JP2023085022A - Algicidal component-containing particle - Google Patents

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

The present invention relates to anti-algae component-containing particles. More particularly, the present invention relates to anti-algae component-containing particles that are useful for applications such as paints, coating agents, and inks, and methods for producing the same.

In recent years, from the standpoint of environmental protection and occupational safety and health, non-polluting paints, coating agents, and inks are desired, and solvent-based paints are becoming water-based. In addition, in general buildings, there is a problem that algae adhere and grow on the outer walls, inner walls, facilities, etc. due to humidity and water, and spoil the appearance. For this reason, conventionally, in order to prevent the occurrence of these algae in advance, it has been practiced to coat the surface of an object to be protected with various agents having an anti-algae effect and paints containing such agents.
For example, Patent Document 1 contains 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 sibutrin and terbutrin, and An anti-algae particle is described, characterized in that the polymer is obtained by polymerizing a vinyl monomer component containing 1% by mass or more and 50% by mass or less of an anionic group-containing vinyl monomer, and the anti-algae component is contained at a high content rate. It is stated that it can contain
In addition, Patent Document 2 describes an anti-algae paint containing a 4-hydroxybenzoic acid ester represented by formula (1), which is excellent in safety and has a high anti-algae effect against algae. It is described that a non-toxic paint can be obtained, and an embodiment in which it is added to a urethane paint is described in the Examples.

[Wherein, R1 represents a hydrogen atom or an alkali metal, and R2 represents an alkyl group or an aryl group having 1 to 22 carbon atoms]

JP 2019-131551 JP 2021-116397

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

An object of the present invention is to provide anti-algae component-containing particles capable of forming a good coating film and suppressing outflow of the anti-algae component from the coating film.

The inventors conducted studies in view of the above problems, and included an algae-proof component, a nonionic surfactant, and an alkyl group-containing ester compound having 15 or more carbon atoms, a nonionic surfactant and a carbon number is 15 or more (mass of nonionic surfactant / mass of alkyl group-containing ester compound having 15 or more carbon atoms) is 60/40 to 90/10, and the average The inventors have found that particles with a particle size of 10 nm to 200 nm can form a good coating film and can suppress the outflow of the anti-algae component from the coating film, and have completed the present invention.

According to the present invention, it is possible to provide anti-algae component-containing particles that are capable of forming a good coating film and suppressing outflow of the anti-algae component from the coating film.

The present invention will be described in detail below.
In this specification, "X to Y" indicating a range means "X or more and Y or less".
The particles of the present invention contain an anti-algae component, a nonionic surfactant and an alkyl group-containing ester compound having 15 or more carbon atoms.

<Particles containing anti-algae component>
Examples of the algae control component of the present disclosure include 2-n-octyl-4-isothiazolin-3-one, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3 -one, Nn-butyl-1,2-benzisothiazolin-3-one and other isothiazoline anti-algae ingredients, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 3- (3,4-dichlorophenyl)-1-methyl-1-methoxyurea, 3-(3,4-dichlorophenyl)-1-(2-methylcyclohexyl), 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(isopropylamino)-S-triazine, 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine, N'-t-butyl -N-Cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine and other triazine algae control components, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide , dipyrrolisol thiuram disulfide, polyethylene thiuram disulfide, etc.; 2-(4-thiazyl)benzimidazole, 2-(carbomethoxyamino)benzimidazole, etc. Pyridine anti-algae ingredients such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, zinc pyrithione anti-algae ingredients such as zinc-2-pyritinethiol-1-oxide, organic halogen compounds , organic metal-based, haloalkylthio-based, and phenylphenol-based anti-algae components, and these anti-algae components may be used singly or in combination of two or more.

A commercially available product can also be used as the anti-algae component of the present disclosure.
Examples of thiazoline-based anti-algae components include Nippon Soda's products "Milcut-180" and "Biocut-LC3", Daiwa Chemical Industry Co.'s "Amolden ALK", and the like.
Examples of isothiazoline anti-algae components include Nippon Soda's product "Biocut-TR120", Arch Chemicals' products "PROXEL GXL" and "PROXEL BDN", and Dow Chemicals' products "KLARIX 4000", "ROZONE 2000", and "ROCIMA."252","ROCIMA200","ROCIMA345","ROCIMA350","ROCIMA553","BIOBAN551S","ScaneM-8" and the like.
Examples of imidazole-based anti-algae components include Nippon Soda's products "Biocut-N35", "Biocut-AF40" and "DX-2", and Dow Chemical Company's product "ROCIMA 363".
Triazine-based anti-algae components include Nippon Soda products "Biocut-N35", "DP-2159", "DP-2615", "DP-2619", "DP-2623", Daiwa Chemical Industry Co., Ltd. products " Amolden NBP-8", "Amolden NBPconc", Sankyo Kasei Co., Ltd. product "Sanalga 1907", and the like.

The solubility of the anti-algae component in water is preferably 10 mg/L or more and 400 mg/L or less, and specific examples include imidazole compounds (for example, Dow Chemical Co. product "ROCIMA 363"), urea compounds, and the like. mentioned. On the other hand, specific examples of anti-algae components having a solubility in water of 0.1 mg/L or more and less than 10 mg/L include imidazole-based compounds (for example, Nippon Soda's product "Biocut-N35") and triazine-based compounds. be done.

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, even more preferably 3 parts by mass or more, from the viewpoint of ensuring anti-algae properties. From the viewpoint of stability, the amount 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.

Nonionic surfactants of the present disclosure include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl 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, allyloxymethylalkoxyethylhydroxypolyoxyethylenes, polyoxyalkylene alkenyl ethers, etc. may be mentioned, but the present invention is not limited to these examples.

HLB (hydrophilic-lipophilic balance) of the nonionic surfactant of the present disclosure is preferably 8 or more, more preferably, from the viewpoint of improving dispersion stability when the particles of the present disclosure are used as an aqueous dispersion. It is 9 or more, more preferably 10 or more, and preferably 17 or less, more preferably 16 or less, and still more preferably 15 or less from the viewpoint of improving the dispersion stability of the emulsion particle-containing aqueous dispersion. In addition, the HLB of the nonionic surfactant is preferably 14 or less, more preferably 13.5 or less, still more preferably 13 or less, from the viewpoint of obtaining an emulsion particle-containing aqueous dispersion containing emulsion particles having a fine particle size. is. 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, especially It is preferably 10-13. The HLB of the nonionic surfactant is based on the Griffin method and has the formula:
[HLB of nonionic surfactant] = 20 x [(molecular weight of hydrophilic portion) / (molecular weight of surfactant)]
is the value obtained by

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, Examples include phenol-type nonionic surfactants, amide-type nonionic surfactants, and the like, but the present invention is not limited to these examples. These surfactants may be used alone or in combination of two or more.

Nonionic surfactants are readily commercially available. Commercially readily available nonionic surfactants include, for example, Kao Corporation, trade name: Latemul PD-420 (HLB: 12.6), Kao Corporation, trade name: Latemul PD-430 (HLB: 14.4), manufactured by Nippon Shokubai Co., Ltd., trade name: Softanol 120 (HLB: 14.5), manufactured by Nippon Shokubai Co., Ltd., trade name: Softanol 90 (HLB: 13.3) ), Nippon Shokubai Co., Ltd., product name: Softanol 70 (HLB: 12.1), etc. Softanol series, manufactured by ADEKA Co., Ltd., product name: Adekaria Soap ER-10 (HLB: 12.1) , manufactured by ADEKA Co., Ltd., trade name: Adekari Soap ER-20 (HLB: 15.1), Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon AN-10 (HLB: 12.7), Co., Ltd. Daiichi Kogyo Seiyaku, trade name: Aqualon AN-20 (HLB: 15.7), Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KN-10 (HLB: 13). , is not limited to such 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.

Among the nonionic surfactants, it is preferable to use a reactive nonionic surfactant from the viewpoint of incorporating the nonionic surfactant into the emulsion particles. Reactive nonionic surfactants are readily commercially available. Commercially readily available reactive nonionic surfactants include, for example, ADEKA Co., Ltd., trade name: Adekari Soap ER-10 (HLB: 12.1); ADEKA, trade name: Adekaria Soap ER-20 (HLB: 15.1), Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon AN-10 (HLB: 12.7), Daiichi Kogyo Seiyaku Co., Ltd. , Product name: Aqualon AN-20 (HLB: 15.7), Daiichi Kogyo Seiyaku Co., Ltd., Product name: Aqualon KN-10 (HLB: 13), Kao Corporation, Product name: Latemul PD-420 (HLB: 12.6), etc., but the present invention is not limited only to such examples.

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 8 parts by mass or more. Preferably, from the viewpoint of obtaining an aqueous dispersion containing core-shell particles having a fine particle size, 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 30 parts by mass or less. is particularly preferred.

