JP2023001833A - Antibacterial particle dispersion - Google Patents

Abstract

To provide an antibacterial particle dispersion, etc., having high safety and a wide antibacterial spectrum and excellent stability and antibacterial effect (including antibacterial effect).SOLUTION: Provided is an antibacterial particle dispersion, comprising at least antibacterial particles dispersed in water, the antibacterial particles being composed of a (meth)acrylate monomer represented by the following general formula (I) and at least one antibacterial component selected from the following group A. [In the above formula (I), A is a hydrogen atom (H) or a methyl group (CH3); and R represents a hydrogen atom (H), a C1-22 alkyl group, or a substituent having a polyalkylene glycol chain in which the carbon number of the alkylene chain is 2-18.] Group A: iodo-propargyl compounds, thiabendazole, p-oxybenzoic acid esters, sodium benzoate, etc.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an antibacterial particle dispersion that exhibits excellent antibacterial effects (including antifungal effects) of its antibacterial components even after a long period of time, as well as excellent safety and stability.

Conventionally, some materials are known as antibacterial particles and the like.
For example, (1) antibiotic active particles characterized in that an antibiotic compound is dispersed in a polymer containing an epoxy group, the polymer comprises a monomer component containing an epoxy group-containing monomer and an antibiotic Antibiotic active particles obtained by dispersing a hydrophobic solution containing an active compound in water and polymerizing the monomer components (see, for example, Patent Document 1),
(2) An antibacterial resin containing an inorganic antibacterial agent, the cosmetic antibacterial resin comprising spherical particles having an average particle size of 0.1 m to 1000 μm. At least one ceramic selected from the group consisting of silica, zeolite, phosphate compounds, calcium carbonate, calcium silicate, bentonite, and titanium oxide, selected from the group consisting of silver, copper, zinc, gold, platinum and nickel antibacterial resin (for example, see Patent Document 2),
(3) Made of a crosslinked (meth)acrylic acid ester resin, having a compressive strength of 0.05 to 0.6 kgf/mm ² and a recovery rate of 3 to 40 when the load is reduced from 1 gf to 0.2 gf. %, capable of releasing an active ingredient of an external preparation (see, for example, Patent Document 3);
(4) dispersing, in the absence of a solvent, a hydrophobic and substantially insoluble antibiotic compound in the hydrophobic polymerizable vinyl monomer; , an oil phase component preparation step of preparing an oil phase component containing a hydrophobic slurry, a water dispersion step of preparing an aqueous dispersion by dispersing the oil phase component in water, and suspension polymerization of the polymerizable vinyl monomer. controlled-release particles characterized by being obtained by a production method comprising a polymerization step of producing a polymer (see, for example, Patent Document 4),
etc. are known.

However, the antibacterial particles and the like described in Patent Documents 1 to 4 have insufficient stability and safety, and the antibacterial effect (including the antifungal effect) of the antibacterial component is impaired after a long period of time. In addition, there are issues such as those that have some adverse effect on other ingredients, and are more stable and safe, and the antibacterial effect of the antibacterial ingredient (antifungal effect) even after a long period of time. Including), there is a strong need for an antibacterial particle dispersion that does not affect other ingredients.

Japanese Patent Application Laid-Open No. 2014-31365 (Claims, Examples, etc.) WO 2002/030365 (Claims, Examples, etc.) Japanese Patent Application Laid-Open No. 2002-265529 (Claims, Examples, etc.) Japanese Patent Application Laid-Open No. 2016-6023 (Claims, Examples, etc.)

In view of the above-mentioned problems of the prior art, the present invention is intended to solve them, and has high stability and safety, and the antibacterial effect (including antifungal effect) of the antibacterial component is excellent after a long period of time. In addition, another object of the present invention is to provide an antibacterial particle dispersion or the like which does not affect other ingredients.

In view of the above-described conventional problems, the present inventors have conducted intensive research and found that antibacterial particles composed of at least a (meth)acrylic acid ester monomer represented by a specific formula and a specific antibacterial component is dispersed in water, the antibacterial particle dispersion for the above purpose can be obtained, and the present invention has been completed.

〔上記式（Ｉ）中、Ａは、水素原子（Ｈ）又はメチル基（ＣＨ_３）であり、Ｒは、水素原子（Ｈ）、炭素数１～２２のアルキル基、又はアルキレン鎖の炭素数が２～１８であるポリアルキレングリコール鎖を有する置換基を表し、該アルキル基又はポリアルキレングリコール鎖を有する置換基は、置換基としてフェニル基、ベンジル基、エポキシ基、水酸基、ジアルキルアミノ基、炭素数１～１８のアルコキシ基、炭素数１～１８のパーフルオロアルキル基、又はトリアルコキシシリル基を有していてもよい。〕
Ａ群：ヨードプロパギル化合物、チアベンダゾール、ペンタクロロフェノールナトリウム、１，２－ベンゾイソチアゾリン－３－オン、２，３，５，６－テトラクロロ－４（メチルスルフォニル）ピリジン、パラオキシ安息香酸エステル、フェノール、安息香酸ナトリウム、デヒドロ酢酸ナトリウム、ソルビン酸カリウム、モルホリン、クレゾール、メチルイソチアゾリノン、クロロメチルイソチアゾリノン、オクチルイソチアゾリノン、ジクロロオクチルイソチアゾリノン、ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－１，３，５－トリアジン、２－ブロモ－２－ニトロプロパン－１，３－ジオール、２－ピリジンチオール－１－オキシドナトリウム、ピリチオンナトリウム、２－（４－チオゾリル）ベンズイミダゾール、４－ターピネノール、１，８－シネオール、チモール、ジイソチオシアネート、ユーカリオイル、ロンギフォーレン、イソプロピルメチルフェノール、２－メチル－４－イソチアゾリン－３－オン、シトラール、オイゲノール、アリルイソチオシアネート、ｄ－リモネン、タンニン酸、エチルパラベン、塩化ベンザルコニウム、カプリル酸グリセリル、グリセリン脂肪酸エステル、クロルフェネシン、サリチル酸、パラオキシ安息香酸エチル、パラオキシ安息香酸ブチル、パラオキシ安息香酸プロピル、パラオキシ安息香酸メチル、ビサボロール、ヒノキチオール、フェニルエチルアルコール、フェネチルアルコール、フェノキシエタノール、ブチルパラベン、プロピルパラベン、ベンザルコニウムクロリド、メチルパラベン
前記一般式（Ｉ）で表される（メタ）アクリル酸エステルモノマーの含有量が抗菌性粒子分散体を構成する全ポリマー成分に対して、３０～９５質量％であることが好ましい。
前記抗菌性成分は、抗菌性粒子を構成する全ポリマー成分に対して、１質量％以上含有されていることが好ましい。
前記抗菌性粒子分散体の抗菌性粒子の平均粒子径は、１０～８００ｎｍであることが好ましい。
前記抗菌性粒子の含有量が、抗菌性粒子分散体全量に対して、０．１～５０質量％であることが好ましい。
体。
本発明の筆記具用水性インク組成物は、前記抗菌性粒子分散体を含むことを特徴とする。 That is, the antibacterial particle dispersion of the present invention comprises at least a (meth)acrylic acid ester monomer represented by the following general formula (I) and at least one antibacterial component selected from Group A below. antibacterial particles are dispersed in water.

