JP3800670B2 - Ink-stain resistant synthetic fiber and method for producing the same - Google Patents

Description

式中、Ｒは低級アルキル基を表わし、ｎ，ａ，ｂは１以上の整数を表わし、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表わし、
前記合成繊維布帛が下記特性を有することを特徴とする耐墨汁汚れ性合成繊維布帛である：
（１）繰返し洗濯（ＪＩＳ Ｌ０２１７−１０３法）２０回後の墨汁汚れＳＲ性がＪＩＳ Ｌ０８０５汚染用グレースケール判定で４級以上である。
（２）繰返し摩耗（ＪＩＳ Ｌ０８２３指定の摩擦試験機ＩＩを用い摩擦子の載荷重が５００ｇ下で３０００回摩耗）後の墨汁汚れＳＲ性がＪＩＳ Ｌ０８０５汚染用グレースケール判定で４級以上である。
ここで、墨汁汚れＳＲ性とは、墨汁（不易糊工業社製：墨彩）の標準汚れをスポイドを用いそれぞれ１滴ずつ滴下し、試料の上にポリエチレン（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時間放置後、ＪＩＳ Ｌ０２１７−１０３法にて１回洗濯後の汚れ除去性を言い、ＪＩＳ Ｌ０８０５汚染用グレースケールによって１〜５級で判定される。
【０００７】
また、本発明は、予め水洗もしくは精練し付着不純物を取り除いた合成繊維布帛を、親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂、非親水性フッ素系撥水撥油剤および架橋剤を重量配合比率が６０〜４０／１５〜４０／２４〜１０／１〜１０で含む水系溶液に含浸し、乾燥後、１４０℃〜１８０℃乾熱下で熱処理し、繊維重量あたり１重量％以上付着させること、及び前記親水性セグメントを有するフッ素系撥水撥油剤が下記一般式（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であることを特徴とする耐墨汁汚れ性合成繊維布帛の製造方法である：
【化２】

式中、Ｒは低級アルキル基を表わし、ｎ，ａ，ｂは１以上の整数を表わし、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表わす。
【０００８】
【発明の実施の形態】
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は、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であるが、ＳＲ性を有するフッ素系撥水撥油剤であれば特に制約はない。
【化１】

式中、Ｒは低級アルキル基を表わし、ｎ，ａ，ｂは１以上の整数を表わし、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表わす。
【０００９】
本発明で用いる親水性ポリエステル系樹脂とは、（１）ジメチルテレフタレート（ＤＭＴ）、ジメチルイソフタレート（ＤＭＩ）、エチレングリコール（ＥＧ）及びポリエチレングリコール（ＰＥＧ）からなる共重合ポリエステル樹脂や、（２）ＤＭＴ、ＥＧおよびＰＥＧからなる共重合ポリエステル樹脂や、（３）テレフタル酸（ＴＰＡ）、アジピン酸（ＡＡ）、５スルホイソフタル酸（ＧＣＭ）、ＥＧ及びジエチレングリコール（ＤＥＧ）からなる共重合ポリエステル樹脂であり、水に可溶性にして、もしくはアニオン系分散剤などで水分散化して使用される。例えば（１）に相当する親水性ポリエステル樹脂の具体例としては、例えばＤＭＴ／ＤＭＩのモル比が７〜９／３〜１で繰返し単位が５〜８であり、ＰＥＧ分子量が１〜３万の共重合ポリエステル樹脂があげられる。
【００１０】
本発明で用いる非親水性フッ素系撥水撥油剤とは、式（Ｉ）で示される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を含まない非親水性フッ素系撥水撥油剤であり、例えば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やパーフルオロアルキル芳香族エステル系化合物等が挙げられる。これらのうちでは、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や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。
【００１１】
本発明の架橋剤とは、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アダクトＭＥＫオキシム付加体）であり、前記の親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂及び非親水性フッ素系撥水撥油剤と特定配合比率で使用して、付着量を最適化することにより、墨汁汚れに対して、従来にない洗濯および摩耗耐久性に優れるＳＲ防汚効果を発現させることができる。かかる効果を得るためには、親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂、非親水性フッ素系撥水撥油剤および架橋剤の重量配合比率は、６０〜４０／１５〜４０／２４〜１０／１〜１０であることが必要であり、またその防汚性成分の付着量は繊維重量あたり１重量％以上であることが必要である。親水性セグメントを有するフッ素系撥水撥油剤および親水性ポリエステル系樹脂の配合比率が７５未満の場合は、洗濯時の墨汁汚れのＳＲ防汚性が低下し易く、非親水性フッ素系撥水撥油剤の配合比率が１０未満の場合や架橋剤が１未満の場合は、洗濯耐久性および摩耗耐久性が低下し易い。また、防汚性成分の付着量が１％未満では十分な洗濯時の墨汁汚れのＳＲ防汚性が発現しない。
【００１２】
本発明におけ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、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およびこれらの綿、麻、レーヨン、ポリノジック系繊維および他の合成繊維との混用品からなる編織物もしくは不織布などのシート状物であり、構成繊維の繊度、断面形状、ダル剤添加量、各種ポリマー安定剤の有無や布帛の組織・目付・密度については特に限定されない。
