JP2009102315A - Antifouling or antimicrobial agent, antifouling or antimicrobial composition and antifouling or antimicrobial treatment method - Google Patents
Antifouling or antimicrobial agent, antifouling or antimicrobial composition and antifouling or antimicrobial treatment method Download PDFInfo
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本発明は、防汚、抗菌、殺菌、防カビ性（以下「防汚・抗菌性」と総称する。）を有する防汚・抗菌剤、該防汚・抗菌剤を含む組成物および基材の防汚・抗菌処理方法に関する。 The present invention relates to an antifouling / antibacterial agent having antifouling, antibacterial, sterilizing, and antifungal properties (hereinafter collectively referred to as “antifouling / antibacterial”), a composition containing the antifouling / antibacterial agent, and a substrate. It relates to antifouling and antibacterial treatment methods.
さらに詳しくは、防汚・抗菌性を有する第４級アンモニウム塩および重合体の存在下、フリーラジカル発生剤を加熱分解させることで得られた生成物を含有する防汚・抗菌剤、防汚・抗菌剤組成物および基材の防汚・抗菌処理方法に関する。 More specifically, an antifouling / antibacterial agent containing a product obtained by thermally decomposing a free radical generator in the presence of an antifouling / antibacterial quaternary ammonium salt and a polymer, The present invention relates to an antibacterial agent composition and an antifouling / antibacterial treatment method for a substrate.
海水中にはフジツボ類、コケムシ類、セルブラ類、ほや類など非常に多くの水棲生物植物や海藻類が生息している。これら水棲生物類が船舶の航行中や停泊中、補修中に船底面や船側面に固着し、水との摩擦抵抗によって航行速度の低下や燃料の消費も増し、また、補修の頻度も増え、経済的にも多大な損失を被るなどの色々な弊害をもたらしている。また、海洋魚類の養殖場においても隔離網に同様に海洋生物が付着し、網の開口部の減少による新鮮な海水の流入などが妨げられ、養殖魚の生育に弊害となっている。 There are a great many aquatic plants and seaweeds such as barnacles, bryozoans, selbras, and frogs in the sea water. These aquatic organisms adhere to the bottom and sides of the ship while navigating, anchoring, and repairing the ship, and the frictional resistance with water reduces navigation speed and fuel consumption, and the frequency of repairs also increases. It causes various adverse effects such as a large loss in terms of economy. Also, in marine fish farms, marine organisms similarly adhere to the segregation nets, preventing the inflow of fresh seawater due to the decrease in the openings of the nets, which is detrimental to the growth of farmed fish.
これら水棲生物類の付着を防止するための船底防汚塗料として錫化合物や銅化合物を含む塗料が使用されてきた。しかしながら、それらの錫化合物や銅化合物は海水中に溶出し、環境の汚染や魚、貝、海藻などへの汚染をもたらし、それらを食料とする人達にも汚染が広がり、健康を阻害するなどの大きな社会問題になってきている。 A paint containing a tin compound or a copper compound has been used as a ship bottom antifouling paint for preventing adhesion of these aquatic organisms. However, those tin compounds and copper compounds are eluted in seawater, causing environmental pollution and pollution to fish, shellfish, seaweeds, etc. It has become a big social problem.
また、日常の社会生活環境においても病院、公共施設や公衆便所などや居住環境、特に台所、風呂、便所などの建造物や住宅などの水周り個所に発生するカビなどの生物的汚れに対する抗菌性塗布材料として、また、衛生性の維持のための抗菌処理や殺菌処理のために多くの無機系および有機系の抗菌剤が使用されている。 In addition, in the daily social life environment, it has antibacterial properties against biological dirt such as mold that occurs in hospitals, public facilities, public toilets, etc. and in living environments, especially in kitchens, baths, toilets, etc. Many inorganic and organic antibacterial agents are used as coating materials and for antibacterial treatment and sterilization treatment for maintaining hygiene.
しかしながら、従来から使用されている金属イオン系の抗菌剤は少なからず毒性を有し、大量使用による金属の蓄積に起因する生態系などの環境への影響が問題になっている。また、有機系としてカチオン系やノニオン系の界面活性剤、特に第４級アンモニウム塩系のカチオン界面活性剤も用いられているが、水溶性塩であり、消毒液としては使用されるものの、耐水性のある持続型の防汚・抗菌剤としては使用できない。 However, metal ion antibacterial agents that have been used in the past are not only toxic, but there is a problem of environmental influences caused by the accumulation of metals due to mass use. In addition, cationic and nonionic surfactants, particularly quaternary ammonium salt cationic surfactants, are used as organic systems, but they are water-soluble salts and are used as disinfecting solutions. It cannot be used as a durable and durable antifouling and antibacterial agent.
従って本発明の目的は、環境への汚染や人の健康を阻害しない難溶性の有機物質を使用し、十分な持続性を有する防汚・抗菌剤の提供およびそれらの含む防汚・抗菌剤組成物および基材の防汚・抗菌処理方法などを提供することである。 Accordingly, an object of the present invention is to provide an antifouling / antibacterial agent having sufficient durability using an insoluble organic substance that does not impair environmental pollution or human health, and an antifouling / antibacterial agent composition containing them It is to provide antifouling and antibacterial treatment methods for materials and substrates.
本発明者らは、上記問題点を解決すべく鋭意研究を重ねた結果、防汚・抗菌性を有する第４級アンモニウム塩および重合体の存在下、フリーラジカル発生剤を加熱分解させることで得られた生成物を含有する塗膜から、水中で防汚・抗菌性成分が溶出し、防汚・抗菌性を長期間にわたって持続する効果を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained by thermally decomposing a free radical generator in the presence of a quaternary ammonium salt and a polymer having antifouling and antibacterial properties. Antifouling / antibacterial components were eluted from the coating film containing the resulting product in water, and the effect of maintaining the antifouling / antibacterial properties over a long period of time was found, and the present invention was completed.
すなわち、本発明は、防汚・抗菌性を有する第４級アンモニウム塩および重合体の存在下に、フリーラジカル発生剤を加熱分解させて得られた生成物を含有することを特徴とする防汚・抗菌剤を提供する。
なお、本発明においては、「防汚・抗菌」または「「防汚性・抗菌性」とは、「防汚性、抗菌性、殺菌性および防カビ性」を意味する。
That is, the present invention comprises an antifouling agent comprising a product obtained by thermally decomposing a free radical generator in the presence of an antifouling / antibacterial quaternary ammonium salt and a polymer.・ Provide antibacterial agents.
