rubber selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber, and the graft portion contains, as a constituent unit, at least one rubber selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer. an antifouling coating composition for underwater structures, the antifouling coating composition comprising a polymer containing structural units derived from one or more monomers selected from the group consisting of methyl methyl acrylate and methyl acrylate; a polymer fine particle (A') having a glass transition temperature of 80°C or lower; and a resin (D) which is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C, the polymer fine particle (A') accounting for 50 to 99% by weight and the resin (D) accounting for 1 to 50% by weight, when the total of the polymer fine particle (A') and the resin (D) is taken as 100% by weight.

[0273] [2] A method for producing a powder containing polymer fine particles (A') and a resin (D), comprising: a powder preparation step of obtaining a powder containing polymer fine particles (A') and a resin (D); and a mixing step of mixing a binder resin (E) with the powder, wherein the polymer fine particles (A') comprise a rubber-containing graft copolymer having an elastomer and a graft portion grafted to the elastomer, the elastomer comprising at least one rubber selected from the group consisting of a diene rubber, a (meth)acrylate rubber, and an organosiloxane rubber, and the graft portion comprises, as constituent units, an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate. a polymer containing structural units derived from one or more monomers selected from the group consisting of acrylate monomers, wherein the polymer microparticles (A') have a glass transition temperature of 80°C or lower, and the resin (D) is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C, and the polymer microparticles (A') account for 50 to 99% by weight and the resin (D) accounts for 1 to 50% by weight, when the total of the polymer microparticles (A') and the resin (D) is 100% by weight.

[0274] According to the second embodiment of the present invention, it is possible to provide an antifouling coating composition for underwater structures that can provide a coating film with excellent durability, and a technique for using the same.

[0275] A second embodiment of the present invention will be described below.

[0276] 1. Technical Concept of Embodiment 2 of the Present Invention As a result of extensive research, the present inventors have found that the techniques described in the above-mentioned Patent Documents 3 and 4 have the following problems.

[0277] The present inventors have independently discovered the problem that paints (coating films) applied to underwater structures may develop cracks due to long-term immersion in water and repeated drying and wetting. Furthermore, coating films made from antifouling coating compositions for underwater structures generally have low strength, and there has been a demand for improved strength. In other words, paints (coating films) applied to underwater structures require greater durability.

[0278] In order to solve these problems, the present inventors conducted extensive research and found that the above problems can be solved by providing an antifouling coating composition for underwater structures containing a binder resin, polymer microparticles having a specific composition, and a resin, and thus completed the present invention.

[0279] Furthermore, the present inventors have discovered the following: In an antifouling coating composition for underwater structures, the degree of dispersion of polymer microparticles in a binder resin affects the durability of a coating film obtained from the antifouling coating composition for underwater structures. Specifically, the better the dispersion of polymer microparticles in a binder resin, the better the durability. In this specification, dispersion of polymer microparticles refers to dispersion of the polymer microparticles as primary particles.

[0280] It is extremely difficult to disperse polymer microparticles in a binder resin in an antifouling coating composition for underwater structures. Therefore, the present inventors conducted extensive research with the aim of uniformly dispersing polymer microparticles in a binder resin. As a result, the present inventors discovered the novel fact that by blending a resin with the binder resin together with the polymer microparticles, the polymer microparticles can be uniformly dispersed in the binder resin, thereby improving the durability of the coating film obtained from the antifouling coating composition for underwater structures.

[0281] 2. Antifouling coating composition for underwater structures An antifouling coating composition for underwater structures according to one embodiment of the present invention comprises a binder resin (E), polymer microparticles (A'), and a resin (D). The polymer microparticles (A') comprise a rubber-containing graft copolymer having an elastomer and a graft portion grafted to the elastomer. The elastomer comprises at least one rubber selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers. The graft portion comprises a polymer containing, as a structural unit, a structural unit derived from at least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. The polymer microparticles (A') have a glass transition temperature of 80°C or lower. The resin (D) is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C. When the total of the polymer microparticles (A') and the resin (D) is taken as 100% by weight, the polymer microparticles (A') account for 50 to 99% by weight and the resin (D) for 1 to 50% by weight. Hereinafter, "glass transition temperature" may also be referred to as "Tg". Hereinafter, "antifouling coating composition for underwater structures" may also be referred to as "composition". Hereinafter, "antifouling coating composition for underwater structures according to one embodiment of the present invention" may also be referred to as "the composition". Hereinafter, "the antifouling coating composition for underwater structures according to one embodiment of the present invention" may also be referred to as "the composition". By applying the composition to an underwater structure, an antifouling coating film (coating film) can be formed on the underwater structure.

[0282] The present composition has the advantage of being able to provide a coating film with excellent durability by containing the polymer microparticles (A'). In this specification, "excellent durability" refers to "excellent strength and elongation." In other words, the polymer microparticles (A') have the function of imparting strength and elongation to a coating film obtained from the antifouling coating composition for underwater structures. More specifically, the present composition can provide a coating film with excellent elongation, which makes it less susceptible to cracking even when the coating film is exposed to long-term immersion in water and repeated drying and wetting. The present composition can provide a coating film with excellent strength, which allows for the high-strength coating film that has been desired. The strength and elongation of the antifouling coating composition for underwater structures can be measured by a tensile test of the coating film obtained from the antifouling coating composition for underwater structures; details of the tensile test will be described later.

[0283] The present inventors have also discovered the novel finding that the inclusion of polymer microparticles (A') in the present composition makes it possible to provide a coating film with a large contact angle and / or a coating film with a low modulus of elasticity. It is presumed that a coating film with a large contact angle is more difficult for organisms to adhere to than a coating film with a small contact angle, and therefore has better antifouling properties. It is also presumed that a coating film with a low modulus of elasticity is more likely to cause attached organisms to fall off with the flow of water than a coating film with a high modulus of elasticity, and therefore has better antifouling properties. That is, the inclusion of polymer microparticles (A') in the present composition has the advantage of being able to provide a coating film to which organisms do not easily adhere and / or from which attached organisms easily fall off, in other words, a coating film with excellent antifouling properties. However, one embodiment of the present invention is not limited by the above-mentioned speculation.

[0284] (2-1. Binder Resin (E)) As the binder resin (E), resins commonly used in antifouling coating compositions for underwater structures can be used. Examples of the binder resin (E) include hydrolyzable resins, hydration-decomposing resins, and silicone-type resins. The hydrolyzable resin refers to a resin that can be decomposed by reaction with water. The hydrolyzable resin is also sometimes called a self-polishing resin, a self-consuming resin, a self-disintegrating resin, etc.

[0285] Examples of hydrolyzable resins include (a) acrylic resins such as silyl group-containing acrylic resins, metal-containing acrylic resins, and copolymers of silyl group-containing acrylic resins and metal-containing acrylic resins, and (b) polyester resins. Examples of hydrolyzable resins also include the acrylic resins, polyester resins, and hydrolyzable resins described in International Publication Nos. WO2005 / 116155 and WO2011 / 046086.

[0286] When the binder resin (E) is a hydrolyzable resin, it is believed that the resulting composition can provide a coating film with better antifouling properties, based on the following assumption: Organisms such as barnacles are thought to adhere to the polymer fine particles (A') in the coating film. When the binder resin (E) is a hydrolyzable resin, the polymer fine particles (A') in the coating film are detached from the coating film as the binder resin (E) is hydrolyzed. At this time, the organisms attached to the polymer fine particles (A') may also detach from the coating film together with the polymer fine particles (A'). As a result, the coating film is less susceptible to the attachment of organisms. One embodiment of the present invention is not limited by such assumption.

[0287] Examples of hydration-decomposable resins include vinyl chloride-vinyl acetate resins, vinyl chloride-vinyl isobutyl ether resins, vinyl methyl ether resins, and hydrophilic group-containing acrylic resins. Hydration-decomposable resins can be said to have an affinity for seawater, or to be slightly soluble resins.

[0288] Examples of silicone-type resins include (a) organopolysiloxanes, (b) organosilanes and / or partial hydrolysis condensates thereof, as described in Japanese Patent No. 6487159 and JP-A-2019-055592, and the like.

[0289] Commercially available binder resins (E) may be used, including (a) products under the names "Unagi Paint Ichiban," "Unagi Paint Ichiban LF-sea," "Unagi Paint Ichiban Vivid," "Manpo," "LF-sea," "A-LF-sea," "Ecoloflex SPC," and "Aqua Terrace," manufactured by Nippon Paint Marine Co., Ltd., and (b) products under the names "SEAFLO NEO," "CMP Bioclean," "Sea Grand Prix," "Sea Premier," and "Sea Tender" manufactured by Chugoku Paint Co., Ltd.

[0290] (2-2. Polymer fine particles (A')) The polymer fine particles (A') contain a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer.

[0291] (2-2-1. Elastic body) The elastomer is not particularly limited and may include natural rubber, diene rubber, (meth)acrylate rubber, polysiloxane rubber elastomer, etc. Preferably, the elastomer includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and polysiloxane rubber elastomer. The elastomer can also be referred to as rubber particles. In this specification, (meth)acrylate means acrylate and / or methacrylate. Polysiloxane rubber elastomers are sometimes referred to as organosiloxane rubber.

[0292] The case where the elastomer contains a diene rubber (Case A) will be described below. In Case A, the resulting composition can provide a coating film that is excellent in toughness and impact resistance and has a large contact angle. A coating film that is excellent in toughness and / or impact resistance can also be said to be a coating film that is excellent in durability.

[0293] The diene rubber is an elastomer containing, as structural units, structural units derived from a diene monomer. The diene monomer can also be referred to as a conjugated diene monomer. In Case A, the diene rubber may contain, based on 100% by weight of structural units, 50 to 100% by weight of structural units derived from a diene monomer and 0 to 50% by weight of structural units derived from a vinyl monomer other than a diene monomer copolymerizable with the diene monomer. In Case A, the diene rubber may contain, as structural units, structural units derived from a (meth)acrylate monomer in an amount less than the structural units derived from the diene monomer.

[0294] Examples of the diene monomer include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2-chloro-1,3-butadiene, etc. These diene monomers may be used alone or in combination of two or more.

[0295] Examples of vinyl monomers other than diene monomers copolymerizable with diene monomers (hereinafter also referred to as vinyl monomer A) include: (a) vinyl arenes such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; (b) vinyl carboxylic acids such as acrylic acid and methacrylic acid; (c) vinyl cyanides such as acrylonitrile and methacrylonitrile; (d) vinyl halides such as vinyl chloride, vinyl bromide, and chloroprene; (e) vinyl acetate; (f) alkenes such as ethylene, propylene, butylene, and isobutylene; and (g) polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The above-mentioned vinyl monomer A may be used alone or in combination of two or more. Among the above-mentioned vinyl monomers A, styrene is particularly preferred.

[0296] In Case A, the diene rubber is preferably butadiene rubber (also called polybutadiene rubber) consisting of structural units derived from 1,3-butadiene, or butadiene-styrene rubber (also called polystyrene-butadiene), which is a copolymer of 1,3-butadiene and styrene. This configuration allows the polymer microparticles (A') to more effectively exhibit the desired effects of including a diene rubber. Furthermore, butadiene-styrene rubber is more preferable in that it can enhance the transparency of the resulting coating film by adjusting the refractive index.

[0297] The case where the elastomer contains a (meth)acrylate rubber (Case B) will be explained. In Case B, a wide range of polymer designs for the elastomer are possible by combining a variety of monomers.