【００１３】
次に本発明の耐墨汁汚れ性合成繊維布帛の製造方法について説明する。親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂、非親水性フッ素系撥水撥油剤および架橋剤を重量配合比率が６０〜４０／１５〜４０／２４〜１０／１〜１０で含む防汚性成分を使用し、繊維表面に繊維重量あたり１重量％以上均一に被覆することによって繰返し洗濯および繰返し摩耗後も優れた墨汁汚れに対する洗濯時のＳＲ防汚性を効果的に発現させる製造方法は以下の方法が挙げられる：
（１）予め水洗もしくは精練し付着不純物を取り除いた合成繊維布帛を親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂、非親水性フッ素系撥水撥油剤および架橋剤の重量配合比率が６０〜４０／１５〜４０／２４〜１０／１〜１０である防汚性成分を含む水系溶液に含浸し、乾燥後、１４０℃〜１８０℃乾熱下で熱処理し繊維重量あたり１重量％以上付着させることを特徴とする耐墨汁汚れ性合成繊維布帛の製造方法。
（２）合成繊維布帛を親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂、非親水性フッ素系撥水撥油剤および架橋剤の重量配合比率が６０〜４０／１５〜４０／２４〜１０／１〜１０である防汚性成分を含む水系溶液に含浸し、乾燥後、１４０℃〜１８０℃乾熱下で熱処理した後、さらに、水洗、乾燥後、１３０℃以上で乾熱処理し繊維重量あたり１重量％以上付着させることを特徴とする耐墨汁汚れ性合成繊維布帛の製造方法。
【００１４】
本発明における洗濯耐久性および摩耗耐久性に優れる防汚効果を的確に発現させる技術的ポイントは、合成繊維布帛に微量残留し易い紡糸もしくは紡績油剤、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等の染色助剤や先染糸に使用される帯電防止剤や柔軟剤や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、本発明による防汚性成分を一定量、均一に付着させる点にある。特に水溶性の親水性不純物が微量残留する合成繊維布帛をそのまま使用すると本来の初期撥水撥油剤や摩耗後の防汚耐久性が得られない。これらの解決策として上記の（１）もしくは（２）に記載の製造方法が有効である。
【００１５】
本発明による防汚性成分の付与方法は通常のパッド・ドライ・キュア法が好適であり、布帛表面に均一に付着させた後、常法で乾燥後、１４０℃〜１８０℃で３０秒〜３分間乾熱セットする方法で繊維表面に防汚性成分の均一被膜を形成させる。本発明の優れたＳＲ防汚効果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も可能である。
【００１６】
本発明における洗濯耐久性および摩耗耐久性に優れるＳＲ防汚効果の発現メカニズムは不詳であるが、特定比率の「親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂、非親水性フッ素系撥水撥油剤及び架橋剤」の防汚性成分をクリーンな合成繊維布帛に所定量付与することでＳＲ防汚効果が達成されることから、（１）繊維表面と配合防汚成分間の強力な密着力、（２）洗濯や乾摩耗に強い、均一なＳＲ防汚性被膜の形成によるものと考えられ、さらに（３）親水性フッ素系撥水撥油剤と親水性ポリエステル系樹脂を洗濯及び摩耗耐久性が低下しない範囲の特定比率で併用することで、従来にないレベルまで墨汁汚れに対するＳＲ防汚性を向上したものと考えられる。
【００１７】
【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。
【００１８】
実施例および比較例の防汚性繊維布帛の評価方法は以下の通りである。
【００１９】
（１）繰返し洗濯試験：ＪＩＳ Ｌ０２１７−１０３法にて２０回洗濯する。
【００２０】
（２）繰返し摩耗試験：ＪＩＳ Ｌ０８２３指定の摩擦試験機IIを用い摩擦子の載荷重が５００ｇ下で３０００回摩耗する。摩擦布は綿金布を使用し、摩耗１０００回毎に新品と交換して摩耗試験する。
【００２１】
（３）墨汁汚れＳＲ（ Soil Release）性：上記繰返し洗濯または繰返し摩耗試験前後の試料について、墨汁（不易糊工業社製：墨彩）の標準汚れをスポイドを用いそれぞれ１滴ずつ滴下し、試料の上に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時間放置後、ＪＩＳ Ｌ０２１７−１０３法にて１回洗濯後の汚れ除去性をＪＩＳ Ｌ０８０５汚染用グレースケールによって１〜５級で判定する。
【００２２】
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、プレセット後、液流染色機にて高圧蛍光染色（ヘキスト社製蛍光染料 Hostalux ERC １．２％で１３０℃×４０分染色）後、還元洗浄、水洗乾燥後、下記処方の配合防汚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、１２０℃で乾燥後、１７０℃×６０秒間の乾熱セットを実施した。得られた耐墨汁汚れ性ポリエステル加工糸編地のＳＲ性を表１にまとめた。
（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） ７．０％
親水性ポリエステル系樹脂（１０％水分散液）
（高松油脂社製 ＳＲ−１８００） ４．０％
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） ２．０％
架橋剤（固形分濃度６０％）
（住友化学工業社製 Sumitex Resin M3） ０．４％
触媒
（住友化学工業社製 Sumitex Accelerater ACX ） ０．２％