In the present invention, “antifouling / antibacterial” or “antifouling / antibacterial” means “antifouling, antibacterial, bactericidal and antifungal”.
上記本発明においては、前記アンモニウム塩が、テトラ（Ｃ1〜Ｃ30）アンモニウム塩、トリ（Ｃ1〜Ｃ30）−フェニルアンモニウム塩、トリ（Ｃ1〜Ｃ30）−ベンジルアンモニウム塩および（Ｃ1〜Ｃ30）−ピリジニウム塩からなる群から選ばれるアンモニウム塩であること；前記重合体が、ハロゲン基および／または酸無水物基を有する単量体単位を有する重合体であること；前記重合体が、クロルメチルスチレン、γ−クロロ−β−ヒドロオキシ−ｎ−プロピル（メタ）アクリレート、無水マレイン酸および／または無水イタコン酸単位を有する重合体であることが好ましい、
なお、上記において「（Ｃ1〜Ｃ30）基」は、炭素数が１〜３０である同一あるいは異なる脂肪族炭化水素基および脂環式炭化水素基を示す。また、フェニル基、ベンジル基、ピリジニウム基は置換基を有する基を含む。以下においても同様である。
In the above-described present invention, the ammonium salt is tetra (C 1 -C 30) ammonium salt, tri (C 1 -C 30) - phenyl ammonium salts, tri (C 1 -C 30) - benzyl ammonium salts and (C 1 -C 30) - it is ammonium salt selected from the group consisting of pyridinium salts; the polymer, it is a polymer having a monomer unit having a halogen group and / or acid anhydride groups; the heavy The polymer is preferably a polymer having chloromethylstyrene, γ-chloro-β-hydroxy-n-propyl (meth) acrylate, maleic anhydride and / or itaconic anhydride units,
In the above, the “(C 1 -C 30 ) group” represents the same or different aliphatic hydrocarbon group and alicyclic hydrocarbon group having 1 to 30 carbon atoms. Moreover, a phenyl group, a benzyl group, and a pyridinium group include a group having a substituent. The same applies to the following.
また、本発明は、前記本発明の防汚・抗菌剤に希釈媒体および／または塗膜形成材料を配合してなることを特徴とする防汚・抗菌性組成物を提供する。ここで、前記塗膜形成材料が、反応性基を有してもよい単量体、オリゴマー、重合体および／または架橋剤を含有する皮膜形成材料であることが好ましい。 The present invention also provides an antifouling / antibacterial composition comprising the antifouling / antibacterial agent of the present invention mixed with a diluent medium and / or a film-forming material. Here, the coating film-forming material is preferably a film-forming material containing a monomer, oligomer, polymer and / or crosslinking agent that may have a reactive group.
また、本発明は、前記本発明の防汚・抗菌剤あるいは前記本発明の防汚・抗菌性組成物を基材に塗布、噴霧または含浸し、必要によりさらに網状化処理することを特徴とする基材の防汚・抗菌処理方法を提供する。 Further, the present invention is characterized in that the antifouling / antibacterial agent of the present invention or the antifouling / antibacterial composition of the present invention is applied to a substrate, sprayed or impregnated, and further reticulated as necessary. Provide antifouling and antibacterial treatment methods for substrates.
従来、防汚塗料や抗菌、殺菌処理剤などに使用されてきた重金属イオン系の防汚剤や抗菌剤は少なからず毒性を有して生態系への影響が問題になっている。また、水溶性の第４級アンモニウム塩は耐水性のある持続型の防汚剤や抗菌剤としては使用できない。 Conventionally, heavy metal ion-based antifouling agents and antibacterial agents that have been used for antifouling paints, antibacterials, bactericides and the like have a considerable toxicity and have an impact on the ecosystem. In addition, water-soluble quaternary ammonium salts cannot be used as water-resistant long-lasting antifouling agents or antibacterial agents.
それに対して本発明の防汚・抗菌剤は、防汚・抗菌性を有する第４級アンモニウム塩および重合体の存在下、フリーラジカル発生剤を加熱分解させることで得られた生成物を含有するものを防汚・抗菌剤にしたものであり、水中に浸漬されていても第４級アンモニウムカチオンが結合状態で、あるいは徐々に放出されることによって、長期間にわたって有効に水棲生物の忌避作用をもたらし、水棲生物の着生を減少させるものと思われる。 In contrast, the antifouling / antibacterial agent of the present invention contains a product obtained by thermally decomposing a free radical generator in the presence of a quaternary ammonium salt and a polymer having antifouling / antibacterial properties. Antifouling and antibacterial agents, and even when immersed in water, the quaternary ammonium cations are released in a bound state or gradually to effectively repel aquatic organisms over a long period of time. This is likely to reduce the aquatic life.
次に発明を実施するための最良の形態を挙げて本発明をさらに詳細に説明する。本発明で使用される第４級アンモニウム化合物カチオンとしては、自身防汚・抗菌性を有するアンモニウムカチオン、あるいは防汚・抗菌性基が直接あるいは連結基を介してアンモニウム窒素に結合しているアンモニウムカチオンが挙げられる。 Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention. The quaternary ammonium compound cation used in the present invention includes an ammonium cation having antifouling and antibacterial properties, or an ammonium cation in which the antifouling and antibacterial groups are bonded to ammonium nitrogen directly or through a linking group. Is mentioned.
アンモニウムカチオンの例としては、テトラ（Ｃ1〜Ｃ30）−アンモニウムカチオン、例えば、トリ（Ｃ1〜Ｃ3）モノ（Ｃ4〜Ｃ30）アンモニウムカチオン、ジ（Ｃ1〜Ｃ3）ジ（Ｃ4〜Ｃ30）アンモニウムカチオン、モノ（Ｃ1〜Ｃ3）トリ（Ｃ4〜Ｃ30）アンモニウムカチオン、テトラ（Ｃ4〜Ｃ30）アンモニウムカチオンなど；トリ（Ｃ1〜Ｃ30）−フェニルアンモニウムカチオン、例えば、ジ（Ｃ1〜Ｃ3）モノ（Ｃ4〜Ｃ30）フェニルアンモニウムカチオン、モノ（Ｃ1〜Ｃ3）ジ（Ｃ4〜Ｃ30）フェニルアンモニウムカチオン、トリ（Ｃ4〜Ｃ30）−フェニルアンモニウムカチオンなどからなる群が挙げられる。 Examples of ammonium cations include tetra (C 1 -C 30 ) -ammonium cations, such as tri (C 1 -C 3 ) mono (C 4 -C 30 ) ammonium cations, di (C 1 -C 3 ) di ( C 4 -C 30 ) ammonium cation, mono (C 1 -C 3 ) tri (C 4 -C 30 ) ammonium cation, tetra (C 4 -C 30 ) ammonium cation, etc .; tri (C 1 -C 30 ) -phenyl ammonium cations, such as di (C 1 ~C 3) mono (C 4 ~C 30) phenyl ammonium cation, mono (C 1 ~C 3) di (C 4 ~C 30) phenyl ammonium cation, tri (C 4 ~ And a group consisting of C 30 ) -phenylammonium cation and the like.