[0298] The (meth)acrylate rubber is an elastomer containing, as structural units, structural units derived from (meth)acrylate monomers. In Case B, the (meth)acrylate rubber may contain, based on 100% by weight of structural units, 50 to 100% by weight of structural units derived from (meth)acrylate monomers and 0 to 50% by weight of structural units derived from vinyl monomers other than (meth)acrylate monomers copolymerizable with the (meth)acrylate monomers. In Case B, the (meth)acrylate rubber may contain, as structural units, structural units derived from diene monomers in an amount less than the structural units derived from the (meth)acrylate monomers.

[0299] Examples of the (meth)acrylate monomer include: (a) alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (b) aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; (c) 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; Examples of suitable (meth)acrylate monomers include hydroxyalkyl (meth)acrylates such as acrylate; (d) glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidyl alkyl (meth)acrylate; (e) alkoxyalkyl (meth)acrylates; (f) allyl alkyl (meth)acrylates such as allyl (meth)acrylate and allyl alkyl (meth)acrylate; and (g) polyfunctional (meth)acrylates such as monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. 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, with butyl (meth)acrylate being more preferred.

[0300] 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, with butyl (meth)acrylate rubber being more preferred. The ethyl (meth)acrylate rubber is a rubber composed of structural units derived from ethyl (meth)acrylate, the butyl (meth)acrylate rubber is a rubber composed of structural units derived from butyl (meth)acrylate, and the 2-ethylhexyl (meth)acrylate rubber is a rubber composed of structural units derived from 2-ethylhexyl (meth)acrylate. This configuration offers the advantage of a low Tg of the elastomer, and therefore a low elastic modulus for the resulting polymer microparticles (A') and a mixture of the resulting polymer microparticles (A') with the resin (D), described below.

[0301] Examples of vinyl monomers other than (meth)acrylate monomers copolymerizable with (meth)acrylate monomers (hereinafter also referred to as vinyl monomers B) include the monomers listed above for vinyl monomers A. Vinyl monomers B may be used alone or in combination of two or more. Among vinyl monomers B, styrene is particularly preferred.

[0302] The case where the elastomer contains a polysiloxane rubber-based elastomer (Case C) will be described. In Case C, the resulting composition can provide a coating film that has sufficient heat resistance and excellent impact resistance at low temperatures. In Case C, the polymer fine particles (A') and the mixture of the polymer fine particles (A') and the resin (D) have the advantage of a large contact angle. Therefore, in Case C, the resulting composition can provide a coating film with a large contact angle.

[0303] Examples of polysiloxane rubber-based elastomers include (a) polysiloxane-based polymers composed of alkyl- or aryl-disubstituted silyloxy units, such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy, and (b) polysiloxane-based polymers composed of alkyl- or aryl-monosubstituted silyloxy units, such as organohydrogensilyloxy in which some of the alkyl groups in the side chains have been substituted with hydrogen atoms. These polysiloxane-based polymers may be used alone or in combination of two or more.

[0304] In this specification, a polymer composed of dimethylsilyloxy units is referred to as dimethylsilyloxy rubber, a polymer composed of methylphenylsilyloxy units is referred to as methylphenylsilyloxy rubber, and a polymer composed of dimethylsilyloxy units and diphenylsilyloxy units is referred to as dimethylsilyloxy-diphenylsilyloxy rubber. In Case C, the polysiloxane rubber-based elastomer is preferably one or more selected from the group consisting of dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenylsilyloxy rubber, (a) because the resulting composition can provide a coating film with excellent heat resistance, and (b) more preferably dimethylsilyloxy rubber, because it is easily available and economical.

[0305] In Case C, the polymer fine particles (A') preferably contain 80% by weight or more, and more preferably 90% by weight or more, of the polysiloxane rubber-based elastomer relative to 100% by weight of the elastomer contained in the polymer fine particles (A'). According to this configuration, the resulting composition can provide a coating film with excellent heat resistance.

[0306] In one embodiment of the present invention, the elastomer is preferably one or more selected from the group consisting of 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, and more preferably one or more selected from the group consisting of butadiene rubber, butadiene-styrene rubber, butyl (meth)acrylate rubber, and dimethylsilyloxy rubber.

[0307] (elastic cross-linked structure) It is preferable that a crosslinked structure be introduced into the elastomer, since this allows the dispersion stability of the polymer microparticles (A') in the binder resin (E) to be maintained. The method for introducing a crosslinked structure into the elastomer is the same as in embodiment 1, and the above description will be used to explain only the differences. Note that the terms "matrix resin" and "thermosetting resin" in embodiment 1 will be read as "binder resin (E)" in embodiment 2.

[0308] Other methods for introducing a crosslinked structure into a polysiloxane rubber-based elastomer include: (a) using a polyfunctional alkoxysilane compound in combination with other materials when polymerizing the polysiloxane rubber-based elastomer; (b) introducing reactive groups such as vinyl reactive groups or mercapto groups into a polysiloxane rubber-based elastomer, and then adding a vinyl polymerizable monomer or an organic peroxide to cause a radical reaction; or (c) mixing a crosslinkable monomer such as a polyfunctional monomer and / or a mercapto group-containing compound with other materials when polymerizing the polysiloxane rubber-based elastomer, and then polymerizing the mixture.

[0309] (glass transition temperature of elastic body) This embodiment is similar to the first embodiment, and the above description will be used to explain only the differences. This configuration allows for the production of polymer fine particles (A') having a low Tg, and a mixture of polymer fine particles (A') having a low Tg and resin (D) described below. As a result, the mixture of polymer fine particles (A') and resin (D) has the advantages of a low modulus of elasticity and high elongation (excellent elongation). As a result, the resulting composition can provide a coating film with excellent toughness, a low modulus of elasticity, and / or an excellent elongation.

[0310] (Volume average particle size of elastic body) This is the same as in the first embodiment, and the above description is incorporated herein, so further explanation will be omitted here.

[0311] (elastic body ratio) This is the same as in the first embodiment, and the above description is incorporated herein, so further explanation will be omitted here.

[0312] (gel content of elastic body) The present embodiment is similar to that of embodiment 1, and the above description will be used to explain only the differences. The elastic body is preferably insoluble in the binder resin (E) used.

[0313] (Modification of elastic body) The present embodiment is similar to that of Embodiment 1, and the above description will be used to explain only the differences. In one embodiment of the present invention, the "elastic material" of the polymer microparticles (A') is, for example, one type selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and polysiloxane rubber elastomers, and may consist of only one type of elastomer having the same composition of structural units.

[0314] In one embodiment of the present invention, the elastomer may be composed of multiple types of elastomers each having a different constitutional unit composition. In this case, the "elastomer" of the polymer microparticles (A') may be, for example, two or more types selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers. In addition, in this case, the "elastomer" of the polymer microparticles (A') may be, for example, one type selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers. In other words, the "elastomer" of the polymer microparticles (A') may be multiple types of diene rubbers, (meth)acrylate rubbers, or organosiloxane rubbers each having a different constitutional unit composition.

[0315] (2-2-2. Graft section) This is the same as the first embodiment, and the above description will be used to explain only the differences.

[0316] (Graft ratio of grafted part) The non-grafted polymer constitutes a part of the polymer fine particles (A') according to one embodiment of the present invention.

[0317] In this embodiment 2, the graft ratio of the grafted portion is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. A graft ratio of 70% or more has the advantage that the viscosity of the composition does not become too high.

[0318] (2-2-3.Surface crosslinked polymer) This is the same as in the first embodiment, and the above description is incorporated herein by reference.

[0319] (2-2-4. Physical Properties of Polymer Microparticles (A')) The physical properties of the polymer fine particles (A') will be explained below.

[0320] (Volume average particle size (Mv) of polymer fine particles (A')) This is the same as in the first embodiment, and the above description is used for the explanation.

[0321] (Glass transition temperature of polymer fine particles (A')) The glass transition temperature of the polymer microparticles (A') 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, more preferably 20°C or lower, more preferably 10°C or lower, more preferably 0°C or lower, more preferably -20°C or lower, more preferably -40°C or lower, more preferably -45°C or lower, more preferably -50°C or lower, more 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, more preferably -85°C or lower, more preferably -90°C or lower, more preferably -95°C or lower, more preferably -100°C or lower, more preferably -105°C or lower, more preferably -110°C or lower, more preferably -115°C or lower, even more preferably -120°C or lower, and particularly preferably -125°C or lower. This method allows for the production of a mixture of polymer fine particles (A') and a resin (D) (described later) having a low Tg. As a result, the mixture of polymer fine particles (A') and a resin (D) has the advantages of a low modulus of elasticity and high elongation. As a result, the resulting composition can provide a coating film with excellent toughness, a low modulus of elasticity, and / or an excellent elongation.

[0322] The Tg of the polymer microparticles (A') can be determined by the composition of the structural units contained in each of the elastomers and / or graft moieties contained in the polymer microparticles (A'). In other words, the Tg of the resulting polymer microparticles (A') can be adjusted by changing the composition of the monomers used in producing (polymerizing) the polymer microparticles (A').

[0323] (Break Strength of Polymer Microparticles (A')) The strength at break (MPa) of the polymer microparticles (A') is preferably 50.0 MPa or less, more preferably 25.0 MPa or less, more preferably 20.0 MPa or less, more preferably 16.0 MPa or less, more preferably 15.0 MPa or less, more preferably 14.0 MPa or less, more preferably 15.0 MPa or less, more preferably 12.0 MPa or less, more preferably 11.0 MPa or less, more preferably 10.0 MPa or less, more preferably 9.0 MPa or less, more preferably 8.0 MPa or less, more preferably 7.0 MPa or less, even more preferably 6.0 MPa or less, and particularly preferably 5.0 MPa or less. The strength at break (MPa) of the polymer microparticles (A') is preferably 1.0 MPa or more, more preferably 2.0 MPa or more, more preferably 3.0 MPa or more, more preferably 4.0 MPa or more, more preferably 5.0 MPa or more, more preferably 6.0 MPa or more, more preferably 7.0 MPa or more, more preferably 8.0 MPa or more, more preferably 9.0 MPa or more, more preferably 10.0 MPa or more, more preferably 11.0 MPa or more, more preferably 12.0 MPa or more, more preferably 13.0 MPa or more, even more preferably 14.0 MPa or more, and particularly preferably 15.0 MPa or more.

[0324] (Elongation of polymer fine particles (A')) The elongation (%) of the polymer microparticles (A') is preferably 1.0% or more, more preferably 5.0% or more, more preferably 10.0% or more, more preferably 50.0% or more, more preferably 60.0% or more, more preferably 70.0% or more, more preferably 80.0% or more, more preferably 90.0% or more, more preferably 100.0% or more, more preferably 110.0% or more, more preferably 120.0% or more, more preferably 130.0% or more, more preferably 140.0% or more, more preferably 150.0% or more, even more preferably 160.0% or more, even more preferably 170.0% or more, and particularly preferably 180.0% or more. According to this configuration, the resulting composition can provide a coating film with excellent elongation. As a result, the resulting composition can provide a coating film with excellent durability. The upper limit of the elongation of the polymer fine particles (A') is not particularly limited, and is usually 300% or less.

[0325] (Elastic modulus of polymer fine particles (A')) The elastic modulus of the polymer microparticles (A') is preferably 50.00 MPa or less, more preferably 10.00 MPa or less, more preferably 2.00 MPa or less, more preferably 1.50 MPa or less, more preferably 1.00 MPa or less, more preferably 0.50 MPa or less, more preferably 0.40 MPa or less, more preferably 0.35 MPa or less, more preferably 0.30 MPa or less, more preferably 0.28 MPa or less, more preferably 0.26 MPa or less, more preferably 0.24 MPa or less, more preferably 0.22 MPa or less, more preferably 0.20 MPa or less, more preferably 0.18 MPa or less, more preferably 0.16 MPa or less, more preferably 0.14 MPa or less, even more preferably 0.12 MPa or less, and particularly preferably 0.10 MPa or less. According to this configuration, the resulting composition may be able to provide a coating film with a low elastic modulus. As a result, the resulting composition may be able to provide a coating film with superior antifouling properties. The lower limit of the elastic modulus of the polymer fine particles (A') is not particularly limited, and is usually 0 MPa or more.

