Thermosetting resin composition, cured product, powder coating material, coating film, and sealing resin composition

Abstract

Provided is a thermosetting resin composition excellent in dispersibility of polymer particles. This thermosetting resin composition contains thermosetting resin and polymer particles in specific amounts. The polymer particles have a specific elastic body and a graft part having a specific constitutional unit. The glass transition temperature of the graft part is 25°C-50°C, and the volume average particle diameter of the polymer particles is 130 nm-800 nm.

Description

Thermosetting resin compositions, cured products, powder coatings, coating films, and encapsulating resin compositions

[0001] This invention relates to thermosetting resin compositions, cured products, powder coatings, coating films, and encapsulating resin compositions.

[0002] Thermosetting resins are used in a variety of fields because they possess various excellent properties such as high heat resistance and mechanical strength. On the other hand, thermosetting resins have the problem of insufficient impact resistance, which is a characteristic of thermosetting resins. To improve the impact resistance of thermosetting resins, a method of adding elastomers such as polymer particles to the thermosetting resin is widely used (for example, Patent Documents 1 and 3).

[0003] Thermosetting resin compositions containing polymer particles can be used in a wide range of applications, including powder coatings and encapsulating resin compositions. As a composition for powder coatings, for example, the technology described in Patent Document 2 is known.

[0004] International Publication WO2012 / 093631, Japanese Patent Publication No. 2000-001633, International Publication WO2022 / 138808, International Publication WO2020 / 196919, International Publication WO2024 / 203994, Japanese Patent Publication No. 2021-095466

[0005] However, the conventional technologies described above were insufficient in terms of the dispersibility of polymer particles in thermosetting resin compositions, and there was room for further improvement.

[0006] One embodiment of the present invention has been made in view of the above-mentioned problems, and its objective is to provide a novel thermosetting resin composition that exhibits excellent dispersibility of polymer particles.

[0007] The inventors of this invention have diligently studied and conducted research to solve the aforementioned problems, and as a result, have completed this invention.

[0008] In other words, a thermosetting resin composition according to one embodiment of the present invention contains a thermosetting resin (A) and polymer particles (B), wherein the polymer particles (B) have an elastic body and a graft portion, the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber, the graft portion contains one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units and (meth)acrylate units as constituent units, the content of the polymer particles (B) is 0.1 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the thermosetting resin (A), the glass transition temperature of the graft portion is 25°C or more and 50°C or less, and the volume average particle diameter of the polymer particles (B) is 130 nm or more and 800 nm or less.

[0009] According to one embodiment of the present invention, it is possible to provide a novel thermosetting resin composition that exhibits excellent dispersibility of polymer particles.

[0010] One embodiment of the present invention is described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Moreover, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic and patent documents mentioned herein are incorporated herein by reference.

[0011] Furthermore, unless otherwise specified in this specification, the constituent units are X １ Constituent units derived from monomers, and X ２ Constituent units derived from monomers, ... and X ｎ A copolymer containing constituent units derived from monomers (where n is an integer of 2 or more) is defined as "X １ / X ２ / ... / X ｎ It is also called a "polymer." １ / X ２ / ... / Xｎ Unless otherwise specified, the polymerization mode of the copolymer is not particularly limited, and it may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.

[0012] In the present specification, the "X unit" contained in a polymer, copolymer or resin is intended to mean a "structural unit derived from an X monomer". For example, "(meth)acrylate unit" is intended to mean a "structural unit derived from a (meth)acrylate monomer". As used herein, "(meth)acrylate" means "acrylate and / or methacrylate".

[0013] [1. Thermosetting resin composition] A thermosetting resin composition according to one embodiment of the present invention contains a thermosetting resin (A) and polymer particles (B), wherein the polymer particles (B) have an elastic body and a graft portion, the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber, the graft portion contains, as structural units, one or more structural units selected from the group consisting of aromatic vinyl units, vinyl cyanide units and (meth)acrylate units, the content of the polymer particles (B) is 0.1 parts by mass or more and 50.0 parts by mass or less relative to 100 parts by mass of the thermosetting resin (A), the glass transition temperature of the graft portion is 25°C or higher and 50°C or lower, and the volume average particle diameter of the polymer particles (B) is 130 nm or more and 800 nm or less.

[0014] In the present specification, the "thermosetting resin composition" may be referred to as "composition", and the "thermosetting resin composition according to one embodiment of the present invention" may be referred to as "the present composition".

[0015] Because this composition has the above-described structure, it has the advantage of having excellent dispersibility of polymer particles (B) within the composition. A composition having excellent dispersibility of polymer particles (B) also has the advantage of having excellent dispersibility of polymer particles (B) in a cured product obtained by curing the composition. Whether or not a novel thermosetting resin composition with excellent dispersibility of polymer particles can be provided can be evaluated by the amount of particles (regions where polymer particles (B) are aggregated or densely packed) in the cured product. These particles in the cured product can be observed as black spots, for example, by SAT observation of the cured product. Alternatively, these particles can be observed as irregularities near the surface of the cured product. Therefore, the thinner the cured product, the easier it is to observe the particles in the cured product. In this specification, the dispersibility of polymer particles (B) within a composition is evaluated by the dispersibility of polymer particles (B) in a cured product obtained by curing the composition. More specifically, in this specification, the dispersibility of polymer particles (B) in a composition is evaluated by the amount of particles in a cured product with a thickness of 40 μm obtained by curing the composition. Details of this evaluation method are described in the following examples.

[0016] <1-1. Thermosetting Resin (A)> The thermosetting resin (A) is not particularly limited, and any thermosetting resin commonly used in the field of compositions can be used as appropriate. From the viewpoint of excellent thermosetting properties, it is preferable that the thermosetting resin (A) contains at least one resin selected from the group consisting of epoxy resin, thermosetting (meth)acrylic resin, thermosetting polyester resin, diallyl phthalate resin, phenol resin, polyol resin, amino-formaldehyde resin, and maleimide resin. As the thermosetting resin (A), only one of the above-mentioned thermosetting resins may be used, or two or more may be used in combination. For example, epoxy resin and thermosetting polyester resin may be used in combination. The thermosetting resin (A) can function as a matrix resin in the composition and cured product. The thermosetting resin (A) is sometimes referred to as a "binding resin".

[0017] (Epoxy resin) The epoxy resin is not particularly limited as long as it has at least one epoxy group in its molecule.

[0018] Specific examples of epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolac type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, rubber-modified epoxy resin containing polybutadiene or NBR, flame-retardant epoxy resins such as glycidyl ether of tetrabromobisphenol A, p-oxybenzoic acid glycidyl ether type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane-based epoxy resin, urethane-modified epoxy resin having urethane bonds, various alicyclic epoxy resins, glycidyl ethers of polyhydric alcohols, hydantoin type epoxy resins, epoxidized products of unsaturated polymers such as petroleum resins, and aminoglycidyl ether resins. Examples of the polyhydric alcohols include polyalkylene glycol diglycidyl ether and glycerin. Examples of epoxy resins include epoxy compounds obtained by adding bisphenol A (or F) compounds or polybasic acids to the epoxy resins mentioned above. The epoxy resins are not limited to these, and commonly used epoxy resins can be used. These epoxy resins may be used individually or in combination of two or more.

[0019] Among the epoxy resins mentioned above, those having at least two epoxy groups per molecule are preferred because they exhibit high reactivity in curing the 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 primarily composed of bisphenol-type epoxy resins are preferred due to their economic efficiency and ease of availability.

[0020] (Thermosetting (meth)acrylic resin) A thermosetting (meth)acrylic resin is a (meth)acrylic resin having a thermosetting reactive group. "(meth)acrylic" means "methacrylic and / or acrylic". For example, "(meth)acrylic resin" means "methacrylic resin and / or acrylic resin". "(meth)acrylic resin" means "a resin containing at least (meth)acrylic units". "Thermosetting reactive group" means "a functional group that exhibits a curing reaction with heat", and can also be said to be "a functional group that hardens with heat". A (meth)acrylic monomer includes a (meth)acrylate monomer, and a (meth)acrylic unit includes a (meth)acrylate unit. It is preferable that the thermosetting (meth)acrylic resin contains the largest total amount (molar amount) of (meth)acrylic units and (meth)acrylate units among all constituent units.

[0021] For the introduction of thermosetting reactive groups into (meth)acrylic resins, it is preferable to use vinyl monomers having thermosetting reactive groups. In other words, it is preferable that thermosetting (meth)acrylic resins contain constituent units derived from vinyl monomers having thermosetting reactive groups. The vinyl monomers having thermosetting reactive groups may be (meth)acrylic monomers (monomers having (meth)acryloyl groups) or vinyl monomers other than (meth)acrylic monomers. "(meth)acryloyl" means "methacryloyl and / or acryloyl". For example, "(meth)acryloyl group" means "methacryloyl group and / or acryloyl group". A thermosetting (meth)acrylic resin can be obtained by polymerizing a monomer mixture comprising (i) a (meth)acrylic monomer without thermosetting reactive groups and a vinyl monomer other than a (meth)acrylic monomer that has thermosetting reactive groups; (ii) a monomer mixture comprising a (meth)acrylic monomer that has thermosetting reactive groups and a vinyl monomer other than a (meth)acrylic monomer that does not have thermosetting reactive groups; (iii) a monomer mixture comprising a (meth)acrylic monomer that has thermosetting reactive groups and a vinyl monomer other than a (meth)acrylic monomer that has thermosetting reactive groups; (iv) a monomer mixture comprising a (meth)acrylic monomer that has thermosetting reactive groups and a (meth)acrylic monomer that does not have thermosetting reactive groups; or (v) a monomer mixture consisting of a (meth)acrylic monomer that has thermosetting reactive groups.

[0022] Examples of thermosetting reactive groups in thermosetting (meth)acrylic resins include epoxy groups, carboxyl groups, hydroxyl groups, amide groups, amino groups, acid anhydrides, and (blocked) isocyanate groups. Among these, it is preferable that the thermosetting reactive group of a thermosetting (meth)acrylic resin be at least one selected from the group consisting of epoxy groups, carboxyl groups, and hydroxyl groups, as this facilitates the production of the thermosetting (meth)acrylic resin. From the viewpoint of excellent storage stability of the composition and appearance of the cured product, it is more preferable that the thermosetting (meth)acrylic resin contains at least an epoxy group as a thermosetting reactive group.

[0023] Examples of vinyl monomers having an epoxy group as a thermosetting reactive group include various chain-type epoxy group-containing monomers (e.g., glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, glycidyl vinyl ether, allyl glycidyl ether, etc.); and various alicyclic epoxy group-containing vinyl monomers (e.g., 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, etc.).

[0024] Examples of vinyl monomers having a carboxyl group as a thermosetting reactive group include various carboxyl group-containing monomers (e.g., (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.); and monoesters of various α,β-unsaturated dicarboxylic acids and monohydric alcohols having 1 to 18 carbon atoms (e.g., monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monoisobutyl fumarate, monotert-butyl fumarate, monohexyl fumarate, monooctyl fumarate, mono2-ethyl fumarate). Examples include monohexyl maleate, monomethyl maleate, monoethyl maleate, monobutyl maleate, monoisobutyl maleate, monotert-butyl maleate, monohexyl maleate, monooctyl maleate, mono2-ethylhexyl maleate, etc.; monoalkyl itaconates (e.g., monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monoisobutyl itaconate, monohexyl itaconate, monooctyl itaconate, mono2-ethylhexyl itaconate, etc.); and so on.

[0025] Examples of vinyl monomers having a hydroxyl group as a thermosetting reactive group include various hydroxyl group-containing (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.); addition reaction products of the above various hydroxyl group-containing (meth)acrylates with ε-caprolactone; and various hydroxyl group-containing vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxypropyl vinyl ether, etc.). Examples include hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, etc.; addition reaction products of the above various hydroxyl-containing vinyl ethers with ε-caprolactone; various hydroxyl-containing allyl ethers (e.g., 2-hydroxyethyl (meth)allyl ether, 3-hydroxypropyl (meth)allyl ether, 2-hydroxypropyl (meth)allyl ether, 4-hydroxybutyl (meth)allyl ether, 3-hydroxybutyl (meth)allyl ether, 2-hydroxy-2-methylpropyl (meth)allyl ether, 5-hydroxypentyl (meth)allyl ether, 6-hydroxyhexyl (meth)allyl ether, etc.); addition reaction products of the above various hydroxyl-containing allyl ethers with ε-caprolactone; and so on.

[0026] Thermosetting (meth)acrylic resins may contain constituent units derived from vinyl monomers other than (meth)acrylic monomers that do not have thermosetting reactive groups, in addition to (meth)acrylic units.

[0027] Examples of vinyl monomers other than (meth)acrylic monomers having no thermosetting reactive group include various α-olefins (e.g., ethylene, propylene, butene-1, etc.); various halogenated olefins excluding fluoroolefins (e.g., vinyl chloride, vinylidene chloride, etc.), various aromatic vinyl monomers (e.g., styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, etc.); diesters of various unsaturated dicarboxylic acids and monohydric alcohols having 1 to 18 carbon atoms (e.g., dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate, etc.); various phosphate group-containing monomers (e.g., diethyl-2-(meth)acryloyloxyethyl phosphate, dibutyl-2-(meth)acryloyloxybutyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, diphenyl-2-(meth)acryloyloxyethyl phosphate, etc.); various hydrolyzable silyl group-containing monomers (e.g., γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, etc.); various aliphatic vinyl carboxylates (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched aliphatic vinyl carboxylates having 9 to 11 carbon atoms, vinyl stearate, etc.); various vinyl esters of carboxylic acids having a cyclic structure (e.g., vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, p-tert-butyl vinyl benzoate, etc.); and the like.

[0028] If a thermosetting (meth)acrylic resin contains constituent units derived from vinyl monomers other than (meth)acrylic monomers as constituent units derived from vinyl monomers having thermosetting reactive groups, then the thermosetting (meth)acrylic resin further contains constituent units derived from (meth)acrylic monomers that do not have thermosetting reactive groups.

[0029] Examples of (meth)acrylic monomers that do not have a thermosetting reactive group include alkyl (meth)acrylates (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyloctyl (meth)acrylate, dodecyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, etc.); various alkoxy esters of (meth)acrylates (e.g., methoxy (meth)acrylate, ethoxy (meth)acrylate, 2-methoxyethyl (meth)acrylate, etc.); each Examples include various alkyl halides of (meth)acrylates (e.g., chloroethyl (meth)acrylate, trifluoroethyl (meth)acrylate, etc.); various aryl esters of (meth)acrylates (e.g., benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.); various alkyl carbitol (meth)acrylates (e.g., ethyl carbitol (meth)acrylate, etc.); various other (meth)acrylate esters (e.g., isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc.); various amino group-containing monomers (e.g., tert-butylaminoethyl (meth)acrylate, tert-butylaminopropyl (meth)acrylate, pyrrolidinyl ethyl (meth)acrylate, piperidinyl ethyl (meth)acrylate, etc.); and so on.

[0030] The number average molecular weight of the thermosetting (meth)acrylic resin is not particularly limited, but is preferably 1,000 or more and 20,000 or less, more preferably 1,500 or more and 15,000 or less. When the number average molecular weight of the thermosetting (meth)acrylic resin is within the above range, there is an advantage that the smoothness and mechanical properties of the cured product are easily improved.

[0031] The number average molecular weight of the thermosetting (meth)acrylic resin is measured by gel permeation chromatography (GPC). The weight average molecular weight and the number average molecular weight are calculated from the measurement results using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. The molecular weight measurement by GPC is performed using a solution obtained by dissolving the thermosetting (meth)acrylic resin in THF as a sample, for example, under the following conditions: Measurement apparatus: GPC·HLC-8420GPC manufactured by Tosoh Corporation, Column: TSKgel SuperHZ column manufactured by Tosoh Corporation, Mobile phase: THF solvent.

[0032] (Thermosetting Polyester Resin) The thermosetting polyester resin is, for example, a polycondensate obtained by at least polycondensing a polybasic acid and a polyhydric alcohol. The introduction of the thermosetting reactive group into the thermosetting polyester resin is carried out by adjusting the usage amounts of the polybasic acid and the polyhydric alcohol. By this adjustment, a thermosetting polyester resin having at least one of a carboxyl group and a hydroxyl group as the thermosetting reactive group can be obtained.

[0033] Examples of the polybasic acid include terephthalic acid, isophthalic acid, phthalic acid, methylterephthalic acid, trimellitic acid, pyromellitic acid, and anhydrides of these acids; succinic acid, adipic acid, azelaic acid, sebacic acid, and anhydrides of these acids; maleic acid, itaconic acid, and anhydrides of these acids; fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and anhydrides of these acids; cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like.

[0034] Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bis-hydroxyethyl terephthalate, cyclohexanedimethanol, octanediol, diethylpropanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentanediol, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, trishydroxyethyl isocyanurate, and hydroxypivalyl hydroxypivalate.

[0035] Thermosetting polyester resins may also be polycondensed with other compounds besides polybasic acids and polyhydric alcohols.

[0036] Other compounds include, for example, compounds having both a carboxyl group and a hydroxyl group in one molecule (e.g., dimethanolpropionic acid, hydroxypivalic acid, etc.), monoepoxy compounds (e.g., glycidyl esters of branched aliphatic carboxylic acids such as "Cardura E10 (Shell)"), various monohydric alcohols (e.g., methanol, propanol, butanol, benzyl alcohol, etc.), various monobasic acids (e.g., benzoic acid, p-tert-butylbenzoic acid, etc.), and various fatty acids (e.g., castor oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, etc.).

[0037] The structure of the thermosetting polyester resin may be either branched or linear.

[0038] It is preferable that the sum of the acid value and hydroxyl value of the thermosetting polyester resin is between 10 mg KOH / g and 250 mg KOH / g. Keeping the sum of the acid value and hydroxyl value within the above range tends to improve the smoothness and mechanical properties of the cured product. The measurement of the acid value and hydroxyl value of the thermosetting polyester resin shall conform to JIS K-0070-1992.

[0039] The thermosetting polyester resin preferably has a number-average molecular weight of 1,000 to 100,000. Keeping the number-average molecular weight within this range improves the smoothness and mechanical properties of the cured product, as well as the storage stability of the composition. The method for measuring the number-average molecular weight of the thermosetting polyester resin is the same as that for measuring the number-average molecular weight of the thermosetting (meth)acrylic resin, except that the thermosetting polyester resin is used instead of the thermosetting (meth)acrylic resin.

[0040] The thermosetting resin (A) may be one of the above-mentioned resins used alone, or two or more may be used in combination.