【００２３】
実施例 ２
アクリル繊維（日本エクスラン工業社製）２／５２′ｓ使いカチオン染料先染ジャガード織物を精練、水洗乾燥後、実施例１と同一の防汚加工配合処方の加工液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℃で乾燥後、１４０℃×６０秒間の乾熱セットを実施した。得られた耐墨汁汚れ性先染ジャガード織物のＳＲ性を表１にまとめた。
【００２４】
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（東洋紡社製）１００ｄ−４８ｆ使い平織物を常法にて糊抜き精練後、酸性染料にて淡緑色にボイル染色、ソーピング、水洗乾燥後、下記処方の配合防汚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℃で乾燥後、１４０℃×３０秒間の乾熱セットを実施した。得られた耐墨汁汚れ性プロミックス系繊維編地のＳＲ性を表１にまとめた。
（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） ６．０％
親水性ポリエステル系樹脂（１０％水分散液）
（高松油脂社製 ＳＲ−１８００） ３．０％
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） ２．０％
架橋剤（固形分濃度６０％）
（住友化学工業社製 Sumitex Resin M3） ０．１％
触媒
（住友化学工業社製 Sumitex Accelerater ACX ） ０．１％
【００２５】
比較例 １
実施例１の防汚加工配合処方のうち、親水性セグメントを有するフッ素系撥水撥油剤（アサヒガード ＧＳ−１）及び親水性ポリエステル系樹脂（ＳＲ−１８００）を使用しない以外は全く同一試料、同一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ＳＲ性を表１にまとめた。
【００２６】
比較例 ２
実施例１の防汚加工配合処方のうち、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と全く同一試料、同一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ＳＲ性を表１にまとめた。
【００２７】
比較例 ３
実施例２の防汚加工配合処方を下記処方に変更する以外は実施例２と全く同一試料、同一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ＳＲ性を表１にまとめた。
（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） ２．５％
親水性ポリエステル系樹脂（１０％水分散液）
（高松油脂社製 ＳＲ−１８００） １．０％
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） ０．５％
架橋剤（固形分濃度６０％）
（住友化学工業社製 Sumitex Resin M3） ０．３％
触媒
（住友化学工業社製 Sumitex Accelerater ACX ） ０．２％
【００２８】
比較例 ４
実施例２の防汚加工配合処方のうち架橋剤及び触媒を使用しない以外は実施例１と全く同一試料、同一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ＳＲ性を表１にまとめた。
【００２９】
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と全く同一試料、同一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ＳＲ性を表１にまとめた。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。
【００３０】
比較例 ６
実施例１の防汚加工配合処方を下記処方に変更する以外は実施例１と全く同一試料、同一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ＳＲ性を表１にまとめた。
（防汚加工配合処方）
親水性ポリエステル系樹脂（１０％水分散液）
（高松油脂社製 ＳＲ−１８００） ５．０％
架橋剤（固形分濃度６０％）
（住友化学工業社製 Sumitex Resin M3） ０．３％
触媒
（住友化学工業社製 Sumitex Accelerater ACX ） ０．２％
【００３１】
比較例 ７
実施例１のうち、防汚加工前のポリエステル加工糸編地のＳＲ性を表１にまとめた。
【００３２】
【表１】

【００３３】
【発明の効果】
以上詳述したように、本発明の耐墨汁汚れ性合成繊維は、親水性セグメントを有するフッ素系撥水撥油剤、親水性ポリエステル系樹脂、非親水性フッ素系撥水撥油剤及び架橋剤を特定比率で配合した防汚性成分を、繊維表面と防汚性成分の密着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を均一に付着し、強固な防汚性被膜を形成させているので、繰返し洗濯および繰返し摩耗使用後も優れた墨汁汚れに対する洗濯時のＳＲ（Soil Release ）防汚効果を発揮する。特に本発明によれば、繰返し洗濯や繰返し摩耗を受けやすいカーペット、椅子張り地、テーブルクロスやユニフォーム、カジュアルニット用衣料などで、墨汁汚れに遭遇しやすい書道・絵画教室や学校用途に好適な繰返し使用耐久性に優れるＳＲ防汚性合成繊維布帛を効果的に提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink stain resistant synthetic fiber fabric excellent in SR (soil release) antifouling property of ink stain after repeated washing and repeated wear, and a method for producing the same.
