JP3852156B2 - Antifouling synthetic fiber fabric and method for producing the same - Google Patents

Description

（式中、Ｒは低級アルキル基を示し、Ｒｆはパーフルオロアルキル基またはパーフルオロアルキレングリコールを含有する基を示し、ｎ、ａおよびｂはそれぞれ１以上の整数を示す。）で表される親水性のフッ素系撥水撥油剤、非親水性のフッ素系撥水撥油剤および架橋剤を含む防汚性成分の被覆層を有し、撥水耐久性が３級以上、撥油耐久性が２級以上および汚れ除去耐久性が３級以上である防汚性合成繊維布帛。
（２）合成繊維上に、上記一般式（Ｉ）（式中、Ｒ、Ｒｆ、ｎ、ａおよびｂは上記と同義である）で表される親水性のフッ素系撥水撥油剤と非親水性のフッ素系撥水撥油剤とを重量比で３５〜６５／６５〜３５有し、さらに上記混合物に対して１〜１５重量％の硬化剤を含む防汚性成分の被覆層を繊維重量あたり１〜２重量％有する防汚性合成繊維布帛。
（３）合成繊維布帛が先染アクリル系繊維布帛、ポリエステル系繊維布帛またはポリアミド系繊維布帛である上記（１）または（２）記載の防汚性合成繊維布帛。
（４）合成繊維布帛を、水洗もしくは精練することによって付着不純物を取り除き、上記一般式（Ｉ）（式中、Ｒ、Ｒｆ、ｎ、ａおよびｂは上記と同義である）で表される親水性のフッ素系撥水撥油剤、非親水性のフッ素系撥水撥油剤および架橋剤を含む水分散液に含浸し、乾燥し、次いで１４０〜１８０℃で乾熱処理することを特徴とする防汚性合成繊維布帛の製造方法。
【０００８】
本明細書において使用される語句について説明する。
（１）撥水耐久性
ＪＩＳ Ｌ ０８２３に規定する摩擦試験機ＩＩを用いて、摩擦子の載荷重が５００ｇで、３０００回摩擦された合成繊維布帛〔摩擦布は綿金布を用い、摩擦を１００回（往復を１回とする）行う毎に新品と交換〕について、イソプロピルアルコール／水混合液法（１〜５級判定）によって判定した撥水性をいう。
【０００９】
【表１】

【００１０】
表１に示す各等級の撥水性測定液を、スポイドで１滴試験布に滴下し、滴下３０秒後の試験布表面の濡れ性を目視評価し、浸透濡れのない等級液で撥水性を判定する。
本発明の防汚性合成繊維布帛は３級以上の撥水耐久性を有する。
【００１１】
（２）撥油耐久性
（１）と同様にして３０００回摩擦された合成繊維繊維布帛について、ＡＡＴＣＣ−１１８−１９７９法（１〜８級判定）によって判定した撥油性をいう。
本発明の防汚性合成繊維布帛は２級以上の撥油耐久性を有する。
【００１２】
（３）汚れ除去耐久性（洗濯）
Ｂ重油（ＪＩＳ Ｋ ２２０５−６０）と墨汁（市販品）の標準汚れをスポイドを用いそれぞれ１滴ずつ、（１）と同様にして３０００回摩擦した合成繊維布帛の上に滴下し、ＰＥフィルムをかぶせガラス板を載せ２ｋｇの荷重下で３０分間汚れを圧着した後、除重し、３時間放置し、ＪＩＳ Ｌ ０２１７−１０３法の規定に従って１回洗濯し、ＪＩＳ Ｌ ０８０５に規定する汚染用グレースケールを用いて判定（１〜５級判定）した汚れ除去性をいう。
本発明の防汚性合成繊維布帛は３級以上の汚れ除去耐久性を有する。
【００１３】
本発明で用いる親水性セグメントを有するフッ素系撥水撥油剤として、下記一般式（Ｉ）で示されるパーフルオロアルキル基含有（メタ）アクリレート共重合体が挙げられる。
【００１４】
【化５】

【００１５】
（式中、Ｒは低級アルキル基を、Ｒｆはパーフルオロアルキル基またはパーフルオロアルキレングリコールを含有する基を、ｎ、ａおよびｂはそれぞれ１以上の整数を示す）
一般式（Ｉ）において、好ましいＲとしては炭素数１〜３のアルキル基が、好ましいＲｆとしては炭素数４〜１０のパーフルオロアルキル基または炭素数４〜２０のパーフルオロアルキレングリコールを含有する基が挙げられる。ｎ、ａおよびｂの好ましい範囲はそれぞれ２〜１０、１〜１０、１〜１０である。
（メタ）アクリレート共重合体（Ｉ）の具体例として、例えば、アサヒガードＧＳ−１（明成化学工業社製）などが挙げられる。
【００１６】
非親水性のフッ素系撥水撥油剤とは、式（Ｉ）で示されるようなポリエチレングリコール単位などのポリアルキレングリコール単位やスルホン酸基などの親水性基を含まないものをいう。具体的には、パーフルオロアクリレート系ポリマー、パーフルオロスルホンアミドアクリレート系ポリマー、パーフルオロアルキルポリエーテル、低分子型パーフルオロアルキルウレタン系オリゴマー、パーフルオロアルキル芳香族エステル系化合物などが挙げられる。特に、ポリマー中のフッ素原子含有量が２０％以上のパーフルオロアクリレート系ポリマーおよびパーフルオロスルホンアミドアクリレート系ポリマーが好ましい。
【００１７】
架橋剤としては、Ｎメチロール基を含有するメチロールメラミン系やブロックイソシアネート（ＴＤＩ／トリメチロールプロパン付加体、ＭＥＫオキシム付加体）が好ましく使用される。
【００１８】
親水性セグメントを有するフッ素系撥水撥油剤と非親水性フッ素系撥水撥油剤との重量比が３５〜６５／６５〜３５の混合物を含み、かつ該混合物に対して１〜１５重量％の硬化剤を含む防汚性成分を使用したばあい、従来にない優れた防汚耐久性を合成繊維布帛に付与することができる。
親水性セグメントを有するフッ素系撥水撥油剤の上記重量比が３５未満のばあいは、洗濯もしくは汚れ拭き取り時の液状汚れの除去性が低下する。また非親水性フッ素系撥水撥油剤の配合比率が３５未満のばあいは、繰返し摩擦による撥水撥油耐久性が低下し易くなる。さらに、硬化剤の親水性セグメントを有するフッ素系撥水撥油剤と非親水性セグメントを有するフッ素系撥水撥油剤との混合物に対する量が１重量％未満のばあいは、初期撥水撥油性（摩擦を行わない布帛の撥水撥油性）および撥水撥油耐久性が十分発現せず、逆に１５重量％を超えると、加工布帛の風合いが硬くなる。
好ましい親水性セグメントを有するフッ素系撥水撥油剤と非親水性フッ素系撥水撥油剤との重量比は４０〜５５／６０〜４５であり、該混合物に対する硬化剤の好ましい重量割合は４〜１０重量％である。
【００１９】
上記３成分の混合物の付着量は、加工すべき合成繊維布帛の重量あたり１〜２重量％である。該混合物の付着量が１重量％未満のばあいは、防汚耐久性が低く、逆に２重量％を越えると風合いが硬化するだけでなく経済的にも不利である。
【００２０】
