JP7454386B2 - Water-based ink composition for writing instruments - Google Patents
Water-based ink composition for writing instruments Download PDFInfo
- Publication number
- JP7454386B2 JP7454386B2 JP2020011020A JP2020011020A JP7454386B2 JP 7454386 B2 JP7454386 B2 JP 7454386B2 JP 2020011020 A JP2020011020 A JP 2020011020A JP 2020011020 A JP2020011020 A JP 2020011020A JP 7454386 B2 JP7454386 B2 JP 7454386B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- ink composition
- cyanoacrylate
- water
- aqueous ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 27
- 239000002245 particle Substances 0.000 claims description 64
- -1 iodopropargyl compound Chemical class 0.000 claims description 49
- 229940099451 3-iodo-2-propynylbutylcarbamate Drugs 0.000 claims description 12
- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 claims description 12
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 12
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- CQVWXNBVRLKXPE-UHFFFAOYSA-N 2-octyl cyanoacrylate Chemical compound CCCCCCC(C)OC(=O)C(=C)C#N CQVWXNBVRLKXPE-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical compound CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 claims description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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Description
本発明は、安全性が高く、広い抗菌スペクトルを有し、保存安定性、筆記性能を損なうことなく、防腐効果（防菌性・防かび性）に優れた筆記具用水性インク組成物に関する。 The present invention relates to an aqueous ink composition for writing instruments that is highly safe, has a broad antibacterial spectrum, and has excellent antiseptic effects (antibacterial and antifungal properties) without impairing storage stability and writing performance.
従来より、筆記具用水性インク組成物に用いられる防腐剤等としては、幾つかの材料が知られている。
例えば、（１）（顔料及び顔料分散剤）および／または樹脂エマルジョン着色体からなる着色料、水溶性有機溶剤、擬塑性付与剤および水からなる水性インキ基本組成物及び水性インキ基本組成物重量の０．０５～０．５重量％の架橋型アクリル酸重合物の塩を含み、更に１，２－ベンズイソチアゾリン－３－オンなどの防腐剤を含む水性ボールペン用インキ組成物（例えば、特許文献１参照）、
（２）水不溶性色材及び微粒子状樹脂組成物を水系媒体に微分散してなる水性インク組成物であって、前記微粒子状樹脂組成物が油溶性防菌防黴剤及び水不溶性高分子からなることを特徴とする水性インク組成物（例えば、特許文献２参照）
（３）水と、水溶性有機溶剤と、（イ）電子供与性呈色性有機化合物、（ロ）電子受容性化合物、（ハ）前記両者の呈色反応の生起温度を決める反応媒体からなる可逆熱変色性組成物を内包させた可逆熱変色性マイクロカプセル顔料と、側鎖にカルボキシル基を有する櫛型高分子分散剤と、水溶性樹脂と、炭素数３以上の糖アルコールと、カチオン性を有する防腐剤とからなる可逆熱変色性水性インキ組成物（例えば、特許文献３参照）、
（４）着色剤と、水と、多価アルコールと、防腐防かび剤と、から少なくともなる水性インキにおいて、前記防腐防かび剤が３－ヨード－２－プロピニルブチルカーバメートを含有することを特徴とする水性インキ（例えば、特許文献４参照）、
などが知られている。
Conventionally, several materials have been known as preservatives and the like used in aqueous ink compositions for writing instruments.
For example, (1) (pigment and pigment dispersant) and/or an aqueous ink basic composition consisting of a colorant consisting of a resin emulsion colored body, a water-soluble organic solvent, a pseudoplasticizer, and water; An aqueous ballpoint pen ink composition containing 0.05 to 0.5% by weight of a salt of a crosslinked acrylic acid polymer and further containing a preservative such as 1,2-benzisothiazolin-3-one (for example, Patent Document 1) reference),
(2) An aqueous ink composition obtained by finely dispersing a water-insoluble coloring material and a particulate resin composition in an aqueous medium, the particulate resin composition comprising an oil-soluble antibacterial and antifungal agent and a water-insoluble polymer. An aqueous ink composition characterized in that (for example, see Patent Document 2)
(3) consisting of water, a water-soluble organic solvent, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of both of the above occurs. A reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition, a comb-shaped polymer dispersant having a carboxyl group in its side chain, a water-soluble resin, a sugar alcohol having 3 or more carbon atoms, and a cationic resin. A reversible thermochromic aqueous ink composition comprising a preservative having (for example, see Patent Document 3),
(4) A water-based ink comprising at least a colorant, water, a polyhydric alcohol, and a preservative and fungicide, characterized in that the preservative and fungicide contains 3-iodo-2-propynylbutyl carbamate. water-based ink (for example, see Patent Document 4),
etc. are known.
一方、抗菌・防腐組成物等としては、例えば、（５）少なくとも１種のヨードプロパルギル化合物を含むマイクロカプセルであって、前記少なくとも１種のヨードプロパルギル化合物が、少なくとも１種のメラミン－ホルムアルデヒドポリマーを含むマイクロカプセル化材料を用いてマイクロカプセル化されている、マイクロカプセル（例えば、特許文献５参照）、
（６）ヨウ素系化合物（３－ヨード－２－プロピニルブチルカルバメート：ＩＰＢＣ）、トリアゾール系化合物、カルバモイルイミダゾール系化合物、ジチオール系化合物、イソチアゾリン系化合物、ニトロアルコール系化合物、パラオキシ安息香酸エステルなどの殺菌防腐防藻防かび剤、ピレスロイド系化合物、ネオニコチノイド系化合物、有機塩素系化合物、有機リン系化合物、カーバメート系化合物、オキサジアジン系化合物などの防虫剤、殺虫剤などから選択される疎水性の抗生物活性化合物を疎水性の重合性ビニルモノマーで溶解することにより、疎水性溶液を調製し、水と乳化剤とを配合して乳化剤水溶液を調製し、前記疎水性溶液を前記乳化剤水溶液中に乳化し、前記重合性ビニルモノマーを、重合開始剤の存在下、ミニエマルション重合して、抗生物活性化合物を含有する平均粒子径１μｍ未満の重合体を生成することにより得られることを特徴とする、徐放性粒子（例えば、特許文献６参照）、などが知られている。
On the other hand, examples of antibacterial/preservative compositions include (5) microcapsules containing at least one iodopropargyl compound, wherein the at least one iodopropargyl compound contains at least one melamine-formaldehyde polymer; Microcapsules that are microencapsulated using a microencapsulation material containing (for example, see Patent Document 5),
(6) Sterilization and preservation of iodine compounds (3-iodo-2-propynylbutyl carbamate: IPBC), triazole compounds, carbamoylimidazole compounds, dithiol compounds, isothiazoline compounds, nitroalcohol compounds, paraoxybenzoic acid esters, etc. Hydrophobic antibiotics selected from insect repellents and insecticides such as algae and fungicides, pyrethroid compounds, neonicotinoid compounds, organochlorine compounds, organophosphorus compounds, carbamate compounds, and oxadiazine compounds. preparing a hydrophobic solution by dissolving an active compound with a hydrophobic polymerizable vinyl monomer, preparing an aqueous emulsifier solution by combining water and an emulsifier, and emulsifying the hydrophobic solution in the aqueous emulsifier solution; Sustained release characterized by being obtained by miniemulsion polymerization of the polymerizable vinyl monomer in the presence of a polymerization initiator to produce a polymer containing an antibiotic active compound and having an average particle diameter of less than 1 μm. known particles (for example, see Patent Document 6).
