JP2023063225A - Aromatic particle dispersion and aqueous ink composition for writing instrument containing the same - Google Patents

Abstract

To provide an aromatic particle dispersion which includes persistence (sustained-release) of aromatic property and antiseptic performance while highly achieving both of them, gives no adverse effect to the other formulation ingredient or the like, and is excellent in dispersion stability, and to provide an aqueous ink composition for a writing instrument containing the same.SOLUTION: An aromatic particle dispersion is such that aromatic particles which comprise at least a (meth)acrylic acid ester monomer represented by formula (I), at least one kind of a perfume component selected from the group A (for instance, borneol, eugenol, d-limonene, citral R or the like), and at least one kind of a preservative component selected from the group B (for instance, iodo propagyl compound, 2-(4-thiazolyl)benzimidazole or the like) are dispersed in water. [in the formula, A represents a hydrogen atom (H) or a methyl group (CH3), and R represents a hydrogen atom (H), a 1-22C alkyl group, or a substituent group having a polyalkylene glycol chain having a 2-18C alkylene chain.]SELECTED DRAWING: None

Description

The present invention has a highly compatible aromatic performance and antiseptic performance, is equipped with these persistence (sustained release), does not adversely affect other ingredients, etc., and has excellent dispersion stability. The present invention relates to a particle dispersion and an aqueous ink composition for writing instruments containing the same.

Conventionally, a wide variety of fragrant particles have been known, and various fragrant particles are known for each application such as hand washing detergents, laundry detergents, cosmetics, fragrances, and inks.

For example, in Patent Document 1, component (A): 0.01 to 1% by mass of encapsulated perfume and component (B): at least one builder selected from phosphates and carboxylic acid polymer compounds. 5 to 13.035% by mass, and (C) component: 0.1% by mass or more of clay minerals other than organophilic smectite clay, and the (A) component is polyacrylic acid ester, melamine-based high A capsule wall is formed by at least one selected from molecules and urethane-based polymers, and the average particle size of component (A) is 0.1 to 100 μm, and is represented by component (C)/component (A). A powder detergent for hand-washing clothes, characterized in that the mass ratio is 2 or more and less than 50, and the mass ratio represented by component (B)/component (A) is 1.5 to 251. is disclosed and
In addition, paragraph [0031] discloses that "additives such as antioxidants and preservatives can be blended as necessary."
Patent Document 2 describes an encapsulated fragrance and a neutral inorganic salt in which the fragrance is encapsulated with at least one polymer compound selected from the group consisting of a polyacrylic acid ester-based polymer, a melamine-based polymer, and a urethane-based polymer. is coated with a fatty acid salt, and the fatty acid salt has 10 to 18 carbon atoms in its carbon chain. Additives such as antioxidants and preservatives can be added depending on the conditions."

Furthermore, in Patent Document 3, a shell containing silica as a component, polymer fine particles containing a polymer of a diester of a diol compound and (meth)acrylic acid inside the shell, a perfume, a perfume precursor, an oil, an oxidizing a monofunctional monomer and a multifunctional monomer having a core containing at least one oil-soluble liquid selected from the group consisting of an inhibitor and a solvent, wherein the polymer fine particles are oil-soluble and have unsaturated double bonds. and crosslinked using the polyfunctional monomer, paragraph [0041] states, "The oil-soluble liquid is an antibacterial agent, an antiseptic, an antioxidant, an insecticidal component and an insect repellent It may be a component.", etc. are disclosed.
US Pat. No. 5,300,000 discloses a composition comprising spherical microparticles for use as a powder coating, said microparticles comprising a polymeric material and, in an amount of from about 0.01% to about 20% by weight of said microparticles, and one or more essential oil compounds incorporated therein, wherein said microparticles have an average particle size of about 0.01 micrometers to about 100 micrometers and a circularity of about 0.93 to about 0.999. wherein the essential oil compound is an organic compound that is liquid at room temperature, soluble in organic solvents, insoluble in water, and extractable from plants by steam distillation, dry distillation, or mechanical processing without heating and isomers thereof, and derivatives made by esterification, hydrogenation, or hydration, wherein said one or more essential oil compounds are syntronellal, citronellol, limonene, etc. is disclosed.

However, the capsule perfumes and perfume particles in which perfume ingredients are encapsulated with polyacrylic acid ester-based polymers and the like described in Patent Documents 1 to 4 above have aromatic performance, but there are problems with their persistence. In addition, the current situation is that there are not a few problems such as adversely affecting fragrance performance and other compounding ingredients and destabilizing dispersion stability when trying to add antiseptic performance. In addition, even when used in applications such as liquids such as inks, the current situation is that there are problems in the sustainability of the fragrance performance, the compatibility between the fragrance performance and the antiseptic performance, the dispersion stability, and the like.

Japanese Patent No. 6789344 (Claims, Examples, etc.) Japanese Patent No. 5593306 (Claims, Examples, etc.) Japanese Patent No. 6659019 (Claims, Examples, etc.) Japanese Patent Application Laid-Open No. 2020-142231 (Claims, Examples, etc.)

In view of the above-mentioned problems and current situation of the prior art, the present invention is intended to solve them, and while highly compatible with fragrance performance and antiseptic performance, it is equipped with these persistence (sustained release), and other It is an object of the present invention to provide an aromatic particle dispersion having excellent dispersion stability and an aqueous ink composition for writing utensils containing the aromatic particle dispersion which does not adversely affect the compounding components of (1).

