Anti-algae ingredients contain particles

Abstract

To provide an algicidal component-containing particle that can form an excellent coating layer, and can suppress an outflow of an algicidal component from the coating layer.SOLUTION: A particle comprises an algicidal component, a nonionic surfactant, and an alkyl group-containing ester compound with 15 or more carbon atoms. The mass ratio between the nonionic surfactant and the alkyl group-containing ester compound with 15 or more carbon atoms (mass of nonionic surfactant / mass of alkyl group-containing ester compound with 15 or more carbon atoms) is 60 / 40-90 / 10. The average particle size is 10 nm-200 nm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to particles containing an anti-algae component. More specifically, the present invention relates to particles containing an anti-algae component that are useful for applications such as paints, coating agents, inks, etc., and to a method for producing the same. [Background technology]

[0002] In recent years, from the viewpoints of environmental protection and occupational safety and health, there has been a demand for non-polluting paints, coating agents, and inks, and solvent-based paints are being replaced with water-based paints. Furthermore, in general buildings, problems have arisen, such as the adhesion and growth of algae on exterior walls, interior walls, and equipment due to humidity and water, which detracts from the aesthetic appearance of the building. For this reason, in order to prevent this from occurring, various anti-algae agents and paints containing such agents have been applied to the surfaces of the objects to be protected. For example, Patent Document 1 describes anti-algae particles that contain a polymer and an anti-algae component dispersed in the polymer, wherein the anti-algae component is at least one triazine compound selected from the group consisting of sibutryn and terbutryn, and the polymer is formed by polymerizing a vinyl monomer component that contains 1% by mass to 50% by mass of an anionic group-containing vinyl monomer, and describes that the particles can contain a high proportion of the anti-algae component. Furthermore, Patent Document 2 describes an anti-algae paint containing a 4-hydroxybenzoic acid ester represented by formula (1), and describes that an anti-algae paint can be obtained that is both safe and has a high anti-algae effect against algae, and describes in the examples an embodiment in which the paint is added to a urethane paint.

[0003] [ka]

[0004] [wherein R1 represents a hydrogen atom or an alkali metal, and R2 represents an alkyl group having 1 to 22 carbon atoms. represents an alkyl or aryl group] [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2019-131551 [Patent Document 2] Patent Publication No. 2021-116397 Summary of the Invention [Problem to be solved by the invention]

[0006] However, it has been found that the anti-algae paint described in Patent Document 1 has a problem in that when it is mixed with the resin emulsion used in the paint to form a coating film, turbidity and whitening occur, resulting in a poor appearance of the coating film. Furthermore, it has been found that it is difficult for the anti-algae paint described in Patent Document 2 to maintain its anti-algae properties for a long period of time.

[0007] An object of the present invention is to provide particles containing an anti-algae component that can form a good coating film and can prevent the anti-algae component from leaking out of the coating film. [Means for solving the problem]

[0008] The inventors have conducted studies in light of the above-mentioned problems and have found that particles containing an anti-algae ingredient, a nonionic surfactant, and an ester compound containing an alkyl group having 15 or more carbon atoms, in which the mass ratio of the nonionic surfactant to the ester compound containing an alkyl group having 15 or more carbon atoms (mass of nonionic surfactant / mass of ester compound containing an alkyl group having 15 or more carbon atoms) is 60 / 40 to 90 / 10 and which have an average particle size of 10 nm to 200 nm, can form a good coating film and can prevent the anti-algae ingredient from leaking out of the coating film, thereby completing the present invention. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide particles containing an anti-algae component that can form a good coating film and can prevent the anti-algae component from leaking out of the coating film. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. In this specification, the range "X to Y" means "not less than X and not more than Y." The particles of the present invention contain an anti-algae component, a nonionic surfactant, and an ester compound containing an alkyl group having 15 or more carbon atoms.

[0011] <Particles containing anti-algae ingredients> Examples of the anti-algae component of the present disclosure include isothiazolin-based anti-algae components such as 2-n-octyl-4-isothiazolin-3-one, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, and Nn-butyl-1,2-benzisothiazolin-3-one; 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU); 3-(3,4-dichlorophenyl)-1-methyl-1-methoxyurea; 3-(3,4-dichlorophenyl)-1-(2-methylcyclohexane)-1-one; hexyl), 3-phenyl-1-(2-methylcyclohexyl)urea, 3-(phenyldimethylmethyl)-1-(4-methylphenyl)urea and other urea-based anti-algae ingredients, 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylthio-4,6-bis(ethylamino)-S-triazine, 2-methylthio-4-ethylamino-6-isopropylamino-S-triazine, 2-methylthio-4,6-bis( Triazine-based anti-algae ingredients such as N'-t-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine, and other triazine-based anti-algae ingredients; thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, dipyrrolidone thiuram disulfide, and polyethylene thiuram disulfide. These include benzimidazole-based anti-algae ingredients such as 2-(4-thiazyl)benzimidazole and 2-(carbomethoxyamino)benzimidazole, pyridine-based anti-algae ingredients such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, zinc pyrithione-based anti-algae ingredients such as zinc-2-pyridinethiol-1-oxide, and organohalogen-based, organometallic-based, haloalkylthio-based, and phenylphenol-based anti-algae ingredients. These anti-algae ingredients may be used alone or in combination of two or more.

[0012] Commercially available products can also be used as the anti-algae component of the present disclosure. Examples of thiazoline-based anti-algae ingredients include Nippon Soda's products "Milcut-180" and "Biocut-LC3," and Yamato Chemical Industry's product "Amorden ALK." Examples of isothiazolinone-based anti-algae ingredients include Nippon Soda's "Biocut-TR120," Arch Chemicals' "PROXEL GXL" and "PROXEL BDN," and Dow Chemical's "KLARIX 4000," "ROZONE 2000," "ROCIMA 252," "ROCIMA 200," "ROCIMA 345," "ROCIMA 350," "ROCIMA 553," "BIOBAN 551S," and "Skein M-8." Imidazole-based anti-algae ingredients include Nippon Soda's products "Biocut-N35," "Biocut-AF40," and "DX-2," and Dow Chemical's product "ROCIMA 363." Examples of triazine-based anti-algae ingredients include Nippon Soda's products "Biocut-N35," "DP-2159," "DP-2615," "DP-2619," and "DP-2623," Yamato Chemical Industry's products "Amorden NBP-8" and "Amorden NBPconc," and Sankyo Kasei's product "Sunalga 1907."

[0013] The water solubility of the anti-algae component is preferably 10 mg / L or more and 400 mg / L or less, and specific examples include imidazole-based compounds (e.g., Dow Chemical's product "ROCIMA 363"), urea-based compounds, etc. On the other hand, specific examples of anti-algae components having a water solubility of 0.1 mg / L or more and less than 10 mg / L include imidazole-based compounds (e.g., Nippon Soda's product "Biocut-N35") and triazine-based compounds.

[0014] The content of the anti-algae component in 100 parts by mass of the particles of the present disclosure is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 3 parts by mass or more, from the viewpoint of ensuring anti-algae properties, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less, from the viewpoint of storage stability.

[0015] Examples of nonionic surfactants of the present disclosure include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensation products of ethylene oxide and aliphatic amines, allyloxymethylalkoxyethylhydroxypolyoxyethylene, polyoxyalkylene alkenyl ethers, and the like; however, the present invention is not limited to these examples.

[0016] The HLB (hydrophilic-lipophilic balance) of the nonionic surfactant of the present disclosure is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more, from the viewpoint of improving dispersion stability when the particles of the present disclosure are used as an aqueous dispersion. From the viewpoint of improving the dispersion stability of an emulsion particle-containing aqueous dispersion, it is preferably 17 or less, more preferably 16 or less, and even more preferably 15 or less. Furthermore, from the viewpoint of obtaining an emulsion particle-containing aqueous dispersion containing emulsion particles having a fine particle size, the HLB of the nonionic surfactant is preferably 14 or less, more preferably 13.5 or less, and even more preferably 13 or less. Therefore, the HLB of the nonionic surfactant is preferably 8 to 17, more preferably 9 to 16, even more preferably 9 to 15, even more preferably 10 to 14, even more preferably 10 to 13.5, and particularly preferably 10 to 13. The HLB of the nonionic surfactant can be calculated based on the Griffin method using the following formula: [HLB of nonionic surfactant] = 20 × [(molecular weight of hydrophilic part) / (molecular weight of surfactant)] This is the value calculated by

[0017] Examples of nonionic surfactants include ester-type nonionic surfactants such as polyglycerin fatty acid esters and sucrose fatty acid esters, ethylene-propylene block copolymer-type nonionic surfactants, alkyl ether-type nonionic surfactants, phenol-type nonionic surfactants, and amide-type nonionic surfactants, but the present invention is not limited to these examples. These surfactants may be used alone or in combination of two or more.

[0018] Nonionic surfactants are readily available commercially. Examples of commercially available nonionic surfactants include the Softanol series, such as those manufactured by Kao Corporation under the trade name Latemul PD-420 (HLB: 12.6), Kao Corporation under the trade name Latemul PD-430 (HLB: 14.4), Nippon Shokubai Co., Ltd. under the trade name Softanol 120 (HLB: 14.5), Nippon Shokubai Co., Ltd. under the trade name Softanol 90 (HLB: 13.3), Nippon Shokubai Co., Ltd. under the trade name Softanol 70 (HLB: 12.1), Nippon Shokubai Co., Ltd. ) ADEKA, trade name: ADEKA REASOAP ER-10 (HLB: 12.1), ADEKA Corporation, trade name: ADEKA REASOAP ER-20 (HLB: 15.1), Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: AQUALON AN-10 (HLB: 12.7), Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: AQUALON AN-20 (HLB: 15.7), Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: AQUALON KN-10 (HLB: 13), etc., but the present invention is not limited to these examples. As the nonionic surfactant, an ethylene-propylene block copolymer type nonionic surfactant is particularly preferred from the viewpoint of obtaining an emulsion particle-containing aqueous dispersion containing emulsion particles having a fine particle size.

[0019] Among nonionic surfactants, it is preferable to use a reactive nonionic surfactant from the viewpoint of incorporating the nonionic surfactant into emulsion particles. Reactive nonionic surfactants are readily available commercially. Examples of commercially available reactive nonionic surfactants include ADEKA Corporation's trade name: ADEKA REASOAP ER-10 (HLB: 12.1), ADEKA Corporation's trade name: ADEKA REASOAP ER-20 (HLB: 15.1), Dai-ichi Kogyo Seiyaku Co., Ltd.'s trade name: AQUALON AN-10 (HLB: 12.7), Dai-ichi Kogyo Seiyaku Co., Ltd.'s trade name: AQUALON AN-20 (HLB: 15.7), Dai-ichi Kogyo Seiyaku Co., Ltd.'s trade name: AQUALON KN-10 (HLB: 13), and Kao Corporation's trade name: LATEMURU PD-420 (HLB: 12.6), but the present invention is not limited to these examples.