In the alkyl group-containing ester compound having 15 or more carbon atoms of the present disclosure, the alkyl ester portion may have 15 or more carbon atoms, and the total number of carbon atoms of the compound is more preferably 15 or more. From the viewpoint of improving the dispersion stability of the particles, the lower limit of the carbon number of the alkyl group-containing ester compound is 15 or more, preferably 18 or more, more preferably 23 or more, and the upper limit is not particularly limited. It is preferably 60 or less, more preferably 50 or less, still more preferably 40 or less, because raw materials are easily available.

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

Among the alkyl group-containing ester compounds having 15 or more carbon atoms, from the viewpoint of suppressing the outflow of the anti-algae component to the coating film, it is preferable to have a polymerizable unsaturated double bond, for example, hexadecyl (meth) Acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, eicosyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate and the like, with stearyl (meth)acrylate and behenyl (meth)acrylate being more preferred.

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

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 (the mass of the nonionic surfactant/the amount of the alkyl group-containing ester compound having 15 or more carbon atoms mass) is preferably 60/40 to 90/10, more preferably 62/38 to 80/20, even more preferably 64/36 to 78/22.

The particles of the present disclosure may further contain other surfactants. Other surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants and the like, and preferably contain anionic surfactants. By including an anionic surfactant, it can be expected that the dispersion stability of particles dispersed in a solvent can be improved for a long period of storage.

Anionic surfactants of the present disclosure include, for example, alkyl sulfate salts such as ammonium dodecyl sulfate, sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate, sodium alkyldiphenylether disulfonate; Alkyl aryl sulfonate salts such as sodium dodecylnaphthalene sulfonate; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; Fatty acid salts such as sodium stearate; bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate ester salt, (meth)acrylic acid polyoxyethylene sulfonate salt, (meth)acrylic acid polyoxyethylene phosphor Sulfuric acid esters having an allyl group such as phonate salts, sulfonate salts of allyloxymethylalkyloxypolyoxyethylene, or salts thereof; However, the invention is not limited to only such exemplifications.

Cationic surfactants of the present disclosure include, for example, alkylammonium salts such as dodecyl ammonium chloride, but the present invention is not limited to such examples.
The amphoteric surfactants of the present disclosure include, for example, betaine ester-type surfactants, but the present invention is not limited to such examples.
Polymeric surfactants of the present disclosure include, for example, 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 the above as a copolymerization component, but the present invention is not limited to such examples.

When a nonionic surfactant and an anionic surfactant are included as the surfactant of the present disclosure, the total amount of the nonionic surfactant and the anionic surfactant is 10 parts per 100 parts by mass of the solid content of the particles. It is preferably at least 15 parts by mass, even more preferably at least 20 parts by mass.
When the surfactant of the present disclosure contains a nonionic surfactant and an anionic surfactant, the mass ratio of the nonionic surfactant and the anionic surfactant is preferably 50/50 to 99/1, 60/40 to 99/1 is more preferred, and 70/30 to 99/1 is even more preferred.

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

Examples of reactive surfactants include propenyl-alkylsulfosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts [for example, Sanyo Chemical Industries, Ltd. manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade names: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salts [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade names: Aqualon BC-10, Aqualon HS-10, etc.], allyloxy sulfonate salt of methylalkyloxypolyoxyethylene [for example, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], polyoxyethylene styrenated propenylphenyl ether sulfate ammonium salt [for example, Dai-ichi Kogyo Seiyaku Co., Ltd.; Co., Ltd., trade names: Aqualon AR-10, Aqualon AR-20, etc.], polyoxyethylene styrenated propenyl phenyl ether [for example, Daiichi Kogyo Seiyaku Co., Ltd., trade names: Aqualon AN-10, Aqualon AN -20, Aqualon AN-30, etc.], allyloxymethyl nonylphenoxyethyl hydroxy polyoxyethylene sulfonate salt [for example, manufactured by ADEKA Co., Ltd., trade name: Adekari Soap SE-10, etc.], allyloxymethylalkoxyethyl hydroxy Polyoxyethylene sulfate ester salts [for example, manufactured by ADEKA Corporation, trade names: Adekari Soap SR-10, SR-20, SR-30, etc.], bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salts [ For example, Nippon Nyukazai Co., Ltd., trade name: Antox MS-60, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, ADEKA Co., Ltd., trade name: Adekaria Soap ER-10, Adekaria Soap ER-20, Adekari Soap ER-30, Adekari Soap ER-40, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.], Examples include allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Co., Ltd., trade name: Adekari Soap NE-10, etc.], but the present invention is not limited to such examples. .

Particles of the present disclosure may comprise a polymer.
The polymer of the present disclosure is preferably a polymer (A) having a structural unit derived from an alkyl group-containing (meth)acrylic acid ester 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 of the present disclosure is obtained by polymerizing an alkyl group-containing (meth)acrylic acid ester monomer having 4 to 12 carbon atoms. An alkyl group-containing (meth)acrylic acid ester monomer having 4 to 12 carbon atoms, which is the resulting structure, may be polymerized, or the structure may be formed by post-modification.

The structural unit derived from the alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms of the present disclosure includes the following general formula (1).

In general formula (1), R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X1 is a single bond, an alkylene group, -O-, -CO-, -NH-, -SO2- or a combination thereof R2 represents an alkyl group having 4 to 12 carbon atoms. Examples of alkyl groups having 4 to 12 carbon atoms include n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 2-ethylhexyl group, n-octyl group, tridecyl group, cyclohexyl group, n-lauryl group, A dodecyl group, an isononyl group, an isobornyl group and the like can be mentioned, and 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.

Examples of the alkyl group-containing (meth)acrylic acid ester monomer having 4 to 12 carbon atoms of the present disclosure include 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, isononyl ( Examples include meth)acrylates, isobornyl (meth)acrylates, etc., 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 concept of alkyl (meth)acrylate includes (meth)acrylates having an alicyclic structure.

As the alkyl group-containing (meth)acrylic acid ester monomer having 4 to 12 carbon atoms of the present disclosure, from the viewpoint of improving the dispersion stability of the particle-containing aqueous dispersion, n-butyl (meth)acrylate, isobutyl (Meth)acrylate, 2-ethylhexyl (meth)acrylate and cyclohexyl (meth)acrylate are preferred. These monomers may be used alone or in combination of two or more.

The 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 the polymer (A) of the present disclosure is 40% by mass or more in total. is preferred, more preferably 50% by mass or more, and even more preferably 60% by mass or more. Further, the monomer A has a total content of structural units derived from an alkyl group-containing (meth)acrylic acid ester having 3 to 12 carbon atoms with respect to 100% by mass of the monomer A is 99% by mass or less. is preferably 97% by mass or less, and even more preferably 95% by mass or less. By setting the amount within the above range, the transparency of the coating film tends to be improved when used as a coating agent or the like.

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. Structural units other than the structural units derived from alkyl group-containing (meth)acrylic acid esters having 4 to 12 carbon atoms are derived from alkyl group-containing ester compounds having a polymerizable unsaturated double bond and having 15 or more carbon atoms. Structural units of, structural units derived from alkyl group-containing (meth) acrylic esters in which the number of carbon atoms in the alkyl group is 1 to 3, structural units derived from acid group-containing monomers, hydroxyl group-containing (meth) acrylic esters derived from Structural units, structural units derived from oxo group-containing monomers, structural units derived from fluorine atom-containing monomers, structural units derived from nitrogen atom-containing monomers, structural units derived from piperidyl group-containing monomers, alkoxyalkyl ( Structural units derived from meth) acrylic acid esters, structural units derived from carbonyl group-containing monomers, structural units derived from styrene monomers, structural units derived from aralkyl (meth) acrylic acid esters, etc., but the present invention is not limited only to such examples. These ethylenically unsaturated double bond-containing monomers may be used alone or in combination of two or more.

Examples of alkyl group-containing ester compounds having a polymerizable unsaturated double bond and having 15 or more carbon atoms of the present disclosure include hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, eicosyl (meth) Acrylate, 2-decyltetradecyl (meth)acrylate, etc., and stearyl (meth)acrylate and behenyl (meth)acrylate are more preferable.
Examples of alkyl group-containing (meth)acrylic acid esters in which the alkyl group of the present disclosure has 1 to 3 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl ( meth)acrylates, etc., but the present invention is not limited only to such examples. These monomers may be used alone or in combination of two or more.

Acid group-containing monomers of the present disclosure include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, Examples include carboxyl group-containing aliphatic monomers such as monomethyl itaconate, monobutyl itaconate, and vinyl benzoic 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.

The nitrogen atom-containing ethylenically unsaturated monomers of the present disclosure include, for example, (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N -n-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, methylenebis (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N, acrylamide compounds such as N-dimethylaminopropyl acrylamide and diacetone acrylamide, nitrogen atom-containing (meth)acrylate compounds such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate, N-vinylpyrrolidone, (meth)acrylonitrile, Examples include N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, etc., but 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. From the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion, Vinylpyrrolidone is preferred.

