JP4723117B2 - Antifouling and washing resistance imparting agents and compositions for fibers - Google Patents

Description

【００１２】
[式中、Ｘは２価の有機残基を示し、Ｙは炭素数１〜６のアルキレンオキシ基を示し、Ｚは水素原子もしくはＲ⁵−Ｏ−（Ｃ＝Ｏ）−（但しＲ⁵は炭素数１〜１０のアルキル基または炭素数１〜１０のヒドロキシアルキル基を示す）を示す。また、Ｒ¹は水素原子もしくはメチル基を示し、Ｒ²、Ｒ³およびＲ⁴は同一もしくは異なる基であって、水素原子または炭素数１〜６のアルキル基またはヒドロキシアルキル基を示す。ｍは０〜２０の整数を示す。ｎは１〜４の整数を示す。]で表されるホスホリルコリン類似基含有単量体。
単量体Ｂ；グリセロールモノ（メタ）アクリレート。
単量体Ｃ；下記の式（２）
【００１３】
【化４】

【００１４】
｛式中、Ｒ⁶は水素原子またはメチル基を示し、Ｌ¹は、−Ｃ₆Ｈ₄−、−Ｃ₆Ｈ₁₀−、−（Ｃ＝Ｏ）Ｏ−、−Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ−（Ｃ＝Ｏ）−、−Ｏ−（Ｃ＝Ｏ）−Ｏ−から選ばれる基を示し、Ｌ²は、水素原子または−（ＣＨ₂）ｐ¹−Ｌ³、−（（ＣＨ₂）ｐ²−Ｏ）ｐ¹−Ｌ³から選ばれる疎水性官能基を示す。ｐ¹は１〜２４、ｐ²は３〜５までの整数を示し、Ｌ³は、水素原子またはメチル基、−Ｃ₆Ｈ₅、−Ｏ−Ｃ₆Ｈ₅から選ばれる官能基を示す。｝で表される疎水性単量体。
【００１５】
〔３〕ホスホリルコリン類似基含有単量体が２−（（メタ）アクリロイルオキシ）エチル−２'−（トリメチルアンモニオ）エチルホスフェートである前記〔１〕または〔２〕に記載の繊維用防汚性及び耐洗濯性付与剤。
〔４〕単量体Ｃの疎水性単量体が、炭素数１〜１８のアルキル基を持つ（メタ）アクリル酸エステルである前記〔１〕〜〔３〕のいずれかに記載の繊維用防汚性及び耐洗濯性付与剤。
〔５〕ホスホリルコリン類似基含有重合体が、単量体Ａのホスホリルコリン類似基含有単量体を１０〜９０重量％、単量体Ｂのグリセロールモノ（メタ）アクリレートを５〜８０重量％および、単量体Ｃの疎水性単量体を５〜６０重量％含む単量体組成物を重合してなる重合体であり、重量平均分子量が、２０，０００〜２，０００，０００の範囲である前記〔１〕〜〔４〕のいずれかに記載の繊維用防汚性及び耐洗濯性付与剤。
〔６〕前記〔１〕〜〔５〕のいずれかに記載のホスホリルコリン類似基含有重合体０．０５〜１０重量％を含む繊維用防汚性及び耐洗濯性付与剤組成物。
【００１６】
〔７〕前記〔１〕〜〔５〕のいずれかに記載のホスホリルコリン類似基含有重合体０．０５〜１０重量％とバインダー成分０．０５〜１０重量％とを含む繊維用防汚性及び耐洗濯性付与剤組成物。
〔８〕バインダーが、アミノ基、カルボキシル基、ヒドロキシ基、エポキシ基のいずれかから選ばれる基を有する重合体である前記〔７〕記載の繊維用防汚性及び耐洗濯性付与剤組成物。
【００１７】
【発明の実施の形態】
本発明の繊維用防汚性及び耐洗濯性付与剤は、特定の単量体Ａのホスホリルコリン類似基含有単量体（以下、ＰＣ単量体と略す。）と単量体Ｂのグリセロールモノ（メタ）アクリレートと単量体Ｃの疎水性単量体とを含む単量体組成物に基づく構成単位を含有する、分子量２０，０００〜２，０００，０００のホスホリルコリン類似基含有重合体（以下、ＰＣ重合体と略す。）を有効成分とするものである。前記ＰＣ重合体は、各々の単量体を含む単量体組成物を重合して得られるが、単量体組成物は、ＰＣ単量体、グリセロールモノ（メタ）アクリレート、疎水性単量体の他に重合可能な他の重合性単量体を含んでいても良い。
【００１８】
具体的には、さらに前記のＰＣ重合体は、単量体Ａのホスホリルコリン類似基含有単量体１０〜９０重量％、単量体Ｂのグリセロールモノ（メタ）アクリレート５〜８０重量％および、単量体Ｃの疎水性単量体５〜６０重量％からなる単量体組成物をラジカル重合してなる重合体を好ましく挙げることができる。より好ましくは、単量体Ａのホスホリルコリン類似基含有単量体を２０〜７０重量％、単量体Ｂのグリセロールモノ（メタ）アクリレートを１０〜６０重量％および、単量体Ｃの疎水性単量体を１０〜５０重量％を含む単量体組成物である。単量体ＡのＰＣ単量体が１０重量％未満であると防汚効果が十分でなく、単量体Ｂのグリセロールモノ（メタ）アクリレートが５重量％未満であるとグリセロールモノ（メタ）アクリレートの水素結合による自己架橋性が十分でなくいため耐洗濯性が十分発揮できない。単量体Ｃの疎水性単量体が５重量％未満であると疎水性相互作用による繊維への密着性が十分でないため耐洗濯性が十分発揮できない。
【００１９】
ここで、前記のＰＣ単量体は、下記の式（１）
【００２０】
【化５】

【００２１】
[式中、Ｘは２価の有機残基を示し、Ｙは炭素数１〜６のアルキレンオキシ基を示し、Ｚは水素原子もしくはＲ⁵−Ｏ−（Ｃ＝Ｏ）−（但しＲ⁵は炭素数１〜１０のアルキル基または炭素数１〜１０のヒドロキシアルキル基を示す。）を示す。また、Ｒ¹は水素原子もしくはメチル基を示し、Ｒ²、Ｒ³およびＲ⁴は同一もしくは異なる基であって、水素原子または炭素数１〜６のアルキル基またはヒドロキシアルキル基を示す。ｍは０〜２０の整数を示す。ｎは１〜４の整数を示す。]で表される。
【００２２】
式（１）中のＸの２価の有機残基としては例えば、−Ｃ₆Ｈ₄−、−Ｃ₆Ｈ₁₀−、−（Ｃ＝Ｏ）Ｏ−、−Ｏ−、−ＣＨ₂−Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ−（Ｃ＝Ｏ）−、−Ｏ−（Ｃ＝Ｏ）−Ｏ−、−Ｃ₆Ｈ₄−Ｏ−、−Ｃ₆Ｈ₄−ＣＨ₂−Ｏ−、−Ｃ₆Ｈ₄−（Ｃ＝Ｏ）−Ｏ−等が挙げられる。式（１）中のＹは、炭素数１〜６のアルキレンオキシ基であり、例えば、メチルオキシ基、エチルオキシ基、プロピルオキシ基、ブチルオキシ基、ペンチルオキシ基、ヘキシルオキシ基等が挙げられる。
【００２３】
式（１）中のＺは水素原子もしくはＲ⁵−Ｏ−（Ｃ＝Ｏ）−で表される有機残基であり、Ｒ⁵は、炭素数１〜１０のアルキル基、または炭素数１〜１０のヒドロキシアルキル基である。炭素数１〜１０のアルキル基としては例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等が挙げられる。炭素数１〜１０のヒドロキシアルキル基としては例えば、ヒドロキシメチル基、２−ヒドロキシエチル基、３−ヒドロキシプロピル基、２−ヒドロキシプロピル基、４−ヒドロキシブチル基、２−ヒドロキシブチル基、５−ヒドロキシペンチル基、２−ヒドロキシペンチル基、６−ヒドロキシヘキシル基、２−ヒドロキシヘキシル基、７−ヒドロキシヘプチル基、２−ヒドロキシヘプチル基、８−ヒドロキシオクチル基、２−ヒドロキシオクチル基、９−ヒドロキシノニル基、２−ヒドロキシノニル基、１０−ヒドロキシデシル基、２−ヒドロキシデシル基等が挙げられる。
【００２４】
ＰＣ単量体としては、具体的には例えば、２−｛（メタ）クリロイルオキシ｝エチル−２’−（トリメチルアンモニオ）エチルホスフェート、３−｛（メタ）クリロイルオキシ｝プロピル−２’−（トリメチルアンモニオ）エチルホスフェート、４−｛（メタ）クリロイルオキシ｝ブチル−２’−（トリメチルアンモニオ）エチルホスフェート、５−｛（メタ）クリロイルオキシ｝ペンチル−２’−（トリメチルアンモニオ）エチルホスフェート、６−｛（メタ）クリロイルオキシ｝ヘキシル−２’−（トリメチルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝エチル−２’−（トリエチルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝エチル−２’−（トリプロピルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝エチル−２’−（トリブチルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝エチル−２’−（トリシクロヘキシルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝エチル−２’−（トリフェニルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝エチル−２’−（トリメタノールアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝プロピル−２’−（トリメチルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝ブチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝ペンチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−｛（メタ）クリロイルオキシ｝ヘキシル−２’−（トリメチルアンモニオ）エチルホスフェート、
【００２５】
２−（ビニルオキシ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（アリルオキシ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（ｐ−ビニルベンジルオキシ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（ｐ−ビニルベンゾイルオキシ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（スチリルオキシ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（ｐ−ビニルベンジル）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（ビニルオキシカルボニル）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（アリルオキシカルボニル）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（アクリロイルアミノ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、２−（ビニルカルボニルアミノ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート、エチル−（２’−トリメチルアンモニオエチルホスホリルエチル）フマレート、ブチル−（２’−トリメチルアンモニオエチルホスホリルエチル）フマレート、ヒドロキシエチル−（２’−トリメチルアンモニオエチルホスホリルエチル）フマレート、エチル−（２’−トリメチルアンモニオエチルホスホリルエチル）マレート、ブチル−（２’−トリメチルアンモニオエチルホスホリルエチル）マレート、ヒドロキシエチル−（２’−トリメチルアンモニオエチルホスホリルエチル）マレート等を挙げることができる。ここで（メタ）アクリロイルは、アクリロイルおよび/またはメタクリロイルを意味する。
【００２６】
この中でも、２−（（メタ）アクリロイルオキシ）エチル−２’−（トリメチルアンモニオ）エチルホスフェートが好ましく、さらに２−（メタクリロイルオキシ）エチル−２’−（トリメチルアンモニオ）エチルホスフェート（略称；ＭＰＣ）が入手性等の点で好ましい。
【００２７】
ＰＣ単量体を重合する際には、前記のＰＣ単量体１種を単独で、もしくは２種以上を混合物として用いることができる。ＰＣ単量体は、公知の方法で製造できる。例えば、特開昭５４−６３０２５号公報に示されている水酸基含有重合性単量体と２−ブロムエチルホスホリルジクロリドとを３級塩基存在下で反応させて得られる化合物と３級アミンとを反応させる方法、特開昭５８−１５４５９１号公報等に示されている、水酸基含有重合性単量体と環状リン化合物との反応で環状化合物を得た後、３級アミンで開環反応する方法等によって製造することができる。
【００２８】
単量体Ｂのグリセロールモノ（メタ）アクリレートは、グリセリンのモノアクリル酸エステル或いはモノメタクリル酸エステルである。
【００２９】
単量体Ｃの疎水性単量体は、式（２）
【００３０】
【化６】