[In the above formula (I), A is a hydrogen atom (H) or a methyl group (CH ₃ ), and R is a hydrogen atom (H), an alkyl group having 1 to 22 carbon atoms, or the number of carbon atoms in the alkylene chain. represents a substituent having a polyalkylene glycol chain of 2 to 18, the alkyl group or a substituent having a polyalkylene glycol chain is a phenyl group, a benzyl group, an epoxy group, a hydroxyl group, a dialkylamino group, a carbon It may have an alkoxy group having 1 to 18 carbon atoms, a perfluoroalkyl group having 1 to 18 carbon atoms, or a trialkoxysilyl group. ]
Group A: iodopropargyl compound, thiabendazole, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, paraoxybenzoic acid ester, phenol , sodium benzoate, sodium dehydroacetate, potassium sorbate, morpholine, cresol, methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, hexahydro-1,3,5-tris(2 -hydroxyethyl)-1,3,5-triazine, 2-bromo-2-nitropropane-1,3-diol, 2-pyridinethiol-1-oxide sodium, pyrithione sodium, 2-(4-thiozolyl)benzimidazole , 4-terpineol, 1,8-cineol, thymol, diisothiocyanate, eucalyptus oil, longifolene, isopropylmethylphenol, 2-methyl-4-isothiazolin-3-one, citral, eugenol, allylisothiocyanate, d-limonene , tannic acid, ethylparaben, benzalkonium chloride, glyceryl caprylate, glycerin fatty acid ester, chlorphenesin, salicylic acid, ethyl parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, methyl parahydroxybenzoate, bisabolol, hinokitiol, Phenylethyl alcohol, phenethyl alcohol, phenoxyethanol, butylparaben, propylparaben, benzalkonium chloride, methylparaben The content of the (meth)acrylate monomer represented by the general formula (I) constitutes the antibacterial particle dispersion. It is preferably 30 to 95% by mass based on the total polymer components.
It is preferable that the antibacterial component is contained in an amount of 1% by mass or more with respect to all polymer components constituting the antibacterial particles.
The average particle size of the antibacterial particles in the antibacterial particle dispersion is preferably 10 to 800 nm.
It is preferable that the content of the antibacterial particles is 0.1 to 50% by mass with respect to the total amount of the antibacterial particle dispersion.
body.
The water-based ink composition for writing instruments of the present invention is characterized by containing the antibacterial particle dispersion.

According to the present invention, the stability and safety are high, the antibacterial effect of the antibacterial component (including the antifungal effect) is excellent after a long period of time, and the antibacterial property does not affect other ingredients. Particle dispersions and aqueous writing instrument ink compositions containing the same are provided.
The objects and advantages of the invention may be realized and obtained by means of the elements and combinations particularly pointed out in the claims. Both the foregoing general description and the following detailed description are exemplary and explanatory, and are not limiting of the invention as claimed.

〔上記式（Ｉ）中、Ａは、水素原子（Ｈ）又はメチル基（ＣＨ_３）であり、Ｒは、水素原子（Ｈ）、炭素数１～２２のアルキル基、又はアルキレン鎖の炭素数が２～１８であるポリアルキレングリコール鎖を有する置換基を表し、該アルキル基又はポリアルキレングリコール鎖を有する置換基は、置換基としてフェニル基、ベンジル基、エポキシ基、水酸基、ジアルキルアミノ基、炭素数１～１８のアルコキシ基、炭素数１～１８のパーフルオロアルキル基、又はトリアルコキシシリル基を有していてもよい。〕 Embodiments of the present invention will be described in detail below. However, it should be noted that the technical scope of the present invention is not limited to each embodiment described in detail below, but extends to the invention described in the claims and equivalents thereof.
The antibacterial particle dispersion of the present invention comprises at least a (meth)acrylic acid ester monomer represented by the following general formula (I) and at least one antibacterial component selected from Group A below. It is characterized in that the organic particles are dispersed in water.

[In the above formula (I), A is a hydrogen atom (H) or a methyl group (CH ₃ ), and R is a hydrogen atom (H), an alkyl group having 1 to 22 carbon atoms, or the number of carbon atoms in the alkylene chain. represents a substituent having a polyalkylene glycol chain of 2 to 18, the alkyl group or a substituent having a polyalkylene glycol chain is a phenyl group, a benzyl group, an epoxy group, a hydroxyl group, a dialkylamino group, a carbon It may have an alkoxy group having 1 to 18 carbon atoms, a perfluoroalkyl group having 1 to 18 carbon atoms, or a trialkoxysilyl group. ]

Group A: iodopropargyl compound, thiabendazole, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, paraoxybenzoic acid ester, phenol , sodium benzoate, sodium dehydroacetate, potassium sorbate, morpholine, cresol, methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, hexahydro-1,3,5-tris(2 -hydroxyethyl)-1,3,5-triazine, 2-bromo-2-nitropropane-1,3-diol, 2-pyridinethiol-1-oxide sodium, pyrithione sodium, 2-(4-thiozolyl)benzimidazole , 4-terpineol, 1,8-cineol, thymol, diisothiocyanate, eucalyptus oil, longifolene, isopropylmethylphenol, 2-methyl-4-isothiazolin-3-one, citral, eugenol, allylisothiocyanate, d-limonene , tannic acid, sodium benzoate, ethylparaben, benzalkonium chloride, glyceryl caprylate, glycerin fatty acid ester, chlorphenesin, salicylic acid, ethyl parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, methyl parahydroxybenzoate, Bisabolol, hinokitiol, phenylethyl alcohol, phenethyl alcohol, phenoxyethanol, butylparaben, propylparaben, benzalkonium chloride, methylparaben

The antibacterial component used in the present invention includes Group A iodopropargyl compounds, thiabendazole, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4 (methylsulfonyl ) pyridine, p-oxybenzoate (ethyl, methyl, propyl, isopropyl, butyl, isobutyl, etc.), phenol, sodium benzoate, sodium dehydroacetate, potassium sorbate, morpholine, cresol, methylisothiazolinone, chloromethylisothiazolinone , octylisothiazolinone, dichlorooctylisothiazolinone, hexahydro-1,3,5-tris(2-hydroxyethyl)-1,3,5-triazine, 2-bromo-2-nitropropane-1,3-diol , 2-pyridinethiol-1-oxide sodium, pyrithione sodium, 2-(4-thiozolyl)benzimidazole, 4-terpinenol, 1,8-cineole, thymol, diisothiocyanate, eucalyptus oil, longifolene, isopropylmethylphenol, 2-methyl-4-isothiazolin-3-one, citral, eugenol, allyl isothiocyanate, d-limonene, tannic acid, sodium benzoate, ethylparaben, benzalkonium chloride, glyceryl caprylate, glycerin fatty acid ester, chlorphenesin , salicylic acid, ethyl parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, methyl parahydroxybenzoate, bisabolol, hinokitiol, phenylethyl alcohol, phenethyl alcohol, phenoxyethanol, butylparaben, propylparaben, benzalkonium chloride, methylparaben (each alone or a mixture of two or more, hereinafter the same).