Piperidyl group-containing monomers of the present disclosure include, for example, 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, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloyl amino-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 the like, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more. Among these piperidyl group-containing monomers, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6- Piperidyl group-containing (meth)acrylates such as 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 nitrogen-containing ethylenically unsaturated monomers.

Styrenic monomers of the present disclosure include, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, tert-methylstyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene and other alkylalkylstyrenes having 1 to 4 carbon atoms in the alkyl group, o-methoxystyrene, m-methoxy Styrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-tert-butoxystyrene, m-tert-butoxystyrene, p-tert-butoxystyrene, etc. The number of carbon atoms in the alkoxy group is 1 to 4 alkoxystyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p- halogen atom-containing styrenes such as bromostyrene; acetoxystyrenes such as o-acetoxystyrene, m-acetoxystyrene and p-acetoxystyrene; 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 the styrene-based monomers, styrene and alkyl styrene having an alkyl group having 1 to 4 carbon atoms are preferable, and styrene is more preferable, from the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion.

The polymer (A) of the present disclosure may have a structural unit derived from a crosslinkable monomer from the viewpoint of suppressing the outflow of the anti-algae component to the coating film.
Examples of the crosslinkable monomers of the present disclosure include compounds having two or more polymerizable unsaturated double bonds, silane group-containing compounds having one or more polymerizable unsaturated double bonds, epoxy group-containing monomers, aziridinyl group-containing monomers, and the like.

Compounds having two or more polymerizable unsaturated double bonds of the present disclosure include polyfunctional (meth)acrylates and the like.
Polyfunctional (meth)acrylates of the present disclosure include, for example, triallyl cyanurate (triallyl cyanurate), triallyl isocyanurate, triallyl phosphate, triallyl compounds having 9 to 20 carbon atoms such as 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, ethylene oxide modified C1 to 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. 10 polyhydric alcohol di(meth)acrylate; polyethylene glycol di(meth)acrylate with 2 to 50 added moles of ethylene oxide, polypropylene glycol di(meth)acrylate with 2 to 50 added moles of propylene oxide, tri Alkyl di(meth)acrylates having 2 to 50 added moles of alkylene oxide groups having 2 to 4 carbon atoms, such as propylene glycol di(meth)acrylate; ) acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, etc., having 1 to 10 carbon atoms tri(meth)acrylate of polyhydric alcohol; tetra( meth)acrylates; penta(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as pentaerythritol penta(meth)acrylate and dipentaerythritol(monohydroxy)penta(meth)acrylate; pentaerythritol hexa(meth)acrylates, etc. hexa (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms; isn't it. These polyfunctional monomers may be used alone or in combination of two or more.

Silane group-containing compounds having one or more polymerizable unsaturated double bonds of the present disclosure include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltri methoxysilane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, γ-(meth)acryloyloxypropylhydroxysilane, γ-(meth)acryloyloxypropylmethylhydroxysilane, etc., but the present invention is limited to these examples only. is not limited to These silane group-containing monomers may be used alone or in combination of two or more.

The epoxy group-containing monomers of the present disclosure include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and glycidyl allyl ether. The examples are not intended to be limiting. These epoxy group-containing monomers may be used alone, respectively, or two or more of them may be used in combination.
Examples of the aziridinyl group-containing monomers of the present disclosure include (meth)acryloylaziridine, 2-aziridinylethyl (meth)acrylate, and the like, but the present invention is not limited only to such examples. do not have. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

The content of the structural unit derived from the crosslinkable monomer in 100 parts by mass of the polymer (A) of the present disclosure is preferably 0.1 parts by mass or more from the viewpoint of suppressing the outflow of the anti-algae component to the coating film. .5 parts by mass or more is more preferable, 1% by mass or more is more preferable, and 2 parts by mass or more is particularly preferable, and from the viewpoint of improving the dispersion stability of the particle-containing aqueous dispersion, 20 parts by mass or less is preferable, and 15 parts by mass. The following is more preferable, and 10 parts by mass or less is even more preferable.

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 containing the anti-algae component. From the viewpoint of film-forming properties when forming a coating film, the temperature is preferably 120° C. or lower, more preferably 110° C. or lower, and even more preferably 100° C. or lower.
The glass transition temperature of the polymer (A) is expressed by the formula (I) using the glass transition temperature of the homopolymer of the monomer used in the monomer component constituting the polymer:
1/Tg=Σ(Wm/Tgm)/100 (I)
[Wherein, Wm is the content (% by mass) of the monomer m in the monomer components constituting the polymer, and Tgm is the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
Means the temperature obtained based on the Fox equation represented by
For monomers with unknown glass transition temperatures such as special monomers and polyfunctional monomers, the total amount of monomers with unknown glass transition temperatures in the monomer components is the mass fraction. is 10% by mass or less, the glass transition temperature is determined using only monomers whose glass transition temperatures are known. When the total amount of monomers with unknown glass transition temperatures in the monomer component exceeds 10% by mass in terms of mass fraction, the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC), differential calorimetry (DTA), thermal mechanical analysis (TMA), or the like.
The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer components. The composition of the monomer component used as the raw material of the polymer composing the particle can be determined in consideration of the glass transition temperature of the polymer composing the particle.

The glass transition temperature of the polymer is, for example, −70° C. for 2-ethylhexyl acrylate homopolymer, −56° C. for n-butyl acrylate homopolymer, 20° C. for n-butyl methacrylate homopolymer, and 20° C. for methyl methacrylate. 105°C for cyclohexyl methacrylate homopolymer, 83°C for tert-butyl methacrylate homopolymer, 107°C for styrene homopolymer, 100°C for styrene homopolymer, 95°C for acrylic acid homopolymer, methacrylic 130°C for the acid homopolymer, 55°C for the 2-hydroxyethyl methacrylate homopolymer, 77°C for the diacetone acrylamide homopolymer, and 70°C for the γ-methacryloxypropyltrimethoxysilane homopolymer. -Methacryloyloxy-1,2,2,6,6-pentamethylpiperidine homopolymer is about 130°C, and glycerin monomethacrylate homopolymer is 55°C.

The particles of the present disclosure may contain various additives as other compounds.
Additives of the present disclosure include, for example, coloring agents such as pigments, leveling agents, UV absorbers, UV stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, metals Deactivators, wetting agents, antifoaming agents, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosive agents, pigment dispersants, flow control agents, peroxide decomposers, mold bleaching agents, Fluorescent brightening agents, organic flame retardants, inorganic flame retardants, anti-dripping agents, melt flow modifiers, anti-static agents, anti-mold agents, flame retardants, slip agents, metal chelating agents, anti-blocking agents, heat resistance Stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, anti-aging agents, preservatives, antistatic agents, antioxidants, film-forming aids, etc. It is not limited only to such examples. These additives may be used alone or in combination of two or more. Since the amount of these additives varies depending on the type of the additive and cannot be generally determined, it is preferable to appropriately determine the amount according to the type of the additive.

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

<Dispersion containing particles containing anti-algae component>
The particles of the present disclosure may be emulsion particles, and the solvent to be used is not particularly specified, but an aqueous solvent is preferable from the viewpoint 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.

The aqueous solvent of the present disclosure includes, for example, water and a mixed solvent of water and a water-soluble organic solvent. 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; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, Examples include polyhydric alcohols such as diethylene glycol; ketones such as acetone and methyl ethyl ketone; however, the present invention is not limited to these examples. These aqueous media may be used alone or in combination of two or more.

The content of water in the aqueous solvent of the present disclosure is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, from the viewpoint of improving the dispersion stability of the particle-containing aqueous dispersion. Even more preferably, it is 80% by mass or more, and the upper limit of the content is 100% by mass. Among the aqueous solvents, water is preferred.

<Method for producing particles containing anti-algae component>
The particles of the present disclosure are preferably obtained as particle-containing dispersions, preferably the particles of the present disclosure are emulsion particles. In addition, the particle-containing dispersion of the present disclosure is preferably a particle-containing aqueous dispersion from the viewpoint 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 the particles of the present invention can be obtained. A step (1) of mixing with an aqueous medium, heating the obtained mixture to 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 under stirring, and then adding the mixture to the mixture It is preferable to have a step (2) of cooling to a temperature lower than the phase inversion start temperature of.

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

Further, as the surfactant used for producing the particles of the present disclosure, a surfactant having a polymerizable group, that is, a so-called reactive surfactant is preferable from the viewpoint of improving weather resistance, and a non-nonyl Phenyl-type surfactants are preferred. Reactive surfactants include the compounds described above.