【００３１】
｛式中、Ｒ⁶は水素原子またはメチル基を示し、Ｌ¹は、−Ｃ₆Ｈ₄−、−Ｃ₆Ｈ₁₀−、−（Ｃ＝Ｏ）Ｏ−、−Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ−（Ｃ＝Ｏ）−、−Ｏ−（Ｃ＝Ｏ）−Ｏ−から選ばれる基を示し、Ｌ²は、水素原子または−（ＣＨ₂）ｐ¹−Ｌ³、−（（ＣＨ₂）ｐ²−Ｏ）ｐ¹−Ｌ³から選ばれる疎水性官能基を示す。ｐ¹は１〜２４、ｐ²は３〜５までの整数を示し、Ｌ³は、水素原子またはメチル基、−Ｃ₆Ｈ₅、−Ｏ−Ｃ₆Ｈ₅から選ばれる官能基を示す。｝で表される。
【００３２】
単量体Ｃの疎水性単量体としては具体的には例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、スチレン、メチルスチレン、クロロメチルスチレン、メチルビニルエーテル、ブチルビニルエーテル、酢酸ビニル、プロピオン酸ビニル等が好ましく挙げられる。
【００３３】
単量体Ｃの疎水性単量体の中でも特に炭素数１〜１８のアルキル基の（メタ）アクリル酸エステルがより好ましく、具体的には例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。
【００３４】
ＰＣ重合体を構成する単量体組成物には、本発明の効果を損なわない範囲において、単量体Ａ、単量体Ｂ、単量体Ｃ以外の他の重合性単量体を混合しても良い。他の重合性単量体としては具体的には例えば、ポリエチレングリコール（メタ）アクリレート、２−ビニルピロリドン２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、（メタ）アクリル酸、スチレンスルホン酸、（メタ）アクリルアミド、（メタ）アクリロイルオキシホスホン酸、アミノエチルメタクリレート、ジメチルアミノエチル（メタ）アクリレート、２−ヒドロキシ−３−（メタ）アクリロイルオキシプロピルトリメチルアンモニウムクロライド等が挙げられる。
【００３５】
ＰＣ重合体は、前記のように単量体ＡのＰＣ単量体と単量体Ｂのグリセロールモノ（メタ）アクリレートと単量体Ｃの疎水性単量体とを含む単量体組成物をラジカル重合することにより得られるが、他の重合性単量体の種類により繊維への密着性が異なるため、処理する繊維の性質を考慮して他の重合性単量体を選択することが望ましい。他の単量体の中でもＰＣ重合体の防汚性付与効果と繊維との密着性との観点から、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル基含有単量体や（メタ）アクリロイルオキシエチルトリメチルアンモニウムクロライド、２−ヒドロキシ−３−（メタ）アクリロイルオキシプロピルトリメチルアンモニウムクロライド等のカチオン性単量体が好ましく挙げられる。
【００３６】
ＰＣ重合体の重量平均分子量は、２０，０００〜２，０００，０００の範囲であることが望ましく、さらに好ましくは、５０，０００〜５００，０００の範囲である。重量平均分子量が２０，０００未満であると重合体の繊維への吸着力が十分でないため耐洗濯性が劣ることになり、２，０００，０００を超えると処理液の粘性が高くなりすぎ繊維に均一に処理剤が浸透するのが困難となり防汚性を十分に発揮することが困難となるので好ましくない。
【００３７】
本発明の繊維用防汚性及び耐洗濯性付与剤組成物は、ＰＣ重合体単独の溶液でも使用可能であるが、ＰＣ重合体０．０５〜１０重量％とバインダー成分０．０５〜１０重量％とを含む組成物とするのが望ましく、より好ましくはＰＣ重合体０．１〜３重量％とバインダー成分０．１〜３重量％の組成物である。ＰＣ重合体の濃度が０．０５重量％未満の場合には、ＰＣ重合体が繊維に付着する量が十分でないため防汚効果を十分に上げることができず、１０重量％を超える場合はＰＣ重合体が残留し繊維の柔軟さを損なう恐れがあるため好ましくない。バインダー成分の濃度が０．０５重量％未満の場合には、架橋反応によりＰＣ重合体を繊維に付着させる能力が十分でないため耐洗濯性を十分に上げることができず、１０重量％を超える場合にはバインダー成分が残留し、繊維の柔軟さを損なう恐れがあるため好ましくない。
【００３８】
繊維用防汚性及び耐洗濯性付与剤組成物の溶媒は、水が最も望ましいが、アルコール系溶剤、ケトン系溶剤、エステル系溶剤等を使用することも可能であるし、水とアルコールの混合液等のように２種以上を混合して溶媒として使用しても良い。
【００３９】
バインダー成分は、化学反応、疎水性結合、イオン性結合等の結合力によりＰＣ重合体を繊維表面へ強固に固定させ耐久性を付与することを目的として使用するが、アクリル系樹脂、ポリエステル系樹脂、グリオキザール系樹脂、エポキシ系樹脂、ウレタン系樹脂、メラミン系樹脂、酢酸ビニル系樹脂、ポリエーテル系樹脂、セルロース系樹脂等、一般に繊維処理に使用されている重合体を使用することができる。バインダー成分は、前記の重合体の中でも、アミノ基、カルボキシル基、ヒドロキシ基、エポキシ基を有する重合体であることが望ましく、具体的には例えば、ポリジメチルアミノエチルメタクリレート、アクリル酸−アルキルメタクリレート共重合体、２−ヒドロキシエチルメタクリレート−メタクリル酸共重合体、ポリ２−ヒドロキシ−３−（メタ）アクリロイルオキシプロピルトリメチルアンモニウムクロライド、ポリエチレングリコール−テレフタル酸重縮合物、末端カルボン酸ポリエチレングリコール、部分ケン化ポリビニルアルコール、ヒドロキシエチルセルロース、カルボキシメチルセルロース、ポリ４−アミノスチレン、ポリエチレンイミン、スチレン−マレイン酸共重合体、マレイン酸−メチルビニルエーテル共重合体、キトサン、プルラン、カゼイン、キサンタンガム、コラーゲン、ヒアルロン酸、ゼラチン、アルギン酸、デキストラン等が好ましく挙げられる。
【００４０】
また、バインダー成分として、アミノ基、カルボキシル基、ヒドロキシ基、エポキシ基の内どれかを有する単量体とＰＣ単量体との共重合体を使用することもできる。具体的には例えば、ＭＰＣ−メタクリル酸共重合体、ＭＰＣ−２−ヒドロキシ−３−（メタ）アクリロイルオキシプロピルトリメチルアンモニウムクロライド共重合体、ＭＰＣ−２−ヒドロキシエチルメタクリレート共重合体等が好ましく挙げられる。
【００４１】
前記組成物により繊維を処理する方法は、組成物に繊維を浸漬する工程と４０〜１９０℃で乾燥および熱処理する工程を含む処理方法が望ましく、さらに好ましくは、９０〜１６０℃で乾燥および熱処理する工程を含む処理方法である。乾燥および熱処理温度が４０℃未満だと架橋反応が困難となるため耐洗濯性が十分でなく、１９０℃を超えると繊維布帛が黄変しやすくなるため好ましくない。また、場合によっては乾燥および熱処理の工程は、乾燥を４０〜１２０℃で行い、その後１００〜１９０℃で熱処理を行う２段階の方法が望ましく、さらに好ましくは、乾燥８０〜１０５℃、熱処理１１０〜１８０℃で行う方法が望ましい。
【００４２】
前記組成物に繊維を浸漬する場合、繊維重量の２０〜２００重量％の含浸量まで組成物溶液を絞った後に乾燥および熱処理の工程に移行することが望ましく、さらに好ましくは繊維重量の５０〜１２０重量％の含浸量まで組成物溶液を絞ることである。
本発明の組成物を使用して繊維処理を行う際には、本発明の効果を損なわない範囲において、形態安定処理剤、防臭剤、吸着剤、界面活性剤、柔軟剤、溶剤、染料、保湿剤、抗菌剤、香料等の他の成分を添加しても良い。本発明の組成物は、通常はＰＣ重合体を１〜４０重量％の濃縮液としておき、処理の際に水で０．０５〜１０重量％の濃度へ希釈することにより前記組成物の液とすることが実用上好ましい。
【００４３】
本発明で使用する繊維とは、糸状、ヒモ状、縄状の繊維であって良く、それらが布状に構成されたものであって良い。また、繊維を構成する素材としては、通常の衣類に使用することのできる素材であればいずれでも良く、例えば、木綿、麻、絹、羊毛、コラーゲン繊維、アクリル繊維、レーヨン、ナイロン、ビニロン、ポリエステル、ポリプロピレン、ポリ塩化ビニル、ポリエチレン、ポリメタフェニレンイソフタルアミド、アラミド、ポリアリレートおよびこれらの混紡品からなる織物、編物、不織布等が挙げられる。この中でもポリエステルおよびポリエステル−綿混紡、ナイロンの繊維に対して、特に本発明の防汚効果が高いため好ましい。本発明で処理され得る繊維の中には、ヒトの皮膚に接触させて使用する場合のあるティッシュペーパーやトイレットペーパー等の主としてセルロース繊維から構成される紙類も含まれる。
【００４４】
【発明の効果】
本発明により得られた被処理繊維は、耐洗濯性に優れた高い防汚性を有し、吸保湿性、帯電防止性にも優れている。
【００４５】
【実施例】
以下に実施例に基づいて本発明をさらに詳しく説明する。
【００４６】
ポリマーの分子量の分析方法
リン酸バッファー（ｐＨ７．４、２０ｍＭ）を溶離液としたゲルパーミエーションクロマトグラフィー（ＧＰＣ）、ポリエチレングリコール標準、ＵＶ（２１０ｎｍ）および屈折率にて検出する。
【００４７】
合成例１（ポリマー１；ＭＰＣ０．４−ＢＭＡ０．２−ＧＬＭ０．４、重量平均分子量３４１，０００）
ＭＰＣ；１１．２ｇ、ブチルメタクリレート（ＢＭＡ）；２．７ｇ、グリセロールメタクリレート（ＧＬＭ）；６．１ｇをエタノール；１８０ｇに溶解し４つ口フラスコに入れ、３０分間窒素を吹込んだ後、５０℃でアゾビスイソブチロニトリル；０．８５ｇを加えて８時間重合反応させた。重合液を３リットルのジエチルエーテル中にかきまぜながら滴下し、析出した沈殿を濾過し、４８時間室温で真空乾燥を行って、粉末１６．１ｇを得た。ＧＰＣにより評価した分子量は重量平均分子量３４１，０００であった。これをポリマー１とする。