しかしながら、上記特許文献１～６に記載の筆記具用水性インク組成物や防腐剤などは、安全性の問題で使用量が制限されているものや、他のインク材料へ何らかの悪影響を与えるもの、または、特定の汚染源への効果が十分でないものがあるなどの課題がある。 However, the water-based ink compositions and preservatives for writing instruments described in Patent Documents 1 to 6 above are limited in usage due to safety issues, or have some adverse effect on other ink materials, or However, there are issues such as some methods not being sufficiently effective against specific pollution sources.
本発明は、上記従来技術の課題等に鑑み、これを解消しようとするものであり、安全性が高く、広い抗菌スペクトルを有し、保存安定性、筆記性能を損なうことなく、防腐効果（防菌性・防かび性）に優れた筆記具用水性インク組成物を提供することを目的とする。 The present invention aims to solve the above-mentioned problems of the prior art, and is highly safe, has a wide antibacterial spectrum, and has a preservative effect (preventive effect) without impairing storage stability or writing performance. The purpose of the present invention is to provide an aqueous ink composition for writing instruments that has excellent antibacterial and antifungal properties.
本発明者らは、上記従来の課題等に鑑み、鋭意研究を行った結果、少なくとも、特定の防菌性・防かび性を有する化合物を内包し、シェルが特定のポリマーで構成される粒子を含有することにより、上記目的の筆記具用水性インク組成物が得られることを見出し、本発明を完成するに至ったのである。 In view of the above-mentioned conventional problems, the present inventors conducted intensive research and found that particles containing at least a compound having specific antibacterial and antifungal properties and whose shell is composed of a specific polymer. It was discovered that by containing the above-mentioned aqueous ink composition for writing instruments, the present invention was completed.
すなわち、本発明の筆記具用水性インク組成物は、少なくとも、ヨードプロパルギル化合物を内包し、シェルがシアノアクリレートで構成される粒子を含有することを特徴とする筆記具用水性インク組成物。
粒子の平均粒子径は、１０～８００ｎｍであることが好ましい。
ヨードプロパルギル化合物は、３－ヨード－２－プロピニルブチルカルバメートを少なくとも含むことが好ましい。
シェルを構成するシアノアクリレートの質量比は、９０～１００質量％であることが好ましい。
シアノアクリレートが、イソブチルシアノアクリレート、ｎ－ブチルシアノアクリレート、ｔｅｒｔ－ブチルシアノアクリレート、ｎ－オクチルシアノアクリレート、２－オクチルシアノアクリレートから選ばれる少なくとも１種を含むことが好ましい。
That is, the aqueous ink composition for a writing instrument of the present invention is characterized in that it contains at least particles that include an iodopropargyl compound and whose shell is composed of cyanoacrylate.
The average particle diameter of the particles is preferably 10 to 800 nm.
Preferably, the iodopropargyl compound contains at least 3-iodo-2-propynylbutyl carbamate.
The mass ratio of cyanoacrylate constituting the shell is preferably 90 to 100% by mass.
It is preferable that the cyanoacrylate contains at least one selected from isobutyl cyanoacrylate, n-butyl cyanoacrylate, tert-butyl cyanoacrylate, n-octyl cyanoacrylate, and 2-octyl cyanoacrylate.
本発明によれば、安全性が高く、広い抗菌スペクトルを有し、保存安定性、筆記性能を損なうことなく、防腐効果（防菌性・防かび性）に優れた筆記具用水性インク組成物が提供される。 According to the present invention, there is provided a water-based ink composition for writing instruments that is highly safe, has a broad antibacterial spectrum, and has excellent preservative effects (antibacterial and antifungal properties) without impairing storage stability and writing performance. provided.
以下に、本発明の実施形態を詳しく説明する。
本発明の筆記具用水性インク組成物は、少なくとも、ヨードプロパルギル化合物を内包し、シェルがシアノアクリレートで構成される粒子を含有することを特徴とするものである。
Embodiments of the present invention will be described in detail below.
The aqueous ink composition for writing instruments of the present invention is characterized in that it contains at least particles that include an iodopropargyl compound and whose shell is composed of cyanoacrylate.
本発明に用いるヨードプロパルギル化合物としては、例えば、３－ヨード－２－プロピニルプロピルカルバメート、３－ヨード－２－プロピニルブチルカルバメート（ＩＰＢＣ）、３－ヨード－２－プロピニルｍ－クロロフェニルカルバメート、３－ヨード－２－プロピニルフェニルカルバメート、３－ヨード－２－プロピニル２，４，５－トリクロロフェニルエーテル、３－ヨード－２－プロピニル４－クロロフェニルホルマール（ＩＰＣＦ）、ジ－（３－ヨード－２－プロピニル）ヘキシルジカルバメート、３－ヨード－２－プロピニルオキシエタノールエチルカルバメート、３－ヨード－２－プロピニルオキシエタノールフェニルカルバメート、３－ヨード－２－プロピニルチオキソチオエチルカルバメート、３－ヨード－２－プロピニルカルバミン酸エステル（ＩＰＣ）、Ｎ－ヨードプロパルギルオキシカルボニルアラニン、Ｎ－ヨードプロパルギルオキシカルボニルアラニンエチルエステル、３－（３－ヨードプロパルギル）ベンズオキサゾール－２－オン、３－（３－ヨードプロパルギル）－６－クロロベンズオキサゾール－２－オン、３－ヨード－２－プロピニルアルコール、４－クロロフェニル３－ヨードプロパルギルホルマール、３－ブロモ－２，３－ジヨード－２－プロペニルエチルカルバメート、３－ヨード－２－プロピニル－ｎ－ヘキシルカルバメート、３－ヨード－２－プロピニルシクロヘキシルカルバメートなどから選ばれる少なくとも１種（各単独又は２種以上の混合物、以下同様）が挙げられる。 Examples of the iodopropargyl compound used in the present invention include 3-iodo-2-propynylpropylcarbamate, 3-iodo-2-propynylbutylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, and 3-iodo-2-propynylpropylcarbamate. -2-Propynylphenyl carbamate, 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal (IPCF), di-(3-iodo-2-propynyl) Hexyldicarbamate, 3-iodo-2-propynyloxyethanolethylcarbamate, 3-iodo-2-propynyloxyethanolphenylcarbamate, 3-iodo-2-propynylthioxothioethylcarbamate, 3-iodo-2-propynylcarbamate 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-propenylethyl carbamate, 3-iodo-2-propynyl-n -hexyl carbamate, 3-iodo-2-propynylcyclohexyl carbamate, and the like (each singly or a mixture of two or more, the same applies hereinafter).
