JP2016147808A - Antibacterial/antifouling material and molding - Google Patents

Antibacterial/antifouling material and molding Download PDF

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JP2016147808A
JP2016147808A JP2013123055A JP2013123055A JP2016147808A JP 2016147808 A JP2016147808 A JP 2016147808A JP 2013123055 A JP2013123055 A JP 2013123055A JP 2013123055 A JP2013123055 A JP 2013123055A JP 2016147808 A JP2016147808 A JP 2016147808A
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acrylate
antibacterial
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渡辺　陽一
Yoichi Watanabe
陽一 渡辺
貴裕 山崎
Takahiro Yamazaki
貴裕 山崎
祐樹 首藤
Yuki Shuto
祐樹 首藤
夏世 蛭田
Natsuyo Hiruta
夏世 蛭田
精明 中村
Seimei Nakamura
精明 中村
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Lixil Corp
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    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/12—Esters of monohydric alcohols or phenols
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Abstract

PROBLEM TO BE SOLVED: To provide a material that has both antibacterial and antifouling properties.SOLUTION: An antibacterial/antifouling material according to an embodiment comprises a crosslinked copolymer in which the copolymers of quaternary ammonium (meth) acrylate (A) and siloxane (meth) acrylate (B) are crosslinked.SELECTED DRAWING: None

Description

本発明は、抗菌性および防汚性を有する材料に関する。   The present invention relates to a material having antibacterial and antifouling properties.

近年、清潔志向の高まりにより、住環境における汚染への対策が強く求められている。住環境における汚染としては、目に見える汚れだけでなく、種々の感染症の原因となりうる、細菌やウイルス等の微生物による汚染が問題となっている。この問題への対策として、住宅等の建材表面を防汚性を有する材料で被覆する技術が開発されている。たとえば、目に見える汚れに対する防汚性に効果があるとされる材料として、特許文献１に記載の組成物が知られている。   In recent years, due to the increase in cleanliness, countermeasures against pollution in the living environment are strongly demanded. As pollution in the living environment, contamination by microorganisms such as bacteria and viruses, which can cause various infectious diseases, is a problem as well as visible dirt. As a countermeasure to this problem, a technique for coating the surface of a building material such as a house with a material having antifouling properties has been developed. For example, a composition described in Patent Document 1 is known as a material that is effective in antifouling properties against visible dirt.

特開２０００−２９０５３５JP 2000-290535 A

従来の防汚性を有する材料については、防汚性について改善の余地があり、微生物による汚染を抑制する抗菌性については効果を奏しておらず、抗菌性および防汚性が両立した材料の開発が望まれている。   For conventional materials with antifouling properties, there is room for improvement in antifouling properties, and there is no effect on antibacterial properties to suppress contamination by microorganisms. Development of materials that have both antibacterial properties and antifouling properties Is desired.

本発明はこうした課題に鑑みてなされたものであり、その目的は、抗菌性と防汚性を兼ね備えた材料の提供にある。   This invention is made | formed in view of such a subject, The objective is to provide the material which has antibacterial property and antifouling property.

本発明のある態様は、抗菌・防汚材料である。当該抗菌・防汚材料は、４級アンモニウム（メタ）アクリレート（Ａ）と、シロキサン（メタ）アクリレート（Ｂ）との共重合体同士が架橋された架橋共重合体を含む。   One embodiment of the present invention is an antibacterial / antifouling material. The antibacterial / antifouling material includes a crosslinked copolymer obtained by crosslinking copolymers of quaternary ammonium (meth) acrylate (A) and siloxane (meth) acrylate (B).

上記態様の抗菌・防汚材料において、４級アンモニウム（メタ）アクリレート（Ａ）が下記一般式（１）で表されてもよい。

Figure 2016147808
上記式（１）中、Ｒ１はＨまたはＣＨ３であり、Ｒ２およびＲ３、Ｒ４は、互いに独立にメチル基またはベンジル基、炭素数１０〜１８のアルキル基であり、ｎ、ｍは０〜６の整数を表す。 In the antibacterial / antifouling material of the above aspect, the quaternary ammonium (meth) acrylate (A) may be represented by the following general formula (1).
Figure 2016147808
 In the above formula (1), R 1 is H or CH 3 , R 2, R 3 and R 4 are each independently a methyl group or a benzyl group, a C10-18 alkyl group, and n, m Represents an integer of 0-6.

また、シロキサン（メタ）アクリレート（Ｂ）が下記一般式で表されてもよい。

Figure 2016147808
上記式（２）中、Ｒ５は水素原子又は炭素数１〜５のアルキル基でありＲ６は炭素数１〜５のアルキル基又は炭素数６〜１０のアリール基であり、ｋは３〜１５０の数を表す。なお、式（２）中の複数のＲ６は互いに同一であってもよく、異なるものであってもよい。 Moreover, siloxane (meth) acrylate (B) may be represented by the following general formula.
Figure 2016147808
 In the above formula (2), R 5 is R 6 is an alkyl group of 1 to 5 hydrogen or C is an aryl group having 6 to 10 alkyl group or a C1-5 carbon, k is 3 Represents the number 150. In addition, several R < 6 > in Formula (2) may mutually be the same, and may differ.

４級アンモニウム（メタ）アクリレート（Ａ）由来のユニットと、シロキサン（メタ）アクリレート（Ｂ）由来のユニットの質量比が５：９５〜９５：５であってもよい。   The mass ratio of the unit derived from the quaternary ammonium (meth) acrylate (A) and the unit derived from the siloxane (meth) acrylate (B) may be 5:95 to 95: 5.

共重合体を構成するモノマーとして、（メタ）アクリルモノマーを含んでもよい。当該（メタ）アクリルモノマーが水酸基を有し、当該水酸基と結合するイソシアネート基を有する架橋剤によって前記共重合体同士が架橋されていてもよい。   A (meth) acryl monomer may be included as a monomer constituting the copolymer. The said (meth) acryl monomer has a hydroxyl group, The said copolymers may be bridge | crosslinked by the crosslinking agent which has the isocyanate group couple | bonded with the said hydroxyl group.

当該（メタ）アクリルモノマーが水酸基を有し、当該水酸基と結合するメラミンを有る架橋剤によって前記共重合体同士が架橋されていてもよい。   The said (meth) acryl monomer has a hydroxyl group, The said copolymers may be bridge | crosslinked by the crosslinking agent which has the melamine couple | bonded with the said hydroxyl group.