[0326] (Contact angle of polymer fine particles (A')) In this specification, the contact angle of the plate material obtained by molding the polymer microparticles (A') into a plate shape is referred to as the contact angle of the polymer microparticles (A'). The contact angle of the polymer microparticles (A') is preferably 50 degrees or more, more preferably 60 degrees or more, more preferably 65 degrees or more, more preferably 70 degrees or more, more preferably 75 degrees or more, more preferably 80 degrees or more, more preferably 85 degrees or more, more preferably 90 degrees or more, more preferably 95 degrees or more, more preferably 100 degrees or more, more preferably 105 degrees or more, more preferably 110 degrees or more, even more preferably 115 degrees or more, and particularly preferably 120 degrees or more. According to this configuration, the resulting composition can provide a coating film with a large contact angle, for example, a coating film with a contact angle of 50 degrees or more. As a result, the resulting composition can provide a coating film with excellent antifouling properties. The upper limit of the contact angle of the polymer microparticles (A') is not particularly limited, and is usually 180 degrees or less.

[0327] The methods for measuring the glass transition temperature, strength at break, elongation, modulus of elasticity and contact angle of the polymer fine particles (A') will be described in detail in the following Examples.

[0328] (2-2-5. Method for producing polymer microparticles (A')) This is the same as the first embodiment, and the above description will be used to explain only the differences.

[0329] (Method of manufacturing elastic body) Consider a case where the elastomer contains at least one selected from the group consisting of diene rubbers and (meth)acrylate rubbers. In this case, the elastomer can be produced by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the production method can be, for example, the method described in WO2005 / 028546.

[0330] Consider a case where the elastomer contains a polysiloxane rubber-based elastomer. In this case, the elastomer can be produced by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the production method can be, for example, the method described in WO2006 / 070664.

[0331] (2-3. Resin (D)) Blending the resin (D) with the binder resin (E) together with the polymer fine particles (A') has the surprising advantage of enabling the polymer fine particles (A') to be uniformly dispersed in the binder resin (E), resulting in a coating film with superior durability.

[0332] This is the same as in embodiment 1, and the above description is used to refer to it, with only the differences being explained. Resin (D) may be, for example, a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin. The thermosetting resin is the same as the thermosetting resin B in embodiment 1, and the thermoplastic resin is the same as resin (D) in embodiment 1, with the above description being used to refer to it. The description under "other" is also used to refer to it.

[0333] The resin (D) may be the same as the binder resin (E) (a resin having the same composition). In the antifouling coating composition for underwater structures, it is preferable that the binder resin (E) and the resin (D) are not phase-separated. The resin (D) is preferably a resin that is compatible with the binder resin (E).

[0334] (Physical properties of resin (D)) This is the same as in Embodiment 1, and the above description will be used to explain only the differences. In Embodiment 2, the viscosity of the resin (D) at 25°C is more preferably 100 mPa·s or more, more preferably 200 mPa·s or more, more preferably 300 mPa·s or more, more preferably 400 mPa·s or more, more preferably 500 mPa·s or more, even more preferably 750 mPa·s or more, even more preferably 1000 mPa·s or more, and particularly preferably 1500 mPa·s or more. In this configuration, the resin (D) does not impregnate the polymer microparticles (A'). Therefore, the resin (D) can prevent the polymer microparticles (A') from fusing together.

[0335] (2-4. Antifouling agent (G)) The composition may further contain an antifouling agent (G). When the composition contains a hydrolyzable resin and / or a hydration-decomposable resin as the binder resin (E), a coating film with superior antifouling properties and / or a coating film in which the antifouling properties last for a longer period of time can be provided, and therefore the composition preferably further contains an antifouling agent (G). When the composition contains a silicone-type resin as the binder resin (E), the composition may not contain an antifouling agent (G). On the other hand, a coating film obtained from a composition that does not contain an antifouling agent (G) is less susceptible to damage than a coating film obtained from a composition that does contain an antifouling agent (G). Therefore, a coating film obtained from a composition that does not contain an antifouling agent (G) has the advantage of being more durable than a coating film obtained from a composition that contains an antifouling agent (G).

[0336] The antifouling agent (G) is not particularly limited, and known antifouling agents can be used. Examples of the antifouling agent (G) include inorganic compounds, organic compounds containing metals, and organic compounds not containing metals.

[0337] Examples of the antifouling agent (G) include metal salts such as zinc oxide, cuprous oxide, 2-pyridinethiol-1-oxide zinc salt (also known as zinc pyrithione) and copper salt, pyrithione salt compounds, p-isopropylpyridinemethyldiphenylborane, pyridinetriphenylborane, tetramethylthiuram disulfide, carbamate compounds (e.g., zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 3-iodo-2-propylbutylcarbamate, bisdimethyldithiocarbamoylzincethylenebis), dithiocarbamate and manganese-2-ethylenebisdithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyldichlorophenylurea, copper rhodanide, 4,5-dichloro-2-n-octyl-3(2H)isothiazolone (also known as 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one), N-(fluorodichloromethylthio)phthalimide, N,N'-dimethyl-N'-phenyl Nyl-(N-fluorodichloromethylthio)sulfamide, Tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, Diiodomethyl paratrisulfone, Phenyl(bispyridyl)bismuth dichloride, 2-(4-thiazolyl)-benzimidazole, Triphenylboron pyridine salt, Stearylamine-triphenylboron, Laurylamine-triphenylboron, 1,1-dichloro-N-[(dimethylamino)sulfamide] N-(4-methylphenyl)-1-fluoro-N-phenylmethanesulfenamide, 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfenamide, N'-(3,4-dichlorophenyl)-N,N'-dimethylurea, N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and the like.

[0338] (2-5. Anti-blocking agent) The composition may further contain an antiblocking agent. When an antiblocking agent is blended into the binder resin (E) together with the polymer fine particles (A') and the resin (D), the polymer fine particles (A') can be uniformly dispersed in the binder resin (E). As a result, the resulting composition can provide a coating film with superior durability. When an antiblocking agent is blended into the binder resin (E) together with the polymer fine particles (A') and the resin (D), the resulting composition may contain the antiblocking agent.

[0339] The anti-blocking agent is the same as in the first embodiment, and the above description will be used to refer to it, with only the differences being explained.

[0340] (2-6. Organic Solvents) The composition may contain an organic solvent. Examples of organic solvents include hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, and alcohols. Examples of hydrocarbon organic solvents include n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, cyclohexane, methylcyclohexane, cyclopentane, toluene, xylene, benzene, ethylbenzene, decalin, white spirit, and naphtha. Examples of halogenated hydrocarbon organic solvents include methylene chloride, chloroform, tetrachloroethane, and trichloroethylene. Examples of ether organic solvents include dioxane, ethyl ether, diethyl ether, butyl diglycol, 2-butoxyethanol, tetrahydrofuran, tetrahydropyran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate (also known as PMAC). Examples of ester organic solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, methoxypropyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, n-butyl acetate, and 2-ethoxyethyl acetate. Examples of ketone organic solvents include acetone, methyl ethyl ketone, diethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone (also known as MIBK), methyl isoamyl ketone, and diacetone alcohol. Examples of the alcoholic organic solvent include methanol, ethanol, n-propanol, (iso)propanol, n-butanol, isobutanol, benzyl alcohol, ethylene glycol, and propylene glycol. A mixture of the above-mentioned alcohols and water can also be used as the organic solvent. Examples of the organic solvent include dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.These organic solvents may be used alone or in combination of two or more.

[0341] In one embodiment of the present invention, the organic solvent is preferably a hydrocarbon organic solvent, more preferably toluene, xylene, benzene, or ethylbenzene, and particularly preferably ethylbenzene.

[0342] (2-7. Other optional ingredients) The composition may contain optional components other than those described above, as needed, such as curing agents, colorants such as pigments and dyes, extender pigments, pigment dispersants, UV absorbers, the antioxidants mentioned above, heat stabilizers (antigelling agents), plasticizers, leveling agents, antifoaming agents, silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, viscosity modifiers, thixotropy-imparting agents, shrinkage-reducing agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, dispersants, thermal conductivity improvers, water binding agents, anti-sagging agents, color separation inhibitors, anti-settling agents, coating wear adjusters, surface conditioners, monobasic organic acids, camphor, and castor oil.

[0343] (2-8. Physical properties of coating film of antifouling coating composition for underwater structures) The physical properties of the coating film of the antifouling coating composition for underwater structures are described below. In this specification, the physical properties of the coating film of the antifouling coating composition for underwater structures are values ​​obtained by measuring using the methods described in the examples below.

[0344] (Coating film strength of antifouling coating composition for underwater structures) The composition preferably satisfies the following conditions: when the antifouling coating composition for underwater structures is formed into a coating film 100 μm thick, the strength of the coating film is 3.20 MPa or more. When the antifouling coating composition for underwater structures is formed into a coating film 100 μm thick, the strength of the coating film is preferably 2.10 MPa or more, more preferably 2.50 MPa or more, more preferably 3.00 MPa or more, more preferably 3.20 MPa or more, more preferably 3.50 MPa or more, more preferably 3.80 MPa or more, more preferably 4.00 MPa or more, more preferably 5.00 MPa or more, even more preferably 6.00 MPa or more, and particularly preferably 7.00 MPa or more. According to this configuration, the resulting composition can provide a coating film with excellent strength. As a result, the resulting composition can provide a coating film with even greater durability. When the antifouling coating composition for underwater structures is formed into a coating film 100 μm thick, there is no particular lower limit to the strength of the coating film, and it is typically 0 MPa or more.

[0345] (Coating film elongation of antifouling coating composition for underwater structures) The composition preferably satisfies the following conditions: when the antifouling coating composition for underwater structures is used to form a coating film 100 μm thick, the elongation of the coating film is 2.0% or more. When the antifouling coating composition for underwater structures is used to form a coating film 100 μm thick, the elongation of the coating film is preferably 1.0% or more, more preferably 1.5% or more, more preferably 2.0% or more, more preferably 2.1% or more, more preferably 2.2% or more, more preferably 2.5% or more, more preferably 3.0% or more, more preferably 3.5% or more, more preferably 4.0% or more, more preferably 4.5% or more, even more preferably 5.0% or more, and particularly preferably 5.5% or more. According to this configuration, the resulting composition can provide a coating film with excellent elongation. As a result, the resulting composition can provide a coating film with even greater durability. When the antifouling coating composition for underwater structures is made into a coating film having a thickness of 100 μm, the upper limit of the elongation of the coating film is not particularly limited, and is usually 300% or less.

[0346] It is preferable that the present composition satisfies the following conditions: when the antifouling coating composition for underwater structures is formed into a coating film having a thickness of 100 μm, (a) the strength of the coating film is 3.20 MPa or more, and (b) the elongation of the coating film is 2.0% or more.

[0347] (Elastic modulus of coating film of antifouling coating composition for underwater structures) The composition preferably satisfies the following condition: when the antifouling coating composition for underwater structures is formed into a coating film 100 μm thick, the elastic modulus of the coating film is 1.50 GPa or less. When the antifouling coating composition for underwater structures is formed into a coating film 100 μm thick, the elastic modulus of the coating film is preferably 50.00 GPa or less, more preferably 10.00 GPa or less, more preferably 5.00 GPa or less, more preferably 2.00 GPa or less, more preferably less than 1.65 GPa, more preferably 1.60 GPa or less, more preferably 1.55 GPa or less, more preferably 1.50 GPa or less, more preferably 1.45 GPa or less, more preferably 1.40 GPa or less, more preferably 1.35 GPa or less, even more preferably 1.30 GPa or less, and particularly preferably 1.25 GPa or less. This configuration allows the resulting composition to provide a coating film with a low elastic modulus. As a result, the obtained composition can provide a coating film with excellent antifouling properties. When the antifouling coating composition for underwater structures is made into a coating film with a thickness of 100 μm, the lower limit of the elastic modulus of the coating film is not particularly limited, and is usually 0 MPa or more.

