JP3711412B2 - Antibacterial agent, antibacterial fiber and method for producing the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、植物由来の細菌及び細菌等の微生物に対して抗菌性を示す抗菌性付与剤並びにその抗菌性付与剤の有効成分を用いた抗菌性繊維及びその製造方法に関する。
【０００２】
【従来の技術】
近年、清潔指向、衛生指向の高まりにより、医療分野、衣料分野はもとより、トイレ用品、台所用品、鮮度保持フィルム、除菌シート等の家庭用品分野、洗濯機、冷蔵庫、フロッピーディスクケース、文房具等の家電・事務用品分野、食品分野等に抗菌性素材が用いられ、また抗菌性素材の一つとして抗菌性繊維も用いられている。
【０００３】
従来、抗菌性繊維の製造方法として、例えば抗菌性を示す金属又は金属化合物微粒子を分散液として有機高分子材料と接触させ、有機高分子材料表面に被覆付着する方法（特開平７−９７７６９号公報）、繊維表面をコロイド粒子サイズの抗菌性金属と他の金属の酸化物で被覆する方法（特開平７−１０９６７４号公報）等が知られている。しかしながら、これらの方法による抗菌性繊維は、抗菌性金属が繊維表面に付着しているだけなので、使用の過程で抗菌性金属が脱落してしまう恐れがある。
【０００４】
また、繊維自体に抗菌性を付与する方法として、アミノ基含有アクリル酸エステルを共重合したアクリロニトリル共重合体繊維を、アルキルハライドで処理してアミノ基窒素を４級化し、抗菌性アクリル繊維とする方法（特開平５−１４０８６８号公報）が知られているが、この方法は、特定の単量体の共重合、アルキルハライドでの処理が必要となり、経済的かつ効率的な方法ではない。
【０００５】
そのほか、抗菌性繊維の製造方法として、抗菌性の銀をシリカ、アルミナ等の球状セラミックス微粒子の表面に担持させたものを繊維表面に付着させる方法、多孔質の天然ゼオライト或いは銀イオンをゼオライトに吸着させたものを素材表面に被覆させる方法等が知られているが、抗菌性金属を物理的に繊維に付着させる方法は、繊維が繊維製品である場合、洗濯やドライクリーニング等で抗菌性金属担持物が脱落し易く、初期の抗菌効果を長期間持続させ難い等の問題がある。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、植物由来の細菌及び細菌等の微生物に対して優れた抗菌性を示す抗菌性付与剤を提供すること、並びにその抗菌性付与剤の有効成分を用いてなる、洗濯やドライクリーニング等による抗菌性成分の脱落が少なく、抗菌効果が持続し耐久性に優れた抗菌性繊維を提供すること、そしてまた、この抗菌性繊維を容易かつ経済的に得ることにある。
【０００７】
【課題を解決するための手段】
本発明は、下記一般式［１］で表される（メタ）アクリル酸誘導体及び／又はその重合体を有効成分とすることを特徴とする抗菌性付与剤、
ＣＨ2＝Ｃ（Ｒ）ＣＯＯＸＹ ［１］
但し、式中、Ｒ、Ｘ、Ｙはそれぞれ下記の置換基を示す。
ＲはＨ又はＣＨ3
Ｘは（ＣＨ2）ａＯｂ（ａは０〜４、ｂは０又は１）
Ｙは下記の群から選ばれる置換基
（１）（ＣＦ2）ｃＺ（ｃは１〜１０、ＺはＨ又はＦ）で表されるフッ化アルキル基
（２）テトラヒドロフルフリル基
（３）フェニル基
（４）イソボルニル基
（５）ノルボルニル基
（６）トリシクロ［５，２，１，０2,6］デカニル基又はデセニル基
【０００８】
並びに、繊維に下記一般式［１］で表される（メタ）アクリル酸誘導体及び／又はその重合体が付着されたことを特徴とする抗菌性繊維、
ＣＨ2＝Ｃ（Ｒ）ＣＯＯＸＹ ［１］
但し、式中、Ｒ、Ｘ、Ｙはそれぞれ下記の置換基を示す。
ＲはＨ又はＣＨ3
Ｘは（ＣＨ2）ａＯｂ（ａは０〜４、ｂは０又は１）
Ｙは下記の群から選ばれる置換基
（１）（ＣＦ2）ｃＺ（ｃは１〜１０、ＺはＨ又はＦ）で表されるフッ化アルキル基
（２）テトラヒドロフルフリル基
（３）フェニル基
（４）イソボルニル基
（５）ノルボルニル基
（６）トリシクロ［５，２，１，０2,6］デカニル基又はデセニル基
【０００９】
及び、繊維を、下記一般式［１］で表される（メタ）アクリル酸誘導体及び／又はその重合体の溶液又は分散液にて付着処理することを特徴とする抗菌性繊維の製造方法、にある。
ＣＨ2＝Ｃ（Ｒ）ＣＯＯＸＹ ［１］
但し、式中、Ｒ、Ｘ、Ｙはそれぞれ下記の置換基を示す。
ＲはＨ又はＣＨ3
Ｘは（ＣＨ2）ａＯｂ（ａは０〜４、ｂは０又は１）
Ｙは下記の群から選ばれる置換基
（１）（ＣＦ2）ｃＺ（ｃは１〜１０、ＺはＨ又はＦ）で表されるフッ化アルキル基
（２）テトラヒドロフルフリル基
（３）フェニル基
（４）イソボルニル基
（５）ノルボルニル基
（６）トリシクロ［５，２，１，０2,6］デカニル基又はデセニル基
【００１０】
【発明の実施の形態】
本発明において、（メタ）アクリル酸誘導体とは、アクリル酸誘導体及びメタクリル酸誘導体を指す。
本発明の抗菌性付与剤の有効成分である前記一般式［１］で表される（メタ）アクリル酸誘導体としては、具体的には、例えば、トリフルオロエチルアクリレート、トリフルオロエチルメタクリレート、オクタフルオロペンチルアクリレート、オクタフルオロペンチルメタクリレート、トリデカフルオロオクチルメタクリレート、ヘプタデカフルオロデシルアクリレート、ヘプタデカフルオロデシルメタクリレート、テトラヒドロフルフリルアクリレート、テトラヒドロフルフリルメタクリレート、フェニルメタクリレート、フェノキシエチルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート、ノルボルニルアクリレート、ノルボルニルメタクリレート、トリシクロ［５，２，１，０2,6］デカニルアクリレート、トリシクロ［５，２，１，０2,6］デカニルメタクリレート、トリシクロ［５，２，１，０2,6］デセニルアクリレート、トリシクロ［５，２，１，０2,6］デセニルオキシエチルアクリレート等が挙げられ、また、これらは、単独であってもよいし或いは２種以上組み合わされていてもよい。
【００１１】