また当該（メタ）アクリルモノマーが多官能（メタ）アクリロイル基を有し、電子線、紫外線等によって前記共重合体同士が架橋されていてもよい。   The (meth) acrylic monomer may have a polyfunctional (meth) acryloyl group, and the copolymers may be cross-linked by an electron beam, ultraviolet rays or the like.

本発明の他の態様は成形品である。当該成形品は、上述したいずれかの態様の抗菌・防汚材料を含む。   Another embodiment of the present invention is a molded article. The molded article includes the antibacterial / antifouling material of any of the above-described aspects.

なお、上述した各要素を適宜組み合わせたものも、本件特許出願によって特許による保護を求める発明の範囲に含まれうる。   A combination of the above-described elements as appropriate can also be included in the scope of the invention for which patent protection is sought by this patent application.

本発明によれば、抗菌性と防汚性を兼ね備えた材料が提供される。   According to the present invention, a material having both antibacterial properties and antifouling properties is provided.

以下、本発明の実施の形態について説明する。   Embodiments of the present invention will be described below.

実施の形態に係る抗菌・防汚材料は、４級アンモニウム（メタ）アクリレート（Ａ）とシロキサン（メタ）アクリレート（Ｂ）との共重合体同士が架橋剤（Ｃ）によって架橋された架橋共重合体を含む。以下、実施の形態に係る抗菌・防汚材料について詳細に説明する。   The antibacterial / antifouling material according to the embodiment is a crosslinked copolymer in which copolymers of quaternary ammonium (meth) acrylate (A) and siloxane (meth) acrylate (B) are crosslinked with a crosslinking agent (C). Includes coalescence. Hereinafter, the antibacterial / antifouling material according to the embodiment will be described in detail.

（４級アンモニウム（メタ）アクリレート（Ａ））
４級アンモニウム（メタ）アクリレート（Ａ）は下記一般式（１）で表される。

Figure 2016147808
上記式（１）中、Ｒ１はＨまたはＣＨ３であり、Ｒ２およびＲ３、Ｒ４は、互いに独立にメチル基またはベンジル基、炭素数１０〜１８のアルキル基であり、ｎ、ｍは０〜６の整数を表す。また、一般的に４級アンモニウムは、対イオンとしてＣｌ−、Ｉ−、Ｂｒ−等のアニオンと塩の形で存在する。この対イオンとしてはこれらに限定されるものではなく、また効果の発現に必須のものではない。 (Quaternary ammonium (meth) acrylate (A))
The quaternary ammonium (meth) acrylate (A) is represented by the following general formula (1).
Figure 2016147808
 In the above formula (1), R 1 is H or CH 3 , R 2, R 3 and R 4 are each independently a methyl group or a benzyl group, a C10-18 alkyl group, and n, m Represents an integer of 0-6. In general, quaternary ammonium is present as a counter ion in the form of a salt with an anion such as Cl − , I − and Br − . This counter ion is not limited to these, and is not essential for the expression of the effect.

（シロキサン（メタ）アクリレート（Ｂ））
シロキサン（メタ）アクリレート（Ｂ）は下記一般式で表される。

Figure 2016147808
上記式（２）中、Ｒ５は水素原子又は炭素数１〜５のアルキル基でありＲ６は炭素数１〜５のアルキル基又は炭素数６〜１０のアリール基であり、ｋは３〜１５０の数を表す。なお、式（２）中の複数のＲ６は互いに同一であってもよく、異なるものであってもよい。 (Siloxane (meth) acrylate (B))
Siloxane (meth) acrylate (B) is represented by the following general formula.
Figure 2016147808
 In the above formula (2), R 5 is R 6 is an alkyl group of 1 to 5 hydrogen or C is an aryl group having 6 to 10 alkyl group or a C1-5 carbon, k is 3 Represents the number 150. In addition, several R < 6 > in Formula (2) may mutually be the same, and may differ.

シロキサン（メタ）アクリレート（Ｂ）の数平均分子量は５００〜１１０００が好ましく、１０００〜１００００がより好ましい。シロキサン（メタ）アクリレート（Ｂ）の数平均分子量が５００未満だと水と油の接触角は低く、かつ水の滑落性、油の滑落性の向上に効果が十分でない。シロキサン（メタ）アクリレート（Ｂ）の数平均分子量が１１０００より大きいと、水酸基を有する（メタ）アクリル酸系重合体との相溶性が悪くなり、硬化塗膜が不透明になるとともに、水滑落性が悪化しやすくなる。   The number average molecular weight of the siloxane (meth) acrylate (B) is preferably 500 to 11,000, more preferably 1000 to 10,000. If the number average molecular weight of the siloxane (meth) acrylate (B) is less than 500, the contact angle between water and oil is low, and the effect of improving the water sliding property and oil sliding property is not sufficient. When the number average molecular weight of the siloxane (meth) acrylate (B) is greater than 11,000, the compatibility with the (meth) acrylic acid polymer having a hydroxyl group is deteriorated, the cured coating film becomes opaque, and the water sliding property is reduced. It becomes easy to get worse.

シロキサン（メタ）アクリレート（Ｂ）として、サイラプレーンＦＭ−０７１１（ＪＮＣ株式会社製、ｎ＝１０、分子量１０００）、サイラプレーンＦＭ−０７２１（ＪＮＣ株式会社製、ｎ＝６１、分子量５０００）、サイラプレーンＦＭ−０７２５（ＪＮＣ株式会社製、ｎ＝１２５、分子量１００００）、Ｘ−２２−５００２（信越化学工業株式会社製、ｎ＝２．８、分子量４２２．８）等が挙げられる。   As Siloxane (meth) acrylate (B), Silaplane FM-0711 (manufactured by JNC Corporation, n = 10, molecular weight 1000), Silaplane FM-0721 (manufactured by JNC Corporation, n = 61, molecular weight 5000), Silaplane FM-0725 (manufactured by JNC Corporation, n = 125, molecular weight 10,000), X-22-5002 (manufactured by Shin-Etsu Chemical Co., Ltd., n = 2.8, molecular weight 422.8) and the like.