Iodopropargyl compounds that can be used include, for example, 3-iodo-2-propynylpropylcarbamate, 3-iodo-2-propynylbutylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo -2-propynyl phenyl carbamate, 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal (IPCF), di-(3-iodo-2-propynyl) hexyl dicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynylthioxothioethylcarbamate, 3-iodo-2-propynylcarbamic acid Ester (IPC), N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargyl)-6-chloro Benzoxazol-2-one, 3-iodo-2-propynyl alcohol, 4-chlorophenyl 3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 3-iodo-2-propynyl-n -hexylcarbamate, 3-iodo-2-propynylcyclohexylcarbamate and the like.

The above group A antibacterial ingredients containing these iodopropargyl compounds have been known for a long time, and are highly safe compounds having antibacterial and antifungal properties. It can be prepared by various production methods, and if there are commercially available products of each compound included in the above group A, they can be used.
In the present invention, 3-iodo-2-propynylbutylcarbamate (hereinafter sometimes simply referred to as “IPBC”) is preferred among the iodopropargyl compounds from the viewpoints of further safety and stability. (IPBC alone or a mixture containing IPBC) is preferable, and other than iodopropargyl compounds, thiabendazole, 2-bromo-2-nitropropane-1,3-diol, phenoxyethanol, 4-terpinenol, 1,8 - at least one of cineol, tannic acid, benzalkonium chloride, glycerin fatty acid ester, potassium sorbate, parabens (butylparaben, propylparaben, ethylparaben, methylparaben), chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone Use of seeds is preferred.

The (meth)acrylic acid ester monomer represented by the above general formula (I) used in the present invention has a strong antibacterial component that can be encapsulated and can produce persistent and stable particles, and has an adverse effect on other compounding ingredients. It is used because it does not affect the effect and the durability of the effect is high.
R in the general formula (I) represents a hydrogen atom (H), an alkyl group having 1 to 22 carbon atoms, or a substituent having a polyalkylene glycol chain having 2 to 18 carbon atoms in the alkylene chain, Substituents having an alkyl group or a polyalkylene glycol chain are phenyl, benzyl, epoxy, hydroxyl, dialkylamino, alkoxy groups having 1 to 18 carbon atoms, and perfluoroalkyl groups having 1 to 18 carbon atoms as substituents. , or may have a trialkoxysilyl group, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, , an epoxy group, a hydroxyl group, a dialkylamino group, an alkyl group optionally having an alkoxy group having 1 to 4 carbon atoms as a substituent, particularly an epoxy group, a hydroxyl group, a substituent having 1 to 6 carbon atoms, An alkyl group having 1 to 2 carbon atoms and optionally having an alkoxy group, and an alkyl group having 1 to 6 carbon atoms and optionally having an epoxy group as a substituent are exemplified.
Preferably, R in the general formula (I) is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a hydroxyl group, a trifluoroethyl group, dimethylaminoethyl group, methoxyethyl group, hydroxyethyl group, hydroxypropyl group, allyl group, tetrahydrofurfuryl group, phenyl group, benzyl group, butoxydiethylene glycol group, methoxypolyethylene glycol group, dimethylaminoethyl group, diethylaminoethyl group, dimethylaminoethyl group , glycidyl group, ethyl phosphate, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol and the like are desirable.
In addition, in this specification, the notation of "(meth)acrylic acid" represents "acrylic acid and/or methacrylic acid."

Specific examples of the (meth)acrylic acid ester represented by the general formula (I) to be used include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( meth)lauryl acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate ) isobornyl acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic Acid 2-methoxyethyl, 2-ethoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate methyl chloride salt, diethylaminoethyl (meth)acrylate, di(meth)acryl ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 2-(Meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, trifluoroethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxytetra(meth)acrylate Ethylene glycol, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, (meth) ) 2-(dimethylamino) ethyl acrylate, 2-(dimethylamino) propyl, 2-(dimethylamino) butyl (meth) acrylate, 2-isocyanoethyl (meth) acrylate, 2-(meth) acrylate acetoacetoxy)ethyl, perfluoroethyl methacrylate having perfluoroalkyl having 1 to 18 carbon atoms, 2-(phosphate) ethyl (meth)acrylate [2-(Methacry at least one of (meth)acrylic acid trialkoxysilylpropyl, (meth)acrylic acid dialkoxymethylsilylpropyl (meth)acrylate (each alone or two or more, the same shall apply hereinafter).
Among these, methyl (meth)acrylate and (meth)acrylic are preferred from the viewpoints of industrial availability, ease of handling and safety during production, and further improvement of the effects of the present invention. ethyl acetate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, ( Octyl meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate are desirable.

In the present invention, in addition to the above (meth)acrylic acid ester monomer, from the viewpoint of obtaining a sustained reduction effect, etc., preferably, a hydrophobic vinyl monomer other than the above (meth)acrylic acid ester monomer and an aqueous monomer are used. can be used.
As the hydrophobic vinyl monomer, for example, at least one monomer other than the (meth)acrylic acid ester monomer can be used, such as styrenes such as styrene and methylstyrene.
Hydrophobic vinyl monomers that can be used include, for example, styrene, methylstyrene, chloromethylstyrene, alkylstyrene having an alkyl group having 1 to 12 carbon atoms, methoxystyrene, chlorostyrene, bromostyrene, divinylbenzene, and phenylstyrene. , vinylnaphthalene, and the like.
Aqueous monomers that can be used include, for example, glycerin monomethacrylate, 2-sulfoethylsodium methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol-propylene glycol monomethacrylate, polyethylene glycol-tetramethylene glycol-monomethacrylate. , propylene glycol-polybutylene glycol-monomethacrylate and the like.