In view of the above-described conventional problems, the present inventors have conducted intensive research and found that at least a (meth)acrylic acid ester monomer represented by a specific formula, a specific perfume component, and a specific preservative component The present inventors have found that the aromatic particle dispersion and the water-based ink composition for writing instruments containing the same can be obtained by, for example, forming a dispersion in which the constituent aromatic particles are dispersed in water. It was 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。〕
前記香料成分は下記Ａ群から選ばれる少なくとも１種であり、前記防腐成分は下記Ｂ群から選ばれる少なくとも1種であることが好ましい。
Ａ群： ボルネオール、オイゲノール、４－ターピネノール、１，８－シネオール、ｄ－リモネン、シトラールＲ、ゲラニオール、バニリン、２－フェニルエタノール、γ－デカラクトン、リナロール、Ｌ－ペリラアルデヒド、ラズベリーケトン、ＤＬ－カンフル、Ｌ－カルビルアセテート、アリオフィレン、Ｌ－シトロネロール、Ｄ－ジヒドロカルベオール、Ｌ－ジヒドロカルベオール、ジヒドロターピネオール、ジヒドロターピネオールアセテート、リナロールオキサイド、ミルテニルアセテート、アリルイソチオシアネート、Ｌ－カルベオール、カリオフィレンオキサイド、１，４－シネオール、ｐ－サイメン、Ｄ－ジヒドロカルボン、Ｌ－ジヒドロカルボン、Ｄ－ジヒドロカルビルアセテート、Ｌ－ジヒドロカルビルアセテート、エレメン、イソボルニルアセテート、Ｌ－リモネン、Ｄ－リモネンオキサイド、Ｌ－リモネンオキサイド、リナロールオキサイド、ｐ―メンタン、Ｌ－メントール、メントン－９０、ミルテナール、ミルテノール、３－オクチルアセテート、Ｌ－ペリリルアルコール、Ｌ－ペリリルアセテート、α－ピネン、β－ピネン、Ｄ－プレゴン、α－テルピネン、ターピネオールＣ、α－ターピネオール、Ｌ－α―ターピネオール、ターピネオール－４、ターピノーレン、α－ターピニルアセテート、ベルベノール、ベルベノン、３－カレン、カレンオキサイド、ヘキシルアセテート、ネロール、サフラン酸エチル、酢酸オイゲニル、チャビコール、エストラゴール、アネトール、マンザネート、γ－テルピネン、シメン、ミルセン、フェランドレン、ファルネセン、ツジェン
Ｂ群： ヨードプロパギル化合物、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、２－（４－チアゾリル）ベンズイミダゾール
前記香料成分は、芳香性粒子を構成する全ポリマー成分に対して、１質量％以上、前記防腐剤成分は、芳香性粒子を構成する全ポリマー成分に対して、０．１質量％以上であることが好ましい。
前記芳香性粒子の平均粒子径が１０～８００ｎｍであることが好ましい。
本発明の筆記具用水性インク組成物は、上記構成の芳香性粒子分散体を含むことを特徴とする。 That is, the aromatic particle dispersion of the present invention comprises at least a (meth)acrylic acid ester monomer represented by the following general formula (I), at least one perfume component, and at least one preservative component. It is characterized in that the constituent fragrant 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. ]
Preferably, the perfume component is at least one selected from Group A below, and the antiseptic component is at least one selected from Group B below.
Group A: borneol, eugenol, 4-terpineol, 1,8-cineol, d-limonene, citral R, geraniol, vanillin, 2-phenylethanol, γ-decalactone, linalool, L-perillaldehyde, raspberry ketone, DL-camphor, L-carbyl acetate, aryophylene, L-citronellol, D-dihydrocarveol, L-dihydrocarveol, dihydroterpineol, dihydroterpineol acetate, linalool oxide, myrtenyl acetate, allyl isothiocyanate, L-carveol, caryophyllene oxide, 1,4-cineol, p-cymene, D-dihydrocarvone, L-dihydrocarvone, D-dihydrocarbyl acetate, L-dihydrocarbyl acetate, element, isobornyl acetate, L-limonene, D-limonene oxide, L- Limonene oxide, linalool oxide, p-menthane, L-menthol, menthone-90, myrtenal, myrtenol, 3-octyl acetate, L-perylyl alcohol, L-perylyl acetate, α-pinene, β-pinene, D- pulegone, α-terpinene, terpineol C, α-terpineol, L-α-terpineol, terpineol-4, terpinolene, α-terpinyl acetate, verbenol, verbenone, 3-carene, carene oxide, hexyl acetate, nerol, saffronic acid Ethyl, eugenyl acetate, chavicol, estragole, anethole, manzanate, γ-terpinene, cymene, myrcene, phellandrene, farnesene, thujen Group B: iodopropargyl compounds, sodium pentachlorophenol, 1,2-benzisothiazoline-3- On, 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, p-hydroxybenzoic acid ester, phenol, sodium benzoate, sodium dehydroacetate, potassium sorbate, morpholine, cresol, methylisothiazolinone, chloromethyl isothiazolinone, 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, isopropyl Methylphenol, 2-methyl-4-isothiazolin-3-one, citral, eugenol, allyl isothiocyanate, 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, 2- (4-thiazolyl)benzimidazole The perfume component is 1% by mass or more with respect to all polymer components constituting the fragrant particles, and the preservative component is 0% with respect to all polymer components constituting the fragrant particles. .1% by mass or more is preferable.
It is preferable that the aromatic particles have an average particle size of 10 to 800 nm.
The water-based ink composition for writing instruments of the present invention is characterized by containing the aromatic particle dispersion having the above structure.

According to the present invention, while maintaining both aromatic performance and antiseptic performance at a high level, it has these sustainability (sustained release), does not adversely affect other compounding ingredients, etc., and is excellent in dispersion stability. An aromatic particle dispersion and an aqueous ink composition for writing instruments 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 aromatic particle dispersion of the present invention comprises at least a (meth)acrylic acid ester monomer represented by the following general formula (I), at least one perfume component, and at least It is characterized in that fragrant particles composed of one antiseptic component 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. ]

The (meth)acrylic acid ester monomer represented by the above general formula (I) used in the present invention has the strength of encapsulating perfume ingredients and preservative ingredients, and the ability to produce persistent and stable particles of these ingredients. It is used because it does not adversely affect other compounded ingredients, etc., and because its effects are long-lasting.
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-(meth)ethyl acrylate [2-(methacryloyloxy)ethyl phosphate], trialkoxy (meth)acrylate At least one of silylpropyl, dialkoxymethylsilylpropyl (meth)acrylate and the like (each alone or two or more, the same shall apply hereinafter) may be mentioned.
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 preferred.

In the present invention, in addition to the above (meth)acrylic acid ester monomer, it is preferable to use a hydrophobic vinyl monomer other than the above (meth)acrylic acid ester monomer from the viewpoint of obtaining a long-lasting aroma and antiseptic effect. , aqueous monomers 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.

Perfume ingredients used in the present invention include, for example, terpene-based perfume compounds, alcohol-based perfume compounds, hydrocarbon-based perfume compounds, phenol-based perfume compounds, ester-based perfume compounds, carbonate-based perfume compounds, aldehyde-based perfume compounds, ketones. at least one of fragrance ingredients such as fragrance compounds, acetal fragrance compounds, ether fragrance compounds, carboxylic acid fragrance compounds, lactone fragrance compounds, nitrile fragrance compounds, Schiff base fragrance compounds, natural essential oils, natural extracts, etc. is mentioned.
As used herein, "perfume compound" of each perfume means a single compound or a mixture of two or more compounds.

Examples of terpene-based fragrance compounds that can be used include monoterpene having 10 carbon atoms and derivatives thereof (including compounds having 10 or more carbon atoms). It is preferably one or more of esters. Here, the monoterpene is a fragrance compound composed of two isoprene units and having 10 carbon atoms, and includes a chain (acyclic) one and a cyclic one containing a ring. Furthermore, the terpene-based perfume in the present invention also includes terpene-based hydrocarbons, terpene-based alcohols, terpene-based esters, and terpene-based aldehydes.
The terpene fragrance to be used is not particularly limited as long as it is a fragrance compound having isoprene as a structural unit or a derivative thereof, and can be appropriately selected according to the purpose. , linear monoterpenes such as linalool, monocyclic monoterpenes such as limonene, menthane, terpinene, phellandrene, terpinolene, cymene, bicyclic monoterpenes such as α-pinene, β-pinene, camphene, carene, sabinene, and thujen Terpenes are mentioned.
Among these terpene-based fragrances, terpene-based hydrocarbons such as limonene, pinene, myrcene, carene, terpinene, and camphene; terpene-based alcohols such as geraniol, citronellol, linalool, nerol, and terpineol; linalyl acetate, terpinyl acetate, and geranyl acetate; Terpene esters such as , neryl acetate, citronellyl acetate and isobornyl acetate, and terpene aldehydes such as citronellal, citral, neral and perillaldehyde are preferable.