本発明の抗菌性付与剤は、これら（メタ）アクリル酸誘導体のみを有効成分として構成されていてもよいし、これら（メタ）アクリル酸誘導体を有効成分とし、水、アルコール等に溶解してなる溶液の形態であってもよく、また、（メタ）アクリル酸誘導体が難溶性であるときは、（メタ）アクリル酸誘導体を有効成分とし、分散剤にて水等に分散させてなる分散液の形態であってもよい。
【００１２】
特に本発明の抗菌性付与剤は、その形態が液状であるときは、繊維等の製品を浸漬して付着処理することにより繊維等の製品に抗菌性を付与することができ、また塗布、スプレイ等の方法を用いることにより住宅建材、家具等の二次製品に簡易に抗菌性を付与することもできる。
【００１３】
また、本発明の抗菌性付与剤における前記一般式［１］で表される（メタ）アクリル酸誘導体は、炭素−炭素二重結合を有し重合性を有することから、（メタ）アクリル酸誘導体のままで適用し、その後重合させることもできるし、また、本発明の抗菌性付与剤が（メタ）アクリル酸誘導体の重合体、又は単量体と重合体とで有効成分が構成されていてもよく、また重合体は、（メタ）アクリル酸誘導体と共重合可能な不飽和化合物との共重合体であってもよく、（メタ）アクリル酸誘導体の重合体からなる抗菌性付与剤は、混練、混合する等により有機高分子からなる樹脂に抗菌性を付与することもできる。
【００１４】
（メタ）アクリル酸誘導体の重合には、任意の公知の方法が用いられ、例えば（メタ）アクリル酸誘導体を、過硫酸アンモニウム等の任意の重合開始剤及び界面活性剤を含み、グラフト重合の効率を上げるため蟻酸等で酸性とした水中で加熱する方法が用いられる。
【００１５】
本発明の抗菌性付与剤は、植物由来の細菌及び細菌等の微生物に対して優れた抗菌性を示し、各種形態の製品や樹脂等に抗菌性を付与することができるものであるが、特に、本発明の抗菌性付与剤の有効成分である前記一般式［１］で表される（メタ）アクリル酸誘導体及び／又はその重合体を付着させた繊維は、抗菌性繊維として有用なるものである。
【００１６】
すなわち、本発明の抗菌性繊維は、繊維に前記一般式［１］で表される（メタ）アクリル酸誘導体及び／又はその重合体が付着されてなるものであり、繊維としては、家蚕、野蚕等の絹繊維、羊毛繊維等の動物性蛋白質繊維、麻、木綿等の天然セルロース繊維、６ナイロン、６，６ナイロン等のポリアミド繊維等が挙げられ、特に絹繊維、羊毛繊維が好ましいものとして挙げられる。繊維の形態は、綿、糸、織物、編物、不織布等の布帛或いはこれら糸、布帛からなる繊維製品のいずれであってもよい。
【００１７】
本発明の抗菌性繊維において、（メタ）アクリル酸誘導体及び／又はその重合体をグラフト重合により繊維の表面及び／又は内部に強固に付着させることは、抗菌性をより長い時間持続させるうえで好ましいことである。
【００１８】
本発明の抗菌性繊維は、次の方法により製造される。
すなわち、本発明の抗菌性繊維は、繊維を前記一般式［１］で表される（メタ）アクリル酸誘導体及び／又はその重合体の溶液又は分散液にて付着処理することより製造される。
【００１９】
（メタ）アクリル酸誘導体及び／又はその重合体の溶液又は分散液は、（メタ）アクリル酸誘導体及び／又はその重合体が、水溶性であれば水溶液、アルコール可溶性であればアルコール溶液、或いは水不溶性であれば界面活性剤等の分散剤により分散させ水分散液とすることがグラフト重合の効率を上げる点で好ましい。
【００２０】
付着処理する方法としては、（メタ）アクリル酸誘導体及び／又はその重合体の溶液又は分散液を処理液とし、（ａ）処理液中に重合開始剤を存在させて繊維を浸漬し、繊維に対し（メタ）アクリル酸誘導体及び／又はその重合体をグラフト重合させる処理方法、（ｂ）処理液中に繊維を浸漬して付着処理する方法が用いられる。その他（ｃ）処理液を繊維に塗布又はスプレイして乾燥する方法等も用いられる。これらの方法うち、特に（ａ）の方法は、より多くの（メタ）アクリル酸誘導体及び／又はその重合体が繊維に付着し、抗菌効果の恒久性に優れ、繊維特性の劣化が軽微なることから好ましく用いられ、特に繊維として絹繊維、羊毛繊維を用いたときにおいて、（ａ）の方法は、有効な方法である。
【００２１】
（ａ）の方法における重合開始剤としては、繊維にグラフト反応の拠点となるラジカルを発生させるラジカル触媒であれば、任意のものが用いられるが、繊維特性を低下させない点で過硫酸アンモニウムが好ましく用いられる。（ｂ）の方法においては、浸漬した後、必要により処理物を水で洗浄し、加熱乾燥するか或いは加温下に浸漬してもよく、また、（ｃ）の方法においては、加熱下に乾燥してもよい。
【００２２】
（ａ）、（ｂ）或いは（ｃ）の付着方法における処理液の（メタ）アクリル酸誘導体及び／又はその重合体の使用量、処理温度、処理時間等の条件は、処理される繊維の種類、抗菌性付与の程度、抗菌性繊維の用途等により、適宜変更することができる。繊維への（メタ）アクリル酸誘導体及び／又はその重合体の付着量としては、優れた抗菌効果を発揮させるうえからは、少なくとも０．０１重量％とすることが好ましい。
【００２３】
本発明の抗菌性繊維は、細菌等の微生物に対し優れた抗菌性を示し、かつ抗菌効果の耐久性に優れたものであり、例えば肌着、シャツ、ブラウス、パジャマ等の衣料品、寝装具、タオル、ハンカチ、包帯等の各種抗菌性製品として、或いはマット、シート、綿体、粉砕体等の各種抗菌性製品の素材として好適なるものである。
【００２４】
また、本発明の抗菌性繊維は、植物細菌に対して優れた抗菌性を示し、特に農業、園芸分野において、液中や土壌中の病原細菌の低減、外部からの病原細菌の侵入の阻止に有効であり、例えば各種植物の養液（水耕）栽培における循環液中の病原細菌を捕捉殺菌する殺菌フィルター材、土壌に混入して病原細菌濃度を減少させる土壌改良消毒材、土壌面に敷設して周囲からの病原細菌の侵入を阻止する或いは植物の根元周辺の土壌からの病原細菌の葉への飛散を阻止する病害防除用マルチシート、樹木の病斑部からの病原細菌の飛散を阻止する或いは樹木の病害治療部、切除部への病原細菌の侵入を阻止するための保護又は傷当てのテープ或いはシート等として用いることができる。
【００２５】
【実施例】