【００４８】
合成例２（ポリマー２；ＭＰＣ０．４−ＢＭＡ０．４−ＧＬＭ０．２、重量平均分子量２９４，０００）
ＭＰＣ；１１．４ｇ、ＢＭＡ；５．５ｇ、ＧＬＭ；３．１ｇをエタノール；１８０ｇに溶解し４つ口フラスコに入れ、３０分間窒素を吹込んだ後、５０℃でアゾビスイソブチロニトリル；０．８５ｇを加えて８時間重合反応させた。重合液を３リットルのジエチルエーテル中にかきまぜながら滴下し、析出した沈殿を濾過し、４８時間室温で真空乾燥を行って、粉末１７．３ｇを得た。ＧＰＣにより評価した分子量は重量平均分子量２９４，０００であった。これをポリマー２とする。
【００４９】
合成例３（ポリマー３；ＭＰＣ０．４−ＥＨＭＡ０．２−ＧＬＭ０．４、重量平均分子量３１０，０００）
ＭＰＣ；１０．６ｇ、２−エチルヘキシルメタクリレート（ＥＨＭＡ）；３．６ｇ、ＧＬＭ；５．８ｇをエタノール；１８０ｇに溶解し４つ口フラスコに入れ、３０分間窒素を吹込んだ後、５０℃でアゾビスイソブチロニトリル；０．８５ｇを加えて８時間重合反応させた。重合液を３リットルのジエチルエーテル中にかきまぜながら滴下し、析出した沈殿を濾過し、４８時間室温で真空乾燥を行って、粉末１５．９ｇを得た。ＧＰＣにより評価した分子量は重量平均分子量３１０，０００であった。これをポリマー３とする。
【００５０】
合成例４（ポリマー４；ＭＰＣ０．４−ＬＭＡ０．２−ＧＬＭ０．４、重量平均分子量２９３，０００）
ＭＰＣ；１０．１ｇ、ラウリルメタクリレート（ＬＭＡ）；４．４ｇ、ＧＬＭ；５．５ｇをエタノール；１８０ｇに溶解し４つ口フラスコに入れ、３０分間窒素を吹込んだ後、５０℃でアゾビスイソブチロニトリル；０．８５ｇを加えて８時間重合反応させた。重合液を３リットルのジエチルエーテル中にかきまぜながら滴下し、析出した沈殿を濾過し、４８時間室温で真空乾燥を行って、粉末１６．３ｇを得た。ＧＰＣにより評価した分子量は重量平均分子量２９３，０００であった。これをポリマー４とする。
【００５１】
合成例５（ポリマー５；ＭＰＣ０．６−ＢＭＡ０．４、重量平均分子量１６８，０００）
ＭＰＣ；１５．１ｇ、ＢＭＡ；４．９ｇをエタノール；１８０ｇに溶解し４つ口フラスコに入れ、３０分間窒素を吹込んだ後、５０℃でアゾビスイソブチロニトリル；０．８５ｇを加えて８時間重合反応させた。重合液を３リットルのジエチルエーテル中にかきまぜながら滴下し、析出した沈殿を濾過し、４８時間室温で真空乾燥を行って、粉末１５．８ｇを得た。ＧＰＣにより評価した分子量は重量平均分子量１６８，０００であった。これをポリマー５とする。
【００５２】
合成例６（ポリマー６；ＭＰＣ０．６−ＧＬＭ０．４、重量平均分子量２１４，０００）
ＭＰＣ；１４．７ｇ、ＧＬＭ；５．３ｇをエタノール；１８０ｇに溶解し４つ口フラスコに入れ、３０分間窒素を吹込んだ後、５０℃でアゾビスイソブチロニトリル；０．８５ｇを加えて８時間重合反応させた。重合液を３リットルのジエチルエーテル中にかきまぜながら滴下し、析出した沈殿を濾過し、４８時間室温で真空乾燥を行って、粉末１５．１ｇを得た。ＧＰＣにより評価した分子量は重量平均分子量２１４，０００であった。これをポリマー６とする。
【００５３】
試験方法
１．（評価試験１−１）汚れの除去性Ａ法
試験布（５ｃｍ×５ｃｍ）を、人工油性汚れ液（牛脂硬化油０．１５％、カーボンブラック０．０１％、石鹸０．１０％）が１５０ｍＬ入ったステンレス容器に硬球１０個とともに入れ、ランドリーで回転させて（４０℃×２０分）、汚れを付着させ、ろ紙上で乾燥する。この時の試験布の汚染度合いを目視判定し、初期汚染度とする。判定基準は表１に示すように５段階とする。次に、家庭洗濯（ＪＩＳ Ｌ−０２１７ １０３法）を１回行った後の汚れの残存状態を目視判定し、洗濯１回後の汚染度とする。また、処理上がり布を汚染布とともに洗濯し、再汚染確認布として汚れの再汚染を目視判定する。
【００５４】
表１
等級 判定基準
５ 汚れが付着していない
４ かすかに汚れが付着している
３ 少し汚れが付着している
２ かなり汚れが付着している
１ たくさん汚れが付着している
【００５５】
２．（評価試験１−２）汚れの除去性Ｂ法
<ふき取り法> 布上に汚れの物質０．１５ｇを滴下し、３分間放置後、ティッシュでふき取り、汚染度合いを表１の基準で目視判定する。
<強汚染法> 布上に汚れの物質０．１５ｇを置き、５００ｇの荷重を１分間かける。その後ティッシュでふき取り、１５時間常温で放置する。次に、家庭洗濯（ＪＩＳ Ｌ−０２１７ １０３法）を１回した後、汚染度合いを表１の基準で目視判定する。
ふき取り法、強汚染法ともに汚れ物質には以下の５つを使用する。
１． 醤油（サンビシ（株）製、サンビシしょうゆ特級本醸造）；水性物質、
２． 墨汁（不易糊工業（株）製、書道用液 墨彩）；水分散系で接着成分を含む物質、
３． 魚血（いわし）；水性物質、
４． 口紅（ＬＡＮＣＯＭＥ ＰＡＲＩＳ ３１３ ＲＯＵＧＥ ＡＺＩＥＱＵＥ ＭＡＴ）；油性固形物質、
５． ダーティモーターオイル（日本石油（株）製、工業用極圧ギヤー油、ボンノックＭ２２０）；油性物質。
【００５６】
３．（評価試験２）吸水性試験
ＪＩＳ Ｌ−１０９６、６．２６、Ａ法；滴下法により吸水性試験を行う。
【００５７】
４．（評価試験３）保湿試験
処理試験布を温度２０℃、相対湿度（ＲＨ）＝８０％のデシケーター中に２、５、２４時間放置し、布の重量測定を行う。次に、処理試験布をＲＨ＝３５％のデシケーターに移し、同様の試験を行う。保湿率を以下のように定義する。なお、処理試験布を８時間の真空乾燥の後の重量を絶乾布の重量とする。
保湿率（％）＝｛（各時間後の布重量−絶乾布の重量）／（絶乾布の重量）｝×１００
【００５８】
５．（評価試験４）帯電性試験
ＪＩＳ Ｌ−１０９４、Ａ法；半減期測定法、およびＪＩＳ Ｌ−１０９４、Ｂ法により帯電性試験を行う。
【００５９】
実施例１−１
通常の方法で糊抜き、精錬、仕上げされた綿１００％、ポリエステル１００％（表中では、Ｅ１００％と略す。）、ポリエステル／綿混紡（ポリエステル：綿＝６５：３５、表中ではＥ／Ｃと略す。）の試験布を用意し、これにヒドロキシアルキル基含有のアクリル酸エステル系樹脂バインダー（大和化学工業（株）製、製品名バインテックスＡ-30Ｇ）を利用した下記処方１の処理液をマングルを用いて付与し、１０５℃で５分間乾燥した。この後、ピンテンターを用いて、１５０℃で２分間の乾熱処理を行い、防汚処理布を得た。
処方１
PC重合体;ポリマー1 50g/L
バインダー;バインテックスＡ-30Ｇ 50g/L
【００６０】
実施例１−２
処理液を下記の処方２とした以外は、実施例１と同様の操作により処理布を得た。
処方２
PC重合体;ポリマー2 50g/L
バインダー;バインテックスＡ-30Ｇ 50g/L
【００６１】
実施例１−３
処理液を下記の処方３とした以外は、実施例１と同様の操作により処理布を得た。
処方３
PC重合体;ポリマー3 50g/L
バインダー;バインテックスＡ-30Ｇ 50g/L
【００６２】
実施例１−４
処理液を下記の処方４とした以外は、実施例１と同様の操作により処理布を得た。
処方４
PC重合体;ポリマー4 50g/L
バインダー;バインテックスＡ-30Ｇ 50g/L
【００６３】
比較例１−１処理液を、パーフルオロオクチルエチルメタクリレート−ポリエチレングリコールモノメタクリレート−ポリプロピレングリコールモノメタクリレート共重合体（重量比＝５０：３５：１５、以下、Ｆ共重合体と略す。）を使用した下記の処方５とした以外は、実施例１と同様の操作により処理布を得た。
処方５
Ｆ共重合体 50g/L
【００６４】
比較例１−２処理液を下記の処方６とした以外は、実施例１と同様の操作により処理布を得た。
処方６
PC重合体；ポリマー5 50g/L
バインダー；バインテックスＡ-30Ｇ 50g/L
【００６５】
比較例１−３処理液を下記の処方７とした以外は、実施例１と同様の操作により処理布を得た。
処方７
PC重合体；ポリマー6 50g/L
バインダー；バインテックスＡ-30Ｇ 50g/L
【００６６】
比較例１−４
実施例１で使用した試験布を未処理のまま試験布とした。
【００６７】
実施例２
実施例１−１〜１−４で得られた処理試験布を使用して、前記評価試験を行った（表中では、初期布として表示した。）。また、実施例１−１〜１−４で得られた処理試験布を洗濯３０回行った処理試験布についても同様に前記評価試験を行った（表中では、Ｌ−３０として表示した。）。
（評価試験１−１）の結果については、表２に結果を示した。表２中の数値ａ／ｂ／ｃは、それぞれａが初期の汚染度、ｂが洗濯１回後の汚染度、ｃが再汚染確認布の汚染度である。
（評価試験１−２）の結果については、表３、４に結果を示した。表３、４中の数値ａ／ｂは、それぞれａがふき取り法、ｂが強汚染法の汚染度である。
（評価試験２）の結果については、表５に結果を示した。
（評価試験３）の結果については、表６に結果を示した。
（評価試験４）の結果については、表７に結果を示した。
【００６８】
比較例２
比較例１−１〜１−４で得られた処理試験布を使用して、実施例２と同様に前記評価試験を行い、結果を表２〜７に示した。
【００６９】
【表１】