The antibacterial particle dispersion of the present invention comprises at least a (meth)acrylic acid ester monomer represented by the above general formula (I) and at least one antibacterial component selected from the above group A. As a method for producing it, for example, the above (meth)acrylic acid ester monomer (each alone or two or more, the same applies hereinafter), or the above (meth)acrylic acid ester monomer and other hydrophobic vinyl monomers And / or a mixed monomer containing an aqueous monomer, the antibacterial component of the group A is dissolved, ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. are used as a polymerization initiator, and a reducing agent is further used as a polymerization initiator. , further triallyl isocyanurate, triallyl isocyanurate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, pentaerythritol acrylate, ditrimethylolpropane acrylate, dipentaerythritol acrylate, methoxylated bisphenol A methacrylate, pentaerythritol methacrylate, ditrimethylolpropane methacrylate, Cross-linking agents such as dipentaerythritol methacrylate and ethoxylated polyglycerin methacrylate, and optionally, polyoxyethylene-1-(allyloxymethyl)-alkyl ether ammonium sulfate, ether sulfate, polyoxyethylene nonylpropenylphenyl ether ammonium sulfate, poly Oxyethylene nonylpropenyl phenyl ether, ammonium polyacrylate, ammonium styrene-maleic acid copolymer, polyoxyethylene alkyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene decyl ether, polyoxyethylene tridecyl ether, alkylbenzene sulfonate, dioctyl sulfosuccinate, sodium lauryl sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene styrenated phenyl ether phosphate, polyoxyethylene styrenated phenyl ether sulfate, polyoxy Ethylene alkyl ether sulfate, polyoxyethylene sorbitan monolaurate (polysorbate 20), polyoxyethylene sorbitan palmitate (polysorbate 40), polyoxyethylene sorbitan monostearate (polysorbate 60), It can be produced by emulsion polymerization using a polymerizable surfactant (emulsifier) such as polyoxyethylene sorbitan phosphate (polysorbate 80). An antibacterial particle dispersion can be obtained by, for example.
The use of a cross-linking agent such as triallyl isocyanurate is preferable because the heat resistance, mechanical properties, hydrolysis resistance and weather resistance of the antibacterial particle dispersion can be improved.

In the present invention, the emulsion polymerization may be carried out by mixing an appropriate amount of dicyclopenta(te)nyl(meth)acrylate monomer or the like with the (meth)acrylic acid ester monomer or the like. When this dicyclopenta (te) nyl (meth) acrylate monomer is further mixed and emulsion polymerized, the stability is unlikely to be impaired even if the water in the dispersion is volatilized, and the antibacterial particle dispersion with excellent stability is obtained. The body becomes what you get.
Dicyclopenta(te)nyl (meth)acrylate monomers that can be used include dicyclopentanyl acrylate monomers, dicyclopentenyl acrylate, dicyclopentanyl methacrylate monomers, dicyclopentenyl methacrylate.
Further, in the present invention, during the emulsion polymerization, in addition to the dicyclopenta(te)nyl (meth)acrylate monomer such as the (meth)acrylic acid ester monomer and the other hydrophobic vinyl monomer, an epoxy group , a hydroxymethylamide group, an isocyanate group, or a polyfunctional monomer having two or more vinyl groups may be blended in an appropriate amount for cross-linking.

In the present invention, among the polymer components constituting the antimicrobial particle dispersion, the content of the (meth)acrylic acid ester monomer is 30% by mass with respect to the total polymer components constituting the antimicrobial particle dispersion. or more, preferably 30 to 95% by mass, more preferably 30 to 70% by mass.
In the present invention, the term "all polymer components" refers to the polymerizable components constituting the antibacterial particle dispersion, specifically, the (meth)acrylic acid ester monomer used, the other monomer components used, It refers to the total amount of a cross-linking agent, which will be described later.
By setting the content of the (meth)acrylic acid ester monomer to 30% by mass or more based on the total polymer components, the effect of the present invention can be exhibited. If there is, the stability over time is deteriorated, which is not preferable.

In addition, among the polymer components constituting the antibacterial particle dispersion, the content of monomer components other than the above-mentioned (meth)acrylic acid ester monomer is determined by the difference between the (meth)acrylic acid ester monomer used and the crosslinking agent described later. This is the remainder of the total amount.
Preferably, the content of the other monomer component is 0.5 to 70% by mass based on the total polymer component from the viewpoints of further exhibiting the effects of the present invention, dispersibility, and reactivity. is desirable.

In the present invention, the (solid content) content of the antibacterial component is set to , 1% by mass or more, preferably 5% by mass or more, more preferably 10 to 50% by mass, particularly preferably 15 to 40% by mass.
By setting the content of the antibacterial component to 1% by mass or more, sufficient antibacterial performance (including antifungal effect) and sustained antibacterial effect can be exhibited. If it is less than 1% by mass, the antibacterial performance is insufficient and the effects of the present invention cannot be exhibited.

The polymerizable surfactant that can be used as necessary is not particularly limited as long as it is a polymerizable surfactant that is usually used in the emulsion polymerization. Or a polymerizable surfactant such as a nonionic type, manufactured by Adeka Co., Ltd. ADEKA ARISOAP NE-10, NE-20, NE-30, NE-40, SE-10N, Kao Corporation Latemul S-180, S-180A, S-120A manufactured by Sanyo Chemical Industries, Ltd., Eleminol JS-20 manufactured by Sanyo Chemical Industries, Ltd., Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like. The amount of these polymerizable surfactants used is desirably 0 to 50% by mass, preferably 0.1 to 50% by mass, based on the total amount of the above monomers.
The content of the cross-linking agent such as triallyl isocyanurate is 0 to 50% by mass, preferably 0.1 to 25% by mass, based on the total amount of the monomers.

In the present invention, the preferred embodiment, specifically, at least, by dissolving the antibacterial component selected from the above group A in the (meth)acrylic acid ester monomer and emulsion polymerization, or at least the above Antibacterial particle dispersion (dispersion liquid) is obtained. The amount of antibacterial particles in the antibacterial particle dispersion obtained under these production conditions varies depending on the amount of the (meth)acrylic acid ester monomer used, the amount of the antibacterial component, and the polymerization conditions. From the standpoint of manufacturability, workability, efficiency, etc., it is preferable to manufacture the solid content to be 1 to 50% by mass. More preferably, it is produced so that the solid content is 10 to 40% by mass.
This antibacterial particle dispersion (dispersion liquid) has stronger and longer lasting antibacterial performance (including antifungal effect) by using the antibacterial particle dispersion of the present invention rather than using the antibacterial component alone. The antibacterial particle dispersion is excellent in stability without adversely affecting other compounded ingredients, etc., while having the property. In particular, it is possible to obtain an antibacterial particle dispersion that can maintain or improve the antibacterial effect (including the antifungal effect) of the antibacterial component even after a long period of time.
In addition, in the present invention, since an oil-soluble (lipophilic) antiseptic component or the like is preferably used as an antibacterial component, the antiseptic component tends to adhere particularly to plastic containers, and the antiseptic power increases over time. In order to solve the problem that the antibacterial effect is impaired, by encapsulating the antibacterial component with particles made of the (meth)acrylic acid component or the like of the present invention, the adhesion to the wall surface of the container is suppressed, and even after a long period of time. It has a peculiar effect that the antibacterial effect can be maintained.