本発明で使用できる合成繊維布帛とは、ポリエチレンテレフタレート系ポリエステル繊維、イソフタル酸や５−スルホイソフタル酸などとの共重合ポリエステル繊維、ナイロン６やナイロン６６などのポリアミド系繊維、カチオン可染性アクリルや酸性可染性アクリルなどのアクリル系繊維、蛋白−アクリロニトリルグラフト共重合体からなるプロミックス繊維などの合成繊維から造られる編物、織物および不織布などのシート状物である。構成繊維の繊度、断面形状、ダル剤添加量や各種ポリマー安定剤の有無、および布帛の組織、目付、密度などについては特に限定されない。
【００２１】
本発明の優れた防汚耐久性を阻害しない範囲で、導電性繊維の混用や帯電防止剤、難燃剤、抗菌剤、防カビ剤や消臭剤などの他の機能剤との併用使用も可能である。
【００２２】
本発明の防汚性合成繊維布帛の製造方法について説明する。
合成繊維布帛を水洗もしくは精練することによって、布帛表面に付着している不純物を取り除く。このように前処理した繊維布帛を、上記した配合割合の親水性セグメントを有するフッ素系撥水撥油剤、非親水性のフッ素系撥水撥油剤および架橋剤を含む水分散液に含浸する。水分散液中の親水性フッ素系撥水撥油剤、非親水性フッ素系撥水撥油剤および架橋剤の含量は、特に限定されず適宜決められるが、上記３成分の合計が合成繊維布帛の重量あたり１〜２重量％になるように調整される。含浸時の温度は４０〜８０℃、時間は５〜３０分が適当である。繊維表面への防汚性成分の層の形成は、上記した含浸法に限らず、スプレー法、パッディング法など用いてもよい。次いで、風乾、乾燥機の使用など常法で乾燥後、１４０〜１８０℃の乾熱で３０秒〜３分間乾熱処理する。
上記した１４０〜１８０℃乾熱処理後、さらに水洗、乾燥し、１３０℃以上で乾熱処理（時間：３秒〜５分）してもよい。
このようにして形成される層は、厚さが０．０１〜３０μｍが好ましく、より好ましくは０．１〜１０μｍである。
【００２３】
摩擦されても優れた防汚耐久性を的確に発現させる技術的ポイントは、特定成分を特定割合で含む防汚性成分の特定量を、合成繊維表面に均一に付着させる点にある。そのためには、合成繊維布帛に微量残留し易い紡糸油剤、紡績油剤、製織糊剤、分散剤、均緩染剤、浴中柔軟剤もしくはカチオン系フィックス剤などの染色助剤、先染糸に使用される帯電防止剤、柔軟剤、平滑剤を主成分とする先染油剤をできるだけきれいに洗浄除去した後、上記した防汚性成分の層を形成することが好ましい。このような観点から、上記した製造方法は有利である。
【００２４】
本発明における摩擦による防汚耐久性に優れるという防汚効果の発現メカニズムは不詳であるが、特定配合比率の親水性セグメントを有するフッ素系撥水撥油剤、非親水性フッ素系撥水撥油剤および架橋剤の防汚性成分を、不純物を取り除いたクリーンな合成繊維布帛に所定量付与することで達成できることから、（１）繊維表面と配合防汚成分間の強力な密着力、（２）摩擦に強い均一な防汚性被膜の形成、（３）布帛に撥水撥油性を付与するパーフルオロアルキル基の配列と洗濯時のＳＲ性を改良する親水性セグメント（例えば、ポリアルキレングリコール成分）の配列バランスが優れるためと考える。
【００２５】
【実施例】
以下、実施例および比較例をあげて、本発明を説明するが、本発明はこれらの実施例に限定されない。実施例および比較例の％は特に断らない限り重量基準である。
【００２６】
実施例における防汚性繊維布帛の評価方法は以下の通りである。
【００２７】
（１）撥水性
前述した表１に示すイソプロピルアルコールＩＰＡ／水混合液法（１〜５級判定）によって判定する。
【００２８】
（２）撥油性
ＡＡＴＣＣ−１１８−１９７９法（１〜８級判定）に準拠して判定する。
【００２９】
（３）汚れ除去性（洗濯）
Ｂ重油（ＪＩＳ Ｋ ２２０５−６０：粘度２３．４ＣＢＴ・残炭素５．５％）と墨汁（不易糊工業社：墨彩）の標準汚れを、スポイドを用いそれぞれ１滴ずつ試験布に滴下し、該布上にＰＥフィルムをかぶせ、ガラス板を載せ２ｋｇの荷重下で３０分間汚れを圧着した後、除重し３時間放置する。その後、ＪＩＳ Ｌ０２１７−１０３法にて１回洗濯し、汚れ除去性をＪＩＳ Ｌ ０８０５に規定する汚染用グレースケールに照らして１〜５級判定する。
【００３０】
（４）汚れ除去性（拭き取り）
（４）で用いたものと同じＢ重油および墨汁を、スポイドでそれぞれ１滴試験布に滴下、滴下して１分後、ティッシュペーパーで１分間予備拭き取りをする。その後、市販合成洗剤（花王マジックリン）０．５％水溶液を含む濡れタオル（木綿）で、繰り返し拭き取り（３０秒×６回）、該試験布を乾燥後、残留汚れをＪＩＳ Ｌ ０８０５に規定する汚染用グレースケールに照らして１〜５級判定する。
【００３１】
（５）撥水耐久性、撥油耐久性、汚れ除去耐久性（洗濯）、汚れ除去耐久性（拭き取り）
試験布として、ＪＩＳ Ｌ ０８２３に規定する摩擦試験機IIを用い、摩擦子の載荷重が５００ｇ下で布帛を３０００回（往復を１回とする）摩擦した布帛を試験布として使用する。摩擦布は綿金布を使用、摩擦１０００回毎に新品と交換する。
【００３２】
（６）初期撥水性、初期撥油性、初期汚れ除去性（洗濯）、初期汚れ除去性（拭き取り）
試験布として、摩擦していない布帛を使用する。
【００３３】
実施例１
ポリエステル加工糸編地（１５０ｄ−４８ｆ−ＳＤ丸断面糸使いＭタイプ仮撚加工糸・３０φ−２２Ｇスムース編地・目付１６０ｇ／ｍ² ）を常法にて精練、プレセットし、液流染色機にて高圧蛍光染色（ヘキスト社蛍光染料Ｈｏｓｔａｌｕｘ ＥＲＣ １．２％で１３０℃×４０分染色）した。その後還元洗浄し、水洗乾燥後、下記処方の防汚性成分を、通常のパッディング法でＷＰＵ（ウェットピックアップ）８０％の絞り率で均一に付与し、１２０℃下で乾燥し、１６０℃×６０秒間の乾熱セットを行った。
【００３４】
（防汚性成分）
・親水性セグメントを有するフッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＧＳ−１ ５％
・非親水性フッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＡＧ９７０ ５％
・架橋剤
住友化学工業社 Sumitex Resin M3 (60% 固形分) ０．３％
住友化学工業社 Sumitex Accelerater ACX (20%固形分) ０．２％
【００３５】
得られた防汚性ポリエステル加工糸編地の各種防汚特性を表２にまとめる。
【００３６】
実施例２
アクリル繊維（日本エクスラン工業社）２／５２’ｓ使いカチオン染料先染ジャガード織物を精練、水洗乾燥した。実施例１と同一の防汚性成分を、通常のパッディング法にてＷＰＵ（ウェットピックアップ）８０％の絞り率で均一に付与し、１１０℃下で乾燥した後、１４０℃×６０秒間の乾熱セットを行った。得られた防汚性先染ジャガード織物の各種防汚特性を表２にまとめる。