【００７０】
【表２】

【００７１】
【表３】

【００７２】
【表４】

【００７３】
【表５】

【００７４】
【表６】

【００７５】
以上の結果より、本発明のＰＣ重合体を用いた実施例１−１〜１−４は、比較例１−１〜１−４に比べて、汚れ除去試験、各種の汚れに対する汚れ除去試験において、綿１００％、ポリエステル／綿混紡、ポリエステル１００％のいずれの布についても優れた効果を示すことがわかる。
また、表５、６および７より、本発明の繊維処理剤で処理した布は、吸水性、保湿性の試験および帯電性試験においても優れた効果を示すことがわかる。[0001]
BACKGROUND OF THE INVENTION
  The present invention provides fibersAntifouling and washing resistance imparting agent and itsRelates to the composition.
[0002]
[Prior art]
Conventionally, treatments for imparting antifouling properties to fibers have been extensively studied, but the most difficult technically, such as clothing stains and cuff stains, blood, protein, and lipstick stains. In the field, a treatment agent for fiber and a treatment method that still provide effective antifouling properties have not yet been found. In addition, in recent years, attention has been paid to safety and environmental pollution other than performance. In particular, when treating clothes, a high degree of antifouling effect that is gentle to the skin and durable is required.
[0003]
Cellulose fibers can be easily removed by washing even when dirt such as red is attached, but it has been difficult to remove stains from outside such as blood, lipstick, and foundation by washing. Conventionally, as a method for imparting antifouling performance to cellulose fibers, for example, JP-A-07-166471 and JP-A-06-2006 have been proposed in order to make the cellulose fibers more hydrophilic and improve the dirt removal performance. As disclosed in JP-A-33271, JP-A-06-313264, etc., the cellulose fabric is dipped in a treatment solution of a water-soluble cellulose derivative, squeezed, dried, and heat-treated to thereby convert the derivative into cellulose fiber. The method of granting is done. However, an aqueous solution of a water-soluble cellulose derivative has a high viscosity and has a drawback that the treatment becomes difficult when a high-concentration solution is used to impart high antifouling performance, and the texture of the fiber to be treated becomes hard. Yes.
[0004]
On the other hand, fluorine compounds, silicone compounds, polyoxyethylene compounds, polyester compounds, urethane compounds, other hydrocarbon compounds, etc. have been used as treatment agent materials for imparting antifouling properties for synthetic fibers. . For example, Japanese Patent Application Laid-Open No. 09-324173 discloses a copolymer having a fluoroalkyl group and a polyethylene glycol group, Japanese Patent Application Laid-Open No. 09-291383 has a polyester / polyalkylene glycol copolymer polyester, and Japanese Patent Application Laid-Open No. 09-273079. Is a cellulose derivative or a sulfonic acid group-containing vinyl polymer, Japanese Patent Application Laid-Open No. 09-268475 is a melamine resin, Japanese Patent Application Laid-Open No. 09-241622 is a fluorinated water repellent oil agent, Japanese Patent Application Laid-Open No. 09-188970 is Vinylsulfonic acid and quaternary ammonium salt, hydrophilic-hydrophobic block copolymer in JP-A No. 09-176961, sulfosuccinate ester type anionic surfactant in JP-A No. 08-325935, -291474 discloses a polyester-based polyurethane. Resin, a technique for treating a compound of alkylene oxide adduct of hydroxy polyolefin fiber surface is disclosed in JP-A-07-268314.
[0005]
The compound for fiber treatment as described above is roughly classified into two methods: a method of developing an antifouling effect by water repellency and a method of developing an antifouling effect by hydrophilicity. In the method of exhibiting the antifouling effect by water repellency, there is a problem that dirt is attracted by electrostatic attraction caused by charging. In the method of expressing the antifouling effect due to the hydrophilicity, since the hydrophilicity is not sufficient, the use of a high-concentration solution in the treatment to forcibly impart a high antifouling property makes the flexibility worse and the texture worsen. There is a problem. In addition, it has drawbacks such as almost no effect on the antifouling effect against blood stains.
[0006]
On the other hand, the phosphorylcholine-like group-containing polymer has excellent biocompatibility such as blood compatibility, complement inactivation, and non-adsorption of biological substances due to the phospholipid-like structure derived from biological membranes. It is known to have excellent properties such as high hydrophilicity and high moisture retention, and active research and development on the synthesis of polymers and their applications for the development of bio-related materials that make use of their respective functions. Has been done.
[0007]
  As a technique for treating fibers with a phosphorylcholine-like group-containing polymer, a method in which a phosphorylcholine-like group-containing monomer is graft polymerized to silk is disclosed (Polym. Preprints, Japan, Vol. 47, No. 3, pp. 606, 1999). In this method, the polymerization operation is complicated, and there is a problem that the production efficiency is very low because a process for removing the initiator, residual monomer, and the like which are worried about toxicity is necessary. The possibility of imparting antifouling properties is not known at all. Japanese Patent Laid-Open No. 2000-26842 discloses a technique in which a phosphorylcholine group-containing polymer can serve as an antistatic agent, but the effect of imparting antifouling properties is not known.Not highIt is also known that it can demonstrate the effect of washing resistanceAbsent.
[0008]
[Problems to be solved by the invention]
  A first object of the present invention is a structural unit based on a phosphorylcholine-like group-containing monomer, glycerol mono (meth) acrylate, and a hydrophobic monomer, which are excellent in antifouling properties, washing resistance, hygroscopicity, and antistatic properties. Fiber made of a copolymer havingAntifouling and washing resistance imparting agentIs to provide.
  The second object of the present invention is to provide the fiberAntifouling and washing resistance imparting agentIn providing the compositionThe
[0009]
[Means for Solving the Problems]
As a result of intensive investigations in view of the above problems, the present inventors have determined that the co-polymerization of a monomer composition containing a specific phosphorylcholine-like group-containing monomer, glycerol mono (meth) acrylate, and a hydrophobic monomer. When the coalescence is processed into fibers, the inventors have obtained knowledge that fibers that are particularly excellent in antifouling property and good washing resistance can be obtained, thereby completing the present invention.
[0010]
  That is, the present invention includes the following [1] to [8].
[1]Monomer A belowA molecular weight of 20,000 to 2 containing a structural unit based on glycerol mono (meth) acrylate (monomer B) and a structural unit based on another hydrophobic monomer (monomer C) An antifouling and washing resistance imparting agent for fibers comprising a polymer of 1,000,000 as an active ingredient.
[2] Antifouling and washing resistance for fibers comprising a phosphorylcholine-like group-containing polymer obtained by polymerizing a monomer composition containing the following monomer A, monomer B and monomer C as an active ingredient Giving agent.
  Monomer A; the following formula (1)
[0011]
[Chemical 3]

[0012]
[Wherein, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, and Z represents a hydrogen atom or R^Five-O- (C = O)-(where R^FiveRepresents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms). R¹Represents a hydrogen atom or a methyl group, R², R^ThreeAnd R^FourAre the same or different groups, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group. m shows the integer of 0-20. n shows the integer of 1-4. A phosphorylcholine-like group-containing monomer represented by the formula:
Monomer B; glycerol mono (meth) acrylate.
Monomer C; the following formula (2)
[0013]
[Formula 4]

[0014]
{Where R is⁶Represents a hydrogen atom or a methyl group, and L¹Is -C₆H_Four-, -C₆H_TenA group selected from-,-(C = O) O-, -O-,-(C = O) NH-, -O- (C = O)-, and -O- (C = O) -O-. L²Is a hydrogen atom or-(CH₂) P¹-L^Three,-((CH₂) P²-O) p¹-L^ThreeA hydrophobic functional group selected from p¹1-24, p²Indicates an integer from 3 to 5, L^ThreeIs a hydrogen atom or a methyl group, -C₆H_Five, -O-C₆H_FiveThe functional group chosen from is shown. } The hydrophobic monomer represented by this.
[0015]
[3] The fiber according to [1] or [2], wherein the phosphorylcholine-like group-containing monomer is 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate.Antifouling and washing resistance imparting agent.
[4] The fiber according to any one of [1] to [3], wherein the hydrophobic monomer of monomer C is a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms.Antifouling and washing resistance imparting agent.
[5] The phosphorylcholine-like group-containing polymer comprises 10 to 90% by weight of the monomer A phosphorylcholine-like group-containing monomer, 5 to 80% by weight of the glycerol mono (meth) acrylate of the monomer B, and A polymer obtained by polymerizing a monomer composition containing 5 to 60% by weight of a hydrophobic monomer of monomer C, and having a weight average molecular weight in the range of 20,000 to 2,000,000. The fiber according to any one of [1] to [4]Antifouling and washing resistance imparting agent.
[6] A fiber containing 0.05 to 10% by weight of the phosphorylcholine-like group-containing polymer according to any one of [1] to [5]Antifouling and washing resistance imparting agentComposition.
[0016]
[7] A fiber containing 0.05 to 10% by weight of the phosphorylcholine-like group-containing polymer according to any one of [1] to [5] and a binder component of 0.05 to 10% by weight.Antifouling and washing resistance imparting agentComposition.
[8] The fiber according to [7], wherein the binder is a polymer having a group selected from any of an amino group, a carboxyl group, a hydroxy group, and an epoxy group.Antifouling and washing resistance imparting agentcompositionobject.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
  The fiber of the present inventionAntifouling and washing resistance imparting agentIs a specific monomer A-containing phosphorylcholine-like group-containing monomer (hereinafter abbreviated as PC monomer), monomer B glycerol mono (meth) acrylate, and monomer C hydrophobic monomer A phosphorylcholine-like group-containing polymer (hereinafter abbreviated as PC polymer) having a molecular weight of 20,000 to 2,000,000 containing a structural unit based on a monomer composition containing is there. The PC polymer is obtained by polymerizing a monomer composition containing each monomer, and the monomer composition includes PC monomer, glycerol mono (meth) acrylate, and hydrophobic monomer. In addition, other polymerizable monomers that can be polymerized may be included.
[0018]
Specifically, the PC polymer further contains 10 to 90% by weight of the monomer A phosphorylcholine-like group-containing monomer, 5 to 80% by weight of glycerol mono (meth) acrylate of the monomer B, and A polymer obtained by radical polymerization of a monomer composition comprising 5 to 60% by weight of the hydrophobic monomer of monomer C can be preferably exemplified. More preferably, the monomer A phosphorylcholine-like group-containing monomer is 20 to 70% by weight, the monomer B glycerol mono (meth) acrylate is 10 to 60% by weight, and the monomer C is a hydrophobic monomer. It is a monomer composition containing 10 to 50% by weight of a monomer. If the PC monomer of monomer A is less than 10% by weight, the antifouling effect is not sufficient, and if the glycerol mono (meth) acrylate of monomer B is less than 5% by weight, glycerol mono (meth) acrylate Since the self-crosslinking property by hydrogen bonding is not sufficient, the washing resistance cannot be sufficiently exhibited. When the amount of the hydrophobic monomer C is less than 5% by weight, the adhesion to the fiber due to the hydrophobic interaction is not sufficient, so that the washing resistance cannot be sufficiently exhibited.
[0019]
Here, the PC monomer is represented by the following formula (1):
[0020]
[Chemical formula 5]