これらのヨードプロパルギル化合物自体は、従来より公知であり、安全性が高く、抗菌性・防かび性を有する化合物であり、また、その製造方法も知られており、種々の製造方法で調製することができ、また、市販品があればそれらを使用することができる。
本発明では、安全性の点、安定性の点などから、好ましくは、３－ヨード－２－プロピニルブチルカルバメート（以下、単に「ＩＰＢＣ」という場合がある）を少なくとも含むもの（ＩＰＢＣ単独又はＩＰＢＣを含む混合物）が好ましい。
These iodopropargyl compounds themselves have long been known, are highly safe, and have antibacterial and antifungal properties, and their manufacturing methods are also known, and they can be prepared using various manufacturing methods. You can also use commercially available products if they are available.
In the present invention, from the viewpoint of safety and stability, it is preferable to use a product containing at least 3-iodo-2-propynylbutyl carbamate (hereinafter sometimes simply referred to as "IPBC") (IPBC alone or IPBC). Mixtures containing) are preferred.
本発明において、上記構成の粒子は、少なくとも、上記ヨードプロパルギル化合物を内包し、シェルがシアノアクリレートで構成されるものであり、例えば、下記式（Ｉ）で表されるポリマーをシェルにしてヨードプロパルギル化合物を内包することにより製造することができる。
上記一般式（Ｉ）中におけるＲの炭素数２～８のアルキル基としては、例えば、エチル基、プロピル基（直鎖、分岐）、ブチル基（直鎖、分岐）、ペンチル基（直鎖、分岐）、ヘキシル基（直鎖、分岐）、ヘプチル基（直鎖、分岐）、オクチル基（直鎖、分岐）などが挙げられ、好ましくは、外科領域において傷口の縫合のための接着剤として用いられている、炭素数４のアルキル基及び炭素数８のオクチル基が望ましく、特に好ましくは、イソブチル基、ｎ－オクチル基及び２－オクチル基である。
本発明の効果を更に発揮せしめる点等から、具体的には、イソブチルシアノアクリレート、ｎ－ブチルシアノアクリレート、ｔｅｒｔ－ブチルシアノアクリレート、ｎ－オクチルシアノアクリレート、２－オクチルシアノアクリレートから選ばれる少なくとも１種を含むもので構成することが望ましい。
また、シェルを構成するシアノアクリレートの質量比は、安全性および安定性の点から、９０～１００質量％であることが好ましい。
Examples of the alkyl group having 2 to 8 carbon atoms for R in the above general formula (I) include ethyl group, propyl group (straight chain, branched), butyl group (straight chain, branched), pentyl group (straight chain, (branched), hexyl group (straight chain, branched), heptyl group (straight chain, branched), octyl group (straight chain, branched), etc., and is preferably used as an adhesive for suturing wounds in the surgical field. Preferred are alkyl groups having 4 carbon atoms and octyl groups having 8 carbon atoms, and particularly preferred are isobutyl, n-octyl and 2-octyl groups.
In order to further exhibit the effects of the present invention, specifically, at least one member selected from isobutyl cyanoacrylate, n-butyl cyanoacrylate, tert-butyl cyanoacrylate, n-octyl cyanoacrylate, and 2-octyl cyanoacrylate. It is desirable to have a structure that includes the following.
Further, the mass ratio of cyanoacrylate constituting the shell is preferably 90 to 100% by mass from the viewpoint of safety and stability.
本発明の粒子は、上記ヨードプロパルギル化合物を内包し、シェルが上記一般式（Ｉ）で表される構造を繰り返し単位中に有するシアノアクリレートのポリマーで構成されるものである。この粒子において、シアノアクリレート自身が細菌の細胞壁に接着し細胞壁合成を妨害し溶菌を生じさせ、細菌（かび類も含む）の発育を阻止することにより、単独で、抗菌効果（防菌性・防かび性）を有するものであり、しかも、本発明では、該粒子に内包される上記ヨードプロパルギル化合物自体も上述のとおり、安全性が高く、抗菌効果を有するものであり、これらの相乗作用により、安全性が高く、広い抗菌スペクトルを有し、安定性に優れ、抗菌効果（防かび効果を含む）に優れたものとなる（これらの点においては後述する実施例等においても詳述する）。 The particles of the present invention include the iodopropargyl compound described above, and the shell is composed of a cyanoacrylate polymer having a structure represented by the general formula (I) in the repeating unit. In these particles, the cyanoacrylate itself adheres to the bacterial cell wall, interferes with cell wall synthesis, causes bacteriolysis, and inhibits the growth of bacteria (including molds), thereby independently exerting antibacterial effects (antibacterial and antibacterial properties). Furthermore, in the present invention, the iodopropargyl compound itself contained in the particles is highly safe and has an antibacterial effect, as described above, and due to their synergistic effect, It is highly safe, has a broad antibacterial spectrum, is excellent in stability, and has excellent antibacterial effects (including antifungal effects) (these points will be explained in detail in the examples below).
この粒子の製造は、例えば、上記一般式（Ｉ）で表される構造単位（モノマー）をアニオン重合により重合する際に、上記ヨードプロパルギル化合物を添加して、粒子の内部に当該ヨードプロパルギル化合物を内包（抱合）させることにより当該粒子を含有する水分散体として得られる。
上記重合の重合開始及び重合の安定化のために重合薬剤を用いることができる。この重合薬剤としては、例えば、ポリオキシエチレンソルビタン脂肪酸エステル、水酸基を有する単糖類及び二糖類から成る群より選ばれる少なくとも１種の糖が挙げられる。
The production of these particles can be carried out, for example, by adding the iodopropargyl compound described above when polymerizing the structural unit (monomer) represented by the above general formula (I) by anionic polymerization, so that the iodopropargyl compound is incorporated into the inside of the particles. By encapsulating (conjugating) the particles, an aqueous dispersion containing the particles can be obtained.
A polymerization agent can be used to initiate the polymerization and stabilize the polymerization. Examples of the polymerization agent include polyoxyethylene sorbitan fatty acid ester, and at least one type of sugar selected from the group consisting of hydroxyl group-containing monosaccharides and disaccharides.