[0002]
[Prior art]
Conventionally, various antifouling processing techniques have been proposed as means for improving the antifouling property of synthetic fibers that easily deposit dirt. For example, antifouling processing techniques for various oily or aqueous liquid stains can be broadly classified as follows: (1) hydrophilic synthetic fibers copolymerized or kneaded with polyalkylene glycols or other hydrophilic compounds, and acrylic acid hydrophilics after processing. A method in which the surface of the fiber is coated with a graft copolymer or a hydrophilic polymer, or the surface of the fiber is made hydrophilic by chemical modification, thereby improving soil removal during washing, that is, SR (Soil Release) 2) Kneading silicon-based or fluorine-based antifouling agent with the raw yarn or coating these antifouling compounds on the fiber surface by post-processing to develop water repellency or oil repellency and make liquid stains difficult to adhere. That is, a method for improving SG (soil guard) properties, (3) a fluorine-based antifouling agent having a hydrophilic group (JP-A-53-134786, JP-A-59-204980) No. 61-266487) or a perfluoroalkyl group-containing (meth) acrylate copolymer having a hydrophilic group, and after drying, a fluorinated water / oil repellent having a water repellency of 90 or more in a JIS L1092 spray test is added. (4) benzoxazole, a method for improving the SGR (Soil Guard & Release) property by making it difficult to get soiled by a two-stage processing method (Japanese Patent Application Laid-Open No. 6-333761) which is applied and dried and heat-treated. An antifouling polyester synthetic fiber (JP-A-3-174068) containing 0.01 to 0.3% by weight of a fluorescent whitening agent and having a zeta potential of -15 mV or less is known.
[0003]
However, all of these antifouling processing techniques are insufficient in washing and wear durability for washing removal (SR antifouling property) against the ink stain. For example, as a countermeasure technique for SR antifouling property at the time of washing with respect to ink stains mixed with aqueous and oily components, the method (1) of hydrophilizing the fiber surface is effective, and a certain antifouling effect can be obtained. The method of copolymerizing or kneading polyalkylene glycol-based other hydrophilic compounds has the disadvantage that the physical properties of fibers and light fastness are liable to decrease, and the method of graft copolymerizing hydrophilic monomers has a sufficient effect. In order to obtain this, there is a drawback that the physical properties of the fiber are likely to deteriorate and the processing is complicated and costly, and the method of imparting the hydrophilic polymer by post-processing has a disadvantage that the washing and wear durability cannot be sufficiently obtained. there were. The method (2) for imparting SG property has a drawback that the ink stain is difficult to temporarily adhere, but once adhered, the SR antifouling property at the time of washing tends to decrease. The method (3) for imparting SGR property has a disadvantage that not only the processing cost is high due to the two-stage processing method but also washing and wear durability cannot be sufficiently obtained. The method of kneading fluorescent whitening agent (4) to control the zeta potential of the fiber surface is excellent in removing dirt during washing and preventing recontamination during washing, but preventing SR during washing of ink stains. There is almost no effect on soiling. In textile products used in the interior field such as carpets and chair upholstery fabrics that are repeatedly washed and repeatedly worn, and in the clothing field such as uniforms and casual knits, the SR antifouling property during washing against ink stains is insufficient. Met.
[0004]
[Problems to be solved by the invention]
The present invention was devised in order to eliminate such disadvantages of the prior art, and the purpose thereof is a fluorine-based water / oil repellent having a hydrophilic segment, a hydrophilic polyester-based resin, and a non-hydrophilic fluorine-based water / oil repellent. And anti-staining components including cross-linking agents, and uniformly covering the fiber surface, greatly improves the SR anti-stain property during washing against repeated washing and after repeated wear. It is in providing a fiber fabric and its manufacturing method.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that a fluorine-containing water / oil repellent having a hydrophilic segment, a hydrophilic polyester resin, a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent are included. It has been found that the SR antifouling property at the time of washing with respect to the ink stain is further improved after repeated washing and repeated wear by blending and using the soiling component at a specific ratio and uniformly covering the fiber surface. The ink-stained synthetic fiber fabric and its production method have been completed.
[0006]
That is, the present invention has a weight blending ratio of 60 to 40/15 to 40/24 of a fluorine-based water / oil repellent having a hydrophilic segment, a hydrophilic polyester resin, a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent. A synthetic fiber cloth in which an antifouling component containing from 10/1 to 10/10 is adhered to the fiber surface in an amount of 1% by weight or more and uniformly coated on the fiber surface, and the fluorine-based water / oil repellent having the hydrophilic segment is A perfluoroalkyl group-containing (meth) acrylate copolymer represented by the following general formula (I):
[Chemical 1]

In the formula, R represents a lower alkyl group, n, a, and b represent an integer of 1 or more, Rf represents a perfluoroalkyl group or a group containing a perfluoroalkylene glycol,
The synthetic fiber fabric is an ink-stain resistant synthetic fiber fabric having the following characteristics:
(1) Repeated washing (JIS L0217-103 method) The ink stain SR property after 20 times is grade 4 or higher according to JIS L0805 contamination gray scale determination.
(2) The ink stain SR property after repeated wear (using the friction tester II specified by JIS L0823, 3000 wear under a friction load of 500 g) is grade 4 or higher according to JIS L0805 contamination gray scale determination.