以下、本発明を実施例により具体的に説明する。なお、実施例中の測定値及び細菌に対する抗菌活性検定試験は、下記の方法に拠った。
【００２６】
〈グラフト率〉
グラフト重合させたときの処理試料のグラフト率は次式により求めた。
グラフト率（％）＝（Ｗ1−Ｗ0）／Ｗ0×１００
式中、Ｗ0はグラフト重合前の試料の重量、Ｗ1はグラフト重合後の試料の重量、なお、各試料重量は１０５℃で２時間乾燥後に測定した。
【００２７】
〈トマトかいよう病菌（Ｃｏｒｙｎｅｂａｃｔｅｒｉｕｍ ｍｉｃｈｉｇａｎｅｓｅ ｐｖ．ｍｉｃｈｉｇａｎｅｓｅ）に対する抗菌活性検定試験法〉
▲１▼加熱溶解後５５℃に保った半合成脇本培地或いはキングＢ培地２５ｍｌと、検定菌（濃度１０9-10個／ｍｌ）２ｍｌを混合してシャーレに流し込んで平板状に固め、この菌液混合平板培地上に評価試料を密着させて置く。
▲２▼この際、試料が（メタ）アクリル酸誘導体の単量体含有液である場合は、培地上に直径８ｍｍの濾紙を置き、試料を１５μｌ滴下する。試料が（メタ）アクリル酸誘導体の重合体である場合は、培地上に直径８ｍｍの薄片状の試料を置く。また、試料が繊維である場合は、培地上に約２ｃｍの長さに切断した試料を置き、試料の両端を培地に埋め込んで試料全体を培地に密着させる。
▲３▼その後２日間２０〜２５℃に保った後、評価試料付近の培地での菌増殖の阻害の程度（抗菌活性度）を下記の判定基準により４段階で評価する。
＋＋＋：明瞭な幅２ｍｍ以上の菌増殖阻止帯を形成
＋＋ ：不明瞭な菌増殖阻止帯を形成、或いは幅１ｍｍ以下の明瞭な菌増殖阻止帯を形成
＋ ：僅かに阻害が認められる
− ：抗菌活性が認められない
【００２８】
〈黄色ブドウ状球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＡＴＣＣ ６５３８ Ｐ）に対する抗菌活性検定試験法〉
繊維製品衛生加工協議会による下記の衛生加工製品加工効果評価試験方法に基づく菌数測定法に拠った。
▲１▼普通ブイヨン培地で調整した黄色ブドウ状球菌を５〜３０×１０5個／ｍｌ含有する試験菌懸濁液０．２ｍｌを、約０．２ｇの試料の上に均一に接種する。
▲２▼試料は、ブランクを６検体、評価試料を３検体用意し、接種後ブランク３検体、評価試料３検体を直ちに３５〜３７℃で１８時間静置培養する。
▲３▼培養しないブランク３検体は接種直後に、また培養したブランク３検体及び評価試料３検体は培養終了後に、滅菌緩衝生理食塩液２０ｍｌを加え、振とうして試料中の生菌を液中に分散させ、この分散菌液から滅菌緩衝生理食塩液で希釈系列を作り、下記のＡ、Ｂ、Ｃのそれぞれの菌数を測定する。
Ａ：接種直後分散回収したブランク（３検体）
Ｂ：１８時間培養後分散回収したブランク（３検体）
Ｃ：１８時間培養後分散回収した評価試料（３検体）
▲４▼菌数測定は、希釈液１ｍｌをシャーレに入れ、標準寒天培地の約１５ｍｌ混釈平板を作成（同一希釈液につき平板を２枚作成）後、３５〜３７℃で２４〜４８時間培養し、生育したコロニー数を測定し、その希釈倍数を乗じて試料中の生菌数を算出する。
▲５▼Ａ、Ｂ、Ｃの菌数の平均したものをそれぞれａ、ｂ、ｃとし、次式により増減値差を計算する。この増減値差の数値の大きいものほど抗菌性に優れる。
増減値差＝［ｌｏｇ（ｂ／ａ）］−［ｌｏｇ（ｃ／ａ）］
▲６▼増減値差により、菌増殖の阻害の程度（抗菌活性度）を下記の判定基準により４段階で評価する。
＋＋＋：増減値差が５．０以上
＋＋ ：増減値差が３．０以上５．０未満
＋ ：増減値差が１．６以上３．０未満
− ：増減値差が１．６未満
【００２９】
（実施例１）
表１に示すような単量体である各（メタ）アクリル酸誘導体からなり、下記形態をなす本発明の抗菌性付与剤について、トマトかいよう病菌に対する抗菌活性検定試験を行い、その結果を表１に示した。
ｍ−Ａ：（メタ）アクリル酸誘導体（液状物）
ｍ−Ｂ：（メタ）アクリル酸誘導体とエタノールとの容量比１：１の溶液
ｍ−Ｃ：（メタ）アクリル酸誘導体と界面活性剤含有水との容量比１：１の 分散液
【００３０】
【表１】
（実施例２）
表２に示すような各（メタ）アクリル酸誘導体の重合体からなる本発明の抗菌性付与剤について、トマトかいよう病菌に対する抗菌活性検定試験を行い、その結果を表２に示した。
なお、（メタ）アクリル酸誘導体の重合体は、次の方法によって得た。
すなわち、ガラス製容器に、（メタ）アクリル酸誘導体８重量部、過硫酸アンモニウム０．５重量部、ニューカルゲン１５１５−２Ｈ（竹本油脂（株）製、界面活性剤）１０．７重量％を含む水２５０重量部を投入し、蟻酸でｐＨ３に調整して攪拌後、液温を２５℃から４５分かけて８５℃に昇温し、この温度で１時間保持した。その後、ガラス製容器の底部に析出した重合物を８０℃のノイゲンＨＣ（第一工業製薬（株）製、界面活性剤）１．７重量％水溶液で２回洗浄し、さらに温水で３回洗浄し、８０℃で乾燥した。
【００３２】
【表２】
（実施例３）
羊毛繊維として、メリノ種羊毛（６４’Ｓ）をベンゼン／エタノール（５０／５０容量％）混合液を用いてソックスレー抽出器にて２．５時間脱脂処理したものを用いた。ニューカルゲン１５１５−２Ｈ（竹本油脂（株）製、界面活性剤）６重量％を含む水溶液に希薄蟻酸を加えてｐＨ３．０に調整した後、表３に示す（メタ）アクリル酸誘導体を１００％ｏｗｆ（ｏｗｆ：対繊維重量）加え、さらに重合開始剤として過硫酸アンモニウムを羊毛繊維と（メタ）アクリル酸誘導体の合計量に対し１．８重量％加えてグラフト加工液を調製した。
【００３４】
グラフト加工液の浴比を１：１５とし、羊毛繊維を浸漬し、液温を２５℃から４５分かけて８０℃に昇温し、８０℃で１時間保持してグラフト重合処理した。処理後、熱水及び流水で十分洗浄して未反応物を除去し、乾燥した。得られた加工羊毛繊維について、それぞれのグラフト率及びトマトかいよう病菌に対する抗菌活性検定試験の結果を表３に示した。
【００３５】
【表３】
（実施例４）
