JP3752713B2 - Fiber processing method with high friction durability - Google Patents

Description

【００１４】
上記の親水性化合物は、いわゆるナイロン用フィックス剤として用いられる公知の化合物であり容易に入手できる。
処理工程１における処理剤１は、上記の特定の親水性化合物および水系媒体を含む。水系媒体としては、水または水と水溶性有機溶剤との混合物が挙げられるが、水のみが好ましい。水溶性有機溶剤としては、水溶性アルコール、グリコール類等が挙げられる。また、水系媒体中の該親水性化合物の量は、０．０２〜０．８重量％が好ましく、特に０．０４〜０．５重量％が好ましい。
【００１５】
処理剤１の処理量は、繊維の１００重量部に対して親水性化合物の量が１．０〜１５．０重量部であり、特に２．０〜１０重量部が好ましい。親水性化合物の量が１．０重量部未満では、洗濯耐久性は発現するものの、より厳しい性能である摩擦に対する耐久性は発現しない。また、親水性化合物の量が繊維の１００重量部に対して１５．０重量部以上である場合、撥水性の発現を阻害したり、風合いが硬くなるという欠点があり好ましくない。上記の親水性化合物は、フィックス剤として知られるものであるが、通常は染料の固着性向上を目的として用いられるものであり、その処理濃度も少ないものである。しかし、本発明は、この親水性化合物を通常よりも高濃度範囲で用いることによって、撥水撥油剤の性能を低下させることなく、摩擦耐久性向上という新しい機能を見いだしたものである。
【００１６】
処理剤１には、上記親水性化合物以外の、他の添加成分を配合することもできる。添加成分としては加工浴のｐＨを調整し、繊維表面への吸着を促進する目的で、酢酸、ギ酸等の有機酸を含有させてもよい。
【００１７】
処理工程１における処理方法としては、吸着を確実に行える点から吸尽法が好ましい。処理温度は特に限定されず、５０〜８０℃程度が好ましく、処理時間は１０〜３０分が好ましい。
【００１８】
本発明においては、繊維を処理工程１で処理した後に処理工程２または処理工程２’で処理するが、処理工程１の後に、過剰に処理された親水性化合物を除去しておくのが好ましい。除去方法としては、通常の場合、水洗による方法が挙げられる。水洗が不充分であると処理剤２または処理剤２’中の微粒子が凝集、沈降等を発生したり、撥水性発現効果を阻害する。また、必要に応じて処理剤２または処理剤２’の処理前に、繊維を乾燥させておくのが好ましい。
【００１９】
処理工程２は、水系媒体中でのゼータ電位が０以上であるＲ ^ｆ 基含有化合物を含む微粒子と水系媒体とを含み、かつ、該微粒子がＲ ^ｆ 基含有重合性単量体の重合した単位を含む重合体の２種以上からなる微粒子である処理剤２を用いて繊維を処理する工程である。
また、処理工程２’は、水系媒体中でのゼータ電位が０以上であるＲ ^ｆ 基含有化合物を含む微粒子と水系媒体とを含み、かつ、該微粒子がＲ ^ｆ 基含有重合性単量体の重合した単位を含む重合体の１種以上とＲ ^ｆ 基を含有しない重合体の１種以上からなる微粒子である処理剤２’を用いて処理する工程である。
【００２０】
該処理剤２または２’に含まれる微粒子は、水系媒体中での表面電位（ゼータ電位）が０以上である微粒子である。ゼータ電位がマイナスであると繊維表面、特にウール繊維表面への微粒子の吸着阻害が起こるおそれがあり、撥水性や摩擦耐久性も低下するおそれがある。ゼータ電位は＋１０ｍＶ〜＋８０ｍＶが好ましい。
また、該微粒子はＲ^ｆ基含有化合物を含む。Ｒ^ｆ基を含有する化合物は、通常の繊維用の撥水撥油処理に用いられる公知ないしは周知の化合物が採用され、Ｒ^ｆ基含有重合性単量体の重合した単位を含む重合体である。
【００２１】
ここで、Ｒ^ｆ基は、アルキル基の水素原子の２個以上がフッ素原子に置換された基である。該アルキル基の水素原子のうちフッ素原子に置換されない水素原子は、塩素原子に置換されていてもよい。また、フッ素原子に置換されない水素原子は、Ｒ^ｆ基中の末端部分に存在していてもよい。Ｒ^ｆ基中のフッ素原子の割合は、［（Ｒ^ｆ基中のフッ素原子の数）／（Ｒ^ｆ基中のフッ素原子の数＋Ｒ^ｆ基中の水素素原子の数）］×１００（％）が６０％以上である場合が好ましく、特に８０％以上である場合が好ましい。また、Ｒ^ｆ基は塩素原子を含んでいてもよい。
【００２２】
Ｒ^ｆ基は、直鎖または分岐の構造が好ましく、特に直鎖の構造が好ましい。分岐の構造である場合には、分岐部分がＲ^ｆ基の末端付近に存在することが好ましい。また、分岐部分は炭素数が１〜４程度の短鎖である場合が好ましい。また、Ｒ^ｆ基の炭素数は４〜２０が好ましく、特に６〜１６が好ましい。Ｒ^ｆ基は、上記のフッ素原子の割合が実質的に１００％である場合のペルフルオロアルキル基またはペルフルオロアルキル基部分を含有するＲ^ｆ基が好ましい。ペルフルオロアルキル基も直鎖の構造が好ましい。直鎖のペルフルオロアルキル基としては、ＣＦ_３（ＣＦ_２）_ｋ−［ただし、ｋは３〜１９の整数である。］で表される基が好ましい。
【００２３】
Ｒ^ｆ基を含有する重合性単量体（以下、Ｒ^ｆ基含有重合性単量体と記す。）は、上記のＲ^ｆ基と重合性不飽和基を有する化合物を意味する。Ｒ^ｆ基含有重合性単量体のＲ^ｆ基は、上記のＲ^ｆ基と同様の意味を示し、好ましい態様も同じである。さらに、Ｒ^ｆ基含有重合性単量体は、Ｒ^ｆ基の炭素数の異なる化合物の２種以上の混合物であってもよく、その場合、Ｒ^ｆ基の平均炭素数は６以上が好ましい。
【００２４】
Ｒ^ｆ基含有重合性単量体としては、前記のＣＦ_３（ＣＦ_２）_ｋ−［ただし、ｋは３〜１９の整数である。］で表されるペルフルオロアルキル基と重合性不飽和基を有するペルフルオロアルキル基含有重合性単量体が好ましい。ペルフルオロアルキル基含有重合性単量体は、ｋの数の異なる化合物の２種以上の混合物であってもよいが、ｋの平均が６以上である場合が好ましい。６未満であると撥水撥油性が低くなり、目的の機能を発現しないおそれがある。ｋの値、またはｋの平均は、６〜１６が好ましく、特に８〜１４が好ましく、さらに９〜１２が好ましい。ｋの値が大きすぎるものは常温で固体状であり、昇華性も高く、取扱いが困難である。
【００２５】
Ｒ^ｆ基含有重合性単量体において、上記のＲ^ｆ基と重合性不飽和基とは、直接または結合基を介して間接的に結合しており、間接的に結合している場合が好ましい。結合基としては、２価以上の結合基が好ましく、特に２価の結合基が好ましく、アルキレン結合、エステル結合、アミド結合、アミノ結合、ウレタン結合、エーテル結合、フェニレンオキシ結合、スルホニル結合、またはこれらの結合を含む結合基が好ましい。これらのＲ^ｆ基含有重合性単量体は、公知ないしは周知の化合物が採用できる。また、Ｒ^ｆ基含有重合性単量体は、Ｒ^ｆ基含有アルコール、Ｒ^ｆ基含有カルボン酸、Ｒ^ｆ基含有スルホン酸等から公知の方法で容易に合成できる。
【００２６】
Ｒ^ｆ基含有重合性単量体としては、Ｒ^ｆ基の１個が、重合性不飽和基と２価の結合基を介して連結している構造の化合物が好ましい。例えば、Ｒ^ｆ基含有アクリレート、Ｒ^ｆ基含有メタクリレート、Ｒ^ｆ基含有スチレン、Ｒ^ｆ基含有ビニルエステル、Ｒ ^ｆ基含有フマレート等が好ましい。
【００２７】
さらに、Ｒ^ｆ基含有重合性単量体は、汎用性の点から、特に、上記のＲ^ｆ基含有アクリレートまたはメタクリレートが好ましい。なお、以下においてアクリレートとメタクリレートとを総称して（メタ）アクリレートと記す。Ｒ^ｆ基含有（メタ）アクリレートは、他のモノマーとの重合性、およびウール繊維表面に形成された皮膜の柔軟性、接着性、溶解性、乳化重合の容易性等の観点からも有利である。
【００２８】
Ｒ^ｆ基含有重合性単量体の具体例を以下に挙げるが、これらに限定されない。なお、以下においてＲは水素原子またはメチル基を示す。
【００２９】
CF₃(CF₂)₉(CH₂)₂OCOCR=CH₂、
(CF₃)₂CF(CF₂)₆(CH₂)₂OCOCR=CH₂ 、
CF₂Cl(CF₂)₉(CH₂)₃OCOCR=CH₂、
HCF₂(CF₂)₉(CH₂)₂OC(O)CR=CH₂ 、