[0041] The thermosetting resin (A) is preferably solid at room temperature (e.g., 25°C) from the viewpoint of its properties as a composition and its handling characteristics. When this composition is used as a powder coating, the thermosetting resin (A) is particularly preferably solid at room temperature (e.g., 25°C).

[0042] (Diallyl phthalate resin) Diallyl phthalate resin includes a diallyl phthalate prepolymer (diallyl phthalate resin) and a diallyl phthalate monomer. The diallyl phthalate prepolymer is a type of allyl resin obtained by polymerizing a diallyl phthalate monomer, which is an ester of phthalic acid and allyl alcohol. Depending on the type of phthalic acid used, these include orthotype using phthalic anhydride or orthophthalic acid, metatype using isophthalic acid, and paratype using terephthalic acid. These may be homopolymers, or copolymers containing two or more types may be included. Furthermore, hydrogen atoms on the benzene ring may be substituted with halogen atoms such as chlorine or bromine, and hydrogenated forms may be used in which all or part of the unsaturated bonds present in the molecule are hydrogenated. These may be used individually or in combination of two or more types. The weight-average molecular weight (measured by GPC and converted to standard polystyrene) of the diallyl phthalate prepolymer is, for example, 20,000 to 60,000, preferably 20,000 to 40,000, and more preferably 20,000 to 30,000. The diallyl phthalate monomer is an ester of phthalic acid and allyl alcohol, and like the diallyl phthalate resin described above, orthotype, metatype, and paratype may be used. The content of the diallyl phthalate monomer is, for example, 0.2 parts by mass to 5 parts by mass, preferably 0.3 parts by mass to 3 parts by mass, and more preferably 0.5 parts by mass to 1.5 parts by mass, per 100 parts by mass of the diallyl phthalate prepolymer. By appropriately adjusting the amount of diallyl phthalate monomer added, the fluidity of the diallyl phthalate resin can be maintained while reducing the content of the diallyl phthalate prepolymer.

[0043] (Phenol Resin) The phenol resin is not particularly limited as long as it is a compound obtained by reacting phenols with aldehydes. The phenols are not particularly limited, but examples include phenol, orthocresol, metacresol, paracresol, xylenol, paratertiary-butylphenol, paraoctylphenol, paraphenylphenol, bisphenol A, bisphenol F, and resorcinol. Particularly preferred phenols include phenol and cresol.

[0044] The aldehydes are not particularly limited, but examples include formaldehyde, acetaldehyde, butyraldehyde, and acrolein, as well as mixtures thereof. The aldehydes can also be the substances that generate the aldehydes mentioned above, or solutions of these aldehydes. Formaldehyde is preferred as the aldehyde because the reaction between phenols and aldehydes is easy.

[0045] When reacting phenols with aldehydes, the molar ratio (P / R) of phenols (P) to aldehydes (R) (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 (P / R) is preferably 0.4 to 1.0, and more preferably 0.5 to 0.8. When an alkali catalyst is used in the reaction, the reaction molar ratio (P / R) is preferably 0.4 to 4.0, and more preferably 0.8 to 2.5. When the reaction molar ratio is above the lower limit, the yield will not be too low, and there is no risk of the molecular weight of the resulting phenol resin being too small. On the other hand, when the reaction molar ratio is below the upper limit, the molecular weight of the phenol resin will not be too high, and the softening point will not be too high, so sufficient fluidity can be obtained when heated. Also, when the reaction molar ratio is below the upper limit, the molecular weight is easy to control, and there is no risk of gelation or partial gelling due to the reaction conditions.

[0046] (Polyol Resins) Polyol resins are compounds having two or more active hydrogen atoms at their ends, and are bifunctional or more polyols with a molecular weight of approximately 50 to 20,000. Examples of polyol resins include aliphatic alcohols, aromatic alcohols, polyether-type polyols, polyester-type polyols, polyolefin polyols, and acrylic polyols.

[0047] Aliphatic alcohols may be dihydric alcohols or trihydric or higher alcohols (trihydric alcohols, tetrahydric alcohols, etc.). Examples of dihydric alcohols include (a) alkylene glycols 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, neopentyl glycol (particularly alkylene glycols with approximately 1 to 6 carbon atoms), and (b) dehydration condensates of two or more molecules (for example, approximately 2 to 6 molecules) of the alkylene glycol compounds (diethylene glycol, dipropylene glycol, tripropylene glycol, etc.). Examples of trihydric alcohols include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol (particularly trihydric alcohols with approximately 3 to 10 carbon atoms). Examples of tetrahydric alcohols include pentaerythritol and diglycerin. Other examples include sugars such as monosaccharides, oligosaccharides, and polysaccharides.

[0048] 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.

[0049] Examples of polyether-type polyols include (a) random copolymers or block copolymers obtained by ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., in the presence of one or more initiators containing active hydrogen, and (b) mixtures of these copolymers. Examples of initiators containing active hydrogen used in ring-opening polymerization of polyether-type 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; sugars such as monosaccharides, oligosaccharides, and polysaccharides; sorbitol; amines such as ammonia, ethylenediamine, urea, monomethyldiethanolamine, and monoethyldiethanolamine.

[0050] Examples of polyester-type polyols include polymers obtained by polycondensing (a) polybasic acids and / or their acid anhydrides, such as maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, dodecanediic acid, isophthalic acid, and azelaic acid, and (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 range of 150°C to 270°C. Furthermore, examples of (a) polyester-type polyols include ring-opening polymers such as ε-caprolactone and valerolactone, and (b) active hydrogen compounds having two or more active hydrogen atoms, such as polycarbonate diols and castor oil.

[0051] Examples of polyolefin-type polyols include polybutadiene polyols, polyisoprene polyols, and their hydrogenated products.

[0052] Examples of acrylic polyols include (a) copolymers of hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, and vinylphenol, and (b) copolymers of common monomers such as n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, as well as mixtures of these copolymers.

[0053] Among these polyol resins, polyether-type polyols are preferred because the resulting composition containing the resulting powder has low viscosity and excellent workability, and the composition provides a cured product with an excellent balance of hardness and toughness. Furthermore, among these polyol resins, polyester-type polyols are preferred because the resulting composition containing the resulting powder has excellent adhesive properties.

[0054] (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 under 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 ethyleneurea. Furthermore, as the amino compound, (a) substituted melamine compounds obtained by substituting the hydrogen of the amino group of melamine with an alkyl group, an alkenyl group, and / or a phenyl group (described in U.S. Patent No. 5,998,573 (corresponding Japanese Publication No. 9-143238)), and (b) substituted melamine compounds obtained by substituting the hydrogen of the amino group of melamine with a hydroxyalkyl group, a hydroxyalkyloxyalkyl group, and / or an aminoalkyl group (described in U.S. Patent No. 5,322,915 (corresponding Japanese Publication No. 5-202157)) can also be used. Among the above-mentioned compounds, melamine, guanamine, acetoguanamine, and benzoguanamine, which are polyfunctional amino compounds, are preferred as the amino compound because they are industrially produced and inexpensive, and melamine is particularly preferred. The above-mentioned amino compounds may be used individually 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.

[0055] Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and furfural. Among the aldehydes, formaldehyde and paraformaldehyde are preferred because they are inexpensive and have good reactivity with the amino compounds mentioned above. In the production of amino-formaldehyde resin, it is preferable to use 1.1 moles to 6.0 moles of aldehydes per mole of amino compound, and particularly preferable to use 1.2 moles to 4.0 moles per mole of active aldehyde group.

[0056] <1-2. Polymer Particles (B)> Polymer particles (B) have an elastic body and a graft portion. Polymer particles (B) can improve the impact resistance and / or toughness of the thermosetting resin. In other words, the composition has the advantage of having excellent impact resistance and / or toughness by including polymer particles (B).

[0057] (Elastic body) The elastic body can also be referred to as an elastic part or rubber particle. Preferably, the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber.

[0058] The case where the elastic body contains a diene-based rubber (Case A) will be described. In Case A, the composition has the advantage of providing a cured product with excellent toughness and impact resistance. A cured product with excellent toughness and / or impact resistance can also be said to be a cured product with excellent durability.

[0059] Diene rubber is an elastic body that contains constituent units derived from diene monomers as constituent units. The diene monomer can also be referred to as a conjugated diene monomer. In case A, the diene rubber may contain the largest amount of diene units among all constituent units. In case A, in addition to diene units, the diene rubber may further contain constituent units derived from vinyl monomers other than diene monomers that are copolymerizable with diene monomers. In this specification, "vinyl monomers other than diene monomers that are copolymerizable with diene monomers" may also be referred to as "vinyl monomer A," and "constituent units derived from vinyl monomer A" may also be referred to as "vinyl unit A." In other words, the elastic body may contain vinyl unit A as a constituent unit.

[0060] Examples of diene monomers include 1,3-butadiene, isoprene(2-methyl-1,3-butadiene), and 2-chloro-1,3-butadiene. These diene monomers may be used individually or in combination of two or more.

[0061] Examples of vinyl monomer A include (i) aromatic vinyl monomers such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; (ii) vinyl carboxylic acids such as acrylic acid and methacrylic acid; (iii) (meth)acrylate monomers; (iv) vinyl cyanides such as acrylonitrile and methacrylonitrile; (v) vinyl halides such as vinyl chloride, vinyl bromide, and chloroprene; (vi) vinyl acetate; (vii) alkenes such as ethylene, propylene, butylene, and isobutylene; and (viiii) polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. One type of vinyl monomer A may be used, or two or more types may be used in combination. Among the vinyl monomer A described above, styrene is particularly preferred. In the diene rubber in case A, the constituent units (vinyl units A) derived from vinyl monomer A are optional components.

[0062] In case A, the diene rubber may contain, in 100% by mass of constituent units, (i) 50% by mass or more and 100% by mass of diene units and 0% by mass or more and 50% by mass of vinyl units A; (ii) more than 50% by mass and 100% by mass or less of diene units and 0% by mass or more and less than 50% by mass of vinyl units A; and (iii) 60% by mass or more and 100% by mass or less of diene units and 0% by mass or more and 40% by mass of vinyl units A. It may contain less than 10% of (iv) diene units in an amount of 70% to 100% by mass and vinyl units A in an amount of 0% to 30% by mass, (v) diene units in an amount of 80% to 100% by mass and vinyl units A in an amount of 0% to 20% by mass, or (vi) diene units in an amount of 90% to 100% by mass and vinyl units A in an amount of 0% to 10% by mass. In case A, the diene rubber may consist only of diene units. As described later, if the diene rubber contains constituent units derived from a monomer that is a vinyl monomer A and is also a crosslinkable monomer or a graftable monomer, the content of such constituent units is not counted (not included) as the content of vinyl units A as described above.

[0063] In case A, the elastic body preferably contains butadiene rubber (hereinafter also referred to as "polybutadiene rubber") consisting of 1,3-butadiene units, and / or butadiene-styrene rubber (also referred to as "polystyrene-butadiene") which is a copolymer of 1,3-butadiene and styrene, and it is particularly preferable that it contains butadiene rubber. With the above configuration, the desired effects due to the polymer particles (B) containing diene-based rubber can be more effectively exhibited. Furthermore, butadiene-styrene rubber is more preferable in that the transparency of the resulting cured product can be increased by adjusting the refractive index.

[0064] Butadiene-styrene rubber may contain, in 100% by mass of butadiene-styrene rubber, (i) more than 50% by mass and 100% by mass or less of butadiene units and 0% by mass or more and less than 50% by mass of styrene units; (ii) 60% by mass or more and 100% by mass or less of butadiene units and 0% by mass or more and 40% by mass or less of styrene units; (iii) 70% by mass or more and 100% by mass or less of butadiene units and 0% by mass or more and 30% by mass or less of styrene units; (iv) 80% by mass or more and 100% by mass or less of butadiene units and 0% by mass or more and 20% by mass or less of styrene units; or (v) 90% by mass or more and 100% by mass or less of butadiene units and 0% by mass or more and 10% by mass or less of styrene units.

[0065] Case B describes the case where the elastic body contains (meth)acrylate rubber. In Case B, the composition has the advantage of providing a cured product with superior toughness and / or impact resistance. A cured product with superior toughness and / or impact resistance can also be said to be a cured product with superior durability. Furthermore, many types of (meth)acrylate monomers with different alkyl group carbon chains are known and readily available. Therefore, in Case B, a wide range of polymer designs for the elastic body are possible by combining various monomers.

[0066] (Meth)acrylate rubber is an elastic body containing (meth)acrylate units as constituent units. In case B, (meth)acrylate rubber may contain the largest amount of (meth)acrylate units among all constituent units. In case B, (meth)acrylate rubber may further contain, in addition to (meth)acrylate units, constituent units derived from vinyl monomers other than (meth)acrylate monomers that are copolymerizable with (meth)acrylate monomers. In this specification, "vinyl monomers other than (meth)acrylate monomers that are copolymerizable with (meth)acrylate monomers" may also be referred to as "vinyl monomer B," and "constituent units derived from vinyl monomer B" may also be referred to as "vinyl unit B." In other words, the elastic body may contain vinyl unit B as a constituent unit.

[0067] (Meth)acrylate rubber may contain, in 100% by mass of constituent units, 50% by mass or more and 100% by mass of (meth)acrylate units and 0% by mass or more and 50% by mass of vinyl units B. In case B, (i) the (meth)acrylate rubber may contain, in 100% by mass of constituent units, (i) 50% by mass or more and 100% by mass of (meth)acrylate units and 0% by mass or more and 50% by mass of vinyl units B; (ii) more than 50% by mass and 100% by mass or less of vinyl units B and 0% by mass or more and less than 50% by mass; and (iii) 60% by mass or more and 100% by mass of (meth)acrylate units and 0% by mass or more and 4% by mass of vinyl units B. It may contain 0% by mass or less, (iv) it may contain 70% by mass or more and 100% by mass or less of (meth)acrylate units and 0% by mass or more and 30% by mass or less of vinyl units B, (v) it may contain 80% by mass or more and 100% by mass or less of (meth)acrylate units and 0% by mass or more and 20% by mass or less of vinyl units B, and (vi) it may contain 90% by mass or more and 100% by mass or less of (meth)acrylate units and 0% by mass or more and 10% by mass or less of vinyl units B. In case B, the (meth)acrylate rubber may consist only of (meth)acrylate units. As described later, if the (meth)acrylate rubber contains constituent units derived from monomers that are (meth)acrylate monomers and are also crosslinkable monomers or graftable monomers, the content of such constituent units is not counted (not included) as the content of (meth)acrylate units as described above. As described later, if the (meth)acrylate rubber contains constituent units derived from a monomer that is a vinyl monomer B and is also a crosslinkable monomer or a graftable monomer, the content of such constituent units is not counted (not included) as part of the content of the vinyl monomer B mentioned above.

[0068] Examples of (meth)acrylate monomers from which (meth)acrylate units are derived 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, 4-hydroxyethyl (meth)acrylate. Examples include (d) hydroxyalkyl (meth)acrylates such as ethyl (meth)acrylate; (e) glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidylalkyl (meth)acrylate; (f) alkoxyalkyl (meth)acrylates such as allyl (meth)acrylate and allylalkyl (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 individually or in combination of two or more. Among these (meth)acrylate monomers, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred, and butyl (meth)acrylate is more preferred.

[0069] Examples of vinyl monomer B include (a) diene monomers such as 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), and 2-chloro-1,3-butadiene; (b) aromatic vinyl monomers such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; (c) vinyl carboxylic acids such as acrylic acid and methacrylic acid; (d) vinyl cyanides such as acrylonitrile and methacrylonitrile; (e) vinyl halides such as vinyl chloride, vinyl bromide, and chloroprene; (f) vinyl acetate; (g) alkenes such as ethylene, propylene, butylene, and isobutylene; and (h) polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The vinyl monomer B described above may be used alone or in combination of two or more types. Among the vinyl monomer B described above, styrene is particularly preferred.

[0070] The (meth)acrylate rubber preferably contains (a) one or more constituent units selected from the group consisting of ethyl (meth)acrylate units, butyl (meth)acrylate units, and 2-ethylhexyl (meth)acrylate units, and may consist only of one or more constituent units selected from the group; (b) more preferably contains butyl (meth)acrylate units, and may consist only of butyl (meth)acrylate units; and (c) even more preferably contains butyl acrylate units, and may consist only of butyl acrylate units. This configuration has the advantage that the resulting composition can provide a cured film in which cracking and / or peeling during cured film deformation is further reduced.

[0071] The (meth)acrylate rubber preferably contains, in 100 parts by mass, more preferably 50 parts by mass and up to 100 parts by mass of one or more constituent units selected from the group consisting of ethyl (meth)acrylate units, butyl (meth)acrylate units, and 2-ethylhexyl (meth)acrylate units, more preferably 60 parts by mass and up to 100 parts by mass, more preferably 70 parts by mass and up to 100 parts by mass, even more preferably 80 parts by mass and up to 100 parts by mass, and particularly preferably 90 parts by mass and up to 100 parts by mass. This configuration has the advantage that the resulting composition can provide a cured film in which cracking and / or peeling during cured film deformation is particularly reduced.

[0072] The elastic body preferably contains (a) one or more constituent units selected from the group consisting of ethyl (meth)acrylate units, butyl (meth)acrylate units, and 2-ethylhexyl (meth)acrylate units, and may consist only of one or more constituent units selected from the group; (b) more preferably contains butyl (meth)acrylate units, and may consist only of butyl (meth)acrylate units; and (c) even more preferably contains butyl acrylate units, and may consist only of butyl acrylate units. This configuration has the advantage that the resulting composition can provide a cured film in which cracking and / or peeling during deformation of the cured film is further reduced.

[0073] The elastic body preferably contains, in 100 parts by mass, one or more constituent units selected from the group consisting of ethyl (meth)acrylate units, butyl (meth)acrylate units, and 2-ethylhexyl (meth)acrylate units, in total amounts of more than 50 parts by mass and up to 100 parts by mass, more preferably 60 parts by mass and up to 100 parts by mass, more preferably 70 parts by mass and up to 100 parts by mass, even more preferably 80 parts by mass and up to 100 parts by mass, and particularly preferably 90 parts by mass and up to 100 parts by mass. This configuration has the advantage that the resulting composition can provide a cured film in which cracking and / or peeling during deformation of the cured film is particularly reduced.