In the present invention, the average particle size of the antibacterial particles in the antibacterial particle dispersion to be obtained varies depending on the (meth)acrylic acid ester monomer, other monomer species used, content, polymerization conditions during polymerization, etc. However, it is preferably 10 to 800 nm, more preferably 20 to 300 nm, still more preferably 30 to 200 nm.
By setting the average particle size within the above preferable range, it is possible to use antibacterial particles that are further excellent in storage stability and have an average particle range suitable for each application described later. When used as an ink, it does not cause clogging in the core of writing instruments such as felt-tip pens, marking pens and ball-point pens, and is excellent in storage stability and the like.
The "average particle size" defined in the present invention is the histogram average particle size obtained by scattered light intensity distribution. ] is the value of the measured value D50.

In the antibacterial particle dispersion of the present invention, the content of the antibacterial particles contained in the dispersion is preferably 0.1 to 50% by mass in terms of solid content depending on each application described later. Preferably, it is desirable to be 1 to 30% by mass.
If the content of the antibacterial particles is less than 0.1% by mass in terms of solid content, the effects of the present invention cannot be exhibited. It will become.

The antibacterial particle aqueous dispersion of the present invention configured in this way can be used, for example, for medical equipment, baby products, nursing care products, bath products, kitchen utensils, tableware, drinking water piping parts, household sanitary products, home appliances, clothing, It can be used to impart antibacterial properties to various products such as construction materials, agricultural materials, automotive interior parts, stationery, writing instruments and ink compositions for inkjet printers.
The antibacterial particle aqueous dispersion of the present invention specifically configured in this way can be used, for example, for medical equipment, baby products, nursing care products, bath products, kitchen utensils, tableware, drinking water piping parts, household sanitary products, home appliances, It can be used to impart antibacterial properties to various products such as clothing, building materials, agricultural materials, automobile interior parts, stationery, writing instruments, and ink compositions for inkjet printers.
In addition to the above, specific uses include, for example, detergents such as laundry detergents, softeners, household detergents, dishwashing agents, and hard surface cleaners; shampoos, rinses, lotions, milky lotions, Personal care applications such as creams, sunscreens, foundations, eye makeup products, antiperspirants, toothpastes, paints, adhesives, building materials, resin emulsions, wood preservatives, cement admixtures, boilers, cooling equipment, wastewater treatment equipment, industry Industrial water treatment applications such as industrial water (papermaking process water in the paper manufacturing process, cooling water and washing water for various industries); medical equipment, food additives, solar cell modules, organic element devices, electronic equipment such as heat ray shielding films, etc. In addition to this, it can be suitably used for water tanks and medicated baths as a water mold inhibitor for aquatic organisms (fish, etc.).
The antibacterial particle aqueous dispersion of the present invention is highly stable and safe, and has excellent antibacterial effect (including antifungal effect) of the antibacterial component after a long period of time, and does not affect other ingredients. Since it is an antibacterial particle dispersion that does not have a , electronic devices, and water mold control for aquatic organisms (fish, etc.) in water tanks and medicinal baths.

The water-based ink composition for writing instruments of the present invention is characterized by containing at least the antibacterial particle dispersion having the above constitution, and in addition to the antibacterial particle dispersion, a colorant and a water-soluble organic solvent are added. can contain.
The content of the antibacterial particles in the ink composition is from 0.1 to 0.1 in terms of solid content based on the total amount of the ink composition, in terms of exhibiting the effects of the present invention without impairing the writing performance, and in terms of storage stability. It is preferably 30.0% by mass, more preferably 1.0 to 15.0% by mass.

Colorants that can be used include water-soluble dyes, pigments such as inorganic pigments, organic pigments, plastic pigments, hollow resin particles with voids inside the particles as white pigments, or dyes with excellent color development and dispersibility. Resin particles (pseudo-pigments) dyed with , thermochromic pigments, photochromic pigments, and the like can also be used.
Any of direct dyes, acid dyes, food dyes, and basic dyes can be used as water-soluble dyes in an appropriate amount within a range that does not impair the effects of the present invention.
The content of these colorants varies depending on the type of writing instrument and the like, but is 1 to 30% by mass with respect to the total amount of the ink composition.

Examples of water-soluble organic solvents that can be used include ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,2-butane. diol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,5-hexanediol, 3-methyl 1,3 -butanediol, 2-methylpentane -2,4-diol, 3-methylpentane-1,3,5-triol, 1,2,3-hexanetriol and other alkylene glycols, polyethylene glycol, polypropylene glycol and other polyalkylene glycols Glycerols such as glycerol, diglycerol, triglycerol, lower alkyl ethers of glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, N- At least one of methyl-2-pyrrolidone, 1,3-dimethyl-2-imidaridinone and the like can be mentioned.

In addition, for example, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, benzyl alcohol, dimethylformamide, Water-soluble solvents such as amides such as diethylacetamide and ketones such as acetone can also be mixed.
The content of these water-soluble organic solvents varies depending on the type of writing instrument such as felt-tip pens, marking pens, and ballpoint pens, and is 1 to 40% by mass relative to the total amount of the ink composition. Therefore, it is particularly effective for ink compositions containing 10% by mass or less, and more preferably 3 to 8% by mass.

The water-based ink composition for writing instruments of the present invention contains particles, a colorant, and a water-soluble solvent having the properties described above, and water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) as the balance as a solvent. In addition, dispersants, lubricants, pH adjusters, rust preventives, thickeners, evaporation inhibitors, surfactants, and the like can be appropriately contained within the range that does not impair the effects of the present invention.

As dispersants that can be used, nonionic, anionic surfactants and water-soluble resins are used. A water-soluble polymer is preferably used.
Examples of lubricants include nonionics such as polyhydric alcohol fatty acid esters, sugar higher fatty acid esters, polyoxyalkylene higher fatty acid esters, and alkyl phosphate esters, and alkylsulfonic acid higher fatty acid amides, which are also used as surface treatment agents for pigments. Salts, anionic surfactants such as alkylallylsulfonates, derivatives of polyalkylene glycol, fluorine-based surfactants, and polyether-modified silicones can be used.