CF₃(CF₂)₉(CH₂)₁₁OCOCR=CH₂ 、
CF₃(CF₂)₉CONH(CH₂)₅OCOCR=CH₂、
CF₃(CF₂)₇SO₂N(C₃H₇)C₂H₄OCOCH=CH₂、
CF₃(CF₂)₉O(CF₂)₂(CH₂)₂OCOCR=CH₂ 、
CF₃(CF₂)₉CH₂COOCH=CH₂ 、
CF₃(CF₂)₉(CH₂)₂COOCH=CH₂、
CF₃(CF₂)₉(CH₂)₃OCOCR=CH₂。
【００３０】
CF₃(CF₂)₇(CH₂)₂OCH=CH₂、
CF₃(CF₂)₇CH₂CF₂CH₂CH₂OCOCR=CH₂、
CF₃(CF₂)₇(CH₂)₄OCOCR=CH₂、
CF₃(CF₂)₇CONH(CH₂)₃CH=CH₂ 、
CF₃(CF₂)₉CONH(CH₂)₂CH=CH₂ 、
CF₃(CF₂)₁₃SO₂NH(CH₂)₂CH=CH₂ 、
CF₃(CF₂)₁₃(CH₂)₆OCOCR=CH₂ 、
HCF₂(CF₂)₉CH=CH₂。
【００３１】
Ｒ^ｆ基含有重合性単量体の重合した単位を含む重合体は、Ｒ^ｆ基含有重合性単量体の重合した単位の１種以上を含む重合体、または、Ｒ^ｆ基含有重合性単量体の重合した単位の１種以上と他の重合性単量体の重合した単位の１種以上を含む重合体のいずれであってもよい。しかし、目的とする性能をより発現させるためには、該重合体中のフッ素含量は、重合体中に５０〜７０重量％とするのが好ましい。
【００３２】
該他の重合性単量体は、上記のＲ^ｆ基含有重合性単量体と重合可能な不飽和基を含有する化合物であれば特に限定されない。また他の重合性単量体は１種以上を用いることができ、２種以上の場合には任意の割合で用いることができる。なお以下において、他の重合性単量体を共重合性モノマーと記す。
【００３３】
共重合性モノマーとしては、（メタ）アクリレート類、（メタ）アクリルアミド類、ビニルエーテル類、ビニルエステル類、フマレート類、マレエート類等が挙げられる。これらの共重合性モノマーは、炭化水素基やベンゼン環を有する場合が好ましく、特に炭化水素基を有する場合が好ましい。また共重合性モノマーとしては、塩化ビニル、エチレン、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、クロロトリフルオロエチレン、スチレン類等であってもよい。
【００３４】
共重合性モノマーは、エポキシ基、ハロゲン原子、水酸基、アミド基、アミノ基、イミノ基、アルコキシシリル基、Ｎ−メチロール基、Ｎ−アルキルオキシアルキル基、ブロック化されたイソシアネート基等の重合性不飽和基以外の反応性基を含有する共重合性モノマーであってもよい。たとえば、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジイソプロピル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、γ−トリメトキシシリルプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート等が好ましい。
【００３５】
ブロック化されたイソシアネート基を有する共重合性モノマーとしては、水酸基含有（メタ）アクリレートとポリイソシアネート化合物とを少なくとも１個のイソシアネート基が残る割合で反応させて得られた反応生成物のブロック化物、水酸基含有（メタ）アクリレートに少なくとも１個のブロック化イソシアネート基と少なくとも１個のイソシアネート基とを有するポリイソシアネート化合物を反応させた反応生成物等が好ましい。
【００３６】
ここで、水酸基含有（メタ）アクリレートとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ジエチレングリコールモノ（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、ポリ（オキシエチレン／オキシプロピレン）グリコールモノ（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、トリメチロールプロパンモノ（メタ）アクリレート等が好ましい。
【００３７】
また、ポリイソシアネート化合物としては、ヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ポリイソシアネート、またはイソホロンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、シクロヘキシレンジイソシアネート、ビス（イソシアネートメチル）シクロヘキサン等の脂環族ポリイソシアネート、およびそれらのヌレート変性体、プレポリマー変性体、ビュレット変性体等が挙げられ、脂肪族ジイソシアネートまたは脂環族ジイソシアネートが好ましい。
【００３８】
また、ブロック化剤としては、オキシム類、アルキルケトオキシム類、フェノール類、β−ジケトン類、マロン酸エステル類、ラクタム類、アルカノール類等が挙げられる。具体的には、シクロヘキサンオキシム、メチルエチルケトオキシム、フェノール、クレゾール、アセチルアセトン、マロン酸ジエチル、イソプロパノール、ｔ−ブタノール、ε−カプロラクタム、マレイン酸イミド、重亜硫酸ナトリウム等が挙げられ、シクロヘキサンオキシム、メチルエチルケトオキム等が好ましい。
【００３９】
処理剤２における微粒子は、（１）Ｒ^ｆ基含有重合性単量体の重合した単位を含む重合体の２種以上からなる微粒子であり、処理剤２’における微粒子は、（２）Ｒ^ｆ基含有重合性単量体の重合した単位を含む重合体の１種以上とＲ^ｆ基を含有しない重合体の１種以上からなる微粒子である。（１）または（２）の微粒子であると、処理剤１との組み合わせで、さらに、高い摩擦耐久性を得ることができる。
【００４０】
微粒子が（１）Ｒ^ｆ基含有重合性単量体の重合した単位を含む重合体の２種以上からなる微粒子である場合、該重合体は、それぞれ、異なるＲ^ｆ基含有重合性単量体の重合した単位を含む重合体、または、フッ素含有量の異なる重合体であるのが好ましい。
【００４１】
また、微粒子が（２）Ｒ^ｆ基含有重合性単量体の重合した単位を含む重合体の１種以上とＲ^ｆ基を含有しない重合体の１種以上からなる微粒子である場合、Ｒ^ｆ基含有重合性単量体の重合した単位を含む重合体の１種とＲ^ｆ基を含有しない重合体の１種からなる微粒子が好ましい。Ｒ^ｆ基を含有しない重合体は、前記の共重合性モノマーから選ばれる１種以上の重合性単量体の重合した単位を含む重合体であるのが好ましい。共重合モノマーとしては上述の共重合モノマーから１種以上を任意に選択できる。
【００４２】
前記の（１）または（２）の微粒子は、いわゆるコアシェル型の微粒子として水系媒体中に存在しているのが摩擦耐久性向上の点から好ましい。コアシェル型の微粒子とは、微粒子が前記の２種以上の異なる重合体を含み、微粒子外殻には、より親水性の重合体部位が、微粒子内殻には、より疎水性の重合体部位が存在する粒子の形態をいう。
【００４３】
このようなＲ^ｆ基含有重合性単量体の重合した単位を含む重合体の微粒子の合成方法としては特に限定されず、公知ないしは周知の重合方法が採用でき、乳化重合法または分散重合法で重合するのが好ましい。特に、コアシェル型の微粒子を製造する場合には、いわゆるシード重合法等の多段階の重合法を採用するのが好ましい。
【００４４】
重合時に乳化剤を用いる場合には、微粒子のゼータ電位の観点からノニオン型、カチオン型、両性型の公知ないしは周知の乳化剤から選ばれる１種以上が採用できるが、アニオン性の乳化剤は好ましくない。乳化剤の量は、重合性単量体の１００重量部に対して、０．５〜２０重量部が好ましく、特に、撥水撥油性および分散液の安定性の点から１〜１０重量部程度が好ましい。
【００４５】