[0074] 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. With this configuration, the elastic body has a low glass transition temperature (Tg). As a result, (a) the composition can provide a cured film with reduced cracking and / or peeling during cured film deformation, (b) a cured product with excellent toughness, and / or (c) a lower viscosity of the composition. Ethyl (meth)acrylate rubber is intended for an elastic body in which the molar amount of ethyl (meth)acrylate units is the largest among all constituent units contained in the elastic body. Butyl (meth)acrylate rubber is intended for an elastic body in which the molar amount of butyl (meth)acrylate units is the largest among all constituent units contained in the elastic body. 2-ethylhexyl (meth)acrylate rubber is intended to be an elastic material in which the molar amount of 2-ethylhexyl (meth)acrylate units is the largest among all the constituent units contained in the elastic material.

[0075] Case C, where the elastic body contains an organosiloxane-based rubber, will be described. In Case C, the resulting composition can provide a cured product that has sufficient heat resistance and excellent impact resistance at low temperatures.

[0076] Examples of organosiloxane-based rubbers include (i) organosiloxane polymers composed of alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy, and (ii) organosiloxane polymers composed of alkyl or aryl monosubstituted silyloxy units such as organohydrogensilyloxy in which part of the alkyl in the side chain is substituted with a hydrogen atom. These organosiloxane polymers may be used individually or in combination of two or more types.

[0077] 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 organosiloxane rubber is preferably one or more selected from the group consisting of dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenylsilyloxy rubber because (i) the resulting composition can provide a cured product with excellent heat resistance, and (ii) dimethylsilyloxy rubber is more preferably selected because it is readily available and economical.

[0078] The elastic body may further contain rubber other than diene rubber, (meth)acrylate rubber, and organosiloxane rubber. Examples of rubber other than diene rubber, (meth)acrylate rubber, and organosiloxane rubber include natural rubber.

[0079] In one embodiment of the present invention, the elastic body 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; more preferably one or more selected from the group consisting of butadiene rubber, butadiene-styrene rubber, ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, 2-ethylhexyl (meth)acrylate rubber, and dimethylsilyloxy rubber; and even more preferably one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber.

[0080] The elastic body preferably contains 50 parts by mass or more and 100 parts by mass or less of (meth)acrylate rubber per 100 parts by mass of the elastic body, preferably 60 parts by mass or more and 100 parts by mass or less, preferably 70 parts by mass or more and 100 parts by mass or less, preferably 80 parts by mass or more and 100 parts by mass or less, more preferably 90 parts by mass or more and 100 parts by mass or less, and particularly preferably 95 parts by mass or more and 100 parts by mass or less. Most preferably, the elastic body contains 100 parts by mass of (meth)acrylate rubber per 100 parts by mass of the elastic body. In other words, it is most preferable that the elastic body is composed solely of (meth)acrylate rubber. When the content of (meth)acrylate rubber in the elastic body is within the above range, the resulting composition has the advantage of providing a cured film with reduced cracking and / or peeling during cured film deformation.

[0081] The (meth)acrylate rubber preferably contains, in 100 parts by mass, one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber, in a total of 50 parts by mass or more and 100 parts by mass or less, preferably 60 parts by mass or more and 100 parts by mass or less, preferably 70 parts by mass or more and 100 parts by mass or less, preferably 80 parts by mass or more and 100 parts by mass or less, more preferably 90 parts by mass or more and 100 parts by mass or less, and particularly preferably 95 parts by mass or more and 100 parts by mass or less. The (meth)acrylate rubber most preferably contains, in a total of 100 parts by mass, one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber, per 100 parts by mass of the (meth)acrylate rubber. In other words, the (meth)acrylate rubber most preferably consists only of one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber. When the total content of one or more selected from the above group in the (meth)acrylate rubber is within the above range, the resulting composition has the advantage of providing a cured film with further reduced cracking and / or peeling during cured film deformation.

[0082] The elastic body preferably contains, as a (meth)acrylate rubber, one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber in a total of 50 parts by mass or more and 100 parts by mass or less, 60 parts by mass or more and 100 parts by mass or less, 70 parts by mass or more and 100 parts by mass or less, 80 parts by mass or more and 100 parts by mass or less, more preferably 90 parts by mass or more and 100 parts by mass or less, and particularly preferably 95 parts by mass or more and 100 parts by mass or less. Most preferably, the elastic body contains, in a total of 100 parts by mass, one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber in a total of 100 parts by mass. In other words, it is most preferable that the elastic body is composed of only one or more (meth)acrylate rubbers selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber. When the total content of one or more selected from the above group in the elastic body is within the above range, the resulting composition has the advantage of providing a cured film in which cracking and / or peeling during cured film deformation is further reduced.

[0083] In the process of forming (polymerizing) an elastic body, it is preferable to use crosslinkable monomers and / or graftable monomers. When crosslinkable monomers and / or graftable monomers are used in the process of forming (polymerizing) an elastic body, a crosslinked structure can be introduced into the elastic body, which has the advantage that the elastic body can retain its particulate form in the composition and cured product. When crosslinkable monomers and / or graftable monomers are used in the process of forming (polymerizing) an elastic body, it also has the advantage that the dispersibility of polymer particles (B) in the composition and cured product can be improved. A polymer obtained using crosslinkable monomers in the process of forming (polymerizing) may have crosslinkable units. A polymer obtained using graftable monomers in the process of forming (polymerizing) may have graftable units. In other words, it is preferable that the elastic body contains crosslinkable units and / or graftable units as constituent units.

[0084] In this specification, "crosslinkable monomer" refers to a monomer having at least two or more identical (same reactivity) polymerizable groups in its molecule, and excluding conjugated diene monomers that do not involve a benzene ring. "Polymerizable group" can also be called a "polymerizable functional group," and refers to a functional group that can serve as the starting point for a polymerization reaction via a radical or the like. The polymerizable group of the crosslinkable monomer may be, for example, a carbon-carbon double bond. Examples of crosslinkable monomers include ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate (e.g., 1,4-butylene glycol diacrylate), butylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and other alkane polyol polyacrylates or alkane polyol polymethacrylates. Examples of crosslinkable monomers include divinylbenzene and triallyl cyanurate. Among these, butylene glycol diacrylate, hexanediol diacrylate, divinylbenzene, and triallyl cyanurate are particularly preferred as crosslinkable monomers.

[0085] Examples of graftable monomers include monomers having at least two polymerizable groups with different reactivity in their molecule. Examples of graftable monomers include allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, and diallyl itaconate, which are allyl esters of unsaturated carboxylic acids. Of these, allyl methacrylate is particularly preferred.

[0086] In the process of forming (polymerizing) an elastic body, the crosslinkable monomer and graftable monomer described above may be used individually or in combination of two or more types. The elastic body may contain only one type of constituent unit derived from one type of monomer among the crosslinkable monomer and graftable monomer described above, or it may contain two or more constituent units derived from two or more types of monomers in any combination.

[0087] In this specification, when examining and calculating the content and presence of constituent units, with the exception of constituent units derived from conjugated diene monomers that do not involve a benzene ring, constituent units derived from monomers that satisfy the definition of a crosslinkable monomer shall be considered as containing crosslinkable units and counted only as the content of crosslinkable units, and shall not be considered as containing constituent units derived from monomers in classifications other than crosslinkable monomers and shall not be included in the content of such constituent units. For example, a constituent unit that is a (meth)acrylate monomer and also satisfies the definition of a crosslinkable monomer shall be considered as containing crosslinkable units and counted only as the content of crosslinkable units when examining and calculating the content and presence of constituent units, and shall not be considered as containing (meth)acrylate units and shall not be included in the content of (meth)acrylate units. In this specification, when considering and calculating the content and presence of constituent units, constituent units derived from monomers that satisfy the definition of a graftable monomer are considered to contain graftable units and are counted only as graftable unit content. Constituent units derived from monomers in classifications other than graftable monomers are not considered to contain graftable units and are not included in the content of such constituent units. For example, a constituent unit that is a (meth)acrylate monomer and also satisfies the definition of a graftable monomer is considered to contain graftable units and is counted only as graftable unit content when considering and calculating the content and presence of constituent units. It is not considered to contain (meth)acrylate units and is not included in the content of (meth)acrylate units.

[0088] When the elastic body contains crosslinkable units, the crosslinkable units in the elastic body preferably include one or more selected from the group consisting of butylene glycol diacrylate units, hexanediol diacrylate units, divinylbenzene units, and triallyl cyanurate units, or may consist of only one or more selected from the group.

[0089] When the elastic body contains graftable units, the graftable units in the elastic body preferably contain allyl methacrylate units, and may consist solely of allyl methacrylate units.

[0090] The elastic body may not contain crosslinkable units but may contain graftable units. The elastic body may not contain crosslinkable units but may contain allyl methacrylate units as graftable units. The elastic body may not contain crosslinkable units but may contain only allyl methacrylate units as graftable units.

[0091] The total content of crosslinkable units and graftable units in an elastic body can be considered as the total amount of crosslinkable monomers and graftable monomers used in the formation (polymerization) process of the elastic body. If the elastic body contains crosslinkable units and / or graftable units, the elastic body preferably contains, in total, more than 0 parts by mass but 4.0 parts by mass or less, more than 0 parts by mass but 3.5 parts by mass or less, more than 0 parts by mass but 3.0 parts by mass or less, more than 0 parts by mass but 2.5 parts by mass or less, more than 0 parts by mass but 2.0 parts by mass or less, more than 0 parts by mass but 1.5 parts by mass or less, more than 0 parts by mass but 1.2 parts by mass or less, more than 0 parts by mass but 1.0 part by mass or less, more than 0 parts by mass but 0.8 parts by mass or less, more than 0 parts by mass but 0.6 parts by mass or less, even more than 0 parts by mass but 0.4 parts by mass or less, and particularly more than 0 parts by mass but 0.2 parts by mass or less. This configuration has the advantage that the resulting composition can provide a cured film in which cracking and / or peeling during deformation of the cured film is further reduced.

[0092] The volume-average particle diameter of the elastic material is preferably 130 nm or more and less than 800 nm, more preferably 130 nm or more and 790 nm or less, more preferably 130 nm or more and 780 nm or less, more preferably 130 nm or more and 770 nm or less, more preferably 130 nm or more and 750 nm or less, more preferably 130 nm or more and 725 nm or less, more preferably 130 nm or more and 700 nm or less, more preferably 130 nm or more and 600 nm or less, more preferably 130 nm or more and 500 nm or less, even more preferably 150 nm or more and 500 nm or less, and particularly preferably 200 nm or more and 500 nm or less. When the volume-average particle diameter of the elastic material is 130 nm or more, there is the advantage that (i) an elastic material having a desired volume-average particle diameter can be stably obtained, (ii) powder or granular polymer particles (B) can be easily obtained, and (iii) the dispersibility of polymer particles (B) during composition preparation is excellent, and as a result, the dispersibility of polymer particles (B) in the composition and cured product is excellent. When the volume-average particle diameter of the elastic material is 800 nm or less, the resulting cured product has the advantage of good heat resistance and impact resistance. The volume-average particle diameter of the elastic material can be measured using a dynamic light scattering particle size distribution analyzer or the like, with aqueous latex containing the elastic material as the sample. The method for measuring the volume-average particle diameter of the elastic material will be described in detail in the examples below.

[0093] The glass transition temperature of the elastic body is preferably less than 0°C, more preferably -10°C or lower, more preferably -20°C or lower, more preferably -30°C or lower, even more preferably -40°C or lower, and particularly preferably -50°C or lower. When the glass transition temperature of the elastic body is within the above range, polymer particles (B) having an elastic body with a low Tg can be obtained. As a result, the resulting composition can provide a cured product with excellent toughness, and thus has the advantage of providing a cured film with reduced cracking and / or peeling during deformation of the cured film. The lower limit of the glass transition temperature of the elastic body is not particularly limited, for example, -150°C. In this specification, "glass transition temperature" may also be referred to as "Tg".

[0094] In this specification, the Tg of an elastic body is one of the following: (a) a value obtained by viscoelasticity measurement using a flat plate made of the elastic body; (b) a value obtained by viscoelasticity measurement using a flat plate made of polymer particles (B); or (c) a value calculated by the FOX formula based on the constituent units of the elastic body other than the crosslinkable units and graftable units.

[0095] This section describes a method for determining the Tg of an elastic material by viscoelasticity measurement using a flat plate made of an elastic material. A viscoelasticity measurement (tensile method, heating rate: 4°C / min, measurement frequency: 1 Hz) is performed using a flat plate (1 mm thick) made of an elastic material, and a graph of the loss tangent (tanδ) is obtained. The peak temperature value in the obtained graph can be adopted as the Tg of the elastic material. For viscoelasticity measurement, for example, a dynamic viscoelasticity measuring device (e.g., DVA-200, manufactured by IT Measurement Control Co., Ltd.) can be used. A flat plate made of an elastic material can be obtained using an aqueous latex of an elastic material by, for example, the following method. First, the elastic material in the aqueous latex of the elastic material is solidified by any method (e.g., salting out, freeze-thaw, shear) to obtain a solidified product of the elastic material. By drying the obtained solidified product, a powder or granule of the elastic material is obtained. Alternatively, the powder or granule of the elastic material is obtained by spray-drying the aqueous latex of the elastic material. Next, a flat plate with a thickness of 1 mm can be obtained by pressing the powder or granule of the elastic material under conditions that allow for a flat plate that is as uniform as possible.

[0096] This section describes a method for determining the Tg of an elastic body by viscoelastic measurement using a flat plate made of polymer particles (B). Viscoelastic measurement (tensile method, heating rate: 4°C / min, measurement frequency: 1 Hz) is performed using a flat plate (thickness 1 mm) made of polymer particles (B), and a graph of the loss tangent (tanδ) is obtained. The Tg of the elastic body is determined from the peak in the obtained tanδ graph. Here, if the composition of the elastic body, graft portion, and any optional intermediate portion contained in the polymer particles (B) is all the same, the tanδ graph obtained by viscoelastic measurement using the flat plate made of polymer particles (B) may have a single clean peak. In that case, the temperature of that peak can be adopted as the Tg of the elastic body. On the other hand, if the composition of the elastic body, graft portion, and any optional intermediate portion contained in the polymer particles (B) are different from each other, the tanδ graph obtained by viscoelastic measurement using the flat plate made of polymer particles (B) may have multiple peaks or peaks with abnormal shapes. Abnormally shaped peaks include, for example, (i) peaks with a shoulder peak, (ii) peaks with peak splitting, (iii) broad peaks, and (iv) tailing or leading peaks. When the compositions of the elastic body, intermediate, and graft portion contained in the polymer particles (B) are different from each other, the glass transition temperature of the elastic body can be determined by combining the data from the tanδ graph with other analytical data such as compositional analysis. For viscoelasticity measurement, for example, a dynamic viscoelasticity measuring device (e.g., DVA-200, manufactured by IT Measurement Control Co., Ltd.) can be used. A flat plate made of polymer particles (B) can be obtained using aqueous latex of polymer particles (B) by, for example, the following method. First, the polymer particles (B) in the aqueous latex of polymer particles (B) are solidified by any method (e.g., salting out, freeze-thaw, shear) to obtain a solidified polymer particle (B). By drying the obtained solidified polymer particle (B) powder. Alternatively, a powder of polymer particles (B) can be obtained by spray-drying an aqueous latex of polymer particles (B). Then, a 1 mm thick flat plate can be obtained by pressing the polymer particle powder under conditions that produce the most uniform flat plate possible.

[0097] Based on the constituent units contained in the elastic body, i.e., the monomers used in the manufacture (polymerization) of the elastic body, the Tg of the elastic body can be calculated using the following FOX formula (Equation 1): 1 / Tg = w １ / Tg １ +w ２ / Tg ２ +...+w ｎ / Tg ｎ (Equation 1); In the FOX formula for calculating the Tg of an elastic body, Tg １ , Tg ２ , ..., Tg ｎ These represent the Tg(K) of the monomer homopolymer from which the constituent units 1, 2, ..., n that make up the elastic body originate, and w １ , lol ２ ,... lol ｎ These represent the mass fractions of the constituent units 1, 2, ..., n that make up the elastic body. Furthermore, the Tg of the homopolymer can be the values ​​listed in, for example, the Polymer Handbook Fourth Edition (edited by J. Brandup et al., John Wiley & Sons, Inc.).

[0098] However, when calculating the Tg of an elastic body using the FOX formula, crosslinkable units and graftable units are not considered. That is, the Tg of the elastic body is calculated using the mass fraction of the constituent units other than crosslinkable and graftable units, and the Tg of the monomer homopolymer from which those constituent units were derived. Therefore, when calculating the Tg of an elastic body using the FOX formula, the "glass transition temperature of the elastic body" can also be said to be the "glass transition temperature of the elastic body excluding the crosslinkable and graftable units."

[0099] When the total content of crosslinking units and grafting units in 100 parts by mass of the elastic body is 4.0 parts by mass or less, the influence of the crosslinking units and grafting units on the Tg of the elastic body is very small. Therefore, when the total content of crosslinking units and grafting units in 100 parts by mass of the elastic body is 4.0 parts by mass or less, the Tg of the elastic body determined by viscoelastic measurement using a flat plate made of the elastic body and the Tg of the elastic body determined by viscoelastic measurement using a flat plate made of polymer particles (B) can be considered to be the same as the Tg of the elastic body calculated by the FOX formula based on the constituent units of the elastic body other than the crosslinking units and grafting units.

[0100] The transition temperature (Tg) of an elastic material can be determined by factors such as the composition of the constituent units contained within the elastic material. In other words, the Tg of the resulting elastic material can be adjusted by changing the composition of the monomers used during the manufacturing (polymerization) process.

[0101] The polymer particles (B) preferably contain an elastic body in an amount of 40.0% to 97.0% by mass, more preferably 60.0% to 95.0% by mass, more preferably 70.0% to 93.0% by mass, even more preferably 70.0% to 90.0% by mass, and particularly preferably 80.0% to 90.0% by mass, based on 100% by mass of the polymer particles (B). When the polymer particles (B) contain an elastic body in (a) 40% by mass or more, the composition has the advantage of being able to provide a cured product with excellent toughness and impact resistance, and when it contains (b) 97% by mass or less, the polymer particles (B) do not easily aggregate (are difficult to aggregate), so the composition does not become highly viscous, and as a result, the composition has the advantage of being easy to handle.

[0102] (Intermediate portion) It is preferable that the polymer particles (B) further have an intermediate portion. In the section on (Intermediate portion), the intermediate portion will be described using an embodiment in which the polymer particles (B) further have an intermediate portion as an example. The intermediate portion can contribute to improving the dispersibility of the polymer particles (B) when preparing the composition, and as a result, it can contribute to improving the dispersibility of the polymer particles (B) in the composition and the cured product. In other words, when the polymer particles (B) further have an intermediate portion, they have excellent dispersibility when preparing the composition, and as a result, they have excellent dispersibility in the composition and the cured product. When the dispersibility of polymer particles (B) in the cured product is good, there is the advantage that (i) cracking and / or peeling when the cured film is deformed is reduced, and (ii) the aesthetic appearance of the cured product (cured film) is good.