さらに、トリ（Ｃ1〜Ｃ30）−ベンジルアンモニウムカチオン、例えば、ジ（Ｃ1〜Ｃ3）モノ（Ｃ4〜Ｃ30）ベンジルアンモニウムカチオン、モノ（Ｃ1〜Ｃ3）ジ（Ｃ4〜Ｃ30）ベンジルアンモニウムカチオン、トリ（Ｃ4〜Ｃ30）ベンジルアンモニウムカチオンなど；ピリジニウムカチオン、例えば、ジ（Ｃ1〜Ｃ30）ピリジニウムカチオン、モノ（Ｃ1〜Ｃ30）ベンジルピリジニウムカチオンなどからなる群が挙げられ、上記群と合わせた群から選ばれる第４級アンモニウムカチオンなどが挙げられる。 Further, tri (C 1 ~C 30) - benzyl ammonium cations, such as di (C 1 ~C 3) mono (C 4 ~C 30) benzyl ammonium cations, mono (C 1 ~C 3) di (C 4 ~ C 30) benzyl ammonium cations, tri (C 4 ~C 30) such as benzyl ammonium cation; pyridinium cation, for example, di (C 1 ~C 30) pyridinium cation, and the like mono (C 1 ~C 30) benzyl pyridinium cation A quaternary ammonium cation selected from the group combined with the above group.
なお、上記において（Ｃ1〜Ｃ30）、（Ｃ1〜Ｃ3）、（Ｃ4〜Ｃ30）は、それぞれ炭素数が１〜３０、１〜３あるいは４〜３０である脂肪族炭化水素基、炭素数４以上の場合はさらに脂環式炭化水素基、炭素数６以上の場合はさらに芳香族炭化水素基を含む。また、「テトラ−、トリ−、ジ−」の炭素数は同一でも、また異なってもよい。フェニル基、ベンジル基およびピリジニウム基はアルキル基、ハロゲン基、ニトロ基などの誘導基を有してもよい。特に断らない限り、以下においても同様である。上記の中でも、炭化水素基として炭素数が１２、１４、１６のアルキル基を有するアンモニウムカチオンが好ましく、また、それにベンジル基を併せ有するアンモニウムカチオンも好ましい。 In the above, (C 1 -C 30 ), (C 1 -C 3 ), and (C 4 -C 30 ) are aliphatic hydrocarbons having 1-30, 1-3, or 4-30 carbon atoms, respectively. When the group has 4 or more carbon atoms, it further includes an alicyclic hydrocarbon group, and when it has 6 or more carbon atoms, it further includes an aromatic hydrocarbon group. Moreover, the carbon number of "tetra-, tri-, di-" may be the same or different. The phenyl group, benzyl group and pyridinium group may have a derivative group such as an alkyl group, a halogen group and a nitro group. The same applies to the following unless otherwise specified. Among these, an ammonium cation having an alkyl group having 12, 14, or 16 carbon atoms as a hydrocarbon group is preferable, and an ammonium cation having a benzyl group is also preferable.
本発明に使用される重合体としては、反応性ハロゲンを有する単量体単位および／または酸無水物基を有する単量体単位を有する重合体が挙げられる。具体的には、クロルメチルスチレン、γ−クロロ−β−ヒドロオキシ−ｎ−プロピル（メタ）アクリレートなどの単量体単位を有する重合体であり、また、無水マレイン酸、無水イタコン酸などの単量体単位を有する重合体が挙げられる。 Examples of the polymer used in the present invention include a polymer having a monomer unit having a reactive halogen and / or a monomer unit having an acid anhydride group. Specifically, it is a polymer having a monomer unit such as chloromethylstyrene, γ-chloro-β-hydroxy-n-propyl (meth) acrylate, or a single amount such as maleic anhydride or itaconic anhydride. The polymer which has a body unit is mentioned.
本発明に使用される重合体の重合方法としては、公知の重合方法、例えば、溶液重合、乳化重合、懸濁重合、ソープフリー重合がすべて使用できる。重合媒体も有機溶剤、水−有機溶剤混合溶媒、水が選ばれる。 As the polymerization method for the polymer used in the present invention, known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and soap-free polymerization can all be used. As the polymerization medium, an organic solvent, a water-organic solvent mixed solvent, and water are selected.
本発明の第４級アンモニウム塩および重合体の存在下、フリーラジカル発生剤を反応させる方法としては、重合体の溶液あるいは分散液中に第４級アンモニウム塩を溶解させ、フリーラジカル発生剤を溶解させ、次いでフリーラジカル発生剤の分解温度に加熱しつつ反応させる方法である。反応媒体は、有機溶剤、水−有機溶剤混合溶媒、水などに適切に選択される。反応の際に、重合体、第４級アンモニウム塩あるいはフリーラジカル発生剤は全量添加でも分割添加でも、あるいは長時間をかけて滴下して添加する方法も使用される。 As a method of reacting a free radical generator in the presence of the quaternary ammonium salt and polymer of the present invention, the quaternary ammonium salt is dissolved in a polymer solution or dispersion, and the free radical generator is dissolved. And then reacting while heating to the decomposition temperature of the free radical generator. The reaction medium is appropriately selected from an organic solvent, a water-organic solvent mixed solvent, water and the like. In the reaction, a method in which the polymer, the quaternary ammonium salt or the free radical generator is added in the whole amount, in divided portions, or dropwise over a long time is also used.