[0020] The lower limit of the content of the nonionic surfactant in 100 parts by mass of the particles of the present disclosure is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 7 parts by mass or more, and particularly preferably 8 parts by mass or more.From the viewpoint of obtaining an aqueous dispersion containing core-shell particles having a fine particle diameter, the upper limit is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

[0021] The alkyl group-containing ester compound having 15 or more carbon atoms according to the present disclosure may have 15 or more carbon atoms in the alkyl ester moiety, and more preferably has 15 or more carbon atoms in the entire compound. From the viewpoint of improving the dispersion stability of the particles, the lower limit of the number of carbon atoms in the alkyl group-containing ester compound is 15 or more, preferably 18 or more, and more preferably 23 or more, and the upper limit is not particularly limited, but is preferably 60 or less, more preferably 50 or less, and even more preferably 40 or less, from the viewpoint of easy availability of raw materials.

[0022] The alkyl group-containing ester compound having 15 or more carbon atoms according to the present disclosure may have a polymerizable unsaturated double bond. Examples of alkyl group-containing ester compounds having 15 or more carbon atoms in the present disclosure include fatty acid esters having an alkyl ester moiety having a polymerizable unsaturated double bond and having 15 or more carbon atoms, such as hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, eicosyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate; fatty acid esters having an alkyl ester moiety having 15 or more carbon atoms, such as hexadecyl 2-ethylhexanoate, stearyl myristate, stearyl 2-ethylhexanoate, and stearyl stearate; and fatty acid esters having an alkyl group having 15 or more carbon atoms, such as ethyl palmitate, ethyl stearate, and 2-ethylhexyl stearate. However, the present invention is not limited to these examples. These alkyl group-containing ester compounds having 15 or more carbon atoms may be used alone or in combination of two or more types.

[0023] Among alkyl group-containing ester compounds having 15 or more carbon atoms, those having a polymerizable unsaturated double bond are preferred from the viewpoint of preventing the anti-algae component from leaking out of the coating film. Examples include hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, eicosyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate, with stearyl (meth)acrylate and behenyl (meth)acrylate being more preferred.

[0024] The content of the alkyl group-containing ester compound having 15 or more carbon atoms per 100 parts by mass of the particles of the present disclosure is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 3 parts by mass or more, from the viewpoint of obtaining an emulsion particle-containing aqueous dispersion containing emulsion particles having a fine particle size, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, from the viewpoint of improving the dispersion stability of the emulsion particle-containing aqueous dispersion.

[0025] In the particles of the present disclosure, the mass ratio of the nonionic surfactant to the alkyl group-containing ester compound having 15 or more carbon atoms (mass of nonionic surfactant / mass of alkyl group-containing ester compound having 15 or more carbon atoms) is preferably 60 / 40 to 90 / 10, more preferably 62 / 38 to 80 / 20, and even more preferably 64 / 36 to 78 / 22.

[0026] The particles of the present disclosure may further contain other surfactants. Examples of other surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants, and it is preferable that the particles contain an anionic surfactant. By containing an anionic surfactant, it is expected that the dispersion stability of the particles dispersed in a solvent can be improved, allowing for long-term storage.

[0027] Examples of the anionic surfactants of the present disclosure include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate and sodium alkyl diphenyl ether disulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinate salts; and aryl sulfonic acid-formalin condensates. fatty acid salts such as ammonium laurate and sodium stearylate; sulfates or salts thereof having an allyl group such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salts, propenyl-alkyl sulfosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts, and sulfonate salts of allyloxymethyl alkyloxy polyoxyethylene; sulfate ester salts of allyloxymethyl alkoxyethyl polyoxyethylene, and polyoxyalkylene alkenyl ether ammonium sulfate salts, but the present invention is not limited to these examples.

[0028] Examples of the cationic surfactant of the present disclosure include alkylammonium salts such as dodecylammonium chloride, but the present invention is not limited to these examples. Examples of amphoteric surfactants of the present disclosure include betaine ester surfactants, but the present invention is not limited to these examples. Examples of polymer surfactants of the present disclosure include poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; and copolymers containing one or more of the monomers constituting these polymers as copolymerization components, but the present invention is not limited to these examples.

[0029] When the surfactant of the present disclosure includes a nonionic surfactant and an anionic surfactant, the total amount of the nonionic surfactant and the anionic surfactant is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of the particle solid content. When the surfactant of the present disclosure contains a nonionic surfactant and an anionic surfactant, the mass ratio of the nonionic surfactant to the anionic surfactant is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 99 / 1, and even more preferably 70 / 30 to 99 / 1.

[0030] Among the surfactants, surfactants having a polymerizable group, i.e., so-called reactive surfactants, are preferred from the viewpoint of improving weather resistance, and non-nonylphenyl surfactants are preferred from the viewpoint of environmental protection.

[0031] Examples of reactive surfactants include propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts (e.g., Sanyo Chemical Industries, Ltd., trade name: Eleminol RS-30, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10, Aqualon HS-10, etc.), and allyloxymethyl alkyloxy polyoxyethylene sulfonates. salts (e.g., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), polyoxyethylene styrenated propenyl phenyl ether sulfate ester ammonium salts (e.g., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon AR-10, Aqualon AR-20, etc.), polyoxyethylene styrenated propenyl phenyl ethers (e.g., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon AN-10, Aqualon AN-20, Aqualon AN-30, etc.), allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene sulfonate salts of (e.g., manufactured by ADEKA Corporation under the trade name of ADEKA REASOAP SE-10, etc.), allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salts (e.g., manufactured by ADEKA Corporation under the trade names of ADEKA REASOAP SR-10, SR-20, SR-30, etc.), bis(polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salts (e.g., manufactured by Nippon Nyukazai Co., Ltd. under the trade name of ANTOX MS-60, etc.), allyloxymethylalkoxyethylhydroxypolyoxyethylene (e.g., manufactured by Nippon Nyukazai Co., Ltd. under the trade name of ANTOX MS-60, etc.), , manufactured by ADEKA CORPORATION, trade names: ADEKA REASOAP ER-10, ADEKA REASOAP ER-20, ADEKA REASOAP ER-30, ADEKA REASOAP ER-40, etc.), polyoxyethylene alkylpropenylphenyl ether [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.], allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, manufactured by ADEKA CORPORATION, trade name: ADEKA REASOAP NE-10, etc.], but the present invention is not limited to these examples.

[0032] The particles of the present disclosure may include a polymer. The polymer of the present disclosure is preferably a polymer (A) having a structural unit derived from a (meth)acrylic acid ester containing an alkyl group having 4 to 12 carbon atoms. The structural unit derived from an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms in the present disclosure is a structure obtained by polymerizing an alkyl group-containing (meth)acrylic acid ester monomer having 4 to 12 carbon atoms, and the structure may be formed by polymerizing an alkyl group-containing (meth)acrylic acid ester monomer having 4 to 12 carbon atoms, or by post-modification.

[0033] Examples of the structural unit derived from an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms according to the present disclosure include the following general formula (1).

[0034] [ka]

[0035] In general formula (1), R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X1 represents a single bond, an alkylene group, -O-, -CO-, -NH-, -SO2-, or a linking group formed by combining these, and R2 represents an alkyl group having 4 to 12 carbon atoms. Examples of the alkyl group having 4 to 12 carbon atoms include an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 2-ethylhexyl group, and an n-octyl group. 、 Examples include a cyclohexyl group, an n-lauryl group, a dodecyl group, an isononyl group, and an isobornyl group. From the viewpoint of improving the dispersion stability of the particle-containing aqueous dispersion, an n-butyl group, an isobutyl group, a 2-ethylhexyl group, and a cyclohexyl group are preferred.

[0036] Examples of the alkyl group-containing (meth)acrylic acid ester monomer having 4 to 12 carbon atoms according to the present disclosure include n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-octyl (meth)acrylate. 、 Examples of the alkyl (meth)acrylate include cyclohexyl (meth)acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, isononyl (meth)acrylate, and isobornyl (meth)acrylate, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more. In the present invention, the alkyl (meth)acrylate is a concept that includes (meth)acrylates having an alicyclic structure.

[0037] In order to improve the dispersion stability of the particle-containing aqueous dispersion, preferred (meth)acrylic acid ester monomers having an alkyl group and having 4 to 12 carbon atoms according to the present disclosure are n-butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and cyclohexyl(meth)acrylate. These monomers may be used alone or in combination of two or more.

[0038] The total content of structural units derived from alkyl group-containing (meth)acrylic acid ester monomers having 4 to 12 carbon atoms in 100 parts by mass of polymer (A) of the present disclosure is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. Furthermore, the total content of structural units derived from alkyl group-containing (meth)acrylic acid esters having 3 to 12 carbon atoms in the monomer A is preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on 100% by mass of monomer A. By ensuring the content is within the above range, the transparency of the coating film tends to be improved when used as a coating agent or the like.

[0039] The polymer (A) of the present disclosure may have a structural unit other than a structural unit derived from an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms. Examples of structural units other than a structural unit derived from an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms include a structural unit derived from an alkyl group-containing ester compound having 15 or more carbon atoms and a polymerizable unsaturated double bond, a structural unit derived from an alkyl group-containing (meth)acrylic acid ester having an alkyl group having 1 to 3 carbon atoms, a structural unit derived from an acid group-containing monomer, a structural unit derived from a hydroxyl group-containing (meth)acrylic acid ester, a structural unit derived from an oxo group-containing monomer, a structural unit derived from a fluorine atom-containing monomer, a structural unit derived from a nitrogen atom-containing monomer, a structural unit derived from a piperidyl group-containing monomer, a structural unit derived from an alkoxyalkyl (meth)acrylic acid ester, a structural unit derived from a carbonyl group-containing monomer, a structural unit derived from a styrene-based monomer, and a structural unit derived from an aralkyl (meth)acrylic acid ester, but the present invention is not limited to these examples. These ethylenically unsaturated double bond-containing monomers may be used alone or in combination of two or more.

[0040] Examples of the alkyl group-containing ester compound having a polymerizable unsaturated double bond and 15 or more carbon atoms according to the present disclosure include hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, eicosyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate, with stearyl (meth)acrylate and behenyl (meth)acrylate being more preferred. Examples of the alkyl group-containing (meth)acrylic acid ester of the present disclosure, in which the alkyl group has 1 to 3 carbon atoms, include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc., but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more.

[0041] Examples of the acid group-containing monomer of the present disclosure include carboxyl group-containing aliphatic monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, itaconic acid monobutyl ester, and vinylbenzoic acid, but the present invention is not limited to these examples. These acid group-containing monomers may be used alone or in combination of two or more kinds.