[0103] The intermediate portion may be formed (polymerized) in the presence of the elastic body after the elastic body has been formed (polymerized) and before the graft portion has been formed (polymerized), as will be described later. Preferably, at least a portion of the intermediate portion covers at least a portion of the elastic body. At least a portion of the intermediate portion may be covered by at least a portion of the graft portion. At least a portion of the intermediate portion may also extend inside the elastic body.

[0104] The constituent units that make up the intermediate portion, or in other words, the constituent units included in the intermediate portion, are not particularly limited. Preferably, the intermediate portion contains one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units, and (meth)acrylate units. This configuration has the advantage of excellent dispersibility of polymer particles (B) during composition preparation, and as a result, excellent dispersibility of polymer particles (B) in the composition and cured product.

[0105] The intermediate portion preferably contains aromatic vinyl units, vinyl cyanide units, and (meth)acrylate units in total at 0% to 84% by mass, more preferably 0% to 80% by mass, even more preferably 0% to 75% by mass, and particularly preferably 0% to 70% by mass, as constituent units, out of 100% by mass of all constituent units in the intermediate portion. This configuration has the advantage of superior dispersibility of polymer particles (B) during composition preparation, resulting in superior dispersibility of polymer particles (B) in the composition and cured product. As described above, if the intermediate portion contains constituent units derived from monomers that are aromatic vinyl monomers and are also crosslinkable monomers or graftable monomers, the content of such constituent units is not counted (not included) in the content of aromatic vinyl units as described above. As described above, if the intermediate portion contains a constituent unit derived from a monomer that is a vinyl cyanide monomer and is also a crosslinkable monomer or a graftable monomer, the content of such constituent unit shall not be counted (included) as part of the content of vinyl cyanide units as described above. As described above, if the intermediate portion contains a constituent unit derived from a monomer that is a (meth)acrylate monomer and is also a crosslinkable monomer or a graftable monomer, the content of such constituent unit shall not be counted (included) as part of the content of (meth)acrylate units as described above.

[0106] The intermediate portion more preferably contains, as a constituent unit, one or more selected from the group consisting of (i) methyl (meth)acrylate units, styrene units, butyl (meth)acrylate units, and acrylonitrile units, and (ii) one or more selected from the group consisting of methyl methacrylate units and styrene units. This configuration has the advantage of providing better dispersibility of polymer particles (B) during composition preparation, and as a result, better dispersibility of polymer particles (B) in the composition and cured product.

[0107] The intermediate portion preferably contains, as constituent units, one or more selected from the group consisting of methyl (meth)acrylate units, styrene units, butyl (meth)acrylate units, and acrylonitrile units in total, at a concentration of 0% to 84% by mass, more preferably 0% to 80% by mass, even more preferably 0% to 75% by mass, and particularly preferably more than 0% by mass and 70% by mass or less, based on 100% by mass of all constituent units of the intermediate portion. This configuration has the advantage of further improving the dispersibility of polymer particles (B) during composition preparation, and as a result, further improving the dispersibility of polymer particles (B) in the composition and cured product.

[0108] In the intermediate formation (polymerization) process, crosslinkable monomers and / or graftable monomers are used. Therefore, the intermediate contains crosslinkable units and / or graftable units. The inclusion of crosslinkable units and / or graftable units in the intermediate provides the advantage of superior dispersibility of polymer particles (B) during composition preparation, resulting in superior dispersibility of polymer particles (B) in the composition and cured product.

[0109] The specific examples of crosslinkable monomers and graftable monomers are the same as those described in the section on (elastic materials) above, so we will refer to that description and omit further explanation here.

[0110] The crosslinkable units in the intermediate portion preferably include one or more selected from the group consisting of butylene glycol diacrylate units, hexanediol diacrylate units, divinylbenzene units, and triallyl cyanurate units, and may consist of only one or more selected from this group.

[0111] The graft units in the intermediate region preferably include allyl methacrylate units, and may consist solely of allyl methacrylate units.

[0112] The intermediate portion may not contain crosslinkable units but may contain graftable units. The intermediate portion may not contain crosslinkable units but may contain allyl methacrylate units as graftable units. The intermediate portion may not contain crosslinkable units but may contain only allyl methacrylate units as graftable units.

[0113] The total content of crosslinkable units and graftable units in the intermediate portion can be considered as the total amount of crosslinkable monomers and graftable monomers used in the formation (polymerization) process of the intermediate portion. The intermediate portion preferably contains 5.0 parts by mass or more of crosslinkable units and graftable units in total, more preferably 8.0 parts by mass or more, more preferably 10.0 parts by mass or more, more preferably 13.0 parts by mass or more, more preferably 15.0 parts by mass or more, more preferably 16.0 parts by mass or more, more preferably 20.0 parts by mass or more, even more preferably 25.0 parts by mass or more, and particularly preferably 30.0 parts by mass or more. This configuration has the advantage of having better dispersibility of polymer particles (B) during composition preparation, and as a result, better dispersibility of polymer particles (B) in the composition and cured product. The upper limit of the total content of crosslinkable units and graftable units in the intermediate portion is not particularly limited, but is, for example, 100 parts by mass or 80 parts by mass. That is, the intermediate portion may consist only of crosslinkable units and / or graftable units.

[0114] The glass transition temperature (Tg) of the intermediate region is preferably 0°C or higher, more preferably 10°C or higher, more preferably 20°C or higher, more preferably 30°C or higher, more preferably 40°C or higher, more preferably 50°C or higher, more preferably 60°C or higher, more preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and particularly preferably 100°C or higher. When the Tg of the intermediate region is within the above range, there is the advantage that the dispersibility of polymer particles (B) in the composition and cured product is even better. The upper limit of the Tg of the intermediate region is not particularly limited, and is, for example, 150°C.

[0115] In this specification, the Tg of the intermediate portion is either (a) a value obtained by viscoelasticity measurement using a flat plate made of polymer particles (B), or (b) a value calculated by the FOX formula based on the constituent units of the intermediate portion other than the crosslinkable units and graftable units.

[0116] A method for determining the Tg of the intermediate region by viscoelastic measurement using a flat plate made of polymer particles (B) is described below. Viscoelastic measurement (tensile method, heating rate: 4°C / min, measurement frequency: 1 Hz) is performed using a flat plate (thickness 1 mm) made of polymer particles (B), and a graph of the loss tangent (tanδ) is obtained. The Tg of the intermediate region is determined from the peaks in the obtained tanδ graph. As described above, if there is one clean peak in the obtained tanδ graph, the temperature of that peak can be adopted as the Tg of the intermediate region. On the other hand, if there are multiple peaks or abnormally shaped peaks in the obtained tanδ graph, the glass transition temperature of the intermediate region can be determined by combining the data from the tanδ graph with other analytical data such as compositional analysis. For viscoelastic measurement, for example, a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.) can be used. The method for preparing the flat plate made of polymer particles (B) is as described in the (elastic body) section above.

[0117] Based on the constituent units contained in the intermediate, i.e., the monomers used in the (polymerization) production of the intermediate, it is possible to calculate the Tg of the intermediate using the FOX formula (Equation 1) described above. In the FOX formula for calculating the Tg of the intermediate, Tg １ , Tg ２ , ..., Tg ｎ These represent the Tg(K) of the monomer homopolymer from which the constituent units 1, 2, ..., n that make up the intermediate part originate, and w １ , lol ２ ,... lol ｎ These represent the mass fractions of the constituent units 1, 2, ..., n that make up the intermediate portion.

[0118] However, when calculating the Tg of the intermediate region using the FOX formula, crosslinkable units and graftable units are not considered. That is, the Tg of the intermediate region is calculated using the mass fraction of the constituent units other than crosslinkable units and graftable units, and the Tg of the monomer homopolymer from which those constituent units were derived. Therefore, when calculating the Tg of the intermediate region using the FOX formula, the "glass transition temperature of the intermediate region" can also be said to be the "glass transition temperature of the intermediate region excluding the crosslinkable units and graftable units."

[0119] The polymer particles (B) preferably contain an intermediate portion in an amount of 0.5% by mass or more and 5.0% by mass or less, more preferably 1.0% by mass or more and 4.0% by mass or less, even more preferably 2.0% by mass or more and 4.0% by mass or less, and particularly preferably 2.5% by mass or more and 4.0% by mass or less, based on 100% by mass of the polymer particles (B). When the polymer particles (B) contain an intermediate portion in (a) 0.5% by mass or more, the dispersibility of the polymer particles (B) during composition preparation is better, and as a result, the dispersibility of the polymer particles (B) in the composition and cured product is better, and when it contains (b) 5.0% by mass or less, the obtained composition has the advantage of providing a cured film in which cracking and / or peeling during deformation of the cured film is further reduced.

[0120] (Graft portion) If the polymer particles (B) do not have an intermediate portion, the "graft portion" refers to the polymer that is graft-bonded to the elastic body. If the polymer particles (B) do not have an intermediate portion, the graft portion can be obtained by forming (polymerizing) the elastic body, and then forming (polymerizing) the graft portion in the presence of the elastic body. If the polymer particles (B) do not have an intermediate portion, it is preferable that at least a portion of the graft portion covers at least a portion of the elastic body. If the polymer particles (B) do not have an intermediate portion, at least a portion of the graft portion may penetrate into the inside of the elastic body. If the polymer particles (B) further have an intermediate portion, the "graft portion" refers to the polymer that is graft-bonded to the elastic body and / or the intermediate portion. If the polymer particles (B) further have an intermediate portion, the graft portion can be obtained by forming (polymerizing) the elastic body, then forming (polymerizing) the intermediate portion in the presence of the elastic body, and then forming (polymerizing) the graft portion in the presence of the polymer including the elastic body and the intermediate portion. If the polymer particle (B) further has an intermediate portion, the graft portion may be graft-bonded to the elastic body only, to the intermediate portion only, or to both the elastic body and the intermediate portion. If the polymer particle (B) further has an intermediate portion, it is preferable that at least a portion of the graft portion covers at least a portion of the elastic body and / or at least a portion of the intermediate portion. If the polymer particle (B) further has an intermediate portion, it is also possible that at least a portion of the graft portion penetrates inside the elastic body and / or the intermediate portion. It is preferable that at least a portion of the graft portion is located on the outermost side of the polymer particle (B).

[0121] The graft portion includes, as a constituent unit, one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units, and (meth)acrylate units. Because the graft portion has the above-mentioned structure, it can perform various roles. These "various roles" include, for example, (a) improving the compatibility between the resin component (e.g., thermosetting resin (A)) in the composition and the polymer particles (B), (b) improving the dispersibility of the polymer particles (B) in the composition and cured product, and (c) enabling the polymer particles (B) to be dispersed in the composition and cured product in the state of primary particles.

[0122] Specific examples of aromatic vinyl monomers from which aromatic vinyl units are derived include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

[0123] Specific examples of vinyl cyanide monomers from which the vinyl cyanide unit is derived include acrylonitrile and methacrylonitrile.

[0124] The specific examples of (meth)acrylate monomers from which the (meth)acrylate unit is derived are the same as those described in the (elastic materials) section above; therefore, we will refer to that description and omit the explanation here.

[0125] The graft portion may contain only one type of constituent unit derived from one type of monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers as described above, or it may contain two or more constituent units derived from two or more types of monomers in any combination.

[0126] The graft portion preferably contains aromatic vinyl units, vinyl cyanide units, and (meth)acrylate units in total at 10% to 95% by mass, more preferably 30% to 92% by mass, even more preferably 50% to 90% by mass, particularly preferably 60% to 87% by mass, and most preferably 70% to 85% by mass, as constituent units of aromatic vinyl units, vinyl cyanide units, and (meth)acrylate units, out of 100% by mass of all constituent units of the graft portion. With this configuration, the resulting composition can provide a cured film with reduced cracking and / or peeling during cured film deformation. In order to particularly exhibit the above-mentioned advantages, the graft portion may contain, in total at 100% by mass of 100% by mass of all constituent units of the graft portion, one or more selected from the group consisting of aromatic vinyl units, vinyl cyanide units, and (meth)acrylate units. In other words, the graft portion may consist of only one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units, and (meth)acrylate units. As described above, if the graft portion contains constituent units derived from a monomer that is an aromatic vinyl monomer and is also a crosslinkable monomer or a graftable monomer, the content of such constituent units shall not be counted (included) as part of the content of aromatic vinyl units as described above. As described above, if the graft portion contains constituent units derived from a monomer that is a vinyl cyanide monomer and is also a crosslinkable monomer or a graftable monomer, the content of such constituent units shall not be counted (included) as part of the content of vinyl cyanide units as described above. As described above, if the graft portion contains constituent units derived from a monomer that is a (meth)acrylate monomer and is also a crosslinkable monomer or a graftable monomer, the content of such constituent units shall not be counted (included) as part of the content of (meth)acrylate units as described above.

[0127] The graft portion more preferably contains, as a constituent unit, one or more selected from the group consisting of (i) methyl (meth)acrylate units, butyl (meth)acrylate units, styrene units, acrylonitrile units, and 2-ethylhexyl (meth)acrylate units, and particularly preferably contains, one or more selected from the group consisting of methyl (meth)acrylate units and butyl (meth)acrylate units. This configuration has the advantage of providing better dispersibility of polymer particles (B) during composition preparation, and as a result, better dispersibility of polymer particles (B) in the composition and cured product.

[0128] The graft portion preferably contains, as constituent units, one or more selected from the group consisting of methyl (meth)acrylate units, butyl (meth)acrylate units, styrene units, acrylonitrile units, and 2-ethylhexyl (meth)acrylate units in total, at a concentration of 50% to 100% by mass, more preferably 60% to 100% by mass, even more preferably 70% to 100% by mass, particularly preferably 80% to 100% by mass, and most preferably 90% to 100% by mass, based on 100% by mass of all constituent units of the graft portion. This configuration has the advantage of further improving the dispersibility of polymer particles (B) during composition preparation, and as a result, further improving the dispersibility of polymer particles (B) in the composition and cured product. In order to particularly exhibit the advantages described above, the graft portion may contain, as constituent units, one or more selected from the group consisting of methyl (meth)acrylate units, butyl (meth)acrylate units, styrene units, acrylonitrile units, and 2-ethylhexyl (meth)acrylate units in total amount of 100% by mass of the total constituent units of the graft portion. In other words, the graft portion may consist of only one or more selected from the group consisting of methyl (meth)acrylate units, butyl (meth)acrylate units, styrene units, acrylonitrile units, and 2-ethylhexyl (meth)acrylate units.

[0129] In the graft formation (polymerization) process, it is preferable to substantially avoid using crosslinkable monomers and graftable monomers. In this specification, "substantially avoid using crosslinkable monomers and graftable monomers in the graft formation (polymerization) process" means that the total content (amount used) of crosslinkable monomers and graftable monomers in 100 parts by mass of the monomer mixture used in the graft formation (polymerization) process is 0.25 parts by mass or less. When crosslinkable monomers and graftable monomers are substantially avoided in the graft formation (polymerization) process, the resulting composition has the advantage of providing a cured film with further reduced cracking and / or peeling during cured film deformation. When crosslinkable monomers and graftable monomers are substantially avoided in the graft formation (polymerization) process, the resulting graft portion substantially does not contain crosslinkable units and graftable units. It is preferable that the graft portion substantially does not contain crosslinkable units and graftable units as constituent units. In this specification, "the graft portion is substantially free of crosslinkable units and graftable units" means that the total content of crosslinkable units and graftable units in the graft portion is 0.25 parts by mass or less per 100 parts by mass of the graft portion. If crosslinkable monomers and graftable monomers are not used in the formation (polymerization) process of the graft portion, the total amount of crosslinkable monomers and graftable monomers used is 0 parts by mass, and the total content of crosslinkable units and graftable units in the graft portion of the resulting polymer particles (B) is 0 parts by mass. In this specification, "the graft portion is substantially free of crosslinkable units and graftable units" can also be expressed as "(i) the graft portion does not contain crosslinkable units and graftable units, or (ii) the graft portion contains crosslinkable units and / or graftable units, and the total content of crosslinkable units and graftable units in 100 parts by mass of the graft portion is greater than 0 parts by mass and 0.25 parts by mass or less."

[0130] The specific examples of crosslinkable monomers and graftable monomers are the same as those described in the section on (elastic materials) above, so we will refer to that description and omit further explanation here.

[0131] In one embodiment of the present invention, the glass transition temperature (Tg) of the graft portion is 25°C or higher and 50°C or lower. In one embodiment of the present invention, having a Tg of 25°C or higher in the graft portion has the advantage that the polymer particles (B) can be easily removed from the aqueous dispersion of polymer particles (Aqueous latex). Furthermore, the higher the Tg of the graft portion, the better the dispersibility of the polymer particles (B) in the composition and cured product, and as a result, the composition has the advantage of providing a thin film with superior appearance. In one embodiment of the present invention, having a Tg of 50°C or lower in the graft portion has the advantage that the polymer particles (B) can be easily dispersed in the thermosetting resin (A). From the viewpoint of further enjoying these advantages, the Tg of the graft portion is preferably 25°C or higher and 49°C or lower, more preferably 27°C or higher and 49°C or lower, more preferably 29°C or higher and 48°C or lower, more preferably 31°C or higher and 48°C or lower, even more preferably 33°C or higher and 47°C or lower, and particularly preferably 35°C or higher and 47°C or lower.

[0132] In this specification, the Tg of the graft portion is either (a) a value obtained by viscoelasticity measurement using a flat plate made of polymer particles (B), or (b) a value calculated by the FOX formula based on the constituent units of the graft portion other than the crosslinkable units and graftable units.

[0133] A method for determining the Tg of a graft by viscoelastic measurement using a flat plate made of polymer particles (B) is described below. Viscoelastic measurement (tensile method, heating rate: 4°C / min, measurement frequency: 1 Hz) is performed using a flat plate (thickness 1 mm) made of polymer particles (B), and a graph of loss tangent (tanδ) is obtained. The Tg of the graft is determined from the peaks in the obtained tanδ graph. As described above, if there is one clean peak in the obtained tanδ graph, the temperature of that peak can be adopted as the Tg of the graft. On the other hand, if there are multiple peaks or abnormally shaped peaks in the obtained tanδ graph, the glass transition temperature of the graft can be determined by combining the data from the tanδ graph with other analytical data such as compositional analysis. For viscoelastic measurement, for example, a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.) can be used. The method for preparing the flat plate made of polymer particles (B) is as described in the (elastic body) section above.