[0348] (Contact angle on the surface of the coating film of the antifouling coating composition for underwater structures) The composition preferably satisfies the following condition: when the antifouling coating composition for underwater structures is formed into a coating film 100 μm thick, the contact angle on the surface of the coating film is 102 degrees or more. When the antifouling coating composition for underwater structures is formed into a coating film 100 μm thick, the contact angle on the surface of the coating film is preferably 50 degrees or more, more preferably 60 degrees or more, more preferably 70 degrees or more, more preferably 80 degrees or more, more preferably 90 degrees or more, more preferably 100 degrees or more, more preferably 101 degrees or more, more preferably 102 degrees or more, more preferably 103 degrees or more, more preferably 104 degrees or more, even more preferably 105 degrees or more, even more preferably 110 degrees or more, and particularly preferably 120 degrees or more. According to this configuration, the resulting composition can provide a coating film with a large contact angle. As a result, the resulting composition can provide a coating film with even better antifouling properties. When the antifouling coating composition for underwater structures is formed into a coating film having a thickness of 100 μm, the upper limit of the contact angle on the surface of the coating film is not particularly limited, and is usually 180 degrees or less.

[0349] 3. Method for producing antifouling coating composition for underwater structures A method for producing an antifouling coating composition for underwater structures according to one embodiment of the present invention comprises a powder preparation step of obtaining a powder containing polymer fine particles (A') and a resin (D), and a mixing step of mixing the powder with a binder resin (E). The polymer fine particles (A') comprise a rubber-containing graft copolymer having an elastomer and a graft moiety grafted to the elastomer. The elastomer comprises one or more rubbers selected from the group consisting of diene rubbers, (meth)acrylate rubbers, and organosiloxane rubbers. The graft moiety comprises a polymer containing, as a structural unit, a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. The glass transition temperature of the polymer fine particles (A') is 80°C or lower. The resin (D) is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C. When the total of the polymer fine particles (A') and the resin (D) is taken as 100% by weight, the polymer fine particles (A') account for 50 to 99% by weight, and the resin (D) accounts for 1 to 50% by weight. The "method for producing an antifouling coating composition for underwater structures according to one embodiment of the present invention" may also be referred to as the "method for producing the present composition" or the "present production method."

[0350] Because the present production method has the above-described configuration, it can provide an antifouling coating composition for underwater structures that can provide a coating film that is excellent in durability, specifically, strength and elongation. Furthermore, because the present production method has the above-described configuration, the composition obtained by the present production method can provide a coating film that is excellent in contact angle and / or low in elastic modulus. As a result, the composition obtained by the present production method has the advantage of being able to provide a coating film that is excellent in antifouling properties.

[0351] Each step of this production method will be described in detail below, but matters other than those described below (e.g., various components and their amounts added) are not particularly limited, and the explanation in the above section [2. Antifouling coating composition for underwater structures] will be used as appropriate.

[0352] (3-1. Powder and granular material preparation process) In the powder / granule preparation step, the method for obtaining powder / granules containing the polymer fine particles (A') and the resin (D) is not particularly limited, and known methods can be used.

[0353] As described above, the polymer microparticles (A') can be obtained as an aqueous latex by emulsion polymerization, etc. In the powder / granule preparation step, for example, (a1) the resin (D) is added to the aqueous latex containing the polymer microparticles (A'), (a2) the polymer microparticles (A') and the resin (D) in the obtained aqueous latex are coagulated together, (a3) ​​the obtained coagulates containing the polymer microparticles (A') and the resin (D) are recovered, and (a4) the recovered coagulates are dried, thereby obtaining a powder / granule containing the polymer microparticles (A') and the resin (D).

[0354] The method for adding the resin (D) to the aqueous latex containing the polymer microparticles (A') is not particularly limited. For example, (a) a method of directly adding the resin (D) to the aqueous latex, (b) a method of separately preparing an aqueous latex containing the resin (D) and then adding the aqueous latex containing the resin (D) to the aqueous latex containing the polymer microparticles (A'), and (c) a method of separately preparing a solution containing the resin (D) and then adding the solution containing the resin (D) to the aqueous latex containing the polymer microparticles (A'). As a method for adding the resin (D) to the aqueous latex, a method of separately preparing an aqueous latex containing the resin (D) and then adding the aqueous latex containing the resin (D) to the aqueous latex containing the polymer microparticles (A') is preferred.

[0355] The powder / granule preparation step may be implemented as follows: (b1) polymerizing resin (D) in an aqueous latex containing polymer microparticles (A'), (b2) agglomerating the polymer microparticles (A') and resin (D) in the resulting aqueous latex, (b3) recovering the resulting agglomerates containing polymer microparticles (A') and resin (D), and (b4) drying the recovered agglomerates to obtain a powder / granule containing polymer microparticles (A') and resin (D).

[0356] The powder preparation step may include a step of obtaining an aggregate containing polymer fine particles (A') and resin (D). The method for agglomerating the polymer fine particles (A') and resin (D) in the aqueous latex is not particularly limited. Examples include known methods such as salting out using a salt, using a solvent, and spraying the aqueous latex. Here, when the polymer fine particles (A') and resin (D) in the aqueous latex are agglomerated together, the mixture containing the aggregate containing the polymer fine particles (A') and resin (D) and the aqueous solvent is also referred to as a slurry.

[0357] In order to improve the blocking resistance and to disperse the polymer fine particles (A') well in the binder resin (E) in the resulting composition, it is preferable that the aggregation of the polymer fine particles (A') and the resin (D) in the aqueous latex is carried out in the presence of an antiblocking agent.

[0358] The method for recovering the aggregates containing the polymer fine particles (A') and the resin (D) is not particularly limited as long as it can separate the aggregates from the aqueous solvent of the slurry, and any known method can be used. Examples of the method for recovering the aggregates containing the polymer fine particles (A') and the resin (D) include filtering the slurry and centrifugal dehydration of the slurry.

[0359] The method for drying the aggregate is not particularly limited, and any known method such as using a dryer can be used.

[0360] The powder / granule preparation step may be implemented as follows: (c1) using an aqueous latex containing only polymer microparticles (A'), the polymer microparticles (A') in the aqueous latex are aggregated, (c2) the obtained aggregates of polymer microparticles (A') are collected, (c3) the collected aggregates of polymer microparticles (A') are mixed with resin (D), and (c4) the obtained mixture is dried to obtain a powder containing polymer microparticles (A') and resin (D).

[0361] The method for recovering the aggregates of polymer microparticles (A') can be the same as the method for recovering the aggregates containing polymer microparticles (A') and resin (D) described above. The method for mixing the recovered aggregates of polymer microparticles (A') with resin (D) is not particularly limited. For example, mechanical mixing methods using a planetary mixer, a planetary mixer, a disperser, etc. can be used.

[0362] (3-1-1. Physical properties of powders and granules) The physical properties of the powder containing the polymer fine particles (A') and the resin (D) obtained in the powder preparation step will be described. The physical properties of the powder can also be rephrased as the physical properties of the mixture of the polymer fine particles (A') and the resin (D).

[0363] (Resin (D) domain in TEM image) From the viewpoint of preventing fusion of the polymer fine particles (A') in the powder or granule, it is preferable that the amount of resin (D) in the powder or granule having a major axis 1.5 times or more the average particle diameter of the primary particles of the polymer fine particles (A') is small. Specifically, when the powder or granule is subjected to transmission electron microscopy (TEM) and a TEM image is obtained, the number of domains in which the major axis of the resin (D) is 1.5 times or more the average particle diameter of the polymer fine particles (A') in the TEM image is preferably 5 or less, more preferably 3 or less, even more preferably 1 or less, and most preferably 0 or less.

[0364] Known methods can be used for the transmission electron microscope analysis. For example, powder or granules are frozen, then sliced ​​using an ultramicrotome to prepare thin slice samples with a thickness of about 100 nm. The thin slices are then stained with osmium (OsO4) and subjected to a transmission electron microscope (TEM). The major axis of the resin (D) refers to the maximum length (the length of the longest straight line connecting two points on the periphery) in a TEM image. The average particle diameter of the primary particles of the polymer microparticles (A') can be calculated, for example, from the average diameter (area-equivalent circle diameter) of circles equal to the projected area of ​​30 randomly selected polymer microparticles (A') in a TEM image.

[0365] (Glass transition temperature of powder) The glass transition temperature of the powder or granule 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, more preferably 20°C or lower, more preferably 10°C or lower, more preferably 0°C or lower, more preferably -20°C or lower, more preferably -40°C or lower, more preferably -50°C or lower, more preferably -60°C or lower, more preferably -70°C or lower, more preferably -80°C or lower, more preferably -90°C or lower, more preferably -100°C or lower, more preferably -110°C or lower, even more preferably -120°C or lower, and particularly preferably -125°C or lower. According to this configuration, the powder or granule, i.e., the mixture of polymer fine particles (A') and resin (D), has the advantages of low elastic modulus and high elongation. As a result, the resulting composition can provide a coating film with excellent toughness, a low elastic modulus, and / or excellent elongation.

[0366] The Tg of the granular material, i.e., the mixture of polymer fine particles (A') and resin (D), can be determined by the Tg of the polymer fine particles (A') and the type of resin (D), etc. In other words, the Tg of the granular material, i.e., the mixture of polymer fine particles (A') and resin (D) can be adjusted by changing the Tg of the polymer fine particles (A') and the type of resin (D).

[0367] (Breaking strength of powder and granular materials) The strength at break (MPa) of the powder or granule is preferably 50.0 MPa or less, more preferably 25.0 MPa or less, more preferably 15.0 MPa or less, more preferably 10.0 MPa or less, more preferably 9.0 MPa or less, more preferably 8.0 MPa or less, more preferably 7.0 MPa or less, more preferably 6.0 MPa or less, even more preferably 5.0 MPa or less, and particularly preferably 4.0 MPa or less. The strength at break (MPa) of the powder or granule is preferably 1.0 MPa or more, more preferably 2.0 MPa or more, more preferably 3.0 MPa or more, more preferably 4.0 MPa or more, more preferably 5.0 MPa or more, more preferably 6.0 MPa or more, more preferably 7.0 MPa or more, even more preferably 8.0 MPa or more, and particularly preferably 9.0 MPa or more.

[0368] (Elongation of powder and granular material) The elongation (%) of the granular material is preferably 1.0% or more, more preferably 5.0% or more, more preferably 10.0% or more, more preferably 50.0% or more, more preferably 75.0% or more, more preferably 100.0% or more, even more preferably 110.0% or more, even more preferably 120.0% or more, and particularly preferably 125.0% or more. According to this configuration, the resulting composition can provide a coating film with excellent elongation. As a result, the resulting composition can provide a coating film with even greater durability. The upper limit of the elongation of the granular material, i.e., the mixture of polymer fine particles (A') and resin (D), is not particularly limited, and is typically 300% or less.