絹繊維として、家蚕繭糸を炭酸ナトリウム０．２重量％水溶液にて９８℃で４５分煮沸して精練し繊維表面の膠着物質のセリシンを除去したものを用いた。ニューカルゲン１５１５−２Ｈ（竹本油脂（株）製、界面活性剤）１２重量％を含む水溶液に希薄蟻酸を加えてｐＨ３．０に調整した後、表４に示す（メタ）アクリル酸誘導体を３５％ｏｗｆ加え、さらに重合開始剤として過硫酸アンモニウムを絹繊維と（メタ）アクリル酸誘導体の合計量に対し１．８重量％加えてグラフト加工液を調製した。
【００３７】
グラフト加工液の浴比を１：１５とし、絹繊維を浸漬し、液温を２５℃から４５分かけて８０℃に昇温し、８０℃で１時間保持してグラフト重合処理した。処理後、熱水及び流水で十分洗浄して未反応物を除去し、乾燥した。得られた加工絹繊維について、それぞれのグラフト率及びトマトかいよう病菌に対する抗菌活性検定試験の結果を表４に示した。
【００３８】
【表４】
（実施例５）
実施例３で用いたのと同じ羊毛繊維を用い、表５に示す（メタ）アクリル酸誘導体を用いて、実施例３と同様にしてグラフト重合処理して加工羊毛繊維を得た。得られた加工羊毛繊維について、それぞれのグラフト率及び黄色ブドウ状球菌に対する抗菌活性検定試験の結果を表５に示した。
【００４０】
【表５】
【発明の効果】
本発明の抗菌性付与剤は、植物由来の細菌及び細菌等の微生物に対して優れた抗菌性を示し、各種製品或いはそれらの素材の樹脂に抗菌性を付与することができ、その抗菌性付与剤の有効成分を用いてなる抗菌性繊維は、洗濯やドライクリーニング等による抗菌性を付与する有効成分の脱落が少なく、抗菌効果が持続し耐久性に優れたものであり、衣料分野、医療分野、家庭用品分野、家電・事務分野、食品分野等の従来抗菌性が要求される分野のみならず、農業、園芸分野においても好適に用いられる。そしてまた、この抗菌性繊維は、容易かつ経済的に製造し得る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antibacterial imparting agent that exhibits antibacterial properties against plant-derived bacteria and microorganisms such as bacteria, an antibacterial fiber using an active ingredient of the antibacterial imparting agent, and a method for producing the same.
[0002]
[Prior art]
In recent years, due to the increase in cleanliness and hygiene, not only in the medical field and clothing field, but also in household goods such as toiletries, kitchenware, freshness-preserving films, sanitizing sheets, washing machines, refrigerators, floppy disk cases, stationery, etc. Antibacterial materials are used in the fields of home appliances, office supplies, foods, etc., and antibacterial fibers are also used as one of the antibacterial materials.
[0003]
Conventionally, as a method for producing antibacterial fibers, for example, metal or metal compound fine particles exhibiting antibacterial properties are brought into contact with an organic polymer material as a dispersion and coated on the surface of the organic polymer material (JP-A-7-97769) And a method of coating the fiber surface with an antibacterial metal having a colloidal particle size and an oxide of another metal (Japanese Patent Laid-Open No. 7-109664). However, since the antibacterial fiber by these methods has only the antibacterial metal adhering to the fiber surface, there is a possibility that the antibacterial metal may fall off during use.
[0004]
As a method for imparting antibacterial properties to the fiber itself, acrylonitrile copolymer fiber copolymerized with an amino group-containing acrylic ester is treated with an alkyl halide to quaternize the amino group nitrogen to obtain an antibacterial acrylic fiber. Although a method (Japanese Patent Laid-Open No. 5-140868) is known, this method requires copolymerization of a specific monomer and treatment with an alkyl halide, and is not an economical and efficient method.