用いることができるポリオキシエチレンソルビタン脂肪酸エステルとしては、例えば、ラウリン酸ポリオキシエチレンソルビタン、パルミチン酸ポリオキシエチレンソルビタン、ステアリン酸ポリオキシエチレンソルビタン、オレイン酸ポリオキシエチレンソルビタンなどが挙げられる。
また、上記ポリオキシエチレンソルビタン脂肪酸エステルとは別に、重合薬剤として糖を用いることで、さらにその効果を高めることができる。
用いることができる糖としては、水酸基を有する単糖又は二糖であればいずれの糖でもよく、好ましい例として、グルコース、マンノース、リボース、フルクトース、マルトース、トレハロース、ラクトース及びスクロースを挙げることができる。これらの糖は、環状、鎖状のいずれの形態であってもよく、また、環状の場合、ピラノース型やフラノース型等のいずれであってもよい。また、糖には種々の異性体が存在するがそれらのいずれでもよい。通常、単糖は、ピラノース型又はフラノース型の形態で存在し、二糖は、それらがα結合又はβ結合したものであり、このような通常の形態にある糖をそのまま用いることができる。単糖及び二糖は、単独で用いることもできるし、２種以上を組み合わせて用いることもできる。
Examples of polyoxyethylene sorbitan fatty acid esters that can be used include polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, and polyoxyethylene sorbitan oleate.
Furthermore, the effect can be further enhanced by using sugar as a polymerization agent in addition to the polyoxyethylene sorbitan fatty acid ester.
The sugar that can be used may be any monosaccharide or disaccharide having a hydroxyl group, and preferred examples include glucose, mannose, ribose, fructose, maltose, trehalose, lactose, and sucrose. These sugars may be in either a cyclic or chain form, and if they are cyclic, they may be in a pyranose type, furanose type, or the like. Furthermore, sugars exist in various isomers, and any of them may be used. Generally, monosaccharides exist in the form of pyranose or furanose types, and disaccharides are those in which they are α-linked or β-linked, and sugars in such normal forms can be used as they are. Monosaccharides and disaccharides can be used alone or in combination of two or more.
重合反応の溶媒は、通常、水（蒸溜水、精製水、純水など）が用いられる。アニオン重合は、水酸イオンにより開始されるので、反応液のｐＨは、重合速度に影響する。反応液のｐＨが高い場合には、水酸イオンの濃度が高くなるので重合が速く、ｐＨが低い場合には重合が遅くなる。通常、ｐＨが２～４程度の酸性下で適度な重合速度が得られる。反応液を酸性にするために添加する酸としては、特に限定されないが、反応に悪影響を与えない、リン酸、塩酸、酢酸、フタル酸、クエン酸などを好ましく用いることができる。 Water (distilled water, purified water, pure water, etc.) is usually used as a solvent for the polymerization reaction. Since anionic polymerization is initiated by hydroxide ions, the pH of the reaction solution affects the polymerization rate. When the pH of the reaction solution is high, the concentration of hydroxide ions becomes high, so polymerization is rapid, and when the pH is low, polymerization is slow. Usually, an appropriate polymerization rate can be obtained under acidic conditions with a pH of about 2 to 4. The acid added to make the reaction solution acidic is not particularly limited, but phosphoric acid, hydrochloric acid, acetic acid, phthalic acid, citric acid, and the like, which do not adversely affect the reaction, can be preferably used.
反応開始時の重合反応液中の上記式（Ｉ）で表される構造単位の濃度は、特に限定されないが、通常、０．１～１０質量％程度、好ましくは、１～５質量％程度である。また、反応開始時の重合反応液中の重合薬剤の濃度（複数種類用いる場合はその合計濃度）は、特に限定されないが、通常、１～３０質量％、好ましくは、５～２０質量％程度である。また、反応温度は、特に限定されないが、室温で行なうことが簡便で好ましい。反応時間は、特に限定されないが、通常、０．５時間～４時間程度である。重合反応は、撹拌下に行なうことが好ましい。なお、粒子は、通常、中性の粒子として用いられるので、反応終了後、必要に応じて、水酸化ナトリウム水溶液等の塩基を反応液に添加して中和することが好ましい。 The concentration of the structural unit represented by the above formula (I) in the polymerization reaction solution at the start of the reaction is not particularly limited, but is usually about 0.1 to 10% by mass, preferably about 1 to 5% by mass. be. In addition, the concentration of the polymerization agent in the polymerization reaction solution at the start of the reaction (or the total concentration if multiple types are used) is not particularly limited, but is usually about 1 to 30% by mass, preferably about 5 to 20% by mass. be. Further, the reaction temperature is not particularly limited, but it is convenient and preferable to carry out the reaction at room temperature. The reaction time is not particularly limited, but is usually about 0.5 to 4 hours. The polymerization reaction is preferably carried out under stirring. In addition, since the particles are usually used as neutral particles, it is preferable to neutralize the reaction solution by adding a base such as an aqueous sodium hydroxide solution to the reaction solution, if necessary, after the reaction is completed.
上記の重合反応により、上記式（Ｉ）で表される構造単位がアニオン重合し、式（Ｉ）で表される構造を繰り返し単位中に有するポリマー粒子が生成すると共に、この粒子の内部に上記ヨードプロパルギル化合物を内包（抱合）したものとなる。
上記ヨードプロパルギル化合物を内包（抱合）させる量は、抗菌剤の用途、使用時に必要な用量等に応じて適宜設定することができる。例えば、粒子全量に対して、０．１～３５質量％程度であるが、これらの範囲に限定されるものではない。
また、上記方法により得られる粒子の平均粒子径は、特に限定されないが、分散安定性の点、表面積の点から、１０００ｎｍ（１μｍ）未満とすることが好ましく、より好ましくは、１０～８００ｎｍ、特に好ましくは、１０～２００ｎｍであるものが望ましい。
この平均粒子径の調整は、反応液中の上記式（Ｉ）で表される構造単位の濃度、用いる重合薬剤種及びその量、反応時間などを調節することにより行うことができる。生成した粒子は、必要に応じて、遠心式限外ろ過等の常法により回収することもできる。
なお、本発明で規定する「平均粒子径」は、散乱光強度分布によるヒストグラム平均粒子径であり、本発明（後述する実施例を含む）では、粒度分布測定装置〔ＦＰＡＲ１０００（大塚電子社製）〕にて、測定したＤ５０の値である。
Through the above polymerization reaction, the structural unit represented by the above formula (I) undergoes anionic polymerization to produce polymer particles having the structure represented by the formula (I) in the repeating unit, and the above-mentioned It contains (conjugates) an iodopropargyl compound.