反応温度は使用されるフリーラジカル発生剤の分解温度に依存するが、通常のラジカル重合に使用される反応温度である６０〜９０℃位が反応条件、特に反応媒体の選定あるいは反応の温度制御などの面から好ましい。 Although the reaction temperature depends on the decomposition temperature of the free radical generator used, the reaction temperature of 60 to 90 ° C., which is the reaction temperature used for normal radical polymerization, is the reaction condition, particularly the selection of the reaction medium or the temperature control of the reaction. From the viewpoint of
本発明に使用されるフリーラジカル発生剤としては、公知のアゾ系フリーラジカル発生剤および過酸化物系フリーラジカル発生剤が挙げられる。アゾ系フリーラジカル発生剤としては、具体的には２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス（２−アミジノプロパン）ジハイドロクロライド、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］、ジメチル２，２’−アゾビスイソブチレート、４，４’−アゾビス（４−シアノペンタノイックアシッド）などが挙げられる。 Examples of the free radical generator used in the present invention include known azo free radical generators and peroxide free radical generators. Specific examples of the azo free radical generator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 2,2′-azobisisobutyronitrile, 2,2′-azobis (methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-amidinopropane) ) Dihydrochloride, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyano) Pentanoic acid).
過酸化物フリーラジカル発生剤としては、具体的には、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、ｐ−クロルベンゾイルパーオキサイド、２，４−ジクロルベンゾイルパーオキサイドなどのジアシルパーオキサイド系、ｔ−ブチルパーイソブチレート、ｔ−ブチルパー２−エチルヘキサノエートなどのパーエステル系、１，１−ジ−ｔ−ブチルパーオキシ−３，３，５−トリメチルシクロヘキサン、１，１−ジ−ｔ−ブチルパーオキシ−シクロヘキサンなどのジアルキルパーオキサイド系などの過酸化物が挙げられる。 Specific examples of the peroxide free radical generator include diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and t-butyl peroxide. Peresters such as isobutyrate, t-butylper-2-ethylhexanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylper And peroxides such as dialkyl peroxides such as oxy-cyclohexane.
本発明の第４級アンモニウム塩と重合体の共存下でのフリーラジカル発生剤による反応生成物の生成メカニズムの解析は難しいが、フリーラジカル発生剤の作用としては、フリーラジカルがアンモニウム塩および重合体に作用し、脱塩素反応、水素引抜き反応、メチル基の離脱反応などによりアンモニウム塩および重合体にフリーラジカルが形成され、さらにそれらのラジカルの再結合反応によりアンモニウム塩と重合体との結合が形成されるものと推測される。さらに並行して起こり得る反応として、第４級アンモニウム塩の触媒作用として反応性ハロゲン基を有する重合体に対して脱ハロゲン反応も推測される。また、酸無水物が開環し、カルボン酸基を生成した場合には該カルボン酸基は第４級アンモニウムカチオンと水不溶性ないし難溶性の塩を形成する。 Although it is difficult to analyze the formation mechanism of the reaction product by the free radical generator in the coexistence of the quaternary ammonium salt of the present invention and the polymer, the action of the free radical generator is that the free radical is an ammonium salt and a polymer. Free radicals are formed in ammonium salts and polymers by dechlorination reaction, hydrogen abstraction reaction, methyl group elimination reaction, etc., and the bond between ammonium salt and polymer is formed by recombination reaction of these radicals. Presumed to be. Further, as a reaction that can occur in parallel, a dehalogenation reaction is presumed for a polymer having a reactive halogen group as a catalytic action of a quaternary ammonium salt. When the acid anhydride is ring-opened to form a carboxylic acid group, the carboxylic acid group forms a water-insoluble or hardly soluble salt with a quaternary ammonium cation.
本発明の防汚・抗菌剤を構成するアンモニウム塩と重合体との反応生成物において、アンモニウム塩の含有量は反応が達成されるように設計すべきで、必要以上に上げる必要はないが、防汚・抗菌剤効果の持続性の観点からはアンモニウム塩の含有量の高い方が望ましい。また、コーティング剤などの組成物中の含有量は皮膜形成材料との対比、塗膜厚などによってもコントロールできるので、防汚・抗菌剤中のアンモニウム塩の含有量は高い方が望ましい。 In the reaction product of the ammonium salt and polymer constituting the antifouling / antibacterial agent of the present invention, the content of the ammonium salt should be designed so that the reaction is achieved, and it is not necessary to increase it more than necessary. From the viewpoint of sustaining antifouling and antibacterial effects, a higher ammonium salt content is desirable. In addition, since the content in the composition such as a coating agent can be controlled by comparison with the film-forming material, the film thickness, etc., it is desirable that the content of the ammonium salt in the antifouling / antibacterial agent is high.
アンモニウム塩と重合体との反応生成物は、溶解する溶剤に溶解させて使用することが好ましい。溶剤溶液あるいは溶剤−水混合溶媒溶液、特にアルコール系溶媒、水−アルコール系の混合溶剤に溶解して塗装液の溶剤あるいは混合溶剤として使用し、単独にか、必要に応じて非反応性重合体、網状構造を形成し得る反応性重合体および／または架橋剤からなる塗膜形成材料を配合して塗装液とする。反応型の塗装液は基材に塗布して後、網状化させることが好ましい。 The reaction product of the ammonium salt and the polymer is preferably used after being dissolved in a dissolving solvent. Solvent solution or solvent-water mixed solvent solution, especially alcohol solvent, water-alcohol mixed solvent and used as solvent or mixed solvent for coating solution, either alone or as needed non-reactive polymer Then, a coating film forming material comprising a reactive polymer capable of forming a network structure and / or a crosslinking agent is blended to obtain a coating liquid. The reactive coating liquid is preferably applied to a substrate and then reticulated.
単独であるいは架橋剤の作用により網状化をもたらす反応性共単量体として、メチロール（メタ）アクリルアミド、アルコキシ（Ｃ1〜Ｃ4）メチル（メタ）アクリルアミド、グリシジル（メタ）アクリレート、マレイン酸無水物など；架橋剤の作用により網状化をもたらす反応性単量体として、ヒドロキシアルキル（Ｃ2〜Ｃ6）（メタ）アクリレート、（メタ）アクリルアミド、（メタ）アクリル酸、マレイン酸など公知の反応性単量体が挙げられる。 As a reactive comonomer that brings about reticulation alone or by the action of a crosslinking agent, methylol (meth) acrylamide, alkoxy (C 1 -C 4 ) methyl (meth) acrylamide, glycidyl (meth) acrylate, maleic anhydride And the like; reactive monomers such as hydroxyalkyl (C 2 -C 6 ) (meth) acrylate, (meth) acrylamide, (meth) acrylic acid, maleic acid, etc., which are used as reactive monomers that bring about reticulation by the action of a crosslinking agent Monomer.