[0005]
In addition, antibacterial fibers can be produced by adhering antibacterial silver supported on the surface of spherical ceramic fine particles such as silica and alumina to the fiber surface, and adsorbing porous natural zeolite or silver ions to the zeolite. There is a known method of covering the surface of the material, but the method of physically attaching the antibacterial metal to the fiber is to carry the antibacterial metal by washing or dry cleaning when the fiber is a fiber product. There is a problem that things easily fall off and it is difficult to maintain the initial antibacterial effect for a long time.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide an antibacterial property-imparting agent having excellent antibacterial properties against plant-derived bacteria and microorganisms such as bacteria, and washing and drying using an active ingredient of the antibacterial property imparting agent. An object of the present invention is to provide an antibacterial fiber having a long lasting antibacterial effect and having excellent durability, and to easily and economically obtain this antibacterial fiber.
[0007]
[Means for Solving the Problems]
The present invention provides an antibacterial property-imparting agent characterized by comprising a (meth) acrylic acid derivative represented by the following general formula [1] and / or a polymer thereof as an active ingredient,
CH 2 = C (R) COOXY [1]
However, in the formula, R, X, and Y each represent the following substituent.
R is H or CH 3
X is (CH 2 ) aOb (a is 0 to 4, b is 0 or 1)
Y is a fluorinated alkyl group (2) a tetrahydrofurfuryl group (3) phenyl represented by a substituent (1) (CF 2 ) cZ (c is 1 to 10, Z is H or F) selected from the following group group (4) isobornyl group (5) norbornyl group (6) tricyclo [5,2,1,0 2,6] decanyl group or decenyl [0008]
And an antibacterial fiber characterized in that a (meth) acrylic acid derivative represented by the following general formula [1] and / or a polymer thereof is attached to the fiber,
CH 2 = C (R) COOXY [1]
However, in the formula, R, X, and Y each represent the following substituent.
R is H or CH 3
X is (CH 2 ) aOb (a is 0 to 4, b is 0 or 1)
Y is a fluorinated alkyl group (2) a tetrahydrofurfuryl group (3) phenyl represented by a substituent (1) (CF 2 ) cZ (c is 1 to 10, Z is H or F) selected from the following group group (4) isobornyl group (5) norbornyl group (6) tricyclo [5,2,1,0 2,6] decanyl group or decenyl [0009]
And a method for producing an antibacterial fiber, characterized in that the fiber is subjected to adhesion treatment with a solution or dispersion of a (meth) acrylic acid derivative represented by the following general formula [1] and / or a polymer thereof. is there.
CH 2 = C (R) COOXY [1]
However, in the formula, R, X, and Y each represent the following substituent.
R is H or CH 3
X is (CH 2 ) aOb (a is 0 to 4, b is 0 or 1)
Y is a fluorinated alkyl group (2) a tetrahydrofurfuryl group (3) phenyl represented by a substituent (1) (CF 2 ) cZ (c is 1 to 10, Z is H or F) selected from the following group group (4) isobornyl group (5) norbornyl group (6) tricyclo [5,2,1,0 2,6] decanyl group or decenyl [0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the (meth) acrylic acid derivative refers to an acrylic acid derivative and a methacrylic acid derivative.
Specific examples of the (meth) acrylic acid derivative represented by the general formula [1] which is an active ingredient of the antibacterial property imparting agent of the present invention include, for example, trifluoroethyl acrylate, trifluoroethyl methacrylate, octafluoro Pentyl acrylate, octafluoropentyl methacrylate, tridecafluorooctyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, isobornyl acrylate, isobornyl alkenyl methacrylate, norbornyl acrylate, norbornyl methacrylate, tricyclo [5,2,1,0 2,6] decanyl acrylate, Rishikuro [5,2,1,0 2,6] decanyl methacrylate, tricyclo [5,2,1,0 2,6] decenyl acrylate, tricyclo [5,2,1,0 2,6] dec Nyloxyethyl acrylate etc. are mentioned, These may be individual or may be combined 2 or more types.
[0011]
The antibacterial property-imparting agent of the present invention may be composed of only these (meth) acrylic acid derivatives as active ingredients, or these (meth) acrylic acid derivatives as active ingredients and dissolved in water, alcohol or the like. It may be in the form of a solution, and when the (meth) acrylic acid derivative is sparingly soluble, the (meth) acrylic acid derivative is used as an active ingredient and the dispersion liquid is dispersed in water or the like with a dispersant. Form may be sufficient.
[0012]
In particular, the antibacterial property-imparting agent of the present invention can impart antibacterial properties to products such as fibers by immersing and adhering products such as fibers when the form is liquid, and can also be applied, sprayed, and sprayed. By using a method such as this, it is possible to easily impart antibacterial properties to secondary products such as house building materials and furniture.
[0013]
Moreover, since the (meth) acrylic acid derivative represented by the general formula [1] in the antibacterial property imparting agent of the present invention has a carbon-carbon double bond and is polymerizable, the (meth) acrylic acid derivative. The antibacterial property-imparting agent of the present invention is a polymer of a (meth) acrylic acid derivative, or an active ingredient is composed of a monomer and a polymer. The polymer may be a copolymer of an unsaturated compound copolymerizable with a (meth) acrylic acid derivative, and the antibacterial property imparting agent comprising a polymer of a (meth) acrylic acid derivative is Antibacterial properties can be imparted to a resin composed of an organic polymer by kneading or mixing.
[0014]
For the polymerization of the (meth) acrylic acid derivative, any known method can be used. For example, the (meth) acrylic acid derivative contains an optional polymerization initiator such as ammonium persulfate and a surfactant to improve the efficiency of graft polymerization. In order to raise, the method of heating in the water acidified with formic acid etc. is used.
[0015]
The antibacterial property imparting agent of the present invention exhibits excellent antibacterial properties against plant-derived bacteria and microorganisms such as bacteria, and can impart antibacterial properties to various forms of products, resins, etc. The fiber to which the (meth) acrylic acid derivative represented by the general formula [1] and / or the polymer thereof, which is an active ingredient of the antibacterial property imparting agent of the present invention, is useful as an antibacterial fiber. is there.
[0016]
That is, the antibacterial fiber of the present invention is obtained by attaching a (meth) acrylic acid derivative represented by the above general formula [1] and / or a polymer thereof to the fiber. Examples include silk fiber such as silk, animal protein fiber such as wool fiber, natural cellulose fiber such as hemp and cotton, polyamide fiber such as 6 nylon and 6 and 6 nylon, and silk fiber and wool fiber are particularly preferable. It is done. The form of the fiber may be any of fabrics such as cotton, yarn, woven fabric, knitted fabric, and non-woven fabric, or fiber products made of these yarn and fabric.