The amount of the iodopropargyl compound to be encapsulated (conjugated) can be appropriately set depending on the purpose of the antibacterial agent, the dose required at the time of use, and the like. For example, the amount is about 0.1 to 35% by mass based on the total amount of particles, but is not limited to these ranges.
Further, the average particle diameter of the particles obtained by the above method is not particularly limited, but from the viewpoint of dispersion stability and surface area, it is preferably less than 1000 nm (1 μm), more preferably 10 to 800 nm, especially Preferably, the thickness is 10 to 200 nm.
The average particle diameter can be adjusted by adjusting the concentration of the structural unit represented by the above formula (I) in the reaction solution, the type and amount of the polymerizing agent used, the reaction time, and the like. The generated particles can also be recovered by conventional methods such as centrifugal ultrafiltration, if necessary.
Note that the "average particle diameter" defined in the present invention is the histogram average particle diameter based on the scattered light intensity distribution, and in the present invention (including the examples described below), a particle size distribution measuring device [FPAR1000 (manufactured by Otsuka Electronics Co., Ltd.)] This is the D50 value measured at ].
得られる粒子は、上記一般式（Ｉ）で表される構造を繰り返し単位中に有するポリマー粒子に上述のヨードプロパルギル化合物を内包（抱合）させることにより、粒子単独での抗菌・防かび効果とヨードプロパルギル化合物の抗菌効果等の一体作用（相乗作用）でヨードプロパルギル化合物の使用量を極力少なくすることができるものとなり、また、ヨードプロパルギル化合物が特定の汚染源への効果が十分でないものでも、上記両者の一体作用（相乗作用）により、安全性が高く、保存安定性に優れ、優れた抗菌性（防カビ効果を含む）を発揮できるものとなる。 The resulting particles have the antibacterial and antifungal effect of the particles alone and the iodopropargyl compound by encapsulating (conjugating) the iodopropargyl compound in the repeating unit of the polymer particles having the structure represented by the general formula (I) above. The combined effect (synergistic effect) of the propargyl compound, such as its antibacterial effect, makes it possible to minimize the amount of iodopropargyl compound used. The combined effect (synergistic effect) of the two makes it highly safe, has excellent storage stability, and can exhibit excellent antibacterial properties (including antifungal effects).
上記特性の粒子は、各単独で、または２種以上を併用することができ、その有効成分の（合計）含有量は、インク組成物全量に対して、０．１～３０質量％、好ましくは、０．１～１０質量％とすることが望ましい。
本発明において、「有効成分」とは、防腐効果（防菌性・防かび性）を発揮する成分のみをいい、上記重合に用いる重合薬剤（ポリオキシエチレンソルビタン脂肪酸エステルや糖）、水などの各成分を含まないものであり、重合薬剤等を含まない粒子そのものと、該粒子に内包するヨードプロパルギル化合物とが有効成分となるものである。
この有効成分の含有量が０．１質量％未満であると、本発明の効果を発揮することができず、一方、３０質量％超過であると、分散安定性が損なわれやすくなり、好ましくない。
The particles having the above characteristics can be used alone or in combination of two or more, and the (total) content of the active ingredients is 0.1 to 30% by mass, preferably 0.1 to 30% by mass, based on the total amount of the ink composition. , preferably 0.1 to 10% by mass.
In the present invention, "active ingredients" refer only to ingredients that exhibit antiseptic effects (antibacterial and antifungal properties), such as polymerization agents (polyoxyethylene sorbitan fatty acid esters and sugars) used in the above polymerization, water, etc. The active ingredients are the particles themselves, which do not contain any components, such as polymerization agents, and the iodopropargyl compound encapsulated in the particles.
If the content of this active ingredient is less than 0.1% by mass, the effects of the present invention cannot be exhibited, while if it exceeds 30% by mass, dispersion stability tends to be impaired, which is undesirable. .
本発明の筆記具用水性インク組成物には、上記特性の粒子の他、筆記具用水性インクに汎用の着色剤、水溶性溶剤が含有される。
用いることができる着色剤としては、水溶性染料、顔料、例えば、無機顔料、有機顔料、プラスチックピグメント、粒子内部に空隙のある中空樹脂粒子は白色顔料として、または、発色性、分散性に優れる染料で染色した樹脂粒子（擬似顔料）等も使用できる。
水溶性染料としては、直接染料、酸性染料、食用染料、塩基性染料のいずれも本発明の効果を損なわない範囲で適宜量用いることができる。
The aqueous ink composition for writing instruments of the present invention contains, in addition to the particles having the above characteristics, a coloring agent and a water-soluble solvent commonly used in aqueous inks for writing instruments.
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 can also be used.
As water-soluble dyes, any of direct dyes, acid dyes, food dyes, and basic dyes can be used in an appropriate amount within a range that does not impair the effects of the present invention.
用いることができる水溶性溶剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、３－ブチレングリコール、チオジエチレングリコール、グリセリン等のグリコール類や、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のグリコールエーテル類を単独或いは混合して使用することができる。この水溶性溶剤の含有量は、筆記具用水性インク組成物全量中、５～４０質量％とすることが望ましい。 Examples of water-soluble solvents that can be used include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin, and ethylene glycol monomethyl ether and diethylene glycol monomethyl ether. Glycol ethers such as , propylene glycol monomethyl ether can be used alone or in combination. The content of this water-soluble solvent is preferably 5 to 40% by mass based on the total amount of the aqueous ink composition for writing instruments.
本発明の筆記具用水性インク組成物には、上記特性の粒子、着色剤、水溶性溶剤の他、残部として溶媒である水（水道水、精製水、蒸留水、イオン交換水、純水等）の他、本発明の効果を損なわない範囲で、分散剤、潤滑剤、ｐＨ調整剤、防錆剤、増粘剤、蒸発抑制剤、界面活性剤などを適宜含有することができる。
用いることができる分散剤としては、ノニオン、アニオン界面活性剤や水溶性樹脂が用いられる。好ましくは水溶性高分子が用いられる。
潤滑剤としては、顔料の表面処理剤にも用いられる多価アルコールの脂肪酸エステル、糖の高級脂肪酸エステル、ポリオキシアルキレン高級脂肪酸エステル、アルキル燐酸エステルなどのノニオン系や、高級脂肪酸アミドのアルキルスルホン酸塩、アルキルアリルスルホン酸塩などのアニオン系、ポリアルキレングリコールの誘導体やフッ素系界面活性剤、ポリエーテル変性シリコーンなどが挙げられる。
The aqueous ink composition for writing instruments of the present invention contains particles with the above characteristics, a colorant, a water-soluble solvent, and the remainder water as a solvent (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.). In addition, a dispersant, a lubricant, a pH adjuster, a rust preventive, a thickener, an evaporation inhibitor, a surfactant, and the like may be appropriately contained within a range that does not impair the effects of the present invention.