架橋剤としては、従来公知の架橋剤、例えば、ヘキサメチロールメラミン、ヘキサメトキシメチルメラミンなどのアミノ樹脂初期縮合物、トリメチロールプロパン−トリ（トリレンジイソシアネート）アダクト、トリメチロールプロパン−トリ（イソホロンジイソシアネート）アダクトなどのポリイソシアネート化合物、モノ〜ポリアルキレン（Ｃ2〜Ｃ6）グリコールジグリシジルエーテル、グリセリントリグリシジルエーテル、ビスフェノールＡ−ジグリシジルエーテル、それらのオリゴマーなどのポリエポキシ化合物などが使用される。 Examples of the crosslinking agent include conventionally known crosslinking agents, for example, amino resin initial condensates such as hexamethylol melamine and hexamethoxymethyl melamine, trimethylolpropane-tri (tolylene diisocyanate) adduct, trimethylolpropane-tri (isophorone diisocyanate). Polyisocyanate compounds such as adducts, polyepoxy compounds such as mono-polyalkylene (C 2 -C 6 ) glycol diglycidyl ether, glycerin triglycidyl ether, bisphenol A-diglycidyl ether, and oligomers thereof are used.
本発明の防汚・抗菌性組成物（塗装材）は、防汚・抗菌剤が塗膜表面に露出する状態を形成する塗料として使用することが好ましい。例えば、防汚・抗菌剤を塗膜形成材料中に高濃度に添加すること、防汚・抗菌剤が相溶しないようにして塗膜中で相分離させて高濃度の膜部分をつくること、防汚・抗菌剤が微粒子の場合は粒径を比較的大きくすることなどが挙げられる。船底防汚塗料などでは塗膜形成材料として徐々に表面から溶解していく自己研磨（セルフ・ポリシング）型の樹脂系を使用すると、塗膜中の防汚・抗菌剤を順次表面に露出させることができるので好ましい。 The antifouling / antibacterial composition (coating material) of the present invention is preferably used as a paint that forms a state in which the antifouling / antibacterial agent is exposed on the surface of the coating film. For example, adding a high concentration of antifouling / antibacterial agent to the coating film forming material, making the antifouling / antibacterial agent incompatible with each other and making the phase separation in the coating film, When the antifouling / antibacterial agent is a fine particle, for example, a relatively large particle size may be mentioned. When using a self-polishing resin system that gradually dissolves from the surface as a coating film forming material for ship bottom antifouling paints, etc., the antifouling and antibacterial agents in the coating film are sequentially exposed to the surface. Is preferable.
本発明の防汚・抗菌剤を構成する塗膜形成材料としては、公知の樹脂材料が使用できる。樹脂の分類からは、例えば、合成ゴム樹脂、アクリル樹脂、ビニル樹脂、塩化ゴム樹脂、アルキッド樹脂、ウレタン樹脂、エポキシ系樹脂、シリコーン樹脂、フッ素樹脂などの塗膜形成材料および紫外線硬化性樹脂系、電子線硬化性樹脂系などのエネルギー線硬化性塗膜形成材料などが挙げられる。上記した防汚・抗菌性塗装材において、防汚・抗菌剤（Ａ）のみの使用を含め、防汚・抗菌剤（Ａ）と塗膜形成材料（Ｂ）との配合質量比は、Ａ：Ｂ＝１００：０〜５：９５であり、防汚・抗菌剤が塗膜表面に高密度に露出させることが好ましい。 As the coating film forming material constituting the antifouling / antibacterial agent of the present invention, known resin materials can be used. From the classification of resins, for example, synthetic rubber resin, acrylic resin, vinyl resin, chlorinated rubber resin, alkyd resin, urethane resin, epoxy resin, silicone resin, fluororesin and other coating film forming materials and ultraviolet curable resin systems, Examples include energy beam curable coating film forming materials such as electron beam curable resin systems. In the above-mentioned antifouling / antibacterial coating material, including only the use of the antifouling / antibacterial agent (A), the blending mass ratio of the antifouling / antibacterial agent (A) and the coating film forming material (B) is A: B = 100: 0 to 5:95, and it is preferable that the antifouling / antibacterial agent is exposed on the surface of the coating film with high density.
本発明の防汚・抗菌剤を基材に塗布、噴霧または含浸し、あるいは基材に混練または内添することにより基材を抗菌処理し、防汚・抗菌処理基材が得られる。本発明の防汚・抗菌剤は従来の防汚塗料と同様の用途、例えば、海洋航行船舶の海水中に没する船底面や船側面の塗装に、また、海洋魚類の養殖場においても隔離網などの広範な用途で使用できる。 By applying, spraying or impregnating the antifouling / antibacterial agent of the present invention to a substrate, or kneading or internally adding to the substrate, the substrate is antibacterial treated to obtain an antifouling / antibacterial treated substrate. The antifouling / antibacterial agent of the present invention is used in the same manner as conventional antifouling paints, for example, for painting the bottom and side of a ship that is submerged in the seawater of marine navigating vessels, and also in marine fish farms. It can be used in a wide range of applications.
さらに、病院、公共施設や公衆便所など、居住環境、特に台所、風呂、便所などの建造物や住宅などの水周り個所の防汚・抗菌性塗布材料として、エアコンディショナー、空気浄化装置などの電気機器や台所用品などの日常生活の衛生性維持のための防汚・抗菌処理や殺菌などの広範な用途で使用できる。また、日常生活で、不特定多数の人の触れるいろいろな物品、例えば、書籍、雑誌類、ノート、パンフレット、記録用紙、印刷や加工される前の紙類の防汚・抗菌処理、表紙への密着カバーフィルムや被覆カバー類など、また、食材や食品などの細菌類の汚染が懸念される食料品などの包装材やラップ類などの保存用軟包装材などに対する防汚・抗菌処理用や殺菌処理用としても使用できる。 In addition, as an antifouling and antibacterial coating material for residential areas such as hospitals, public facilities and public toilets, especially in the surrounding areas of buildings such as kitchens, baths and toilets, and houses, it is used as an air conditioner, an air purification device, etc. It can be used in a wide range of applications such as antifouling, antibacterial treatment and sterilization for maintaining hygiene in daily life such as equipment and kitchen utensils. Also, in everyday life, various articles that are touched by an unspecified number of people, such as books, magazines, notebooks, pamphlets, recording paper, antifouling and antibacterial treatment of paper before printing and processing, cover Antifouling / antibacterial treatment and sterilization of adhesive cover films, covering covers, etc., packaging materials such as foodstuffs and foodstuffs, food packaging, and soft packaging materials for storage such as wraps It can also be used for processing.