[0042] Examples of the nitrogen atom-containing ethylenically unsaturated monomer of the present disclosure include acrylamide compounds such as (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropylacrylamide, and diacetone acrylamide; nitrogen atom-containing (meth)acrylate compounds such as dimethylaminoethyl(meth)acrylate and diethylaminoethyl(meth)acrylate; N-vinylpyrrolidone, (meth)acrylonitrile, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide; however, the present invention is not limited to these examples. These nitrogen atom-containing ethylenically unsaturated monomers may be used alone or in combination of two or more kinds, but N-vinylpyrrolidone is preferred from the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion.

[0043] Examples of the piperidyl group-containing monomer of the present disclosure include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2, Examples of the monomer include 6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more. Among these piperidyl group-containing monomers, piperidyl group-containing (meth)acrylates such as 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, and 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine are preferred. In the present invention, piperidyl group-containing monomers are not included in the nitrogen-containing ethylenically unsaturated monomers.

[0044] Examples of the styrene-based monomer of the present disclosure include alkylstyrenes having an alkyl group having 1 to 4 carbon atoms, such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, tert-methylstyrene, o-tert-butylstyrene, m-tert-butylstyrene, and p-tert-butylstyrene; o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, and o-tert-butoxystyrene. Examples of suitable styrene monomers include styrene, m-tert-butoxystyrene, p-tert-butoxystyrene, and other alkoxystyrenes having an alkoxy group with 1 to 4 carbon atoms; o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, and p-bromostyrene, and other halogen-containing styrenes; o-acetoxystyrene, m-acetoxystyrene, and p-acetoxystyrene, and other acetoxystyrenes; and vinyltoluene, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more. Among styrene-based monomers, styrene and alkylstyrenes having an alkyl group with 1 to 4 carbon atoms are preferred, with styrene being more preferred, from the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion.

[0045] The polymer (A) of the present disclosure may have a structural unit derived from a crosslinkable monomer from the viewpoint of suppressing the anti-algae component from leaking out of the coating film. Examples of the crosslinkable monomer of the present disclosure include a compound having two or more polymerizable unsaturated double bonds, a silane group-containing compound having one or more polymerizable unsaturated double bonds, an epoxy group-containing monomer, and an aziridinyl group-containing monomer.

[0046] Examples of the compound having two or more polymerizable unsaturated double bonds of the present disclosure include polyfunctional (meth)acrylates. Examples of the polyfunctional (meth)acrylate of the present disclosure include triallyl compounds having 9 to 20 carbon atoms, such as triallyl cyanurate (triallyl cyanurate), triallyl isocyanurate, triallyl phosphate, and triallylamine; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and ethylene oxide-modified 1,6-hexanediol di(meth)acrylate. di(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; alkylene glycols having 2 to 4 carbon atoms such as polyethylene glycol di(meth)acrylate having 2 to 50 moles of ethylene oxide added, polypropylene glycol di(meth)acrylate having 2 to 50 moles of propylene oxide added, and tripropylene glycol di(meth)acrylate; Alkyl di(meth)acrylates having an added mole number of oxide groups of 2 to 50; tri(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as ethoxylated glycerin tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxytri(meth)acrylate, and trimethylolpropane triethoxytri(meth)acrylate; pentaerythritol tetra(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; penta(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as pentaerythritol penta(meth)acrylate and dipentaerythritol(monohydroxy)penta(meth)acrylate; hexa(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as pentaerythritol hexa(meth)acrylate;Examples of suitable polyfunctional (meth)acrylates include bisphenol A di(meth)acrylate, but the present invention is not limited to these examples. These polyfunctional monomers may be used alone or in combination of two or more types.

[0047] Examples of silane group-containing compounds having one or more polymerizable unsaturated double bonds according to the present disclosure include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, γ-(meth)acryloyloxypropylhydroxysilane, and γ-(meth)acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to these examples. These silane group-containing monomers may be used alone or in combination of two or more.

[0048] Examples of the epoxy group-containing monomer of the present disclosure include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and glycidyl allyl ether, but the present invention is not limited to these examples. These epoxy group-containing monomers may be used alone or in combination of two or more. Examples of the aziridinyl group-containing monomer of the present disclosure include (meth)acryloylaziridine, 2-aziridinylethyl (meth)acrylate, etc., but the present invention is not limited to these examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

[0049] The content of structural units derived from crosslinkable monomers in 100 parts by mass of polymer (A) of the present disclosure is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1% by mass or more, and particularly preferably 2 parts by mass or more, from the viewpoint of suppressing outflow of the anti-algae component from the coating film; and from the viewpoint of improving the dispersion stability of the particle-containing aqueous dispersion, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0050] The glass transition temperature of the polymer (A) of the present disclosure is preferably -40°C or higher, more preferably -30°C or higher, and even more preferably -20°C or higher, from the viewpoint of improving the stability of the anti-algae component content, and is preferably 120°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower, from the viewpoint of film-forming properties when made into a coating film. The glass transition temperature of the polymer (A) can be calculated by the formula (I): 1 / Tg=Σ(Wm / Tgm) / 100 (I) (wherein Wm represents the content (mass%) of monomer m in the monomer components constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of a homopolymer of monomer m.) This refers to the temperature calculated based on the Fox equation, For monomers with unknown glass transition temperatures, such as special monomers and polyfunctional monomers, if the total amount of monomers with unknown glass transition temperatures in the monomer composition is 10% by mass or less, the glass transition temperature can be determined using only monomers with known glass transition temperatures. If the total amount of monomers with unknown glass transition temperatures in the monomer composition exceeds 10% by mass, the glass transition temperature of the polymer can be determined by differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermomechanical analysis (TMA), etc. The glass transition temperature of a polymer can be easily adjusted by adjusting the composition of the monomer components. The composition of the monomer components used as raw materials for the polymer constituting the particles can be determined in consideration of the glass transition temperature of the polymer constituting the particles.

[0051] The glass transition temperatures of the polymers are, for example, −70°C for a homopolymer of 2-ethylhexyl acrylate, −56°C for a homopolymer of n-butyl acrylate, 20°C for a homopolymer of n-butyl methacrylate, 105°C for a homopolymer of methyl methacrylate, 83°C for a homopolymer of cyclohexyl methacrylate, 107°C for a homopolymer of tert-butyl methacrylate, 100°C for a homopolymer of styrene, 95°C for a homopolymer of acrylic acid, 130°C for a homopolymer of methacrylic acid, 55°C for a homopolymer of 2-hydroxyethyl methacrylate, 77°C for a homopolymer of diacetone acrylamide, 70°C for a homopolymer of γ-methacryloxypropyltrimethoxysilane, approximately 130°C for a homopolymer of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, and 55°C for a homopolymer of glycerin monomethacrylate.

[0052] The particles of the present disclosure may contain various additives as other compounds. Examples of additives of the present disclosure include colorants such as pigments, leveling agents, UV absorbers, UV stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, metal deactivators, wetting agents, antifoaming agents, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosion agents, pigment dispersants, flow control agents, peroxide decomposers, mold bleaching agents, fluorescent brighteners, organic flame retardants, inorganic flame retardants, anti-dripping agents, melt flow modifiers, antistatic agents, mildew inhibitors, flame retardants, slip agents, metal chelating agents, antiblocking agents, heat stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, antioxidants, preservatives, antistatic agents, antioxidants, and film-forming aids, but the present invention is not limited to these examples. These additives may be used alone or in combination of two or more. The amounts of these additives vary depending on the type of additive and cannot be determined in general terms, so it is preferable to determine them appropriately depending on the type of additive.

[0053] The average particle size of the particles of the present disclosure is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more, and is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less, from the viewpoint of contributing to the dispersion stability of the aqueous dispersion and contributing to the transparency of a coating film. The average particle size of the core-shell particles of the present disclosure is measured in accordance with JIS Z 8828, measured by a dynamic light scattering method, and is defined as the cumulant average particle size, and can be specifically measured by the method described in the Examples.

[0054] <Dispersion containing particles containing anti-algae component> The particles of the present disclosure may be emulsion particles, and although the solvent used is not particularly specified, an aqueous solvent is preferred from the viewpoints of environmental protection and workplace safety. In other words, the anti-algae component-containing particles of the present disclosure are preferably used as an aqueous dispersion.

[0055] Examples of aqueous solvents in the present disclosure include water and mixed solvents of water and water-soluble organic solvents. Examples of water-soluble organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol; polyhydric alcohols such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol; and ketones such as acetone and methyl ethyl ketone, but the present invention is not limited to these examples. These aqueous media may be used alone or in combination of two or more.

[0056] From the viewpoint of improving the dispersion stability of the particle-containing aqueous dispersion, the water content in the aqueous solvent of the present disclosure is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and still more preferably 80% by mass or more, with the upper limit of the water content being 100% by mass. Among aqueous solvents, water is preferred.

[0057] <Method of manufacturing particles containing anti-algae ingredients> The particles of the present disclosure are preferably obtained as a particle-containing dispersion, and the particles of the present disclosure are preferably emulsion particles. Furthermore, the particle-containing dispersion of the present disclosure is preferably a particle-containing aqueous dispersion from the viewpoints of environmental protection and workplace safety. The method for producing the particle-containing dispersion of the present disclosure is not particularly limited as long as it can produce the particles of the present invention, but it preferably includes a step (1) of mixing an anti-algae component, a nonionic surfactant, and an alkyl group-containing ester compound having 15 or more carbon atoms with an aqueous medium, and a step (2) of heating the resulting mixture under stirring to a temperature equal to or higher than the phase inversion onset temperature of the mixture but lower than the boiling point of the aqueous medium, and then cooling the mixture to a temperature lower than the phase inversion onset temperature of the mixture.

[0058] The mass ratio of the nonionic surfactant to the ester compound containing an alkyl group having 15 or more carbon atoms (mass of nonionic surfactant / mass of ester compound containing an alkyl group having 15 or more carbon atoms) is as described above. In the method for producing the particle-containing dispersion of the present disclosure, in addition to the nonionic surfactant, other surfactants may be used. Examples of other surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants. From the viewpoint of particle dispersion stability, it is preferable to use anionic surfactants. Other compounds used as surfactants and the amounts used are as described above.

[0059] In addition, as the surfactant used in producing the particles of the present disclosure, a surfactant having a polymerizable group, i.e., a so-called reactive surfactant, is preferred from the viewpoint of improving weather resistance, and a non-nonylphenyl type surfactant is preferred from the viewpoint of environmental protection. Examples of the reactive surfactant include the compounds described above.

[0060] When the particles of the present disclosure contain a polymer, the polymer may be added in the above step (1), or a step of adding a monomer and then polymerizing the monomer may be performed. The method for polymerizing the monomer is not particularly limited, but from the viewpoint of obtaining particles with a small particle size, emulsion polymerization is preferred, and phase inversion emulsification is more preferred, but the present invention is not limited to such a method. Emulsion particles containing the polymer of the present disclosure may also be referred to as polymer emulsion particles.