As dispersants that can be used, nonionic and anionic surfactants and water-soluble resins are used. Preferably, water-soluble polymers are used.
As lubricants, nonionic lubricants such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphate esters, which are also used as surface treatment agents for pigments, and alkyl sulfonic acids of higher fatty acid amides are used. Examples include salts, anionic substances such as alkylaryl sulfonates, derivatives of polyalkylene glycol, fluorine-based surfactants, and polyether-modified silicones.
ｐＨ調整剤としては、アンモニア、尿素、モノエタノーアミン、ジエタノールアミン、トリエタノールアミンや、トリポリリン酸ナトリウム、炭酸ナトリウムなとの炭酸やリン酸のアルカリ金属塩、水酸化ナトリウムなどのアルカリ金属の水和物などが挙げられる。また、防錆剤としては、ベンゾトリアゾール、トリルトリアゾール、ジシクロへキシルアンモニウムナイトライト、サポニン類などが挙げられる。
増粘剤としては、カルボキシメチルセルロース（ＣＭＣ）又はその塩、発酵セルロース、結晶セルロース、多糖類などが挙げられる。用いることができる多糖類としては、例えば、キサンタンガム、グアーガム、ヒドロキシプロピル化グアーガム、カゼイン、アラビアガム、ゼラチン、アミロース、アガロース、アガロペクチン、アラビナン、カードラン、カロース、カルボキシメチルデンプン、キチン、キトサン、クインスシード、グルコマンナン、ジェランガム、タマリンドシードガム、デキストラン、ニゲラン、ヒアルロン酸、プスツラン、フノラン、ＨＭペクチン、ポルフィラン、ラミナラン、リケナン、カラギーナン、アルギン酸、トラガカントガム、アルカシーガム、サクシノグリカン、ローカストビーンガム、タラガムなどが挙げられ、これらは１種単独で使用してもよく、２種以上を併用してもよい。また、これらの市販品があればそれを使用することができる。
蒸発抑制剤としては、例えば、ペンタエリスリトール、ｐ―キシレングリコール、トリメチロールプロパン、トリエチロールプロパン、デキストリンなどが挙げられる。
界面活性剤としては、例えば、フッ素系、シリコーン系、アセチレングリコール系などが挙げられる。
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. Examples include. Further, examples of rust preventives include benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, and saponins.
Examples of the thickener include carboxymethyl cellulose (CMC) or a salt thereof, fermented cellulose, crystalline cellulose, polysaccharides, and the like. Examples of polysaccharides that can be used include xanthan gum, guar gum, hydroxypropylated guar gum, casein, gum arabic, gelatin, amylose, agarose, agaropectin, arabinan, curdlan, callose, carboxymethyl starch, chitin, chitosan, and quince seed. , glucomannan, gellan gum, tamarind seed gum, dextran, nigeran, hyaluronic acid, pustulan, funolan, HM pectin, porphyran, laminaran, lichenan, carrageenan, alginic acid, tragacanth gum, alkasi gum, succinoglycan, locust bean gum, tara gum, etc. These may be used alone or in combination of two or more. Moreover, if these commercially available products are available, they can be used.
Examples of the evaporation inhibitor include pentaerythritol, p-xylene glycol, trimethylolpropane, triethylolpropane, and dextrin.
Examples of the surfactant include fluorine-based, silicone-based, and acetylene glycol-based surfactants.
本発明の筆記具用水性インク組成物は、上記特性の粒子、水溶性溶剤、その他の各成分を筆記具用（ボールペン用、マーキングペン用等）インクの用途に応じて適宜組み合わせて、ホモミキサー、ホモジナイザーもしくはディスパー等の攪拌機により攪拌混合することにより、更に必要に応じて、ろ過や遠心分離によってインク組成物中の粗大粒子を除去すること等によって筆記具用水性インク組成物を調製することができる。 The aqueous ink composition for writing instruments of the present invention can be prepared by combining particles with the above-mentioned characteristics, a water-soluble solvent, and other components as appropriate depending on the use of the ink for writing instruments (for ballpoint pens, marking pens, etc.), and then using a homomixer, homogenizer, etc. Alternatively, an aqueous ink composition for a writing instrument 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.
また、本発明の筆記具用水性インク組成物のｐＨ（２５℃）は、使用性、安全性、インク自身の安定性、インク収容体とのマッチング性の点からｐＨ調整剤などにより５～１０に調整されることが好ましく、更に好ましくは、６～９．５とすることが望ましい。 In addition, the pH (25°C) of the aqueous ink composition for writing instruments of the present invention is adjusted to 5 to 10 by using a pH adjuster etc. from the viewpoint of usability, safety, stability of the ink itself, and matching with the ink container. It is preferably adjusted, more preferably from 6 to 9.5.
本発明の筆記具用水性インク組成物は、ボールペンチップ、繊維チップ、フェルトチップ、プラスチックチップなどのペン先部を備えたボールペン、マーキングペン等に搭載される。
ボールペンとしては、上記組成の筆記具用水性インク組成物を直径が０．１８～２．０ｍｍのボールを備えたボールペン用インク収容体（リフィール）に収容すると共に、該インク収容体内に収容された水性インク組成物とは相溶性がなく、かつ、該水性インク組成物に対して比重が小さい物質、例えば、ポリブテン、シリコーンオイル、鉱油等がインク追従体として収容されるものが挙げられる。
なお、ボールペン、マーキングペンの構造は、特に限定されず、例えば、軸筒自体をインク収容体として該軸筒内に上記構成の筆記具用水性インク組成物を充填したコレクター構造（インク保持機構）を備えた直液式のボールペン、マーキングペンであってもよいものである。
The aqueous ink composition for writing instruments of the present invention is installed in ballpoint pens, marking pens, and the like having a pen tip such as a ballpoint tip, fiber tip, felt tip, or plastic tip.
As a ballpoint pen, the aqueous ink composition for writing instruments having the above composition is stored in an ink container (refill) for a ballpoint pen equipped with a ball having a diameter of 0.18 to 2.0 mm, and the aqueous ink composition contained in the ink container is Examples include those in which a substance that is incompatible with the ink composition and has a low specific gravity relative to the aqueous ink composition, such as polybutene, silicone oil, mineral oil, etc., is accommodated as an ink follower.
Note that the structure of the ballpoint pen and marking pen is not particularly limited, and for example, a collector structure (ink holding mechanism) in which the barrel itself is used as an ink container and the barrel is filled with the aqueous ink composition for writing instruments having the above structure. A direct liquid ballpoint pen or a marking pen may be used.