４級アンモニウム（メタ）アクリレート（Ａ）由来のユニットと、シロキサン（メタ）アクリレート（Ｂ）由来のユニットの質量比は５：９５〜９５：５であることが好ましい。上記質量比の範囲において、抗菌性および防汚性だけでなく、抗ウイルス性・防黴性・防藻性の効果が生じうる。４級アンモニウム（メタ）アクリレート（Ａ）の量が少なすぎると、抗菌性、抗ウイルス性、防黴性、防藻性が十分でなくなり、シロキサン（メタ）アクリレート（Ｂ）の量が少なすぎると、防汚性が十分でなくなる。   The mass ratio of the unit derived from the quaternary ammonium (meth) acrylate (A) and the unit derived from the siloxane (meth) acrylate (B) is preferably 5:95 to 95: 5. Within the above mass ratio range, not only antibacterial and antifouling properties but also antiviral, antifungal and antialgal properties can be produced. If the amount of quaternary ammonium (meth) acrylate (A) is too small, antibacterial properties, antiviral properties, antifungal properties, and antialgae properties will be insufficient, and if the amount of siloxane (meth) acrylate (B) is too small , Antifouling property is not enough.

（（メタ）アクリルモノマー（β））
実施の形態に係る抗菌・防汚材料を構成する共重合体は、共重合可能なモノマーとして（メタ）アクリルモノマー（β）をさらに含む。（メタ）アクリルモノマー（β）は、ラジカル重合性二重結合を有していれば特に限定されるものではないが、例えば分子中に（メタ）アクリロイル基を１つ持つモノマーであるメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート等の脂肪族または環式（メタ）アクリレート類を挙げることができ、更に分子中に（メタ）アクリロイル基を２つ以上持つ単量体であるペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート等のペンタエリスリトール類、トリメチロールプロパンジ（メタ）アクリレート等のメチロール類、ビスフェノールＡジエポキシアクリレート等のエポキシアクリレート類を挙げることができる。 ((Meth) acrylic monomer (β))
The copolymer constituting the antibacterial / antifouling material according to the embodiment further contains a (meth) acrylic monomer (β) as a copolymerizable monomer. The (meth) acrylic monomer (β) is not particularly limited as long as it has a radical polymerizable double bond. For example, methyl (meta) which is a monomer having one (meth) acryloyl group in the molecule. ) Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, and other aliphatic or cyclic (meth) acrylates. 2 or more (meth) acryloyl groups Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, etc. And pentaerythritols, methylols such as trimethylolpropane di (meth) acrylate, and epoxy acrylates such as bisphenol A diepoxy acrylate.

また、（メタ）アクリルモノマー（β）として、例えばメチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル等のビニルエーテル類、スチレン、α−メチルスチレン等のスチレン類、アクリロニトリル、メタクリロニトリル等のニトリル系単量体を挙げることができる。   Examples of the (meth) acrylic monomer (β) include vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, styrenes such as styrene and α-methyl styrene, acrylonitrile, and methacrylate. Examples thereof include nitrile monomers such as rhonitrile.

また、（メタ）アクリルモノマー（β）は、ラジカル重合性二重結合と合わせて水酸基を有してもよい。このような（メタ）アクリルモノマー（β）として、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、２−ヒドロキシ−３−アクリロイロイキシプロピル（メタ）アクリレート等のヒドロキシ（メタ）アクリレートを挙げることができる。これらは、架橋の機能点としての役割も果たすことがある。   The (meth) acrylic monomer (β) may have a hydroxyl group together with the radical polymerizable double bond. Examples of such (meth) acrylic monomer (β) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Examples include hydroxy (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth) acrylate. These may also serve as functional points for crosslinking.

（架橋剤（Ｃ））
架橋剤（Ｃ）は、上述した水酸基と結合する官能基、たとえば、イソシアネート基を有してれば特に限定されないが、たとえば、４，４’−ジフェニルメタンジイソシアネート、２，４−トルエンジイソシアネート、２，６−トルエンジイソシアネートなどが挙げられる。他には水酸基と結合するメラミン類、例えば、ヘキサメトキシメチルメラミン、ベンゾグアナミン、アセトグアナミン、スピログアナミン、ジシアンジアミド、およびそのメチロール化物などが挙げられる。 (Crosslinking agent (C))
The crosslinking agent (C) is not particularly limited as long as it has a functional group that binds to the above-described hydroxyl group, for example, an isocyanate group. For example, 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2, Examples include 6-toluene diisocyanate. Other examples include melamines that bind to hydroxyl groups, such as hexamethoxymethylmelamine, benzoguanamine, acetoguanamine, spiroguanamine, dicyandiamide, and methylolated products thereof.

また、（メタ）アクリルモノマーとしてペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート等のペンタエリスリトール類、トリメチロールプロパンジ（メタ）アクリレート等を用いれば、架橋剤を用いずに、電子線、紫外線等で架橋させることができる。   Moreover, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) as (meth) acrylic monomers If pentaerythritols such as acrylate, trimethylolpropane di (meth) acrylate, or the like is used, crosslinking can be performed with an electron beam, ultraviolet rays or the like without using a crosslinking agent.