【００３７】
実施例３
蛋白−ポリアクリロニトリルグラフト共重合体からなるプロミックス系繊維：シノン（東洋紡績株式会社）１００ｄ−４８ｆ使い平織物を、常法にて糊抜き、精練後、酸性染料にて淡赤色にボイル染色した。ソーピング、水洗乾燥後、下記した防汚性成分を通常のパッディング法にて、ＷＰＵ（ウェットピックアップ）８０％の絞り率で均一に付与し、１００℃下で乾燥した。その後、１４０℃×３０秒間の乾熱セットを行った。得られた防汚性プロミックス繊維編地の各種防汚特性を表２にまとめる。
【００３８】
（防汚性成分）
・親水性セグメントを有するフッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＧＳ−１ ４％
・非親水性フッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＡＧ９７０ ４％
・架橋剤
住友化学工業社 Sumitex Resin M3 (60% 固形分) ０．１％
住友化学工業社 Sumitex Accelerater ACX (20%固形分) ０．１％
【００３９】
実施例４
アクリル繊維（日本エクスラン工業社）２／５２’ｓ使いカチオン染料先染ジャガード織物に、実施例１と同一の防汚性成分を、通常のパッディング法にてＷＰＵ（ウェットピックアップ）８０％の絞り率で均一に付与し、１１０℃下で乾燥後、１４０℃×６０秒間の乾熱セットを行った。その後、オープンソパーにて拡布状で連続水洗を実施、乾燥後、１３０℃×３０秒の乾熱セットを行った。得られた防汚性先染ジャガード織物の各種防汚特性を表２にまとめる。
【００４０】
比較例１
実施例１の防汚性成分のうち、親水性セグメントを有するフッ素系撥水撥油剤（アサヒガートＧＳ−１）を使用しない以外は全く同一の試料、条件にて加工を実施した。得られたポリエステル加工糸編地の各種防汚特性を表２にまとめる。
【００４１】
比較例２
実施例１の防汚性成分のうち、非親水性フッ素系撥水撥油剤（アサヒガードＡＧ９７０）を使用しない以外は実施例１と全く同一の試料、条件にて加工を実施した。得られたポリエステル加工糸編地の各種防汚特性を表２にまとめた。
【００４２】
比較例３
実施例２の防汚性成分を下記処方に変更する以外は実施例２と全く同一の試料、条件にて加工を実施した。得られた先染ジャガード織物の各種防汚特性を表２にまとめる。
（防汚加工配合処方）
・親水性セグメントを有するフッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＧＳ−１ ２％
・非親水性フッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＡＧ９７０ ８％
・架橋剤
住友化学工業社 Sumitex Resin M3 (60% 固形分) ０．３％
住友化学工業社 Sumitex Accelerater ACX (20%固形分) ０．２％
【００４３】
比較例４
実施例２の防汚加工配合処方のうち、架橋剤および触媒を使用しない以外は実施例２と全く同一の試料、条件にて加工を実施した。得られた先染ジャガード織物の各種防汚特性を表２にまとめた。
【００４４】
比較例５
実施例２のうち、防汚加工前の精練水洗乾燥を実施しない以外は実施例２と全く同一の試料、条件にて加工を実施した。得られた先染ジャガード織物の各種防汚特性を表２にまとめる。なお加工前の先染ジャガード織物には、帯電防止性能を有するカチオン系柔軟剤が繊維重量あたり０．３％付着していた。
【００４５】
比較例６
下記した防汚性成分を使用した以外は実施例１と全く同一の試料、条件にて加工を実施した。得られたポリエステル加工糸編地の各種防汚特性を表２にまとめた。
【００４６】
（防汚性成分）
・親水性セグメントを有するフッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＧＳ−１ ２％
・非親水性フッ素系撥水撥油剤（２０％水分散液）
明成化学工業社製 アサヒガード ＡＧ９７０ ２％
・架橋剤
住友化学工業社 Sumitex Resin M3 (60% 固形分) ０．２％
住友化学工業社 Sumitex Accelerater ACX (20%固形分) ０．１％
【００４７】
【表２】

【００４８】
【発明の効果】
本発明によれば、親水性セグメントを有するフッ素系撥水撥油剤、非親水性フッ素系撥水撥油剤および架橋剤を特定比率で配合した防汚性成分を、撥水撥油性を阻害する不純残留成分のない、クリーンな合成繊維布帛に所定量、均一に付着させ、強固な防汚性被膜を形成させることで、繰返し摩擦されても優れた撥水撥油性を保持し、また、そのような状態でも汚れ、特に液状汚れを付着し難くする。即ち、頑固な油性および水性液状沈着汚れに対する洗濯もしくは拭き取り時の汚れ除去を容易にする汚れ除去性に優れ、かつ優れた撥水撥油耐久性をもつという、一見すると相反する防汚特性を兼備させることで、汚れが付き難く洗濯などで簡単に取れやすい従来にない摩擦による防汚耐久性に優れる繊維布帛を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antifouling synthetic fiber fabric capable of maintaining excellent antifouling properties even when repeatedly rubbed, and a method for producing the same. More specifically, even if the fabric is repeatedly rubbed, it maintains a desired level of water and oil repellency (excellent in water and oil repellency), and oily and aqueous stains can be easily removed by washing and wiping (dirt In other words, the present invention relates to an antifouling synthetic fiber fabric and a method for producing the same. The fabric of the present invention is useful as an antifouling fabric for interior applications such as uniforms, sports clothing, outdoor clothing, car seats, and chair upholstery fabrics that are subjected to severe friction.