防汚・抗菌処理をする素材および物品は、特に限定されるものではなく、例えば、合成樹脂成型品、金属製品、木材製品、ガラス製品、スレートボード、繊維、不織布紙などが挙げられる。合成樹脂素材としてはポリプロピレン樹脂、ポリエチレン樹脂、ポリ塩化ビニル樹脂、合成ゴム、ポリスチレン樹脂、ＡＢＳ樹脂、ナイロン樹脂、ポリエステル樹脂、ポリカーボネート樹脂などの公知の樹脂が挙げられる。合成繊維素材としては、ポリプロピレン繊維、ポリエチレン繊維、ポリアクリロニトリル繊維、ナイロン繊維、ポリエステル繊維などの公知の繊維が挙げられる。 The materials and articles for antifouling and antibacterial treatment are not particularly limited, and examples thereof include synthetic resin molded products, metal products, wood products, glass products, slate boards, fibers, and non-woven paper. Examples of the synthetic resin material include known resins such as polypropylene resin, polyethylene resin, polyvinyl chloride resin, synthetic rubber, polystyrene resin, ABS resin, nylon resin, polyester resin, and polycarbonate resin. Examples of the synthetic fiber material include known fibers such as polypropylene fiber, polyethylene fiber, polyacrylonitrile fiber, nylon fiber, and polyester fiber.
次に実施例および比較例を挙げて本発明をさらに具体的に説明する。なお、文中、「部」または「％」とあるのは質量基準である。
［合成例１］
（１）加熱装置としてのウオーターバス、撹拌機、液滴下装置および逆流冷却器を備えた反応装置を準備し、反応容器に無水マレイン酸２４．５２ｇ、クロルメチルスチレン３８．１６ｇおよび酢酸ブチル２５９．５ｇを仕込み、攪拌し、溶解した。反応溶液を７０℃に加温し、アゾビスイソブチロニトリル１．０ｇを添加し、攪拌して８時間重合反応させた。
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, “part” or “%” is based on mass.
[Synthesis Example 1]
(1) A reaction apparatus equipped with a water bath, a stirrer, a droplet dropping apparatus and a back-flow cooler as a heating apparatus was prepared, and 24.52 g of maleic anhydride, 38.16 g of chloromethylstyrene and 259. 5 g was charged, stirred and dissolved. The reaction solution was heated to 70 ° C., 1.0 g of azobisisobutyronitrile was added, and the mixture was stirred and allowed to polymerize for 8 hours.
（２）別に、テトラデシルジメチルベンザルコニウム塩酸塩２６．７をアセトン１０６．８ｇに溶解させた。上記（１）で得られた重合体溶液を１００ｇ分取し、上記ベンザルコニウム塩のアセトン溶液を添加し、攪拌しながら徐々に７０℃に加熱し、アゾビスイソブチロニトリル１．０ｇを添加し、攪拌して１晩反応させた。反応後酢酸ブチルを主体とする反応溶剤を溜去、乾燥させた後、メタノールに再溶解し、水中に滴下して樹脂分を析出させ、濾過、水洗した。含水樹脂分を７０℃で１晩乾燥し、「アンモニウム塩結合重合体−１」を得た。 (2) Separately, 26.7 tetradecyldimethylbenzalkonium hydrochloride was dissolved in 106.8 g of acetone. 100 g of the polymer solution obtained in the above (1) was taken, the acetone solution of the benzalkonium salt was added, and the mixture was gradually heated to 70 ° C. with stirring, and 1.0 g of azobisisobutyronitrile was added. Added, stirred and allowed to react overnight. After the reaction, the reaction solvent mainly composed of butyl acetate was distilled off and dried, then redissolved in methanol, dropped into water to precipitate the resin, filtered and washed with water. The water-containing resin content was dried at 70 ° C. overnight to obtain “ammonium salt-bound polymer-1”.
［合成例２］
合成例１（１）で得られた重合体溶液を１００ｇ分取し、反応容器に仕込んだ。別に、テトラデシルジメチルベンザルコニウム塩酸塩２６．７をアセトン１０６．８ｇに溶解させ、また、過酸化ベンゾイル９．２３ｇを酢酸ブチル１７５．３７ｇに溶解させた。上記ベンザルコニウム塩のアセトン溶液を添加し、攪拌した。次いで０℃に冷却し、過酸化ベンゾイル溶液を０℃にて６時間かけて滴下、添加し、さらに一晩攪拌を継続した。反応後、酢酸ブチルを主体とする反応溶剤を溜去し、乾燥させて後、メタノールに再溶解し、水中に滴下して樹脂分を析出させ、濾過、水洗した。含水樹脂分を７０℃で１晩乾燥し、「アンモニウム塩結合重合体−２」を得た。
[Synthesis Example 2]
100 g of the polymer solution obtained in Synthesis Example 1 (1) was collected and charged into a reaction vessel. Separately, 26.7 tetradecyldimethylbenzalkonium hydrochloride was dissolved in 106.8 g acetone, and 9.23 g benzoyl peroxide was dissolved in 175.37 g butyl acetate. The acetone solution of the benzalkonium salt was added and stirred. Subsequently, it cooled to 0 degreeC, the benzoyl peroxide solution was dripped and added over 6 hours at 0 degreeC, and also stirring was continued overnight. After the reaction, the reaction solvent mainly composed of butyl acetate was distilled off, dried, redissolved in methanol, dropped into water to precipitate a resin, filtered and washed with water. The water-containing resin was dried at 70 ° C. overnight to obtain “ammonium salt-bound polymer-2”.