When the particles of the present disclosure contain a polymer, the polymer may be added in step (1) above, or a step of polymerizing after adding a monomer may be performed. The method for polymerizing the monomer is not particularly limited, but from the viewpoint of obtaining fine particles, emulsion polymerization is preferred, and phase inversion emulsification is more preferred. is not limited to Emulsion particles comprising polymers of the present disclosure are sometimes described as polymer emulsion particles.

In the step (1), the temperature at which the anti-algae component, the nonionic surfactant, the alkyl group-containing ester compound having 15 or more carbon atoms, and the aqueous medium are mixed varies depending on the phase inversion temperature described later, etc. Although the temperature cannot be determined, it is usually preferably 5 to 45°C, more preferably 5 to 40°C, and still more preferably 5 to 35°C. When mixing, in order to uniformly disperse the various components in the aqueous medium, the anti-algae component, the nonionic surfactant, and the alkyl group-containing ester compound having 15 or more carbon atoms are added to the aqueous medium while stirring. preferably. As means for stirring the aqueous medium, there is no need to use conventional high-viscosity paint mixers, high-pressure homogenizers, and other special devices. The components, the nonionic surfactant and the alkyl group-containing ester compound having 15 or more carbon atoms can be uniformly dispersed in the aqueous medium.

Next, after mixing the anti-algae component, the nonionic surfactant, the alkyl group-containing ester compound having 15 or more carbon atoms, and the aqueous medium, the resulting mixture is heated to a temperature equal to or higher than the phase inversion start temperature of the mixture under stirring. After heating to a temperature lower than the boiling point of the aqueous medium, the mixture is cooled to a temperature lower than the phase inversion initiation temperature under stirring. In the present invention, since this operation is adopted, a particle-containing dispersion having excellent dispersion stability can be obtained.

In step (2) in the present disclosure, the phase inversion temperature of the mixture can be determined using the electrical conductivity in the reaction vessel, and the phase inversion start temperature is the temperature at which the electrical conductivity continues to decrease as the temperature rises. The phase inversion end temperature is the temperature at which the electric conductivity becomes 1.00 μS or less. In addition, if the electrical conductivity does not become 1.00 μS or less even if the upper limit of the measurable temperature of the conductivity meter is exceeded, 3 minutes or more have passed since the temperature higher than the phase inversion start temperature was reached under stirring. The end point of the phase inversion temperature is the temperature at which no change occurs in the appearance of the mixture. Specifically, it can be measured by the method described in the Examples.

When the anti-algae component-containing particles of the present disclosure are an aqueous dispersion, the phase inversion start temperature among the phase inversion temperatures is preferably 35° C. or higher from the viewpoint of improving the dispersion stability of the aqueous dispersion. , more preferably 45° C. or higher, and even more preferably 50° C. or higher. From the viewpoint of improving the stability of the emulsion, 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.
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 preferably an inert gas such as nitrogen gas or argon gas.

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 starting temperature of the mixture from the viewpoint of improving the dispersion stability of the aqueous dispersion. The temperature is preferably 0.5° C. or higher than the initiation temperature, and more preferably 1° C. or higher than the phase inversion initiation temperature of the mixture. In addition, 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 from the viewpoint of improving the dispersion stability of the core particle-containing aqueous dispersion. It is more preferably 0.5° C. or higher than the phase inversion end temperature of the mixture.
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 lower than the boiling point of the aqueous medium by 3 ° C. or more, more preferably a temperature of the aqueous medium. It is a temperature that is 5°C or more lower than the temperature of the boiling point.

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.
The means for cooling the mixture is not particularly limited. The mixture may be cooled, for example, by standing to cool, or may be cooled by air cooling. The mixture is cooled to a temperature below the phase inversion onset temperature of the mixture. The mixture is preferably heated at a temperature lower than the phase inversion starting temperature of the mixture by 10°C or more, more preferably at a temperature lower than the phase inversion starting temperature of the mixture by 20°C or more, and more preferably than the phase inversion starting temperature of the mixture. is also cooled to a temperature at least 25°C below, even more preferably at least 30°C below the phase inversion onset temperature of the mixture.
Through the above operations, a dispersion of algae-preventing component-containing particles having a fine particle size is obtained.

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

In the step (3) of the present disclosure, the polymer (A) is obtained by polymerizing a monomer containing an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms after the step (2). A method for polymerizing the monomers is emulsion polymerization, and includes a method of dissolving a surfactant in the emulsion particle-containing aqueous dispersion and adding a polymerization initiator to the resulting solution. is not limited only to such methods.
In this specification, the particles in which the monomer is dispersed in the step (2) may also be expressed as monomer emulsion particles, and the particles containing the polymer may also be expressed as polymer emulsion.

When step (3) is included in the method for producing particles of the present disclosure, the amount of surfactant contained in 100 parts by mass of the particle-containing aqueous dispersion is 0.3 mass from the viewpoint of improving polymerization stability. parts by mass or more, more preferably 0.5 parts by mass or more, and from the viewpoint of improving weather resistance, scratch resistance, blocking resistance, and hardness, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and 5 parts by mass. Part or less is more preferable.

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

From the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomers, the amount of the polymerization initiator of the present disclosure is preferably per 100 parts by mass of the total monomers constituting the polymer (A). It is 0.03 parts by mass or more, more preferably 0.04 parts by mass or more, and from the viewpoint of improving weather resistance, it is preferably 2 parts by mass or less, more preferably 1 part by mass or less.
The method of adding the polymerization initiator of the present disclosure is not particularly limited. Examples of the method of addition include batch charging, divided charging, and continuous dropwise addition.
In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a decomposing agent for the polymerization initiator such as a transition metal salt such as ferrous sulfate are added to the reaction system in an appropriate amount. good too.

A chain transfer agent can also be used to adjust the weight average molecular weight of the polymer (A). Examples of chain transfer agents include 2-ethylhexyl thioglycolate, tert-dodecylmercaptan, n-octylmercaptan, n-dodecylmercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, α-methyl Examples include styrene dimer and the like, but the present invention is not limited to such examples. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent per 100 parts by mass of the monomers constituting the polymer (A) is 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. is preferred.
For the particle-containing dispersion of the present disclosure, additives such as a chelating agent, film-forming aid, and pH buffer may be added to the reaction system in appropriate amounts, if necessary.

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 preferable.
The polymerization temperature for polymerizing the polymer (A) of the present disclosure is not particularly limited, but is generally 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 appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 9 hours.

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

Monomers (B) of the present disclosure include monofunctional monomers and multifunctional monomers. Monofunctional monomers and polyfunctional monomers may be used alone or in combination.
Monofunctional monomers include, for example, ethylenically unsaturated double bond-containing monomers, but the present invention is not limited to such examples.

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 monomer, amide group-containing monomer, epoxy group-containing monomer, alkoxyalkyl (meth)acrylate, silane group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer, styrene system monomers, aralkyl (meth)acrylates, etc., but the present invention is not limited to such examples. These ethylenically unsaturated double bond-containing monomers may be used alone or in combination of two or more.

Examples of alkyl (meth)acrylates include 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 Alkyl (meth)acrylates having 1 to 18 carbon atoms in the ester portion such as acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl methacrylate, etc., but the present invention is limited only to such examples. not to be These monomers may be used alone or in combination of two or more.

Examples of acid group-containing monomers include (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, and monomethyl itaconate. Examples thereof include carboxyl group-containing aliphatic monomers such as esters, monobutyl itaconate, and vinyl benzoic acid, but are not limited to these examples.
Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxy Examples thereof include hydroxyl group-containing (meth)acrylates having an ester group having 1 to 18 carbon atoms, such as butyl (meth)acrylate, but are not limited to these examples. Among them, 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.

Examples of oxo group-containing monomers include (di)ethylene glycol (methoxy) (meth)acrylate such as ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. ) acrylates and the like, but are not limited to these examples. Each of these oxo group-containing monomers may be used alone, or two or more of them may be used in combination.
Examples of fluorine atom-containing monomers include fluorine atom-containing alkyl ester groups having 2 to 6 carbon atoms, such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and octafluoropentyl (meth)acrylate. Examples thereof include (meth)acrylates, but are not limited to these examples. These fluorine atom-containing monomers may be used alone, respectively, or two or more of them may be used in combination.
Amide group monomers include, for example, (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, di Examples include acrylamide compounds such as acetone acrylamide, N-vinylpyrrolidone, and the like, but are not limited to these examples. Among them, (meth)acrylamide, diacetoneacrylamide, 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 epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and glycidyl allyl ether, but are limited to these examples. not something. These epoxy group-containing monomers may be used alone or in combination of two or more.