[0002]
[Prior art]
Conventionally, various antifouling processing techniques have been proposed as a method for improving the antifouling property of a synthetic fiber that easily deposits dirt. The antifouling processing techniques for various oily or aqueous, particularly liquid stains are roughly classified as follows.
(1) Method for improving dirt removal property (SR property) by washing For example, a hydrophilic compound such as a polyalkylene glycol compound is copolymerized or kneaded into a synthetic fiber to form a hydrophilic synthetic fiber, or after a fiber fabric Processing, for example, by graft-copolymerizing a hydrophilic monomer such as an acrylic acid monomer on the fiber fabric surface, coating the fabric surface with a hydrophilic polymer, or chemically modifying the fabric surface To impart hydrophilicity.
(2) A method for improving the property (SG property) to prevent dirt from adhering, for example, by kneading a silicon-based or fluorine-based antifouling agent into the raw yarn to make the raw yarn water-repellent or oil-repellent, By coating the antifouling agent in post-processing, the fabric surface is made to exhibit water repellency or oil repellency.
(3) A method for improving the property (SGR property) that dirt is difficult to be attached and is easily removed by washing and wiping. For example, after imparting hydrophilicity to a fiber fabric, imparting water repellency or oil repellency. Specifically, for example, a fluorine-based antifouling agent having a hydrophilic group (JP-A-53-134786, 59-204980, 61-266487) or a perfluoroalkyl having a hydrophilic group. A two-stage processing method in which a group-containing (meth) acrylate copolymer is applied to a fiber fabric and dried, and then a fluorine-based water / oil repellent having a water repellency of 90 or more in JIS L 1092 spray test is applied and dried, followed by heat treatment. (Japanese Patent Laid-Open No. 6-333761).
[0003]
Among the above-described antifouling processing techniques, the method (3) for improving the SGR property is convenient because various oily and aqueous living liquid stains are difficult to adhere and a fabric that can be easily removed by washing even if the stains adhere is obtained. In recent years, it has attracted attention as an antifouling processing technology with excellent properties.
[0004]
[Problems to be solved by the invention]
However, this method (3) is also required for products such as chair upholstery, car seats, uniforms and sports knits, although it has washing durability before and after home washing 20 as defined in JIS L 0217-103. Antifouling durability due to repeated friction was insufficient.