[0061] In step (1), the temperature at which the anti-algae component, nonionic surfactant, and alkyl group-containing ester compound having 15 or more carbon atoms are mixed with the aqueous medium cannot be determined in general because it varies depending on factors such as the phase inversion temperature described below, but is typically preferably 5 to 45°C, more preferably 5 to 40°C, and even more preferably 5 to 35°C. When mixing, the anti-algae component, nonionic surfactant, and alkyl group-containing ester compound having 15 or more carbon atoms are preferably added to the aqueous medium under stirring to uniformly disperse the various components in the aqueous medium. There is no need to use specialized equipment, such as a conventional high-viscosity paint mixer or high-pressure homogenizer, to stir the aqueous medium. For example, the anti-algae component, nonionic surfactant, and alkyl group-containing ester compound having 15 or more carbon atoms can be uniformly dispersed in the aqueous medium using simple stirring devices such as a stirring rod or magnetic stirrer.

[0062] Next, the anti-algae component, the nonionic surfactant, and the alkyl group-containing ester compound having 15 or more carbon atoms are mixed with the aqueous medium, and the resulting mixture is heated with stirring to a temperature equal to or higher than the phase inversion temperature of the mixture but lower than the boiling point of the aqueous medium, and then cooled with stirring to a temperature lower than the phase inversion temperature. This procedure is employed in the present invention, resulting in a particle-containing dispersion with excellent dispersion stability.

[0063] In step (2) of the present disclosure, the phase inversion temperature of the mixture can be determined using the electrical conductivity in the reaction vessel. The phase inversion onset temperature is the temperature at which the electrical conductivity begins to decrease continuously with increasing temperature, and the phase inversion end temperature is the temperature at which the electrical conductivity falls to 1.00 μS or less. If the electrical conductivity does not fall to 1.00 μS or less even when the upper limit of the measurable temperature of the conductivity meter is exceeded, the temperature at which the appearance of the mixture does not change even after 3 minutes or more have passed since the mixture reached a temperature higher than the phase inversion onset temperature under stirring is considered to be the end point of the phase inversion temperature. Specifically, this can be measured by the method described in the Examples.

[0064] When the anti-algae component-containing particles of the present disclosure are in the form of an aqueous dispersion, the phase inversion starting temperature is preferably 35° C. or higher, more preferably 45° C. or higher, and even more preferably 50° C. or higher, from the viewpoint of improving the dispersion stability of the aqueous dispersion. Furthermore, the phase inversion end temperature is preferably 98° C. or lower, more preferably 97° C. or lower, and even more preferably 96° C. or lower, from the viewpoint of improving the stability of the emulsion. The atmosphere in which the mixture is heated is not particularly limited, but from the viewpoint of avoiding the influence of oxygen contained in the air, it is preferable to use an inert gas such as nitrogen gas or argon gas.

[0065] The lower limit of the heating temperature (maximum temperature when heated) of the mixture is a temperature equal to or higher than the phase inversion start temperature of the mixture, from the viewpoint of improving the dispersion stability of the aqueous dispersion, but is preferably a temperature 0.5°C or higher than the phase inversion start temperature of the mixture, and more preferably a temperature 1°C or higher than the phase inversion start temperature of the mixture. Furthermore, the lower limit of the heating temperature (maximum temperature when heated) of the mixture is preferably a temperature equal to or higher than the phase inversion end temperature of the mixture, and more preferably 0.5°C or higher than the phase inversion end temperature of the mixture, from the viewpoint of improving the dispersion stability of the core particle-containing aqueous dispersion. The upper limit of the heating temperature (maximum temperature when heated) of the mixture is usually a temperature below the boiling point of the aqueous medium, preferably a temperature that is 3°C or more lower than the boiling point of the aqueous medium, and more preferably a temperature that is 5°C or more lower than the boiling point of the aqueous medium.

[0066] Next, after the temperature of the mixture reaches a temperature equal to or higher than the phase inversion starting temperature of the mixture and lower than the boiling point of the aqueous medium, the mixture is cooled to a temperature equal to or lower than the phase inversion temperature of the mixture. There are no particular limitations on the means for cooling the mixture. The mixture may be cooled, for example, by standing to cool or by air cooling. The mixture is cooled to a temperature equal to or lower than the phase inversion onset temperature of the mixture. The mixture is preferably cooled to a temperature 10°C or more lower than the phase inversion onset temperature of the mixture, more preferably 20°C or more lower than the phase inversion onset temperature of the mixture, even more preferably 25°C or more lower than the phase inversion onset temperature of the mixture, and even more preferably 30°C or more lower than the phase inversion onset temperature of the mixture. By the above operations, a dispersion of particles containing the anti-algae component having a fine particle size is obtained.

[0067] When the particles of the present disclosure contain polymer (A), it is preferable to include step (3) of mixing a monomer containing an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms in step (1) of the present disclosure, and polymerizing the monomer after step (2). It is preferable to use a polymerization initiator when polymerizing a monomer containing a (meth)acrylic acid ester having an alkyl group with a carbon number of 4 to 12. The polymerization initiator of the present disclosure is preferably added in step (1) and / or step (2).

[0068] In step (3) of the present disclosure, after step (2), a monomer containing an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms is polymerized to obtain polymer (A). Examples of a method for polymerizing the monomer include emulsion polymerization, in which a surfactant is dissolved in the emulsion particle-containing aqueous dispersion and a polymerization initiator is added to the resulting solution, but the present invention is not limited to only this method. In this specification, the particles in which the monomer is dispersed in step (2) may also be referred to as monomer emulsion particles, and particles containing a polymer may also be referred to as polymer emulsion.

[0069] When the particle production method of the present disclosure includes step (3), the amount of surfactant contained in 100 parts by mass of the particle-containing aqueous dispersion is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, from the viewpoint of improving polymerization stability, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less, from the viewpoint of improving weather resistance, scratch resistance, blocking resistance, and hardness.

[0070] The polymerization initiator of the present disclosure is not particularly limited, but a water-soluble polymerization initiator is preferred. Examples of polymerization initiators of the present disclosure include azo compounds such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide, but the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.

[0071] The amount of the polymerization initiator of the present disclosure is preferably 0.03 parts by mass or more, more preferably 0.04 parts by mass or more, per 100 parts by mass of the total of the monomers constituting the polymer (A), from the viewpoint of increasing the polymerization rate and reducing the amount of remaining unreacted monomers, and is preferably 2 parts by mass or less, more preferably 1 part by mass or less, from the viewpoint of improving weather resistance. The method for adding the polymerization initiator of the present disclosure is not particularly limited, and examples of the addition method include batch addition, divided addition, and continuous dropwise addition. In order to promote the decomposition of the polymerization initiator, a suitable amount of a decomposer for the polymerization initiator, such as a reducing agent such as sodium hydrogen sulfite or a transition metal salt such as ferrous sulfate, may be added to the reaction system.

[0072] A chain transfer agent can be used to adjust the weight-average molecular weight of polymer (A). Examples of chain transfer agents include 2-ethylhexyl thioglycolate, tert-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, and α-methylstyrene dimer, but the present invention is not limited to these examples. These chain transfer agents may be used alone or in combination of two or more. The amount of chain transfer agent per 100 parts by mass of the monomers constituting polymer (A) is preferably 0.01 to 10 parts by mass, from the viewpoint of adjusting the weight-average molecular weight of the polymer contained in the emulsion particles. If necessary, additives such as a chelating agent, a film-forming aid, and a pH buffer may be added to the particle-containing dispersion of the present disclosure in appropriate amounts to the reaction system.

[0073] The atmosphere in which the polymer (A) of the present disclosure is polymerized is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, an inert gas such as nitrogen gas or argon gas is preferred. The polymerization temperature when polymerizing the polymer (A) of the present disclosure is not particularly limited, but is usually preferably 50 to 100° C., more preferably 60 to 85° C. The polymerization temperature may be constant or may be changed during the polymerization reaction. The polymerization time for polymerizing the polymer (A) of the present disclosure is not particularly limited and may be set appropriately depending on the progress of the polymerization reaction, but is usually about 2 to 9 hours.

[0074] <Core-shell particles containing anti-algae ingredients> The anti-algae component-containing particles of the present disclosure may be core-shell particles having the anti-algae component-containing particle as a core layer and the polymer (B) as a shell layer. The polymer (B) of the present disclosure is a polymer having a structural unit derived from the following monomer (B).

[0075] The monomer (B) of the present disclosure includes a monofunctional monomer and a polyfunctional monomer. The monofunctional monomer and the polyfunctional monomer may be used alone or in combination. Examples of monofunctional monomers include ethylenically unsaturated double bond-containing monomers, but the present invention is not limited to these examples.

[0076] Examples of ethylenically unsaturated double bond-containing monomers include alkyl (meth)acrylates, acid group-containing monomers, hydroxyl group-containing (meth)acrylates, piperidyl group-containing monomers, oxo group-containing monomers, fluorine atom-containing monomers, amide group-containing monomers, epoxy group-containing monomers, alkoxyalkyl (meth)acrylates, silane group-containing monomers, carbonyl group-containing monomers, aziridinyl group-containing monomers, styrene-based monomers, and aralkyl (meth)acrylates, but the present invention is not limited to these examples. These ethylenically unsaturated double bond-containing monomers may be used alone or in combination of two or more.

[0077] Examples of alkyl (meth)acrylates include alkyl (meth)acrylates having an ester moiety of 1 to 18 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isobornyl methacrylate, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more.

[0078] Examples of the acid group-containing monomer include, but are not limited to, carboxyl group-containing aliphatic monomers such as (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, itaconic acid monobutyl ester, and vinylbenzoic acid. Examples of hydroxyl group-containing (meth)acrylates include hydroxyl group-containing (meth)acrylates having an ester group containing 1 to 18 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, but are not limited to these examples. Among these, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred. These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.

[0079] Examples of oxo group-containing monomers include, but are not limited to, (di)ethylene glycol (methoxy) (meth)acrylates such as ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth)acrylate, diethylene glycol (meth)acrylate, and diethylene glycol methoxy (meth)acrylate. These oxo group-containing monomers may be used alone or in combination of two or more. Examples of fluorine atom-containing monomers include, but are not limited to, fluorine atom-containing alkyl (meth)acrylates having an ester group containing 2 to 6 carbon atoms, such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and octafluoropentyl (meth)acrylate. These fluorine atom-containing monomers may be used alone or in combination of two or more. Examples of amide group monomers include, but are not limited to, acrylamide compounds such as (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropylacrylamide, and diacetone acrylamide, and N-vinylpyrrolidone. Among these, (meth)acrylamide, diacetone acrylamide, and N-vinylpyrrolidone are preferred. These amide group-containing monomers may be used alone or in combination of two or more. Examples of epoxy group-containing monomers include, but are not limited to, epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and glycidyl allyl ether. These epoxy group-containing monomers may be used alone or in combination of two or more.