重合媒体としては、水または水に有機溶剤を含ませたものが挙げられる。有機溶剤としては水溶性の有機溶剤が好ましく、エステル系、ケトン系、エーテル系等の有機溶剤が好ましい。エステル系の有機溶剤としては、酢酸エチル、酢酸ブチル、コハク酸ジエチル等が好ましく、ケトン系の有機溶剤としては、メチルエチルケトン、メチルイソブチルケトン、アセトン等が好ましく、エーテル系の有機溶剤としては、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、グリコール、およびこれらのモノメチルエーテルまたはジメチルエーテル、ジエチルエーテル等が好ましい。これらのうち、有機溶剤としては、引火性が低い等の点からエーテル系の有機溶剤が好ましい。水と有機溶剤の比率は特に限定されず、いずれの割合であってもよい。
【００４６】
重合開始剤としては、水溶性または油溶性の重合開始剤が好ましく、アゾ系、過酸化物系、レドックス系等の汎用の開始剤が重合温度に応じて使用できる。重合温度は特に限定されないが、２０℃〜１５０℃が好ましい。重合終了後のゼータ電位をプラスにするためにはアゾアミジン類の開始剤が特に好ましい。
【００４７】
重合反応は、重合を開始する前段階として重合性単量体、水および乳化剤からなる混合物を、ホモミキサーまたは高圧乳化機等で処理し、あらかじめ前分散させた後に実施するのが好ましい。
【００４８】
処理剤２または処理剤２’における微粒子は、エマルジョンまたはディスパージョンとして水系媒体中に存在するのが好ましい。
【００４９】
処理剤２または処理剤２’は、Ｒ^ｆ基含有化合物の濃度が水系媒体の１００重量部に対して１〜５０重量部程度であるのが好ましく、該濃度となるように水で調整するのが好ましい。濃度は目的や組成物の形態によって適宜変更され得る。また、処理剤２または処理剤２’の処理量は処理剤１を処理する前の繊維の１００重量部に対して固形分濃度で０．１〜１０重量部が好ましく、特に０．２〜５重量部が好ましい。処理剤２または処理剤２’の処理量が少ないと、摩擦耐久性が低下するおそれがある。
【００５０】
さらに、処理剤２または処理剤２’には、上記以外の添加成分を配合することもできる。たとえば、他の撥水剤や撥油剤、架橋剤、防虫剤、難燃剤、帯電防止剤、防シワ剤などの添加剤を適宜添加併用することが可能である。
【００５１】
処理工程２または処理工程２’は、通常のパディング法、または、吸尽法等の処理方法で実施するのが好ましく、処理の簡便性の点からパディング法が好ましい。
【００５２】
本発明の繊維処理方法は、特にポリアミド構造を有する各種繊維に有効な方法であり、さらにウール繊維に適した処理方法である。ウール繊維としては、ウール繊維およびウール繊維と他の繊維との混紡繊維のいずれであってもよい。また、該ウール繊維は、繊維製品となっていてもよく、スーツ、スポーツウェア等の外衣類、作業着、ユニフォーム類が挙げられる。また、ウール以外の繊維としてはナイロン等が挙げられる。
【００５３】
本発明の繊維処理方法によればこれらの繊維に撥水撥油性、防汚性、その耐洗濯性、耐ドライクリーニング性を付与できる。そしてさらに、摩擦に対する耐久性に優れたこれらの性能を付与できる。
【００５４】
【実施例】
以下、本発明を実施例および比較例を挙げて具体的に説明するが、本発明はこれらの例に限定されない。なお、実施例における各種評価は以下に示す方法および基準にしたがって実施した。
【００５５】
［撥水性の評価方法］
ＪＩＳ−Ｌ−１０９２のスプレー法による撥水性ナンバー（表１参照）で表した。通常シャワー水温は２７℃とした。なお、下記の撥水性ナンバーに＋（−）印を付して表した評価結果は、それぞれの評価がナンバーで表したものよりもわずかに良い（悪い）ものを示す。
【００５６】
［ドライクリーニング方法］
ＪＩＳ−Ｌ−１０９２．３．２．（２）記載の方法にしたがった。
【００５７】
［摩擦耐久後降雨試験の評価方法］
試料を湿綿布を装着したピリングテスタで５分間摩擦（押し圧４５０ｇ）した後に、ＪＩＳ−Ｌ−１０９２（Ｃ）法記載の方法（ブンデスマン試験）にしたがい、降雨量を１００ｃｃ／分、降雨水温を２０℃、降雨時間１０分とする条件で降雨させ、表面の濡れ状態を表１の撥水性ナンバーにしたがって判定した。
【００５８】
［撥油性の評価方法］
表２に示す試験溶液を試験布上の２ケ所に数滴（径約４ｍｍ）置き、３０秒後の浸透状態により判別した（ＡＡＴＣＣ−ＴＭ１１８−１９６６）。
【００５９】
【表１】

【００６０】
【表２】

【００６１】
［参考例１］処理剤２の製造例
ペルフルオロアルキルエチルアクリレート［Ｃ _ｑ Ｆ_{２ｑ ＋１}（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２：ｑは、６、８、１０、１２、１４、１６の混合物で、平均は９である。］（以下ＦＡと記す。）３０１３ｇ、ドデシルメルカプタン５５．８ｇ、ノニオン系乳化剤のポリオキシエチレン２級アルキルエーテル１５５ｇ、カチオン性乳化剤のアルキルジメチルアミン酢酸塩１５．５ｇ、水５０３２ｇをホモジナイザーで前分散した後、高圧ホモジナイザー（マントンゴウリン社製乳化機）を用いて、４００ｋｇ／ｃｍ^２で処理し乳化液を得た。
【００６２】
乳化液の７０００ｇを１０リットルのステンレス製オートクレーブにいれ、アゾビスイソブチロニトリル３９．８ｇを加えた後、窒素置換した。６０℃に昇温後、８時間重合させた（固形分３８．８％（重合収率９７．０％））。１０リットルステンレス製オートクレーブに、上記のポリマー分散液（固形分濃度３８．８％）の５０００ｇ（固形分１９４０ｇ；１００重量部）、ＦＡの３４９ｇ（６０重量部）、シクロヘキシルメタクリレートの１７５ｇ（３０重量部）、グリシジルメタクリレートの５８．２重量部（１０重量部）を仕込んだ。
【００６３】
さらにジプロピレングリコールモノメチルエーテル２５２ｇ、水３５９ｇを加え、総固形分量が４０重量％になるように調整した。混合物を撹拌した後、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩２５．０ｇを加え、窒素置換の後、６０℃で１５時間重合させた。冷却後、分散液を取り出した。固形分濃度は３８．２重量％であった。エマルジョン粒子の透過型電子顕微鏡観察を行ったところ、得られた粒子はコアシェル構造を有する粒子径約０．２μｍの微粒子であった。またｐＨ６の水溶液のエマルジョンのゼータ電位は＋１６ｍＶを示した。得られた分散液の固形分濃度を２０重量％に調整して処理剤２原液とした。
【００６４】
［参考例２］ゼータ電位がマイナスである撥水剤ラテックスの製造例
参考例１で用いたカチオン性乳化剤のアルキルジメチルアミン酢酸塩の代わりに、アニオン性乳化剤のポリオキシエチレンラウリル硫酸ナトリウムを使用する以外は、参考例１と同様の操作によりペルフルオロアルキル基含有水性分散体を得て、撥水剤ラテックスを調整した。得られたエマルジョンのゼータ電位はｐＨ７で−６ｍＶを示した。
【００６５】
［参考例３］処理剤２’の製造例
ＦＡ３１００ｇ、ステアリルアクリレート１６５０ｇ、２−ヒドロキシエチルメタクリレート１６５ｇ、Ｎ−メチロールアクリルアミド８５ｇ、ドデシルメルカプタン１３ｇ、ポリオキシエチレン２級アルキルエーテル３００ｇ、アルキルジメチルアミン酢酸塩３０ｇ、ジプロピレングリコールモノメチルエーテル２０００ｇ、水５０００ｇを、６０℃においてホモジナイザーで前分散した後、高圧ホモジナイザー（マントンゴウリン社製乳化機）を用いて、６０℃、４００ｋｇ／ｃｍ^２で処理し白色乳化液を得た。
【００６６】
乳化液の７０００ｇを１０リットルのステンレス製オートクレーブにいれ、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩２５．０ｇを加えた後、窒素置換した。６０℃に昇温後、１２時間重合させた（固形分４０．９％（重合収率９４％）。冷却後、分散液を取り出した。エマルジョン粒子の透過型電子顕微鏡観察を行ったところ、得られた粒子は粒子径約０．１５μｍの微粒子であった。またｐＨ６の水溶液のエマルジョンのゼータ電位は＋２０ｍＶを示した。得られた分散液の固形分濃度をイオン交換水で２０重量％に調整して処理剤２’原液とした。
【００６７】
［実施例１］
（処理工程１）