[0005]
It is an object of the present invention to maintain both excellent water and oil repellency and excellent stain removability even when repeatedly subjected to friction, in other words, a synthetic fiber fabric having excellent antifouling durability and a method for producing the same Is to provide.
[0006]
[Means for Solving the Problems]
As a result of diligent investigations to solve the above problems, the present inventors have surfaced an antifouling component containing a fluorine-based water / oil repellent having a hydrophilic segment, a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent. Synthetic fiber fabrics that are uniformly coated with water repellency, oil repellency, and dirt removal durability controlled to a certain level maintain excellent water and oil repellency even when repeatedly rubbed. The present inventors have found that the soil removability is also maintained, and have completed the present invention.
Furthermore, the present inventors have repeatedly rubbed a fiber fabric having a uniform layer composed of a specific amount of a mixture of a hydrophilic fluorine-based water / oil repellent and a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent in a specific blending ratio. However, the present inventors have found that the antifouling durability is excellent and have completed the present invention.
[0007]
That is, according to the present invention, the following antifouling synthetic fiber fabric and a method for producing the same are provided.
(1) On the synthetic fiber, the following general formula (I)
[Formula 4]

(Wherein R represents a lower alkyl group, Rf represents a perfluoroalkyl group or a group containing perfluoroalkylene glycol, and n, a and b each represent an integer of 1 or more). sexual fluorine-containing water- and oil-repellent, has a coating layer of antifouling component comprising a non-hydrophilic fluorine-containing water- and oil-repellent and a crosslinking agent, water repellent durability tertiary or higher, oil repellent durability 2 Antifouling synthetic fiber fabric having a grade of 3 or higher and a soil removal durability of 3 or higher.
(2) on the synthetic fibers, the general formula (I) (wherein, R, Rf, n, a and b are as defined above) a hydrophilic fluorine-containing water- and oil-repellent and non-hydrophilic represented by An antifouling component coating layer containing 35 to 65/65 to 35 by weight of a water-soluble fluorine-based water / oil repellent and further containing 1 to 15% by weight of a curing agent based on the above-mentioned mixture. Antifouling synthetic fiber fabric having 1 to 2% by weight.
(3) The antifouling synthetic fiber fabric according to the above (1) or (2), wherein the synthetic fiber fabric is a pre-dyed acrylic fiber fabric, a polyester fiber fabric or a polyamide fiber fabric.
(4) Adhering impurities are removed by washing or scouring the synthetic fiber fabric, and the hydrophilicity represented by the above general formula (I) (wherein R, Rf, n, a and b are as defined above). sexual fluorine-containing water- and oil-repellent, antifouling which impregnates the aqueous dispersion containing a non-hydrophilic fluorine-containing water- and oil-repellent and a crosslinking agent, dried and then characterized by dry heat treatment at 140 to 180 ° C. For producing a synthetic fiber fabric.
[0008]
The terms used in this specification will be described.
(1) Water repellency durability Using a friction tester II specified in JIS L 0823, a synthetic fiber fabric rubbed 3000 times with an applied load of the friction element of 500 g (the friction fabric is made of cotton cloth, The water repellency determined by the isopropyl alcohol / water mixed liquid method (1st to 5th class determination) for “replace with a new product every time 100 rounds (one round trip)”.
[0009]
[Table 1]

[0010]
Drop each drop of the water repellency measuring solution shown in Table 1 onto the test cloth with a dropper, visually evaluate the wettability of the test cloth surface 30 seconds after dropping, and determine the water repellency with a grade liquid without penetrating wetting. To do.
The antifouling synthetic fiber fabric of the present invention has a water repellency durability of grade 3 or higher.
[0011]
(2) Oil repellency durability The synthetic fiber fiber fabric rubbed 3000 times in the same manner as in (1) refers to the oil repellency determined by the AATCC-118-1979 method (1-8 grade determination).
The antifouling synthetic fiber fabric of the present invention has an oil repellency durability of grade 2 or higher.
[0012]
(3) Dirt removal durability (washing)
1 drop each of standard oil of B heavy oil (JIS K 2205-60) and Indian ink (commercially available) using a dropper on a synthetic fiber fabric rubbed 3000 times in the same manner as in (1). A cover glass plate is placed, and the dirt is pressure-bonded under a load of 2 kg for 30 minutes, then deweighed, left for 3 hours, washed once in accordance with JIS L 0217-103 method, and the gray for contamination specified in JIS L 0805. The dirt removal property determined using the scale (1-5 grade determination).
The antifouling synthetic fiber fabric of the present invention has a third or higher grade stain removal durability.
[0013]
Examples of the fluorine-based water / oil repellent having a hydrophilic segment used in the present invention include a perfluoroalkyl group-containing (meth) acrylate copolymer represented by the following general formula (I).
[0014]
[Chemical formula 5]

[0015]
(In the formula, R represents a lower alkyl group, Rf represents a perfluoroalkyl group or a group containing perfluoroalkylene glycol, and n, a, and b each represents an integer of 1 or more)
In general formula (I), R is preferably an alkyl group having 1 to 3 carbon atoms, and Rf is preferably a group containing a perfluoroalkyl group having 4 to 10 carbon atoms or a perfluoroalkylene glycol having 4 to 20 carbon atoms. Is mentioned. The preferable ranges of n, a and b are 2 to 10, 1 to 10, and 1 to 10, respectively.
Specific examples of the (meth) acrylate copolymer (I) include Asahi Guard GS-1 (manufactured by Meisei Chemical Industry Co., Ltd.).