[0134] Based on the constituent units contained in the graft, i.e., the monomers used in the (polymerization) production of the graft, it is possible to calculate the Tg of the graft using the FOX formula (Equation 1) described above. In the FOX formula for calculating the Tg of the graft, Tg １ , Tg ２ , ..., Tg ｎ Each of these represents the Tg(K) of the monomer homopolymer from which the constituent units 1, 2, ..., n that make up the graft portion originate, and w １ , lol ２ ,... lol ｎ These represent the mass fractions of the constituent units 1, 2, ..., n that make up the graft portion.

[0135] However, when calculating the Tg of the graft using the FOX formula, crosslinkable units and graftable units are not considered. That is, the Tg of the graft is calculated using the mass fraction of the constituent units other than crosslinkable units and graftable units, and the Tg of the monomer homopolymer from which those constituent units were derived. Therefore, when calculating the Tg of the graft using the FOX formula, the "glass transition temperature of the graft" can also be said to be the "glass transition temperature of the graft excluding the crosslinkable units and graftable units."

[0136] If the graft portion substantially does not contain crosslinkable units and graftable units, the influence of the crosslinkable units and graftable units on the Tg of the graft portion is extremely small and negligible. Therefore, if the graft portion substantially does not contain crosslinkable units and graftable units, the Tg of the graft portion obtained by viscoelastic measurement using a flat plate made of polymer particles (B) can be considered to be the same as the Tg of the graft portion calculated by the FOX formula based on the constituent units other than crosslinkable units and graftable units among the constituent units that make up the graft portion.

[0137] The polymer particles (B) preferably contain graft portions in an amount of 3.0% to 60.0% by mass, 5.0% to 60.0% by mass, more preferably 7.5% to 40.0% by mass, even more preferably 10.0% to 30.0% by mass, and particularly preferably 12.5% ​​to 20.0% by mass, based on 100% by mass of the polymer particles (B). When the polymer particles (B) contain graft portions in an amount of (a) 3.0% by mass or more, the dispersibility of the polymer particles (B) during composition preparation is better, resulting in the advantage of better dispersibility of the polymer particles (B) in the composition and cured product. When the graft portions contain (b) 60.0% by mass or less, the resulting composition has the advantage of providing a cured film with further reduced cracking and / or peeling during cured film deformation.

[0138] In this specification, a monomer having one or more reactive functional groups X selected from the group consisting of oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups, benzoxazine groups, and cyanate ester groups is also referred to as "reactive monomer X". In this specification, a constituent unit derived from reactive monomer X is also referred to as "constituent unit X".

[0139] In the manufacturing process of polymer particles (B), it is preferable to substantially not use reactive monomer X. In this specification, "substantially not using reactive monomer X in the manufacturing process of polymer particles (B)" means that the total content (amount used) of reactive monomer X in the monomer mixture used in the manufacturing process of polymer particles (B) is 0.25 parts by mass or less per 100 parts by mass of the total amount of reactive monomer X. When reactive monomer X is substantially not used in the manufacturing process of polymer particles (B), the resulting composition has the advantage of being able to provide a cured film with further reduced cracking and / or peeling during cured film deformation. When reactive monomer X is substantially not used in the manufacturing process of polymer particles (B), the resulting polymer particles (B) substantially do not contain constituent units X derived from reactive monomer X. It is preferable that polymer particles (B) substantially do not contain constituent units X derived from reactive monomer X. In this specification, "polymer particles (B) substantially contain no constituent units X derived from reactive monomer X" means that the total content of constituent units X derived from reactive monomer X in polymer particles (B) is 0.25 parts by mass or less per 100 parts by mass of polymer particles (B). If reactive monomer X is not used in the manufacturing process of polymer particles (B), the total amount of reactive monomer X used is 0 parts by mass, and the total content of constituent units X derived from reactive monomer X in the resulting polymer particles (B) is 0 parts by mass.

[0140] Specific examples of reactive monomers having an oxetane group include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl]alkyloxetane.

[0141] Specific examples of reactive monomers having hydroxyl groups include, for example, (a) hydroxylinear alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate (particularly preferred are hydroxylinear C1-6 alkyl (meth)acrylates); (b) caprolactone-modified hydroxy (meth)acrylates; (c) hydroxybranched alkyl (meth)acrylates such as α-(hydroxymethyl)methyl acrylate and α-(hydroxymethyl)ethyl acrylate; and (d) hydroxyl group-containing (meth)acrylates such as mono(meth)acrylates of polyester diols obtained from divalent carboxylic acids (such as phthalic acid) and divalent alcohols (such as propylene glycol) (particularly preferred are saturated polyester diols). Note that "linear C1-6 alkyl" refers to linear alkyls having 1 to 6 carbon atoms.

[0142] Specific examples of reactive monomers having an epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and glycidyl group-containing vinyl monomers such as allyl glycidyl ether. Among these, from the viewpoint of reactivity, glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether are preferred as reactive monomers having an epoxy group, glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether are more preferred, and glycidyl methacrylate is even more preferred.

[0143] Specific examples of reactive monomers having an amino group include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, 2-vinylpyridine, 4-vinylpyridine, and these are H＋ X － Examples include compounds having a structure obtained by neutralization with an acid represented by .

[0144] Specific examples of reactive monomers having an imide group include maleimide, phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-benzylmaleimide.

[0145] Specific examples of reactive monomers having a carboxylic acid group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, as well as dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. From the viewpoint of reactivity, monocarboxylic acids are preferably used as monomers having a carboxylic acid group.

[0146] Specific examples of reactive monomers having a carboxylic acid anhydride group include maleic anhydride.

[0147] If the polymer particle (B) does not have an intermediate portion, the elastic body and the graft portion in the polymer particle (B) may have a layered structure. If the polymer particle (B) does not have an intermediate portion, for example, an embodiment in which the elastic body exists as the innermost layer and the graft portion exists as the outermost layer is also one embodiment of the present invention. If the polymer particle (B) further has an intermediate portion, the elastic body, intermediate portion and graft portion in the polymer particle (B) may have a layered structure. If the polymer particle (B) further has an intermediate portion, for example, an embodiment in which the elastic body exists as the innermost layer, the intermediate portion exists as an intermediate layer, and the graft portion exists as the outermost layer is also one embodiment of the present invention.

[0148] (Volume-average particle diameter (Mv) of polymer particles (B)) The volume-average particle diameter (Mv) of polymer particles (B) is 130 nm or more and 800 nm or less, preferably 130 nm or more and 790 nm or less, more preferably 130 nm or more and 780 nm or less, more preferably 130 nm or more and 770 nm or less, more preferably 130 nm or more and 750 nm or less, more preferably 130 nm or more and 725 nm or less, more preferably 130 nm or more and 700 nm or less, more preferably 130 nm or more and 600 nm or less, more preferably 130 nm or more and 500 nm or less, even more preferably 150 nm or more and 500 nm or less, and particularly preferably 200 nm or more and 500 nm or less. When the volume-average particle diameter (Mv) of the polymer particles (B) is 130 nm or greater, (i) it has the advantage that powder or granular polymer particles (B) can be easily obtained, and (ii) the dispersibility of the polymer particles (B) during composition preparation is excellent, resulting in excellent dispersibility of the polymer particles (B) in the composition and cured product. When the volume-average particle diameter of the polymer particles (B) is 800 nm or less, it has the advantage that the resulting cured product has good heat resistance and impact resistance. Furthermore, when the volume-average particle diameter of the polymer particles (B) is within the above range, it also has the advantage that a composition with the desired viscosity and high stability can be obtained. In this specification, "volume-average particle diameter (Mv) of polymer particles (B)" refers to the volume-average particle diameter of the primary particles of polymer particles (B), unless otherwise specified. The volume-average particle diameter of polymer particles (B) can be measured using a dynamic light scattering particle size distribution analyzer or the like, with aqueous latex containing polymer particles (B) as a sample. The volume-average particle diameter of polymer particles (B) will be described in detail in the following examples. The volume-average particle diameter of polymer particles (B) can also be measured by cutting the cured product of the composition (e.g., a cured film), imaging the cut surface using an electron microscope or the like, and using the obtained imaging data (image).

[0149] (Method for producing polymer particles (B)) Polymer particles (B) without an intermediate portion can be produced by performing (S1) and (S2) below in order: (S1) Polymerize the elastic body; (S2) Polymerize the graft portion in the presence of the obtained elastic body. The polymerization of the graft portion in (S2) is graft polymerization. Polymer particles (B) having an intermediate portion can be produced by performing (T1) to (T3) below in order: (T1) Polymerize the elastic body; (T2) Polymerize the intermediate portion in the presence of the obtained elastic body; (T3) Polymerize the graft portion in the presence of the obtained elastic body and the polymer having an intermediate portion. The polymerization of the graft portion in (T3) is graft polymerization. An example of a method for producing polymer particles (B) (polymerization method) will be described below.

[0150] Polymer particles (B) can be produced by known methods, such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Specifically, the polymerization of the elastic body, the intermediate portion, and the graft portion (graft polymerization) in polymer particles (B) can each be carried out by known methods (e.g., emulsion polymerization, suspension polymerization, microsuspension polymerization, etc.). Among these, emulsion polymerization is particularly preferred as a method for producing polymer particles (B). Emulsion polymerization has the advantages of (a) easy composition design of polymer particles (B) and (b) easy industrial production of polymer particles (B). When polymer particles (B) are obtained by emulsion polymerization, a latex containing polymer particles (B) (e.g., aqueous latex) can be obtained.

[0151] When employing emulsion polymerization as a method for producing polymer particles (B), known emulsifiers (dispersants) can be used to produce polymer particles (B).

[0152] Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives. Examples of anionic emulsifiers include sulfur-based emulsifiers, phosphorus-based emulsifiers, sarcosinic acid-based emulsifiers, and carboxylic acid-based emulsifiers. Examples of sulfur-based emulsifiers include sodium dodecylbenzenesulfonate (abbreviated as SDBS). Examples of phosphorus-based emulsifiers include sodium polyoxyethylene lauryl ether phosphate.

[0153] When emulsion polymerization is used as the method for producing polymer particles (B), a thermal decomposition initiator can be used to produce the polymer particles (B). Examples of known thermal decomposition initiators include (a) 2,2'-azobisisobutyronitrile and (b) peroxides such as organic peroxides and inorganic peroxides. Examples of organic peroxides include t-butyl peroxyisopropyl carbonate, paramentane 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.

[0154] A redox-type initiator can also be used in the production of polymer particles (B). The redox-type initiator is an initiator comprising (a) a peroxide such as an organic peroxide or an inorganic peroxide, and (b) a transition metal salt such as iron(II) sulfate, and / or a reducing agent such as sodium formaldehyde sulfoxylate or glucose. In addition to the transition metal salt and / or reducing agent, a chelating agent such as disodium ethylenediaminetetraacetate and, if necessary, a phosphorus-containing compound such as sodium pyrophosphate may also be used.

[0155] When a redox-type initiator is used, polymerization can be carried out even at low temperatures in which the peroxide does not substantially decompose thermally, allowing the polymerization temperature to be set over a wide range. For this reason, it is preferable to use a redox-type initiator. Among redox-type initiators, those using organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide, and t-butyl hydroperoxide as peroxides are preferred. The amount of the initiator used, and the amounts of the reducing agent, transition metal salt, and chelating agent used when a redox-type initiator is used, can be used within known ranges.

[0156] In the production of polymer particles (B), a chain transfer agent may be used. When a chain transfer agent is used, the molecular weight and / or degree of crosslinking of the resulting elastic body, intermediate, or graft can be easily adjusted.

[0157] In addition to the components described above, surfactants may be used in the production of polymer particles (B). The type and amount of the surfactant used are within a known range.

[0158] In the production of polymer particles (B), the polymerization temperature, pressure, and deoxygenation conditions can be appropriately applied from known numerical ranges.

[0159] (Content of polymer particles (B)) The content of polymer particles (B) in this composition is not particularly limited. The content of polymer particles (B) in this composition is 0.1 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of thermosetting resin (A), preferably 0.1 parts by mass or more and 30.0 parts by mass or less, more preferably 0.3 parts by mass or more and 20.0 parts by mass or less, even more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, and particularly preferably 0.8 parts by mass or more and 5.0 parts by mass or less. When the content of polymer particles (B) in the composition is (a) 0.1 parts by mass or more per 100 parts by mass of thermosetting resin (A), the composition has the advantage of being able to provide a cured film with reduced cracking and / or peeling during cured film deformation, and (b) when it is 50.0 parts by mass or less, the resulting composition has the advantage of having excellent surface properties.

[0160] <1-3. Pigment (C)> In one embodiment of the present invention, the composition may or may not contain pigment (C). When the composition is used as a powder coating, it is preferable that the composition contains pigment (C). In this specification, "pigment (C)" may be referred to as "component (C)".

[0161] The pigment (C) is not particularly limited, but examples include (a) extender pigments with very low opacity, (b) coloring pigments (colored pigments), and (c) luminous pigments, which, when dispersed in the cured product, impart a sparkling property to the cured product.

[0162] While not particularly limited, suitable examples of extender pigments include barita powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, hydrated magnesium silicate, alumina white, gloss white, and mica powder.

[0163] The coloring pigment is not particularly limited, and known inorganic pigments and known organic pigments can be used. Specific examples of coloring pigments include: white pigments such as titanium dioxide (titanium white), zinc oxide, lead white, basic lead sulfate, lead sulfate, lithopone, zinc sulfide, and antimony white; black pigments such as carbon black, acetylene black, lamp black, graphite, iron black (black iron oxide), and aniline black; yellow pigments such as naphthol yellow S, Hansa yellow, pigment yellow L, benzidine yellow, permanent yellow, and pyrite (yellow iron oxide); orange pigments such as chrome orange, chrome vermilion, and permanent orange; brown pigments such as iron oxide and amber; red pigments such as red iron oxide, red lead, permanent red, quinacridone-based red pigments, and diketopyrrolopyrrole-based red pigments; purple pigments such as cobalt purple, fast violet, and methyl violet lake; blue pigments such as ultramarine, Prussian blue, cobalt blue, phthalocyanine blue, and indigo; and green pigments such as chrome green, pigment green B, and phthalocyanine green. The coloring pigments are not limited to these.

[0164] The luminous pigments are not particularly limited, but examples include metallic pigments that shine in a metallic manner and pearlescent pigments that shine in a pearlescent manner. Metallic pigments are preferred as luminous pigments. Examples of metallic pigments include aluminum pigments for paints (e.g., aluminum particles, aluminum foil, vapor-deposited aluminum, aluminum oxide, and aluminum oxide coated with at least one of titanium oxide and iron oxide), copper, zinc, brass, nickel, glass flakes, and glass flakes coated with at least one of titanium oxide and iron oxide. Examples of pearlescent pigments include mica powder and mica powder coated with at least one of titanium oxide and iron oxide.

[0165] Furthermore, as pigments (C), pigments described in "Dictionary of Pigments" edited by Seijiro Ito (published in 2000), "Industrial Organic Pigments" by W. Herbst and K. Hunger, Japanese Patent Publication No. 2002-12607, Japanese Patent Publication No. 2002-188025, Japanese Patent Publication No. 2003-26978, and Japanese Patent Publication No. 2003-342503 may also be used.

[0166] If the composition contains a pigment (C), the amount of pigment (C) in the composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1.0% by mass or more, more preferably 5.0% by mass or more, even more preferably 10.0% by mass or more, and particularly preferably 15.0% by mass or more, based on 100% by mass of the composition. This configuration has the advantage that the cured product obtained by curing the composition has excellent color development. The upper limit of the amount of pigment (C) in the composition is not particularly limited, but is, for example, 50% by mass or less, based on 100% by mass of the composition.

[0167] This composition may not contain pigment (C). If this composition does not contain pigment (C), it can provide a colorless, transparent, or slightly cloudy transparent cured product.

[0168] <1-4. Curing Agent (D)> In one embodiment of the present invention, the composition may or may not contain a curing agent (D). In this specification, "curing agent (D)" may be referred to as "component (D)".

[0169] The curing agent (D) used in one embodiment of the present invention is not particularly limited, but a curing agent that can accelerate the curing of the thermosetting resin (A) by heat is preferred.

[0170] The curing agent (D) may be appropriately selected depending on the thermosetting resin (A) contained in the composition, or depending on the type of thermosetting reactive group of the thermosetting resin (A).

[0171] When the thermosetting reactive group of the thermosetting resin (A) is an epoxy group, examples of curing agents (D) include acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebatic acid, dodecanediic acid, eicosanedioic acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, anhydrides of these acids, and urethane-modified products of these acids. Among these, aliphatic dibasic acids are preferred as curing agents (D) because they provide excellent physical properties of the cured product and storage stability of the composition, and dodecanediic acid is particularly preferred because it provides even better physical properties of the cured product.

[0172] When the thermosetting reactive group of the thermosetting resin (A) is a carboxyl group, the curing agent (D) can be, for example, various epoxy resins (e.g., polyglycidyl ether of bisphenol A); various epoxy group-containing acrylic resins (e.g., glycidyl group-containing acrylic resin); various polyglycidyl ethers of polyhydric alcohols (e.g., 1,6-hexanediol, trimethylolpropane, trimethylolethane); polyglycidyl esters of various polycarboxylic acids (e.g., phthalic acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, trimellitic acid, pyromellitic acid); various alicyclic epoxy group-containing compounds (e.g., bis(3,4-epoxycyclohexyl)methyl adipate); hydroxyamides (e.g., triglycidyl isocyanurate, β-hydroxyalkylamide); and the like.

[0173] When the thermosetting reactive group of the thermosetting resin (A) is a hydroxyl group, examples of the curing agent (D) include polyblock isocyanate and aminoplast. Examples of polyblocked isocyanates include various aliphatic diisocyanates (e.g., hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), various cyclic aliphatic diisocyanates (e.g., xylylene diisocyanate, isophorone diisocyanate, etc.), and various aromatic diisocyanates (e.g., tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, etc.); adducts of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins (e.g., polyester polyols), or water; polymers of these organic diisocyanates (polymers including isocyanurate-type polyisocyanate compounds); various polyisocyanate compounds such as isocyanate biuret forms blocked with known and conventional blocking agents; and self-blocked polyisocyanate compounds having uretdione bonds as constituent units.

[0174] The hardening agent (D) may be used alone or in combination of two or more types.

[0175] <1-5. Resin (E)> The composition preferably further contains resin (E). The resin (E) is preferably contained in the granular polymer particles (B) described later. In other words, the granular polymer particles (B) preferably contain resin (E). This configuration has the remarkable advantage that the polymer particles (B) have excellent dispersibility in the composition.