Alkoxyalkyl (meth)acrylates include, for example, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, trimethylolpropane tripropoxy (meth)acrylate, etc., but these are only examples. is not limited to These alkoxyalkyl (meth)acrylates may be used alone or in combination of two or more.
Silane group-containing monomers include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltri Examples thereof include chlorosilane, γ-(meth)acryloyloxypropylhydroxysilane, γ-(meth)acryloyloxypropylmethylhydroxysilane, but are not limited to these examples. These silane group-containing monomers may be used alone or in combination of two or more.
Examples of carbonyl group-containing monomers include acrolein, bomylstyrene, vinyl ethyl ketone, (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl (meth)acrylate. Acetylacetate, butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate and the like, but are not limited to these examples. Among them, 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 aziridinyl group-containing monomers include (meth)acryloylaziridine and 2-aziridinylethyl (meth)acrylate, but are not limited to these examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

Examples of styrene-based monomers include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, and vinyltoluene, but are not limited to these examples. These styrenic monomers may be used alone or in combination of two or more. Styrenic monomers have functional groups such as alkyl groups such as methyl groups and tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups and halogen atoms on the benzene ring. may Among the styrene-based monomers, styrene is preferred from the viewpoint of enhancing water resistance.
Aralkyl (meth)acrylates include, for example, aralkyls 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. Examples thereof include (meth)acrylates, but are not limited to these examples. These aralkyl (meth)acrylates may be used alone or in combination of two or more.

In addition, the monomer (B) forming the polymer (B) has UV stability within a range that does not hinder the object of the present invention from the viewpoint of imparting UV stability or UV absorbency to the core-shell particles. It is preferred to contain a monomer or a UV-absorbing monomer. By imparting ultraviolet absorbability to the resin layer, it is possible to obtain an aqueous dispersion containing core-shell particles that is excellent in film-forming properties and weather resistance.

UV-stable monomers include, for example, 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, 4-croto noylamino-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, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like, but the present invention is not limited only to such examples. do not have. These monomers may be used alone or in combination of two or more. Among these UV-stable monomers are 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6- Piperidyl group-containing (meth)acrylates such as pentamethylpiperidine and 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine are preferred.
Examples of UV-absorbing monomers include benzotriazole-based UV-absorbing monomers and benzophenone-based UV-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.

Benzotriazole-based UV-absorbing monomers include, for example, 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)acryloylaminomethyl-5′-tert-octylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxypropylphenyl]-2H-benzo triazole, 2-[2′-hydroxy-5′-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-3′-tert-butyl-5′-(meth)acryloyloxy ethylphenyl]-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-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyl oxyethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′-hydroxy-5′-(β-(meth)acryloyloxyethoxy)-3′-tert-butylphenyl]-4-tert -Butyl-2H-benzotriazole and the like, but the present invention is not limited only to such examples. These monomers may be used alone or in combination of two or more.
Benzophenone-based UV-absorbing monomers include, for example, 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, 2-hydroxy-3-tert-butyl-4- Examples thereof include [2-(meth)acryloyloxy]butoxybenzophenone and the like, but the present invention is not limited only to such examples. These monomers may be used alone or in combination of two or more.

The monomer (B) preferably contains a total of 60% by mass or more, more preferably 70% by mass or more, of the alkyl (meth)acrylate with respect to 100% by mass of the monomer (B). It is more preferable to contain more than mass %. In addition, the monomer (B) preferably has a total alkyl (meth)acrylate content of 100% by mass or less, and 99% by mass or less, relative to 100% by mass of the monomer (B). is more preferable, and 98% by mass or less is even more preferable. By setting the amount within the above range, the transparency of the coating film tends to be improved when used as a coating agent or the like.

The content of the UV-stable monomer in the polymer (B) of the present disclosure is 1 to 5% by mass from the viewpoint of improving the UV stability and improving the dispersion stability of the core-shell particle-containing aqueous dispersion. is preferred. In addition, the content of the ultraviolet absorbing monomer in the monomer (B) is 1 to 5% by mass from the viewpoint of improving the ultraviolet stability and improving the dispersion stability of the core-shell particle-containing aqueous dispersion. is preferred.

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 it has a crosslinked structure, but when it does not have a crosslinked structure, it is 5 million or less from the viewpoint of improving film-forming properties. Preferably.
From the viewpoint of improving the dispersion stability of the core-shell particle-containing aqueous dispersion, 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 −30° C. or higher. It is more 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 polymer (B) can be determined by the same method as for polymer (A).

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

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

The core-shell particle-containing aqueous dispersion of the present disclosure may contain, for example, additives within a range that does not hinder the object of the present invention. As the additive, those mentioned above can be exemplified. Since the amount of the additive varies depending on the type of the additive, it cannot be determined unconditionally. Therefore, it is preferable to appropriately determine the amount according to the type of the additive.

<Aqueous dispersion containing core-shell particles>
The core-shell particles of the present disclosure are preferably used as an aqueous medium and henceforth as an aqueous dispersion from the viewpoint of environmental protection and work safety and health.
Examples of the aqueous medium of 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; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, Examples include polyhydric alcohols such as diethylene glycol; ketones such as acetone and methyl ethyl ketone; however, 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 content of water in the aqueous medium is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 70% by mass or more. It is preferably 80% by mass or more, and the upper limit of the content is 100% by mass. Among the aqueous media, water is preferred.

The solid content (non-volatile content) of the core-shell particle-containing aqueous dispersion of the present disclosure is preferably adjusted appropriately according to the application of the core-shell particle-containing aqueous dispersion, but is preferably 20 from the viewpoint of improving productivity. It is at least 25% by mass, more preferably at least 25% by mass, and preferably at most 70% by mass, more preferably at most 60% by mass, from the viewpoint of improving handleability. Therefore, the solid content in 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 in the aqueous resin dispersion is obtained by weighing 1 g of the aqueous resin dispersion, drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour, and using the resulting residue as a non-volatile matter.
[Solid content (mass%) in aqueous resin dispersion]
= ([mass of residue] ÷ [1 g of aqueous resin dispersion]) × 100
means a value determined based on

The core-shell particle-containing aqueous dispersion of the present disclosure may contain other additives as long as the object of the present invention is not hindered.
Other additives include coloring agents such as pigments, leveling agents, UV absorbers, UV stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, metal deactivators, agent, wetting agent, antifoaming agent, surfactant, reinforcing agent, plasticizer, lubricant, antifogging agent, anticorrosion agent, pigment dispersant, flow control agent, peroxide decomposer, mold bleaching agent, fluorescence Brightening agent, organic flame retardant, inorganic flame retardant, anti-dripping agent, melt flow modifier, anti-static agent, anti-mold agent, flame retardant, slip agent, metal chelating agent, anti-blocking agent, heat stabilizer , processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, anti-aging agents, preservatives, antistatic agents, silane coupling agents, antioxidants, and film-forming aids. The invention is not limited to only such exemplifications. These additives may be used alone or in combination of two or more. Since the amount of these additives varies depending on the type of the additive, it cannot be determined unconditionally. The anti-algae component-containing particles forming the layer preferably contain the polymer (A).

<Method for producing core-shell particles containing anti-algae component>
The method for producing the anti-algae component-containing core-shell particles of the present disclosure includes the step (1) of mixing the anti-algae component, the nonionic surfactant, and the alkyl group-containing ester compound having 15 or more carbon atoms with an aqueous medium. Then, the obtained mixture is heated with 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 the mixture is cooled to a temperature lower than the phase inversion initiation temperature of the mixture. It can be obtained by having a step (2) and having a step (4) of polymerizing the monomer (B) after adding the monomer (B).
From the viewpoint of stably producing the core-shell particles of the present disclosure, a polymer can be added in step (1), or a monomer component constituting the polymer (A) is added, and the ) followed by the step (3) of polymerizing, and then the step (4) of polymerizing the monomer (B).
The monomer (B) of the present disclosure is as described above.

As the step (4) of the present disclosure, the monomer (B) is added and the monomer (B) is polymerized.
A method for polymerizing the monomer (B) is emulsion polymerization, 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 resulting solution. The method of adding is mentioned, but the present invention is not limited only to such a method.
Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymeric surfactants, etc. These surfactants may be used alone. may be used, or two or more types may be used in combination

From the viewpoint of improving the polymerization stability, the amount of the surfactant used for emulsion polymerization of the monomer (B) is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the monomer (B). , More preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more, still more preferably 2 parts by mass or more, and from the viewpoint of improving weather resistance, preferably 10 parts by mass or less, more preferably 6 parts by mass parts or less, 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 the polymerization initiator per 100 parts by mass of the monomer (B) is preferably 0.05 parts by mass or more, more preferably 0.1 part by mass, from the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomers. It is at least 1 part by mass, preferably 1 part by mass or less, more preferably 0.5 part by mass or less from the viewpoint of improving weather resistance.
The method of adding the polymerization initiator is not particularly limited. Examples of the method of addition include batch charging, divided charging, and continuous dropwise addition. Moreover, from the viewpoint of advancing the completion time of the polymerization reaction, part of the polymerization initiator may be added before or after the addition of the resin layer-forming monomer component to the reaction system.
In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a decomposing agent for the polymerization initiator such as a transition metal salt such as ferrous sulfate are added to the reaction system in an appropriate amount. good too.