このように構成される本発明の筆記具用水性インク組成物にあっては、用いる上記特性の粒子が筆記具用水性インク組成物中に配合されているため、インク組成物中で防腐効果（防菌性・防かび性）を発揮することができ、その持続効果を長期間に亘り、しかも、これらの粒子は保存安定性、筆記性能を損なわないため、ボールペン、マーキングペンなどの筆記具に好適な筆記具用水性インク組成物が得られることとなる。 In the aqueous ink composition for writing instruments of the present invention configured as described above, since the particles having the above-mentioned characteristics are blended into the aqueous ink composition for writing instruments, the ink composition has a preservative effect (antibacterial effect). It is suitable for writing instruments such as ballpoint pens and marking pens because these particles have long-lasting effects and do not impair storage stability or writing performance. A water-based ink composition will be obtained.
次に、製造例、実施例及び比較例などにより本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。 Next, the present invention will be explained in more detail with reference to production examples, working examples, comparative examples, etc., but the present invention is not limited to the following examples.
〔製造例１～７：粒子Ａ～Ｇの製造〕
下記製造例１～７により、各粒子Ａ～Ｇを製造した。なお、以下の「部」は質量部を表す。
[Production Examples 1 to 7: Production of particles A to G]
Particles A to G were produced according to Production Examples 1 to 7 below. In addition, the following "parts" represent parts by mass.
（製造例１：粒子Ａの製造）
２リットルのフラスコに、撹拌機、還流冷却器、温度計を取り付け、水槽にセットし、蒸留水８９．８部、モノラウリン酸ポリオキシエチレンソルビタン（２０Ｅ．Ｏ）２部、リン酸０．２部、式（Ｉ）中のＲがiso-ブチルのモノマー６部、ヨードプロパルギル化合物：３－ヨード－２－プロピニルブチルカルバメート２部を仕込んで、約１５分撹拌してアニオン重合を終了し、粒子の分散液（粒子Ａ）を得た。なお、粒子の平均粒子径は、８３ｎｍであった。
(Production example 1: Production of particles A)
A 2-liter flask was equipped with a stirrer, a reflux condenser, and a thermometer, set in a water tank, and mixed with 89.8 parts of distilled water, 2 parts of polyoxyethylene sorbitan monolaurate (20E.O.), and 0.2 parts of phosphoric acid. , 6 parts of a monomer in which R in formula (I) is iso-butyl, and 2 parts of iodopropargyl compound: 3-iodo-2-propynylbutyl carbamate were charged, and the anionic polymerization was completed by stirring for about 15 minutes. A dispersion liquid (particles A) was obtained. Note that the average particle diameter of the particles was 83 nm.
（製造例２～７：粒子Ｂ～Ｇの製造）
下記表１に示す配合組成で、上記製造例１と同様にして各粒子の分散液（粒子Ｂ～Ｇ）を得た。なお、各粒子の平均粒子径は、下記表１に示す。
(Production Examples 2 to 7: Production of particles B to G)
Dispersions of each particle (particles B to G) were obtained in the same manner as in Production Example 1 above using the formulation shown in Table 1 below. Note that the average particle diameter of each particle is shown in Table 1 below.
（実施例１～７及び比較例１）
上記で得た製造例１～７の各粒子Ａ～Ｇを用いて、下記表２に示す配合組成（粒子Ａ～Ｇ、着色樹脂微粒子、トリエタノールアミン、エチレングリコール、蒸留水）で、常法により筆記具用水性インク組成物を得た。粒子Ａ～Ｇは、各粒子の分散液を有効成分２５質量％となるまで濃縮して得た各分散液（粒子）を用いた。比較例１は、各粒子Ａ～Ｇを含まない配合組成となる筆記具用水性インク組成物である。
(Examples 1 to 7 and Comparative Example 1)
Using each of the particles A to G of Production Examples 1 to 7 obtained above, the formulation composition shown in Table 2 below (particles A to G, colored resin fine particles, triethanolamine, ethylene glycol, distilled water) was prepared using a conventional method. An aqueous ink composition for writing instruments was obtained. For Particles A to G, each dispersion (particle) obtained by concentrating the dispersion of each particle to 25% by mass of the active ingredient was used. Comparative Example 1 is an aqueous ink composition for writing instruments that does not contain any of the particles A to G.
着色樹脂微粒子は、下記製造法により得た着色樹脂微粒子分散液を用いた。
（着色樹脂微粒子の製造）
２リットルのフラスコに、撹拌機、還流冷却器、温度計、窒素ガス導入管、モノマー投入用１０００ｍｌ分液漏斗を取り付け、温水槽にセットし、蒸留水５００ｇ、重合性界面活性剤〔アデカ社製“アデカリアソープＳＥ－１０Ｎ”〕５０ｇおよび過硫酸アンモニウム３ｇを仕込んで、窒素ガスを導入しながら、内温を５０℃まで昇温した。
一方、モノマーとして、フタル酸－２－メタクリロイルオキシエチル〔三菱レイヨン（株）製、アクリルエステルＰＡ）３００ｇと、他のモノマーとして、メタクリル酸ｎ－ブチル２００ｇとからなる混合モノマー５００ｇに、水溶性塩基性染料〔保土谷化学工業（株）製、「ＡＩＺＥＮ ＣＡＴＨＩＬＯＮ ＲＥＤ ＢＬＨ ２００％」〕４０ｇを混合した液を調製した。
この調製液を上記分液漏斗から温度５０℃付近に保った上記フラスコ内に撹拌下で３時間にわたって添加し、乳化重合を行った。さらに５時間熟成して重合を終了し、水性インク用着色樹脂微粒子の分散液（粒子）を得た。この着色樹脂微粒子の平均粒子径は８０ｎｍであり、樹脂固形分は３０質量％であった。
得られた各筆記具用水性インク組成物（全量１００質量％）について、下記評価方法により、抗菌性について評価した。
これらの結果を下記表２に示す。
As the colored resin fine particles, a colored resin fine particle dispersion obtained by the following manufacturing method was used.
(Manufacture of colored resin fine particles)
A 2-liter flask was equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a 1,000 ml separating funnel for introducing monomer, and was placed in a hot water tank. 50 g of "Adekaria Soap SE-10N" and 3 g of ammonium persulfate were charged, and the internal temperature was raised to 50° C. while introducing nitrogen gas.
On the other hand, a water-soluble base A liquid was prepared by mixing 40 g of a sex dye [“AIZEN CATHILON RED BLH 200%” manufactured by Hodogaya Chemical Industry Co., Ltd.].
This prepared solution was added from the separatory funnel into the flask kept at a temperature of around 50° C. over a period of 3 hours with stirring to perform emulsion polymerization. The mixture was further aged for 5 hours to complete polymerization, and a dispersion (particles) of colored resin fine particles for water-based ink was obtained. The average particle diameter of the colored resin fine particles was 80 nm, and the resin solid content was 30% by mass.