[0016]
The non-hydrophilic fluorine-based water and oil repellent agent refers to a substance that does not contain a polyalkylene glycol unit such as a polyethylene glycol unit represented by the formula (I) or a hydrophilic group such as a sulfonic acid group. Specific examples include perfluoroacrylate polymers, perfluorosulfonamide acrylate polymers, perfluoroalkyl polyethers, low molecular perfluoroalkyl urethane oligomers, and perfluoroalkyl aromatic ester compounds. In particular, a perfluoroacrylate polymer and a perfluorosulfonamide acrylate polymer having a fluorine atom content of 20% or more in the polymer are preferable.
[0017]
As the cross-linking agent, a methylol melamine system containing N methylol group or a blocked isocyanate (TDI / trimethylolpropane adduct, MEK oxime adduct) is preferably used.
[0018]
A mixture of a fluorine-based water / oil repellent having a hydrophilic segment and a non-hydrophilic fluorine-based water / oil repellent having a weight ratio of 35 to 65/65 to 35, and 1 to 15% by weight based on the mixture When an antifouling component containing a curing agent is used, excellent antifouling durability unprecedented can be imparted to the synthetic fiber fabric.
When the above-mentioned weight ratio of the fluorine-based water / oil repellent having a hydrophilic segment is less than 35, the removability of liquid stains at the time of washing or wiping off stains is lowered. When the blending ratio of the non-hydrophilic fluorine-based water / oil repellent is less than 35, the water / oil repellent durability due to repeated friction tends to be lowered. Further, if the amount of the curing agent based on the mixture of the fluorine-based water / oil repellent having a hydrophilic segment and the fluorine-based water / oil repellent having a non-hydrophilic segment is less than 1% by weight, the initial water / oil repellent property ( The water and oil repellency of the fabric that does not rub) and the water and oil repellency durability are not sufficiently exhibited. On the contrary, when the amount exceeds 15% by weight, the texture of the processed fabric becomes hard.
The weight ratio of the fluorine-based water / oil repellent having a preferred hydrophilic segment to the non-hydrophilic fluorine-based water / oil repellent is 40 to 55/60 to 45, and the preferred weight ratio of the curing agent to the mixture is 4 to 10 % By weight.
[0019]
The adhesion amount of the mixture of the three components is 1 to 2% by weight per weight of the synthetic fiber fabric to be processed. When the adhering amount of the mixture is less than 1% by weight, the antifouling durability is low, and when it exceeds 2% by weight, not only the texture is cured but also economically disadvantageous.
[0020]
The synthetic fiber fabric that can be used in the present invention includes polyethylene terephthalate polyester fiber, copolymerized polyester fiber such as isophthalic acid and 5-sulfoisophthalic acid, polyamide fiber such as nylon 6 and nylon 66, cationic dyeable acrylic, Sheet-like materials such as knitted fabrics, woven fabrics and non-woven fabrics made from synthetic fibers such as acrylic fibers such as acid-dyeable acrylics and promix fibers made of protein-acrylonitrile graft copolymers. There are no particular limitations on the fineness of the constituent fibers, the cross-sectional shape, the amount of dal agent added, the presence or absence of various polymer stabilizers, the fabric structure, basis weight, density, and the like.
[0021]
Within the range that does not impair the excellent antifouling durability of the present invention, it is possible to mix conductive fibers and use together with other functional agents such as antistatic agents, flame retardants, antibacterial agents, fungicides and deodorants. It is.
[0022]
A method for producing the antifouling synthetic fiber fabric of the present invention will be described.
The synthetic fiber fabric is washed or scoured to remove impurities adhering to the fabric surface. The fiber fabric pretreated in this manner is impregnated with an aqueous dispersion containing a fluorine-based water / oil repellent having a hydrophilic segment with the above-described blending ratio, a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent. The contents of the hydrophilic fluorine-based water / oil repellent, the non-hydrophilic fluorine-based water / oil repellent and the crosslinking agent in the aqueous dispersion are not particularly limited and can be appropriately determined. The total of the above three components is the weight of the synthetic fiber fabric. It is adjusted to be 1 to 2% by weight per unit. The temperature at the time of impregnation is suitably 40 to 80 ° C., and the time is suitably 5 to 30 minutes. The formation of the antifouling component layer on the fiber surface is not limited to the above-described impregnation method, and a spray method, a padding method, or the like may be used. Next, after drying by a conventional method such as air drying or using a dryer, dry heat treatment is performed at 140 to 180 ° C. for 30 seconds to 3 minutes.
After the above-described 140 to 180 ° C. dry heat treatment, it may be further washed with water and dried, and may be dry heat treated at 130 ° C. or higher (time: 3 seconds to 5 minutes).
The layer thus formed preferably has a thickness of 0.01 to 30 μm, more preferably 0.1 to 10 μm.
[0023]
A technical point to accurately exhibit excellent antifouling durability even when rubbed is to uniformly adhere a specific amount of the antifouling component containing a specific component in a specific ratio to the surface of the synthetic fiber. For that purpose, dyeing aids such as spinning oils, spinning oils, weaving glues, dispersing agents, leveling dyes, bath softeners or cationic fixants, which tend to remain in a small amount in synthetic fiber fabrics, are used for dyed yarns. It is preferable to form the above-mentioned antifouling component layer after washing and removing as much as possible the dyeing agent mainly composed of an antistatic agent, a softening agent and a smoothing agent. From such a viewpoint, the manufacturing method described above is advantageous.
[0024]
The expression mechanism of the antifouling effect of excellent antifouling durability due to friction in the present invention is not known, but a fluorine-based water / oil repellent having a hydrophilic segment with a specific blending ratio, a non-hydrophilic fluorine-based water / oil repellent and Since it can be achieved by applying a predetermined amount of the antifouling component of the crosslinking agent to a clean synthetic fiber fabric from which impurities have been removed, (1) strong adhesion between the fiber surface and the compounded antifouling component, (2) friction Formation of a uniform antifouling film that is resistant to water, (3) the arrangement of perfluoroalkyl groups that impart water and oil repellency to the fabric, and hydrophilic segments (for example, polyalkylene glycol components) that improve SR properties during washing This is because the arrangement balance is excellent.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples. In the examples and comparative examples, “%” is based on weight unless otherwise specified.