親水性化合物（前記式（１）におけるｎが２〜５、ｍが１の混合物であり、平均分子量が１８００の化合物）を０．２７ｇ、イオン交換水３００ｇを５００ｍｌビーカーにいれ、ここにウールトロピカル布（布重量１０．０ｇ）を浸漬し、これをウォーターバスに装着した（布重量１００に対する親水性化合物の重量は２．７重量％、浴比約１：３０、加工浴中の親水性化合物の濃度０．０９％）。浴温度を７０℃にあげ、ゆっくり撹拌しながらそのまま１５分保持した後に布帛を取り出し、イオン交換水で充分洗浄し、風乾した。
【００６８】
（処理工程２）
参考例１で製造した処理剤２原液（固形分濃度２０％）８％、メラミン樹脂（住友化学社製スミテックスレジンＭ３）０．３％、触媒（住友化学社製スミテックスアクセラレーターＡＣＸ）０．３％、イソプロパノール１．５％を含む加工浴水溶液を調製し、これに処理工程１のウールトロピカル布を浸漬、２本のゴムローラーの間で布をしぼって、ウエットピックアップを６０重量％とした（浸漬と絞りをそれぞれ２回ずつ繰り返した）。ついで、処理布を１１０℃で９０秒間乾燥し、さらに１５０℃で６０秒間熱処理し、試験布を得た。得られた試験布について撥水撥油性能を測定したところ、撥水性ナンバーは１００、撥油性ナンバーは６であった。
【００６９】
また、摩擦後降雨試験を上記で得られた試験布について行ったところ撥水性ナンバーは９０であった。さらに、この試験布を同様の方法で５回繰り返しドライクリーニングを行った後、９０℃で６０秒間乾燥し摩擦後降雨試験を実施したところ、撥水性ナンバーは８０を維持していた。
【００７０】
［実施例２］
親水性化合物の量を０．５４ｇ使用する以外は実施例１と同様に処理工程１（布重量１００に対する親水性化合物の重量は５．４重量％、浴比約１：３０、加工浴中の親水性化合物の濃度０．１８％）、つぎに処理工程２を経て試験布を得た。得られた試験布の初期撥水性、撥油性、摩擦後降雨試験後の撥水性はそれぞれ、１００、６、１００−であった。さらにドライクリーニング５回後、９０℃で６０秒乾燥したものの摩擦後降雨試験を実施したところ、撥水性ナンバーは８０であった。
【００７１】
［実施例３］
処理剤２原液として参考例３で製造した処理剤２’原液を使用する以外は実施例１と同様の操作により試験布を得た。得られた試験布について撥水撥油性能を測定したところ、撥水性ナンバーは１００、撥油性ナンバーは６であった。
【００７２】
また、摩擦後降雨試験を上記で得られた試験布について行ったところ撥水性ナンバーは８０−であった。さらに、この試験布を同様の方法で５回繰り返しドライクリーニングを行った後、９０℃で６０秒間乾燥し摩擦後降雨試験を実施したところ、撥水性ナンバーは７０であった。
【００７３】
［実施例４］
処理布をナイロンタフタに変更する以外は実施例２と同様の操作により試験布を得た。得られた試験布について撥水撥油性能を測定したところ、撥水性ナンバーは１００、撥油性ナンバーは７であった。
【００７４】
また、摩擦後降雨試験を上記で得られた試験布について行ったところ撥水性ナンバーは１００であった。さらに、この試験布を同様の方法で１０回繰り返し洗濯を行った後、室温で乾燥し摩擦後降雨試験を実施したところ、撥水性ナンバーは８０であった。
【００７５】
［比較例１］処理工程１を省略した例
実施例１で処理工程１を行わないこと以外は同様の操作により試験布を得た。試験布の初期撥水性ナンバーは１００、撥油ナンバーは３であった。摩擦後降雨試験を実施したところ撥水性ナンバーは５０であった。
【００７６】
［比較例２］
親水性化合物として実施例１と同じ化合物を２．０ｇ使用する以外は実施例１と同様に処理工程１（布重量１００に対する親水性化合物の重量は２０重量％、浴比約１：３０、加工浴中の親水性化合物の濃度０．６６％）、つぎに処理工程２を経て試験布を得た。得られた試験布の初期撥水性、撥油性、摩擦後降雨試験後の撥水性はそれぞれ、８０、３であった。
【００７７】
［比較例３］ゼータ電位がマイナスである処理剤を使用した例
実施例１の処理工程２における処理剤２原液の代わりに参考例２で製造した撥水剤ラテックスを用いる以外は、実施例１と同様の操作により試験布を得た。試験布の初期撥水性ナンバーは７０、撥油性ナンバーは４であった。摩擦後降雨試験を行ったところ撥水性ナンバーは０であった。
【００７８】
【発明の効果】
本発明の繊維処理方法によれば、繊維および繊維製品に優れた撥水撥油性能を付与できる。また、本発明の方法によれば、実用上重要な性能である優れた摩擦耐久性、および降雨に対する撥水性も付与できる。該摩擦耐久性は、ドライクリーニング後においても発揮し得る。また、従来、これらの性能を付与することが困難であったウール繊維等のポリアミド系繊維、および、該繊維製品に対しても、優れた性能を付与できる利点もある。
また、本発明で用いる処理剤は、いずれも水系の処理剤であるため、取扱や環境保護の点からも有利である。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a fiber processing method with excellent friction durability.To the lawRelated. More specifically, the present invention relates to a method for imparting excellent water and oil repellency to a fiber having a polyamide structure such as wool and the friction durability of the performance.
[0002]
[Prior art]
Conventionally, a polyfluoroalkyl group (hereinafter R^fIt is written as a group. ) -Containing polymerizable monomers or copolymers, or R^fA technique for treating a compound containing a group into a fiber product or the like as an organic solvent solution or an aqueous dispersion to impart water and oil repellency to the surface thereof is known.
[0003]
Conventionally, for the purpose of improving durability of water and oil repellency against washing, dry cleaning, etc., R^fCopolymerizing a monomer monomer having an adhesive group together with a group-containing polymerizable monomer, or R^fAttempts have been made to blend polymers containing groups with polymers having high film strength.
[0004]
In addition, as a water repellent processing method for textile products, first, R^fProcessed with an aqueous dispersion of a group-containing compound, then R^fA method of treating with an organic solvent solution of a compound containing a group is known.
[0005]