（抗菌・防汚材料の作製方法）
実施の形態に係る抗菌・防汚材料の作製方法としては、少なくとも以下の３つの手順が存在する。
（１）上述した各モノマーを混合した後、１０℃〜２００℃、２時間〜４８時間の重合条件で反応させた後、架橋剤の適量を混合する方法。
（２）上述した各モノマーの一部について前駆体を用い、当該前駆体と残りのモノマーを１０℃〜２００℃、２時間〜２４時間の重合条件で反応させた後、当該前駆体に必要な官能基等を付加させた後、架橋剤の適量を混合させる方法。
（３）上述した各モノマーの一部について前駆体を用い、当該前駆体と残りのモノマーを１０℃〜２００℃、２時間〜２４時間の重合条件で反応させた後、架橋剤の適量を混合、その後、当該前駆体に必要な官能基等を付加させる方法。
たとえば、
ａ）４級アンモニウム（メタ）アクリレート（Ａ）の前駆体として、エポキシ基を有する（メタ）アクリレートを用い、重合反応を行ったのち、エポキシ基に３級アミン塩酸塩を付加反応させる方法、
ｂ）４級アンモニウム（メタ）アクリレート（Ａ）の前駆体として３級アミンを有する（メタ）アクリレートを用い、重合反応を行ったのち、３級アミンにハロゲン化アルキルを付加反応させる方法。
等が挙げられる。 (Production method of antibacterial and antifouling materials)
As a method for producing the antibacterial / antifouling material according to the embodiment, at least the following three procedures exist.
(1) A method in which each monomer described above is mixed and then reacted under polymerization conditions of 10 ° C. to 200 ° C. for 2 hours to 48 hours, and then an appropriate amount of a crosslinking agent is mixed.
(2) Using a precursor for a part of each monomer described above, the precursor and the remaining monomer are reacted under polymerization conditions of 10 ° C. to 200 ° C. for 2 hours to 24 hours, and then necessary for the precursor. A method of adding an appropriate amount of a crosslinking agent after adding a functional group or the like.
(3) Using a precursor for a part of each monomer described above, reacting the precursor and the remaining monomer under polymerization conditions of 10 ° C. to 200 ° C. for 2 hours to 24 hours, and then mixing an appropriate amount of the crosslinking agent Then, a method of adding a necessary functional group or the like to the precursor.
For example,
a) As a precursor of the quaternary ammonium (meth) acrylate (A), a (meth) acrylate having an epoxy group is used, and after the polymerization reaction, a tertiary amine hydrochloride is added to the epoxy group,
b) A method in which a (meth) acrylate having a tertiary amine is used as a precursor of the quaternary ammonium (meth) acrylate (A), a polymerization reaction is performed, and then an alkyl halide is added to the tertiary amine.
Etc.

なお、実施の形態に係る抗菌・防汚材料を構成する共重合体を作製するにあたり、２，２’アゾビスイソブチロニトリル、１，１’−アゾビス（シクロヘキサンカルボニトリル）などのアゾ化合物、過酸化ベンゾイル等の過酸化物に代表される重合開始剤を用いてもよい。   In preparing the copolymer constituting the antibacterial / antifouling material according to the embodiment, an azo compound such as 2,2′azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), A polymerization initiator represented by a peroxide such as benzoyl peroxide may be used.

（抗菌・防汚材料の用途）
実施の形態に係る抗菌・防汚材料の用途は、抗菌性および防汚性が求められる成形品であれば特に限定されないが、たとえば、内壁・外壁・タイル・サッシ・カーポート・ドアノブ・床材などが挙げられる。なお、当該成形品は、その全体が実施の形態に係る抗菌・防汚材料で形成される形態や、他の材料で形成された基材の表面に実施の形態に係る抗菌・防汚材料で形成された表層が積層された形態を取り得る。また、この場合の表層は、実施の形態に係る抗菌・防汚材料を含む塗液を用いてスプレー法にて形成してもよい。 (Use of antibacterial and antifouling materials)
The use of the antibacterial / antifouling material according to the embodiment is not particularly limited as long as it is a molded product that requires antibacterial and antifouling properties. For example, the inner wall / outer wall / tile / sash / carport / door knob / floor material Etc. In addition, the molded product is formed of the antibacterial / antifouling material according to the embodiment on the surface formed of the antibacterial / antifouling material according to the embodiment as a whole or the surface of a substrate formed of another material. The formed surface layer can take the form laminated | stacked. Further, the surface layer in this case may be formed by a spray method using a coating liquid containing the antibacterial / antifouling material according to the embodiment.

以上説明した実施の形態に係る抗菌・防汚材料によれば、主に４級アンモニウム（メタ）アクリレート（Ａ）によって発揮される抗菌性と、主にシロキサン（メタ）アクリレート（Ｂ）によって発揮される撥水性、撥油性から得られる防汚性の両方を兼ね備えることができる。また、４級アンモニウム（メタ）アクリレート（Ａ）による帯電防止性能により防塵性も発揮されうる。   According to the antibacterial / antifouling material according to the embodiment described above, the antibacterial property exhibited mainly by the quaternary ammonium (meth) acrylate (A) and the main effect exhibited by the siloxane (meth) acrylate (B). It can have both antifouling properties obtained from water repellency and oil repellency. Moreover, dustproofness can also be exhibited by the antistatic performance by quaternary ammonium (meth) acrylate (A).

以下、本発明の実施例を説明するが、これら実施例は、本発明を好適に説明するための例示に過ぎず、なんら本発明を限定するものではない。   Examples of the present invention will be described below. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.

（４級アンモニウムメタクリレート１の合成）
Ｎ，Ｎ−ジメチルオクタデシルアミン（日油株式会社製、商品名：３級アミンＡＢ）１５ｇをエタノール（関東化学製）１５ｇに溶解した。これに塩酸（関東化学製）５．１ｇをエタノール（関東化学製）５．１ｇに溶解したものを滴下した。固形物をロート上にてエタノールにより洗浄、乾燥することにより、Ｎ，Ｎ−ジメチルオクタデシルアミン塩酸塩を得た。 (Synthesis of quaternary ammonium methacrylate 1)
15 g of N, N-dimethyloctadecylamine (manufactured by NOF Corporation, trade name: tertiary amine AB) was dissolved in 15 g of ethanol (manufactured by Kanto Chemical). A solution prepared by dissolving 5.1 g of hydrochloric acid (manufactured by Kanto Chemical) in 5.1 g of ethanol (manufactured by Kanto Chemical) was added dropwise thereto. The solid was washed with ethanol on the funnel and dried to obtain N, N-dimethyloctadecylamine hydrochloride.

このＮ，Ｎ−ジメチルオクタデシルアミン塩酸塩１９ｇ、メタクリル酸２，３−エポキシプロピル（日油株式会社製、商品名：ブレンマーＧ）８．１ｇ、ヒドロキノン（関東化学製）０．０８ｇをベンジルアルコール（関東化学製）２７．１ｇ中で、６０℃で６時間反応させた。得られた溶液にジエチルエーテル（関東化学製）を大量に加えて生成した沈殿を濾過、ジエチルエーテルで洗浄、乾燥することにより、４級アンモニウムメタクリレート１を得た。   19 g of this N, N-dimethyloctadecylamine hydrochloride, 2,3-epoxypropyl methacrylate (manufactured by NOF Corporation, trade name: Blenmer G), 8.1 g of hydroquinone (manufactured by Kanto Chemical Co., Ltd.), 0.08 g of benzyl alcohol ( In 27.1 g (manufactured by Kanto Chemical Co., Ltd.) at 60 ° C. for 6 hours. Quaternary ammonium methacrylate 1 was obtained by adding a large amount of diethyl ether (manufactured by Kanto Chemical Co., Inc.) to the resulting solution and filtering the precipitate formed, washing with diethyl ether and drying.