Alcohol-based fragrance compounds include aliphatic alcohols, terpene-based alcohols, aromatic alcohols, and other alcohols. Among these, aliphatic alcohols are preferred.
Examples of aromatic alcohol-based fragrance compounds include phenylethyl alcohol, benzyl alcohol, dimethylbenzyl carbinol, phenylethyl dimethyl carbinol, phenylhexanol and the like.
Aliphatic alcohol-based fragrance compounds include cis-3-hexenol, 1-(2,2,6-trimethylcyclohexyl)-3-hexanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopentene -1-yl)-2-buten-1-ol, ethylnorbornylcyclohexanol, 4-methyl-3-decen-5-ol, isobornylcyclohexanol.
Other alcohol-based fragrance compounds include glycols such as dipropylene glycol, 4-methyl-2-(2-methylpropyl)tetrahydro-2H-4-pyranol, and the like.
Phenolic perfume compounds include guaiacol, eugenol, dihydroeugenol, isoeugenol, thymol, paracresol, vanillin, ethyl vanillin and the like.

Ester-based fragrance compounds include aliphatic carboxylic acid esters, aromatic carboxylic acid esters, and other carboxylic acid esters.
Aliphatic carboxylic acids forming aliphatic carboxylic acid esters include linear and branched carboxylic acids having 1 to 18 carbon atoms, among which carboxylic acids having 1 to 6 carbon atoms such as formic acid, acetic acid and propionic acid. , especially acetic acid. Examples of aromatic carboxylic acids that form aromatic carboxylic acid esters include benzoic acid, anisic acid, phenylacetic acid, cinnamic acid, salicylic acid, and anthranilic acid. Alcohols that form aliphatic and aromatic esters include straight and branched chain aliphatic alcohols having 1 to 5 carbon atoms and the perfume ingredient alcohols described above.
Formic acid esters include linalyl formate, citronellyl formate, geranyl formate and the like.
Acetates include ethyl acetate, isoamyl acetate (isopentyl acetate), benzyl acetate, hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyr acetate, bornyl acetate, isobornyl acetate, acetyl eugenol, acetyl isoeugenol, o-tert-butylcyclohexyl acetate, p-tert-butyl cyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, phenylethyl acetate, styraryl acetate, cinnamyl acetate, dimethylbenzylcarbylacetate, phenylethylphenylacetate, 3-pentyltetrahydropyran-4-ylacetate, paracresylphenylacetate and the like;
Propionate esters include citronellyl propionate, tricyclodecenyl propionate, allylcyclohexyl propionate, ethyl 2-cyclohexyl propionate, benzyl propionate, styraryl propionate and the like.
Examples of butyric acid esters include citronellyl butyrate, dimethylbenzylcarbinyl n-butyrate, tricyclodecenyl isobutyrate and the like. Valerate esters include methyl valerate, ethyl valerate, butyl valerate, amyl valerate, benzyl valerate, phenylethyl valerate, etc.; hexanoate esters include methylhexanoate, ethylhexanoate, allylhexa noate, linalyl hexanoate, citronellyl hexanoate and the like. Examples of heptanoic acid esters include methylheptanoate and allylheptanoate. Nonenoic acid esters include methyl 2-nonenoate, ethyl 2-nonenoate, ethyl 3-nonenoate and the like.

Benzoates include methyl benzoate, benzyl benzoate, 3,6-dimethyl benzoate and the like. Cinnamic acid esters include methyl cinnamate, benzyl cinnamate and the like. Salicylates include methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, cyclohexyl salicylate, benzyl salicylate and the like. Furthermore, brassylate esters include ethylene brassylate and the like. Tiglic acid esters include geranyl tiglate, 1-hexyl tiglate, cis-3-hexenyl tiglate and the like. Jasmonates include methyl jasmonate, methyl dihydrojasmonate and the like. Glycidates include methyl 2,4-dihydroxy-ethylmethylphenylglycidate, 4-methylphenylethylglycidate, and the like. Anthranilate includes methyl anthranilate, ethyl anthranilate, dimethyl anthranilate and the like. Glycolic acid esters include allyl cyclohexyl glycolate and the like. Still other esters include ethyl dihydrocyclogelate, ethyl-2-cyclohexylpropionate, ethyltricyclo[5.2.1.02.6]decane-2-carboxylate, methyl jasmonate, dihydrojasmonic acid. methyl, methyl(2-pentyl-3-oxocyclopentyl)acetate and the like.

Carbonate-based perfume compounds include cis-3-hexenylmethyl carbonate, methyl-cyclooctyl carbonate, ethyl-2-t-butylcyclohexyl carbonate and the like.
Aldehyde fragrance compounds include n-octanal, n-nonanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, 2,4- dimethyl-3-cyclohexene-1-carboxaldehyde, dimethyl-3-cyclohexenyl-1-carboxaldehyde, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, cinnamic aldehyde, dimethyltetrahydrobenzaldehyde, 3-(4-tert-butylphenyl) propanal, hydroxymyracaldehyde, 2-cyclohexylpropanal, p-tert-butyl-α-methylhydrocinnamic aldehyde, p-isopropyl-α-methylhydrocinnamic aldehyde, 3-(o-(and p-) ethylphenyl)-2,2-dimethylpropionaldehyde, α-amyl cinnamic aldehyde, α-hexyl cinnamic aldehyde, heliotropine, alpha-methyl-1,3-benzodioxol-5-propanal, 2-methyl -3-(paramethoxyphenyl)propanal and the like.

Ketone fragrance compounds include methylheptenone, dimethyloctenone, 3-octanone, hexylcyclopentanone, dihydrojasmon, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-(2-(4-methyl- 3-cyclohexen-1-yl)propyl)cyclopentanone, ionone, β-ionone, methylionone, methylionone-G, γ-methylionone, damascone, α-damascone, β-damascone, δ-damascone, 1-(2,4 ,4-trimethyl-2-cyclohexyl)-trans-2-butanone, damascenone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, iron, 1,2, 3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one, 1-(1,2,3,4,5,6,7,8-octahydro -2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one, 7-methyl-3,4-dihydro-2H-benzodioxepin-3-one, carvone, menthone, acetylse drain, isolongifolanone, nootkatone, benzylacetone, raspberry ketone, benzophenone, 6-acetyl-1,1,2,4,4,7-hexamethyltetrahydronaphthalene, β-methylnaphthyl ketone, ethyl maltol, camphor, muscone, 3-methyl-5-cyclopentadecen-1-one, civetone, 8-cyclohexadecenone, methyl nonyl ketone, cis-jasmone, p-amylcyclohexanone (4-pentylcyclohexanone) and the like.

Acetals include acetaldehyde ethyl phenyl propyl acetal, citral diethyl acetal, phenyl acetaldehyde glyceryl acetal, ethyl acetoacetate ethylene glycol acetal and the like.
Ethers include ethyl linalool, cedryl methyl ether, estragole, anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, nerol oxide, 1,8-cineole, rosefuran, [ 3aR-(3aα,5aβ,9aα,9bβ)]dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan, 3,3,5-trimethylcyclohexylethyl ether, hexamethylhexahydrocyclocyclo Examples include pentabenzopyran, phenylacetaldehyde dimethylacetal, and the like.