[0080] Examples of alkoxyalkyl (meth)acrylates include, but are not limited to, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, trimethylolpropane tripropoxy (meth)acrylate, etc. These alkoxyalkyl (meth)acrylates may be used alone or in combination of two or more. Examples of silane group-containing monomers include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, γ-(meth)acryloyloxypropylhydroxysilane, and γ-(meth)acryloyloxypropylmethylhydroxysilane. These silane group-containing monomers may be used alone or in combination of two or more. Examples of carbonyl group-containing monomers include, but are not limited to, acrolein, humyl styrene, vinyl ethyl ketone, (meth)acryloxyalkyl propenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl (meth)acrylate acetylacetate, butanediol-1,4-acrylate acetylacetate, and 2-(acetoacetoxy)ethyl (meth)acrylate. Among these, 2-(acetoacetoxy)ethyl (meth)acrylate is preferred. These carbonyl group-containing monomers may be used alone or in combination of two or more. Examples of the aziridinyl group-containing monomer include, but are not limited to, (meth)acryloylaziridine, 2-aziridinylethyl (meth)acrylate, etc. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

[0081] Examples of styrene-based monomers include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, and vinyltoluene. These styrene-based monomers may be used alone or in combination of two or more. The styrene-based monomer may have a functional group such as an alkyl group (e.g., methyl group, tert-butyl group), a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group, or a halogen atom on the benzene ring. Among styrene-based monomers, styrene is preferred from the viewpoint of enhancing water resistance. Examples of aralkyl (meth)acrylates include, but are not limited to, aralkyl (meth)acrylates having an aralkyl group having 7 to 18 carbon atoms, such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate. These aralkyl (meth)acrylates may be used alone or in combination of two or more.

[0082] Furthermore, from the viewpoint of imparting UV stability or UV absorption to the core-shell particles, it is preferable that the monomer (B) forming the polymer (B) contains a UV-stable monomer or a UV-absorbing monomer within the range that does not impair the object of the present invention. By imparting UV absorption to the resin layer, it is possible to obtain an aqueous dispersion containing core-shell particles with excellent film-forming properties and weather resistance.

[0083] Examples of ultraviolet-stable monomers include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, and 4-crotonoyl Examples of the monomers include 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, and 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more. Among these ultraviolet-stable monomers, piperidyl group-containing (meth)acrylates such as 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, and 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine are preferred. Examples of ultraviolet absorbing monomers include benzotriazole-based ultraviolet absorbing monomers and benzophenone-based ultraviolet absorbing monomers, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more.

[0084] Examples of the benzotriazole-based ultraviolet absorbing monomer include 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, ) acryloylaminomethyl-5'-tert-octylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxypropylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole , 2-[2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl-3'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole Examples of the monomers include 2-[2'-hydroxy-5'-(β-(meth)acryloyloxyethoxy)-3'-tert-butylphenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(β-(meth)acryloyloxyethoxy)-3'-tert-butylphenyl]-4-tert-butyl-2H-benzotriazole, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more. Examples of benzophenone-based ultraviolet-absorbing monomers include 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-[2-hydroxy-3-(meth)acryloyloxy]propoxybenzophenone, 2-hydroxy-4-[2-(meth)acryloyloxy]ethoxybenzophenone, 2-hydroxy-4-[3-(meth)acryloyloxy-2-hydroxypropoxy]benzophenone, and 2-hydroxy-3-tert-butyl-4-[2-(meth)acryloyloxy]butoxybenzophenone, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more.

[0085] The monomer (B) preferably contains 60% by mass or more of alkyl (meth)acrylate in total, based on 100% by mass of the monomer (B), more preferably 70% by mass or more, and even more preferably 80% by mass or more. Furthermore, the content of alkyl (meth)acrylate in total, based on 100% by mass of the monomer (B), is preferably 100% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. By ensuring the content within the above range, the transparency of the coating film tends to be improved when used as a coating agent or the like.

[0086] The content of the ultraviolet-stable monomer in the polymer (B) of the present disclosure is preferably 1 to 5 mass% from the viewpoints of improving the ultraviolet stability and the dispersion stability of the core-shell particle-containing aqueous dispersion. Also, the content of the ultraviolet-absorbing monomer in the monomer (B) is preferably 1 to 5 mass% from the viewpoints of improving the ultraviolet stability and the dispersion stability of the core-shell particle-containing aqueous dispersion.

[0087] The weight average molecular weight of the polymer (B) of the present disclosure is preferably 100,000 or more, more preferably 150,000 or more, and even more preferably 200,000 or more, from the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion. The upper limit is not particularly limited because it is difficult to measure the weight average molecular weight when a crosslinked structure is present, but when a crosslinked structure is not present, it is preferably 5,000,000 or less from the viewpoint of improving film-forming properties. The glass transition temperature of the polymer (B) of the present disclosure is preferably −50° C. or higher, more preferably −40° C. or higher, and even more preferably −30° C. or higher, from the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion; and is preferably 80° C. or lower, more preferably 70° C. or lower, and even more preferably 60° C. or lower, from the viewpoint of film-forming properties when used as a coating film. The glass transition temperature of the polymer (B) can be determined by the same method as that for the polymer (A).

[0088] The average particle size of the core-shell particles of the present disclosure is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more, and is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less, from the viewpoint of contributing to the dispersion stability of the aqueous dispersion and contributing to the transparency of a coating film. The average particle size of the core-shell particles of the present disclosure is measured in accordance with JIS Z 8828, measured by a dynamic light scattering method, and is defined as the cumulant average particle size, and can be specifically measured by the method described in the Examples.

[0089] The mass ratio of the core layer to the shell layer of the core-shell particle of the present disclosure is generally preferably 5 / 95 to 80 / 20, and more preferably 10 / 90 to 75 / 25. In the core-shell particles of the present disclosure, the mass ratio of the polymer (A) to the polymer (B) is usually preferably 5 / 95 to 80 / 20, more preferably 10 / 90 to 75 / 25. In the core-shell particles of the present disclosure, the mass ratio of the total amount of the anti-algae component and polymer (A) to the total amount of polymer (B) is usually preferably 5 / 95 to 80 / 20, more preferably 10 / 90 to 75 / 25.

[0090] The core-shell particle-containing aqueous dispersion of the present disclosure may contain, for example, additives, etc., to the extent that the object of the present invention is not impaired. Examples of additives include those described above. The amount of additive varies depending on the type of additive and cannot be determined in general. Therefore, it is preferable to determine the amount appropriately depending on the type of additive.

[0091] <Aqueous dispersion containing core-shell particles> From the viewpoints of environmental protection and occupational safety and hygiene, the core-shell particles of the present disclosure are preferably used in an aqueous medium, ie, an aqueous dispersion. Examples of aqueous media in the present disclosure include water and mixed solvents of water and water-soluble organic solvents. Examples of water-soluble organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol; polyhydric alcohols such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol; and ketones such as acetone and methyl ethyl ketone, but the present invention is not limited to these examples. These aqueous media may be used alone or in combination of two or more. From the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion, the water content in the aqueous medium is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, with the upper limit of this content being 100% by mass. Among aqueous media, water is preferred.

[0092] The solid content (non-volatile content) of the core-shell particle-containing aqueous dispersion of the present disclosure is preferably adjusted appropriately depending on the application of the core-shell particle-containing aqueous dispersion, but from the viewpoint of improving productivity, it is preferably 20% by mass or more, more preferably 25% by mass or more, and from the viewpoint of improving handleability, it is preferably 70% by mass or less, more preferably 60% by mass or less. Therefore, the solid content of the core-shell particle-containing aqueous dispersion is preferably 20 to 70% by mass, more preferably 25 to 60% by mass. In this specification, the solid content of the aqueous resin dispersion is determined by weighing 1 g of the aqueous resin dispersion, drying it in a hot air dryer at a temperature of 110°C for 1 hour, and taking the resulting residue as the nonvolatile content, and calculating it using the formula: [Solid content (mass%) in aqueous resin dispersion] = ([mass of residue] ÷ [1 g of aqueous resin dispersion]) × 100 This means the value calculated based on

[0093] The core-shell particle-containing aqueous dispersion of the present disclosure may contain other additives within the range that does not impair the object of the present invention. Other additives include, for example, colorants such as pigments, leveling agents, UV absorbers, UV stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, metal deactivators, wetting agents, antifoaming agents, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosion agents, pigment dispersants, flow control agents, peroxide decomposers, mold bleaching agents, fluorescent brighteners, organic flame retardants, inorganic flame retardants, anti-dripping agents, melt flow modifiers, antistatic agents, mildew inhibitors, flame retardants, slip agents, metal chelating agents, antiblocking agents, heat stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, antioxidants, preservatives, antistatic agents, silane coupling agents, antioxidants, and film-forming aids, but the present invention is not limited to these examples. These additives may be used alone or in combination of two or more. The amount of these additives varies depending on the type of additive and cannot be determined in general, so it is preferable to determine it appropriately depending on the type of additive. In the core-shell particles of the present disclosure, the anti-algae component-containing particle that forms the core layer preferably contains a polymer (A).

[0094] <Method of manufacturing core-shell particles containing anti-algae ingredients> The method for producing the anti-algae component-containing core-shell particles of the present disclosure includes step (1) of mixing the anti-algae component, a nonionic surfactant, and an alkyl group-containing ester compound having 15 or more carbon atoms with an aqueous medium, step (2) of heating the resulting mixture under stirring to a temperature equal to or higher than the phase inversion onset temperature of the mixture but lower than the boiling point of the aqueous medium, and then cooling the mixture to a temperature lower than the phase inversion onset temperature of the mixture, and step (4) of adding monomer (B) and then polymerizing the monomer (B). From the viewpoint of stable production of the core-shell particles of the present disclosure, a polymer may be added in step (1), or a monomer component constituting polymer (A) may be added and polymerized after step (2), followed by step (3), and then step (4) of polymerizing monomer (B). The monomer (B) of the present disclosure is as described above.

[0095] In step (4) of the present disclosure, the monomer (B) is added and polymerized. The method for polymerizing the monomer (B) is emulsion polymerization, and examples thereof include a method in which a surfactant is dissolved in the core particle-containing aqueous dispersion obtained in step (3) and a polymerization initiator is added to the obtained solution, but the present invention is not limited to only such a method. Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants. These surfactants may be used alone or in combination of two or more.

[0096] The amount of surfactant used when emulsion polymerizing the monomer (B) is, from the viewpoint of improving polymerization stability, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the monomer (B); from the viewpoint of improving weather resistance, it is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, even more preferably 5.5 parts by mass or less, and even more preferably 5 parts by mass or less. The polymerization initiator is as described above. The amount of polymerization initiator per 100 parts by mass of monomer (B) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, from the viewpoint of increasing the polymerization rate and reducing the amount of remaining unreacted monomer, and is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, from the viewpoint of improving weather resistance. The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch addition, divided addition, continuous dropwise addition, etc. In order to hasten the completion of the polymerization reaction, a portion of the polymerization initiator may be added before or after the completion of the addition of the monomer components for forming the resin layer into the reaction system. In order to promote the decomposition of the polymerization initiator, a suitable amount of a decomposer for the polymerization initiator, such as a reducing agent such as sodium hydrogen sulfite or a transition metal salt such as ferrous sulfate, may be added to the reaction system.