[0369] (Elastic modulus of powder and granular material) The modulus of elasticity of the powder or granule is preferably 50.00 MPa or less, more preferably 10.00 MPa or less, more preferably 2.00 MPa or less, more preferably 1.00 MPa or less, more preferably 0.50 MPa or less, more preferably 0.40 MPa or less, more preferably 0.30 MPa or less, more preferably 0.25 MPa or less, more preferably 0.20 MPa or less, even more preferably 0.15 MPa or less, and particularly preferably 0.10 MPa or less. According to this configuration, the resulting composition may be able to provide a coating film with a low modulus of elasticity. As a result, the resulting composition may be able to provide a coating film with superior antifouling properties. The lower limit of the modulus of elasticity of the powder or granule, i.e., the mixture of polymer fine particles (A') and resin (D), is not particularly limited, and is usually 0 MPa or more.

[0370] (Contact angle of powder particles) The contact angle of the powder or granule is preferably 50° or more, more preferably 60° or more, more preferably 65° or more, more preferably 70° or more, more preferably 72° or more, more preferably 75° or more, more preferably 80° or more, more preferably 85° or more, more preferably 90° or more, more preferably 95° or more, more preferably 100° or more, more preferably 105° or more, more preferably 110° or more, even more preferably 115° or more, and particularly preferably 120° or more. According to this configuration, the resulting composition can provide a coating film with a large contact angle, for example, a coating film with a contact angle of 50° or more. As a result, the resulting composition can provide a coating film with excellent antifouling properties. The upper limit of the contact angle of the powder or granule, i.e., the mixture of polymer fine particles (A') and resin (D), is not particularly limited, and is typically 180° or less.

[0371] The methods for measuring the glass transition temperature, strength at break, elongation, modulus of elasticity and contact angle of the powder or granule, that is, the mixture of polymer fine particles (A') and resin (D), will be described in detail in the examples below.

[0372] The powder or granular material has excellent blocking resistance. In this specification, the blocking resistance of the powder or granular material can be evaluated by the force required to break the block of the powder or granular material. It is preferable that the force required to break the block of the powder or granular material is 30,000 Pa or less. Here, the block is obtained by placing a 6.3 kg weight on 30 g of the powder or granular material contained in a cylindrical container with a diameter of 50 mm, and leaving the powder or granular material to stand at 60°C for 2 hours, and then applying a load of 6.3 kg to the powder or granular material. The force (the force required to break the block of the powder or granular material) is a value obtained by measurement using a rheometer.

[0373] (3-2. Mixing process) In the mixing step of mixing the binder resin (E) with the powder or granules, the method for mixing the binder resin (E) with the powder or granules is not particularly limited, and examples thereof include mechanical mixing methods using a planetary mixer, a planetary mixer, a disperser, etc.

[0374] 4. Method of using antifouling coating composition for underwater structures The method for using the present composition can also be said to be a method for applying a coating film (antifouling coating film) using the composition. The method for using the present composition includes a step of applying the antifouling coating composition for underwater structures to an underwater structure. According to this method, a coating film made of the composition can be formed on the surface or inner surface of the underwater structure.

[0375] The method for applying the composition in the application step is not particularly limited, and any known method can be used, such as casting, dipping, spraying, brush coating, roller coating, dip coating, electrostatic coating, and electrodeposition coating.

[0376] The coating step may use a coating robot. The coating robot may be used to extrude the composition onto the underwater structure in the form of a bead, monofilament, or swirl. The composition may also be applied onto the underwater structure using a jet spray method or a streaming method.

[0377] The composition applied to the underwater structure may be dried. As described above, by applying the composition to the underwater structure and optionally drying the composition, a coating film having antifouling properties can be formed on the underwater structure.

[0378] [5. Coating] A coating film formed by the method described in the above section [4. Method for using an antifouling coating composition for underwater structures] is also one embodiment of the present invention. That is, a coating film according to one embodiment of the present invention is a coating film made from the antifouling coating composition for underwater structures described in the above section [2. Antifouling coating composition for underwater structures]. Furthermore, a coating film according to another embodiment of the present invention is a coating film made from the antifouling coating composition for underwater structures produced by the production method described in the above section [3. Method for producing an antifouling coating composition for underwater structures].

[0379] The coating film according to one embodiment of the present invention has the above-described structure, which is advantageous in that it has excellent durability. Furthermore, the coating film according to one embodiment of the present invention has the above-described structure, which is advantageous in that it has excellent elongation. Furthermore, the coating film according to one embodiment of the present invention has the above-described structure, which is advantageous in that it has a large contact angle, which results in excellent antifouling properties.

[0380] A coating film according to one embodiment of the present invention comprises a binder resin (E), polymer fine particles (A'), and a resin (D). The polymer fine particles (A') comprise a rubber-containing graft copolymer having (a) an elastomer and (b) a graft moiety grafted to the elastomer and comprising a polymer containing, as a structural unit, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. The polymer fine particles (A') account for 50 to 99% by weight, and the resin (D) accounts for 1 to 50% by weight, assuming that the total of the polymer fine particles (A') and the resin (D) is 100% by weight. The glass transition temperature of the mixture of the polymer fine particles (A') and the resin (D) is 80°C or lower. The coating film according to one embodiment of the present invention may also optionally comprise an antifouling agent (G).

[0381] (5-1. Physical properties of coating film) The respective aspects of the strength (MPa), elongation (%) and modulus of elasticity (GPa) of the coating film include preferred aspects, and the respective aspects of the strength (MPa), elongation (%) and modulus of elasticity (GPa) of the coating film when the antifouling coating composition for underwater structures is formed into a coating film with a thickness of 100 μm, as described above, can be used as appropriate. The contact angle (degrees) of the coating film surface includes preferred aspects, and the respective aspects of the contact angle (degrees) of the coating film surface when the antifouling coating composition for underwater structures is formed into a coating film with a thickness of 100 μm, as described above, can be used as appropriate.

[0382] [6.Applications] The composition can be suitably used as an antifouling paint for preventing fouling on the surfaces or interior surfaces of various underwater structures, such as ships, aquaculture and fishing materials (e.g., ropes, fishing nets, fishing gear, floats, buoys, tetrapods, etc.), oil fences, water supply and drainage outlets of thermal or nuclear power plants, piping for cooling water pipes and seawater utilization equipment, undersea tunnels, undersea bases, megafloats, port facilities, various marine civil engineering works such as canals and waterways, industrial water systems, bridges, buoys, etc.

[0383] (1) A powder containing polymer fine particles (A) for incorporation into a thermosetting resin, the polymer fine particles (A) comprising a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer, the elastomer comprising a structural unit derived from butadiene, the graft portion comprising a polymer comprising a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer, the volume-average particle diameter of the polymer fine particles (A) being 90 nm or more, and the weight-average molecular weight of the polymer in the graft portion being 200,000 or less.

[0384] (2) The powder or granule for thermosetting resin according to (1), further comprising a resin (D), which is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C, and which comprises 50 to 99% by weight of the polymer fine particles (A) and 1 to 50% by weight of the resin (D), when the total of the polymer fine particles (A) and the resin (D) is 100% by weight.

[0385] (3) The powder or granule for thermosetting resin according to (1) or (2), wherein the polymer microparticles (A) further contain, as a structural unit, a free polymer (FP) consisting of a polymer containing a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers, and the content of the free polymer (FP) is 8% by weight or less.

[0386] (4) The powder or granule for a thermosetting resin according to any one of (1) to (3), wherein the graft ratio of the graft portion is 80% or more.

[0387] (5) The particulate material for a thermosetting resin according to any one of (1) to (4), wherein the elastic body accounts for 70% by weight or more of the polymer fine particles (A).

[0388] (6) The powder or granule for a thermosetting resin according to any one of (1) to (5), wherein the graft portion contains a polymer containing, as a constituent unit, a constituent unit derived from a (meth)acrylate monomer.

[0389] (7) The powder or granule for a thermosetting resin according to (3), wherein the free polymer (FP) comprises a polymer containing, as a constituent unit, a constituent unit derived from a (meth)acrylate monomer.

[0390] (8) The powder or granular material according to any one of (1) to (7), wherein the force required to break the block of the powder or granular material is 30,000 Pa or less: Here, the block is obtained by placing a 6.3 kg weight on 30 g of the powder or granular material contained in a cylindrical container with a diameter of 50 mm, and leaving the powder or granular material to stand at 60°C for 2 hours, and applying a load of 6.3 kg to the powder or granular material, and the force is a value obtained by measurement using a rheometer.

[0391] (9) The powder or granule according to any one of (1) to (8), wherein the powder or granule has a volume average particle diameter (Mv) of 30 μm to 500 μm.

[0392] (10) A resin composition containing the powder or granule according to any one of (1) to (9) and a thermosetting resin (B).

[0393] (11) A cured product obtained by curing the resin composition according to (10).

[0394] (12) A thermosetting structural adhesive comprising the powder or granule according to any one of (1) to (9), a thermosetting resin (B), and an inorganic filler (C).

[0395] Furthermore, one embodiment of the present invention includes the following configuration.

[0396] [1] A binder resin (E), polymer fine particles (A'), and a resin (D), wherein the polymer fine particles (A') contain a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer, the elastomer containing at least one rubber selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber, and the graft portion contains, as a constituent unit, at least one rubber selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer. an antifouling coating composition for underwater structures, the antifouling coating composition comprising a polymer containing structural units derived from one or more monomers selected from the group consisting of methyl methyl acrylate and methyl acrylate; a polymer fine particle (A') having a glass transition temperature of 80°C or lower; and a resin (D) which is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C, the polymer fine particle (A') accounting for 50 to 99% by weight and the resin (D) accounting for 1 to 50% by weight, when the total of the polymer fine particle (A') and the resin (D) is taken as 100% by weight.

[0397] [2] The antifouling coating composition for underwater structures according to [1], further comprising an antifouling agent (G).

[0398] [3] The antifouling coating composition for underwater structures according to [1] or [2], wherein the elastomer comprises a polysiloxane rubber-based elastomer.

[0399] [4] The antifouling coating composition for underwater structures according to any one of [1] to [3], wherein the polymer fine particles (A') have an elastic modulus of 2.00 MPa or less.

[0400] [5] The antifouling coating composition for underwater structures according to any one of [1] to [4], wherein the polymer fine particles (A') have an elongation of 10.0% or more.

[0401] [6] The antifouling coating composition for underwater structures according to any one of [1] to [5], wherein the polymer fine particles (A') have a contact angle of 50 degrees or more.

[0402] [7] An antifouling coating composition for underwater structures according to any one of [1] to [6], which satisfies the following conditions: when the antifouling coating composition for underwater structures is formed into a coating film having a thickness of 100 μm, (a) the strength of the coating film is 3.20 MPa or more, and (b) the elongation of the coating film is 2.0% or more.

[0403] [8] The antifouling coating composition for underwater structures according to [7], which satisfies the following condition: when the antifouling coating composition for underwater structures is formed into a coating film having a thickness of 100 μm, the contact angle on the surface of the coating film is 102 degrees or more.

[0404] [9] An antifouling coating composition for underwater structures according to [7] or [8], which satisfies the following condition: when the antifouling coating composition for underwater structures is formed into a coating film having a thickness of 100 μm, the modulus of elasticity of the coating film is 1.50 GPa or less.

[0405]

[10] A coating film comprising the antifouling coating composition for underwater structures according to any one of [1] to [9].

[0406]

[11] A method for producing a powder or granule comprising: a powder or granule preparation step of obtaining a powder or granule containing polymer fine particles (A') and a resin (D); and a mixing step of mixing a binder resin (E) with the powder or granule, wherein the polymer fine particles (A') comprise a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer, the elastomer comprising at least one rubber selected from the group consisting of a diene rubber, a (meth)acrylate rubber, and an organosiloxane rubber, and the graft portion comprises, as constituent units, an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate. A method for producing an antifouling coating composition for underwater structures, the antifouling coating composition comprising: a polymer containing structural units derived from one or more monomers selected from the group consisting of acrylate monomers; the polymer microparticles (A') have a glass transition temperature of 80°C or lower; the resin (D) is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C; and the polymer microparticles (A') account for 50 to 99% by weight and the resin (D) accounts for 1 to 50% by weight, when the total of the polymer microparticles (A') and the resin (D) is 100% by weight.