Here, the sumi-stain stain SR property means that a drop of standard stain of sumi-in (made by Infugi Kogyo Kogyo Co., Ltd .: sumi) is dropped with a dropper, and a polyethylene (PE) film is placed on the sample and a glass plate is placed. After pressurizing dirt for 30 minutes under a load of 2 kg, deweighting and leaving it to stand for 3 hours, the dirt removal property after washing once by JIS L0217-103 method is said, and grades 1 to 5 according to JIS L0805 contamination gray scale It is determined by.
[0007]
The present invention also provides a synthetic fiber fabric that has been washed or scoured in advance to remove adhering impurities, a fluorine-based water / oil repellent having a hydrophilic segment, a hydrophilic polyester-based resin, a non-hydrophilic fluorine-based water / oil repellent, and a cross-linking. 1% by weight per fiber weight after impregnating an aqueous solution containing the agent in a weight blending ratio of 60 to 40/15 to 40/24 to 10/1 to 10, after drying and heat-treating at 140 ° C. to 180 ° C. under dry heat The ink-stained ink stain, wherein the fluorine-based water / oil repellent having the hydrophilic segment is a perfluoroalkyl group-containing (meth) acrylate copolymer represented by the following general formula (I): Is a method for producing a synthetic fiber fabric:
[Chemical formula 2]

In the formula, R represents a lower alkyl group, n, a and b represent an integer of 1 or more, and Rf represents a perfluoroalkyl group or a group containing a perfluoroalkylene glycol.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The fluorine-based water / oil repellent having a hydrophilic segment used in the present invention is a perfluoroalkyl group-containing (meth) acrylate copolymer represented by the following general formula (I), but it has SR properties. If it is a water and oil repellent, there will be no restriction | limiting in particular.
[Chemical 1]

In the formula, R represents a lower alkyl group, n, a and b represent an integer of 1 or more, and Rf represents a perfluoroalkyl group or a group containing a perfluoroalkylene glycol.
[0009]
The hydrophilic polyester resin used in the present invention includes (1) a copolymer polyester resin composed of dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), ethylene glycol (EG), and polyethylene glycol (PEG), and (2) Copolyester resin composed of DMT, EG and PEG, and (3) Copolyester resin composed of terephthalic acid (TPA), adipic acid (AA), 5 sulfoisophthalic acid (GCM), EG and diethylene glycol (DEG) It is used after being soluble in water or water-dispersed with an anionic dispersant. For example, specific examples of the hydrophilic polyester resin corresponding to (1) include a molar ratio of DMT / DMI of 7 to 9/3 to 1, a repeating unit of 5 to 8, and a PEG molecular weight of 1 to 30,000. Examples thereof include copolymer polyester resins.
[0010]
The non-hydrophilic fluorine-based water / oil repellent used in the present invention is a non-hydrophilic fluorine-based water / oil repellent which does not contain a polyalkylene glycol unit such as a polyethylene glycol unit represented by formula (I) or a sulfonic acid group. Yes, for example, perfluoroacrylate polymers, perfluorosulfonamide acrylate polymers, perfluoroalkyl polyethers, low molecular perfluoroalkyl urethane oligomers, perfluoroalkyl aromatic ester compounds, and the like. Among these, a perfluoroacrylate polymer or a perfluorosulfonamide acrylate polymer having a fluorine atom content of 20% or more in the polymer is particularly preferable.
[0011]
The cross-linking agent of the present invention is a methylol melamine-based or block isocyanate (TDI / trimethylolpropane adduct MEK oxime adduct) containing an N-methylol group, and a fluorine-based water / oil repellent having the above-mentioned hydrophilic segment, hydrophilic Anti-SR with excellent washing and wear resistance against ink stains by optimizing the amount of adhesion using a water-soluble polyester resin and non-hydrophilic fluorine-based water and oil repellent at a specific blending ratio. A stain effect can be expressed. In order to obtain such an effect, the weight blending ratio of the fluorine-based water / oil repellent having a hydrophilic segment, the hydrophilic polyester-based resin, the non-hydrophilic fluorine-based water / oil repellent and the crosslinking agent is 60 to 40/15 to It is necessary to be 40/24 to 10/1 to 10, and the adhesion amount of the antifouling component is required to be 1% by weight or more per fiber weight. When the blending ratio of the fluorine-based water / oil repellent having hydrophilic segments and the hydrophilic polyester-based resin is less than 75, the SR antifouling property of the ink stain during washing tends to be lowered, and the non-hydrophilic fluorine-based water / water repellent property is reduced. When the blending ratio of the oil agent is less than 10 or when the crosslinking agent is less than 1, the washing durability and the wear durability are likely to be lowered. Moreover, if the adhesion amount of the antifouling component is less than 1%, sufficient SR antifouling property of the ink stain during washing is not exhibited.