[0097] The chain transfer agent can be used to adjust the weight average molecular weight of the polymer (B). The amount of the chain transfer agent per 100 parts by mass of the monomer (B) is preferably 0.01 to 10 parts by mass. When the monomer (B) is emulsion polymerized, a suitable amount of a silane coupling agent may be used to improve the weather resistance of the core-shell particles. Examples of the silane coupling agent include silane coupling agents having a polymerizable unsaturated bond such as a (meth)acryloyl group, a vinyl group, an allyl group, or a propenyl group, but the present invention is not limited to these examples.

[0098] When the monomer (B) is emulsion polymerized, additives such as a chelating agent, a film-forming aid, a pH buffer, etc. may be added to the reaction system as needed. The amount of the additive varies depending on the type and cannot be determined in general, but is usually preferably about 0.01 to 5 parts by mass, more preferably about 0.1 to 3 parts by mass, per 100 parts by mass of the monomer (B). The atmosphere in which the polymer (B) is emulsion polymerized is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, it is preferably an inert gas such as nitrogen gas. The polymerization temperature for the polymer (B) is not particularly limited, but is usually preferably 50 to 100° C., more preferably 60 to 85° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

[0099] The polymerization time for emulsion polymerization of the polymer (B) is not particularly limited and may be appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 9 hours. By emulsion polymerizing the monomer (B) as described above, an aqueous dispersion containing core-shell particles can be obtained. The thickness of the polymer (B) that forms the shell layer of the core-shell particles cannot be determined in general because it varies depending on the application, but is usually about 2 to 50 nm.

[0100] <Paint> The particles of the present disclosure can be used as a particle-containing dispersion, and can be suitably used, for example, in a coating liquid such as an aqueous paint. The aqueous paint contains the particles or particle-containing dispersion of the present disclosure, and it is particularly preferable to use a particle-containing aqueous dispersion. The paint of the present disclosure may be used by mixing with a paint resin other than the particle-containing dispersion of the present disclosure. The paint resin other than the particles of the present disclosure is preferably a resin emulsion, and more preferably an acrylic resin emulsion from the viewpoint of storage stability after mixing. The volume average particle size of the resin emulsion other than the particles of the present disclosure is preferably 80 to 450 nm. The average particle diameter of the resin particles is more preferably 400 nm or less, and even more preferably 350 nm or less. The average particle diameter is preferably 100 nm or more. The average particle diameter of the resin emulsion can be measured as the volume average particle diameter using a particle size distribution analyzer based on dynamic light scattering (such as the NICOM P Model 380 manufactured by Particle Sizing Systems Co., Ltd.). Alternatively, the average particle diameter (hydrodynamic diameter) can be determined by determining an autocorrelation function by photon correlation analysis using a multi-analyte nanoparticle size measurement system (manufactured by Otsuka Electronics Co., Ltd., product name: NANO SAQLA), which is a particle size measurement device based on dynamic light scattering.

[0101] Even when the particles (emulsion particles) of the present disclosure are added to a resin emulsion other than the particles of the present disclosure, they are expected to have little effect on the appearance of the coating film, such as turbidity or whitening, and to form a good coating film. The amount of particles of the present disclosure added per 100 parts by mass of the non-volatile content of the resin emulsion other than the particles of the present disclosure is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, and is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less.

[0102] In the paint of the present disclosure, the content of the anti-algae component is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, per 100 parts by mass of the total amount of the particles and the polymer of the resin emulsion; from the viewpoint of coating film properties such as weather resistance, it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less. The aqueous paint may be composed only of an aqueous resin dispersion, or may contain, within the scope of the object of the present invention, one or more of, for example, a film-forming aid, a plasticizer, a foam inhibitor, an antifoaming agent, a foam breaker, a pigment, a thickener, a matting agent, a dispersant, a wetting agent, an ultraviolet absorber, an ultraviolet stabilizer, a filler, a leveling agent, a stabilizer, a pigment, a dye, an antioxidant, an antiseptic, etc. Examples of aqueous paints include enamel paints and clear paints. The water-based paint may be applied alone in a single layer, or may be applied by overcoating two or more layers. When overcoating two or more layers, only some of the layers may be formed with the water-based paint, or all of the layers may be formed with the water-based paint. Examples of overcoating methods include applying a paint for a first layer (e.g., an undercoat layer) to a substrate that has been treated with a primer or a sealer, drying the paint, and then overcoating a paint for a second layer (e.g., a topcoat layer) and drying the paint, but the present invention is not limited to such a method.

[0103] Examples of methods for applying the water-based paint include application methods using a brush, a bar coater, an applicator, an air spray, an airless spray, a roll coater, a flow coater, etc., but the present invention is not limited to these examples. Water-based paints can be suitably used for painting, for example, the exterior walls of buildings and automobile bodies, as well as for inorganic building materials such as ceramic building materials. Examples of ceramic building materials include roof tiles and exterior wall materials. Ceramic building materials are obtained by adding inorganic fillers, fibrous materials, etc. to a hydraulic adhesive, which is the raw material for the inorganic hardened body, molding the resulting mixture, and curing and hardening the resulting molded body. Examples of inorganic building materials that constitute the exterior of buildings include flexible boards, calcium silicate boards, gypsum slag perlite boards, wood chip cement boards, precast concrete boards, ALC boards, and gypsum boards.

[0104] In addition, the water-based paint of the present disclosure can be overcoated on a coating film of an oil-based paint, and it is also possible to overcoat a coating film of an oil-based paint on a coating film of the water-based paint of the present invention. When an oil-based paint is overcoated on a coating film of the water-based paint of the present invention, from the viewpoint of weather resistance, it is particularly preferable to use an oil-based paint containing an ultraviolet absorber. Furthermore, the paint of the present disclosure can be used for a variety of applications, including, for example, buildings, automobiles, automobile parts (for example, bodies made of various materials, bumpers, spoilers, mirrors, wheels, interior materials, etc.), metal plates such as steel plates, motorcycles, motorcycle parts, road materials (for example, guardrails, traffic signs, soundproof walls, etc.), tunnel materials (for example, sidewall panels, etc.), ships, railway vehicles, aircraft, furniture, musical instruments, home appliances, building materials, containers, office supplies, sporting goods, toys, etc. [Example]

[0105] The present invention will now be described in more detail based on examples, but the present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". In the following examples and comparative examples, the abbreviations for each compound mean the following compounds. EHA: 2-Ethylhexyl acrylate CHMA: Cyclohexyl methacrylate IBOA: Isobornyl acrylate TMPTMA: Trimethylolpropane trimethacrylate AD-TMP: Ditrimethylolpropane tetraacrylate A-DPH: Dipentaerythritol polyacrylate KBM-503: Methacryloxypropyltrimethoxysilane C18A: Stearyl acrylate C18MA: Stearyl methacrylate C22A: Behenyl acrylate C22MA: Behenyl methacrylate MMA: Methyl methacrylate St: Styrene NVP: n-vinylpyrrolidone CS-16: 2,2,4-trimethyl-1,3-pentanediol diisobutyrate AA: Acrylic acid HEMA: 2-hydroxyethyl methacrylate

[0106] Example 1 A reaction vessel equipped with a stirrer, temperature sensor, condenser, nitrogen inlet tube, and dropping funnel was charged with 188 parts of deionized water, 32.1 parts of a nonionic emulsifier polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6), 5.7 parts of MMA, 19.5 parts of CHMA, 5.0 parts of St, 1.0 parts of TMPTMA, 12.7 parts of C18A, and 24.0 parts of an anti-algae ingredient (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured according to the following method. As a result, the phase inversion temperature was 76 to 86 ° C. [Method for measuring phase inversion temperature] A 2 L (liter) reaction vessel was equipped with a stirring device and a temperature sensor, and 1000 g of the mixture was placed in the reaction vessel and stirred. The reaction vessel was heated in a water bath, and the electrical conductivity was measured every time the temperature of the mixture in the reaction vessel increased by 1°C using a conductivity meter (manufactured by EUTECH, trade name: Lacom Tester PC450). The electrical conductivity was plotted for each temperature increase, and the temperature at which the electrical conductivity began to decrease continuously with increasing temperature was taken as the phase inversion starting temperature, and the temperature at which the electrical conductivity became 1.00 μS or less was taken as the phase inversion end temperature. In addition, if the electrical conductivity did not become 1.00 μS or less even when the upper limit of the measurable temperature of the conductivity meter was exceeded, the temperature at which the appearance of the mixture did not change even after 3 minutes or more had passed since it reached a temperature higher than the phase inversion starting temperature under stirring was taken as the end point of the phase inversion temperature. After measuring the phase inversion temperature of the mixture, the reaction vessel was heated in a water bath under stirring while nitrogen gas was introduced into the reaction vessel. After the internal temperature of the reaction vessel reached 88°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Then, 1.8 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride was added to the reaction vessel, and the mixture was allowed to react at an internal temperature of 58°C for 1 hour. After that, the contents of the reaction vessel were heated with stirring at an internal temperature of 60°C for 5 hours, thereby polymerizing the monomers contained in the monomer emulsion particles and obtaining aqueous dispersion 1 containing polymer emulsion particles. The average particle size of the polymer emulsion particles contained in the aqueous dispersion containing the polymer emulsion particles obtained above was measured by the following method, and the result was that the average particle size of the polymer emulsion particles was 39 nm. [Method for measuring average particle size] The average particle size obtained by cumulant analysis was measured using a multi-analyte nanoparticle size measurement system (manufactured by Otsuka Electronics Co., Ltd., product name: nanoSAQLA), which is a particle size measurement device using dynamic light scattering.

[0107] Example 2 A reaction vessel equipped with a stirrer, temperature sensor, condenser, nitrogen inlet tube, and dropping funnel was charged with 188 parts of deionized water, 32.8 parts of a polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: LATEMURU PD-420, HLB: 12.6) as a nonionic emulsifier, 7.0 parts of MMA, 10.5 parts of CHMA, 5.0 parts of TMPTMA, 8.7 parts of KBM-503, 12.0 parts of C18MA, and 24.0 parts of an anti-algae ingredient (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured in the same manner as in Example 1. The resulting phase inversion temperature was 72 to 83 °C. After the internal temperature of the reaction vessel reached 86°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Then, 1.8 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride was added to the reaction vessel, and the mixture was allowed to react at an internal temperature of 58°C for 1 hour. After that, the contents of the reaction vessel were heated with stirring at an internal temperature of 60°C for 5 hours, thereby polymerizing the monomers contained in the monomer emulsion particles and obtaining aqueous dispersion 2 containing polymer emulsion particles. The average particle size of the polymer emulsion particles contained in the aqueous dispersion containing the polymer emulsion particles obtained above was measured by the following method, and the result was that the average particle size of the polymer emulsion particles was 42 nm.