[0176] The resin (E) may be, for example, a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin.

[0177] (1-5-1. Thermosetting Resins) The thermosetting resin in resin (E) is not particularly limited, but it is preferable to include at least one selected from the group consisting of epoxy resins, thermosetting (meth)acrylic resins and thermosetting polyester resins, phenolic resins, polyol resins and amino-formaldehyde resins. Examples of thermosetting resins in resin (E) include resins containing polymers obtained by polymerizing aromatic polyester raw materials. In resin (E), only one type of thermosetting resin may be used, or two or more types may be used in combination.

[0178] (Epoxy resin) Specific examples of epoxy resin are the same as those described in the section (Epoxy resin) in section <1-1. Thermosetting resin (A)> above, so we will refer to that description and omit the explanation here.

[0179] (Thermosetting (meth)acrylic resins) Specific examples of thermosetting (meth)acrylic resins are the same as those described in the section (Thermosetting (meth)acrylic resins) in section <1-1. Thermosetting resins (A)> above, so we will refer to that description and omit the explanation here.

[0180] (Thermosetting polyester resin) Specific examples of thermosetting polyester resin are the same as those described in the section (Thermosetting polyester resin) in section <1-1. Thermosetting resin (A)> above, so we will refer to that description and omit the explanation here.

[0181] (Phenolic resin) Specific examples of phenolic resin are the same as those described in the section (Phenolic resin) in section <1-1. Thermosetting resin (A)> above, so we will refer to that description and omit the explanation here.

[0182] (Polyol Resins) Specific examples of polyol resins are the same as those described in the section (Polyol Resins) in section <1-1. Thermosetting Resins (A)> above, so we will refer to that description and omit the explanation here.

[0183] (Amino-formaldehyde resin) Specific examples of amino-formaldehyde resin are the same as those described in the section on (amino-formaldehyde resin) in section <1-1. Thermosetting resin (A)> above, so we will refer to that description and omit the explanation here.

[0184] (Aromatic polyester raw materials) Examples of aromatic polyester raw materials include aromatic vinyl compounds, (meth)acrylic acid derivatives, vinyl cyanide compounds, radical polymerizable monomers such as maleimide compounds, dimethyl terephthalate, and alkylene glycol. In this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid.

[0185] The thermosetting resin in resin (E) includes compounds obtained by bonding an ethylenically unsaturated monomer to a compound having a reactive group (e.g., epoxy group, oxetane group, hydroxyl group, amino group, imide group, carboxylic acid group, carboxylic acid anhydride group, cyclic ester, cyclic amide, benzoxazine group, and cyanate ester group, etc.) by a method other than radical polymerization, and also includes compounds having at least one ethylenically unsaturated bond in the molecule. In this specification, "compounds obtained by bonding an ethylenically unsaturated monomer to a compound having a reactive group by a method other than radical polymerization" may also be referred to as "reactive group-ethylenically unsaturated bond-containing monomers." The thermosetting resin in resin (E) also includes reactive group-ethylenically unsaturated bond-containing monomers.

[0186] Compounds having a reactive group also include thermosetting resins such as resins containing polymers obtained by polymerizing the epoxy resin, phenolic resin, polyol resin, amino-formaldehyde resin, and aromatic polyester raw materials mentioned above. The reactive group-ethylenically unsaturated bond-containing monomer may be a compound obtained by bonding an ethylenically unsaturated monomer to one or more polymers selected from the group consisting of epoxy resin, phenolic resin, polyol resin, amino-formaldehyde resin, and aromatic polyester raw materials by a method other than radical polymerization.

[0187] Examples of monomers containing reactive groups and ethylenically unsaturated bonds include unsaturated polyester resins, vinyl ester resins, and epoxy acrylates. These may be used individually or in combination of two or more types.

[0188] (1-5-2. Thermoplastic Resins) Examples of thermoplastic resins in resin (E) include thermoplastic (meth)acrylic resins, vinyl copolymers, polycarbonates, polyamides, thermoplastic polyesters, polyphenylene ethers, polyurethanes, and polyvinyl acetate. These may be used individually or in combination of two or more types.

[0189] A thermoplastic (meth)acrylic resin is a (meth)acrylic resin that does not have a thermosetting reactive group. The thermoplastic (meth)acrylic resin contains at least (meth)acrylic units that do not have a thermosetting reactive group. Preferably, the (meth)acrylic units that do not have a thermosetting reactive group contained in the thermoplastic (meth)acrylic resin have 1 to 20 carbon atoms in the part other than the (meth)acryloyl group. The thermoplastic (meth)acrylic resin may be a homopolymer of (meth)acrylic monomers that do not have a thermosetting reactive group. The thermoplastic (meth)acrylic resin may be a copolymer of (a) a (meth)acrylic monomer that does not have a thermosetting reactive group and (b) (b-1) a monomer that does not have a thermosetting reactive group, such as an unsaturated fatty acid, acrylamide monomer, maleimide monomer, vinyl acetate, or (b-2) a vinyl copolymer that does not have a thermosetting reactive group (hereinafter also referred to as a thermoplastic (meth)acrylic copolymer). It is preferable that the thermoplastic (meth)acrylic resin contains the largest total amount (molar amount) of (meth)acrylic units that do not have thermosetting reactive groups among all constituent units.

[0190] Specific examples of (meth)acrylic monomers that do not have thermosetting reactive groups are the same as those described in the section on (thermosetting (meth)acrylic resins) in section <1-1. Thermosetting resins (A)> above, so we will refer to that description and omit the explanation here.

[0191] In a thermoplastic acrylic copolymer, "constituent units derived from (meth)acrylic monomers that do not have thermosetting reactive groups" are defined as "constituent unit (a)". In a thermoplastic acrylic copolymer, "constituent units derived from monomers that do not have thermosetting reactive groups, such as unsaturated fatty acids, acrylamide monomers, maleimide monomers, vinyl acetate, and vinyl copolymers that do not have thermosetting reactive groups" are defined as "constituent unit (b)". In a thermoplastic acrylic copolymer, it is preferable that, of the total 100% by mass of constituent unit (a) and constituent unit (b), constituent unit (a) is 50% by mass or more and 100% by mass or less, and constituent unit (b) is 0% by mass or more and 50% by mass or less.

[0192] The thermoplastic (meth)acrylic resin preferably contains 50% by mass or more of constituent units derived from butyl acrylate (BA), more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.

[0193] Vinyl copolymers are obtained by copolymerizing a mixture of vinyl monomers containing one or more monomers selected from the group consisting of aromatic vinyl monomers, cyanide vinyl monomers, and unsaturated carboxylate alkyl ester monomers. The mixture of vinyl monomers may further contain other monomers copolymerizable with the above-mentioned monomers (hereinafter also referred to as monomer C).

[0194] Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and vinyltoluene. These vinyl monomers may be used individually or in combination of two or more. Among these, aromatic vinyl monomers are preferred, and styrene is more preferred, from the viewpoint that the refractive index can be easily increased.

[0195] The unsaturated carboxylate 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 substituents such as hydroxyl groups or halogen groups.

[0196] Examples of esters of an alcohol 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, and 2,3,4,5-tetrahydroxypentyl (meth)acrylate. These may be used individually or in combination of two or more.

[0197] Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile. These may be used individually or in combination of two or more.

[0198] Monomer C is a vinyl monomer other than the aromatic vinyl monomer, unsaturated carboxylate alkyl ester monomer, and vinyl cyanide monomer, 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 (meth)acrylic acid ester monomers. These may be used individually or in combination of two or more.

[0199] Unsaturated fatty acids can be selected from, for example, itaconic acid, maleic acid, fumaric acid, butenic acid, acrylic acid, methacrylic acid, and the like.

[0200] Examples of acrylamide monomers can be selected from acrylamide, methacrylamide, N-methylacrylamide, and the like.

[0201] Examples of maleimide monomers can be selected from N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like.

[0202] There are no particular limitations on the method for producing vinyl copolymers, but examples include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.

[0203] Furthermore, in the method for producing vinyl copolymers, a polymerization initiator may be used as necessary. As a polymerization initiator, one or more can be appropriately selected from the group consisting of, for example, peroxides, azo compounds, potassium persulfate, etc. The amount of polymerization initiator added is not particularly limited.

[0204] 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. Among these, cumene hydroperoxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)cyclohexane are particularly preferred.

[0205] 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-carbonitrate, azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl2,2'-azobisisobutyrate, 1-t-butylazo-2-cyanobutane, and 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane. Among these, 1,1'-azobiscyclohexane-1-carbonitrate is particularly preferred.

[0206] 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, and the like. These may be used individually or in combination of two or more.

[0207] Examples of thermoplastic polyesters include polyethylene terephthalate and polybutylene terephthalate.

[0208] Resin (E) may be the same resin (a resin having the same composition) as thermosetting resin (A), or it may be a different resin from thermosetting resin (A). In the composition, it is preferable that thermosetting resin (A) and resin (E) do not undergo phase separation. Resin (E) is preferably a resin that is compatible with thermosetting resin (A).

[0209] When resin (E) is the same resin as the thermosetting resin (A) described above, there is the advantage that resin (E) does not affect the various physical properties of the resulting composition or cured product containing the powder or granules.

[0210] As an example, consider the case where resin (E) is the same type of resin as thermosetting resin (A). In this case, it is not possible to distinguish between thermosetting resin (A) and resin (E) in the composition. Therefore, outwardly, the composition appears to (a) contain thermosetting resin (A) but not resin (E), or (b) contain resin (E) but not thermosetting resin (A). Next, consider the case where resin (E) is a different type of resin from thermosetting resin (A). In this case, thermosetting resin (A) and resin (E) are distinguishable in the composition. In this case, the composition may contain thermosetting resin (A) and resin (E) as a resin other than thermosetting resin (A).

[0211] (1-5-3. Others) In this specification, oils and fats and fatty acid esters are also included in resin (E). Resin (E) preferably contains oils and fats, and more preferably consists of oils and fats. Suitable oils and fats for use as resin (E) include epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil. These resins may be used individually or in combination of two or more. Resin (E) preferably contains epoxidized soybean oil, and more preferably consists of epoxidized soybean oil. Commercially available epoxidized soybean oil can be used, for example, Adekaiser O-130P manufactured by ADEKA Corporation. Suitable fatty acid esters for use as resin (E) include epoxidized fatty acid esters such as epoxidized fatty acid butyl, epoxidized fatty acid 2-ethylhexyl, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.

[0212] Epoxylated oils and fats and epoxylated fatty acid esters are sometimes referred to as epoxy plasticizers. That is, in this specification, epoxy plasticizers are also included in resin (E). Examples of epoxy plasticizers other than epoxylated oils and fats and epoxylated fatty acid esters include diepoxystearyl epoxyhexahydrophthalate and di-2-ethylhexyl epoxyhexahydrophthalate.

[0213] Each of the above-mentioned thermosetting resins, thermoplastic resins, mixtures of thermosetting resins and thermoplastic resins, oils and fats, and fatty acid esters can be used in combination with antioxidants. In this specification, antioxidants are considered part of resin (E) only when used in combination with each of the above-mentioned substances. When antioxidants are used alone, they are not considered part of resin (E). The case in which only antioxidants are used instead of resin (E) will be described below. Since antioxidants are components that do not contribute to crosslinking, the physical properties of the cured product obtained by curing the composition tend to be inferior. For example, the Tg of the cured product may decrease, or its impact resistance may be inferior.

[0214] The antioxidant is not particularly limited. Examples of antioxidants include (a) primary antioxidants such as phenolic antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants, and (b) secondary antioxidants such as sulfur-based antioxidants and phosphorus-based antioxidants.

[0215] Examples of the aforementioned phenolic antioxidants include hindered phenolic antioxidants. Examples of hindered phenolic antioxidants include compounds having a hindered phenol structure or a partial hindered phenol structure in their molecule. Commercially available phenolic antioxidants can also be used, such as Irganox 245 manufactured by BASF Japan Ltd.

[0216] The amine-based antioxidant is not particularly limited, and conventionally known ones can be widely used. Specific examples of amine-based antioxidants include amine-ketone compounds such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and reaction products of diphenylamine and acetone.

[0217] The aforementioned amine-based antioxidants also include aromatic amine compounds. Examples of aromatic amine compounds include naphthylamine-based antioxidants, diphenylamine-based antioxidants, and p-phenylenediamine-based antioxidants.

[0218] The lactone-based antioxidant, hydroxylamine-based antioxidant, and sulfur-based antioxidant are not particularly limited, and conventionally known ones can be widely used.

[0219] The phosphorus-based antioxidant is not particularly limited, and conventionally known ones can be widely used. Phosphoric acid and phosphate esters containing active hydrogen may adversely affect the storage stability of the composition and the heat resistance of the cured product provided by the composition. Therefore, alkyl phosphates, aryl phosphates, alkylaryl phosphate compounds, etc., which do not contain phosphoric acid or phosphate esters in their molecules, are preferred as phosphorus-based antioxidants.

[0220] Other conventionally known substances may be used as the antioxidant. Various substances listed in, for example, the "Antioxidant Handbook" published by Taisei-sha (first edition published October 25, 1976) and the "Polymer Additive Handbook" published by CMC Publishing (edited by Toru Haruna, first edition published November 7, 2010) may be used as antioxidants.

[0221] The resin (E) 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 plasticizers, and mixtures of epoxy plasticizers 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, epoxy plasticizers, and mixtures of epoxy plasticizers and antioxidants; even more preferably one or more selected from the group consisting 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. According to this configuration, (a) the composition has the advantage of being able to provide a cured product with excellent heat resistance and improving the dispersibility of polymer particles (B) in the composition.

[0222] (1-5-4. Physical Properties of Resin (E)) Resin (E) is a liquid, semi-solid, or solid with a viscosity of 100 mPa·s or more and 1,000,000 mPa·s or less at 25°C, and its other properties are not particularly limited. Note that "Resin (E) has a viscosity of 100 mPa·s or more and 1,000,000 mPa·s or less at 25°C" means "Resin (E) at 25°C has a viscosity of 100 mPa·s or more and 1,000,000 mPa·s or less."

[0223] When the resin (E) is a liquid, the viscosity of the resin (E) 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, the resin (E) has the advantage of having excellent fluidity.

[0224] Furthermore, the viscosity of the resin (E) 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. With this configuration, the resin (E) does not impregnate the polymer particles (B). Therefore, the resin (E) can prevent the polymer particles (B) from fusing together.

[0225] The viscosity of resin (E) 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.

[0226] If resin (E) is semi-solid at 25°C, it can also be said that resin (E) is semi-liquid at 25°C, and that resin (E) has a viscosity greater than 1,000,000 mPa·s at 25°C. When resin (E) is semi-solid or solid at 25°C, the resulting composition has the advantage of being less sticky and easier to handle.

[0227] The viscosity of resin (E) can be measured using a viscometer. The method for measuring the viscosity of resin (E) is described in detail in the following example.

[0228] Furthermore, the resin (E) is preferably a resin whose differential scanning calorimetry (DSC) thermogram has an endothermic peak at 25°C or below, and more preferably a resin whose endothermic peak has an endothermic peak at 0°C or below.

[0229] <1-6. Additives> This composition may contain other optional components (additives) in addition to the components described above, as needed. Examples of other optional components (additives) include various additives used in the composition. Specifically, examples of other optional components (additives) include defoaming agents, antifoaming agents, leveling agents, silicone compounds, waxes, surface modifiers (silicone oil, acrylic oligomers, etc.), anti-foaming agents (e.g., benzoin, benzoin derivatives, etc.), curing accelerators (amine compounds, imidazole compounds, cationic polymerization catalysts, etc.), plasticizers, charge control agents, antioxidants, ultraviolet absorbers, light stabilizers, pigment dispersants, magnetic powders, flame retardants, flow imparters, flow modifiers, and spreading agents.

[0230] <1-7. Method for Producing Thermosetting Resin Composition> This composition can be produced by mixing the components described above. For example, this composition can be produced by mixing a powder containing polymer particles (B) and optionally a resin (E) with each component other than polymer particles (B) (for example, thermosetting resin (A)), or a commercially available product containing each component.

[0231] A method for producing a thermosetting resin composition according to one embodiment of the present invention may have the following configuration: A method for producing a thermosetting resin composition comprising the steps of: preparing a powder containing polymer particles (B); and mixing the powder with a thermosetting resin (A) to prepare a thermosetting resin composition, wherein the polymer particles (B) have an elastic body and a graft portion, the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber, the graft portion contains one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units and (meth)acrylate units as constituent units, the content of the polymer particles (B) is 0.1 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the thermosetting resin (A), the glass transition temperature of the graft portion is 25°C or more and 50°C or less, and the volume average particle diameter of the polymer particles (B) is 130 nm or more and 800 nm or less.

[0232] In a method for producing a thermosetting resin composition according to one embodiment of the present invention, the powder may further contain resin (E). That is, a method for producing a thermosetting resin composition according to one embodiment of the present invention may have the following configuration: A method for producing a thermosetting resin composition comprising the steps of: preparing a powder containing polymer particles (B) and resin (E); and mixing the powder with a thermosetting resin (A) to prepare a thermosetting resin composition, wherein the polymer particles (B) have an elastic body and a graft portion, the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber, the graft portion contains one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units and (meth)acrylate units as constituent units, the content of the polymer particles (B) is 0.1 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the thermosetting resin (A), the glass transition temperature of the graft portion is 25°C or more and 50°C or less, and the volume average particle diameter of the polymer particles (B) is 130 nm or more and 800 nm or less.

[0233] (Powdered and Granular Materials) Powdered and granular materials containing polymer particles (B) can be obtained by drying aggregates of polymer particles (B). Therefore, "powdered and granular materials containing polymer particles (B)" can also be called "secondary particles of polymer particles (B)". It is preferable that the powdered and granular materials containing polymer particles (B) further contain resin (E). Powdered and granular materials containing polymer particles (B) and resin (E) can be obtained by drying aggregates containing polymer particles (B) and resin (E).

[0234] In this specification, "powder and granules" refers to an aggregate of powders, granules, etc., including both powders and granules. When a distinction is made, "powder" refers to materials with a volume-average particle diameter of 0.01 mm or more and 0.1 mm or less, and "granules" refers to materials with a volume-average particle diameter greater than 0.1 mm and 10 mm or less. That is, the volume-average particle diameter of powder and granules is, for example, 0.01 mm or more and 10 mm or less. However, powder and granules may contain coarse particles of 10 mm or more. The "volume-average particle diameter" of powder and granules 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 Microtrac Bell Co., Ltd.). The "volume-average particle diameter" of powder and granules in the range of 10 μm or more can be measured using a laser diffraction particle size distribution analyzer Microtrac MT3000 II (manufactured by Microtrac Bell Co., Ltd.). The volume-average particle diameter of the secondary particles of the granular material, i.e., polymer particles (B), is preferably greater than 10 μm (0.01 mm). This configuration has the advantage of providing better dispersibility of the polymer particles (B) during composition preparation, and consequently, better dispersibility of the polymer particles (B) in the composition and cured product.