[0021]
[Wherein, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, and Z represents a hydrogen atom or R^Five-O- (C = O)-(where R^FiveRepresents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms. ). R¹Represents a hydrogen atom or a methyl group, R², R^ThreeAnd R^FourAre the same or different groups, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group. m shows the integer of 0-20. n shows the integer of 1-4. It is represented by
[0022]
Examples of the divalent organic residue of X in the formula (1) include -C₆H_Four-, -C₆H_Ten-,-(C = O) O-, -O-, -CH₂—O—, — (C═O) NH—, —O— (C═O) —, —O— (C═O) —O—, —C₆H_Four-O-, -C₆H_Four-CH₂-O-, -C₆H_Four-(C = O) -O- and the like. Y in Formula (1) is an alkyleneoxy group having 1 to 6 carbon atoms, and examples thereof include a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, and a hexyloxy group.
[0023]
Z in the formula (1) is a hydrogen atom or R^FiveAn organic residue represented by -O- (C = O)-, R^FiveIs a C1-C10 alkyl group or a C1-C10 hydroxyalkyl group. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 2-hydroxybutyl group, and a 5-hydroxy group. Pentyl group, 2-hydroxypentyl group, 6-hydroxyhexyl group, 2-hydroxyhexyl group, 7-hydroxyheptyl group, 2-hydroxyheptyl group, 8-hydroxyoctyl group, 2-hydroxyoctyl group, 9-hydroxynonyl group , 2-hydroxynonyl group, 10-hydroxydecyl group, 2-hydroxydecyl group and the like.
[0024]
Specific examples of the PC monomer include 2-{(meth) acryloyloxy} ethyl-2 ′-(trimethylammonio) ethyl phosphate, 3-{(meth) acryloyloxy} propyl-2 ′. -(Trimethylammonio) ethyl phosphate, 4-{(meth) acryloyloxy} butyl-2 '-(trimethylammonio) ethyl phosphate, 5-{(meth) acryloyloxy} pentyl-2'-(trimethylammoni E) Ethyl phosphate, 6-{(meth) acryloyloxy} hexyl-2 '-(trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-2'-(triethylammonio) ethyl phosphate , 2-{(meth) acryloyloxy} ethyl-2 ′-(tripropylammonio) ethylphos 2-{(meth) acryloyloxy} ethyl-2 ′-(tributylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-2 ′-(tricyclohexylammonio) ethyl phosphate, 2 -{(Meth) acryloyloxy} ethyl-2 '-(triphenylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-2'-(trimethanolammonio) ethyl phosphate, 2- { (Meth) acryloyloxy} propyl-2 ′-(trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} butyl-2 ′-(trimethylammonio) ethyl phosphate, 2-{(meth) acrylic Royloxy} pentyl-2 ′-(trimethylammonio) ethyl phosphate, 2-{( Data) acryloyloxy} hexyl-2 '- (trimethylammonio) ethyl phosphate,
[0025]
2- (vinyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxy) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyloxy) ethyl-2'- (Trimethylammonio) ethyl phosphate, 2- (p-vinylbenzoyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (styryloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2 -(P-vinylbenzyl) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (vinyloxycarbonyl) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2 '-(Trimethylammonio) ethylfo Fate, 2- (acryloylamino) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (vinylcarbonylamino) ethyl-2 ′-(trimethylammonio) ethyl phosphate, ethyl- (2′-trimethylammonio) Ethyl phosphorylethyl) fumarate, butyl- (2′-trimethylammonioethyl phosphorylethyl) fumarate, hydroxyethyl- (2′-trimethylammonioethyl phosphorylethyl) fumarate, ethyl- (2′-trimethylammonioethyl phosphorylethyl) Examples thereof include malate, butyl- (2′-trimethylammonioethyl phosphorylethyl) malate, and hydroxyethyl- (2′-trimethylammonioethyl phosphorylethyl) malate. Here, (meth) acryloyl means acryloyl and / or methacryloyl.
[0026]
Among these, 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate is preferable, and 2- (methacryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate (abbreviation: MPC). ) Is preferable in terms of availability.
[0027]
When the PC monomer is polymerized, one of the above PC monomers can be used alone, or two or more of them can be used as a mixture. The PC monomer can be produced by a known method. For example, a compound obtained by reacting a hydroxyl group-containing polymerizable monomer and 2-bromoethyl phosphoryl dichloride disclosed in JP-A-54-63025 in the presence of a tertiary base and a tertiary amine are reacted. A method in which a cyclic compound is obtained by the reaction of a hydroxyl group-containing polymerizable monomer and a cyclic phosphorus compound, and a ring-opening reaction with a tertiary amine, as shown in JP-A-58-154591, etc. Can be manufactured by.
[0028]
The glycerol mono (meth) acrylate of monomer B is a monoacrylic acid ester or monomethacrylic acid ester of glycerin.
[0029]
The hydrophobic monomer of monomer C has the formula (2)
[0030]
[Chemical 6]