（４級アンモニウムメタクリレート２の合成）
２−（ジメチルアミノ）エチルメタクリレート（ＡＬＤＲＩＣＨ製）１０ｇ、１−ヨードオクタデカン（ＡＬＤＲＩＣＨ製）２２ｇ、ハイドロキノン（関東化学製）０．００５ｇを混合し、窒素気流下５０℃で６時間反応させた。これをジエチルエーテルで洗浄、乾燥することにより、４級アンモニウムメタクリレート２を得た。 (Synthesis of quaternary ammonium methacrylate 2)
10 g of 2- (dimethylamino) ethyl methacrylate (manufactured by ALDRICH), 22 g of 1-iodooctadecane (manufactured by ALDRICH), and 0.005 g of hydroquinone (manufactured by Kanto Chemical) were mixed and reacted at 50 ° C. for 6 hours in a nitrogen stream. This was washed with diethyl ether and dried to obtain quaternary ammonium methacrylate 2.

（ポリマーの合成）
（実施例１）
窒素気流下、ポリジメチルシロキサンマクロモノマー（ＪＮＣ株式会社製、商品名：サイラプレーンＦＭ−０７２１）９．２ｇ、上記で得た４級アンモニウムメタアクリレート１（７．５ｇ）、メタクリル酸メチル（関東化学製）３１．３ｇ、メタクリル酸ｎ−ブチル（関東化学製）９．４ｇ、メタクリル酸２−ヒドロキシエチル（関東化学製）１２．５ｇ、メタクリル酸（関東化学製）０．６ｇをｔ−ブチルアルコール（関東化学）３１．３ｇ、４‐メチル‐２‐ペンタノン（関東化学製）３４．４ｇ、シクロヘキサノン（関東化学製）９．４ｇの混合溶媒に溶解し７０℃に加温した。 (Polymer synthesis)
Example 1
Under a nitrogen stream, 9.2 g of polydimethylsiloxane macromonomer (manufactured by JNC Corporation, trade name: Silaplane FM-0721), quaternary ammonium methacrylate 1 (7.5 g) obtained above, methyl methacrylate (Kanto Chemical) 31.3 g, n-butyl methacrylate (Kanto Chemical Co.) 9.4 g, 2-hydroxyethyl methacrylate (Kanto Chemical Co.) 12.5 g, methacrylic acid (Kanto Chemical Co.) 0.6 g was added to t-butyl alcohol (Kanto Chemical) 31.3 g, 4-methyl-2-pentanone (manufactured by Kanto Chemical) 34.4 g and cyclohexanone (manufactured by Kanto Chemical) 9.4 g were dissolved in a mixed solvent and heated to 70 ° C.

ここに２，２′−アゾビスイソブチロニトリル（関東化学製）１．８ｇを４−メチル−２−ペンタノン１８．３ｇに溶解したものを添加し、９０℃に昇温し窒素気流下で２時間反応させることにより、４級アンモニウム塩−ポリジメチルシロキサン共重合ポリマー溶液を得た。   A solution prepared by dissolving 1.8 g of 2,2′-azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) in 18.3 g of 4-methyl-2-pentanone was added, and the temperature was raised to 90 ° C. under a nitrogen stream. By reacting for 2 hours, a quaternary ammonium salt-polydimethylsiloxane copolymer solution was obtained.

この４級アンモニウム−ポリジメチルシロキサン共重合ポリマー溶液５ｇ、タケネートＤ−１７０Ｎ（三井化学社製）１ｇを混合、ＡＢＳ板に塗布し、８０℃で３０分間加熱することにより、４級アンモニウム−ポリジメチルシロキサン共重合ポリマー塗膜を得た。   5 g of this quaternary ammonium-polydimethylsiloxane copolymer solution and 1 g of Takenate D-170N (Mitsui Chemicals) were mixed, applied to an ABS plate, and heated at 80 ° C. for 30 minutes for quaternary ammonium-polydimethyl. A siloxane copolymer film was obtained.

（実施例２）
実施例１の組成を表１のように変更する以外は実施例１と同様に実施した。 (Example 2)
The same procedure as in Example 1 was performed except that the composition of Example 1 was changed as shown in Table 1.

（実施例３）
実施例１の組成を表１のように変更する以外は実施例１と同様に実施した。 (Example 3)
The same procedure as in Example 1 was performed except that the composition of Example 1 was changed as shown in Table 1.

（比較例１）
実施例１のポリジメチルシロキサンマクロマーを０にする以外は実施例１と同様に行なった。 (Comparative Example 1)
The same procedure as in Example 1 was performed except that the polydimethylsiloxane macromer of Example 1 was changed to 0.

（比較例２）
実施例１の４級アンモニウムメタクリレート１を０にする以外は実施例１と同様に行なった。 (Comparative Example 2)
The same procedure as in Example 1 was performed except that the quaternary ammonium methacrylate 1 of Example 1 was changed to 0.

（実施例４）
４級アンモニウムメタクリレートとして４級アンモニウムメタクリレート２を用い、組成を表１にする以外は実施例１と同様に実施した。 Example 4
The same procedure as in Example 1 was performed except that quaternary ammonium methacrylate 2 was used as the quaternary ammonium methacrylate and the composition was changed to Table 1.