Each of the obtained aqueous ink compositions for writing instruments (total amount 100% by mass) was evaluated for antibacterial properties by the following evaluation method.
These results are shown in Table 2 below.
〔防腐効果（防菌性・防かび性）の試験方法〕
ＩＳＯ １１９３０：２０１２（保存効力試験または微生物学的リスク評価、またはその両方によって生成されたデータの解釈のための手順）に準拠した下記の微生物試験方法で行った。
下記細菌群、酵母、糸状菌の三群でチャレンジテストを実施した。
細菌群： Stapylococcus aureus NBRC13276、 Escherichia coli NBRC3972
酵母： Candida albicans NBRC1594
糸状菌： Aspergillus brasiliensis
[Test method for antiseptic effect (antibacterial/antifungal properties)]
The following microbiological test method was carried out in accordance with ISO 11930:2012 (Procedure for the interpretation of data generated by preservative efficacy tests and/or microbiological risk assessment).
A challenge test was conducted with the following three groups: bacteria, yeast, and filamentous fungi.
Bacterial group: Stapylococcus aureus NBRC13276, Escherichia coli NBRC3972
Yeast: Candida albicans NBRC1594
Filamentous fungi: Aspergillus brasiliensis
〈接種菌液の調製〉
接種菌液の調製：ＩＳＯ １１９３０：２０１２に従って菌液を調製した。
細菌群：各菌種毎にＩＳＯ １１９３０：２０１２に従って菌液を調製した。菌種毎に１×１０７～１×１０８ｃｆｕ／ｍｌに調整した菌液を三種等量混合し接種菌液とした。
酵母：ＩＳＯ １１９３０：２０１２に従い、１×１０６～１×１０７ｃｆｕ／ｍｌになるように菌液を調製した。
糸状菌：ＩＳＯ １１９３０：２０１２に従い、１×１０６～ １×１０７ｃｆｕ／ｍｌになるように菌液を調製した。
〈接種〉
筆記具用インク組成物に対し、１質量％の量の菌液を接種した。
〈保管〉
接種した筆記具用インク組成物は、温度２２．５±２．５℃に保管し指定された期間ごとに検出培養を行った。
Preparation of inoculum
Preparation of inoculum: The inoculum was prepared according to ISO 11930:2012.
Bacteria group: A bacterial solution was prepared for each bacterial species according to ISO 11930: 2012. Three equal amounts of bacterial solutions adjusted to 1 x 10 7 to 1 x 10 8 cfu/ml for each bacterial species were mixed to prepare an inoculum.
Yeast: A bacterial solution was prepared according to ISO 11930:2012 to give a concentration of 1×10 6 to 1×10 7 cfu/ml.
Filamentous fungi: A bacterial solution was prepared according to ISO 11930:2012 to give a bacterial concentration of 1×10 6 to 1×10 7 cfu/ml.
Inoculation
The ink composition for a writing instrument was inoculated with the bacterial liquid in an amount of 1% by mass.
<storage>
The inoculated ink composition for a writing instrument was stored at a temperature of 22.5±2.5° C. and subjected to detection culture at specified intervals.
〈検出培養〉
細菌群はＳＣＤ寒天培地で、酵母はＳＤ寒天培地で、糸状菌はＰＤ寒天培地でそれぞれ１０枚に合計１ｇ塗抹し、細菌群と酵母は３２．５℃、２日間、糸状菌は２２．５℃、５日間培養した。
〈評価基準〉
Ａ：７日目の時点でコロニーが出現しない。
Ｂ：２１日目の時点でコロニーが出現しない。
Ｃ：２８日目の時点で数個から数十個のコロニーが出現している。
Ｄ：２８日の時点で明らかに増えている。
<Detection culture>
A total of 1 g was smeared on 10 plates each on SCD agar medium for bacteria, SD agar medium for yeast, and PD agar medium for filamentous fungi. The cells were cultured at ℃ for 5 days.
<Evaluation criteria>
A: No colonies appear on the 7th day.
B: No colonies appear on the 21st day.
C: Several to several dozen colonies have appeared on the 28th day.
D: As of the 28th, the number has clearly increased.
上記表１～表２を考察すると、本発明の粒子Ａ～Ｇを含有する実施例１～７の筆記具用水性インク組成物は、本発明の範囲外となる比較例１の筆記具用水性インク組成物に較べ、防腐効果（防菌性・防かび性）に優れていることが判った。
また、実施例１～７の各筆記具用水性インク組成物について、密閉容器に入れ、２６℃下で３ヶ月保存した後、目視により凝集物等を官能評価したところ、全く粒子等の凝集はなく、保存安定性も問題ないことが判った。
Considering Tables 1 and 2 above, the aqueous writing instrument ink compositions of Examples 1 to 7 containing particles A to G of the present invention are different from the writing instrument aqueous ink composition of Comparative Example 1, which is outside the scope of the present invention. It was found that the antiseptic effect (antibacterial and antifungal properties) is superior to that of other materials.
In addition, for each of the aqueous ink compositions for writing instruments of Examples 1 to 7, after storing them in an airtight container at 26°C for 3 months, visual observation and sensory evaluation of aggregates etc. revealed that there was no aggregation of particles. It was also found that there were no problems with storage stability.
更に、上記保存安定性評価後の実施例１～７の各筆記具用インク組成物を用いて水性マーキングペンを作製した。具体的には、マーキングペン〔三菱鉛筆株式会社製、商品名：プロパス・ウインドウ ＰＵＳ－１０２Ｔ、ペン先、太：ＰＥ樹脂、細：ＰＥＴ繊維〕に上記各水性インクを充填し、マーキングペンを作製した。得られた各マーキングペンを用いて、ＰＰＣ用紙へ直径２ｃｍ程度の円を連続して描くように１０周螺旋筆記したところ、カスレが無く良好に筆記でき、筆記性能にも問題ないことが判った。 Furthermore, water-based marking pens were produced using each of the ink compositions for writing instruments of Examples 1 to 7 after the above-mentioned storage stability evaluation. Specifically, a marking pen [manufactured by Mitsubishi Pencil Co., Ltd., product name: Propass Window PUS-102T, nib, thick: PE resin, thin: PET fiber] was filled with each of the above water-based inks to produce a marking pen. did. Using each of the marking pens obtained, we wrote 10 times in a spiral on PPC paper, continuously drawing circles with a diameter of about 2 cm, and it was found that we could write well without any smearing, and there were no problems with writing performance. .
マーキングペン、ボールペンなどの筆記具に好適な筆記具用水性インク組成物が得られる。 An aqueous ink composition for writing instruments suitable for writing instruments such as marking pens and ballpoint pens is obtained.
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