For example, JP-A-58-46176 discloses a low molecular weight fluorine-containing compound (monomer) which reacts nylon fiber with a phenol group after treating the nylon fiber with a polyphenol compound as a carpet antifouling processing method. A method of reacting in an organic solvent has been proposed. Japanese Patent Laid-Open No. 60-110981 proposes a method of processing a cellulosic fiber with a resin and then performing a water repellent process. JP-B-5-12469 and JP-A-2-259165 propose a method in which a polyamide fiber is treated with a sulfonated phenol formaldehyde or a styrenesulfonic acid treatment agent and then treated with a fluorinated water repellent. JP-A-3-213572 proposes an antifouling processing method in which silk fibers are treated with an epoxy compound and then treated with a fluorine-based water repellent.
[0006]
[Problems to be solved by the invention]
However, in the conventional water repellent and water repellent processing method, even if the treatment in an organic solvent, the water and oil repellency washing durability, or the dry cleaning durability is a satisfactory level, The water-repellent friction durability and the water-repellent durability expression for rain, which are practical durability functions required for clothing, were insufficient. In particular, if the material is wool, it has a relatively hydrophilic polyamide structure, and there is a cuticle as a single fiber surface structure. Before performing, the water-repellent function was remarkably lowered due to the influence of friction at the time of wearing, which was a practical problem.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have studied in detail the durability development mechanism of the water and oil repellency for polyamide fibers such as wool fibers and the method for enhancing the water repellency function.
[0008]
As a result, the fiber is R^fWhen treating with a group-containing compound, the fiber product is treated with a specific hydrophilic compound in advance as a pretreatment, thereby treating only the water and oil repellent agent.WhenIt has been found that the water and oil repellency of friction durability, which is a practical problem, is remarkably improved, and that when the amount of a specific hydrophilic compound is set within a specific range, the friction durability is remarkably improved. . In addition, R^fBaseMaterializationIt has been found that the use of a compound having a specific structure as a compound further improves the effect.
[0009]
  That is, the present invention is characterized in that the fiber is treated in the following treatment step 2 after the following treatment step 1.PolyamideA fiber processing method is provided.
  Treatment step 1: A hydrophilic compound having one or more anionic residues and two or more benzene rings and an aqueous medium are contained, and the amount of the hydrophilic compound is 1.0 with respect to 100 parts by weight of the fiber. The process processed using the processing agent 1 which is -15.0 weight part.
  Treatment step 2: R having a zeta potential of 0 or more in an aqueous medium^fA fine particle containing a group-containing compound and an aqueous medium, and the fine particle is R^fFine particles comprising two or more kinds of polymers containing polymerized units of a group-containing polymerizable monomer.In addition, the outer shell of the fine particle is a core-shell type fine particle in which a more hydrophilic polymer site is present and a more hydrophobic polymer site is present in the fine particle inner shell.The process of processing a fiber using the processing agent 2 to be. However, the fine particles contain two or more different polymers.