[0108] Example 3 A reaction vessel equipped with a stirrer, temperature sensor, cooling tube, nitrogen inlet tube, and dropping funnel was charged with 188 parts of deionized water, 32.8 parts of a polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: LATEMURU PD-420, HLB: 12.6) as a nonionic emulsifier, 7.0 parts of MMA, 9.0 parts of CHMA, 0.6 parts of IBOA, 1.5 parts of St, 5.0 parts of TMPTMA, 8.7 parts of KBM-503, 11.4 parts of C22A, and 24.0 parts of an anti-algae ingredient (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured in the same manner as in Example 1. As a result, the phase inversion temperature was 75 to 86 ° C. After the internal temperature of the reaction vessel reached 90°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Then, 1.8 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride was added to the reaction vessel, and the mixture was allowed to react at an internal temperature of 58°C for 1 hour. After that, the contents of the reaction vessel were heated with stirring at an internal temperature of 60°C for 5 hours, thereby polymerizing the monomers contained in the monomer emulsion particles and obtaining aqueous dispersion 3 containing polymer emulsion particles. The average particle size of the polymer emulsion particles contained in the aqueous dispersion containing the polymer emulsion particles obtained above was measured by the following method, and the result was that the average particle size of the polymer emulsion particles was 43 nm.

[0109] Example 4 A reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, a nitrogen inlet tube, and a dropping funnel was charged with 205.3 parts of deionized water, 33.0 parts of a polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6) as a nonionic emulsifier, 9.0 parts of MMA, 10.2 parts of EHA, 3.0 parts of AD-TMP, 10.8 parts of C22MA, 2.0 parts of NVP, 24.0 parts of an anti-algae component (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3), 4.0 parts of an ultraviolet absorber (manufactured by BASF, trade name: Tinuvin® 400), 1.0 parts of a hindered amine light stabilizer (manufactured by ADEKA Corporation, trade name: Adekastab LA-87), and 3.0 parts of CS-16. A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured based on the same method as in Example 1. As a result, the phase inversion temperature was 73 to 86°C. After the internal temperature of the reaction vessel reached 88°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Then, 1.8 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride was added to the reaction vessel, and the mixture was allowed to react at an internal temperature of 58°C for 1 hour. After that, the contents of the reaction vessel were heated with stirring at an internal temperature of 60°C for 5 hours, thereby polymerizing the monomers contained in the monomer emulsion particles and obtaining aqueous dispersion 4 containing polymer emulsion particles. The average particle size of the polymer emulsion particles contained in the aqueous dispersion containing the polymer emulsion particles obtained above was measured by the following method, and the result was that the average particle size of the polymer emulsion particles was 43 nm.

[0110] Example 5 A reaction vessel equipped with a stirrer, temperature sensor, cooling tube, nitrogen inlet tube, and dropping funnel was charged with 189.2 parts of deionized water, 35.0 parts of polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: LATEMURU PD-430, HLB: 14.4) as a nonionic emulsifier, 11.0 parts of MMA, 3.1 parts of CHMA, 6.0 parts of IBOA, 1.5 parts of St, 1.0 parts of NVP, 3.0 parts of TMPTMA, 2.0 parts of A-DPH, 2.0 parts of KBM-503, 11.4 parts of C22A, and 24.0 parts of an anti-algae component (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured based on the same method as in Example 1. As a result, the phase inversion temperature was 90 to 95 ° C. After the internal temperature of the reaction vessel reached 96°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Thereafter, 3.0 parts of a 5% aqueous solution of potassium persulfate was added to the reaction vessel, and the contents of the reaction vessel were heated with stirring at an internal temperature of 80°C for 4 hours to form monomer emulsion particles. The contained monomers were polymerized to obtain aqueous dispersion 5 containing polymer emulsion particles. The average particle size of the polymer emulsion particles contained in the aqueous dispersion containing the polymer emulsion particles obtained above was measured by the following method, and the result was that the average particle size of the polymer emulsion particles was 60 nm.

[0111] Example 6 A reaction vessel equipped with a stirrer, temperature sensor, cooling tube, nitrogen inlet tube, and dropping funnel was charged with 8.0 parts of deionized water, 1.4 parts of a polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: LATEMURU PD-420, HLB: 12.6) as a nonionic emulsifier, 0.3 parts of MMA, 0.6 parts of CHMA, 0.1 parts of St, 0.2 parts of TMPTMA, 0.2 parts of KBM-503, 0.5 parts of C18MA, and 1.0 parts of an anti-algae component (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured in the same manner as in Example 1. The result was a phase inversion temperature of 72 to 83 ° C. After the internal temperature of the reaction vessel reached 86°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Next, 0.07 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride and 3.0 parts of a 5% aqueous solution of potassium persulfate were added to the reaction vessel, and the contents of the reaction vessel were heated with stirring at an internal temperature of 58°C for 4 hours. After that, 88.7 parts of deionized water was added and the internal temperature was raised to 80°C. Ten minutes after the temperature was raised, a mixture of 40.0 parts of deionized water, 13.6 parts of a 25% aqueous solution of a nonionic emulsifier (manufactured by ADEKA Corporation, trade name: Adeka Reasoap ER-10), 37.1 parts of MMA, 30.6 parts of EHA, 21.9 parts of CHMA, 1.2 parts of a hindered amine light stabilizer (manufactured by ADEKA Corporation, trade name: Adeka STAB LA-87), and 1.6 parts of HEMA was added dropwise to the reaction vessel with stirring over 90 minutes. Thirty minutes after the completion of the dropwise addition, the reaction vessel was removed from the water bath, and the internal temperature of the reaction vessel was cooled to 40°C or below. 0.1 parts of a preservative (manufactured by DuPont, trade name: KORDEK MLX) was then added to the reaction vessel to obtain aqueous dispersion 6 containing polymer emulsion particles having a resin layer formed by polymerizing the monomer component for forming the resin layer on the surface of the polymer emulsion particles. The average particle diameter was 120 nm.

[0112] Example 7 A reaction vessel equipped with a stirrer, temperature sensor, condenser, nitrogen inlet tube, and dropping funnel was charged with 22.1 parts of deionized water, 4.2 parts of polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: LATEMURU PD-420, HLB: 12.6) as a nonionic emulsifier, 0.9 parts of MMA, 1.8 parts of CHMA, 0.1 parts of IBOA, 0.3 parts of St, 0.6 parts of TMPTMA, 0.6 parts of KBM-503, 1.5 parts of C22A, 3.0 parts of an anti-algae component (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3), and 0.5 parts of an ultraviolet absorber (manufactured by BASF, trade name: Tinuvin® 400). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured based on the same method as in Example 1. As a result, the phase inversion temperature was 75 to 86 ° C. After the internal temperature of the reaction vessel reached 88°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Next, 0.2 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride and 3.0 parts of a 5% aqueous solution of potassium persulfate were added to the reaction vessel, and the contents of the reaction vessel were heated with stirring at an internal temperature of 58°C for 4 hours. After that, 79.6 parts of deionized water was added and the internal temperature was raised to 80°C. Ten minutes after the temperature was raised, a mixture of 33.5 parts of deionized water, 11.2 parts of a 25% aqueous solution of a nonionic emulsifier (manufactured by ADEKA Corporation, trade name: Adeka Reasoap ER-10), 31.3 parts of MMA, 28.9 parts of EHA, 20.7 parts of CHMA, 1.2 parts of a hindered amine light stabilizer (manufactured by ADEKA Corporation, trade name: Adeka STAB LA-87), and 1.6 parts of HEMA was added dropwise to the reaction vessel with stirring over 90 minutes. Thirty minutes after the completion of the dropwise addition, the reaction vessel was removed from the water bath, and the internal temperature of the reaction vessel was cooled to 40°C or below. 0.1 parts of a preservative (manufactured by DuPont, trade name: KORDEK MLX) was then added to the reaction vessel to obtain polymer emulsion particle-containing aqueous dispersion 7 having a resin layer formed by polymerizing the resin layer-forming monomer component on the surface of the polymer emulsion particle. The average particle diameter was 95 nm.

[0113] Example 8 A reaction vessel equipped with a stirrer, temperature sensor, cooling tube, nitrogen inlet tube, and dropping funnel was charged with 44.2 parts of deionized water, 8.4 parts of a polyoxyalkylene alkenyl ether (manufactured by Kao Corporation, trade name: LATEMURU PD-420, HLB: 12.6) as a nonionic emulsifier, 1.8 parts of MMA, 3.6 parts of CHMA, 0.2 parts of IBOA, 0.6 parts of St, 1.2 parts of TMPTMA, 1.2 parts of KBM-503, 3.0 parts of C22A, 6.0 parts of an anti-algae component (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3), and 1.0 parts of an ultraviolet absorber (manufactured by BASF, trade name: Tinuvin® 400). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured based on the same method as in Example 1. As a result, the phase inversion temperature was 75 to 86 ° C. After the internal temperature of the reaction vessel reached 88°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Next, 0.4 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride and 3.0 parts of a 5% aqueous solution of potassium persulfate were added to the reaction vessel, and the contents of the reaction vessel were heated with stirring at an internal temperature of 58°C for 4 hours. After that, 64.4 parts of deionized water was added and the internal temperature was raised to 80°C. Ten minutes after the temperature was raised, a mixture of 30.4 parts of deionized water, 10.4 parts of a 25% aqueous solution of a nonionic emulsifier (manufactured by ADEKA Corporation, trade name: Adeka Reasoap ER-10), 25.0 parts of MMA, 24.3 parts of EHA, 17.9 parts of CHMA, 2.0 parts of a hindered amine light stabilizer (manufactured by ADEKA Corporation, trade name: Adeka STAB LA-87), and 1.2 parts of HEMA was added dropwise to the reaction vessel with stirring over 90 minutes. Thirty minutes after the completion of the dropwise addition, the reaction vessel was removed from the water bath, and the internal temperature of the reaction vessel was cooled to 40°C or below. 0.1 parts of a preservative (manufactured by DuPont, trade name: KORDEK MLX) was then added to the reaction vessel to obtain polymer emulsion particle-containing aqueous dispersion 8 having a resin layer formed by polymerizing the resin layer-forming monomer component on the surface of the polymer emulsion particle. The average particle diameter was 72 nm.