（実施例５）
窒素気流下、ポリジメチルシロキサンマクロマー（ＪＮＣ株式会社製、商品名：サイラプレーンＦＭ−０７２１）９．７ｇ、メタクリル酸２，３−エポキシプロピル（日油株式会社製、商品名：ブレンマーＧ）２．６ｇ、メタクリル酸メチル（関東化学製）３１．３ｇ、メタクリル酸ｎ−ブチル（関東化学製）９．４ｇ、メタクリル酸２−ヒドロキシエチル（関東化学製）１２．５ｇ、メタクリル酸（関東化学製）０．６ｇをｔ−ブチルアルコール（関東化学）３１．３ｇ、４−メチル−２−ペンタノン（関東化学製）３４．４ｇ、シクロヘキサノン（関東化学製）９．４ｇの混合溶媒に溶解し７０℃に加温した。 (Example 5)
Under a nitrogen stream, 9.7 g of polydimethylsiloxane macromer (manufactured by JNC Corporation, trade name: Silaplane FM-0721), 2,3-epoxypropyl methacrylate (manufactured by NOF Corporation, trade name: Bremmer G) 2. 6 g, 31.3 g of methyl methacrylate (manufactured by Kanto Chemical), 9.4 g of n-butyl methacrylate (manufactured by Kanto Chemical), 12.5 g of 2-hydroxyethyl methacrylate (manufactured by Kanto Chemical), methacrylic acid (manufactured by Kanto Chemical) 0.6 g was dissolved in a mixed solvent of 31.3 g of t-butyl alcohol (Kanto Chemical), 34.4 g of 4-methyl-2-pentanone (Kanto Chemical), and 9.4 g of cyclohexanone (Kanto Chemical) and dissolved at 70 ° C. Warmed up.

ここに２，２′−アゾビスイソブチロニトリル（関東化学製）１．８ｇを４−メチル−２−ペンタノン１８．３ｇに溶解したものを添加し、９０℃に昇温して窒素気流下で２時間反応させることにより、ポリジメチルシロキサン共重合ポリマー溶液を得た。   A solution prepared by dissolving 1.8 g of 2,2′-azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) in 18.3 g of 4-methyl-2-pentanone was added, and the temperature was raised to 90 ° C. under a nitrogen stream. For 2 hours to obtain a polydimethylsiloxane copolymer solution.

このポリジメチルシロキサン共重合ポリマー溶液５ｇに上記で得たＮ，Ｎ−ジメチルオクタデシルアミン塩酸塩０．１７ｇを添加し、８０℃で２４時間反応させることにより、４級アンモニウム−ポリジメチルシロキサン共重合ポリマー溶液を得た。   By adding 0.17 g of N, N-dimethyloctadecylamine hydrochloride obtained above to 5 g of this polydimethylsiloxane copolymer solution and reacting at 80 ° C. for 24 hours, a quaternary ammonium-polydimethylsiloxane copolymer polymer is obtained. A solution was obtained.

この４級アンモニウム−ポリジメチルシロキサン共重合ポリマー溶液に、タケネートＤ−１７０Ｎ（三井化学社製）１ｇを混合、ＡＢＳ板に塗布し、８０℃で３０分間加熱することにより、４級アンモニウム塩−ポリジメチルシロキサン共重合塗膜を得た。   To this quaternary ammonium-polydimethylsiloxane copolymer solution, 1 g of Takenate D-170N (Mitsui Chemicals) was mixed, applied to an ABS plate, and heated at 80 ° C. for 30 minutes to quaternary ammonium salt-poly A dimethylsiloxane copolymer coating film was obtained.

（実施例６）
窒素気流下、ポリジメチルシロキサンマクロマー（ＪＮＣ株式会社製、商品名：サイラプレーンＦＭ−０７２１）９．７ｇ、メタクリル酸２，３−エポキシプロピル（日油株式会社製、商品名：ブレンマーＧ）２．６ｇ、メタクリル酸メチル（関東化学製）３１．３ｇ、メタクリル酸ｎ−ブチル（関東化学製）９．４ｇ、メタクリル酸２−ヒドロキシエチル（関東化学製）１２．５ｇ、メタクリル酸（関東化学製）０．６ｇをｔ−ブチルアルコール（関東化学）３１．３ｇ、４‐メチル‐２‐ペンタノン（関東化学製）３４．４ｇ、シクロヘキサノン（関東化学製）９．４ｇの混合溶媒に溶解し７０℃に加温した。 (Example 6)
Under a nitrogen stream, 9.7 g of polydimethylsiloxane macromer (manufactured by JNC Corporation, trade name: Silaplane FM-0721), 2,3-epoxypropyl methacrylate (manufactured by NOF Corporation, trade name: Bremmer G) 2. 6 g, 31.3 g of methyl methacrylate (manufactured by Kanto Chemical), 9.4 g of n-butyl methacrylate (manufactured by Kanto Chemical), 12.5 g of 2-hydroxyethyl methacrylate (manufactured by Kanto Chemical), methacrylic acid (manufactured by Kanto Chemical) 0.6 g was dissolved in a mixed solvent of 31.3 g of t-butyl alcohol (Kanto Chemical), 34.4 g of 4-methyl-2-pentanone (manufactured by Kanto Chemical), and 9.4 g of cyclohexanone (manufactured by Kanto Chemical) and heated to 70 ° C. Warmed up.

ここに２，２′−アゾビスイソブチロニトリル（関東化学製）１．８ｇを４−メチル−２−ペンタノン１８．３ｇに溶解したものを添加し、９０℃に昇温し窒素気流下で２時間反応させることにより、ポリジメチルシロキサン共重合ポリマー溶液を得た。   A solution prepared by dissolving 1.8 g of 2,2′-azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) in 18.3 g of 4-methyl-2-pentanone was added, and the temperature was raised to 90 ° C. under a nitrogen stream. By reacting for 2 hours, a polydimethylsiloxane copolymer solution was obtained.

このポリジメチルシロキサン共重合ポリマー溶液を５ｇ、タケネートＤ−１７０Ｎ（三井化学社製）１ｇを混合、ＡＢＳ板に塗布し、８０℃で３０分間加熱することにより、ポリジメチルシロキサン共重合塗膜を得た。   5 g of this polydimethylsiloxane copolymer solution and 1 g of Takenate D-170N (Mitsui Chemicals) were mixed, applied to an ABS plate, and heated at 80 ° C. for 30 minutes to obtain a polydimethylsiloxane copolymer coating film. It was.

更にこのポリジメチルシロキサン共重合塗膜をＮ，Ｎ−ジメチルオクタデシルアミン塩酸塩３ｇ、イソプロパノール（関東化学製）８０ｇ、水２０ｇの溶液に浸漬し、８０℃で３０分間反応させて４級アンモニウム−ポリジメチルシロキサン共重合ポリマー塗膜を得た。   Furthermore, this polydimethylsiloxane copolymer coating film was immersed in a solution of 3 g of N, N-dimethyloctadecylamine hydrochloride, 80 g of isopropanol (manufactured by Kanto Chemical), and 20 g of water, and reacted at 80 ° C. for 30 minutes to quaternary ammonium-poly A dimethylsiloxane copolymer polymer coating film was obtained.