[0012]
The synthetic fiber fabric in the present invention is a polyethylene terephthalate polyester fiber, a polyester fiber copolymerized with isophthalic acid or 5-sulfoisophthalic acid, an acrylic fiber such as cationic dyeable acrylic acid or acid dyeable acrylic, or protein-acrylonitrile. Synthetic fibers such as promix fibers made of graft copolymers, and sheet-like materials such as knitted fabrics or non-woven fabrics made of these, cotton, hemp, rayon, polynosic fibers and other synthetic fibers, and constituent fibers There are no particular restrictions on the fineness, cross-sectional shape, amount of added dal agent, presence or absence of various polymer stabilizers, and the structure, basis weight, and density of the fabric.
[0013]
Next, a method for producing the ink-stained stain-resistant synthetic fiber fabric of the present invention will be described. Weight ratio of fluorine-based water / oil repellent having hydrophilic segment, hydrophilic polyester resin, non-hydrophilic fluorine-based water / oil repellent and crosslinking agent is 60-40 / 15-40 / 24-10 / 1-10 By using the antifouling component contained in, and uniformly covering the fiber surface by 1% by weight or more per fiber weight, it effectively exhibits SR antifouling properties during washing against repeated ink washing and repeated ink wear. The manufacturing method to be performed includes the following methods:
(1) A synthetic fiber fabric that has been washed or scoured in advance to remove adhering impurities, and is blended in weight with a fluorine-based water and oil repellent having hydrophilic segments, a hydrophilic polyester resin, a non-hydrophilic fluorine-based water and oil repellent and a crosslinking agent. Impregnated into an aqueous solution containing an antifouling component having a ratio of 60 to 40/15 to 40/24 to 10/1 to 10, dried, and then heat treated under dry heat at 140 ° C. to 180 ° C. to 1 weight per fiber weight A method for producing an ink-stain-resistant synthetic fiber fabric characterized by adhering at least%.
(2) The synthetic fiber fabric has a weight blending ratio of a fluorine-based water / oil repellent having a hydrophilic segment, a hydrophilic polyester-based resin, a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent of 60 to 40/15 to 40 /. It is impregnated with an aqueous solution containing an antifouling component of 24 to 10/1 to 10, dried, heat treated under dry heat at 140 ° C. to 180 ° C., further washed with water, dried, and then subjected to dry heat treatment at 130 ° C. or higher. A method for producing an ink-stain-resistant synthetic fiber fabric, wherein 1% by weight or more is adhered per weight of the woven fiber.
[0014]
The technical point of accurately expressing the antifouling effect excellent in washing durability and wear durability in the present invention is a spinning or spinning oil agent, a weaving paste, a dispersing agent, a leveling dyeing agent, After washing and removing as much as possible the dyeing assistant such as a softener in the bath or a cationic fixing agent, and an antistatic agent used for the pre-dyed yarn, a softener and a smoothing agent as a main component, and according to the present invention. The point is that a certain amount of the antifouling component is adhered uniformly. In particular, when a synthetic fiber fabric in which a small amount of water-soluble hydrophilic impurities remain is used as it is, the original initial water / oil repellent and antifouling durability after wear cannot be obtained. As a solution to these problems, the production method described in (1) or (2) above is effective.
[0015]
The method for applying an antifouling component according to the present invention is preferably an ordinary pad dry cure method, after uniformly adhering to the fabric surface, drying in a conventional manner, and 140 ° C. to 180 ° C. for 30 seconds to 3 A uniform film of the antifouling component is formed on the fiber surface by a dry heat setting for a minute. As long as the excellent SR antifouling effect of the present invention is not inhibited, it is possible to mix conductive fibers and use with other functional agents such as antistatic agents, flame retardants, antibacterial agents, fungicides and deodorants. is there.
[0016]
Although the mechanism of expression of the SR antifouling effect excellent in washing durability and wear durability in the present invention is not known, a specific ratio of “fluorinated water and oil repellent having hydrophilic segments, hydrophilic polyester resin, non-hydrophilic” The SR antifouling effect is achieved by applying a predetermined amount of the antifouling component of “fluorinated water / oil repellent and crosslinking agent” to a clean synthetic fiber fabric. (1) Between fiber surface and blended antifouling component (2) It is thought to be due to the formation of a uniform SR antifouling film that is resistant to washing and dry wear, and (3) a hydrophilic fluorine-based water- and oil-repellent agent and a hydrophilic polyester-based resin. It is considered that the SR antifouling property against ink stains is improved to an unprecedented level by using together at a specific ratio within a range where the washing and wear durability are not lowered.
[0017]
【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.
[0018]
The evaluation method of the antifouling fiber fabrics of Examples and Comparative Examples is as follows.
[0019]
(1) Repeated washing test: Washed 20 times by JIS L0217-103 method.
[0020]
(2) Repeated wear test: The friction tester II specified by JIS L0823 is used to wear 3000 times under a load of 500 g. A cotton cloth is used as the friction cloth, and a wear test is performed by replacing it with a new one every 1000 times.