[0407]

[12] The antifouling coating composition for underwater structures according to

[11] , wherein the modulus of elasticity of the powder or granule is 2.00 MPa or less.

[0408]

[13] The antifouling coating composition for underwater structures according to

[11] or

[12] , wherein the elongation of the powder or granule is 10.0% or more.

[0409]

[14] The antifouling coating composition for underwater structures according to any one of

[11] to

[13] , wherein the contact angle of the powder or granule is 50 degrees or more.

[0410]

[15] A method for producing an antifouling coating composition for underwater structures according to any one of

[11] to

[14] , wherein the force required to break the powder or granule block is 30,000 Pa or less: the block is obtained by placing a 6.3 kg weight on 30 g of the powder or granule contained in a cylindrical container with a diameter of 50 mm, and leaving the powder or granule to stand at 60°C for 2 hours, thereby applying a load of 6.3 kg to the powder or granule, and the force is a value obtained by measurement using a rheometer. [Example]

[0411] 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 practiced with appropriate modifications within the scope of the above-mentioned or below-mentioned purpose, and all such modifications are included within the technical scope of the present invention. In the following examples and comparative examples, "parts" and "%" mean parts by weight or % by weight.

[0412] [Example A] <Evaluation method> First, the evaluation methods for the resin compositions produced in the examples and comparative examples will be described below.

[0413] (Measurement of volume average particle size) The volume average particle size (Mv) of the elastomer or polymer microparticles (A) dispersed in the aqueous latex was measured using a Nanotrac Wave II-EX150 (Microtrackbell Corporation). The aqueous latex was diluted with deionized water and used as the measurement sample. The measurement was performed by inputting the refractive index of water and the elastomer or polymer microparticles (A) obtained in each production example, measuring for 120 seconds, and adjusting the sample concentration so that the loading index was within the range of 1 to 10.

[0414] The volume average particle diameter (Mv) of the powder or granule was measured using a laser diffraction particle size distribution measuring device, Microtrac MT3000II (manufactured by Microtrac Bell Co., Ltd.).

[0415] (Dispersibility of polymer fine particles (A) in resin composition) The resin composition was placed on a grind meter (grind gauge), and the polymer fine particles (A) on the gauge were scraped off with a metal scraper, and the dispersion state was visually confirmed. The scale was read at the position where 5 to 10 granular marks caused by the scraper movement appeared within a 3 mm wide band. This dispersibility evaluation method can also evaluate the level of foreign matter.

[0416] (Amount of free polymer (FP) contained in polymer microparticles (A)) 2 g of polymer microparticle (A) powder was dissolved in 50 mL of methyl ethyl ketone. The resulting MEK solution was then separated into a MEK-soluble component (MEK solubles) and a MEK-insoluble component (MEK insolubles). Specifically, the resulting MEK solution was centrifuged at 30,000 rpm for 1 hour using a centrifuge (Hitachi Koki Co., Ltd., CP60E), separating the solution into MEK-solubles and MEK insolubles. Three sets of centrifugation were performed. Next, 20 mL of the concentrated MEK-solubles were mixed with 200 mL of methanol, and an aqueous calcium chloride solution prepared by dissolving 0.01 g of calcium chloride in water was added. The mixture was then stirred for 1 hour. The mixture was then separated into a methanol-soluble component and a methanol-insoluble component, and the amount of the methanol-insoluble component was determined as the amount of free polymer (FP).

[0417] (Weight-average molecular weight of free polymer (FP) contained in polymer fine particles (A)) 20 mg of the free polymer obtained above was dissolved in 10 ml of THF, and the weight average molecular weight was measured using HLC-82201 (manufactured by Tosoh Corporation).

[0418] (Compound viscosity of resin composition) The viscosity of the resin composition was measured using a digital viscometer DV-II+Pro manufactured by BROOKFIELD at a measurement temperature of 50°C, while changing the shear rate and spindle as necessary.

[0419] (Blocking resistance of mixture (powder) of polymer fine particles and resin (D)) The powder and granules obtained in each production example were used to prepare a block of powder and granules by carrying out the following steps (1) to (3) in order: (1) 30 g of powder and granules were placed in a cylindrical container with a diameter of 50 mm; (2) a 6.3 kg weight was placed on the powder and granules in the container, and the powder and granules were allowed to stand at 60°C for 2 hours, thereby applying a load of 6.3 kg to the powder and granules; (3) the resulting block was removed from the container. Next, the force required to break the resulting block of powder and granules was measured using a rheometer. Based on the results obtained, blocking resistance was evaluated according to the following criteria. Pass: The force required to break the powder block is 30,000 Pa or less. Fail: The force required to break the block of powder exceeds 30,000 Pa.

[0420] <1. Polymerization of Elastic Materials> (Production Example 1-1: Preparation of polybutadiene rubber latex (R-1)) A pressure-resistant polymerization vessel was charged with 200 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 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. Next, while stirring the charged raw materials, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen to thoroughly remove oxygen from the vessel. Then, 100 parts by weight of butadiene (Bd) was charged into the vessel, and the temperature inside the vessel was raised to 45°C. Next, 0.03 parts by weight of paramenthane hydroperoxide (PHP) was charged into the vessel, followed by 0.10 parts by weight of sodium formaldehyde sulfoxylate (SFS), to initiate polymerization. Fifteen hours after the start of polymerization, the polymerization was terminated by removing the remaining monomers under reduced pressure. During the polymerization, PHP, EDTA, and ferrous sulfate heptahydrate were added to the pressure polymerization reactor in desired amounts and at desired times. This polymerization yielded an aqueous latex (R-1) containing an elastomer whose main component was polybutadiene rubber. The volume average particle size of the elastomer contained in the resulting aqueous latex was 70 nm.

[0421] (Production Example 1-2: Preparation of polybutadiene rubber latex (R-2)) A pressure-resistant polymerization vessel was charged with 7 parts by weight (solids) of the polybutadiene rubber latex (R-1) obtained above, 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. Next, while stirring the charged raw materials, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen to thoroughly remove oxygen from inside the vessel. Then, 93 parts by weight of Bd was charged into the pressure-resistant polymerization vessel, and the temperature inside the vessel was raised to 45°C. Next, 0.02 parts by weight of PHP was charged into the pressure-resistant polymerization vessel, followed by 0.10 parts by weight of SFS, to initiate polymerization. Thirty hours after the start of polymerization, the vessel was volatilized under reduced pressure to remove the remaining monomers not used in the polymerization, thereby terminating the polymerization. During the polymerization, PHP, EDTA, ferrous sulfate heptahydrate, and SDBS were added to the pressure polymerization reactor in desired amounts and at desired times. This polymerization yielded an aqueous latex (R-2) containing an elastomer whose main component was polybutadiene rubber. The volume-average particle size of the elastomer contained in the resulting aqueous latex was 195 nm.

[0422] (Production Example 1-3: Preparation of polystyrene-butadiene rubber latex (R-3)) A pressure-resistant polymerization vessel was charged with 160 parts by weight of deionized water, 0.002 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, 0.029 parts by weight of polyoxyethylene lauryl ether phosphate, and 0.003 parts by weight of sodium hydroxide. In the presence of sodium hydroxide, the polyoxyethylene lauryl ether phosphate became sodium polyoxyethylene lauryl ether phosphate, which functioned as an emulsifier. Next, while stirring the charged raw materials, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen to thoroughly remove oxygen from the vessel. Then, 76.5 parts by weight of Bd and 23.5 parts by weight of styrene (St) were charged into the pressure-resistant polymerization vessel, and the temperature inside the vessel was raised to 45°C. Then, 0.03 parts by weight of PHP was charged into the pressure-resistant polymerization vessel, followed by 0.05 parts by weight of SFS, to initiate polymerization. Twenty hours after the start of polymerization, the polymerization was terminated by removing the remaining monomers that were not used in the polymerization by volatilization under reduced pressure. During the polymerization, PHP, polyoxyethylene lauryl ether phosphate, and sodium hydroxide were each added to the pressure polymerization reactor in desired amounts and at desired times. This polymerization yielded an aqueous latex (R-3) containing an elastomer composed primarily of polystyrene-butadiene rubber. The volume average particle diameter of the elastomer contained in the resulting aqueous latex was 192 nm.

[0423] (Production Example 1-4: Preparation of polystyrene-polybutadiene rubber latex (R-4)) A pressure-resistant polymerization vessel was charged with 200 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 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. Next, while stirring the charged raw materials, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen to thoroughly remove oxygen from the vessel. Then, 76.5 parts by weight of Bd and 23.5 parts by weight of styrene (St) were charged into the vessel, and the temperature inside the vessel was raised to 45°C. Next, 0.03 parts by weight of paramenthane hydroperoxide (PHP) was charged into the vessel, followed by 0.10 parts by weight of sodium formaldehyde sulfoxylate (SFS), to initiate polymerization. Thirteen hours after the start of polymerization, the polymerization was terminated by removing the remaining monomers under reduced pressure. During the polymerization, PHP, EDTA, and ferrous sulfate heptahydrate were added to the pressure polymerization reactor in desired amounts and at desired times. This polymerization yielded an aqueous latex (R-4) containing an elastomer whose main component was polybutadiene rubber. The volume average particle size of the elastomer contained in the resulting aqueous latex was 70 nm.

[0424] (Production Example 1-5: Preparation of polystyrene-butadiene rubber latex (R-5)) A pressure-resistant polymerization vessel was charged with 160 parts by weight of deionized water, 0.002 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, 0.02 parts by weight of polyoxyethylene lauryl ether phosphate, and 0.003 parts by weight of sodium hydroxide. In the presence of sodium hydroxide, the polyoxyethylene lauryl ether phosphate became polyoxyethylene lauryl ether sodium phosphate, which functioned as an emulsifier. Next, while stirring the charged raw materials, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen to thoroughly remove oxygen from the vessel. Then, 76.5 parts by weight of Bd and 23.5 parts by weight of styrene (St) were charged into the pressure-resistant polymerization vessel, and the temperature inside the vessel was raised to 45°C. Then, 0.03 parts by weight of PHP was charged into the pressure-resistant polymerization vessel, followed by 0.05 parts by weight of SFS, to initiate polymerization. Twenty-five hours after the start of polymerization, the polymerization was terminated by devolatilization under reduced pressure to remove the remaining monomers that were not used in the polymerization. During the polymerization, PHP, polyoxyethylene lauryl ether phosphate, and sodium hydroxide were each added to the pressure polymerization reactor in desired amounts and at desired times. This polymerization yielded an aqueous latex (R-5) containing an elastomer primarily composed of polystyrene-butadiene rubber. The volume average particle diameter of the elastomer contained in the resulting aqueous latex was 220 nm.

[0425] (Production Example 1-6: Preparation of polystyrene-butadiene rubber latex (R-6)) A pressure-resistant polymerization vessel was charged with 160 parts by weight of deionized water, 0.002 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, 0.06 parts by weight of polyoxyethylene lauryl ether phosphate, and 0.003 parts by weight of sodium hydroxide. In the presence of sodium hydroxide, the polyoxyethylene lauryl ether phosphate became polyoxyethylene lauryl ether sodium phosphate, which functioned as an emulsifier. Next, while stirring the charged raw materials, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen to thoroughly remove oxygen from the vessel. Then, 76.5 parts by weight of Bd and 23.5 parts by weight of styrene (St) were charged into the pressure-resistant polymerization vessel, and the temperature inside the vessel was raised to 45°C. Then, 0.03 parts by weight of PHP was charged into the pressure-resistant polymerization vessel, followed by 0.05 parts by weight of SFS, to initiate polymerization. Twenty-five hours after the start of polymerization, the polymerization was terminated by devolatilization under reduced pressure to remove the remaining monomers that were not used in the polymerization. During the polymerization, PHP, polyoxyethylene lauryl ether phosphate, and sodium hydroxide were each added to the pressure polymerization reactor in desired amounts and at desired times. This polymerization yielded an aqueous latex (R-6) containing an elastomer primarily composed of polystyrene-butadiene rubber. The volume average particle size of the elastomer contained in the resulting aqueous latex was 160 nm.