Carboxylic acid fragrance compounds include benzoic acid, phenylacetic acid, cinnamic acid, hydrocinnamic acid, butyric acid, 2-hexenoic acid and the like.
Lactone fragrance compounds include ambrettolide, γ-decalactone, δ-decalactone, γ-valerolactone, γ-nonalactone, γ-undecalactone, δ-hexalactone, γ-jasmolactone, whiskey lactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, 11-oxahexadecanolide, butylidenephthalide and the like.
Nitrile fragrance compounds include tridecene-2-nitrile, geranyl nitrile, citronellyl nitrile, dodecane nitrile and the like.
Examples of Schiff base fragrance compounds include aurantiol and ligandral.
Natural essential oils and extracts include orange, lemon, lime, bergamot, vanilla, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, rockrose, geranium, jasmine, ylang-ylang, Anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, lemongrass, labdanum, grapefruit, elemi oil and the like.

Among these perfume ingredients, more preferably, those that have a strong lingering fragrance strength and do not adversely affect the contained preservative ingredients, and at least one selected from the following group A in terms of ease of production, etc. is desirable.
Group A: borneol, eugenol, 4-terpineol, 1,8-cineol, d-limonene, citral R, geraniol, vanillin, 2-phenylethanol, γ-decalactone, linalool, L-perillaldehyde, raspberry ketone, DL-camphor, L-carbyl acetate, aryophylene, L-citronellol, D-dihydrocarveol, L-dihydrocarveol, dihydroterpineol, dihydroterpineol acetate, linalool oxide, myrtenyl acetate, allyl isothiocyanate, L-carveol, caryophyllene oxide, 1,4-cineol, p-cymene, D-dihydrocarvone, L-dihydrocarvone, D-dihydrocarbyl acetate, L-dihydrocarbyl acetate, element, isobornyl acetate, L-limonene, D-limonene oxide, L- Limonene oxide, linalool oxide, p-menthane, L-menthol, menthone-90, myrtenal, myrtenol, 3-octyl acetate, L-perylyl alcohol, L-perylyl acetate, α-pinene, β-pinene, D- pulegone, α-terpinene, terpineol C, α-terpineol, L-α-terpineol, terpineol-4, terpinolene, α-terpinyl acetate, verbenol, verbenone, 3-carene, carene oxide, hexyl acetate, nerol, saffronic acid Ethyl, eugenyl acetate, chavicol, estragole, anethole, manzanate, γ-terpinene, cymene, myrcene, phellandrene, farnesene, thujen Fragrant ingredients of Group A may contain a perfumery acceptable solvent. . Solvents are used in the fragrance industry to dilute olfactory-potent ingredients, dissolve solid ingredients, facilitate handling of solid ingredients by treating them as liquids, or simply reduce the overall fragrance cost per unit mass. It is customarily used as a diluent to reduce Typically, suitable solvents are water-soluble solvents such as glycols, including propylene glycol, dipropylene glycol, and butylene glycol, and solvents that are immiscible with water, eg, solvents with a water solubility of less than 10 g/L. Examples of perfumingly acceptable solvents are water-insoluble carbohydrate solvents (e.g. the Isopar® family from ExxonMobil), benzyl benzoate, isopropyl myristate, benzyl salicylate, dialkyl adipates, citrate esters (e.g. , acetyltriethyl citrate and acetyltributyl citrate) and diethyl phthalate, hydrogenated rosin methyl ester. If present, water-miscible solvents (eg, water-soluble solvents greater than 10 g/100 mL) such as propylene glycol, dipropylene glycol, and butylene glycol should be added at the lowest possible concentration.

Among the above group A, particularly preferred perfume ingredients include borneol, eugenol, 4-terpineol, 1,8-cineol, D- Limonene, citral, geraniol, vanillin, 2-phenylethanol, γ-decalactone, linalool, L-perillaldehyde, DL-camphor, L-carbyl acetate, aryophylene, L-citronellol, linalool oxide, myrtenyl acetate, allyl iso Thiocyanate, 1,4-cineol, isobornyl acetate, D-limonene, linalool oxide, L-menthol, 3-octyl acetate, L-perylyl alcohol, L-perylyl acetate, α-pinene, β-pinene, α - terpinene, terpineol-4, nerol, ethyl saffronate, eugenyl acetate, chavicol, estragole, anethole, manzanate, γ-terpinene, cymene, myrcene, phellandrene, farnesene, and thujene are preferable, and encapsulation into aromatic particles is preferred. For ease of use, it is desirable that the solubility in water is 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less.

The fragrance component of Group A may be either a natural fragrance or a synthetic fragrance, or a mixture thereof. Furthermore, in addition to the above group A, for example, perfume ingredients described in "Synthetic Perfume Chemistry and Product Knowledge" (written by Genichi Indo, Kagaku Kogyo Nippo Co., Ltd.) can also be included within a range that does not impair the effects of the present invention.

The antiseptic component used in the present invention includes, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloarylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8- Oxyquinoline, benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organic tin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate , brominated indanone-based compounds, benzylbromoacetate-based compounds, inorganic salt-based compounds, and the like.
Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include 2-pyridinethiol-1-oxide sodium, and specific examples of isothiazoline compounds. is, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like.
Among these antiseptic components, those that do not adversely affect the contained fragrance components and those that are excellent in long-term antiseptic components are used, preferably at least selected from the following group B One type is desirable.
Group B: iodopropargyl compound, pentachlorophenol sodium, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, paraoxybenzoic acid ester, phenol, benzoin sodium acetate, sodium dehydroacetate, potassium sorbate, morpholine, cresol, methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, hexahydro-1,3,5-tris(2-hydroxy ethyl)-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, allyl isothiocyanate, d-limonene, tannin 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, 2-(4-thiazolyl)benzimidazole

Among the above group B, more preferable antiseptic components include iodopropargyl compounds and 1,2-benzoin from the viewpoints of stability over time, relatively easy availability and low cost, and safety. Isothiazolin-3-one, 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, sodium benzoate, sodium dehydroacetate, potassium sorbate, cresol, methylisothiazolinone, chloromethylisothiazolinone, octyl isothiazolinone, 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, diisothiocyanate, isopropylmethylphenol, 2-methyl-4-isothiazoline-3- On, citral, eugenol, allyl isothiocyanate, D-limonene, tannic acid, ethylparaben, benzalkonium chloride, glycerin fatty acid ester, salicylic acid, ethyl parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, methyl parahydroxybenzoate , hinokitiol, phenylethyl alcohol, phenethyl alcohol, phenoxyethanol, butylparaben, propylparaben, benzalkonium chloride, methylparaben, and 2-(4-thiazolyl)benzimidazole.