[0021]
(3) Ink-stain stain SR (Soil Release) property: About the sample before and after the above-described repeated washing or repeated wear test, a drop of the standard stain of ink-stained ink (manufactured by Infugi Kogyo Kogyo Co., Ltd .: sumi) was dropped using a dropper. Put a PE film on top and put a glass plate on it, press the dirt under a load of 2 kg for 30 minutes, deweight it, leave it for 3 hours, and then remove the dirt after washing once by JIS L0217-103 method according to JIS L0805. Judged by grades 1 to 5 according to the gray scale for contamination.
[0022]
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 pre-set by conventional methods, then liquid dyeing machine After high pressure fluorescent dyeing (Hoechst fluorescent dye Hostalux ERC 1.2% dyed at 130 ° C. for 40 minutes), after reducing and washing, washing and drying, the compounding antifouling component of the following formulation is WPU by the usual padding method. (Wet pickup) The film was uniformly applied at a drawing ratio of 80%, dried at 120 ° C., and then subjected to a dry heat setting of 170 ° C. × 60 seconds. Table 1 shows the SR properties of the obtained ink-stained stain-resistant polyester processed yarn knitted fabric.
(Anti-fouling formulation)
Fluorine-based water and oil repellent with hydrophilic segment (20% aqueous dispersion)
(Asahi Guard GS-1 manufactured by Meisei Chemical Industry Co., Ltd.) 7.0%
Hydrophilic polyester resin (10% aqueous dispersion)
(SR-1800, manufactured by Takamatsu Yushi Co., Ltd.) 4.0%
Non-hydrophilic fluorine-based water and oil repellent (20% aqueous dispersion)
(Asahi Guard AG970 manufactured by Meisei Chemical Co., Ltd.) 2.0%
Cross-linking agent (solid content concentration 60%)
(Sumitomo Chemical Industries Sumitex Resin M3) 0.4%
Catalyst (Sumitomo Chemical Co., Ltd. Sumitex Accelerater ACX) 0.2%
[0023]
Example 2
Acrylic fiber (made by Nippon Exlan Kogyo Co., Ltd.) 2/52's was used to scour the cationic dye-dyed jacquard fabric, washed with water and dried. WPU (wet pickup) was uniformly applied at a drawing rate of 80%, dried at 110 ° C., and then subjected to a dry heat setting of 140 ° C. × 60 seconds. Table 1 summarizes the SR properties of the resulting ink-stained soil-resistant dyed jacquard fabric.
[0024]
Example 3
Promix fiber made of protein-polyacrylonitrile graft copolymer: Shinon (Toyobo Co., Ltd.) 100d-48f Using plain fabric, scouring and scouring using plain dye, boil dyeing with acid dye, soaping, water washing After drying, the blending antifouling component of the following formulation is uniformly applied with a WPU (wet pickup) 80% squeezing ratio by a normal padding method, dried at 100 ° C, and then set at 140 ° C for 30 seconds. Carried out. Table 1 shows the SR properties of the resulting ink-stain-resistant soil-resistant promix fiber fabrics.
(Anti-fouling formulation)
Fluorine-based water and oil repellent with hydrophilic segment (20% aqueous dispersion)
(Asahi Guard GS-1 manufactured by Meisei Chemical Industry Co., Ltd.) 6.0%
Hydrophilic polyester resin (10% aqueous dispersion)
(SR-1800 manufactured by Takamatsu Yushi Co., Ltd.) 3.0%
Non-hydrophilic fluorine-based water and oil repellent (20% aqueous dispersion)
(Asahi Guard AG970 manufactured by Meisei Chemical Co., Ltd.) 2.0%
Cross-linking agent (solid content concentration 60%)
(Sumitomo Chemical Industries Sumitex Resin M3) 0.1%
Catalyst (Sumitex Chemical Co., Ltd. Sumitex Accelerater ACX) 0.1%
[0025]
Comparative Example 1
Of the antifouling processing compounding formulation of Example 1, the same sample except that the fluorine-based water and oil repellent (Asahi Guard GS-1) having a hydrophilic segment and the hydrophilic polyester resin (SR-1800) are not used, Processing was performed under the same conditions. Table 1 shows the SR properties of the obtained polyester processed yarn knitted fabric.
[0026]
Comparative Example 2
Of the antifouling processing formulation of Example 1, processing was carried out under exactly the same samples and the same conditions as in Example 1 except that the non-hydrophilic fluorine-based water / oil repellent (Asahi Guard AG970) was not used. Table 1 shows the SR properties of the obtained polyester processed yarn knitted fabric.
[0027]
Comparative Example 3
Processing was carried out under exactly the same samples and conditions as in Example 2, except that the antifouling processing formulation of Example 2 was changed to the following formulation. Table 1 shows the SR properties of the obtained dyed jacquard fabric.