[0010]
The fiber of the present inventionRestorationFirst, the treatment method is a specific hydrophilic compound as treatment step 1.ThingsYoWaterA fiber is processed with the processing agent 1 containing a system medium. The specific hydrophilic compound is a hydrophilic compound having one or more anionic residues and two or more benzene rings in the molecule. Examples of the anionic residue include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. In the case where the anionic residue in the hydrophilic compound is a site exhibiting hydrophilicity, and the fiber is a polyamide fiber, the anionic residue is considered to be adsorbed to the amino residue of the polyamide structure. There may be one kind or two or more kinds of anionic residues in the same molecule of the hydrophilic compound, and a sulfonic acid group is preferable from the viewpoint of water solubility and adsorptivity to wool fibers. Further, the hydrophilic compound may have a group other than the anionic residue bonded to the benzene ring, and preferably has a hydroxyl group.
[0011]
500-5000 are preferable, as for the molecular weight of this hydrophilic compound, 1000-3000 are especially preferable, and 1000-2000 are more preferable. Processes with molecular weights that are too low tend to be too hydrophilic.Or processing step 2 'Treatment agent 2Or treatment agent 2 'InR ^f There is a possibility that the water repellency of the group-containing compound may be inhibited. On the other hand, a compound having a too high molecular weight is difficult to adsorb on the fiber.
[0012]
As preferred specific examples of the hydrophilic compound included in the treatment step 1, the following compounds may be exemplified. However, in the following formula, n represents an integer of 2 to 5, m represents an integer of 1 to 5, 1 or 2 is preferable, and 1 is particularly preferable.
[0013]
[Chemical 1]

[0014]
Said hydrophilic compound is a well-known compound used as a fixing agent for so-called nylon, and can be easily obtained.
The treatment agent 1 in the treatment step 1 includes the specific hydrophilic compound and an aqueous medium. Examples of the aqueous medium include water or a mixture of water and a water-soluble organic solvent, but only water is preferable. Examples of the water-soluble organic solvent include water-soluble alcohols and glycols. The amount of the hydrophilic compound in the aqueous medium is 0.02 to 0.8% by weight.ButLikeEspecially0.04 to 0.5% by weightIs preferred.
[0015]
Treatment amount of treatment agent 1 is fiberofHydrophilic compound for 100 parts by weightofamountButIt is 1.0-15.0 weight part, and 2.0-10 weight part is especially preferable. Hydrophilic compoundAmount of1.0 weightPartFullsoHowever, although it exhibits washing durability, it does not exhibit durability against friction, which is a more severe performance. Also hydrophilic compoundsofQuantity is fiberofWhen the amount is 15.0 parts by weight or more with respect to 100 parts by weight, it is not preferable because there is a defect that the expression of water repellency is inhibited or the texture becomes hard. The above hydrophilic compound is known as a fixing agent, but is usually used for the purpose of improving the fixing property of the dye and has a low treatment concentration. However, this departureTomorrow, This hydrophilic compound in a higher concentration range than usualUseThus, a new function of improving friction durability has been found without deteriorating the performance of the water / oil repellent.
[0016]
The treatment agent 1 can also contain other additive components other than the hydrophilic compound. As an additive component, an organic acid such as acetic acid or formic acid may be contained for the purpose of adjusting the pH of the processing bath and promoting adsorption to the fiber surface.
[0017]
As the treatment method in the treatment step 1, the exhaust method is preferable because adsorption can be performed reliably. The treatment temperature is not particularly limited, and is preferably about 50 to 80 ° C., and the treatment time is preferably 10 to 30 minutes.
[0018]
In the present invention, after the fiber is treated in treatment step 1, treatment step 2Or processing step 2 'However, after the treatment step 1, it is preferable to remove the excessively treated hydrophilic compound. As a removing method, a method of washing with water is usually used. Treatment agent 2 when washing with water is insufficientOr treatment agent 2 'The fine particles inside cause aggregation, sedimentation and the like, or inhibit the water repellency expression effect. If necessary, treatment agent 2Or treatment agent 2 'It is preferable to dry the fibers before the treatment.
[0019]
In the treatment step 2, the zeta potential in the aqueous medium is 0 or more.R ^f Containing fine particles containing a group-containing compound and an aqueous medium.And the fine particles are R ^f Fine particles comprising two or more kinds of polymers containing polymerized units of a group-containing polymerizable monomerTreatment agent 2UsingIt is the process of processing a fiber.
Further, in the treatment step 2 ′, the zeta potential in the aqueous medium is 0 or more. ^f A fine particle containing a group-containing compound and an aqueous medium, and the fine particle is R ^f One or more polymers containing polymerized units of a group-containing polymerizable monomer and R ^f In this step, the treatment agent 2 ′ is a fine particle composed of one or more polymers not containing a group.
[0020]
Treatment agent 2Or 2 'The fine particles contained in are fine particles having a surface potential (zeta potential) of 0 or more in an aqueous medium. If the zeta potential is negative, there is a risk that the adsorption of fine particles on the fiber surface, particularly the wool fiber surface, may occur, and the water repellency and friction durability may also be reduced. The zeta potential is preferably +10 mV to +80 mV.
The fine particles are R^fIncluding group-containing compounds. R^fAs the compound containing a group, a known or well-known compound used for a normal water- and oil-repellent treatment for fibers is adopted.^fPolymer containing polymerized unit of group-containing polymerizable monomerIs.
[0021]
Where R^fThe group is a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. Of the hydrogen atoms of the alkyl group, a hydrogen atom that is not substituted with a fluorine atom may be substituted with a chlorine atom. In addition, a hydrogen atom that is not substituted with a fluorine atom is R^fIt may be present at the terminal portion in the group. R^fThe proportion of fluorine atoms in the group is [(R^fNumber of fluorine atoms in the group) / (R^fNumber of fluorine atoms in the group + R^fThe number of hydrogen atoms in the group)] × 100 (%) is preferably 60% or more, particularly preferably 80% or more. R^fThe group may contain a chlorine atom.
[0022]
R^fThe group preferably has a linear or branched structure, and particularly preferably has a linear structure. In the case of a branched structure, the branched portion is R^fIt is preferably present near the end of the group. The branched portion is preferably a short chain having about 1 to 4 carbon atoms. R^f4-20 are preferable and, as for carbon number of group, 6-16 are especially preferable. R^fThe group contains a perfluoroalkyl group or a perfluoroalkyl group moiety when the proportion of fluorine atoms is substantially 100%.^fGroups are preferred. The perfluoroalkyl group also preferably has a linear structure. As a linear perfluoroalkyl group, CF₃(CF₂)_k− [Where k is an integer of 3 to 19. ] Is preferable.
[0023]
R^fGroup-containing polymerizable monomer (hereinafter, R^fIt is described as a group-containing polymerizable monomer. ) Is the above R^fIt means a compound having a group and a polymerizable unsaturated group. R^fR of group-containing polymerizable monomer^fThe group is R^fThe meaning similar to a group is shown, and a preferable aspect is also the same. In addition, R^fThe group-containing polymerizable monomer is R^fIt may be a mixture of two or more compounds having different carbon numbers in the group, in which case R^fThe average carbon number of the group is preferably 6 or more.