[0026]
The evaluation method of the antifouling fiber fabric in the examples is as follows.
[0027]
(1) Water repellency: Determined by the isopropyl alcohol IPA / water mixed solution method (1st to 5th grade determination) shown in Table 1 above.
[0028]
(2) Determined according to the oil repellency AATCC-118-1979 method (1-8 grade determination).
[0029]
(3) Dirt removal (washing)
Standard soil of B heavy oil (JIS K 2205-60: Viscosity 23.4CBT / Remaining carbon 5.5%) and Ink juice (Non-Gai Kogyo Co., Ltd .: Sumika) are dropped on the test cloth one by one using a spoid. A PE film is placed on the cloth, a glass plate is placed thereon, and the dirt is pressure-bonded for 30 minutes under a load of 2 kg. Then, it wash | cleans once by JISL0217-103 method, and 1-5 grade is judged in light of the stain | pollution | contamination gray scale prescribed | regulated to JISL0805.
[0030]
(4) Dirt removal (wiping off)
The same B heavy oil and black ink as used in (4) are dropped onto the test cloth with a dropper, and after 1 minute of dropping, pre-wipe with tissue paper for 1 minute. Thereafter, with a wet towel (cotton) containing a 0.5% aqueous solution of a commercially available synthetic detergent (Kao Magiclin), it is wiped off repeatedly (30 seconds × 6 times), the test cloth is dried, and the residual dirt is defined in JIS L 0805. Judge 1-5 grade in light of the gray scale for contamination.
[0031]
(5) Water-repellent durability, oil-repellent durability, dirt removal durability (washing), dirt removal durability (wiping off)
As a test cloth, using a friction tester II specified in JIS L 0823, a cloth that is rubbed 3000 times (with one reciprocation) under a load of 500 g of the friction element is used as the test cloth. A cotton cloth is used as the friction cloth, and is replaced with a new one every 1000 times.
[0032]
(6) Initial water repellency, initial oil repellency, initial stain removal (washing), initial stain removal (wiping)
As a test cloth, a cloth that is not rubbed is used.
[0033]
Example 1
Polyester processed yarn knitted fabric (150d-48f-SD round section yarn using M type false twisted yarn, 30φ-22G smooth knitted fabric, basis weight 160g / m ² ) is scoured and preset by conventional methods, and liquid dyeing machine And high-pressure fluorescent staining (Hoechst fluorescent dye Hostalux ERC 1.2% staining at 130 ° C. for 40 minutes). Then, after reducing and washing, washing with water and drying, the antifouling component of the following formulation was uniformly applied with a drawing rate of 80% WPU (wet pickup) by a normal padding method, dried at 120 ° C, and 160 ° C x A 60-second dry heat set was performed.
[0034]
(Anti-fouling component)
・ Fluorine-based water / oil repellent (20% aqueous dispersion) with hydrophilic segments
Asahi Guard GS-1 5%, manufactured by Meisei Chemical Industry Co., Ltd.
・ Non-hydrophilic fluorine-based water / oil repellent (20% aqueous dispersion)
Asahi Guard AG970 5%, manufactured by Meisei Chemical Industry Co., Ltd.
・ Crosslinking agent Sumitex Resin M3 (60% solids) 0.3%
Sumitex Accelerater ACX (20% solids) 0.2%
[0035]
Various antifouling properties of the obtained antifouling polyester processed yarn knitted fabric are summarized in Table 2.
[0036]
Example 2
A cationic dye-dyed jacquard fabric was scoured using acrylic fiber (Nippon Exlan Industrial Co., Ltd.) 2/52's, washed with water and dried. The same antifouling component as in Example 1 was uniformly applied with a drawing rate of 80% WPU (wet pickup) by a normal padding method, dried at 110 ° C., and then dried at 140 ° C. for 60 seconds. A heat set was performed. Table 2 summarizes the various antifouling properties of the obtained antifouling dyed jacquard fabric.
[0037]
Example 3
Promix fiber consisting of protein-polyacrylonitrile graft copolymer: Chinon (Toyobo Co., Ltd.) 100d-48f Plain fabric was dezipped by a conventional method, scoured, and then boiled with acid dye to boil red . After soaping, washing with water and drying, the following antifouling components were uniformly applied with a drawing rate of 80% WPU (wet pickup) by a normal padding method and dried at 100 ° C. Thereafter, a dry heat setting at 140 ° C. for 30 seconds was performed. Various antifouling properties of the obtained antifouling promix fiber fabric are summarized in Table 2.
[0038]
(Anti-fouling component)
・ Fluorine-based water / oil repellent (20% aqueous dispersion) with hydrophilic segments
Asahi Guard GS-1 4%, manufactured by Meisei Chemical Industry Co., Ltd.
・ Non-hydrophilic fluorine-based water / oil repellent (20% aqueous dispersion)
Asahi Guard AG970 4%, manufactured by Meisei Chemical Industry Co., Ltd.
・ Crosslinking agent Sumitex Resin M3 (60% solids) 0.1%
Sumitex Accelerater ACX (20% solids) 0.1%
[0039]
Example 4
Acrylic fiber (Nippon Exlan Kogyo Co., Ltd.) 2/52's cationic dye pre-dyed jacquard fabric with the same antifouling component as in Example 1 and 80% WPU (wet pick-up) squeezing by ordinary padding method After uniformly drying at 110 ° C., a dry heat set of 140 ° C. × 60 seconds was performed. Then, continuous water washing was performed in an open soper in a spread form, and after drying, a dry heat set of 130 ° C. × 30 seconds was performed. Table 2 summarizes the various antifouling properties of the obtained antifouling dyed jacquard fabric.