Moreover, 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 weight of the monomer (B) is preferably 0.01 to 10 parts by weight.
When emulsion-polymerizing the monomer (B), an appropriate amount of a silane coupling agent may be used from the viewpoint of improving the weather resistance of the core-shell particles. Silane coupling agents include, for example, (meth)acryloyl groups, vinyl groups, allyl groups, silane coupling agents having polymerizable unsaturated bonds such as propenyl groups, etc., but the present invention is limited to such examples only. It is not limited.

Additives such as a chelating agent, a film-forming aid, and a pH buffer may be added to the reaction system when the monomer (B) is emulsion-polymerized, if necessary. The amount of the additive varies depending on its type and cannot be determined unconditionally. It is about 1 to 3 parts by mass.
The atmosphere in emulsion polymerization of the polymer (B) is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, an inert gas such as nitrogen gas is preferable.
Although the polymerization temperature of the polymer (B) is not particularly limited, it is generally 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 emulsion polymerization of the polymer (B) is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.
By emulsion-polymerizing the monomer (B) as described above, a core-shell particle-containing aqueous dispersion can be obtained. The thickness of the polymer (B) forming the shell layer with the core-shell particles varies depending on the application and cannot be determined unconditionally, but is usually about 2 to 50 nm.

<Paint>
The particles of the present disclosure can be used as particle-containing dispersions, and can be suitably used, for example, in coating liquids such as water-based paints. The water-based paint contains the particles or particle-containing dispersion of the present disclosure, and it is particularly preferred to use the particle-containing aqueous dispersion.
The paint of the present disclosure may be used in combination with paint resins other than the particle-containing dispersion of the present disclosure.
The coating 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 size of the resin particles is more preferably 400 nm or less, still more preferably 350 nm or less. Also, the average particle size is preferably 100 nm or more. The average particle size of the resin emulsion can be measured by volume average particle size using a dynamic light scattering particle size distribution analyzer (“NICOM P Model 380” manufactured by Particle Sizing Systems Co., Ltd.). Using a multi-analyte nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., trade name: NANO SAQLA], which is a particle size measurement device using a static light scattering method, the autocorrelation function was obtained by the photon correlation method, and the result was obtained by cumulant analysis. Average particle size (hydrodynamic diameter) can also be used.

The particles (emulsion particles) of the present disclosure are expected to form a good coating film with little effect on the appearance of the coating film, such as turbidity and whitening, even when added to resin emulsions other than the particles of the present disclosure. can.
The amount of the particles of the present disclosure added to 100 parts by mass of the nonvolatile 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, and further preferably 5 parts by mass or more. It is preferably at most parts by mass, more preferably at most 90 parts by mass, even more preferably at most 85 parts by mass.

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, with respect to 100 parts by mass of the total amount of the polymer of the particles and the resin emulsion. 0.8 parts by mass or more is more preferable, and from the viewpoint of coating film physical properties such as weather resistance, 3 parts by mass or less is preferable, 2 parts by mass or less is more preferable, and 1.5 parts by mass or less is even more preferable.
The water-based paint may be composed only of a water-based resin dispersion, and within a range that does not hinder the object of the present invention, for example, film-forming aids, plasticizers, foam inhibitors, antifoamers, foam breakers, One or two of pigments, thickeners, matting agents, dispersants, wetting agents, UV absorbers, UV stabilizers, fillers, leveling agents, stabilizers, pigments, dyes, antioxidants, preservatives, etc. It may contain more than Examples of water-based paints include enamel paints and clear paints.
The water-based paint may be applied as a single layer, or may be applied as two or more layers. In the case of coating by overcoating two or more layers, only a part of the layers may be formed with the water-based paint, or all the layers may be formed with the water-based paint. Overcoating is, for example, the first layer (e.g., undercoat layer) on the substrate that has been subjected to primer treatment or sealer treatment, and after drying, the second layer (e.g., topcoat layer) for Examples include a method of topcoating and drying the paint, but the present invention is not limited to such a method.

Examples of the method of applying the water-based coating include coating methods using a brush, bar coater, applicator, air spray, airless spray, roll coater, flow coater, etc. However, the present invention is limited only to such examples. not something.
Water-based paints can be suitably used, for example, when coating exterior walls of buildings, car bodies, etc., and can also be suitably used for inorganic building materials such as ceramic building materials. Ceramic building materials include, for example, roof tiles and exterior wall materials. Ceramic building materials are made by adding inorganic fillers, fibrous materials, etc. to the hydraulic glue material, which is the raw material of the inorganic hardening material, molding the resulting mixture, and curing and hardening the resulting molding. can get. 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.

In addition, the water-based paint of the present disclosure can be overcoated on the oil-based paint film, and it is also possible to overcoat the oil-based paint film on the water-based paint film of the present invention. . From the viewpoint of weather resistance, it is particularly preferable to use an oil-based paint containing an ultraviolet absorber when an oil-based paint is applied over the coating film of the water-based paint of the present invention.
In addition, the paint of the present disclosure can be used for various purposes, for example, buildings, automobiles, automobile parts (for example, bodies of various materials, bumpers, spoilers, mirrors, wheels, interior materials, etc.), metals such as steel plates Plates, motorcycles, motorcycle parts, road materials (e.g. guardrails, traffic signs, soundproof walls, etc.), tunnel materials (e.g., side wall plates, etc.), ships, railway vehicles, aircraft, furniture, musical instruments, home appliances, construction Materials, containers, office supplies, sporting goods, toys, and the like.

EXAMPLES Next, the present invention will be described in more detail based on examples, but the present invention is not limited only to these examples.
In the following examples and comparative examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.
In the following examples and comparative examples, the abbreviation of each compound means 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-pentadiol diisobutyrate AA: acrylic acid HEMA: 2-hydroxyethyl methacrylate

Example 1
188 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD- 420, HLB: 12.6] 32.1 parts, MMA 5.7 parts, CHMA 19.5 parts, St 5.0 parts, TMPTMA 1.0 parts, C18A 12.7 parts, anti-algae component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3] 24.0 parts was charged, a part of the obtained mixture was taken out, and the phase inversion temperature of the mixture was measured based on the following method. As a result, the phase inversion temperature was 76-86°C.
[Method for measuring phase inversion temperature]
A stirring device and a temperature sensor were attached to a 2 L (liter) reaction vessel, and 1000 g of the mixture was placed in the reaction vessel and stirred.
While raising the temperature of the reaction vessel with a water bath, the electrical conductivity was measured with a conductivity meter [manufactured by EUTECH, trade name: Lacombe Tester PC450] every time the temperature of the mixture in the reaction vessel increased by 1 ° C. It was measured.
The electrical conductivity is plotted for each temperature when the temperature is raised, and the temperature at which the electrical conductivity begins to decrease continuously as the temperature rises is defined as the phase inversion start temperature, and when the electrical conductivity becomes 1.00 μS or less. was taken as the phase inversion end point temperature.
In addition, if the electrical conductivity does not become 1.00 μS or less even if the upper limit of the measurable temperature of the conductivity meter is exceeded, 3 minutes or more have passed since the temperature higher than the phase inversion start temperature was reached under stirring. The end point of the phase inversion temperature was the temperature at which no change occurred in the appearance of the mixture.
After measuring the phase inversion temperature of the mixture, the reaction vessel was heated using 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, after stirring for 10 minutes at room temperature while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 1.8 parts of a 15% 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride aqueous solution was added to the reaction vessel, and the internal temperature was 58°C. After reacting for 1 hour at 60° C., the content of the reaction vessel is heated with stirring for 5 hours at an internal temperature of 60° C. to polymerize the monomers contained in the monomer emulsion particles, resulting in an aqueous dispersion 1 containing polymer emulsion particles. got
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. As a result, the average particle size of the polymer emulsion particles was 39 nm.
[Method for measuring average particle size]
The average particle size obtained by the cumulant analysis method was measured using a multi-analyte nanoparticle size measuring system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measuring device using the dynamic light scattering method.

Example 2
188 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD- 420, HLB: 12.6] 32.8 parts, MMA 7.0 parts, CHMA 10.5 parts, TMPTMA 5.0 parts, KBM-503 8.7 parts, C18MA 12.0 parts, anti-algae component [manufactured by Nippon Soda Co., Ltd. , trade name: Biocut LC3] was charged, a part of the obtained mixture was taken out, 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 72-83°C.
After the internal temperature of the reaction vessel reached 86°C, the reaction vessel was taken out of the water bath and air-cooled with stirring until the internal temperature reached 40°C or less to obtain an aqueous dispersion containing monomer emulsion particles.
Next, after stirring at room temperature for 10 minutes while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 1.8 parts of a 15% 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride aqueous solution was added to the reaction vessel, and the internal temperature was 58°C. After reacting for 1 hour at 60° C., the content of the reaction vessel is heated with stirring for 5 hours at an internal temperature of 60° C. to polymerize the monomers contained in the monomer emulsion particles, resulting in aqueous dispersion 2 containing polymer emulsion particles. got
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. As a result, the average particle size of the polymer emulsion particles was 42 nm.