[0235] (Method for producing powders and granules (step for preparing powders and granules)) In one embodiment of the present invention, the method for producing powders and granules containing polymer particles (B) (step for preparing powders and granules) is not particularly limited. The method for producing powders and granules containing polymer particles (B) may include an aggregation step of preparing aggregates containing polymer particles (B), and a drying step of drying the aggregates.

[0236] (Agglutination Step) The agglutination step is not particularly limited as long as an aggregate containing polymer particles (B) can be obtained in the end. In the agglutination step, it is preferable to obtain an aggregate containing polymer particles (B) and resin (E) in the end. In the agglutination step, for example, an aqueous latex containing polymer particles (B) obtained by emulsion polymerization and optionally resin (E) is used. The method for agglutinating polymer particles (B) or polymer particles (B) and resin (E) using an aqueous latex containing polymer particles (B) and optionally resin (E) is not particularly limited. Known methods include, for example, a method using a coagulant, a method using a solvent, and a method of spraying aqueous latex. Here, the "mixture containing an aggregate containing polymer particles (B) and optionally resin (E) and an aqueous solvent" obtained by agglutinating polymer particles (B) and optionally resin (E) in aqueous latex is also called a slurry.

[0237] Methods for obtaining an aqueous latex containing polymer particles (B) and resin (E) include, for example, (i) adding resin (E) to the reaction solution during the polymerization step of polymer particles (B), (ii) adding resin (E) to the aqueous latex of polymer particles (B), and (iii) polymerizing resin (E) in the aqueous latex of polymer particles (B).

[0238] The coagulation step preferably employs a method using a coagulant. The coagulant is not particularly limited as long as it is a substance that has the property of agglomerating (also referred to as coagulation and solidification) the polymer particles (B) in the aqueous latex containing polymer particles (B) and optionally a resin (E) when brought into contact with the aqueous latex. Examples of coagulants include aqueous solutions of inorganic salts (e.g., calcium chloride), aqueous solutions of inorganic acids, aqueous solutions of organic salts, aqueous solutions of organic acids, and polymer coagulants.

[0239] The polymer particles (B) can be agglomerated by contacting an aqueous latex containing polymer particles (B) with a coagulant or a solution of a coagulant (e.g., an aqueous solution). For example, by mixing an aqueous latex containing polymer particles (B) with an aqueous solution of a coagulant, the polymer particles (B) can be agglomerated in the resulting mixture. As a result, aggregates containing polymer particles (B) can be obtained. Furthermore, by contacting an aqueous latex containing polymer particles (B) and resin (E) with a coagulant or a solution of a coagulant (e.g., an aqueous solution), either (i) the polymer particles (B) and resin (E) can be agglomerated together, or (ii) the polymer particles (B) can be agglomerated while incorporating the resin (E). For example, by mixing an aqueous latex containing polymer particles (B) and resin (E) with an aqueous solution of a coagulant, either (i) the polymer particles (B) and resin (E) can be agglomerated together, or (ii) the polymer particles (B) can be agglomerated while incorporating the resin (E). As a result, aggregates containing polymer particles (B) and resin (E) can be obtained.

[0240] Before mixing the aqueous latex containing polymer particles (B) and optionally resin (E) with the aqueous solution of the coagulant, the aqueous latex containing polymer particles (B) and optionally resin (E) may be preheated, the aqueous solution of the coagulant may be preheated, or both the aqueous latex containing polymer particles (B) and optionally resin (E) and the aqueous solution of the coagulant may be preheated. The mixture obtained by mixing the aqueous latex containing polymer particles (B) and optionally resin (E) with the aqueous solution of the coagulant may be heated.

[0241] The aggregation step may further include a recovery step of recovering the resulting aggregates, i.e., aggregates containing polymer particles (B) and optionally resin (E), from the slurry.

[0242] The recovery process is not particularly limited, as long as it can separate the aqueous solvent and aggregates of the slurry, and known methods can be used. Examples of recovery processes include filtering the slurry and centrifugal dehydration of the slurry.

[0243] (Drying Process) The drying process is a process of drying the aggregates obtained by the aggregation process described above, which contain polymer particles (B) and optionally resin (E). The method for drying the aggregates is not particularly limited, and known methods can be used. For example, the aggregates can be dried by leaving them in a dryer set to a certain temperature (drying temperature).

[0244] The ambient temperature (i.e., drying temperature) during the drying process is not particularly limited. Since the resulting powder can provide a composition with superior dispersibility of polymer particles (B), the drying temperature is preferably 40°C to 100°C, more preferably 40°C to 80°C, and even more preferably 40°C to 60°C.

[0245] The drying process time is not particularly limited and can be set as appropriate depending on the drying temperature and the degree of drying of the aggregate. The drying time may be, for example, 1 minute or more and 24 hours or less, 1 minute or more and 12 hours or less, or 1 minute or more and 6 hours or less.

[0246] A washing step may be further included between the coagulation step and the drying step to wash the aggregates obtained in the coagulation step. If a recovery step is carried out, the washing step may be carried out between the recovery step and the drying step. By washing the aggregates, a powder with a low content of impurities can be obtained. In the washing step, it is more preferable to wash the aggregates with water, and even more preferable to wash them with deionized water or pure water.

[0247] (Step for preparing a thermosetting resin composition) In the step for preparing a thermosetting resin composition, the specific method for mixing the powder containing polymer particles (B) and optionally resin (E) with the thermosetting resin (A) and optionally components other than the thermosetting resin (A), polymer particles (B), and resin (E) is not particularly limited, and known methods can be used as appropriate. The mixing of the powder containing polymer particles (B) and optionally resin (E) with the thermosetting resin (A) and optionally components other than the thermosetting resin (A), polymer particles (B), and resin (E) is, for example, dry mixing. Various mixers such as Henschel mixers, Banbury mixers, high-speed mixers, and Nauter mixers can be used in this dry mixing. The mixture obtained in this way, which contains at least the thermosetting resin (A) and polymer particles (B) (or a mixture containing the thermosetting resin (A), polymer particles (B), and optionally resin (E)), may be used as the thermosetting resin composition.

[0248] In the production of a thermosetting resin composition, the mixture obtained by the above method, which contains a thermosetting resin (A), polymer particles (B), and optionally a resin (E), may be further (U1) melt-kneaded, (U2) cooled, and (U3) pulverized. The pulverized material containing the thermosetting resin (A) and polymer particles (B) obtained by the above method may be used as the thermosetting resin composition. When this composition is used as a powder coating, the thermosetting resin composition, which is a pulverized material containing the thermosetting resin (A), polymer particles (B), and optionally a resin (E) obtained by the above method, may be used as the powder coating. In other words, the powder coating according to one embodiment of the present invention, which includes the thermosetting resin composition according to one embodiment of the present invention, may be in the form of a pulverized material. When this composition is used as a sealing resin composition, the thermosetting resin composition, which is a pulverized material containing the thermosetting resin (A) and polymer particles (B) obtained by the above method, may be used as the sealing resin composition. In other words, the sealing resin composition according to one embodiment of the present invention, which includes the thermosetting resin composition according to one embodiment of the present invention, may be in the form of a pulverized product.

[0249] In (U1) above, a heated roll machine, a heated kneader, an extruder, etc., can be used as the apparatus for melting and kneading the mixture.

[0250] The melt-kneading temperature of (U1) is not particularly limited and is, for example, a temperature above the softening point of the thermosetting resin (A). The melt-kneading temperature of (U1) is, for example, 50°C or more and 140°C or less, preferably 50°C or more and 130°C or less, more preferably 60°C or more and 110°C or less, and even more preferably 80°C or more and 130°C or less.

[0251] In (U2), for example, the molten mixture obtained in (U1) is cooled to 50°C or below. Any method can be used to cool the molten mixture, such as leaving it at room temperature, using cooling rolls, or a cooling conveyor.

[0252] In (U3) above, the pulverizer used for pulverizing the cooled material obtained in (U2) above is not particularly limited. The pulverizer may be a mechanical pulverizer or an air-jet pulverizer. For example, an impact pulverizer such as a hammer mill or pin mill can be used as the pulverizer. Furthermore, the pulverization of the cooled material in (U3) above may be carried out in two steps, for example, coarse pulverization and fine pulverization.

[0253] The pulverized material obtained by (U1) to (U3) above, which contains thermosetting resin (A), polymer particles (B), and optionally resin (E), may be further classified to obtain a desired particle size. The classifier is not particularly limited, and sieves (vibrating sieves) and pneumatic classifiers can be used.

[0254] The weight-average particle size of this composition is not particularly limited, but is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 80 μm or less.

[0255] By applying pressure to the pulverized material containing the thermosetting resin (A) and polymer particles (B) obtained by the method described above, the pulverized material can be solidified into a tablet. Such a tablet is also a thermosetting resin composition according to one embodiment of the present invention. When this composition is used as a sealing resin composition, the thermosetting resin composition, which is a tablet containing the thermosetting resin (A) and polymer particles (B) obtained by the method described above, may be used as the sealing resin composition. In other words, the sealing resin composition according to one embodiment of the present invention, which includes the thermosetting resin composition according to one embodiment of the present invention, may also be in the form of a tablet.

[0256] Regarding the method for producing a thermosetting resin composition according to one embodiment of the present invention, aspects (matters) other than those described in detail in section <1-7. Method for producing a thermosetting resin composition> above (for example, aspects relating to the thermosetting resin (A) and polymer particles (B)) shall be appropriately referred to in the above description (for example, the description in sections <1-1. Thermosetting resin (A)> to <1-5. Resin (E)>).

[0257] <1-8. Applications> The thermosetting resin composition according to one embodiment of the present invention can be used for a variety of applications. For example, the thermosetting resin composition according to one embodiment of the present invention can be used as a powder coating. That is, one embodiment of the present invention provides a powder coating containing the thermosetting resin composition according to one embodiment of the present invention. The powder coating according to one embodiment of the present invention can be used to coat any substance (substrate). The powder coating according to one embodiment of the present invention can be particularly suitably used to coat the metal exteriors of various devices, automobile parts, and automobile bodies.

[0258] A thermosetting resin composition according to one embodiment of the present invention can be used as a sealing resin composition. That is, one embodiment of the present invention provides a sealing resin composition comprising a thermosetting resin composition according to one embodiment of the present invention. The sealing resin composition according to one embodiment of the present invention can be used, for example, to form a sealing material for sealing electronic components. The electronic components are not particularly limited, but semiconductor elements are preferred. Examples of semiconductor elements, not particularly limited, include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and solid-state image sensors.

[0259] Furthermore, the thermosetting resin composition according to one embodiment of the present invention is also preferably used in applications such as adhesives, coatings, binders for reinforcing fibers, composite materials, 3D printer molding materials, electronic circuit boards, ink binders, wood chip binders, rubber chip binders, foam chip binders, casting binders, rock solidification materials for flooring and ceramics, and urethane foam.

[0260] [2. Cured product] The cured product according to one embodiment of the present invention is preferably obtained by curing the composition described in [1. Thermosetting resin composition] above. With this configuration, the cured product according to one embodiment of the present invention has the advantage of excellent dispersibility of polymer particles (B) in the cured product.

[0261] A cured product according to one embodiment of the present invention can be obtained by heating the composition to a certain temperature (e.g., 50°C or higher) to cure the composition. After applying the composition to a substrate, a film-like cured product can be obtained on the substrate by heating the composition to a certain temperature (e.g., 50°C or higher) to cure the composition. In this specification, a "film-like cured product" may be referred to as a "cured film". In one embodiment of the present invention, after applying a powder coating containing the composition to a substrate, a film-like cured product (also called a "coating film") can be obtained on the substrate by heating the powder coating to a certain temperature (e.g., 50°C or higher) to cure the powder coating. One embodiment of the present invention provides a powder coating containing a thermosetting resin composition according to one embodiment of the present invention, that is, a coating film obtained by curing a powder coating according to one embodiment of the present invention.

[0262] The substrate to which the composition is applied is not particularly limited, and examples include metals such as iron, zinc, tin, stainless steel, copper, and aluminum, and inorganic materials such as glass. Heat-resistant substrates are preferred, and metals are particularly preferred. The substrate may be pre-treated with surface treatments such as blasting, iron phosphate, or zinc phosphate before applying the composition. The substrate may also be pre-treated with a primer and / or intermediate coat before applying the composition.

[0263] The method for applying the composition to the substrate is not particularly limited and includes general coating methods such as electrostatic coating, electrostatic powder spraying, fluid immersion, and electrostatic fluid immersion.

[0264] The film thickness of the coating of the composition is not particularly limited, but examples include 15 μm or more and 1 mm or less, or 30 μm or more and 300 μm or less.

[0265] The curing temperature is not particularly limited, but is preferably above the melting point of the thermosetting resin (A). Examples of curing temperatures include 100°C or higher and 280°C or lower, 130°C or higher and 250°C or lower, or 120°C or higher and 250°C or lower.

[0266] The curing time is not particularly limited; for example, it can be between 5 minutes and 60 minutes.

[0267] This section describes how to use this composition when it is used as a sealing resin composition, or how to use a sealing resin composition containing this composition. The method for forming a sealing material using this composition or a sealing resin composition is not particularly limited, but examples include transfer molding, compression molding, and injection molding. A sealing material can be formed by molding and curing this composition or a sealing resin composition using these methods. When forming a sealing material, the curing temperature is not particularly limited, but the above-mentioned temperature range is possible. When forming a sealing material, the curing time is not particularly limited, but the above-mentioned curing time range is possible.

[0268] One embodiment of the present invention may include the following configuration:

[0269] [1] A thermosetting resin composition comprising a thermosetting resin (A) and polymer particles (B), wherein the polymer particles (B) have an elastic body and a graft portion, the elastic body comprises one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber, the graft portion comprises one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units and (meth)acrylate units as constituent units, the content of the polymer particles (B) is 0.1 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the thermosetting resin (A), the glass transition temperature of the graft portion is 25°C or more and 50°C or less, and the volume average particle diameter of the polymer particles (B) is 130 nm or more and 800 nm or less.

[0270] [2] The thermosetting resin composition according to [1], wherein the volume-average particle diameter of the elastic body is 130 nm or more and less than 800 nm.

[0271] [3] The thermosetting resin composition according to [1] or [2], wherein the polymer particles (B) substantially do not contain constituent units X derived from a reactive monomer X having one or more reactive functional groups X selected from the group consisting of oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups, benzoxazine groups, and cyanate ester groups.

[0272] [4] The thermosetting resin composition according to any one of [1] to [3], wherein the elastic body comprises a crosslinkable unit and / or a graftable unit as constituent units, and the elastic body contains the crosslinkable unit and the graftable unit in total in an amount greater than 0 parts by mass and 4.0 parts by mass or less per 100 parts by mass of the elastic body.

[0273] [5] The thermosetting resin composition according to any one of [1] to [4], wherein the polymer particles (B) contain the elastic body in an amount of 70.0% by mass or more and 90.0% by mass or less of 100% by mass of the polymer particles (B).

[0274] [6] The thermosetting resin composition according to any one of [1] to [5], wherein the graft portion substantially does not contain crosslinkable units and graftable units as constituent units.

[0275] [7] The thermosetting resin composition according to any one of [1] to [6], wherein the polymer particles (B) contain the graft portion in an amount of 10.0% by mass or more and 30.0% by mass or less of the polymer particles (B)

[0276] [8] The thermosetting resin composition according to any one of [1] to [7], wherein the glass transition temperature of the elastic body is less than 0°C.

[0277] [9] The thermosetting resin composition according to any one of [1] to [8], wherein the polymer particles (B) further have an intermediate portion, and the intermediate portion contains, as constituent units, a total of 5.0 parts by mass or more of crosslinkable units and graftable units in 100 parts by mass of the intermediate portion.

[0278]

[10] The thermosetting resin composition according to [9], wherein the polymer particles (B) contain the intermediate portion in an amount of 0.5% by mass or more and 5.0% by mass or less of the polymer particles (B) by 100% by mass.

[0279]

[11] The thermosetting resin composition according to [9] or

[10] , wherein the intermediate portion is composed solely of crosslinkable units and / or graftable units.

[0280]

[12] The thermosetting resin composition according to any one of [9] to

[11] , wherein the glass transition temperature of the intermediate portion is 0°C or higher.

[0281]

[13] A thermosetting resin composition according to any one of [1] to

[12] , further comprising resin (E).

[0282] A cured product obtained by curing any one of the thermosetting resin compositions described in

[14] [1] to

[13] .

[0283] A powder coating comprising any one of the thermosetting resin compositions described in

[15] [1] to

[13] .

[0284] A coating film obtained by curing the powder coating described in

[16] and

[15] .

[0285] A sealing resin composition comprising any one of the thermosetting resin compositions described in

[17] [1] to

[13] .

[0286]

[18] A method for producing a thermosetting resin composition, comprising the steps of: preparing a powder containing polymer particles (B); and mixing the powder with a thermosetting resin (A) to prepare a thermosetting resin composition, wherein the polymer particles (B) have an elastic body and a graft portion, the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber, the graft portion contains one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units and (meth)acrylate units as constituent units, the content of the polymer particles (B) is 0.1 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the thermosetting resin (A), the glass transition temperature of the graft portion is 25°C or more and 50°C or less, and the volume average particle diameter of the polymer particles (B) is 130 nm or more and 800 nm or less.

[0287]

[19] The method for producing the thermosetting resin composition according to

[18] , wherein the powder further comprises resin (E).

[0288] One embodiment of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. One embodiment of the present invention can be implemented with appropriate modifications within the scope that is consistent with the spirit of the above or below, and all such modifications are included within the technical scope of the present invention.

[0289] [Measurement Method and Evaluation Method] (Volume-average particle diameter of elastic and polymer particles (B)) The volume-average particle diameter (Mv) of elastic and polymer particles (B) dispersed in aqueous latex was measured using Nanotrac Wave II-EX150 (manufactured by Microtrac Bell Co., Ltd.). The aqueous latex of elastic and polymer particles (B) diluted with deionized water was used as the measurement sample. The measurement was performed by inputting the refractive index of water and each polymer particle, adjusting the sample concentration so that the measurement time was 120 seconds and the loading index was within the range of 1 to 10.