The aromatic particle dispersion of the present invention comprises at least a (meth)acrylic acid ester monomer represented by the above general formula (I), at least one selected from the above perfume components, and at least one selected from the above preservative components. The method for producing it is, 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 Dissolving the perfume component, preferably the perfume component of Group A, and the preservative component, preferably the preservative component of Group B, in mixed monomers containing other hydrophobic vinyl monomers and/or aqueous monomers, Ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. are used as polymerization initiators, and polymerization initiators further combined with reducing agents are used. Cross-linking agents such as erythritol acrylate, ditrimethylolpropane acrylate, dipentaerythritol acrylate, methoxylated bisphenol A methacrylate, pentaerythritol methacrylate, ditrimethylolpropane methacrylate, dipentaerythritol methacrylate, ethoxylated polyglycerol methacrylate, and optionally poly Oxyethylene-1-(allyloxymethyl)-alkyl ether ammonium sulfate, ether sulfate, polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate, polyoxyethylene nonylpropenyl phenyl ether, ammonium polyacrylate, styrene-maleic acid copolymer ammonium, polyoxyethylene Alkyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene decyl ether, polyoxyethylene tridecyl ether, alkyl benzene sulfonate, dioctyl sulfosuccinate, sodium lauryl sulfate, polyoxyethylene alkyl Ether phosphate, polyoxyethylene styrenated phenyl ether phosphate, polyoxyethylene styrenated phenyl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene sorbitan monolaurate (polysorbate 20), polyoxyethylene palmitate Production by emulsion polymerization using a polymerizable surfactant (emulsifier) such as sorbitan (polysorbate 40), polyoxyethylene sorbitan monostearate (polysorbate 60), polyoxyethylene sorbitan oleate (polysorbate 80) After being produced as a dispersion liquid of the aromatic particle dispersion, it can be made into aromatic particles by drying or the like.
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 aromatic 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 not easily impaired even if the water in the dispersion is volatilized, and the aromatic particle dispersion has excellent stability. A dispersion of solids and an aromatic particle dispersion are obtained.
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 aromatic particle dispersion, the content of the (meth)acrylic acid ester monomer is 30% by mass with respect to the total polymer components constituting the aromatic 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 aromatic particle dispersion, specifically, the (meth)acrylic acid ester monomer used, 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 aromatic particle dispersion, the content of monomer components other than the (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 perfume component is 1 mass with respect to all polymer components from the viewpoints of obtaining sufficient fragrance performance, obtaining a persistent scent effect, and stability. % 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 fragrance component to 1% by mass or more, it is possible to exhibit sufficient fragrance performance and a persistent scent effect. Performance is not sufficient, and the effects of the present invention cannot be exhibited.

In addition, the (solid content) content of the antiseptic component is 0.1 with respect to the total polymer component from the viewpoints of obtaining sufficient antiseptic performance, obtaining a sustained antiseptic effect, and stability. % by mass or more, preferably 0.5% by mass or more, more preferably 1 to 40% by mass, particularly preferably 3 to 30% by mass.
By setting the content of the antiseptic component to 0.1% by mass or more, sufficient antiseptic performance and sustained antiseptic effect can be exhibited, while the content of the antiseptic component is 0.1% by mass. If it is less than that, antiseptic performance will be insufficient and the effects of the present invention will not 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 the (meth) acrylic acid ester monomer, at least one perfume component selected from the above group A and at least one selected from the above group B By dissolving the preservative component and emulsion polymerization, or at least by dissolving the perfume component and the preservative component after polymerization of the mixed monomer containing the (meth)acrylic acid ester monomer and other monomer components. Emulsion polymerization gives an aromatic particle dispersion (dispersion liquid) in which the aromatic particles are dispersed in water. The production amount of the aromatic particles in the aromatic particle dispersion obtained under these production conditions varies depending on the above-mentioned (meth)acrylic acid ester monomer, the amount of the perfume component and the preservative component, and the polymerization conditions. From the standpoint of manufacturability, workability, efficiency, etc., it is preferable to produce the solid content of 1 to 50% by mass. More preferably, it is produced so that the solid content is 10 to 40% by mass.

In the present invention, the average particle size of the aromatic particle dispersion to be obtained varies depending on the (meth)acrylic acid ester monomer, other monomer species used, content, polymerization conditions during polymerization, etc. , 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 becomes excellent in storage stability and the like, and when used for water-based ink for writing instruments, clogging occurs in the pen core of writing instruments such as felt-tip pens, marking pens, and ballpoint pens. Furthermore, it becomes 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 aromatic particle dispersion of the present invention, the content of the aromatic particles contained in the dispersion is preferably 0.1 to 50% by mass in terms of solid content, more preferably 0.1 to 50% by mass, depending on the above applications. is preferably 1 to 30% by mass.
If the content of the aromatic particles is less than 0.1% by mass in terms of solid content, the effect of the present invention cannot be exhibited. It will be.

As described above, the aromatic particle dispersion (dispersion) of the present invention configured in this way achieves both aromatic performance and antiseptic performance at a higher level than those using the above perfume component or preservative component alone. , It has these sustainability (sustained release), does not adversely affect other ingredients, etc., and is excellent in dispersion stability (This point will be further described in the production examples, examples, etc. (detailed in).
Since the aromatic particle dispersion (dispersion) of the present invention exhibits excellent effects as described above, it can be used, for example, in medical devices, baby products, nursing care products, bath products, kitchen products, tableware, and drinking water piping parts. , sanitary products, household appliances, clothing, construction materials, agricultural materials, automobile interior parts, stationery, ink compositions for writing instruments and inkjet printers, etc. can be used. When the aromatic particle dispersion (dispersion) of the present invention is used by filling it in a plastic container, it is preferable to use the above aromatic component or preservative component alone over time. Since it is possible to suppress the adsorption of the antiseptic component and the antiseptic component, it is possible to exhibit the effect over a long period of time.
Furthermore, the aromatic particle dispersion (dispersion) of the present invention may be used by kneading, impregnating, or applying to coloring materials such as wood, paper, plastic resin, rubber, and pigments.
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, Face care products such as creams, sunscreens, foundations, and eye makeup products; body care products such as hair care products; antiperspirants; oral care products such as toothpaste; Care of cloth products, sanitary products, pet products, space fragrance products, stationery items such as stationery, erasers, pencils and solid writing instruments, paints, air conditioning home appliances (household appliances) such as humidifiers, paints, adhesives, building materials , resin emulsions, wood preservatives, cement admixtures, boilers, cooling equipment, wastewater treatment equipment, industrial water treatment applications such as industrial water (papermaking process water in the papermaking process, cooling water and washing water for various industrial uses); medical equipment , a food additive, and a water mold suppressant for water tanks and medicated baths.

Furthermore, the form and the like when the aromatic particle dispersion (dispersion liquid) of the present invention is used in a water-based ink composition for writing instruments such as felt-tip pens, marking pens and ball-point pens will be described in detail below.
The water-based ink composition for writing instruments of the present invention is characterized by containing at least the aromatic particle dispersion having the above constitution, and in addition to the aromatic particle dispersion, a colorant and a water-soluble organic solvent can contain.
The content of the aromatic 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, from the viewpoint of exhibiting the effects of the present invention without impairing the writing performance, and from the viewpoint 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-pigment) or the like dyed with 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 prepared by appropriately combining the particles having the above properties, the water-soluble solvent, and other components according to the application of the ink for writing instruments (for ballpoint pens, marking pens, etc.) and using a homomixer or homogenizer. Alternatively, the aqueous ink composition for writing instruments can be prepared by stirring and mixing with a stirrer such as a disper and, if necessary, removing coarse particles in the ink composition by filtration or centrifugation.