(Anti-fouling formulation)
Fluorine-based water and oil repellent with hydrophilic segment (20% aqueous dispersion)
(Asahi Guard GS-1 manufactured by Meisei Chemical Industry Co., Ltd.) 2.5%
Hydrophilic polyester resin (10% aqueous dispersion)
(SR-1800 manufactured by Takamatsu Yushi Co., Ltd.) 1.0%
Non-hydrophilic fluorine-based water and oil repellent (20% aqueous dispersion)
(Asahi Guard AG970, Meisei Chemical Industry Co., Ltd.) 0.5%
Cross-linking agent (solid content concentration 60%)
(Sumitomo Chemical Industries Sumitex Resin M3) 0.3%
Catalyst (Sumitomo Chemical Co., Ltd. Sumitex Accelerater ACX) 0.2%
[0028]
Comparative Example 4
The processing was carried out under exactly the same samples and the same conditions as in Example 1 except that the crosslinking agent and the catalyst were not used in the antifouling processing compounding formulation of Example 2. Table 1 shows the SR properties of the obtained dyed jacquard fabric.
[0029]
Comparative Example 5
In Example 2, processing was carried out under exactly the same samples and the same conditions as in Example 2 except that the scouring water washing drying before antifouling processing was not performed. Table 1 shows the SR 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.
[0030]
Comparative Example 6
The processing was carried out under exactly the same samples and the same conditions as in Example 1, except that the antifouling processing formulation of Example 1 was changed to the following formulation. Table 1 shows the SR properties of the obtained polyester processed yarn knitted fabric.
(Anti-fouling formulation)
Hydrophilic polyester resin (10% aqueous dispersion)
(SR-1800, manufactured by Takamatsu Yushi Co., Ltd.) 5.0%
Cross-linking agent (solid content concentration 60%)
(Sumitomo Chemical Industries Sumitex Resin M3) 0.3%
Catalyst (Sumitomo Chemical Co., Ltd. Sumitex Accelerater ACX) 0.2%
[0031]
Comparative Example 7
Table 1 summarizes the SR properties of the polyester processed yarn knitted fabric before the antifouling processing.
[0032]
[Table 1]

[0033]
【The invention's effect】
As described above in detail, the ink-stained stain-resistant synthetic fiber of the present invention specifies a fluorine-based water / oil repellent having a hydrophilic segment, a hydrophilic polyester-based resin, a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent. A predetermined amount of antifouling component formulated in proportion is uniformly attached to a clean synthetic fiber fabric without impure residual components that hinder the adhesion between the fiber surface and the antifouling component, and a strong antifouling coating is formed. Since it is formed, it exhibits an excellent SR (Soil Release) antifouling effect at the time of washing against ink ink stains after repeated washing and repeated wear. In particular, according to the present invention, it is suitable for calligraphy / painting classrooms and school applications that tend to encounter ink stains on carpets, chair upholstery, table cloths, uniforms, casual knit clothing, etc. that are susceptible to repeated washing and repeated wear. It is possible to effectively provide an SR antifouling synthetic fiber fabric excellent in use durability.

Claims (3)

Weight ratio of fluorine-based water / oil repellent having hydrophilic segment, hydrophilic polyester resin, non-hydrophilic fluorine-based water / oil repellent and crosslinking agent is 60-40 / 15-40 / 24-10 / 1-10 A synthetic fiber fabric in which the antifouling component contained in 1 is attached to the fiber surface uniformly by 1% by weight or more per fiber weight, and the fluorine-based water and oil repellent having the hydrophilic segment is represented by the following general formula (I) A perfluoroalkyl group-containing (meth) acrylate copolymer represented by:

In the formula, R represents a lower alkyl group, n, a, and b represent an integer of 1 or more, Rf represents a perfluoroalkyl group or a group containing a perfluoroalkylene glycol,
The synthetic fiber fabric has the following characteristics:
(1) Repeated washing (JIS L0217-103 method) The ink stain SR property after 20 times is grade 4 or higher according to JIS L0805 contamination gray scale determination.
(2) The ink stain SR property after repeated wear (using friction tester II specified by JIS L0823 and worn 3000 times under a load of 500 g) is grade 4 or higher according to JIS L0805 contamination gray scale determination.   2. The ink-stain resistant synthetic fiber fabric according to claim 1, wherein the hydrophilic polyester resin is a copolyester resin comprising dimethyl terephthalate, dimethyl isophthalate, ethylene glycol, and polyethylene glycol. A synthetic fiber fabric that has been washed or scoured in advance to remove adhering impurities, and a weight ratio of a fluorine-based water / oil repellent having a hydrophilic segment, a hydrophilic polyester-based resin, a non-hydrophilic fluorine-based water / oil repellent and a cross-linking agent. Impregnating an aqueous solution containing 60 to 40/15 to 40/24 to 10/1 to 10, after drying, heat-treating at 140 ° C. to 180 ° C. under dry heat, and attaching 1% by weight or more per fiber weight; and Production of ink-stain-resistant synthetic fiber fabric, wherein the fluorine-based water / oil repellent having the hydrophilic segment is a perfluoroalkyl group-containing (meth) acrylate copolymer represented by the following general formula (I): Method:

In the formula, R represents a lower alkyl group, n, a and b represent an integer of 1 or more, and Rf represents a perfluoroalkyl group or a group containing a perfluoroalkylene glycol.