[0114] Example 9 A reaction vessel equipped with a stirrer, a temperature sensor, a condenser, a nitrogen inlet tube, and a dropping funnel was charged with 44.2 parts of deionized water, 8.4 parts of polyoxyalkylene alkenyl ether as a nonionic emulsifier (manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6), 1.8 parts of MMA, 3.6 parts of CHMA, 0.2 parts of IBOA, 0.6 parts of St, and 1.2 parts of TMPTMA. 1.2 parts of KBM-503, 3.0 parts of C22A, 6.0 parts of an anti-algae component (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3), and 1.0 part of an ultraviolet absorber (manufactured by BASF, trade name: Tinuvin (registered trademark) 400) were charged, and a portion of the resulting mixture was taken out and the phase inversion temperature of the mixture was measured in the same manner as in Example 1. The result was that the phase inversion temperature was 75 to 86°C. After the internal temperature of the reaction vessel reached 88°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or lower, thereby obtaining an aqueous dispersion containing monomer emulsion particles. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated in the water bath with stirring until the internal temperature of the reaction vessel reached 58°C. Next, 0.4 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride and 3.0 parts of a 5% aqueous solution of potassium persulfate were added to the reaction vessel, and the contents of the reaction vessel were heated with stirring at an internal temperature of 58°C for 4 hours. After that, 64.4 parts of deionized water was added and the internal temperature was raised to 80°C. Ten minutes after the temperature was raised, a mixture of 30.4 parts of deionized water, 10.4 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA Corporation, trade name: Adeka Reasoap SR-20), 25.0 parts of MMA, 24.3 parts of EHA, 17.9 parts of CHMA, 2.0 parts of a hindered amine light stabilizer (manufactured by ADEKA Corporation, trade name: Adeka STAB LA-87), and 1.2 parts of HEMA was added dropwise to the reaction vessel with stirring over 90 minutes. Thirty minutes after the completion of the dropwise addition, the reaction vessel was removed from the water bath, and the internal temperature of the reaction vessel was cooled to 40°C or below. 0.1 parts of a preservative (manufactured by DuPont, trade name: KORDEK MLX) was then added to the reaction vessel to obtain aqueous dispersion 9 containing polymer emulsion particles having a resin layer formed by polymerizing the resin layer-forming monomer component on the surface of the polymer emulsion particles. The average particle diameter was 69 nm.

[0115] Comparative Example 1 In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, a nitrogen inlet tube, and a dropping funnel A pre-emulsion for dropping was prepared in a dropping funnel, consisting of 22 parts of deionized water, 9 parts of a 25% aqueous solution of an emulsifier (Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10), 14 parts of EHA, 5 parts of CHMA, 23 parts of MMA, 5 parts of St, 1 part of methacrylic acid, and 2.0 parts of an anti-algae ingredient (Nippon Soda Co., Ltd., trade name: Biocut LC3). Eight parts of this, equivalent to 5% of the total amount of polymerizable monomer components, were added to the flask. The temperature was raised to 70°C while slowly blowing in nitrogen gas, and 1.4 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Next, the remainder of the pre-emulsion for dropping, 4.3 parts of a 5% aqueous ammonium persulfate solution, and 3.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise to the flask over 180 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 70°C for 60 minutes. Subsequently, a second-stage pre-emulsion was prepared, consisting of 22.5 parts deionized water, 9.0 parts of a 25% aqueous solution of emulsifier (Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10), 4.0 parts of EHA, 5.0 parts of CHMA, 40.0 parts of MMA, and 1.0 part of acrylic acid. Then, 4.3 parts of a 5% aqueous solution of ammonium persulfate and 3.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise to the flask over 180 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 70°C for 60 minutes. The pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was terminated. The resulting reaction solution was cooled to room temperature and filtered through a 300-mesh wire mesh to prepare Resin Emulsion A. The average particle size of the resulting resin emulsion was 200 nm.

[0116] Comparative Example 2 A reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, a nitrogen inlet pipe, and a dropping funnel was charged with 188 parts of deionized water, 32.8 parts of an anionic emulsifier (manufactured by ADEKA Corporation, trade name: ADEKA REASOAP SR-20), 15.3 parts of MMA, 20.9 parts of CHMA, 5.0 parts of St, 2.0 parts of TMPTMA, and 24.0 parts of an anti-algae ingredient (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3). A portion of the resulting mixture was removed, and the phase inversion temperature of the mixture was measured according to the following method, but no phase inversion was confirmed. After the internal temperature of the reaction vessel reached 88°C, the reaction vessel was removed from the water bath and air-cooled with stirring until the internal temperature reached 40°C or less. Next, the contents were stirred at room temperature for 10 minutes while introducing nitrogen gas into the reactor, and then the reaction vessel was placed in a water bath and heated with stirring until the internal temperature of the reaction vessel reached 58°C. Then, 1.8 parts of a 15% aqueous solution of 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride was added to the reaction vessel, and the mixture was allowed to react at an internal temperature of 58°C for 1 hour. After that, the contents of the reaction vessel were heated with stirring at an internal temperature of 60°C for 5 hours, and a polymer precipitated from the water. The compositions, particle sizes, etc. of Examples 11 to 9, Comparative Examples 1 and 2 are shown in Tables 1 and 2.

[0117] [Table 1]

[0118] [Table 2]

[0119] Experimental Example The polymer emulsion particle-containing aqueous dispersions 1 to 9 and resin emulsion A obtained in each Example or Comparative Example were mixed with an acrylic resin emulsion (manufactured by Nippon Shokubai Co., Ltd., trade name: Acryset EF-005, resin solids content: 40%) so that the concentration of the anti-algae component in the total resin solids after mixing was 1 wt%. As an additional control for comparison, an anti-algae component (manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3) was directly mixed with an acrylic resin emulsion (manufactured by Nippon Shokubai Co., Ltd., trade name: Acryset EF-005, resin solids content: 40%) so that the concentration of the anti-algae component in the total resin solids after mixing was 1 wt%. The resin emulsion of Example 6 was used alone without being mixed with the acrylic resin emulsion. 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (manufactured by JNC Corporation, product number: CS-12) was added as a film-forming aid to each mixed solution in an amount of 8% based on the total amount of the mixed solution, and the mixed solution was then allowed to stand overnight at room temperature.

[0120] [Haze measurement method] Each aqueous dispersion containing acrylic polymer emulsion particles was applied to a glass plate with an applicator so that the thickness of the coating film after drying would be 100 μm, and the film was dried in a dryer at 80°C for 2 hours to form a coating, thereby obtaining a test plate. The haze of the coating surface of the test plate obtained above was measured using a spectrophotometer (manufactured by Konica Minolta, Inc., product number: CM-3700A) in accordance with the conditions specified in ASTM-D-1003-97-C. The results are shown in Tables 3 and 4.

[0121] [Amount of anti-algae ingredient outflow] A release paper was placed on a glass plate, and a mold was created using adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cloth Adhesive Tape 102N) to create a frame with a thickness of approximately 200 μm after drying. Each resin emulsion, with the resin solid content adjusted by adding water, was poured into the frame and dried at room temperature to create a film-like molded body with a thickness of approximately 200 μm. The molded body was cut into 1 cm squares with a cutter to create samples. 1.0 g of each sample was weighed out and placed in separate containers, and 20.0 g of water heated to 40°C was added to each container, which was then sealed. Each container was placed in a 40°C oven, shaken every three days, and kept warm for one month. After one month, the water in the container was collected and the amount of anti-algae component that had leaked into the water was quantified by LC under the following conditions. The results are shown in Tables 3 and 4. LC conditions: Apparatus: Prominence UFLC (Shimadzu Corporation) Column: GF-310HQ Column oven: 40℃ Mobile phase: AN / 10 mol ammonia formate water = 7 / 3 Flow rate: 0.5ml / min

[0122] The compositions and evaluation results of Experimental Examples 1-11 are shown in Tables 3 and 4.

[0123]

Table 3

[0124]

Table 4

Claims

1. The particles contain an anti-algae component, a nonionic surfactant, and an alkyl group-containing ester compound having 15 or more carbon atoms, the mass ratio of the nonionic surfactant to the alkyl group-containing ester compound having 15 or more carbon atoms (mass of nonionic surfactant / mass of alkyl group-containing ester compound having 15 or more carbon atoms) being 60 / 40 to 90 / 10, and the average particle size being 10 nm to 200 nm, the particles contain a polymer (A), the alkyl group-containing ester compound having 15 or more carbon atoms is an alkyl group-containing ester compound having 15 or more carbon atoms and a polymerizable unsaturated double bond, the polymer (A) has a structural unit derived from an alkyl-containing ester compound having a polymerizable unsaturated double bond and having 15 or more carbon atoms, a structural unit derived from an alkyl-containing (meth)acrylic acid ester having 4 to 12 carbon atoms, and a structural unit derived from a crosslinkable monomer, The content of the structural unit derived from the crosslinkable monomer in 100 parts by mass of the polymer (A) is 0.1 parts by mass or more and 20 parts by mass or less.

2. Particles as described in claim 1, wherein the solubility of the anti-algae component in water is 10 mg / L or more and 400 mg / L or less.

3. A core-shell particle having a particle according to claim 1 or claim 2 as a core layer and a polymer (B) as a shell layer.

4. A core-shell particle as described in claim 3, wherein the polymer (A) does not have a structural unit derived from an acid group-containing monomer.

5. An aqueous dispersion comprising particles according to claim 1 or claim 2, or core-shell particles according to claim 3 or claim 4.

6. An aqueous paint comprising particles according to claim 1 or claim 2, or core-shell particles according to claim 3 or claim 4.

7. A coating film obtained by applying the water-based coating material according to claim 6.

8. The method includes a step (1) of mixing an anti-algae component, a nonionic surfactant, an ester compound containing an alkyl group having 15 or more carbon atoms, and an aqueous medium, wherein the mass ratio of the nonionic surfactant to the ester compound containing an alkyl group having 15 or more carbon atoms (mass of the nonionic surfactant / mass of the ester compound containing an alkyl group having 15 or more carbon atoms) is 60 / 40 to 90 / 10, a step (2) of heating the obtained mixture under stirring to a temperature equal to or higher than the phase inversion initiation temperature of the mixture and lower than the boiling point of the aqueous medium, and then cooling the mixture to a temperature lower than the phase inversion initiation temperature of the mixture; A method for producing particles containing a polymer (A), comprising a step (3) of polymerizing the polymer (A) using a polymerization initiator, the alkyl group-containing ester compound having 15 or more carbon atoms is an alkyl group-containing ester compound having 15 or more carbon atoms and a polymerizable unsaturated double bond, Further, in step (1), a (meth)acrylic acid ester containing an alkyl group having 4 to 12 carbon atoms and a crosslinkable monomer are mixed, The method for producing particles, wherein the crosslinkable monomer is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the total of the monomers constituting the polymer (A).

9. A method for producing particles as described in claim 6, wherein a polymerization initiator is added in step (1) and / or step (2).

10. A method for producing particles as described in Claim 8, wherein the solubility of the anti-algae component in water is 10 mg / L or more and 400 mg / L or less.

Images