[0031]
{Where R is⁶Represents a hydrogen atom or a methyl group, and L¹Is -C₆H_Four-, -C₆H_TenA group selected from-,-(C = O) O-, -O-,-(C = O) NH-, -O- (C = O)-, and -O- (C = O) -O-. L²Is a hydrogen atom or-(CH₂) P¹-L^Three,-((CH₂) P²-O) p¹-L^ThreeA hydrophobic functional group selected from p¹1-24, p²Indicates an integer from 3 to 5, L^ThreeIs a hydrogen atom or a methyl group, -C₆H_Five, -O-C₆H_FiveThe functional group chosen from is shown. }.
[0032]
Specific examples of the hydrophobic monomer C include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, methyl vinyl ether, butyl vinyl ether, vinyl acetate And vinyl propionate are preferred.
[0033]
Among the hydrophobic monomers of the monomer C, a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms is more preferable, specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, Examples include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.
[0034]
In the monomer composition constituting the PC polymer, other polymerizable monomers other than the monomer A, the monomer B, and the monomer C are mixed within a range that does not impair the effects of the present invention. May be. Specific examples of other polymerizable monomers include polyethylene glycol (meth) acrylate, 2-vinylpyrrolidone 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) ) Acrylate, (meth) acrylic acid, styrenesulfonic acid, (meth) acrylamide, (meth) acryloyloxyphosphonic acid, aminoethyl methacrylate, dimethylaminoethyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl Examples include trimethylammonium chloride.
[0035]
The PC polymer is a monomer composition comprising the PC monomer of monomer A, the glycerol mono (meth) acrylate of monomer B, and the hydrophobic monomer of monomer C as described above. It can be obtained by radical polymerization, but the adhesiveness to the fiber differs depending on the type of other polymerizable monomer, so it is desirable to select another polymerizable monomer in consideration of the properties of the fiber to be treated. . Among other monomers, from the viewpoint of imparting antifouling property of PC polymer and adhesion to fibers, hydroxyalkyl group containing 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc. Preferred examples include monomers and cationic monomers such as (meth) acryloyloxyethyltrimethylammonium chloride and 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride.
[0036]
The weight average molecular weight of the PC polymer is desirably in the range of 20,000 to 2,000,000, and more preferably in the range of 50,000 to 500,000. If the weight average molecular weight is less than 20,000, the adsorptive power of the polymer to the fiber is not sufficient, so that the washing resistance is poor. It is not preferable because it is difficult for the treatment agent to penetrate uniformly and it becomes difficult to sufficiently exhibit the antifouling property.
[0037]
  The fiber of the present inventionAntifouling and washing resistance imparting agent compositionCan be used in a solution of a PC polymer alone, but it is desirable to use a composition containing 0.05 to 10% by weight of a PC polymer and 0.05 to 10% by weight of a binder component, more preferably PC. A composition comprising 0.1 to 3% by weight of a polymer and 0.1 to 3% by weight of a binder component. When the concentration of the PC polymer is less than 0.05% by weight, the amount of the PC polymer adhering to the fiber is not sufficient, so that the antifouling effect cannot be sufficiently increased. This is not preferable because the polymer may remain and impair the flexibility of the fiber. When the concentration of the binder component is less than 0.05% by weight, the ability to attach the PC polymer to the fiber by the crosslinking reaction is not sufficient, so that the washing resistance cannot be sufficiently increased, and the concentration exceeds 10% by weight. In this case, the binder component remains, which is not preferable because the flexibility of the fiber may be impaired.
[0038]
  fiberAntifouling and washing resistance imparting agent compositionThe solvent is most preferably water, but it is also possible to use an alcohol solvent, a ketone solvent, an ester solvent, or a mixture of two or more solvents such as a mixture of water and alcohol. May be used as
[0039]
The binder component is used for the purpose of imparting durability by firmly fixing the PC polymer to the fiber surface by a bonding force such as chemical reaction, hydrophobic bond, ionic bond, etc., but acrylic resin, polyester resin Polymers generally used for fiber treatment such as glyoxal resins, epoxy resins, urethane resins, melamine resins, vinyl acetate resins, polyether resins, and cellulose resins can be used. The binder component is preferably a polymer having an amino group, a carboxyl group, a hydroxy group, or an epoxy group among the aforementioned polymers. Specifically, for example, polydimethylaminoethyl methacrylate and acrylic acid-alkyl methacrylate copolymer are used. Polymer, 2-hydroxyethyl methacrylate-methacrylic acid copolymer, poly-2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, polyethylene glycol-terephthalic acid polycondensate, terminal carboxylic acid polyethylene glycol, partial saponification Polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, poly-4-aminostyrene, polyethyleneimine, styrene-maleic acid copolymer, maleic acid-methyl vinyl ether copolymer, Chitosan, pullulan, casein, xanthan gum, collagen, hyaluronic acid, gelatin, alginic acid, dextran, and the like preferably.
[0040]
As the binder component, a copolymer of a monomer having an amino group, a carboxyl group, a hydroxy group, or an epoxy group and a PC monomer can also be used. Specific examples include MPC-methacrylic acid copolymer, MPC-2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride copolymer, MPC-2-hydroxyethyl methacrylate copolymer and the like. .
[0041]
  AboveCompositionTo treat fiber byThe pairA treatment method including a step of immersing the fiber in the composition and a step of drying and heat treatment at 40 to 190 ° C. is desirable, and a treatment method including a step of drying and heat treatment at 90 to 160 ° C. is more preferable. When the drying and heat treatment temperature is less than 40 ° C., the crosslinking reaction becomes difficult, so that the washing resistance is not sufficient. In some cases, the drying and heat treatment steps are preferably a two-stage method in which the drying is performed at 40 to 120 ° C. and then the heat treatment is performed at 100 to 190 ° C., and more preferably, the drying is performed at 80 to 105 ° C. Desirable to perform at 180 ° CThat's right.
[0042]
  The groupWhen the fiber is immersed in the composition, the impregnation amount is 20 to 200% by weight of the fiber weight.PairIt is desirable to move to a drying and heat treatment step after squeezing the composition solution, and more preferably to an impregnation amount of 50 to 120% by weight of the fiber weight.PairSqueezing the composition solution.
  The present inventionSet ofWhen fiber treatment is carried out using the composition, the form stabilizing agent, deodorant, adsorbent, surfactant, softener, solvent, dye, moisturizer, antibacterial agent are used as long as the effects of the present invention are not impaired. You may add other components, such as an agent and a fragrance | flavor. The present inventionSet ofThe composition is usually 1-40% by weight of PC polymer.Darkness ofBy condensing and diluting with water to a concentration of 0.05-10% by weight during treatmentOf the compositionIt is practically preferable to use a liquid.
[0043]
  The fibers used in the present invention may be yarn-like, string-like, or rope-like fibers, and they may be configured in a cloth shape. The material constituting the fiber may be any material that can be used for ordinary clothing, such as cotton, hemp, silk, wool, collagen fiber, acrylic fiber, rayon, nylon, vinylon, polyester. , Polypropylene, polyvinyl chloride, polyethylene, polymetaphenylene isophthalamide, aramid, polyarylate, and woven fabrics, knitted fabrics, nonwoven fabrics and the like of these blends. Among these, polyester, polyester-cotton blend, and nylon fibers are preferred because the antifouling effect of the present invention is particularly high. Main departureIn the lightThe fibers that can be treated include papers mainly composed of cellulose fibers such as tissue paper and toilet paper that may be used in contact with human skin.
[0044]
【The invention's effect】
The treated fiber obtained by the present invention has high antifouling properties with excellent washing resistance, and is also excellent in moisture absorption and antistatic properties.
[0045]
【Example】
Hereinafter, the present invention will be described in more detail based on examples.
[0046]
Analysis method of molecular weight of polymer
Detection is performed by gel permeation chromatography (GPC) using a phosphate buffer (pH 7.4, 20 mM) as an eluent, polyethylene glycol standard, UV (210 nm) and refractive index.
[0047]
Synthesis Example 1 (Polymer 1; MPC0.4-BMA0.2-GLM0.4, weight average molecular weight 341,000)
MPC; 11.2 g, butyl methacrylate (BMA); 2.7 g, glycerol methacrylate (GLM); 6.1 g dissolved in ethanol; 180 g, put into a four-necked flask, blown with nitrogen for 30 minutes, and then cooled to 50 ° C. And 0.85 g of azobisisobutyronitrile was added and allowed to undergo a polymerization reaction for 8 hours. The polymerization solution was added dropwise while stirring in 3 liters of diethyl ether, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.1 g of powder. The molecular weight evaluated by GPC was a weight average molecular weight of 341,000. This is polymer 1.