[0024]
R^fAs the group-containing polymerizable monomer, the CF₃(CF₂)_k− [Where k is an integer of 3 to 19. ] And a perfluoroalkyl having a polymerizable unsaturated groupGroup-containing weightA compatible monomer is preferred. PerfluoroalkylGroup-containing weightThe compatible monomer may be a mixture of two or more compounds having different numbers of k, but the average of k is preferably 6 or more. If it is less than 6, the water and oil repellency is lowered, and the intended function may not be exhibited. The value of k or the average of k is preferably 6 to 16, particularly preferably 8 to 14, and more preferably 9 to 1.2 ispreferable. Those having a value of k that is too large are solid at room temperature, have high sublimation properties, and are difficult to handle.
[0025]
R^fIn the group-containing polymerizable monomer, the above R^fGroup and polymerizable unsaturated group directlyAlsoAre indirectly bonded via a bonding group, and are preferably indirectly bonded. The linking group is a divalent or higher valent linking group.Is preferred,In particularDivalent linking groupIs preferred, Alkylene bond, ester bond, amide bond, amino bond, urethane bond, ether bond, phenyleneoxy bond, sulfonyl bond,AlsoIs preferably a linking group containing these bonds. These R^fAs the group-containing polymerizable monomer, a known or well-known compound can be adopted. R^fThe group-containing polymerizable monomer is R^fGroup-containing alcohol, R^fGroup-containing carboxylic acid,R^fIt can be easily synthesized from a group-containing sulfonic acid or the like by a known method.
[0026]
R^fAs the group-containing polymerizable monomer, R^fOne of the groups is polymerizedGenderA compound having a structure in which a saturated group and a divalent linking group are connected is preferable. For example, R^fGroup-containing acrylate, R^fGroup-containing methacrylate, R^fGroup-containing styrene, R^fGroup-containing vinyl ester, R ^fA group-containing fumarate or the like is preferable.
[0027]
In addition, R^fIn view of versatility, the group-containing polymerizable monomer is particularly preferably R^fGroup-containing acrylates or methacrylates are preferred. Hereinafter, acrylate and methacrylate are collectively referred to as (meth) acrylate. R^fThe group-containing (meth) acrylate is advantageous from the viewpoints of polymerizability with other monomers and the flexibility, adhesiveness, solubility, and ease of emulsion polymerization of the film formed on the surface of the wool fiber.
[0028]
R^fSpecific examples of the group-containing polymerizable monomer are shown below, but are not limited thereto. In the following, R represents a hydrogen atom or a methyl group.
[0029]
  CF_Three(CF₂)₉(CH₂)₂OCOCR = CH₂,
  (CF_Three)₂CF (CF₂)₆(CH₂)₂OCOCR = CH₂ ,
  CF₂Cl (CF₂)₉(CH₂)_ThreeOCOCR = CH₂,
  HCF₂(CF₂)₉(CH₂)₂OC (O) CR = CH₂ ,
  CF_Three(CF₂)₉(CH₂)₁₁OCOCR = CH₂ ,
  CF_Three(CF₂)₉CONH (CH₂)_FiveOCOCR = CH₂,
  CF_Three(CF₂)₇SO₂N (C_ThreeH₇) C₂H_FourOCOCH = CH₂,
  CF_Three(CF₂)₉O (CF₂)₂(CH₂)₂OCOCR = CH₂ ,
  CF_Three(CF₂)₉CH₂COOCH = CH₂ ,
  CF_Three(CF₂)₉(CH₂)₂COOCH = CH₂,
  CF_Three(CF₂)₉(CH₂)_ThreeOCOCR = CH₂.
[0030]
  CF_Three(CF₂)₇(CH₂)₂OCH = CH₂,
  CF_Three(CF₂)₇CH₂CF₂CH₂CH₂OCOCR = CH₂,
  CF_Three(CF₂)₇(CH₂)_FourOCOCR = CH₂,
  CF_Three(CF₂)₇CONH (CH₂)_ThreeCH = CH₂ ,
  CF_Three(CF₂)₉CONH (CH₂)₂CH = CH₂ ,
  CF_Three(CF₂)₁₃SO₂NH (CH₂)₂CH = CH₂ ,
  CF_Three(CF₂)₁₃(CH₂)₆OCOCR = CH₂ ,
  HCF₂(CF₂)₉CH = CH₂.
[0031]
R^fThe polymer containing the polymerized unit of the group-containing polymerizable monomer is R^fPolymerized unit of group-containing polymerizable monomerofA polymer containing one or more, or R^fAny of the polymer containing 1 or more types of the unit which the group-containing polymerizable monomer polymerized and 1 or more types of the unit which the other polymerizable monomer polymerized may be sufficient. However, the fluorine content in the polymer is preferably 50 to 70% by weight in the polymer in order to achieve the desired performance.
[0032]
The other polymerizable monomer is the above R^fThe compound is not particularly limited as long as it is a compound containing an unsaturated group polymerizable with a group-containing polymerizable monomer. Moreover, 1 or more types can be used for another polymerizable monomer, and when it is 2 or more types, it can be used in arbitrary ratios. In the following, other polymerizable monomers are referred to as copolymerizable monomers.
[0033]
Examples of the copolymerizable monomer include (meth) acrylates, (meth) acrylamides, vinyl ethers, vinyl esters, fumarates, maleates and the like. These copolymerizable monomers preferably have a hydrocarbon group or a benzene ring, and particularly preferably have a hydrocarbon group. The copolymerizable monomer may be vinyl chloride, ethylene, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, styrenes, and the like.
[0034]
Copolymerizable monomers include polymerizable groups such as epoxy groups, halogen atoms, hydroxyl groups, amide groups, amino groups, imino groups, alkoxysilyl groups, N-methylol groups, N-alkyloxyalkyl groups, and blocked isocyanate groups. SaturationBaseIt may be a copolymerizable monomer containing a reactive group other than. For example, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, γ-trimethoxysilylpropyl (meth) acrylate, glycidyl (meth) acrylate, etc. preferable.
[0035]
As a copolymerizable monomer having a blocked isocyanate group, a blocked product of a reaction product obtained by reacting a hydroxyl group-containing (meth) acrylate and a polyisocyanate compound in a ratio in which at least one isocyanate group remains, A reaction product obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyisocyanate compound having at least one blocked isocyanate group and at least one isocyanate group is preferred.
[0036]
Here, as the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (oxyethylene / Oxypropylene) glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate and the like are preferable.
[0037]
Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate, or alicyclic polyisocyanates such as isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, and bis (isocyanatomethyl) cyclohexane. Isocyanates, and their nurate-modified products, prepolymer-modified products, burette-modified products, etc., and aliphatic diisocyanatesTomaOr alicyclic diisocyanate is preferable.
[0038]
Examples of the blocking agent include oximes, alkyl ketoximes, phenols, β-diketones, malonic esters, lactams, alkanols and the like. Specific examples include cyclohexane oxime, methyl ethyl ketoxime, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butanol, ε-caprolactam, maleic imide, sodium bisulfite and the like, cyclohexane oxime, methyl ethyl keto oxime, etc. Is preferred.
[0039]
The fine particles in treatment agent 2 are (1) R^fFine particles comprising two or more types of polymers containing polymerized units of group-containing polymerizable monomersAnd,Fine particles in treatment agent 2 ′(2) R^fOne or more polymers containing polymerized units of a group-containing polymerizable monomer and R^fFine particles composed of at least one polymer not containing a groupTheFine particles of (1) or (2)To beFurther, in combination with the treatment agent 1, higher friction durability can be obtained.