[0017]
In the antibacterial fiber of the present invention, it is preferable that the (meth) acrylic acid derivative and / or the polymer thereof is firmly attached to the surface and / or inside of the fiber by graft polymerization in order to maintain the antibacterial property for a longer time. That is.
[0018]
The antibacterial fiber of the present invention is produced by the following method.
That is, the antibacterial fiber of the present invention is produced by subjecting the fiber to adhesion treatment with a solution or dispersion of the (meth) acrylic acid derivative represented by the general formula [1] and / or a polymer thereof.
[0019]
The solution or dispersion of the (meth) acrylic acid derivative and / or polymer thereof is an aqueous solution if the (meth) acrylic acid derivative and / or polymer thereof is water-soluble, an alcohol solution or water if it is alcohol-soluble. If it is insoluble, it is preferable to disperse it with a dispersant such as a surfactant to form an aqueous dispersion from the viewpoint of increasing the efficiency of graft polymerization.
[0020]
As a method for the adhesion treatment, a solution or dispersion of a (meth) acrylic acid derivative and / or a polymer thereof is used as a treatment liquid, (a) a fiber is immersed in the treatment liquid in the presence of a polymerization initiator, On the other hand, a treatment method in which a (meth) acrylic acid derivative and / or a polymer thereof is graft-polymerized, and (b) a method in which fibers are immersed in a treatment solution and attached are used. Others (c) A method of applying or spraying the treatment liquid on the fiber and drying it is also used. Among these methods, in particular, the method (a) is such that more (meth) acrylic acid derivatives and / or polymers thereof adhere to the fibers, have excellent antibacterial effects, and have a slight deterioration in fiber properties. The method (a) is an effective method particularly when silk fibers and wool fibers are used as the fibers.
[0021]
As the polymerization initiator in the method (a), any radical catalyst can be used as long as it is a radical catalyst that generates a radical that becomes a base of a graft reaction on the fiber. However, ammonium persulfate is preferably used because it does not deteriorate the fiber characteristics. It is done. In the method (b), after immersing, the treated product may be washed with water if necessary, and dried by heating or immersed under heating. In the method (c), under heating. It may be dried.
[0022]
Conditions such as the amount of (meth) acrylic acid derivative and / or its polymer used in the treatment liquid in the adhesion method (a), (b) or (c), treatment temperature, treatment time, etc. are the types of fibers to be treated. Depending on the degree of imparting antibacterial properties, the use of antibacterial fibers, etc., it can be changed as appropriate. The amount of the (meth) acrylic acid derivative and / or polymer thereof attached to the fiber is preferably at least 0.01% by weight from the viewpoint of exerting an excellent antibacterial effect.
[0023]
The antibacterial fiber of the present invention exhibits excellent antibacterial properties against microorganisms such as bacteria, and has excellent durability of antibacterial effects, such as clothing such as underwear, shirts, blouses, pajamas, bedding, It is suitable as various antibacterial products such as towels, handkerchiefs and bandages, or as materials for various antibacterial products such as mats, sheets, cotton bodies and pulverized bodies.
[0024]
In addition, the antibacterial fiber of the present invention exhibits excellent antibacterial properties against plant bacteria, particularly in agriculture and horticulture, for reducing pathogenic bacteria in liquids and soils and preventing invasion of pathogenic bacteria from outside. Effective, for example, a sterilizing filter material that captures and sterilizes pathogenic bacteria in the circulating fluid in nutrient solution (hydroponic) cultivation of various plants, a soil improvement disinfectant that reduces the concentration of pathogenic bacteria by mixing with soil, and lays on the soil surface Multi-sheet for disease control that prevents the invasion of pathogenic bacteria from the surroundings or prevents the pathogenic bacteria from spreading to the leaves from the soil around the root of the plant, preventing the pathogenic bacteria from scattering from the lesions of the tree Or it can be used as a tape or sheet for protecting or scratching to prevent the invasion of pathogenic bacteria into the disease treatment section or excision section of trees.
[0025]
【Example】
Hereinafter, the present invention will be specifically described by way of examples. In addition, the measured value in an Example and the antibacterial activity test for bacteria were based on the following method.
[0026]
<Graft ratio>
The graft ratio of the treated sample when graft polymerized was determined by the following formula.
Graft rate (%) = (W 1 −W 0 ) / W 0 × 100
In the formula, W 0 is the weight of the sample before graft polymerization, W 1 is the weight of the sample after graft polymerization, and each sample weight was measured after drying at 105 ° C. for 2 hours.
[0027]
<Antibacterial activity test method for tomato scab fungus (Corynebacterium michiganese pv. Michiganese)>
(1) Mix 25ml of semi-synthetic Wakimoto medium or King B medium maintained at 55 ° C after heating and dissolution with 2 ml of test bacteria (concentration 10 9-10 cells / ml), and pour them into a petri dish to harden them into plates. An evaluation sample is placed in close contact with the liquid mixed plate medium.
(2) If the sample is a monomer-containing liquid of a (meth) acrylic acid derivative, place a filter paper having a diameter of 8 mm on the medium, and drop 15 μl of the sample. When the sample is a polymer of a (meth) acrylic acid derivative, a flaky sample having a diameter of 8 mm is placed on the medium. When the sample is a fiber, a sample cut to a length of about 2 cm is placed on the medium, and both ends of the sample are embedded in the medium to bring the entire sample into close contact with the medium.
(3) After maintaining at 20 to 25 ° C. for 2 days, the degree of inhibition of bacterial growth (antibacterial activity) in the medium in the vicinity of the evaluation sample is evaluated in 4 stages according to the following criteria.
++++: Formation of a clear bacterial growth inhibition zone with a width of 2 mm or more ++: Formation of an unclear bacterial growth inhibition zone, or formation of a clear bacterial growth inhibition zone with a width of 1 mm or less +: Slight inhibition is observed-: Antibacterial No activity observed [0028]
<Antimicrobial activity assay test method against Staphylococcus aureus ATCC 6538 P>
It was based on the microbe count method based on the following sanitary processed product processing effect evaluation test method by the textile product sanitary processing council.