[0048]
Synthesis Example 2 (Polymer 2; MPC0.4-BMA0.4-GLM0.2, weight average molecular weight 294,000)
MPC; 11.4 g, BMA; 5.5 g, GLM; 3.1 g dissolved in ethanol; 180 g, put into a four-necked flask, blown with nitrogen for 30 minutes, and then azobisisobutyronitrile at 50 ° C .; 0.85 g was added and the polymerization reaction was carried out for 8 hours. The polymerization solution was added dropwise while stirring in 3 liters of diethyl ether, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.3 g of powder. The molecular weight evaluated by GPC was a weight average molecular weight of 294,000. This is polymer 2.
[0049]
Synthesis Example 3 (Polymer 3; MPC0.4-EHMA0.2-GLM0.4, weight average molecular weight 310,000)
MPC; 10.6 g, 2-ethylhexyl methacrylate (EHMA); 3.6 g, GLM; 5.8 g dissolved in ethanol; 180 g, put into a four-necked flask, blown with nitrogen for 30 minutes, and then azo Bisisobutyronitrile (0.85 g) was added and a polymerization reaction was carried out for 8 hours. The polymerization solution was added dropwise while stirring in 3 liters of diethyl ether, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.9 g of powder. The molecular weight evaluated by GPC was a weight average molecular weight of 310,000. This is polymer 3.
[0050]
Synthesis Example 4 (Polymer 4; MPC0.4-LMA0.2-GLM0.4, weight average molecular weight 293,000)
MPC; 10.1 g, lauryl methacrylate (LMA); 4.4 g, GLM; 5.5 g dissolved in ethanol; 180 g, put into a four-necked flask, blown with nitrogen for 30 minutes, and then azobisiso Butyronitrile; 0.85 g was added and a polymerization reaction was carried out for 8 hours. The polymerization solution was added dropwise with stirring in 3 liters of diethyl ether, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.3 g of powder. The molecular weight evaluated by GPC was a weight average molecular weight of 293,000. This is polymer 4.
[0051]
Synthesis Example 5 (Polymer 5; MPC0.6-BMA0.4, weight average molecular weight 168,000)
MPC; 15.1 g, BMA; 4.9 g dissolved in ethanol; 180 g, put into a four-necked flask, blown with nitrogen for 30 minutes, and then add azobisisobutyronitrile at 0.8 ° C. at 0.8 ° C. The polymerization reaction was carried out for 8 hours. The polymerization solution was added dropwise while stirring in 3 liters of diethyl ether, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.8 g of powder. The molecular weight evaluated by GPC was a weight average molecular weight of 168,000. This is designated as Polymer 5.
[0052]
Synthesis Example 6 (Polymer 6; MPC0.6-GLM0.4, weight average molecular weight 214,000)
MPC; 14.7 g, GLM; 5.3 g dissolved in ethanol; 180 g, put into a four-necked flask, blown with nitrogen for 30 minutes, and then added azobisisobutyronitrile at 0.8 ° C. at 0.8 ° C. The polymerization reaction was carried out for 8 hours. The polymerization solution was added dropwise while stirring in 3 liters of diethyl ether, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 15.1 g of powder. The molecular weight evaluated by GPC was a weight average molecular weight of 214,000. This is designated as Polymer 6.
[0053]
Test method
1. (Evaluation Test 1-1) Dirt Removal A Method
Put the test cloth (5cm x 5cm) with 10 hard balls in a stainless steel container containing 150mL of artificial oily soil liquid (beef tallow oil 0.15%, carbon black 0.01%, soap 0.10%). Rotate (40 ° C. × 20 minutes) to attach dirt and dry on filter paper. At this time, the degree of contamination of the test cloth is visually determined to obtain the initial degree of contamination. As shown in Table 1, there are five criteria. Next, the remaining state of the soil after the home laundry (JIS L-0217 103 method) is performed once is determined visually, and the degree of contamination after the first laundry is obtained. Further, the processed cloth is washed together with the contaminated cloth, and the recontamination of the dirt is visually determined as a recontamination confirmation cloth.
[0054]
Table 1
grade Judgment criteria
5 No dirt
4 Slightly dirty
3 A little dirty
2 There is a lot of dirt
1 There is a lot of dirt
[0055]
2. (Evaluation Test 1-2) Dirt Removal Method B
<Wipe method> 0.15 g of a soiling substance is dropped on the cloth, left for 3 minutes, wiped with a tissue, and the degree of contamination is visually judged according to the criteria shown in Table 1.
<Strong Contamination Method> Place 0.15 g of soil substance on the cloth and apply a load of 500 g for 1 minute. Then wipe off with a tissue and leave at room temperature for 15 hours. Next, after home washing (JIS L-0217 103 method) is performed once, the degree of contamination is visually determined based on the criteria in Table 1.
For the wiping method and the strong pollution method, the following five substances are used as soiling substances.
1. Soy sauce (manufactured by Sanbishi Co., Ltd., Sanbishi soy sauce special grade brewing);
2. Ink juice (made by Infugi Kogyo Co., Ltd., calligraphy ink, ink); an aqueous dispersion containing an adhesive component,
3. Fish blood; water-based substances;
4). Lipstick (LANCOME PARIS 313 ROUGE AZIEQUE MAT); oily solid substance,
5. Dirty motor oil (manufactured by Nippon Oil Co., Ltd., industrial extreme pressure gear oil, Bonnock M220); oily substance.
[0056]
3. (Evaluation test 2) Water absorption test
JIS L-1096, 6.26, Method A; Water absorption test is performed by the dropping method.
[0057]
4). (Evaluation Test 3) Moisturizing test
The treated test cloth is left in a desiccator at a temperature of 20 ° C. and a relative humidity (RH) = 80% for 2, 5 and 24 hours to measure the weight of the cloth. Next, the treated test cloth is transferred to a desiccator with RH = 35%, and the same test is performed. The moisturizing rate is defined as follows. The weight of the treated test cloth after vacuum drying for 8 hours is defined as the weight of the absolutely dry cloth.
Moisturizing rate (%) = {(weight of cloth after each time−weight of absolutely dry cloth) / (weight of absolutely dry cloth)} × 100
[0058]
5. (Evaluation Test 4) Chargeability test
The chargeability test is conducted according to JIS L-1094, method A; half-life measurement method, and JIS L-1094, method B.
[0059]
Example 1-1
100% cotton, 100% polyester (abbreviated as E100% in the table), polyester / cotton blend (polyester: cotton = 65: 35, E / C in the table) A test cloth of the following formula 1 using a hydroxyalkyl group-containing acrylic ester resin binder (manufactured by Daiwa Chemical Industry Co., Ltd., product name Vinetex A-30G) is prepared. Was applied using a mangle and dried at 105 ° C. for 5 minutes. Thereafter, using a pin tenter, a dry heat treatment was performed at 150 ° C. for 2 minutes to obtain an antifouling cloth.
Formula 1
PC polymer; Polymer 1 50g / L
Binder; Vinetex A-30G 50g / L
[0060]
Example 1-2
A treated cloth was obtained by the same operation as in Example 1 except that the treatment liquid was changed to the following formulation 2.
Formula 2
PC polymer; Polymer 2 50g / L
Binder; Vinetex A-30G 50g / L
[0061]
Example 1-3
A treated cloth was obtained in the same manner as in Example 1 except that the treatment liquid was changed to the following formulation 3.
Formula 3
PC polymer; Polymer 3 50g / L
Binder; Vinetex A-30G 50g / L
[0062]
Example 1-4
A treated cloth was obtained by the same operation as in Example 1 except that the treatment liquid was changed to the following formulation 4.
Formula 4
PC polymer; Polymer 4 50g / L
Binder; Vinetex A-30G 50g / L
[0063]
  Comparative Example 1-1 The treatment liquid used was a perfluorooctylethyl methacrylate-polyethylene glycol monomethacrylate-polypropylene glycol monomethacrylate copolymer (weight ratio = 50: 35: 15, hereinafter abbreviated as F copolymer). belowFormula 5A treated cloth was obtained by the same operation as in Example 1 except that.
  Formula 5
  F copolymer 50g / L
[0064]
  Comparative Example 1-2Formula 6A treated cloth was obtained by the same operation as in Example 1 except that.
  Formula 6
  PC polymer; polymer 5 50g / L
  Binder; Vinetex A-30G 50g / L
[0065]
  Comparative Example 1-3Formula 7A treated cloth was obtained by the same operation as in Example 1 except that.
  Formula 7
  PC polymer; polymer 6 50g / L
  Binder; Vinetex A-30G 50g / L
[0066]
Comparative Example 1-4
The test cloth used in Example 1 was used as an untreated test cloth.
[0067]
Example 2
The evaluation test was performed using the treated test cloths obtained in Examples 1-1 to 1-4 (indicated in the table as the initial cloth). Moreover, the said evaluation test was similarly done about the treatment test cloth which performed the washing | cleaning test cloth obtained in Examples 1-1 to 1-4 30 times (it displayed as L-30 in the table | surface). .
The results of (Evaluation Test 1-1) are shown in Table 2. The numerical values a / b / c in Table 2 are a degree of initial contamination, b a degree of contamination after one wash, and c a degree of contamination of the recontamination confirmation cloth.
The results of (Evaluation Test 1-2) are shown in Tables 3 and 4. The numerical values a / b in Tables 3 and 4 are the degree of contamination of the wiping method and b of the strong contamination method, respectively.
The results of (Evaluation Test 2) are shown in Table 5.
The results of (Evaluation Test 3) are shown in Table 6.
The results of (Evaluation Test 4) are shown in Table 7.
[0068]
Comparative Example 2
The evaluation test was conducted in the same manner as in Example 2 using the treated test cloths obtained in Comparative Examples 1-1 to 1-4, and the results are shown in Tables 2-7.
[0069]
[Table 1]