[0040]
Comparative Example 1
Of the antifouling components of Example 1, processing was carried out under exactly the same samples and conditions except that the fluorine-based water / oil repellent (Asahigarto GS-1) having a hydrophilic segment was not used. Table 2 summarizes the various antifouling properties of the polyester processed yarn knitted fabric obtained.
[0041]
Comparative Example 2
Of the antifouling components of Example 1, processing was carried out under exactly the same samples and conditions as Example 1 except that a non-hydrophilic fluorine-based water / oil repellent (Asahi Guard AG970) was not used. Various antifouling properties of the obtained polyester processed yarn knitted fabric are summarized in Table 2.
[0042]
Comparative Example 3
Processing was carried out under exactly the same samples and conditions as in Example 2 except that the antifouling component of Example 2 was changed to the following formulation. Table 2 summarizes the various antifouling properties of the obtained dyed jacquard fabric.
(Anti-fouling formulation)
・ Fluorine-based water / oil repellent (20% aqueous dispersion) with hydrophilic segments
Asahi Guard GS-1 2%, manufactured by Meisei Chemical Industry Co., Ltd.
・ Non-hydrophilic fluorine-based water / oil repellent (20% aqueous dispersion)
Asahi Guard AG970 8% manufactured by Meisei Chemical Industry Co., Ltd.
・ Crosslinking agent Sumitex Resin M3 (60% solids) 0.3%
Sumitex Accelerater ACX (20% solids) 0.2%
[0043]
Comparative Example 4
Of the antifouling processing formulation of Example 2, processing was carried out using exactly the same samples and conditions as Example 2 except that no crosslinking agent and catalyst were used. Various antifouling properties of the obtained dyed jacquard fabric are summarized in Table 2.
[0044]
Comparative Example 5
In Example 2, processing was carried out under exactly the same samples and conditions as in Example 2 except that scouring water washing drying before antifouling processing was not performed. Table 2 summarizes the various antifouling properties of the obtained dyed jacquard fabric. In addition, the pre-dyed jacquard woven fabric had 0.3% of a cationic softening agent having antistatic properties attached to the fiber weight.
[0045]
Comparative Example 6
Processing was carried out under exactly the same samples and conditions as in Example 1 except that the following antifouling components were used. Various antifouling properties of the obtained polyester processed yarn knitted fabric are summarized in Table 2.
[0046]
(Anti-fouling component)
・ Fluorine-based water / oil repellent (20% aqueous dispersion) with hydrophilic segments
Asahi Guard GS-1 2%, manufactured by Meisei Chemical Industry Co., Ltd.
・ Non-hydrophilic fluorine-based water / oil repellent (20% aqueous dispersion)
Asahi Guard AG970 2% made by Meisei Chemical Co., Ltd.
・ Crosslinking agent Sumitex Resin M3 (60% solids) 0.2%
Sumitex Accelerater ACX (20% solids) 0.1%
[0047]
[Table 2]

[0048]
【The invention's effect】
According to the present invention, an antifouling component containing a fluorine-based water / oil repellent having a hydrophilic segment, a non-hydrophilic fluorine-based water / oil repellent and a cross-linking agent in a specific ratio is used to impair the water / oil repellency. Precisely adhere to a clean synthetic fiber fabric with no residual components and form a strong antifouling coating to maintain excellent water and oil repellency even when repeatedly rubbed. Make it difficult to attach dirt, especially liquid dirt. In other words, it has excellent antifouling properties that make it easy to remove stains when washing or wiping against stubborn oily and aqueous liquid deposit stains, and has excellent water and oil repellency and durability, which are contradictory at first glance. By doing so, it is possible to provide a fiber fabric excellent in antifouling durability due to unprecedented friction that is difficult to get dirty and easily removed by washing.

Claims (4)

On the synthetic fiber, the following general formula (I):

(Wherein R represents a lower alkyl group, Rf represents a perfluoroalkyl group or a group containing perfluoroalkylene glycol, and n, a and b each represent an integer of 1 or more). sexual fluorine-containing water- and oil-repellent, has a coating layer of antifouling component comprising a non-hydrophilic fluorine-containing water- and oil-repellent and a crosslinking agent, water repellent durability tertiary or higher, oil repellent durability 2 Antifouling synthetic fiber fabric having a grade of 3 or higher and a soil removal durability of 3 or higher. On the synthetic fiber, the following general formula (I):

(Wherein R represents a lower alkyl group, Rf represents a perfluoroalkyl group or a group containing perfluoroalkylene glycol, and n, a and b each represent an integer of 1 or more). sexual having fluorine-containing water- and oil-repellent and non-hydrophilic and a fluorine-containing water- and oil-repellent in a weight ratio 35-65 / 65-35, further comprising 1 to 15% by weight of the curing agent to the mixture An antifouling synthetic fiber fabric having a coating layer of an antifouling component in an amount of 1 to 2% by weight per fiber weight.   The antifouling synthetic fiber fabric according to claim 1 or 2, wherein the synthetic fiber fabric is a pre-dyed acrylic fiber fabric, a polyester fiber fabric or a polyamide fiber fabric. The synthetic fiber fabric is washed or scoured with water to remove adhering impurities, and the following general formula (I):

(Wherein R represents a lower alkyl group, Rf represents a perfluoroalkyl group or a group containing perfluoroalkylene glycol, and n, a and b each represent an integer of 1 or more). sexual fluorine-containing water- and oil-repellent, antifouling which impregnates the aqueous dispersion containing a non-hydrophilic fluorine-containing water- and oil-repellent and a crosslinking agent, dried and then characterized by dry heat treatment at 140 to 180 ° C. For producing a synthetic fiber fabric.