(1) 0.2 ml of a test cell suspension containing 5 to 30 × 10 5 cells / ml of Staphylococcus aureus prepared in a normal broth medium is uniformly inoculated on a sample of about 0.2 g.
(2) Prepare 6 samples of blanks and 3 samples of evaluation samples, and immediately incubate 3 samples of blanks and 3 samples of evaluation samples at 35 to 37 ° C. for 18 hours after inoculation.
(3) Immediately after inoculation for 3 blank specimens that are not cultured, and for 3 cultured blank specimens and 3 specimens for evaluation after completion of culture, add 20 ml of sterilized buffered saline and shake to shake viable bacteria in the specimen. Then, a dilution series is made from this dispersed bacterial solution with a sterile buffered physiological saline solution, and the number of each of the following A, B, and C bacteria is measured.
A: Blanks (3 samples) collected and collected immediately after inoculation
B: Blanks (3 specimens) dispersed and recovered after 18 hours of culture
C: Evaluation samples (3 samples) dispersed and recovered after 18 hours of culture
(4) To measure the number of bacteria, put 1 ml of the diluted solution in a petri dish, prepare approximately 15 ml of a mixed agar plate of standard agar medium (create two plates for the same diluted solution), and incubate at 35-37 ° C. for 24-48 hours. Then, the number of grown colonies is measured, and the number of viable bacteria in the sample is calculated by multiplying by the dilution factor.
(5) The average numbers of A, B, and C bacteria are a, b, and c, respectively, and an increase / decrease value difference is calculated by the following equation. The larger the value of the increase / decrease value difference, the better the antibacterial property.
Increase / decrease value difference = [log (b / a)]-[log (c / a)]
{Circle around (6)} The degree of inhibition of bacterial growth (antibacterial activity) is evaluated in four stages according to the following criteria based on the difference in increase / decrease value.
++: Increase / decrease value difference is 5.0 or more ++: Increase / decrease value difference is 3.0 or more and less than 5.0 +: Increase / decrease value difference is 1.6 or more and less than 3.0 −: Increase / decrease value difference is less than 1.6 ]
(Example 1)
The antibacterial property-imparting agent of the present invention comprising the respective (meth) acrylic acid derivatives as monomers shown in Table 1 and having the following forms was subjected to an antibacterial activity assay test against tomato squash fungi, and the results are shown in Table 1. It was shown to.
m-A: (meth) acrylic acid derivative (liquid)
m-B: a 1: 1 volume ratio solution of (meth) acrylic acid derivative and ethanol m-C: a 1: 1 volume ratio dispersion of (meth) acrylic acid derivative and surfactant-containing water
[Table 1]
(Example 2)
The antibacterial property-imparting agent of the present invention composed of a polymer of each (meth) acrylic acid derivative as shown in Table 2 was tested for antibacterial activity against tomato scab disease fungi, and the results are shown in Table 2.
In addition, the polymer of the (meth) acrylic acid derivative was obtained by the following method.
That is, water containing 8 parts by weight of a (meth) acrylic acid derivative, 0.5 parts by weight of ammonium persulfate, and 10.7% by weight of Neukalgen 1515-2H (manufactured by Takemoto Yushi Co., Ltd., surfactant) in a glass container. After adding 250 parts by weight, adjusting the pH to 3 with formic acid and stirring, the liquid temperature was raised from 25 ° C. to 85 ° C. over 45 minutes, and kept at this temperature for 1 hour. Thereafter, the polymer deposited on the bottom of the glass container was washed twice with a 1.7% by weight aqueous solution of Neugen HC (Daiichi Kogyo Seiyaku Co., Ltd., surfactant) at 80 ° C., and further washed three times with warm water. And dried at 80 ° C.
[0032]
[Table 2]
(Example 3)
As the wool fiber, merino wool (64 ′S) degreased for 2.5 hours with a Soxhlet extractor using a benzene / ethanol (50/50 vol%) mixed solution was used. After adjusting the pH to 3.0 by adding dilute formic acid to an aqueous solution containing 6% by weight of Neukalgen 1515-2H (manufactured by Takemoto Yushi Co., Ltd., surfactant), 100% of the (meth) acrylic acid derivative shown in Table 3 was added. A grafting solution was prepared by adding owf (owf: fiber weight) and further adding 1.8% by weight of ammonium persulfate as a polymerization initiator to the total amount of wool fiber and (meth) acrylic acid derivative.
[0034]
The graft ratio was 1:15, the wool fiber was immersed, the temperature of the solution was raised from 25 ° C. to 80 ° C. over 45 minutes, and held at 80 ° C. for 1 hour for graft polymerization. After the treatment, it was sufficiently washed with hot water and running water to remove unreacted substances and dried. Table 3 shows the results of the antibacterial activity test for the graft ratio and tomato scab of the obtained processed wool fiber.
[0035]
[Table 3]
(Example 4)
A silk fiber was used in which rabbit yarn was boiled in a 0.2 wt% aqueous solution of sodium carbonate at 98 ° C for 45 minutes and scoured to remove sericin, a glue substance on the fiber surface. After adjusting the pH to 3.0 by adding dilute formic acid to an aqueous solution containing 12% by weight of Neucalgen 1515-2H (manufactured by Takemoto Yushi Co., Ltd., surfactant), 35% of the (meth) acrylic acid derivative shown in Table 4 was added. A grafting solution was prepared by adding owf and further adding 1.8% by weight of ammonium persulfate as a polymerization initiator to the total amount of silk fiber and (meth) acrylic acid derivative.
[0037]
The graft ratio was 1:15, the silk fiber was immersed, the temperature of the solution was raised from 25 ° C. to 80 ° C. over 45 minutes, and held at 80 ° C. for 1 hour for graft polymerization. After the treatment, it was sufficiently washed with hot water and running water to remove unreacted substances and dried. Table 4 shows the results of the antibacterial activity assay test for the obtained grafted silk fibers and their respective graft rates and tomato scab.