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 aromatic particle dispersion having the above-described characteristics to be used is blended in the water-based ink composition for writing instruments, the aromatic content in the ink composition is reduced. While maintaining both performance and antiseptic performance at a high level, it has these sustainability (sustained release properties), does not adversely affect other ink ingredients, etc., and is excellent in dispersion stability, so it has excellent fragrance performance and antiseptic performance. These particles maintain their performance and lasting effects for a long period of time, and these particles do not impair storage stability or writing performance, so they can further increase the degree of freedom in ink design, making them suitable for writing instruments such as ballpoint pens and marking pens. A water-based ink composition for writing instruments is thus obtained.

EXAMPLES Next, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples and the like.
[Production Examples 1 to 13: Production of aromatic particle dispersions (particles 1 to 13)]
Each aromatic particle dispersion was produced according to Production Examples 1 to 11 below. In addition, the following "parts" represent mass parts. Fragrance and preservative components are solids amounts.

(Production 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 50 parts of cyclohexyl methacrylate monomer and 20 parts of n-butyl methacrylate, 17 parts of aromatic component (d-limonene, manufactured by Nippon Terpene Chemical Co., Ltd.), preservative component (phenoxyethanol, manufactured by Yokkaichi Gosei Co., Ltd.) ) and 10 parts of a cross-linking agent [triallyl isocyanurate, manufactured by Nippon Kasei Co., Ltd., TAIC] were mixed to prepare a solution.
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 aromatic particle dispersion (dispersion liquid) (particle 1).
The content of the methacrylic acid ester monomer is 60% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 25% by mass based on the total polymer components, and the preservative component The content was 15% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 91 nm.

(Production example 2)
In Production Example 1 above, the amount of distilled water was 310 parts, the amount of cyclohexyl methacrylate monomer was 53 parts, the amount of n-butyl methacrylate was 17 parts, and 2-phenylethanol (2-phenyl ethyl alcohol), manufactured by Inoue Perfumery Co., Ltd., 20 parts, and benzisothiazolinone (BIT), manufactured by Daiwa Chemical Industry Co., Ltd., 2 parts as a preservative component. An organic particle dispersion (dispersion liquid) (particles 2) was obtained.
The content of the methacrylic acid ester monomer is 55% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 30% by mass based on the total polymer components, and the preservative component The content was 15% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 80 nm.

(Production example 3)
In Production Example 1 above, 300 parts of distilled water, 55 parts of cyclohexyl methacrylate monomer, 15 parts of n-butyl methacrylate, and 20 parts of CITRAL manufactured by Kuraray Co., Ltd. An aromatic particle dispersion (dispersion) (particles 3) was obtained in the same manner as in Production Example 1, except that 2 parts of methylisothiazoline (MIT) manufactured by Daiwa Chemical Industry Co., Ltd. was used as the preservative component.
The content of the methacrylic acid ester monomer is 55% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 40% by mass based on the total polymer components, and the preservative component The content was 5% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 98 nm.

(Production example 4)
In Production Example 1 above, the amount of distilled water was 310 parts, the amount of cyclohexyl methacrylate monomer was 50 parts, and the amount of n-butyl methacrylate was 20 parts. Fragrant particles in the same manner as in Production Example 1, except that 30 parts manufactured by Seisakusho Co., Ltd. and 12 parts of chloromethylisothiazolinone/methylisothiazolinone (CMIT/MIT) manufactured by Daiwa Chemical Industry Co., Ltd. were used as preservative components. A dispersion (dispersion liquid) (particles 4) was obtained.
The content of the methacrylic acid ester monomer is 60% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 28% by mass based on the total polymer components, and the preservative component The content was 12% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 78 nm.

(Production example 5)
In the above production example 1, the amount of distilled water was 295 parts, the amount of cyclohexyl methacrylate monomer was 45 parts, the amount of n-butyl methacrylate was 25 parts, and the aromatic component was eugenol, manufactured by Nippon Terpene Chemical Co., Ltd. 26 Aromatic particle dispersion (dispersion liquid) (Particles 5) was obtained in the same manner as in Production Example 1 except that 14 parts of paraben manufactured by Ueno Pharmaceutical Co., Ltd. was used as the antiseptic component.
The content of the methacrylic acid ester monomer is 50% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 36% by mass based on the total polymer components, and the preservative component The content was 14% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 101 nm.

(Production example 6)
In Production Example 1 above, the amount of distilled water was 310 parts, the amount of cyclohexyl methacrylate monomer was 50 parts, and the amount of n-butyl methacrylate was 30 parts. Co., Ltd. 35 parts, iodopropargyl compound: 3-iodo-2-propynyl carbamate, Lonza Co. (omacide IPBC 100), 10 parts as a preservative component. A particle dispersion (dispersion liquid) (particles 6) was obtained.
The content of the methacrylic acid ester monomer is 52% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 43% by mass based on the total polymer components, and the preservative component The content was 5% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 94 nm.

(Production Example 7)
In Production Example 1 above, the amount of distilled water was 300 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, the amount of n-butyl methacrylate was 45 parts, and 1,8-cineol and Japanese terpene were used as aromatic components. An aromatic particle dispersion (dispersion liquid) (Particles 7) was obtained in the same manner as in Production Example 1 above, except that 25 parts of Kagaku Co., Ltd. was used as the preservative component.
The content of the methacrylic acid ester monomer is 50% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 40% by mass based on the total polymer components, and the preservative component The content was 10% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 76 nm.

(Production Example 8)
In the above production example 1, the amount of distilled water was 300 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, the amount of n-butyl methacrylate was 45 parts, and 25 parts of γ-terpinene was used as the aromatic component. An aromatic particle dispersion (dispersion liquid) (particles 8) was obtained in the same manner as in Production Example 1 above, except that 5 parts of methylisothiazoline (MIT) manufactured by Daiwa Chemical Industry Co., Ltd. was used as the agent component.
The content of the methacrylic acid ester monomer is 50% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 42% by mass based on the total polymer components, and the preservative component. The content was 8% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 88 nm.

(Production Example 9)
In Production Example 1 above, the amount of distilled water was 300 parts, the amount of cyclohexyl methacrylate monomer was 30 parts, the amount of n-butyl methacrylate was 45 parts, and 25 parts of cymene was used as an aromatic component, and a preservative component. An aromatic particle dispersion (dispersion liquid) (particles 9) was obtained in the same manner as in Production Example 1 above, except that 5 parts of methylisothiazoline (MIT) manufactured by Daiwa Chemical Industry Co., Ltd. was used as the aromatic particle dispersion.
The content of the methacrylic acid ester monomer is 45% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 45% by mass based on the total polymer components, and the preservative component The content was 10% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 101 nm.

(Production Example 10)
In Production Example 1 above, the amount of distilled water was 300 parts, the amount of cyclohexyl methacrylate monomer was 35 parts, the amount of n-butyl methacrylate was 40 parts, and 25 parts of myrcene as an aromatic component and a preservative component. As an iodopropargyl compound: 3-iodo-2-propynylcarbamate, manufactured by Lonza (omacide IPBC 100), except that 10 parts were used, in the same manner as in Production Example 1 above, to prepare an aromatic particle dispersion (dispersion) ( Particles 10) were obtained.
The content of the methacrylic acid ester monomer is 56% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 38% by mass based on the total polymer components, and the preservative component The content was 6% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 95 nm.