Examples of pH adjusters include ammonia, urea, monoethanolamine, diethanolamine, triethanolamine, alkali metal salts of carbonic acid and phosphoric acid such as sodium tripolyphosphate and sodium carbonate, and alkali metal hydrates such as sodium hydroxide. etc. Examples of rust preventives include benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, saponins and the like.
Examples of thickening agents include carboxymethyl cellulose (CMC) or salts thereof, fermented cellulose, crystalline cellulose, polysaccharides, and the like. Polysaccharides that can be used include, for example, xanthan gum, guar gum, hydroxypropylated guar gum, casein, gum arabic, gelatin, amylose, agarose, agaropectin, arabinan, curdlan, callose, carboxymethyl starch, chitin, chitosan, quince seed. , glucomannan, gellan gum, tamarind seed gum, dextran, nigelan, hyaluronic acid, pustulan, funoran, HM pectin, porphyran, laminaran, lichenan, carrageenan, alginic acid, tragacanth gum, alkasi gum, succinoglycan, locust bean gum, tara gum, etc. These may be used singly or in combination of two or more. Moreover, if these commercial products are available, they can be used.
Evaporation inhibitors include, for example, pentaerythritol, p-xylene glycol, trimethylolpropane, triethylolpropane, and dextrin.
Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and acetylene glycol-based surfactants.

The water-based ink composition for writing instruments of the present invention is obtained by appropriately combining the antibacterial particle dispersion having the characteristics described above, the water-soluble solvent, and other components according to the application of the ink for writing instruments (for ballpoint pens, marking pens, etc.), By stirring and mixing with a stirrer such as a homomixer, homogenizer, or disper, and if necessary, by removing coarse particles in the ink composition by filtration or centrifugation, etc., to prepare an aqueous ink composition for writing instruments. can be done.

The pH (25° C.) of the water-based ink composition for writing instruments of the present invention is adjusted to 5 to 10 with a pH adjuster or the like from the viewpoints of usability, safety, stability of the ink itself, and compatibility with the ink container. It is preferably adjusted, more preferably 6 to 9.5.

The water-based ink composition for writing instruments of the present invention is mounted in a ball-point pen, a marking pen, or the like having a pen tip such as a ball-point tip, fiber tip, felt tip, or plastic tip.
As a ballpoint pen, the water-based ink composition for writing instruments having the above composition is
mm ballpoint pen ink container (refill), has no compatibility with the aqueous ink composition contained in the ink container, and has a specific gravity with respect to the aqueous ink composition. Small substances such as polybutene, silicone oil, mineral oil, etc. may be included as ink followers.
The structure of the ballpoint pen and the marking pen is not particularly limited. It may be a direct liquid type ballpoint pen or marking pen.

In the water-based ink composition for writing instruments of the present invention configured as described above, since the antibacterial particle dispersion having the characteristics described above is blended in the water-based ink composition for writing instruments, antibacterial properties are maintained in the ink composition. While having strength and durability of performance (including antifungal effect), it does not adversely affect other compounding ingredients, etc., so the effect can be maintained for a long period of time. Since the writing performance is not impaired, the degree of freedom in ink design can be further increased, and a water-based ink composition for writing instruments suitable for writing instruments such as ballpoint pens and marking pens can be obtained.
In the above, the case where the antibacterial particle aqueous dispersion of the present invention is used in an aqueous ink composition for writing instruments has been described. (including antifungal effect) and is highly safe. By selecting the antibacterial ingredient to be used, it is possible to use one with a wide antibacterial spectrum, which has an adverse effect on other compounding ingredients. In addition, it is used as a detergent application, personal care application, industrial water treatment application, food additive, electronic device application, and water mold suppression for aquatic organisms (fish etc.) in aquariums and It can be implemented at a blending ratio suitable for chemical bath applications.

EXAMPLES Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 9: Production of antimicrobial particle dispersions (particles 1 to 9)]
Each antibacterial particle dispersion was produced according to Examples 1 to 9 below. In addition, the following "parts" represent mass parts. The antimicrobial component is the solids content.

(Example 1)
A 2-liter flask was equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a 1000-ml separatory funnel for charging monomers. , manufactured by NOF Corporation] 5 parts, 2-sulfoethyl sodium methacrylate [acrylic ester SEM-Na, manufactured by Mitsubishi Chemical Corporation] 5 parts, polymerizable surfactant [ADEKA Corporation, Adekaria Soap SE-10N, Ether Sal ft] and 0.5 part of ammonium persulfate were charged, and the internal temperature was raised to 50° C. while introducing nitrogen gas.

On the other hand, a mixed monomer consisting of 55 parts of cyclohexyl methacrylate monomer and 20 parts of n-butyl methacrylate was added with an antibacterial component [iodopropargyl compound: 3-iodo-2-propynyl carbamate, manufactured by Lonza (omacide IPBC 100)]. A liquid was prepared by mixing 20 parts, 14 parts of tannin [(Tannic acid S) manufactured by Fuji Kagaku Kogyo Co., Ltd.] and 10 parts of a cross-linking agent [triallyl isocyanurate, manufactured by Nippon Kasei Co., Ltd., TAIC].
This prepared liquid was added from the separating funnel to the flask maintained at a temperature of about 50° C. over 3 hours with stirring to carry out emulsion polymerization. Polymerization was completed by further aging for 5 hours to obtain an antibacterial particle dispersion (dispersion liquid) (particle 1).
The content of the methacrylic acid ester monomer was 50% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component was 36.2% by mass with respect to the total polymer components. . Also, the average particle size of the antibacterial particles was 56 nm.

(Example 2)
In Example 1 above, the amount of distilled water was 340.5 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, and the amount of n-butyl methacrylate was 45 parts. Propargyl compound: 3-iodo-2-propynylcarbamate, manufactured by Lonza (omacide IPBC 100)] 30 parts Antibacterial particle dispersion (dispersion) (Particle 2) in the same manner as in Example 1 ).
The content of the methacrylic acid ester monomer is 37.5% by mass based on the total polymer components constituting the antimicrobial particles, and the content of the antimicrobial component is based on the total polymer components.
It was 46.2% by mass. Also, the average particle size of the antibacterial particles was 73 nm.

(Example 3)
In Example 1 above, the amount of distilled water was 309.5 parts, the amount of cyclohexyl methacrylate monomer was 60 parts, and the amount of n-butyl methacrylate was 35 parts. , manufactured by Yokkaichi Gosei Co., Ltd.] was used in the same manner as in Example 1 to obtain an antibacterial particle dispersion (dispersion liquid) (particles 3).
The content of the methacrylic acid ester monomer is 35.1% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component is 37.8% by mass with respect to the total polymer components. there were. Also, the average particle size of the antibacterial particles was 85 nm.

(Example 4)
In Example 1 above, the amount of distilled water was 340.5 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, and the amount of n-butyl methacrylate was 45 parts. , manufactured by Ueno Pharmaceutical Co.] was used in the same manner as in Example 1 to obtain an antibacterial particle dispersion (dispersion liquid) (particles 4).
The content of the methacrylic acid ester monomer is 49.3% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component is 35.3% by mass with respect to the total polymer components. there were. Also, the average particle size of the antibacterial particles was 83 nm.