Example 3
188 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD- 420, HLB: 12.6] 32.8 parts, MMA 7.0 parts, CHMA 9.0 parts, IBOA 0.6 parts, St 1.5 parts, TMPTMA 5.0 parts, KBM-503 8.7 parts, C22A 11.4 part, 24.0 parts of an algae-proofing component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3] was charged, a part 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. measured based on As a result, the phase inversion temperature was 75-86°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, after stirring for 10 minutes at room temperature while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 1.8 parts of a 15% 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride aqueous solution was added to the reaction vessel, and the internal temperature was 58°C. After reacting for 1 hour at 60° C. for 5 hours, the content of the reaction vessel is heated with stirring to polymerize the monomers contained in the monomer emulsion particles, resulting in aqueous dispersion 3 containing polymer emulsion particles. got
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. As a result, the average particle size of the polymer emulsion particles was 43 nm.

Example 4
205.3 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6] 33.0 parts, MMA 9.0 parts, EHA 10.2 parts, AD-TMP 3.0 parts, C22MA 10.8 parts, NVP 2.0 parts, anti-algae component [manufactured by Nippon Soda Co., Ltd. , trade name: Biocut LC3] 24.0 parts, ultraviolet absorber [manufactured by BASF, trade name: Tinuvin (registered trademark) 400] 4.0 parts, hindered amine light stabilizer [manufactured by ADEKA Corporation, trade name : ADEKA STAB LA-87] 1.0 parts and CS-16 3.0 parts were charged, a part 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. bottom. As a result, the phase inversion temperature was 73-86°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, after stirring for 10 minutes at room temperature while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 1.8 parts of a 15% 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride aqueous solution was added to the reaction vessel, and the internal temperature was 58°C. After reacting for 1 hour at 60° C. for 5 hours, the contents of the reaction vessel are heated with stirring to polymerize the monomers contained in the monomer emulsion particles, resulting in an aqueous dispersion 4 containing polymer emulsion particles. got
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. As a result, the average particle size of the polymer emulsion particles was 43 nm.

Example 5
189.2 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD-430, HLB: 14.4] 35.0 parts, MMA 11.0 parts, CHMA 3.1 parts, IBOA 6.0 parts, St 1.5 parts, NVP 1.0 parts, TMPTMA 3.0 parts, A-DPH 2.0 Part, 2.0 parts of KBM-503, 11.4 parts of C22A, and 24.0 parts of algae-proof component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3] were charged, and a part of the resulting mixture was taken out, and the 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 90-95°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, after stirring at room temperature for 10 minutes while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
After that, 3.0 parts of a 5% potassium persulfate aqueous solution is added to the reaction vessel, and the content of the reaction vessel is heated at an internal temperature of 80° C. for 4 hours while stirring to obtain the content of the monomer emulsion particles. An aqueous dispersion 5 containing polymer emulsion particles was obtained by polymerizing the monomer.
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. As a result, the average particle size of the polymer emulsion particles was 60 nm.

Example 6
8.0 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6] 1.4 parts, MMA 0.3 parts, CHMA 0.6 parts, St 0.1 parts, TMPTMA 0.2 parts, KBM-503 0.2 parts, C18MA 0.5 parts, 1.0 part of the algae component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3] was charged, a portion of the resulting mixture was taken out, and the phase inversion temperature of the mixture was measured based on the same method as in Example 1. bottom. As a result, the phase inversion temperature was 72-83°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, after stirring for 10 minutes at room temperature while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 0.07 parts of 15% 2,2′-bis(2-imidazolin-2-yl)[2,2′-azobispropane]-2 hydrochloride aqueous solution and 3 parts of 5% potassium persulfate aqueous solution were placed in the reaction vessel. After heating the contents of the reaction vessel with stirring at an internal temperature of 58°C for 4 hours, 88.7 parts of deionized water was added and the internal temperature was raised to 80°C. 10 minutes after the completion of heating, 40.0 parts of deionized water, 13.6 parts of a 25% aqueous solution of a nonionic emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Soap ER-10], 37.1 parts of MMA, and 30 EHA. A mixture of 6 parts, 21.9 parts of CHMA, 1.2 parts of a hindered amine light stabilizer [manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB LA-87], and 1.6 parts of HEMA was poured into a reaction vessel while stirring. It was added dropwise over a period of minutes. After 30 minutes from the end of dropping, the reaction vessel was removed from the water bath, and after cooling the internal temperature of the reaction vessel to 40 ° C. or less, 0.1 part of an antiseptic (manufactured by DuPont, trade name: KORDEK MLX) was added to the reaction vessel. Aqueous dispersion 6 containing polymer emulsion particles having a resin layer formed by polymerizing the monomer component for resin layer formation on the surface of the polymer emulsion particles was obtained. The average particle size was 120 nm.

Example 7
22.1 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6] 4.2 parts, MMA 0.9 parts, CHMA 1.8 parts, IBOA 0.1 parts, St 0.3 parts, TMPTMA 0.6 parts, KBM-503 0.6 parts, C22A1 .5 parts, 3.0 parts of anti-algae component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3], and 0.5 parts of ultraviolet absorber [manufactured by BASF, trade name: Tinuvin (registered trademark) 400], A portion of the obtained mixture was taken out, 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 75-86°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, after stirring for 10 minutes at room temperature while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 0.2 parts of 15% 2,2′-bis(2-imidazolin-2-yl)[2,2′-azobispropane]-2 hydrochloride aqueous solution and 3 parts of 5% potassium persulfate aqueous solution were added to the reaction vessel. After heating the contents of the reaction vessel with stirring at an internal temperature of 58°C for 4 hours, 79.6 parts of deionized water was added and the internal temperature was raised to 80°C. 10 minutes after the completion of heating, 33.5 parts of deionized water, 11.2 parts of a 25% aqueous solution of a nonionic emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Soap ER-10], 31.3 parts of MMA, and EHA28. 9 parts of CHMA, 20.7 parts of CHMA, 1.2 parts of a hindered amine light stabilizer [manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB LA-87], and 1.6 parts of HEMA were stirred into a reaction vessel. It was added dropwise over a period of minutes. After 30 minutes from the end of dropping, the reaction vessel was removed from the water bath, and after cooling the internal temperature of the reaction vessel to 40 ° C. or less, 0.1 part of an antiseptic (manufactured by DuPont, trade name: KORDEK MLX) was added to the reaction vessel. Aqueous dispersion 7 containing polymer emulsion particles having a resin layer formed by polymerizing the monomer component for forming a resin layer on the surface of the polymer emulsion particles was obtained. The average particle size was 95 nm.

Example 8
44.2 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6] 8.4 parts, MMA 1.8 parts, CHMA 3.6 parts, IBOA 0.2 parts, St 0.6 parts, TMPTMA 1.2 parts, KBM-503 1.2 parts, C22A3 .0 parts, 6.0 parts of algae-preventing component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3], and 1.0 part of ultraviolet absorber [manufactured by BASF, trade name: Tinuvin (registered trademark) 400] are charged, A portion of the obtained mixture was taken out, 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 75-86°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, after stirring for 10 minutes at room temperature while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 0.4 parts of 15% 2,2′-bis(2-imidazolin-2-yl)[2,2′-azobispropane]-2 hydrochloride aqueous solution and 5% potassium persulfate aqueous solution were placed in the reaction vessel. 3.0 parts was added, and the contents of the reaction vessel were heated with stirring at an internal temperature of 58°C for 4 hours. 10 minutes after the completion of heating, 30.4 parts of deionized water, 10.4 parts of a 25% aqueous solution of a nonionic emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Soap ER-10], 25.0 parts of MMA, and 24 EHA. 3 parts of CHMA, 17.9 parts of CHMA, 2.0 parts of a hindered amine light stabilizer [manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB LA-87], and 1.2 parts of HEMA were stirred into a reaction vessel. It was added dropwise over a period of minutes. After 30 minutes from the end of dropping, the reaction vessel was removed from the water bath, and after cooling the internal temperature of the reaction vessel to 40 ° C. or less, 0.1 part of an antiseptic (manufactured by DuPont, trade name: KORDEK MLX) was added to the reaction vessel. Aqueous dispersion 8 containing polymer emulsion particles having a resin layer formed by polymerizing a monomer component for forming a resin layer on the surface of the polymer emulsion particles was obtained. The average particle size was 72 nm.