（比較例４、５、６）
窒素気流下、ポリジメチルシロキサンマクロマー（ＪＮＣ株式会社製、商品名：サイラプレーンＦＭ−０７２１）９．７ｇ、メタクリル酸メチル（関東化学製）３１．３ｇ、メタクリル酸ｎ−ブチル（関東化学製）９．４ｇ、メタクリル酸２−ヒドロキシエチル（関東化学製）１２．５ｇ、メタクリル酸（関東化学製）０．６ｇをｔ−ブチルアルコール（関東化学）３１．３ｇ、４‐メチル‐２‐ペンタノン（関東化学製）３４．４ｇ、シクロヘキサノン（関東化学製）９．４ｇの混合溶媒に溶解し７０℃に加温した。 (Comparative Examples 4, 5, 6)
Under a nitrogen stream, polydimethylsiloxane macromer (manufactured by JNC Corporation, trade name: Silaplane FM-0721) 9.7 g, methyl methacrylate (manufactured by Kanto Chemical) 31.3 g, methacrylate n-butyl (manufactured by Kanto Chemical) 9 .4 g, 2-hydroxyethyl methacrylate (manufactured by Kanto Chemical) 12.5 g, methacrylic acid (manufactured by Kanto Chemical) 0.6 g, t-butyl alcohol (Kanto Chemical) 31.3 g, 4-methyl-2-pentanone (Kanto) (Chemical) 34.4 g and cyclohexanone (Kanto Chemical) 9.4 g were dissolved in a mixed solvent and heated to 70 ° C.

ここに２，２′−アゾビスイソブチロニトリル（関東化学製）１．８ｇを４−メチル−２−ペンタノン１８．３ｇに溶解したものを添加し、９０℃に昇温し窒素気流下で２時間反応させることにより、ポリジメチルシロキサン共重合ポリマー溶液を得た。   A solution prepared by dissolving 1.8 g of 2,2′-azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) in 18.3 g of 4-methyl-2-pentanone was added, and the temperature was raised to 90 ° C. under a nitrogen stream. By reacting for 2 hours, a polydimethylsiloxane copolymer solution was obtained.

このポリジメチルシロキサン共重合ポリマー溶液に、反応基を持たない４級アンモニウム塩として、塩化オクタデシルトリメチルアンモニウム（東邦化学製、商品名：カチナールＳＴＣ−７０ＥＴ、固形分７０％）を表１のように添加した。この混合液５ｇ、タケネートＤ−１７０Ｎ（三井化学社製）１ｇを混合、ＡＢＳ板に塗布し、８０℃で３０分間加熱することにより、ポリジメチルシロキサン共重合、４級アンモニウム混合塗膜を得た。

Figure 2016147808
To this polydimethylsiloxane copolymer solution, octadecyltrimethylammonium chloride (manufactured by Toho Chemical Co., Ltd., trade name: Katchinal STC-70ET, solid content 70%) as a quaternary ammonium salt having no reactive group is added as shown in Table 1. did. 5 g of this mixed solution and 1 g of Takenate D-170N (Mitsui Chemicals) were mixed, applied to an ABS plate, and heated at 80 ° C. for 30 minutes to obtain a polydimethylsiloxane copolymer and a quaternary ammonium mixed coating film. .
Figure 2016147808

＜抗菌性評価＞
実施例１〜４、比較例１〜５の各試験片について、ＪＩＳ Ｚ ２８０１に準拠して抗菌試験を行なった。試験対象菌はＥｓｃｈｅｒｉｃｈｉａ ｃｏｉｌ（ＮＢＲＣ３９７２）とした。具体的には、試験片（５ｃｍ×５ｃｍ）を滅菌シャーレに入れ、接種用菌液０．４ｍＬを試験品に接種し、さらに４ｃｍ角のポリプロピレンフィルムで試験片の上面を覆った。これを温度３５℃、ＲＨ９０％以上のデシケーターの中に置き、接触時間１０分後の生菌数を下記の測定方法により測定した。また、試験片の代わりに同サイズの無加工フィルム（ＡＢＳフィルム）を用いた対照品についても同様に接種用菌液を接種し、接種直後、接触時間１０分後の生菌数を試験片と同様に下記の測定方法により測定した。 <Antimicrobial evaluation>
About each test piece of Examples 1-4 and Comparative Examples 1-5, the antimicrobial test was done based on JISZ2801. The test subject was Escherichia coil (NBRC 3972). Specifically, a test piece (5 cm × 5 cm) was placed in a sterile petri dish, 0.4 mL of the inoculum bacterial solution was inoculated into the test product, and the upper surface of the test piece was covered with a 4 cm square polypropylene film. This was placed in a desiccator at a temperature of 35 ° C. and RH 90% or more, and the viable cell count after 10 minutes of contact time was measured by the following measuring method. In addition, for the control product using the same size unprocessed film (ABS film) instead of the test piece, the inoculum was inoculated in the same manner. Similarly, it was measured by the following measuring method.

（生菌数の測定方法）
ポリプロピレンフィルムと試験片をともにストマッカー用滅菌ポリ袋に入れ、ＳＣＤＬＰ培地１０ｍｌを加え、手またはストマッカーで試験菌を洗い出した。この洗い出し液１ｍｌ中の生菌数を、ＳＣＤＬＰ寒天培地混釈法により測定した。生菌数は、試験片１ｃｍ２あたりに換算した。 (Measurement method of viable count)
Both the polypropylene film and the test piece were placed in a sterile plastic bag for stomacher, 10 ml of SCDLP medium was added, and the test bacteria were washed out by hand or stomacher. The number of viable bacteria in 1 ml of this washing solution was measured by the SCDLP agar medium pour method. The number of viable bacteria was converted per 1 cm 2 of the test piece.