[0426] (Production Example 1-7: Preparation of polystyrene-butadiene rubber latex (R-7)) A pressure-resistant polymerization vessel was charged with 160 parts by weight of deionized water, 0.002 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, 0.08 parts by weight of polyoxyethylene lauryl ether phosphate, and 0.003 parts by weight of sodium hydroxide. In the presence of sodium hydroxide, the polyoxyethylene lauryl ether phosphate became polyoxyethylene lauryl ether sodium phosphate, which functioned as an emulsifier. Next, while stirring the charged raw materials, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen to thoroughly remove oxygen from the vessel. Then, 76.5 parts by weight of Bd and 23.5 parts by weight of styrene (St) were charged into the pressure-resistant polymerization vessel, and the temperature inside the vessel was raised to 45°C. Then, 0.03 parts by weight of PHP was charged into the pressure-resistant polymerization vessel, followed by 0.05 parts by weight of SFS, to initiate polymerization. Twenty-five hours after the start of polymerization, the polymerization was terminated by devolatilization under reduced pressure to remove the remaining monomers that were not used in the polymerization. During the polymerization, PHP, polyoxyethylene lauryl ether phosphate, and sodium hydroxide were each added to the pressure polymerization reactor in desired amounts and at desired times. This polymerization yielded an aqueous latex (R-7) containing an elastomer primarily composed of polystyrene-butadiene rubber. The volume average particle size of the elastomer contained in the resulting aqueous latex was 140 nm.

[0427] <2. Preparation of polymer microparticles (A) (polymerization of grafted portion)> (Production Example 2-1: Preparation of polymer particle latex (L-1)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-3) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-1) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-1) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-1) was 30%.

[0428] (Production Example 2-2: Preparation of polymer particle latex (L-2)) A glass reactor was charged with 172 parts by weight of the polybutadiene rubber latex (R-2) (containing 60 parts by weight of an elastomer primarily composed of polybutadiene rubber) and 128 parts by weight of deionized water. The reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-2) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-2) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-2) was 30%.

[0429] (Production Example 2-3: Preparation of polymer particle latex (L-3)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-3) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 40°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-3) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-3) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-3) was 30%.

[0430] (Production Example 2-4: Preparation of polymer particle latex (L-4)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-3) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of cumene hydroperoxide (CHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of CHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-4) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-4) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-4) was 30%.

[0431] (Production Example 2-5: Preparation of polymer particle latex (L-5)) A glass reactor was charged with 172 parts by weight of the polybutadiene rubber latex (R-1) (containing 60 parts by weight of an elastomer primarily composed of polybutadiene rubber) and 128 parts by weight of deionized water. The reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed device. The gas in the reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-5) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-5) was 80 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-5) was 30%.

[0432] (Production Example 2-6: Preparation of polymer particle latex (L-6)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-4) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-6) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-6) was 80 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-6) was 30%.

[0433] (Production Example 2-7: Preparation of polymer particle latex (L-7)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-3) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 288 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-7) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-7) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-7) was 20%.

[0434] (Production Example 2-8: Preparation of polymer particle latex (L-8)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-3) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.34 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-8) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-8) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-8) was 30%.

[0435] (Production Example 2-9: Preparation of polymer particle latex (L-9)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-5) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-9) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-9) was 230 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-9) was 30%.

[0436] (Production Example 2-10: Preparation of polymer particle latex (L-10)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-6) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-10) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-10) was 170 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-10) was 30%.

[0437] (Production Example 2-11: Preparation of polymer particle latex (L-11)) A glass reactor was charged with 172 parts by weight of the polystyrene-polybutadiene rubber latex (R-7) (containing 60 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 128 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 38 parts by weight of methyl methacrylate (MMA), 2 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-11) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-11) was 150 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-11) was 30%.

[0438] (Production Example 2-12: Preparation of polymer particle latex (L-14)) A glass reactor was charged with 201 parts by weight of the polystyrene-polybutadiene rubber latex (R-3) (containing 70 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 109 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 28.5 parts by weight of methyl methacrylate (MMA), 1.5 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 60 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-14) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-14) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-14) was 30%.

[0439] (Production Example 2-13: Preparation of polymer particle latex (L-15)) A glass reactor was charged with 230 parts by weight of the polystyrene-polybutadiene rubber latex (R-3) (containing 80 parts by weight of an elastomer primarily composed of polystyrene-polybutadiene rubber) and 90 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed system. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 19 parts by weight of methyl methacrylate (MMA), 1 part by weight of butyl acrylate, and 0.1 part by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 40 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-15) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-15) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-15) was 30%.

[0440] (Production Example 2-14: Preparation of polymer particle latex (L-16)) A glass reactor was charged with 201 parts by weight of the polybutadiene rubber latex (R-2) (containing 70 parts by weight of an elastomer primarily composed of polybutadiene rubber) and 109 parts by weight of deionized water. The reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed device. The gas in the reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the reactor and stirred for 10 minutes. A mixture of 28.5 parts by weight of methyl methacrylate (MMA), 1.5 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the reactor over 60 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-16) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-16) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-16) was 30%.

[0441] (Production Example 2-15: Preparation of polymer particle latex (L-17)) A glass reactor was charged with 230 parts by weight of the polybutadiene rubber latex (R-2) (containing 80 parts by weight of an elastomer primarily composed of polybutadiene rubber) and 90 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 19 parts by weight of methyl methacrylate (MMA), 1 part by weight of butyl acrylate, and 0.1 part by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 40 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-17) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-17) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-17) was 30%.

[0442] (Production Example 2-16: Preparation of polymer particle latex (L-18)) A glass reactor was charged with 244 parts by weight of the polybutadiene rubber latex (R-2) (containing 85 parts by weight of an elastomer primarily composed of polybutadiene rubber) and 81 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 14.25 parts by weight of methyl methacrylate (MMA), 0.75 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over 30 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-18) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-18) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-18) was 30%.

[0443] (Production Example 2-17: Preparation of polymer particle latex (L-19)) A glass reactor was charged with 258 parts by weight of the polybutadiene rubber latex (R-2) (containing 90 parts by weight of an elastomer primarily composed of polybutadiene rubber) and 72 parts by weight of deionized water. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the glass reactor and stirred for 10 minutes. A mixture of 9.5 parts by weight of methyl methacrylate (MMA), 0.5 parts by weight of butyl acrylate, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the glass reactor over a 20-minute period. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-19) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-19) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-19) was 30%.

[0444] (Production Example 2-18: Preparation of polymer particle latex (L-20)) A glass reactor was charged with 172 parts by weight of the polybutadiene rubber latex (R-2) (containing 60 parts by weight of an elastomer primarily composed of polybutadiene rubber) and 128 parts by weight of deionized water. The reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer feed device. The gas in the reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added to the reactor and stirred for 10 minutes. A mixture of 20 parts by weight of methyl methacrylate (MMA), 20 parts by weight of styrene, and 0.1 parts by weight of t-butyl hydroperoxide (BHP) was then continuously added to the reactor over 80 minutes. Then, 0.012 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for another hour to complete the polymerization. Through the above operations, an aqueous latex (L-20) containing polymer microparticles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer microparticles (A) contained in the obtained aqueous latex (L-20) was 200 nm. The solids concentration (concentration of polymer microparticles (A)) in the obtained aqueous latex (L-20) was 30%.

[0445] <3. Preparation of powder and granules> Example 1A (Production Example 3-1: Preparation of Powder (P-1)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 333 parts by weight of aqueous latex (L-1), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-1). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0446] Example 2A (Production Example 3-2: Preparation of Powder (P-2)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 333 parts by weight of aqueous latex (L-2), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-2). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0447] Comparative Example 1A (Production Example 3-3: Preparation of Powder (P-3)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. 333 parts by weight of aqueous latex (L-3), equivalent to 100 parts by weight of polymer microparticles (A) (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50 ° C. for 48 hours to obtain a powder (P-3).

[0448] Example 3A (Production Example 3-4: Preparation of Powder (P-4)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 333 parts by weight of aqueous latex (L-4), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-4). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0449] Comparative Example 2A (Production Example 3-5: Preparation of Powder (P-5)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Furthermore, 333 parts by weight of aqueous latex (L-5) equivalent to 100 parts by weight of polymer microparticles (A) (A) and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed to obtain an aqueous latex. The resulting aqueous latex was poured into 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. Furthermore, the obtained wet powder was poured into 500 parts by weight of ion-exchanged water and centrifuged for a total of two cycles to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50 ° C. for 48 hours to obtain a powder (P-5).

[0450] Comparative Example 3A (Production Example 3-6: Preparation of Powder (P-6)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Furthermore, 333 parts by weight of aqueous latex (L-6), equivalent to 100 parts by weight of polymer microparticles (A) (A), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed to obtain an aqueous latex. The resulting aqueous latex was poured into 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder, which was the coagulated product. Furthermore, the obtained wet powder was poured into 500 parts by weight of ion-exchanged water and centrifuged for a total of two cycles to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50 ° C. for 48 hours to obtain a powder (P-6).

[0451] Example 4A (Production Example 3-7: Preparation of Powder (P-7)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 500 parts by weight of aqueous latex (L-7), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was poured into 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The wet powder was then poured into 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-7). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0452] Example 5A (Production Example 3-8: Preparation of Powder (P-8)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 333 parts by weight of aqueous latex (L-8), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-8). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0453] Example 6A (Production Example 3-9: Preparation of Powder (P-9)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 333 parts by weight of aqueous latex (L-9), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-9). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0454] Example 7A (Production Example 3-10: Preparation of Powder (P-10)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 333 parts by weight of aqueous latex (L-10), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-10). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0455] Example 8A (Production Example 3-11: Preparation of Powder (P-11)) Four parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70°C. 333 parts by weight of aqueous latex (L-11), equivalent to 100 parts by weight of polymer microparticles (A), was mixed with 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.). The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product of polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then added to 500 parts by weight of ion-exchanged water and centrifuged twice to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-11). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0456] Example 9A (Production Example 3-12: Preparation of Powder (P-12)) A glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer addition device was charged with 220 parts by weight of deionized water, 0.9 parts by weight of polyoxyethylene lauryl ether phosphate, and 0.1 parts by weight of sodium hydroxide. The charged materials were stirred at 68°C while thoroughly purging with nitrogen to remove oxygen from the glass reactor. A mixture of 100 parts by weight of BA, 7.0 parts by weight of 2-ethylhexyl thioglycolate, and 1.0 part by weight of BHP was then continuously added to the glass reactor over 300 minutes. Next, 0.05 parts by weight of BHP was added to the glass reactor, and the reaction mixture was stirred for an additional hour to complete the polymerization. This procedure yielded an aqueous emulsion (L-12) containing polybutyl acrylate as resin (D). The polymerization conversion of the monomer components was over 99%. The volume average particle size of the resin (D) contained in the obtained aqueous emulsion (L-12) was 80 nm, and the solid content concentration (concentration of the resin (D)) was 33%.