(Production Example 11)
In Production Example 1 above, the amount of distilled water was 300 parts, the amount of cyclohexyl methacrylate monomer was 35 parts, the amount of n-butyl methacrylate was 40 parts, and 25 parts of phellandrene was used as an aromatic component, and a preservative. Iodopropargyl compound: 3-iodo-2-propynyl carbamate, manufactured by Lonza (omacide IPBC 100), as a component, in the same manner as in Production Example 1 above, except that 10 parts was used to prepare an aromatic particle dispersion (dispersion liquid). (Particle 11) was obtained.
The content of the methacrylic acid ester monomer is 56% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 35% by mass based on the total polymer components, and the preservative component The content was 9% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 100 nm.

(Production Example 12)
In Production Example 1 above, the amount of distilled water was 300 parts, the amount of cyclohexyl methacrylate monomer was 45 parts, the amount of n-butyl methacrylate was 30 parts, and farnesene was 25 parts as an aromatic component, and a preservative component. An aromatic particle dispersion (dispersion liquid) (particles 12) was obtained in the same manner as in Production Example 1 above, except that 10 parts of paraben manufactured by Ueno Pharmaceutical Co., Ltd. was used as the agent.
The content of the methacrylic acid ester monomer is 59% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 35% by mass based on the total polymer components, and the preservative component The content was 6% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 95 nm.

(Production Example 13)
In Production Example 1 above, the amount of distilled water was 300 parts, the amount of cyclohexyl methacrylate monomer was 45 parts, the amount of n-butyl methacrylate was 30 parts, and 25 parts of thujen was used as the aromatic component, and the antiseptic component. An aromatic particle dispersion (dispersion liquid) (particles 13) was obtained in the same manner as in Production Example 1 above, except that 10 parts of paraben manufactured by Ueno Pharmaceutical Co., Ltd. was used as the aromatic particle dispersion.
The content of the methacrylic acid ester monomer is 57% by mass based on the total polymer components constituting the aromatic particles, the content of the aromatic component is 35% by mass based on the total polymer components, and the content of the preservative component is 57% by mass. The content was 8% by mass with respect to all polymer components. Also, the average particle size of the aromatic particles was 98 nm.

Each aromatic particle dispersion (dispersion liquid) obtained in Production Examples 1 to 13 was obtained. The solid content of the aromatic particles in each of the aromatic particle dispersions obtained in Production Examples 1-13 was 35-40% by mass.
Using the aromatic particle dispersions (dispersions) of Production Examples 1 to 13 obtained above, lingering fragrance strength, dispersion stability, and antiseptic performance were evaluated by the following evaluation methods.
As a reference example, a dispersion obtained by mixing an aromatic component and an antiseptic component having a solid content similar to that of Production Example 1 was used for comparison.
These results are shown in Table 1 below.

(Evaluation method for residual scent intensity)
The aromatic particle dispersions (dispersions) of Production Examples 1 to 13 obtained above were diluted in a beaker so that the solid content was 40% by mass, and cotton cloth (100% cotton, size 50 x 100 mm) was placed there. was immersed, stirred by hand 30 times, and left for 15 minutes.
Next, the moisture on the cotton cloth was squeezed out by hand and dried under constant temperature and humidity conditions of 25° C. and 35% RH for 3 weeks to obtain a treated cloth for evaluation.
Sensory evaluation of the lingering scent intensity was carried out according to the following evaluation criteria for the scent felt from each cotton cloth thus obtained.
<Lingering scent strength>
Five evaluators evaluated the lingering scent strength of the treated cloth for evaluation treated by the above method according to the following criteria. The evaluation results of five persons are shown in Table 1 below.
(Evaluation criteria for residual scent intensity)
A: Perceives strong lingering scent B: Perceives weak lingering scent C: Does not perceive lingering scent

(Method for evaluating dispersion stability)
Using the aromatic particle dispersions (dispersions) of Production Examples 1 to 13 obtained above, 50 ml of each of the aromatic particle aqueous dispersions obtained is placed in a 100 ml highly transparent plastic bottle made of PP with a lid. After filling and sealing, the container was stored at 40° C. for 1 month with the cap facing upward, and then the dispersion stability was evaluated according to the following evaluation criteria.
Evaluation criteria:
A: No separation of the dispersion liquid was observed, and there was no sediment at the bottom, which was good.
B: Slight separation is observed in the dispersion liquid, and a slight sediment can be confirmed at the bottom.
C: Remarkable separation is observed in the dispersion liquid, and a large amount of sediment can be confirmed at the bottom.

(Test method for antiseptic performance (antibacterial and antifungal properties))
Using the aromatic particle dispersions (dispersions) of Production Examples 1 to 13 obtained above, ISO 11930:2012 (preservative efficacy test or microbiological risk assessment, or interpretation of data generated by both The following microbial test method was performed in accordance with the procedure for
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>
The aromatic particle dispersion was inoculated with 1% by mass of the bacterial solution. <Storage> The inoculated aromatic particle 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.
<Evaluation criteria>
A: Colonies do not appear at the 7th day.
B: Colonies do not appear at the 21st day.
C: Several to several tens of colonies have appeared on the 28th day.
D: Clearly increasing as of the 28th.

As is clear from the results in Table 1 above, the aromatic particle dispersions (dispersions) of Production Examples 1 to 13 obtained above are excellent in residual fragrance strength, dispersion stability, and antiseptic performance compared to Reference Examples. It turned out that there is In addition, although not shown in Table 1, in Production Examples 2 to 13 for comparison, each dispersion was prepared by mixing an aromatic component and a preservative component that had the same solid content as in Reference Example. Then, each dispersion was evaluated for lingering fragrance strength, dispersion stability, and antiseptic properties in the same manner as in Reference Example.

[Examples 1 to 13 and Comparative Examples 1 to 3: Preparation of water-based ink compositions for writing instruments]
For Examples 1 to 13, each aromatic particle dispersion (dispersion liquid) obtained in Production Examples 1 to 13 was obtained. The solid content of the aromatic particles in each of the aromatic particle dispersions obtained in Production Examples 1-11 was 35-40% by mass.
On the other hand, for Comparative Examples 1 to 3, the following three known perfumes and preservatives were used.
Comparative Example 1 is an aromatic component (d-limonene, manufactured by Nippon Terpene Chemical Co., Ltd.) and a preservative component (phenoxyethanol, manufactured by Yokkaichi Synthetic Co., Ltd.), Comparative Example 2 is an aromatic component: 2-phenylethanol (2-phenylethyl alcohol). , Inoue Perfumery Co., Ltd. and antiseptic component: benzisothiazolinone (BIT), Daiwa Chemical Industry Co., Ltd., Comparative Example 3 is aromatic component CITRAL, Kuraray Co., Ltd. and antiseptic component: methylisothiazoline (MIT), Daiwa Chemical Industry I used the company's product. The ink composition for writing instruments was adjusted so that the aromatic component and the antiseptic component had solid contents equivalent to those in Examples 1 to 13.