[0290] (Method for measuring (calculating) the glass transition temperature) The glass transition temperatures of the elastic body, intermediate section, and graft section were calculated using the FOX formula described above.

[0291] The Tg of the homopolymers is as follows: methyl methacrylate (MMA); 105°C, styrene (St); 80°C, butyl acrylate (BA); -54°C, ethyl acrylate (EA); -22°C, hydroxyethyl methacrylate; 55°C.

[0292] (Method for evaluating cupping resistance) Test specimens (coated boards) obtained using the thermosetting resin compositions obtained in the examples and comparative examples were evaluated for their flexibility (cupping resistance) in accordance with JIS K 5600-5-2 (Cupping Resistance Test). Specifically, the back side of the coated surface of the test specimen was extruded using a cupping test machine with a 20 mm diameter punch, while varying the extrusion height (gradually increasing it). The extrusion height (mm) immediately before cracking occurred in the cured film was evaluated as the flexibility (cupping resistance). The results are shown in Tables 1 and 2.

[0293] (Method for evaluating dispersibility) Test specimens (coated boards) obtained using the thermosetting resin compositions obtained in the examples and comparative examples were evaluated for the presence and amount of particles (areas where polymer particles (B) are aggregated or densely packed). Specifically, a randomly selected 5 cm × 5 cm area of ​​the coated surface (cured film) of the test specimen was visually observed, and the number of particles (protrusions and raised areas) present in that area was measured. The dispersibility of polymer particles (B) in the thermosetting resin composition was evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2. A (Excellent): There are 2 or fewer particles in the area. B (Good): There are 3 to 5 particles in the area. C (Poor): There are 6 or more particles in the area.

[0294] <1. Formation of Elastic Body> (Production Example 1-1; Preparation of Aqueous Latex (R-1)) 182 parts by mass of deionized water, 0.006 parts by mass of disodium ethylenediaminetetraacetate (EDTA), 0.0015 parts by mass of ferrous sulfate heptahydrate, 0.2 parts by mass of sodium formaldehyde sulfoxylate (SFS), and 0.02 parts by mass of sodium dodecylbenzenesulfonate (SDBS) were added to a glass reactor. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer and emulsifier addition device. The added raw materials were stirred at 50°C while replacing the gas in the glass reactor with nitrogen (i.e., in a nitrogen stream). Next, a mixture of 82.2 parts by mass of butyl acrylate (BA), 0.42 parts by mass of allyl methacrylate (ALMA), and 0.021 parts by mass of t-butyl hydroperoxide was continuously added dropwise to a glass reactor over 175 minutes to initiate polymerization. After the addition of the mixture was complete, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through these operations, an elastic aqueous latex (R-1) was obtained. The volume-average particle size of the obtained elastic material was measured using the method described above and was found to be 302 nm. The glass transition temperature of the obtained elastic material was calculated using the FOX formula described above and was found to be -54°C.

[0295] (Production Example 1-2; Preparation of Aqueous Latex (R-2)) 182 parts by mass of deionized water, 0.006 parts by mass of EDTA, 0.0015 parts by mass of ferrous sulfate heptahydrate, 0.2 parts by mass of SFS, and 0.3 parts by mass of SDBS were added to a glass reactor. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer and emulsifier addition device. The added raw materials were stirred at 50°C while replacing the gas in the glass reactor with nitrogen (i.e., in a nitrogen stream). Next, a mixture of 82.2 parts by mass of BA, 0.42 parts by mass of ALMA, and 0.021 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 175 minutes to start polymerization. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through the above procedure, an aqueous latex material (R-2) was obtained. The volume-average particle size of the obtained elastic material was measured using the method described above and was found to be 116 nm. The glass transition temperature of the obtained elastic material was calculated to be -54°C using the FOX formula described above.

[0296] (Production Example 1-3; Preparation of Aqueous Latex (R-3)) 182 parts by mass of deionized water, 0.006 parts by mass of EDTA, 0.0015 parts by mass of ferrous sulfate heptahydrate, 0.2 parts by mass of SFS, and 0.02 parts by mass of SDBS were added to a glass reactor. The glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer and emulsifier addition device. The added raw materials were stirred at 50°C while replacing the gas in the glass reactor with nitrogen (i.e., in a nitrogen stream). Next, a mixture of 82.2 parts by mass of BA, 0.82 parts by mass of ALMA, and 0.021 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 175 minutes to start polymerization. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through the above procedure, an aqueous latex material (R-3) was obtained. The volume-average particle size of the obtained elastic material was measured using the method described above and was found to be 301 nm. The glass transition temperature of the obtained elastic material was calculated using the FOX formula described above and was found to be -54°C.

[0297] <2. Formation of the Intermediate Part> (Production Example 2-1; Preparation of Aqueous Latex (M-1)) Following the formation of the elastic body in Production Example 1-1, the following operations were carried out using the glass reactor (containing 82.62 parts by mass of the elastic body) after the production of aqueous latex (R-1). A mixture of 1.0 part by mass of styrene (St), 1.8 parts by mass of ALMA, and 0.4 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 15 minutes to polymerize it into the elastic body. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through the above operations, aqueous latex (M-1) polymer particles having an elastic body and an intermediate part were obtained.

[0298] (Production Example 2-2; Preparation of Aqueous Latex (M-2)) Following the formation of the elastic body in Production Example 1-1, the following operations were carried out using the glass reactor (containing 82.62 parts by mass of the elastic body) that had been used to produce aqueous latex (R-1). A mixture of 1.8 parts by mass of St, 1.0 part by mass of ALMA, and 0.4 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 15 minutes to polymerize it into the elastic body. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through these operations, aqueous latex (M-2) of polymer particles having an elastic body and an intermediate part was obtained.

[0299] (Production Example 2-3; Preparation of Aqueous Latex (M-3)) Following the formation of the elastic body in Production Example 1-1, the following operations were carried out using the glass reactor (containing 82.62 parts by mass of the elastic body) that had been used to produce aqueous latex (R-1). A mixture of 1.0 part by mass of methyl methacrylate (MMA), 1.8 parts by mass of ALMA, and 0.4 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 15 minutes to polymerize it into the elastic body. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through these operations, aqueous latex (M-3) was obtained, which is polymer particles having an elastic body and an intermediate part. In the production of the intermediate part of the polymer particles of aqueous latex (M-3), MMA and ALMA were used as graftable monomers. Therefore, the Tg of the intermediate portion of the aqueous latex (M-3) polymer particles, in other words, the glass transition temperature of the structure excluding the crosslinkable and graftable units, is 105°C, the same as the Tg value of the MMA homopolymer, according to the FOX formula described above.

[0300] (Production Example 2-4; Preparation of Aqueous Latex (M-4)) Following the formation of the elastic body in Production Example 1-2, the following operations were carried out using the glass reactor (containing 82.62 parts by mass of the elastic body) after the production of aqueous latex (R-2). A mixture of 1.0 part by mass of St, 1.8 parts by mass of ALMA, and 0.4 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 15 minutes to polymerize it into the elastic body. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through these operations, aqueous latex (M-4) with polymer particles having an elastic body and an intermediate part was obtained.

[0301] (Production Example 2-5; Preparation of Aqueous Latex (M-5)) Following the formation of the elastic body in Production Example 1-3, the following operations were carried out using the glass reactor (containing 82.62 parts by mass of the elastic body) that had been used to produce aqueous latex (R-3). A mixture of 1.0 part by mass of St, 1.8 parts by mass of ALMA, and 0.4 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 15 minutes to polymerize it into the elastic body. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through these operations, aqueous latex (M-5) with polymer particles having an elastic body and an intermediate part was obtained.

[0302] In the production of the intermediate portion of the aqueous latex polymer particles (M-1), (M-2), (M-4), and (M-5), St and ALMA were used as graftable monomers. Therefore, the Tg of the intermediate portion of the aqueous latex polymer particles (M-1), (M-2), (M-4), and (M-5), in other words, the glass transition temperature of the composition excluding the crosslinkable and graftable units, is 80°C, the same as the Tg value of the St homopolymer, according to the FOX formula described above.

[0303] <3. Preparation of Polymer Particles (Formation of Graft Part)> (Production Example 3-1; Preparation of Aqueous Latex (L-1) of Polymer Particles) Following the formation of the intermediate part in Production Example 2-1, the following operations were carried out using a glass reactor (containing 85.7 parts by mass of polymer particles having an elastic body and an intermediate part) after producing aqueous latex (M-1). A mixture of 13.5 parts by mass of methyl methacrylate (MMA), 1.5 parts by mass of butyl acrylate (BA), and 0.01 parts by mass of t-butyl hydroperoxide was continuously added dropwise to the glass reactor over 60 minutes to polymerize the elastic body and intermediate part. After the addition of the mixture was completed, stirring of the mixture in the glass reactor was continued for another 0.5 hours to complete the polymerization. Through the above operations, aqueous latex (L-1) of polymer particles having an elastic body, an intermediate part, and a graft part was obtained.

[0304] (Production Examples 3-2 to 3-4; Preparation of Aqueous Latex Polymer Particles (L-2) to (L-4)) Aqueous latex polymer particles (L-2) to (L-4) having an elastic body, an intermediate part, and a graft part were obtained by the same method (operation) as in Production Example 3-1, except for the following: The amount (parts by mass) of MMA and BA used was changed to the amounts (parts by mass) indicated in the "MMA" column and the "BA" column of the "Graft Part" column in Table 1, respectively.

[0305] (Production Examples 3-5 to 3-8; Preparation of Aqueous Latex Polymer Particles (L-5) to (L-8)) Aqueous latex polymer particles (L-5) to (L-8) having elastic bodies, intermediate parts, and graft parts were obtained by the same method (operation) as in Production Example 3-2, except that the glass reactor used after producing aqueous latex (M-1) was replaced with the glass reactor used after producing aqueous latex (M-2) to (M-5).

[0306] In the manufacturing process of aqueous latex (L-1) to (L-8) (specifically, the graft formation process), no crosslinkable monomers or graftable monomers are used. Therefore, the graft portions of the polymer particles contained in the resulting aqueous latex (L-1) to (L-8) do not contain crosslinkable units or graftable units.

[0307] Reactive monomer X is not used in the manufacturing process of aqueous latex (L-1) to (L-8). Therefore, the polymer particles contained in the resulting aqueous latex (L-1) to (L-8) do not contain constituent unit X.

[0308] The Tg of the graft portion of polymer particles (B) in aqueous latex (L-1) to (L-8), in other words, the glass transition temperature of the structure excluding the crosslinkable and graftable units, was calculated using the FOX formula described above. Furthermore, the volume-average particle size of polymer particles (B) in each aqueous latex (L-1) to (L-8) was measured using the method described above. The results are shown in Tables 1 and 2.

[0309] <4. Preparation of Powdered Polymer Particles (B)> (Preparation of Powdered Material (P-1)) 4 parts by mass of calcium chloride and 596 parts by mass of ion-exchanged water were mixed to dissolve the calcium chloride, and 600 parts by mass of an aqueous calcium chloride solution was prepared, which was heated to 50°C. Next, 280 parts by mass of aqueous latex (L-1), equivalent to 100 parts by mass of polymer particles (B), was added to the 600 parts by mass of the aqueous calcium chloride solution to obtain a slurry containing solidified polymer particles (B). Next, the slurry was centrifuged to obtain wet powder, which is the solidified material. Furthermore, using the obtained wet powder, the operation of adding the wet powder to 500 parts by mass of ion-exchanged water and the operation of centrifuging the obtained mixture were repeated for a total of two cycles to obtain washed wet powder. Finally, the wet powder was dried in a dryer at 50°C for 48 hours to obtain powdered polymer particles (P-1).

[0310] (Preparation of polymer particle (B) powders (P-2) to (P-6) and (P-8)) Polymer particle (B) powders (P-2) to (P-6) and (P-8) were obtained by the same method (operation) as described in the section (Preparation of powder (P-1)) above, except that aqueous latex (L-1) was replaced with aqueous latex (L-2) to (L-6) and (L-8), respectively. Furthermore, an attempt was made to prepare powders by the same method (operation) as described in the section (Preparation of polymer particle (B) powders (P-1)) above, except that aqueous latex (L-7) was used instead of aqueous latex (L-1). However, no powders were obtained; instead, a crumbly substance was obtained.

[0311] <5. Preparation of Thermosetting Resin Compositions> In the following examples and comparative examples, a polyester resin having a hydroxyl group as a thermosetting reactive group (hydroxyl group-containing polyester resin, GV-500 manufactured by Yupika Co., Ltd.) was used as the thermosetting resin (A), blocked isocyanate (VESTAGON B-1530 manufactured by EVONIK) was used as the curing agent (D), and titanium dioxide (CR-95 manufactured by Ishihara Sangyo Co., Ltd.) was used as the pigment (C).

[0312] (Example 1: Preparation of Thermosetting Resin Composition) 61 parts by mass of thermosetting resin (A), 3 parts by mass of powder (P-2), 10 parts by mass of curing agent (D), 25 parts by mass of pigment (C), 0.5 parts by mass of defoaming agent, and 1.0 part by mass of leveling agent were mixed. The resulting mixture was then melt-kneaded using an extruder, cooled, and then finely ground. Subsequently, the obtained finely ground material was sieved through a sieve with a mesh size of 100 μm to obtain a thermosetting resin composition.

[0313] (Examples 2 to 6: Preparation of thermosetting resin compositions) Thermosetting resin compositions were obtained in the same manner as in Example 1, except that powders (P-3) to (P-6) and (P-8) were used instead of powder (P-2).

[0314] (Comparative Example 1: Preparation of Thermosetting Resin Composition) A thermosetting resin composition was obtained by the same method as in Example 1, except that powder (P-1) was used instead of powder (P-2).

[0315] (Comparative Example 2: Preparation of Thermosetting Resin Composition) A thermosetting resin composition was obtained by the same method as in Example 1, except that a crumb-like substance containing polymer particles (B), obtained using aqueous latex (L-7), was used instead of powder (P-2).

[0316] <6. Application of Thermosetting Resin Composition and Production of Cured Products (Cured Films)> The thermosetting resin compositions obtained in each example and comparative example were applied (painted) to steel plates (0.7 × 70 × 150 mm) that had been treated with zinc phosphate conversion to film thicknesses of 60 μm and 40 μm. Subsequently, the steel plates were heated at a temperature of 190°C for 30 minutes to bake and cure the thermosetting resin composition onto the steel plates, forming cured products (cured films). Test specimens (painted plates) were prepared by this procedure. The cupping resistance of the obtained 60 μm film thickness test specimens was evaluated using the method described above. The dispersibility (aesthetic appearance) of the obtained 40 μm film thickness test specimens was evaluated using the method described above. The results are shown in Tables 1 and 2.

[0317] As described above, by applying (painting) the thermosetting resin composition of the example to a substrate (steel plate) and heating (baking) it, the thermosetting resin composition can be cured to form a film-like cured product (cured film). The cured film covered the applied surface of the steel plate. From these results, it can be seen that the thermosetting resin composition of the example can be used as a powder coating and a sealing resin composition. In other words, the thermosetting resin composition of the example can also be called a powder coating and a sealing resin composition.

[0318] According to one embodiment of the present invention, a thermosetting resin composition with excellent dispersibility of polymer particles can be provided. Therefore, one embodiment of the present invention can be particularly suitably used in fields such as powder coatings, encapsulating resin compositions, adhesives, coating materials, binders for reinforcing fibers, composite materials, 3D printing materials, electronic circuit boards, ink binders, wood chip binders, rubber chip binders, foam chip binders, casting binders, rock solidification materials for flooring and ceramics, and urethane foam.

Claims

1. A thermosetting resin composition comprising a thermosetting resin (A) and polymer particles (B), wherein the polymer particles (B) have an elastic body and a graft portion, the elastic body comprises one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and organosiloxane rubber, the graft portion comprises one or more constituent units selected from the group consisting of aromatic vinyl units, vinyl cyanide units and (meth)acrylate units, the content of the polymer particles (B) is 0.1 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the thermosetting resin (A), the glass transition temperature of the graft portion is 25°C or more and 50°C or less, and the volume average particle diameter of the polymer particles (B) is 130 nm or more and 800 nm or less.

2. The thermosetting resin composition according to claim 1, wherein the volume-average particle diameter of the elastic body is 130 nm or more and less than 800 nm.

3. The thermosetting resin composition according to claim 1, wherein the polymer particles (B) substantially do not contain constituent units X derived from a reactive monomer X having one or more reactive functional groups X selected from the group consisting of oxetane groups, hydroxyl groups, epoxy groups, amino groups, imide groups, carboxylic acid groups, carboxylic acid anhydride groups, cyclic ester groups, cyclic amide groups, benzoxazine groups, and cyanate ester groups.

4. The thermosetting resin composition according to claim 1, wherein the elastic body comprises a crosslinkable unit and / or a graftable unit as constituent units, and the elastic body contains the crosslinkable unit and the graftable unit in total in an amount greater than 0 parts by mass and 4.0 parts by mass or less per 100 parts by mass of the elastic body.

5. The thermosetting resin composition according to claim 1, wherein the polymer particles (B) contain the elastic body in an amount of 70.0% by mass or more and 90.0% by mass or less of the polymer particles (B) by mass.

6. The thermosetting resin composition according to claim 1, wherein the graft portion substantially does not contain crosslinkable units and graftable units as constituent units.

7. The thermosetting resin composition according to claim 1, wherein the polymer particles (B) contain the graft portion in an amount of 10.0% by mass or more and 30.0% by mass or less of the polymer particles (B) by 100% by mass.

8. The thermosetting resin composition according to claim 1, wherein the glass transition temperature of the elastic body is less than 0°C.

9. The thermosetting resin composition according to claim 1, wherein the polymer particles (B) further have an intermediate portion, and the intermediate portion contains, as constituent units, at least 5.0 parts by mass of crosslinkable units and graftable units in total per 100 parts by mass of the intermediate portion.

10. The thermosetting resin composition according to claim 9, wherein the polymer particles (B) contain the intermediate portion in an amount of 0.5% by mass or more and 5.0% by mass or less of the polymer particles (B) by 100% by mass.

11. The thermosetting resin composition according to claim 1, further comprising resin (E).

12. A cured product obtained by curing a thermosetting resin composition according to any one of claims 1 to 11.

13. A powder coating comprising the thermosetting resin composition according to any one of claims 1 to 11.

14. A coating film obtained by curing the powder coating described in claim 13.

15. A encapsulating resin composition comprising the thermosetting resin composition according to any one of claims 1 to 11.

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