［実施例１］（防汚性塗装板の調製）
合成例で得られたアンモニウム塩結合重合体の海洋水棲生物防汚剤としての性能を評価するために防汚性塗装板を調製する。合成例１で得られたアンモニウム塩結合重合体−１の５０ｇを酢酸ブチル１００ｇに溶解させ、下記の固着用塩化ビニル−ビニルイソブチルエーテル共重合体（ＢＡＳＦ社製、商品名ラロフレックスＭＰ３５）２５ｇ／ロジン２５ｇ（荒川化学工業社製、商品名ロジンＷＷ）混合樹脂の酢酸ブチル溶液１００ｇ（固形分５０％）と混合（固形分質量比；１：１）した。そこへ酢酸ブチル８３ｇを加え、固形分３０％に調整し、防汚塗料を調製した。
[Example 1] (Preparation of antifouling coated plate)
In order to evaluate the performance of the ammonium salt-bonded polymer obtained in the synthesis example as a marine aquatic biofouling agent, an antifouling coated plate is prepared. 50 g of the ammonium salt-bonded polymer-1 obtained in Synthesis Example 1 was dissolved in 100 g of butyl acetate, and the following fixing vinyl chloride-vinyl isobutyl ether copolymer (trade name Laroflex MP35, manufactured by BASF) was 25 g / 25 g of rosin (trade name rosin WW, manufactured by Arakawa Chemical Industries, Ltd.) mixed resin was mixed with 100 g of butyl acetate solution (solid content 50%) (solid content mass ratio; 1: 1). Thereto, 83 g of butyl acetate was added to adjust the solid content to 30%, and an antifouling paint was prepared.
防錆処理を施した試験用鋼板の周囲の上下左右および中央に境界を作り、それぞれ約１ｃｍの幅でエポキシ系下塗り塗料を塗布し、保護面と境界を作った。その下半分に上記の防汚塗料を厚く塗布して常温下で１０日間乾燥した。塗膜の厚みはほぼ１１０〜１３０μｍであった。上半分は下記比較例１で示すように比較用の塩化ビニル−ビニルイソブチルエーテル共重合体／ロジン樹脂を塗布した。得られた塗板は、以下防汚性塗装板−１と称する。 Borders were created on the top, bottom, left, right, and center of the test steel sheet that had been subjected to rust prevention treatment, and an epoxy-based primer was applied in a width of about 1 cm to create a protective surface and a boundary. The antifouling paint was thickly applied to the lower half and dried at room temperature for 10 days. The thickness of the coating film was approximately 110 to 130 μm. The upper half was coated with a comparative vinyl chloride-vinyl isobutyl ether copolymer / rosin resin as shown in Comparative Example 1 below. The obtained coated plate is hereinafter referred to as antifouling coated plate-1.
また、上記の試験用鋼板はテストパネル社製の中目両面サンドプラスト鋼板（幅×長さ×厚さ：７０×１５０×１ｍｍ）にタールエポキシ系の下塗り塗料を乾燥後で約１５０μｍで塗布し、風乾して準備した。 In addition, the test steel plate was applied to a medium-sized double-sided sand plast steel plate (width × length × thickness: 70 × 150 × 1 mm) manufactured by Test Panel Co., Ltd., and a tar epoxy base coat was applied at about 150 μm after drying. Prepared by air drying.
［比較例１］
実施例１で調製した各塗板上の区分した上半分に、防汚性能の比較のために実施例１に記載の塩化ビニル−ビニルイソブチルエーテル共重合体／ロジン樹脂塗料を塗布し、常温下で１０日間乾燥した。塗膜の厚みはほぼ１１０〜１３０μｍであった。実施例２においても同様に上下に分けて塗布し、比較した。
[Comparative Example 1]
For comparison of antifouling performance, the vinyl chloride-vinylisobutyl ether copolymer / rosin resin paint described in Example 1 was applied to the upper half of each coated plate prepared in Example 1 at room temperature. Dried for 10 days. The thickness of the coating film was approximately 110 to 130 μm. In Example 2 as well, it was applied separately in the upper and lower directions and compared.
［実施例２］（防汚性塗装板の調製）
実施例１で述べた塗料の調製方法および塗装方法に従い、合成例２で得られたアンモニウム塩結合重合体−２を使用し、固着用塩化ビニル−ビニルイソブチルエーテル共重合体／ロジン樹脂（固形分質量比；１：１）とを組み合わせた塗料を作成して下半分に塗装し、上半分には比較例１の塗料を塗布して、防汚性塗装板−２を調製した。膜厚はほぼ１１０〜１３０μｍであった。
[Example 2] (Preparation of antifouling coated plate)
According to the coating preparation method and the coating method described in Example 1, the ammonium salt-bound polymer-2 obtained in Synthesis Example 2 was used, and the vinyl chloride-vinylisobutyl ether copolymer / rosin resin for fixing (solid content) A paint having a mass ratio of 1: 1) was prepared and applied to the lower half, and the paint of Comparative Example 1 was applied to the upper half to prepare an antifouling coating plate-2. The film thickness was approximately 110 to 130 μm.
［試験方法および塗装鋼板浸漬試験結果］
（１）試験方法
試験用塗装鋼板の海水浸漬試験は内湾の比較的海水流の少ない、幼魚の成育場に隣接する場所で、魚の餌が投与されることから栄養分の多い環境である。水温は凡そ２５〜２８℃、ＣＯＤ濃度は４〜１０ｍｇ／Ｌを示した。ＣＯＤ濃度については瀬戸内海の比較的海水のきれいなところで１〜２ｍｇ／Ｌ、港の中など水の色が緑から黄色に見えるところでは３〜５ｍｇ／Ｌと言われている。実施例１および２、および比較例１で調製した塗装した試験用鋼板をポリ塩化ビニル製の枠に上下固定して吊るした。ポリ塩化ビニル製枠を海面より１〜２ｍの深さに浸漬した。６週間にわたって１週間ごとに試験用鋼板を上げて試験用鋼板の上半分、下半分のフジツボの付着状態を観察し、状態の変化を評価した。
[Test method and coated steel plate immersion test results]
(1) Test method The seawater immersion test of the coated steel sheet for the test is an environment with a high nutrient content because fish food is administered in a place adjacent to the young fish breeding ground in the inner bay with relatively little seawater flow. The water temperature was about 25 to 28 ° C., and the COD concentration was 4 to 10 mg / L. The COD concentration is said to be 1 to 2 mg / L in the Seto Inland Sea where the seawater is relatively clean, and 3 to 5 mg / L where the color of the water looks green to yellow, such as in a harbor. The coated steel plates for test prepared in Examples 1 and 2 and Comparative Example 1 were suspended and fixed to a frame made of polyvinyl chloride. A polyvinyl chloride frame was immersed at a depth of 1 to 2 m from the sea surface. The test steel plate was raised every week for 6 weeks, and the adhesion state of the upper and lower half barnacles was observed, and the change in the state was evaluated.