下記式に従って各試験片の抗菌活性値を算出した。
抗菌活性値＝対照品の１０分後生菌数対数値−試験片の１０分後の生菌数対数値
得られた抗菌活性値が２以上の場合を○（抗菌性良好）、２未満の場合を×（抗菌性不良）とした。抗菌活性値について得られた結果を表２に示す。 The antibacterial activity value of each test piece was calculated according to the following formula.
Antibacterial activity value = logarithmic value of viable bacteria after 10 minutes of control product-logarithmic value of viable bacteria after 10 minutes of test piece ○ When the obtained antibacterial activity value is 2 or more ○ (good antibacterial) Was marked with x (poor antibacterial properties). The results obtained for the antibacterial activity values are shown in Table 2.

＜接触角測定方法＞
接触角計ＣＡ−Ｘ１５０型（ＦＡＣＥ社製）を用い、蒸留水および食用菜種油（日清オイリオグループ株式会社製、商品名：キャノーラ油）を用いて、接触角（度）を測定した。得られた接触角が５０°以上の場合を○（防汚性良好）、５０°未満の場合を×（防汚性不良）とした。接触角について得られた結果を表２に示す。

Figure 2016147808
<Contact angle measurement method>
Using a contact angle meter CA-X150 (manufactured by FACE), the contact angle (degree) was measured using distilled water and edible rapeseed oil (trade name: canola oil, manufactured by Nisshin Oilio Group, Inc.). The case where the obtained contact angle was 50 ° or more was evaluated as ◯ (good antifouling property), and the case where the contact angle was less than 50 ° was evaluated as × (defective antifouling property). The results obtained for the contact angle are shown in Table 2.
Figure 2016147808

表２に示すように、実施例１〜４では、抗菌活性値、接触角ともに良好な結果が得られたのに対して、比較例１〜５では、抗菌活性値と接触角のどちらか一方でしか良好な結果が得られなかった。   As shown in Table 2, in Examples 1 to 4, good results were obtained for both the antibacterial activity value and the contact angle, whereas in Comparative Examples 1 to 5, either the antibacterial activity value or the contact angle was obtained. Only good results were obtained.

Claims (9)

４級アンモニウム（メタ）アクリレート（Ａ）と、
シロキサン（メタ）アクリレート（Ｂ）との共重合体同士が架橋された架橋共重合体を含む抗菌・防汚材料。 Quaternary ammonium (meth) acrylate (A);
An antibacterial / antifouling material comprising a crosslinked copolymer obtained by crosslinking copolymers with siloxane (meth) acrylate (B). 前記４級アンモニウム（メタ）アクリレート（Ａ）が下記一般式（１）で表される請求項１に記載の抗菌・防汚材料。
Figure 2016147808
 上記式（１）中、Ｒ１はＨまたはＣＨ３であり、Ｒ２およびＲ３、Ｒ４は、互いに独立にメチル基またはベンジル基、炭素数１０〜１８のアルキル基であり、ｎ、ｍは０〜６の整数を表す。 The antibacterial / antifouling material according to claim 1, wherein the quaternary ammonium (meth) acrylate (A) is represented by the following general formula (1).
Figure 2016147808
 In the above formula (1), R 1 is H or CH 3 , R 2, R 3 and R 4 are each independently a methyl group or a benzyl group, a C10-18 alkyl group, and n, m Represents an integer of 0-6. 前記シロキサン（メタ）アクリレート（Ｂ）が下記一般式で表される請求項１に記載の抗菌・防汚材料。
Figure 2016147808
 上記式（２）中、Ｒ５は水素原子又は炭素数１〜５のアルキル基でありＲ６は炭素数１〜５のアルキル基又は炭素数６〜１０のアリール基であり、ｋは３〜１５０の数を表す。なお、式（２）中の複数のＲ６は互いに同一であってもよく、異なるものであってもよい。 The antibacterial / antifouling material according to claim 1, wherein the siloxane (meth) acrylate (B) is represented by the following general formula.
Figure 2016147808
 In the above formula (2), R 5 is R 6 is an alkyl group of 1 to 5 hydrogen or C is an aryl group having 6 to 10 alkyl group or a C1-5 carbon, k is 3 Represents the number 150. In addition, several R < 6 > in Formula (2) may mutually be the same, and may differ. 前記４級アンモニウム（メタ）アクリレート（Ａ）由来のユニットと、前記シロキサン（メタ）アクリレート（Ｂ）由来のユニットの質量比が５：９５〜９５：５である請求項１乃至３のいずれか１項に記載の抗菌・防汚材料。   The mass ratio of the unit derived from the quaternary ammonium (meth) acrylate (A) and the unit derived from the siloxane (meth) acrylate (B) is 5:95 to 95: 5. Antibacterial and antifouling materials as described in the section 前記共重合体を構成するモノマーとして、（メタ）アクリルモノマーを含む請求項１乃至４のいずれか１項に記載の抗菌・防汚材料。   The antibacterial / antifouling material according to any one of claims 1 to 4, comprising a (meth) acrylic monomer as a monomer constituting the copolymer. 前記（メタ）アクリルモノマーが水酸基を有し、
当該水酸基と結合するイソシアネート基を有する架橋剤によって前記共重合体同士が架橋されている請求項５に記載の抗菌・防汚材料。 The (meth) acrylic monomer has a hydroxyl group;
The antibacterial / antifouling material according to claim 5, wherein the copolymers are crosslinked with a crosslinking agent having an isocyanate group bonded to the hydroxyl group. 前記（メタ）アクリルモノマーが水酸基を有し、
当該水酸基と結合するメラミンを有する架橋剤によって前記共重合体同士が架橋されている請求項５に記載の抗菌・防汚材料。 The (meth) acrylic monomer has a hydroxyl group;
The antibacterial / antifouling material according to claim 5, wherein the copolymers are crosslinked with a crosslinking agent having a melamine bonded to the hydroxyl group. 前記（メタ）アクリルモノマーが、多官能（メタ）アクリロイル基を有し、電子線、紫外線等によって前記共重合体同士が架橋されている請求項５に記載の抗菌・防汚材料。 The antibacterial / antifouling material according to claim 5, wherein the (meth) acrylic monomer has a polyfunctional (meth) acryloyl group, and the copolymers are cross-linked by an electron beam, ultraviolet rays or the like. 請求項１乃至８のいずれか１項に記載の抗菌・防汚材料を含む成形品。   A molded article comprising the antibacterial / antifouling material according to any one of claims 1 to 8.
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