Using each aromatic particle dispersion (particles 1 to 13) produced by the above Production Examples 1 to 13 and the above Comparative Examples 1 to 3, the composition shown below (total amount 100% by mass) for each writing instrument by a conventional method An aqueous ink composition was prepared.
Ink composition: (Total amount 100% by mass)
Each aromatic particle dispersion (particles 1 to 13) or 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

Each of the obtained water-based ink compositions for writing instruments (total amount: 100% by mass) was evaluated for lingering fragrance strength, dispersion stability, and antiseptic performance by the following evaluation methods. These evaluation results are shown in Table 2 below.

(Evaluation method of lingering scent strength with writing instrument ink)
The water-based ink composition for writing instruments obtained above was applied to a water-based felt-tip pen [PM-120T: manufactured by Mitsubishi Pencil Co., Ltd., ink absorbing body built-in, pen core: (fine) PET fiber, (ultra-fine) POM resin, hereinafter the same configuration] A pen body was produced by housing it in Furthermore, after storing the pen body axis sideways at a temperature of 40 ° C. for a period of 1 month, writing was performed on a paper surface (high-quality paper) with a pen core (fine), and the lingering scent intensity was evaluated by 5 evaluators according to the following criteria. bottom.
Evaluation criteria:
A: There is a fragrance at the time of writing, and the fragrance of the handwriting can be felt even after 6 hours.
B: There is a fragrance at the time of writing, and a slight lingering fragrance is felt in the handwriting after 6 hours.
C: There is a scent at the time of writing, and no scent remains on the handwriting after 6 hours.

(Method for evaluating dispersion stability)
Using PM-120T (manufactured by Mitsubishi Pencil Co., Ltd.), the aqueous ink composition for writing instruments obtained above was stored at 40° C. for 2 weeks with the fine print side facing downward, and then circled on writing paper with the fine print side. , was evaluated according to the following criteria.
Evaluation criteria:
A: Same level as the initial writing B: Fast writing C: Slightly blurry D: Poor writing (cannot write)

For each resulting water-based ink composition for writing instruments (total amount 100% by weight), conforming to ISO 11930:2012 (procedure for interpretation of data generated by preservative efficacy test and/or microbiological risk assessment) It was carried out by the following microorganism test method.
In the microbial test method, in order to more strictly confirm the antiseptic effect, each water-based ink composition for writing instruments was tested with Posca PC-5M (manufactured by Mitsubishi Pencil Co., Ltd., shaft material PP resin, stirring ball: stainless steel (φ: 6.4 mm). )), stored at a temperature of 40° C. for a period of one month, and then the ink extracted from the pen body was tested by the following evaluation method.
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 at 1×10 ⁶ to 1×10 ⁷ cfu/ml.
Filamentous fungi: 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>
A fungus solution was inoculated in an amount of 1% by mass with respect to the ink composition for writing instruments.
<storage>
The inoculated ink composition for writing instruments was stored at a temperature of 22.5±2.5° C. and cultured for detection at specified intervals. <Detection culture> SCD agar medium for bacterial group, SD agar medium for yeast, and PD agar medium for filamentous fungus were each smeared with a total of 1 g on 10 plates. was cultured at 22.5°C for 5 days.
<Evaluation criteria>
A: Colonies do not appear at the 7th day.
B: Colonies do not appear at the 21st day.
C: Several to several tens of colonies have appeared on the 28th day.
D: Clearly increasing as of the 28th.

Considering the above Table 2, Examples 1 to 13, which are within the scope of the present invention, have excellent lingering fragrance strength and dispersion stability without affecting other ink ingredients, compared to Comparative Example 3, which is outside the scope of the present invention. , was confirmed to be excellent in antiseptic performance. In addition, when the writing properties of Examples 1 to 13 were evaluated by writing on paper, it was confirmed that the lines were well drawn without blurring.

The aromatic particle dispersion of the present invention is highly compatible with aromatic performance and antiseptic performance, has these sustainability (sustained release properties), does not adversely affect other ingredients, etc., and is dispersed Due to its excellent stability, it can be used, for example, in medical equipment, baby products, nursing care products, bath products, kitchen utensils, tableware, drinking water pipe parts, sanitary products, household appliances, clothing, construction materials, agricultural materials, and automobile interiors. It can be used to impart fragrance and antiseptic properties to various products such as parts, stationery, writing instruments and ink compositions for inkjet printers.

Claims (5)

Fragrant particles composed of at least a (meth)acrylic acid ester monomer represented by the following general formula (I), at least one perfume component, and at least one preservative component are dispersed in water. An aromatic particle dispersion characterized by comprising:

[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. ] 2. The aromatic particle dispersion according to claim 1, wherein the perfume component is at least one selected from Group A below, and the antiseptic component is at least one selected from Group B below.
Group A: borneol, eugenol, 4-terpineol, 1,8-cineole, d-limonene, citral, geraniol, vanillin, 2-phenylethanol, γ-decalactone, linalool, L-perillaldehyde, raspberry ketone, DL-camphor, L - carvyl acetate, aryophylene, L-citronellol, D-dihydrocarveol, L-dihydrocarveol, dihydroterpineol, dihydroterpineol acetate, linalool oxide, myrtenyl acetate, allyl isothiocyanate, L-carveol, caryophyllene oxide, 1 , 4-cineole, p-cymene, D-dihydrocarvone, L-dihydrocarvone, D-dihydrocarbyl acetate, L-dihydrocarbyl acetate, elemen, isobornyl acetate, D-limonene, D-limonene oxide, L-limonene Oxide, linalool oxide, p-menthane, L-menthol, menthone-90, myrtenal, myrtenol, 3-octyl acetate, L-perylyl alcohol, L-perylyl acetate, α-pinene, β-pinene, D-pulegone , α-terpinene, terpineol C, α-terpineol, L-α-terpineol, terpineol-4, terpinolene, α-terpinyl acetate, verbenol, verbenone, 3-carene, carene oxide, hexyl acetate, nerol, ethyl saffronate , eugenyl acetate, chavicol, estragole, anethole, manzanate, γ-terpinene, cymene, myrcene, phellandrene, farnesene, thujen Group B: iodopropargyl compounds, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one , 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, p-oxybenzoic acid ester, phenol, sodium benzoate, sodium dehydroacetate, potassium sorbate, morpholine, cresol, methylisothiazolinone, chloromethylisothio azolinone, 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, isopropyl methyl Phenol, 2-methyl-4-isothiazolin-3-one, citral, eugenol, allyl isothiocyanate, 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, 2-( 4-thiazolyl)benzimidazole The perfume component is 1% by mass or more with respect to all polymer components constituting the fragrant particles, and the preservative component is 0.1% by mass or more with respect to all polymer components constituting the fragrant particles. 3. The aromatic particle dispersion according to claim 1 or 2, characterized in that: 3. The aromatic particle dispersion according to claim 1, wherein the aromatic particles have an average particle size of 10 to 800 nm. An aqueous ink composition for writing instruments, comprising the aromatic particle dispersion according to claim 1 or 2.