(Example 5)
In Example 1 above, the amount of distilled water was 340.5 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, and the amount of n-butyl methacrylate was 45 parts. Methylisothiazolinone/methylisothiazolinone (CMIT/MIT, manufactured by Daiwa Chemical Industry Co., Ltd.)] was used in the same manner as in Example 1 above, except that 15 parts of the antibacterial particle dispersion (dispersion liquid) (particles 5) was obtained. rice field.
The content of the methacrylic acid ester monomer is 33.2% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component is 38.9% by mass with respect to the total polymer components. there were. Also, the average particle size of the antibacterial particles was 78 nm.

(Example 6)
In Example 1 above, the amount of distilled water was 340.5 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, and the amount of n-butyl methacrylate was 45 parts. An antibacterial particle dispersion (dispersion liquid) (particles 6) was obtained in the same manner as in Example 1 except that 30 parts of isothiazolinone (BIT), manufactured by Daiwa Chemical Industry Co., Ltd. was used.
The content of the methacrylic acid ester monomer is 31.6% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component is 47.9% by mass with respect to the total polymer components. there were. Also, the average particle size of the antibacterial particles was 100 nm.

(Example 7)
In Example 1 above, the amount of distilled water was 340.5 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, and the amount of n-butyl methacrylate was 45 parts. An antibacterial particle dispersion (dispersion liquid) (particles 7) was obtained in the same manner as in Example 1 except that 25 parts of isothiazoline (MIT), manufactured by Daiwa Chemical Industry Co., Ltd. was used.
The content of the methacrylic acid ester monomer is 31.6% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component is 47.9% by mass with respect to the total polymer components. there were. Also, the average particle size of the antibacterial particles was 90 nm.

(Example 8)
In Example 1 above, the amount of distilled water was 340.0 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, and the amount of n-butyl methacrylate was 45 parts. , MOLDBAN-TZ, manufactured by Mitsui Bussan Chemicals Co., Ltd.] was used in the same manner as in Example 1 to obtain an antibacterial particle dispersion (dispersion liquid) (particles 8).
The content of the methacrylic acid ester monomer is 28.9% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component is 48.3% by mass with respect to the total polymer components. there were. Also, the average particle size of the antibacterial particles was 87 nm.

(Example 9)
In Example 1 above, the amount of distilled water was 345.0 parts, the amount of cyclohexyl methacrylate monomer was 45 parts, and the amount of n-butyl methacrylate was 30 parts. -bromo-2-nitropropane-1,3-diol, MOLDBAN-BNP, manufactured by Mitsui & Co. Chemicals Co., Ltd.] in the same manner as in Example 1 above, except that 30 parts of the antibacterial particle dispersion (dispersion liquid) was used. (Particle 8) was obtained.
The content of the methacrylic acid ester monomer is 29.3% by mass with respect to the total polymer components constituting the antibacterial particles, and the content of the antibacterial component is 45.1% by mass with respect to the total polymer components. there were. Also, the average particle size of the antibacterial particles was 98 nm.

(Comparative Examples 1 to 3)
The content of the antibacterial component before forming particles is 15% by mass without using each antibacterial particle for each of the antibacterial particle aqueous dispersions B, C, and D of Examples 2, 3, and 4. A prepared water dispersion containing each antibacterial component was used.

The obtained antibacterial particle aqueous dispersions of Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated for antibacterial effect (bacteria group, yeast, filamentous fungi) by the following evaluation method.
Each antibacterial particle dispersion (dispersion liquid) obtained in Examples 1 to 9 was used. The solid content of the antimicrobial particles in each of the antimicrobial particle dispersions obtained in Examples 1 to 7 was 35 to 40% by mass.
For each antibacterial particle aqueous dispersion obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the initial antibacterial effect (bacteria group, yeast, filamentous fungus) after 3 months at 40 ° C. was evaluated by the following evaluation method ) was evaluated.
These results are shown in Table 1 below.

[Test method for antibacterial effect (antibacterial and antifungal)]
The following microbiological test method in compliance with ISO 11930:2012 (Procedures for interpretation of data generated by preservative efficacy testing and/or microbiological risk assessment) was performed.
A challenge test was performed with the following three groups of bacteria, yeast, and filamentous fungi.
Bacterial group: Stapylococcus aureus NBRC13276, Escherichia coli NBRC3972
Yeast: Candida albicans NBRC1594
Filamentous Fungi: Aspergillus brasiliensis

<Preparation of inoculum solution>
Preparation of inoculum: Inoculum was prepared according to ISO 11930:2012.
Bacterial group: A bacterial solution was prepared according to ISO 11930:2012 for each bacterial species. Equal amounts of the bacterial solution adjusted to 1×10 ⁷ to 1×10 ⁸ cfu/ml for each bacterial species were mixed to prepare an inoculum solution.
Yeast: According to ISO 11930:2012, a bacterial solution was prepared so as to have a concentration of 1×10 ⁶ to 1×10 ⁷ cfu/ml.
Filamentous fungus: According to ISO 11930:2012, a fungal solution was prepared so as to have a concentration of 1×10 ⁶ to 1×10 ⁷ cfu/ml.

<Inoculation>
1% by mass of the fungus solution was inoculated to the antibacterial particle aqueous dispersion.
<storage>
The inoculated antibacterial particle aqueous dispersion was stored at a temperature of 22.5±2.5° C. and cultured for detection at specified intervals.
<Detection culture>
A total of 1 g was smeared on 10 sheets each of SCD agar medium for bacteria, SD agar medium for yeast, and PD agar medium for filamentous fungi. °C for 5 days.

<40°C, antibacterial effect after 3 months>
Each antibacterial particle aqueous dispersion of Examples 1 to 9 and each of the antibacterial particle aqueous dispersions of Comparative Examples 1 to 3 obtained were filled into a 60 ml polyethylene bottle with a lid and sealed. , and 40° C. for 3 months, the above-described antibacterial effects (antibacterial properties and antifungal properties) were evaluated for each aqueous dispersion, and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A-1: Colonies do not appear at the 7th day.
A-2: Colonies do not appear on the 21st day.
B-1: Several to several tens of colonies have appeared on the 28th day.
B-2: Clearly increasing as of the 28th.

Considering Table 1 above, Examples 1 to 9, which are within the scope of the present invention, show that bacteria, yeast, and filamentous fungi that are sources of contamination, etc. It has been found to have excellent antibacterial effects (including antifungal effects) against bacteria (Escherichia coli, Staphylococcus aureus), high safety, and excellent stability. Further, each antibacterial particle aqueous dispersion of Examples 1 to 9 was placed in a sealed container and stored at 26 ° C. for 3 months. It was found that there was no problem with storage stability.