[0038]
[Table 4]
(Example 5)
Using the same wool fiber as used in Example 3, using the (meth) acrylic acid derivatives shown in Table 5, graft polymerization treatment was performed in the same manner as in Example 3 to obtain a processed wool fiber. About the obtained processed wool fiber, Table 5 shows the results of the respective graft ratios and antibacterial activity assay tests against Staphylococcus aureus.
[0040]
[Table 5]
【The invention's effect】
The antibacterial property-imparting agent of the present invention exhibits excellent antibacterial properties against microorganisms such as plant-derived bacteria and bacteria, and can impart antibacterial properties to various products or resins of those materials. The antibacterial fibers made from the active ingredients of the agent are less likely to drop off the active ingredients that impart antibacterial properties due to washing, dry cleaning, etc., have long lasting antibacterial effects, and have excellent durability. It is suitably used not only in fields where antibacterial properties are conventionally required, such as household products, home appliances / office work, and food, but also in agriculture and horticulture. And this antimicrobial fiber can be easily and economically produced.
Claims (7)
ＣＨ2＝Ｃ（Ｒ）ＣＯＯＸＹ ［１］
但し、式中、Ｒ、Ｘ、Ｙはそれぞれ下記の置換基を示す。
ＲはＨ又はＣＨ3
Ｘは（ＣＨ2）ａＯｂ（ａは０〜４、ｂは０又は１）
Ｙは下記の群から選ばれる置換基
（１）（ＣＦ2）ｃＺ（ｃは１〜１０、ＺはＨ又はＦ）で表されるフッ化アルキル基
（２）テトラヒドロフルフリル基
（３）フェニル基
（４）イソボルニル基
（５）ノルボルニル基
（６）トリシクロ［５，２，１，０2,6］デカニル基又はデセニル基An antibacterial property-imparting agent comprising a (meth) acrylic acid derivative represented by the following general formula [1] and / or a polymer thereof as an active ingredient.
CH 2 = C (R) COOXY [1]
However, in the formula, R, X, and Y each represent the following substituent.
R is H or CH 3
X is (CH 2 ) aOb (a is 0 to 4, b is 0 or 1)
Y is a fluorinated alkyl group represented by a substituent (1) (CF 2 ) cZ (c is 1 to 10, Z is H or F) selected from the following group (2) tetrahydrofurfuryl group (3) phenyl group (4) isobornyl group (5) norbornyl group (6) tricyclo [5,2,1,0 2,6] decanyl group or decenyl
ＣＨ2＝Ｃ（Ｒ）ＣＯＯＸＹ ［１］
但し、式中、Ｒ、Ｘ、Ｙはそれぞれ下記の置換基を示す。
ＲはＨ又はＣＨ3
Ｘは（ＣＨ2）ａＯｂ（ａは０〜４、ｂは０又は１）
Ｙは下記の群から選ばれる置換基
（１）（ＣＦ2）ｃＺ（ｃは１〜１０、ＺはＨ又はＦ）で表されるフッ化アルキル基
（２）テトラヒドロフルフリル基
（３）フェニル基
（４）イソボルニル基
（５）ノルボルニル基
（６）トリシクロ［５，２，１，０2,6］デカニル基又はデセニル基An antibacterial fiber, wherein a (meth) acrylic acid derivative represented by the following general formula [1] and / or a polymer thereof is attached to the fiber.
CH 2 = C (R) COOXY [1]
However, in the formula, R, X, and Y each represent the following substituent.
R is H or CH 3
X is (CH 2 ) aOb (a is 0 to 4, b is 0 or 1)
Y is a fluorinated alkyl group represented by a substituent (1) (CF 2 ) cZ (c is 1 to 10, Z is H or F) selected from the following group (2) tetrahydrofurfuryl group (3) phenyl group (4) isobornyl group (5) norbornyl group (6) tricyclo [5,2,1,0 2,6] decanyl group or decenyl
ＣＨ2＝Ｃ（Ｒ）ＣＯＯＸＹ ［１］
但し、式中、Ｒ、Ｘ、Ｙはそれぞれ下記の置換基を示す。
ＲはＨ又はＣＨ3
Ｘは（ＣＨ2）ａＯｂ（ａは０〜４、ｂは０又は１）
Ｙは下記の群から選ばれる置換基
（１）（ＣＦ2）ｃＺ（ｃは１〜１０、ＺはＨ又はＦ）で表されるフッ化アルキル基
（２）テトラヒドロフルフリル基
（３）フェニル基
（４）イソボルニル基
（５）ノルボルニル基
（６）トリシクロ［５，２，１，０2,6］デカニル基又はデセニル基A method for producing an antibacterial fiber, characterized in that the fiber is subjected to adhesion treatment with a solution or dispersion of a (meth) acrylic acid derivative represented by the following general formula [1] and / or a polymer thereof.
CH 2 = C (R) COOXY [1]
However, in the formula, R, X, and Y each represent the following substituent.
R is H or CH 3
X is (CH 2 ) aOb (a is 0 to 4, b is 0 or 1)
Y is a fluorinated alkyl group represented by a substituent (1) (CF 2 ) cZ (c is 1 to 10, Z is H or F) selected from the following group (2) tetrahydrofurfuryl group (3) phenyl group (4) isobornyl group (5) norbornyl group (6) tricyclo [5,2,1,0 2,6] decanyl group or decenyl
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01597497A JP3711412B2 (en) | 1997-01-14 | 1997-01-14 | Antibacterial agent, antibacterial fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01597497A JP3711412B2 (en) | 1997-01-14 | 1997-01-14 | Antibacterial agent, antibacterial fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10204776A JPH10204776A (en) | 1998-08-04 |
| JP3711412B2 true JP3711412B2 (en) | 2005-11-02 |
Family
ID=11903689
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01597497A Expired - Lifetime JP3711412B2 (en) | 1997-01-14 | 1997-01-14 | Antibacterial agent, antibacterial fiber and method for producing the same |
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| Country | Link |
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| JP (1) | JP3711412B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007070650A2 (en) * | 2005-12-14 | 2007-06-21 | 3M Innovative Properties Company | Antimicrobial adhesive films |
| CN115821580B (en) * | 2022-12-09 | 2024-05-07 | 罗莱生活科技股份有限公司 | Modified silk fiber and preparation method and application thereof |
-
1997
- 1997-01-14 JP JP01597497A patent/JP3711412B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH10204776A (en) | 1998-08-04 |
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