[0070]
[Table 2]

[0071]
[Table 3]

[0072]
[Table 4]

[0073]
[Table 5]

[0074]
[Table 6]

[0075]
From the above results, Examples 1-1 to 1-4 using the PC polymer of the present invention were compared with Comparative Examples 1-1 to 1-4 in the stain removal test and the stain removal test for various stains. It can be seen that all the fabrics of 100% cotton, polyester / cotton blend, and 100% polyester exhibit excellent effects.
From Tables 5, 6 and 7, it can be seen that the fabric treated with the fiber treatment agent of the present invention exhibits excellent effects in water absorption, moisture retention tests and chargeability tests.

Claims (8)

A structural unit based on the following monomer A, a structural unit based on glycerol mono (meth) acrylate (monomer B), and a structural unit based on another hydrophobic monomer (monomer C), An antifouling and washing resistance imparting agent for fibers comprising a polymer having a molecular weight of 20,000 to 2,000,000 as an active ingredient.
Monomer A; the following formula (1)

[Wherein X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, Z represents a hydrogen atom or R ⁵ —O— (C═O) — (where R ⁵ represents An alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m shows the integer of 0-20. n shows the integer of 1-4. A phosphorylcholine-like group-containing monomer represented by the formula: An antifouling and washing resistance imparting agent for fibers, comprising as an active ingredient a phosphorylcholine-like group-containing polymer obtained by polymerizing a monomer composition containing the following monomer A, monomer B, and monomer C.
Monomer A; the following formula (1)

[Wherein X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, Z represents a hydrogen atom or R ⁵ —O— (C═O) — (where R ⁵ represents An alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m shows the integer of 0-20. n shows the integer of 1-4. A phosphorylcholine-like group-containing monomer represented by the formula:
Monomer B; glycerol mono (meth) acrylate.
Monomer C; the following formula (2)

{In the formula, R ⁶ represents a hydrogen atom or a methyl group, and L ¹ represents —C ₆ H ₄ —, —C ₆ H ₁₀ —, — (C═O) O—, —O—, — (C═ O) represents a group selected from NH—, —O— (C═O) —, —O— (C═O) —O—, and L ² represents a hydrogen atom or — (CH ₂ ) p ¹ -L ^3. , - shows a ^{_{((CH 2) p 2 -O}} ) hydrophobic functional group selected from p ¹ -L ^3. p ¹ represents an integer of ¹ to 24, p ² represents an integer of 3 to 5, and L ³ represents a functional group selected from a hydrogen atom or a methyl group, —C ₆ H ₅ , —O—C ₆ H ₅ . } The hydrophobic monomer represented by this. The antifouling and washing resistance imparting agent for fibers according to claim 1 or 2, wherein the phosphorylcholine-like group-containing monomer is 2-((meth) acryloyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate. . Hydrophobic monomers of the monomer C has an alkyl group having 1 to 18 carbon atoms (meth) fibers for antifouling and anti according to claim 1 is an acrylic acid ester Washing agent . The phosphorylcholine-like group-containing polymer comprises 10 to 90% by weight of the monomer A phosphorylcholine-like group-containing monomer, 5 to 80% by weight of the glycerol mono (meth) acrylate of the monomer B, and the monomer C. A polymer obtained by polymerizing a monomer composition containing 5 to 60% by weight of a hydrophobic monomer having a weight average molecular weight in the range of 20,000 to 2,000,000. 5. The antifouling and washing resistance imparting agent for fibers according to any one of 4 An antifouling and washing resistance imparting composition for fibers comprising 0.05 to 10% by weight of the phosphorylcholine-like group-containing polymer according to any one of claims 1 to 5. 6. Textile antifouling and washing resistance imparting agent composition further comprising 0.05 to 10 wt% Ba Indah component. The antifouling and washing resistance imparting agent composition for fibers according to claim 7, wherein the binder is a polymer having a group selected from any of amino groups, carboxyl groups, hydroxy groups, and epoxy groups.