[Examples 10 to 18 and Comparative Examples 4 to 6: Preparation of water-based ink compositions for writing instruments]
For Examples 10 to 18, the antibacterial particle dispersions obtained in Examples 1 to 9 above and the antibacterial particle dispersions of Comparative Examples 1 to 3 (IPBC, phenoxyethanol, paraben) were used as shown below. Each water-based ink composition for writing instruments was prepared according to the formulation composition (total amount: 100% by mass) by a conventional method.
Ink composition: (Total amount 100% by mass)
Each antibacterial particle dispersion (Examples 1 to 7), antibacterial dispersions of Comparative Examples 1 to 3 15.0% by mass
Colorant (carbon black MA100, manufactured by Mitsubishi Chemical Corporation) 5.4% by mass
pH adjuster (triethanolamine) 1.4% by mass
Water-soluble organic solvent (propylene glycol) 15.0% by mass
Ion-exchanged water 63.2% by mass

The obtained water-based ink composition for each writing instrument (total amount: 100% by mass) was evaluated for writing performance (difference in density of upper and lower drawn lines), stability, and antibacterial effect (antibacterial and antifungal properties) according to the following evaluation method. was evaluated.
The evaluation results of Examples 10 to 18 and Comparative Examples 4 to 6 are shown in Table 2 below.

(Writing instrument: production of ballpoint pen)
Using the shaft of a ballpoint pen [Mitsubishi Pencil Co., Ltd., product name: Signo UM-100], inner diameter 4.0 mm, length 113 mm Polypropylene ink storage tube and stainless steel tip (carbide ball, ball diameter 0.5 mm) ) and a refill consisting of a joint connecting the storage tube and the tip with each of the above water-based ink compositions, and an ink follower containing mineral oil as a main component was loaded at the trailing end of the ink to prepare a water-based ball-point pen.

[Evaluation method for writing performance (difference in density between upper and lower drawn lines)]
Each water-based ballpoint pen having the above configuration is left at room temperature (25 ° C., hereinafter the same) for 1 month, and then written until the end of the stroke, and the density difference between the start and end of writing is compared and evaluated according to the following evaluation criteria. bottom.
Evaluation criteria:
A: No density difference.
B: Some difference in density is recognized.
C: Density difference is clearly recognized.
D: The difference in density is remarkable, and there are places where it is difficult to visually recognize the drawn lines.

<Stability evaluation method>
Each ball-point pen having the above structure was stored at 50° C. for 3 months with the tip pointing downward, and then the state of each ink was visually observed and evaluated according to the following criteria.
Evaluation criteria:
A: Separation and aggregation did not occur.
B: Slight separation or aggregation.
C: There is separation or aggregation.
D: Significant separation or aggregation.

[Test method for antibacterial effect (antibacterial and antifungal)]
For the water-based ink compositions for writing instruments of Examples 10 to 18 and Comparative Examples 4 to 6, which are within the scope of the present invention, the antibacterial effects (antibacterial properties and antifungal properties) were tested using the antibacterial particle aqueous dispersion described above. (By inoculating 1% by mass of fungal solution with respect to the water-based ink composition for writing instruments).

Considering the above Table 2, Examples 10 to 18, which are within the scope of the present invention, are superior to Comparative Examples 4 to 6, which are outside the scope of the present invention, in writability (difference in density of upper and lower drawn lines) and stability. It was confirmed that the antibacterial properties are strong and durable, and that they do not adversely affect other ink ingredients.
In addition, it was confirmed that the ball-point pen produced as described above had a sufficient drawn line density without smudging, did not bleed, and formed a clear drawn line.

The antibacterial particle dispersion of the present invention can be used for detergent applications, personal care applications, industrial water treatment applications, food additives, electronic equipment applications, and water tank and medicinal bath applications as a water mold inhibitor for aquatic organisms (fish, etc.). It can be suitably used, and is also used as a compounding component of a water-based ink composition for writing instruments suitable for writing instruments such as felt-tip pens, marking pens and ballpoint pens.

Claims (6)

Antibacterial particles composed of at least a (meth)acrylic acid ester monomer represented by the following general formula (I) and at least one antibacterial component selected from Group A below are dispersed in water. An antimicrobial particle dispersion characterized by:

[In the above formula (I), A is a hydrogen atom (H) or a methyl group (CH ₃ ), and R is a hydrogen atom (H), an alkyl group having 1 to 22 carbon atoms, or the number of carbon atoms in the alkylene chain. represents a substituent having a polyalkylene glycol chain of 2 to 18, the alkyl group or a substituent having a polyalkylene glycol chain is a phenyl group, a benzyl group, an epoxy group, a hydroxyl group, a dialkylamino group, a carbon It may have an alkoxy group having 1 to 18 carbon atoms, a perfluoroalkyl group having 1 to 18 carbon atoms, or a trialkoxysilyl group. ]
Group A: iodopropargyl compound, thiabendazole, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, phenol, sodium benzoate, Sodium dehydroacetate, potassium sorbate, morpholine, cresol, methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, hexahydro-1,3,5-tris(2-hydroxyethyl)- 1,3,5-triazine, 2-bromo-2-nitropropane-1,3-diol, 2-pyridinethiol-1-oxide sodium, pyrithione sodium, 2-(4-thiozolyl)benzimidazole, 4-terpinenol, 1,8-cineol, thymol, diisothiocyanate, eucalyptus oil, longifolene, isopropylmethylphenol, 2-methyl-4-isothiazolin-3-one, citral, eugenol, allyl isothiocyanate, d-limonene, tannic acid, ethyl Paraben, benzalkonium chloride, glyceryl caprylate, glycerin fatty acid ester, chlorphenesin, salicylic acid, ethyl parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, methyl parahydroxybenzoate, bisabolol, hinokitiol, phenylethyl alcohol, phenethyl Alcohol, phenoxyethanol, butylparaben, propylparaben, benzalkonium chloride, methylparaben The content of the (meth)acrylic acid ester monomer represented by the general formula (I) is 30 to 95% by mass with respect to the total polymer components constituting the antimicrobial particle dispersion. 2. The antimicrobial particle dispersion according to 1. 3. The antibacterial particle dispersion according to claim 1, wherein the antibacterial component is contained in an amount of 1% by mass or more with respect to all polymer components constituting the antibacterial particles. The antibacterial particle dispersion according to any one of claims 1 to 3, wherein the antibacterial particles in the antibacterial particle dispersion have an average particle size of 10 to 800 nm. The antibacterial particle dispersion according to any one of claims 1 to 4, wherein the content of the antibacterial particles is 0.1 to 30% by mass with respect to the total amount of the antibacterial particle dispersion. body. An aqueous ink composition for writing instruments, comprising the antibacterial particle dispersion according to any one of claims 1 to 5.