Example 9
44.2 parts of deionized water and polyoxyalkylene alkenyl ether as a nonionic emulsifier [manufactured by Kao Corporation, trade name: Latemul PD-420, HLB: 12.6] 8.4 parts, MMA 1.8 parts, CHMA 3.6 parts, IBOA 0.2 parts, St 0.6 parts, TMPTMA 1.2 parts, KBM-503 1.2 parts, C22A3 .0 parts, 6.0 parts of algae-preventing component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3], and 1.0 part of ultraviolet absorber [manufactured by BASF, trade name: Tinuvin (registered trademark) 400] are charged, A portion of the obtained mixture was taken out, 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 75-86°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, after stirring for 10 minutes at room temperature while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 0.4 parts of 15% 2,2′-bis(2-imidazolin-2-yl)[2,2′-azobispropane]-2 hydrochloride aqueous solution and 3 parts of 5% potassium persulfate aqueous solution were placed in the reaction vessel. After heating the contents of the reaction vessel with stirring at an internal temperature of 58°C for 4 hours, 64.4 parts of deionized water was added and the internal temperature was raised to 80°C. 10 minutes after the completion of heating, 30.4 parts of deionized water, 10.4 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Soap SR-20], 25.0 parts of MMA, and 24 EHA. 3 parts of CHMA, 17.9 parts of CHMA, 2.0 parts of a hindered amine light stabilizer [manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB LA-87], and 1.2 parts of HEMA were stirred into a reaction vessel. It was added dropwise over a period of minutes. After 30 minutes from the end of dropping, the reaction vessel was removed from the water bath, and after cooling the internal temperature of the reaction vessel to 40 ° C. or less, 0.1 part of an antiseptic (manufactured by DuPont, trade name: KORDEK MLX) was added to the reaction vessel. Aqueous Dispersion 9 containing polymer emulsion particles having a resin layer formed by polymerizing the monomer component for forming a resin layer on the surface of the polymer emulsion particles was obtained. The average particle size was 69 nm.

Comparative example 1
A reaction vessel equipped with a stirrer, temperature sensor, condenser, nitrogen inlet tube and dropping funnel was charged with 53 parts of deionized water. 22 parts of deionized water, 9 parts of 25% aqueous solution of emulsifier [Daiichi 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 and methacrylic acid were added to a dropping funnel. A pre-emulsion for dripping was prepared consisting of 1 part and 2.0 parts of an anti-algae component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3], of which 8 parts corresponding to 5% of the total amount of all polymerizable monomer components were added. It was added into a flask, heated to 70° C. while gently blowing nitrogen gas, and 1.4 parts of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Next, the remainder of the pre-emulsion for dropping, 4.3 parts of 5% aqueous ammonium persulfate solution, and 3.0 parts of 2.5% aqueous sodium hydrogen sulfite solution were uniformly dropped into the flask over 180 minutes.
After the completion of dropping, the contents of the flask were maintained at 70° C. for 60 minutes, followed by adding 22.5 parts of deionized water and 25% of an emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10]. A second stage pre-emulsion was prepared consisting of 9.0 parts of aqueous solution, 4.0 parts of EHA, 5.0 parts of CHMA, 40.0 parts of MMA and 1.0 part of acrylic acid, and 4.3 parts of 5% aqueous ammonium persulfate solution and 2 parts of acrylic acid. 3.0 parts of a 5% sodium hydrogen sulfite aqueous solution was uniformly dropped into the flask over 180 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 70° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction solution to room temperature, the resin emulsion A was prepared by filtering through a 300-mesh wire mesh. The average particle size of the resulting resin emulsion was 200 nm.

Comparative example 2
188 parts of deionized water and 32.8 parts of an anionic emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekaria Soap SR-20] were placed in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, a nitrogen inlet pipe and a dropping funnel. Part, 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 component [manufactured by Nippon Soda Co., Ltd., trade name: Biocut LC3] were charged, and the resulting mixture A portion was taken out, and the phase inversion temperature of the mixture was measured based on the following method, but phase inversion could not be 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 lower. Next, after stirring at room temperature for 10 minutes while introducing nitrogen gas into the reactor, the reaction vessel is placed in a water bath, and the internal temperature of the reaction vessel is raised to 58 ° C. in the water bath while stirring. I warmed up.
Then, 1.8 parts of a 15% 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]-2 hydrochloride aqueous solution was added to the reaction vessel, and the internal temperature was 58°C. After reacting for 1 hour at , the contents of the reaction vessel were heated with stirring at an internal temperature of 60° C. for 5 hours, but the polymer precipitated out of the water.
Tables 1 and 2 show the compositions, particle sizes, etc. of Examples 11-9 and Comparative Examples 1 and 2.

Experimental Examples The polymer emulsion particle-containing aqueous dispersions 1 to 9 obtained in each example or comparative example and the resin emulsion A were mixed with an acrylic resin so that the concentration of the anti-algae component in the total resin solid content after mixing was 1 wt%. It was mixed with a resin emulsion [manufactured by Nippon Shokubai Co., Ltd., product name: Acryset EF-005, resin solid content: 40%]. In addition, as an additional comparison target, an acrylic resin emulsion [ Nippon Shokubai Co., Ltd., product name: Acryset EF-005, resin solid content: 40%] was also prepared.
Further, 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 Co., Ltd., product number: CS-12] was added to each mixed solution as a film-forming aid at 8% of the mixed solution. After mixing, it was allowed to stand overnight at room temperature.

[Method for measuring haze]
Each acrylic polymer emulsion particle-containing aqueous dispersion was applied to a glass plate with an applicator so that the thickness of the coating film after drying was 100 μm, and dried in a dryer at 80 ° C. for 2 hours to form a coating and test. got a board
The haze of the coating surface of the test plate obtained above was measured using a spectrophotometer [manufactured by Konica Minolta Co., Ltd., product number: CM-3700A] in accordance with the conditions specified in ASTM-D-1003-97-C. measured by Tables 3 and 4 show the results.

[Amount of anti-algae component outflow]
Release paper is set on a glass plate, and an adhesive tape (manufactured by Nichiban Co., Ltd., product name: cloth adhesive tape 102N) is used to create a mold so that the thickness after drying is about 200 μm, and water is added to solidify the resin. Each resin emulsion liquid with adjusted concentration was poured into the frame and dried at room temperature to prepare a film-like molding with a thickness of about 200 μm. A sample was prepared by cutting the molded body into a 1 cm square with a cutter.
1.0 g of each sample was weighed into separate containers, and 20.0 g of water heated to 40° C. was added to each container and sealed. Each container was placed in an oven at 40° C. and shaken every 3 days and kept warm for 1 month.
After one month, the water in the container was sampled, and the amount of the anti-algae component that flowed into the water was quantified by LC under the following conditions. Tables 3 and 4 show the results.
LC conditions Apparatus: Prominence UFLC (manufactured by Shimadzu Corporation)
Column: GF-310HQ
Column oven: 40°C
Mobile phase: AN/10 mol aqueous ammonium formate = 7/3
Flow rate: 0.5ml/min

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

Claims (10)

An algae control component, a nonionic surfactant, and an alkyl group-containing ester compound having 15 or more carbon atoms are included, and the mass ratio of the nonionic surfactant to the alkyl group-containing ester compound having 15 or more carbon atoms (nonionic Particles having a weight of surfactant/mass of alkyl group-containing ester compound having 15 or more carbon atoms) of 60/40 to 90/10 and an average particle diameter of 10 nm to 200 nm. 2. The particles according to claim 1, further comprising a polymer (A) having a structural unit derived from an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms. The alkyl group-containing ester compound having 15 or more carbon atoms according to claim 1 is an alkyl group-containing (meth)acrylic acid ester having 15 or more carbon atoms, and the polymer (A) has 15 carbon atoms. 3. The particles according to claim 2, having structural units derived from the above alkyl group-containing (meth)acrylic acid ester. A core-shell particle comprising the particle according to any one of claims 1 to 3 as a core layer and a polymer (B) as a shell layer. An aqueous dispersion comprising the particles according to any one of claims 1 to 3 or the core-shell particles according to any one of claims 4. A water-based paint comprising the particles according to any one of claims 1 to 3 or the core-shell particles according to any one of claims 4. A coating film obtained by applying the water-based coating composition according to claim 6 . It has a step (1) of mixing an algae-proof component, a nonionic surfactant, an alkyl group-containing ester compound having 15 or more carbon atoms, and an aqueous medium, wherein the nonionic surfactant and the carbon number are 15 or more. The mass ratio to the alkyl group-containing ester compound (mass of the nonionic surfactant/mass of the alkyl group-containing ester compound having 15 or more carbon atoms) is 60/40 to 90/10, and the resulting mixture is stirred. (2) of heating the mixture to a temperature 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. Production method. 9. The method for producing particles according to claim 8, wherein an alkyl group-containing (meth)acrylic acid ester having 4 to 12 carbon atoms is further mixed in step (1). 10. The method for producing particles according to claim 8 or 9, further comprising the step (3) of polymerizing with a polymerization initiator.