[0457] 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Furthermore, 333 parts by weight of aqueous latex (L-1) equivalent to 100 parts by weight of polymer microparticles (A), 16.1 parts by weight of the resin aqueous emulsion (L-12) (equivalent to 5.3 parts by weight of resin (D)), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl)octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The resulting slurry was centrifuged to obtain a wet powder of the coagulated product. Furthermore, the resulting wet powder was added to 500 parts by weight of ion-exchanged water and centrifuged to obtain a wet powder, which was then subjected to a total of two cycles. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-12). The blocking resistance of the obtained powder was evaluated and found to be acceptable. The volume average particle diameter of the obtained powder was measured and found to be 10 mm or less.

[0458] Example 10A (Production Example 3-13: Preparation of Powder (P-13)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-1) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for two cycles to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-13). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0459] Example 11A (Production Example 3-14: Preparation of Powder (P-14)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-14) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for dehydration, a total of two cycles of which were repeated to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-14). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0460] Example 12A (Production Example 3-15: Preparation of Powder (P-15)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-15) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for dehydration, a total of two cycles of which were repeated to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-15). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0461] Example 13A (Production Example 3-16: Preparation of Powder (P-16)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-16) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for dehydration, a total of two cycles of which were repeated to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-16). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0462] Example 14A (Production Example 3-17: Preparation of Powder (P-17)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-17) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for dehydration, a total of two cycles of which were repeated to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-17). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0463] Example 15A (Production Example 3-18: Preparation of Powder (P-18)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-18) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for two cycles to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-18). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0464] Example 16A (Production Example 3-19: Preparation of Powder (P-19)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-19) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for dehydration, a total of two cycles of which were repeated to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powder (P-19). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0465] Example 17A (Production Example 3-20: Preparation of Powder (P-20)) 4 parts by weight of calcium chloride was dissolved in 600 parts by weight of ion-exchanged water adjusted to 70 ° C. Also, 333 parts by weight of aqueous latex (L-20) equivalent to 100 parts by weight of polymer microparticles (A), 8.8 parts by weight of liquid epoxy resin aqueous emulsion W2821R70 (L-13) (manufactured by Mitsubishi Chemical Corporation, solid content 70% by weight, epoxy resin content 60%) as resin (D) (equivalent to 5.3 parts by weight of epoxy resin), and 1.1 parts by weight of Irganox 1135 (3-(4-hydroxy-3,5-diisopropylphenyl) octyl propionate, manufactured by BASF Japan Ltd.) were mixed. The resulting aqueous latex was added to 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated product containing polymer microparticles (A). The obtained slurry was centrifuged to obtain a wet powder of the coagulated product. The resulting wet powder was then placed in 500 parts by weight of ion-exchanged water and centrifuged for dehydration, a total of two cycles of which were repeated to obtain a wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain a powder (P-20). The blocking resistance of the resulting powder was evaluated and found to be acceptable. The volume average particle diameter of the resulting powder was measured and found to be 10 mm or less.

[0466] For the powder particles (P-1) to (P-20), various physical properties of the powder particles (particle size, free polymer (FP) content (FP content), weight-average molecular weight of the grafted portion which correlates with the weight-average molecular weight of FP, MEK-insoluble content, ratio of elastomer in polymer microparticle (A) (elastomer ratio), graft ratio, and composition of the grafted portion of polymer microparticle (A) (grafted portion composition) were measured. The results are shown in Table 1.

[0467] <Preparation of Resin Composition> In addition, 20 parts by weight of powder particles (P-1) to (P-20) and 80 parts by weight of bisphenol A epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) were weighed and mixed in a planetary centrifugal mixer at 2000 rpm for 80 minutes to obtain a resin composition. The dispersibility (30 minutes, 80 minutes) and blend viscosity of these resin compositions were measured. The results are shown in Table 1.

[0468] [Table 1] [Example B] <Evaluation method> First, the evaluation methods for the antifouling coating compositions for underwater structures produced in the Examples and Comparative Examples will be described below. In the following description, unless otherwise specified, the term "polymer fine particles" includes both polymer fine particles (A') which are polymer fine particles according to one embodiment of the present invention and polymer fine particles outside the scope of the present invention.

[0469] (Measurement of volume average particle size) This is the same as in the first embodiment, and the above description is incorporated herein by reference.

[0470] (Differential scanning calorimetry (DSC) of resin (D)) Resin (D) used (a mixture of 67 parts by weight of epoxidized soybean oil (ADEKA Corporation, Adeka Cizer O-130P) and 33 parts by weight of triethylene glycol bis[3-(-t-butyl-4-hydroxy-5-methylphenyl)propionate] (Irganox 245, BASF Japan Ltd.)) was measured using a DSC7020 (Hitachi High-Tech Science Corporation) at a heating rate of 10°C / min. The result was -17.3°C.

[0471] (Viscosity measurement of resin (D)) Resin (D) was used (a mixture of 67 parts by weight of epoxidized soybean oil (ADEKA Corporation, Adeka Cizer O-130P) and 33 parts by weight of triethylene glycol bis[3-(-t-butyl-4-hydroxy-5-methylphenyl)propionate] (Irganox 245, BASF Japan Ltd.)). Viscosity was measured at 25°C using a Brookfield DV-II+ Pro digital viscometer with a CPE-52 spindle, varying the shear rate as needed depending on the viscosity range. The result was 1800 mPa·s.

[0472] (Method for preparing a flat plate made of polymer fine particles or a flat plate made of a mixture of polymer fine particles and resin (D)) As the polymer microparticles, powders (P-1) and (P-6) to (P-8) were used. As the mixture of polymer microparticles and resin (D), powders (P-2) to (P-5) were used. The powders obtained in each production example were rolled at 200°C, and then subjected to a pressure of 200°C and 100 kgf / cm. 2 The powder particles were molded into plates by pressing under the conditions shown below. By this molding, flat plates made of polymer fine particles (A') or flat plates made of a mixture of polymer fine particles and resin (D) were obtained. The thickness of the flat plates was 1 mm.

[0473] (Method for measuring the glass transition temperature of polymer microparticles or a mixture of polymer microparticles and resin (D)) Using a flat plate made of polymer microparticles or a flat plate made of a mixture of polymer microparticles and resin (D), dynamic viscoelasticity measurements were performed under tensile conditions using a dynamic viscoelasticity measuring device DVA-200 (IT Measurement & Control Co., Ltd.), and a tan δ graph was obtained. The peak temperature of tan δ in the obtained tan δ graph was taken as the glass transition temperature. When two peaks were obtained in the tan δ graph, the lower peak temperature was taken as the glass transition temperature of the polymer microparticles or the mixture of polymer microparticles and resin (D) in this specification. The results are shown in Table 2.

[0474] (Method for measuring strength at break, elongation and elastic modulus of polymer microparticles or a mixture of polymer microparticles and resin (D)) A dumbbell shape according to JIS K-7113-2 was punched out from a flat plate made of polymer microparticles or a flat plate made of a mixture of polymer microparticles and resin (D) to prepare samples. Using the obtained samples, a tensile test was performed at 10 mm / min using a Shimadzu tensile tester to measure the strength at break, elongation, and modulus of elasticity. The sample was stretched at 10 mm / min, and the stress at which the sample broke was defined as the "strength at break," and the elongation of the sample at which the sample broke was defined as the "elongation." The results are shown in Table 2.

[0475] (Method for measuring contact angle of polymer fine particles or a mixture of polymer fine particles and resin (D)) The contact angle was measured using a contact angle meter on a flat plate made of polymer fine particles (A') or a flat plate made of a mixture of polymer fine particles and resin (D). The results are shown in Table 2.

[0476] (Blocking resistance of mixture (powder) of polymer fine particles and resin (D)) The powder and granules obtained in each production example were used to prepare a block of powder and granules by carrying out the following steps (1) to (3) in order: (1) 30 g of powder and granules were placed in a cylindrical container with a diameter of 50 mm; (2) a 6.3 kg weight was placed on the powder and granules in the container, and the powder and granules were allowed to stand at 60°C for 2 hours, thereby applying a load of 6.3 kg to the powder and granules; (3) the resulting block was removed from the container. Next, the force required to break the resulting block of powder and granules was measured using a rheometer. Based on the results obtained, blocking resistance was evaluated according to the following criteria. Pass: The force required to break the powder block is 30,000 Pa or less. Fail: The force required to break the block of powder exceeds 30,000 Pa.

[0477] (Method for preparing a coating film made from an antifouling coating composition for underwater structures) The antifouling coating composition for underwater structures obtained in each Example and Comparative Example was applied to a Teflon (registered trademark) sheet to a thickness of 100 μm. The obtained Teflon (registered trademark) sheet was left at 23°C for 2 days to form a coating film of the antifouling coating composition for underwater structures to a thickness of 100 μm on the Teflon (registered trademark) sheet. The formed coating film was peeled off from the Teflon (registered trademark) sheet to form a coating film.

[0478] (Methods for measuring strength, elongation and elastic modulus of coating film) A 1 cm wide strip was cut out from the resulting coating film to serve as a sample. A tensile test was conducted on the resulting sample at 20 mm / min using a Shimadzu tensile t...

Claims

1. A powder containing polymer fine particles (A) to be blended with a thermosetting resin, the polymer fine particles (A) contain a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer, The elastic body includes, as a constituent unit, a constituent unit derived from butadiene, the graft portion includes a polymer containing, as a structural unit, a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer; the volume average particle diameter of the polymer microparticles (A) measured by a dynamic light scattering (DLS) particle size distribution analyzer is 90 nm or more and less than 10 μm, the weight average molecular weight of the polymer in the graft portion is 200,000 or less; Further, it contains a resin (D), the resin (D) is a liquid, semi-solid, or solid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C; When the total amount of the polymer fine particles (A) and the resin (D) is 100% by weight, the polymer fine particles (A) account for 50 to 99% by weight and the resin (D) accounts for 1 to 50% by weight, the thermosetting resin is at least one selected from the group consisting of a resin containing a polymer obtained by polymerizing an ethylenically unsaturated monomer, an epoxy resin, a phenol resin, a polyol resin, and an amino-formaldehyde resin; The polymer fine particles (A) further comprise a non-graft polymer comprising a polymer (excluding those identical to the resin (D)) containing, as a structural unit, a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer.

2. A powder or granular material for thermosetting resins as described in claim 1, wherein the content of the non-grafted polymer is 8% by weight or less.

3. 3. The powder or granule for a thermosetting resin according to claim 1, wherein the graft ratio of the graft portion is 80% or more.

4. 4. The powder or granule for thermosetting resins according to claim 1, wherein the elastic body accounts for 70% by weight or more of the polymer fine particles (A).

5. The powder or granule for a thermosetting resin according to any one of claims 1 to 4, wherein the graft portion comprises a polymer containing, as a constituent unit, a constituent unit derived from a (meth)acrylate monomer.

6. The powder or granule for a thermosetting resin according to claim 2 , wherein the non-graft polymer comprises a polymer containing, as a constituent unit, a constituent unit derived from a (meth)acrylate monomer.

7. The powder or granular material according to any one of claims 1 to 6, wherein a force required to break the block of the powder or granular material is 30,000 Pa or less. Here, the block is obtained by placing a 6.3 kg weight on 30 g of the powder or granule contained in a cylindrical container having a diameter of 50 mm, and allowing the powder or granule to stand at 60°C for 2 hours, and applying a load of 6.3 kg to the powder or granule; The force is a value obtained by measurement using a rheometer.

8. The powder or granule according to any one of claims 1 to 7, wherein the powder or granule has a volume average particle diameter (Mv) of 30 µm to 500 µm.

9. A resin composition comprising the powder or granule according to any one of claims 1 to 8 and a thermosetting resin (B), The thermosetting resin (B) is at least one selected from the group consisting of a resin containing a polymer obtained by polymerizing an ethylenically unsaturated monomer, an epoxy resin, a phenol resin, a polyol resin, and an amino-formaldehyde resin. A resin composition.

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