（２）状態観察の結果および評価
アンモニウム塩結合重合体を使用していない塗板がフジツボの付着は時間と共に進み塗板に強固に付着して脱落しなかったのに対し、防汚性塗装板−１および防汚性塗装板−２のいずれもフジツボの付着が著しく遅くなることが認められ、徐放性防汚塗料としての機能を有していると判断された。
(2) Results of state observation and evaluation The coated plate not using the ammonium salt-bonded polymer did not drop off because the adhesion of the barnacle progressed with time and adhered firmly to the coated plate, whereas the antifouling coated plate-1 It was recognized that both the antifouling coating plate-2 and the barnacle adhered significantly slowed down, and it was judged to have a function as a sustained release antifouling coating.
［実施例３］
ガラスシャーレを１５０℃で２４時間加熱処置した後、紫外線ランプを点灯させたクリーンベンチ内で保管した。ガラスシャーレの底面に幅５ｍｍのテープで、５０ｍｍ角の正方形にマスキングした。このマスキングした内側に上記合成例１（２）で得られたアンモニウム塩結合重合体−１の３０％酢酸ブチル溶液を流し込んでキャスト膜（５０ｍｍ角）を作製した。別に、比較のために上記合成例１（１）で得られたベンザルコニウム塩を反応させていない重合体溶液を使用して同様にキャスト膜を調製した。キャスト膜の乾燥はクリーンベンチ内で行い、紫外線ランプを照射し続けた。膜が乾燥した後、ＪＩＳ Ｚ ２８０１に従って抗菌試験を行った。
[Example 3]
The glass petri dish was heated at 150 ° C. for 24 hours, and then stored in a clean bench where an ultraviolet lamp was lit. The bottom of the glass petri dish was masked with a 5 mm wide tape into a 50 mm square. A cast film (50 mm square) was prepared by pouring the 30% butyl acetate solution of the ammonium salt-bonded polymer-1 obtained in Synthesis Example 1 (2) into the masked inside. Separately, for comparison, a cast film was prepared in the same manner using the polymer solution obtained by reacting the benzalkonium salt obtained in Synthesis Example 1 (1). The cast film was dried in a clean bench and irradiated with an ultraviolet lamp. After the membrane was dried, an antibacterial test was conducted according to JIS Z 2801.
ベンザルコニウム塩を反応させていないキャスト膜は大腸菌のコロニーが多数確認できるが、アンモニウム塩結合重合体−１のキャスト膜には、全く観察されなかった。 Although many colonies of E. coli were confirmed in the cast film not reacted with the benzalkonium salt, it was not observed at all in the cast film of the ammonium salt-bound polymer-1.
［実施例２］
実施例１と同様にして、ガラスシャーレの底面に５０ｍｍ角の正方形にマスキングした内側に上記合成例２で得られたアンモニウム塩結合重合体−２の酢酸ブチル溶液を流し込んでキャスト膜（５０ｍｍ角）を作製した。キャスト膜はクリーンベンチ内で紫外線ランプを照射し、乾燥した。乾燥した膜を、ＪＩＳ Ｚ ２８０１に従って抗菌試験を行った。アンモニウム塩結合重合体−２のキャスト膜には、合成例１の重合体膜と同様に全く観察されなかった。
[Example 2]
In the same manner as in Example 1, the butyl acetate solution of the ammonium salt-bonded polymer-2 obtained in Synthesis Example 2 was poured into the inner side of the glass petri dish masked into a square of 50 mm square, and cast film (50 mm square) Was made. The cast film was dried by irradiating an ultraviolet lamp in a clean bench. The dried membrane was subjected to an antibacterial test according to JIS Z 2801. Similar to the polymer film of Synthesis Example 1, no film was observed in the cast film of the ammonium salt-bonded polymer-2.
従来から防汚塗料に使用されてきた錫化合物や銅化合物の忌避作用は、それらのイオンが徐々に溶出して水棲生物に作用し、忌避あるいは死滅させる作用である。本発明の防汚・抗菌剤は、第４級アンモニウム塩および重合体の存在下、フリーラジカル発生剤を加熱分解させることで得られた生成物を含有する新規な防汚・抗菌剤である。 The repellent action of tin compounds and copper compounds conventionally used in antifouling paints is the action of those ions eluting gradually and acting on aquatic organisms to repel or kill them. The antifouling / antibacterial agent of the present invention is a novel antifouling / antibacterial agent containing a product obtained by thermally decomposing a free radical generator in the presence of a quaternary ammonium salt and a polymer.
本発明の防汚・抗菌剤は、従来の防汚塗料と同様の用途、例えば、海洋航行船舶の海水中に没する船底面や船側面の塗装や海洋魚類の養殖場においても隔離網などの防汚塗料の用途に使用できる。 The antifouling / antibacterial agent of the present invention is used in the same applications as conventional antifouling paints, for example, painting of the bottom and side of a ship submerged in the seawater of a marine navigation ship and a segregation net in a marine fish farm. Can be used for antifouling paint applications.
また、本発明の防汚・抗菌剤は、病院、公共施設や公衆便所などの多くに人が利用する社会生活上の衛生環境の管理、維持のため、また、建造物や住宅などで洗濯場、洗い場、流し、洗面所、風呂場などの水周り個所などの居住環境におけるカビなどの生物的汚れに適用される。また、日常生活で、不特定多数の人の触れるいろいろな物品の衛生処理として、例えば、書籍、ノート、パンフレット、記録用紙などに直接防汚・抗菌処理、それに加工される前の紙類の防汚・抗菌処理、表紙への密着カバーフィルムや被覆カバー類など、また、食材や食品などの細菌類の汚染が懸念される食料品などの包装材やラップ類などの保存用軟包装材などに対する防汚・抗菌処理用や殺菌処理用としても使用できる。 In addition, the antifouling / antibacterial agent of the present invention is used for the management and maintenance of a hygienic environment for social life that is used by many people in hospitals, public facilities, public toilets, etc. It is applied to biological dirt such as mold in the living environment such as washing places, sinks, washrooms, bathrooms, and other places around the water. Also, as a sanitary treatment of various articles that are touched by an unspecified number of people in daily life, for example, antifouling / antibacterial treatment directly on books, notebooks, brochures, recording paper, etc. Contamination, antibacterial treatment, cover cover film and cover covers for covers, etc., and packaging materials such as foodstuffs and foods that are likely to be contaminated with bacteria such as foodstuffs and soft packaging materials for storage such as wraps It can also be used for antifouling / antibacterial treatment and sterilization treatment.
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