[0040]
Fine particles are (1) R^fIn the case of fine particles comprising two or more kinds of polymers containing polymerized units of group-containing polymerizable monomers, the polymers are different from each other in R^fA polymer containing a polymerized unit of a group-containing polymerizable monomer or a polymer having a different fluorine content is preferred.
[0041]
Also fine particlesBut(2) R^fOne or more polymers containing polymerized units of a group-containing polymerizable monomer and R^fIn the case of fine particles comprising at least one polymer not containing a group, R^fOne type of polymer containing polymerized units of a group-containing polymerizable monomer and R^fFine particles composed of one kind of polymer containing no group are preferred. R^fThe polymer containing no group is preferably a polymer containing a polymerized unit of one or more polymerizable monomers selected from the above copolymerizable monomers. As a copolymerization monomer, 1 or more types can be arbitrarily selected from the above-mentioned copolymerization monomer.
[0042]
The fine particles (1) or (2) are preferably present in the aqueous medium as so-called core-shell fine particles from the viewpoint of improving the friction durability. The core-shell type fine particles include two or more kinds of different polymers, and the outer shell of the fine particles has a more hydrophilic polymer portion, and the inner shell of the fine particles has a more hydrophobic polymer portion. It refers to the form of particles present.
[0043]
R like this^fThe method for synthesizing the fine particles of the polymer containing a polymerized unit of the group-containing polymerizable monomer is not particularly limited, and a known or well-known polymerization method can be adopted, and polymerization is preferably performed by an emulsion polymerization method or a dispersion polymerization method. . In particular, when producing core-shell type fine particles, it is preferable to employ a multistage polymerization method such as a so-called seed polymerization method.
[0044]
When using an emulsifier during polymerization,FineFrom the viewpoint of the zeta potential of the particles, one or more selected from nonionic, cationic and amphoteric known or well-known emulsifiers can be employed, but anionic emulsifiers are not preferred. The amount of the emulsifier is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer, particularly about 1 to 10 parts by weight from the viewpoint of water / oil repellency and dispersion stability. preferable.
[0045]
Examples of the polymerization medium include water or water containing an organic solvent. As the organic solvent, water-soluble organic solvents are preferable, and ester-based and ketone-based solvents., DOrganic solvents such as ethers are preferred. As the ester organic solvent, ethyl acetate, butyl acetate, diethyl succinate and the like are preferable. As the ketone organic solvent, methyl ethyl ketone, methyl isobutyl ketone, acetone and the like are preferable. As the ether organic solvent, diethylene glycol, Dipropylene glycol, triethylene glycol, glycol, and their monomethyl ether or dimethyl ether, diethyl ether and the like are preferable. Among these, as the organic solvent, an ether organic solvent is preferable from the viewpoint of low flammability. The ratio of water and organic solvent is not particularly limited, and any ratio may be used.
[0046]
As the polymerization initiator, water-soluble or oil-soluble polymerization initiators are preferable, and general-purpose initiators such as azo-based, peroxide-based, and redox-based initiators can be used depending on the polymerization temperature. Although polymerization temperature is not specifically limited, 20 to 150 degreeC is preferable. In order to make the zeta potential after the polymerization positive, an initiator of azoamidines is particularly preferable.
[0047]
The polymerization reaction is a polymerizable monomer as a pre-stage for starting the polymerization,WaterIt is preferable to carry out the mixture comprising an emulsifier and an emulsifier after the mixture is pre-dispersed by treatment with a homomixer or a high-pressure emulsifier.
[0048]
Treatment agent 2Or treatment agent 2 'The fine particles in are preferably present in the aqueous medium as an emulsion or dispersion.
[0049]
Treatment agent 2Or treatment agent 2 'Is R^fThe concentration of the group-containing compound is preferably about 1 to 50 parts by weight with respect to 100 parts by weight of the aqueous medium, and is preferably adjusted with water so that the concentration is reached. The concentration can be appropriately changed depending on the purpose and the form of the composition. Treatment agent 2Or treatment agent 2 'The treatment amount of 0.1 to 10 parts by weight in terms of solid content with respect to 100 parts by weight of the fiber before treating agent 1Is preferred, especially0.2-5 weightPartpreferable. Treatment agent 2Or treatment agent 2 'If the amount of treatment is small, the friction durability may be reduced.
[0050]
Furthermore, treatment agent 2Or treatment agent 2 'In addition, an additive component other than the above can be blended. For example, other water repellents and oil repellents, cross-linking agents, insect repellents, flame retardants, antistatic agents, anti-wrinkle agents and the like can be used in combination as appropriate.
[0051]
Processing step 2Or processing step 2 'Is preferably carried out by a conventional padding method or a treatment method such as an exhaustion method, and the padding method is preferred from the viewpoint of simplicity of treatment.
[0052]
The fiber treatment method of the present invention is particularly effective for various fibers having a polyamide structure, and is a treatment method suitable for wool fibers. The wool fiber may be a wool fiber or a mixed fiber of a wool fiber and another fiber. In addition, the wool fiber may be a textile product, and examples thereof include outer clothing such as a suit and sportswear, work clothes, and uniforms. Moreover, nylon etc. are mentioned as fibers other than wool.
[0053]
BookInvention fiberAccording to the treatment method, these fibers can be imparted with water / oil repellency, antifouling property, washing resistance and dry cleaning resistance. And further against frictionExcellent durabilityThese sexNohCan be granted.
[0054]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these examples. Various evaluations in the examples were performed according to the following methods and criteria.
[0055]
[Evaluation method of water repellency]
It was represented by the water repellency number (see Table 1) by the spray method of JIS-L-1092. Usually, the shower water temperature was 27 ° C. In addition, the evaluation result which attached | subjected + (-) mark to the following water-repellent number shows a thing slightly better (bad) than what each evaluation represented by the number.
[0056]
[Dry cleaning method]
JIS-L-1092.3.2. (2) The method described was followed.
[0057]
[Evaluation method of rainfall test after friction endurance]
After rubbing the sample with a pilling tester equipped with a cotton swab for 5 minutes (pressing pressure 450 g), according to the method described in the JIS-L-1092 (C) method (Bundesmann test), the rainfall amount is 100 cc / min, the rain water temperature Was rained under the conditions of 20 ° C. and a rain time of 10 minutes, and the wet state of the surface was determined according to the water repellency number in Table 1.
[0058]
[Evaluation method of oil repellency]
Several drops (about 4 mm in diameter) of the test solution shown in Table 2 were placed at two locations on the test cloth, and the test solution was discriminated by the permeation state after 30 seconds (AATCC-TM118-1966).
[0059]
[Table 1]

[0060]
[Table 2]

[0061]
[Reference Example 1] Production Example of Treatment Agent 2
Perfluoroalkylethyl acrylate [C _q F_{2 q +1}(CH₂)₂OCOCH = CH₂:qIs a mixture of 6, 8, 10, 12, 14, 16 with an average of 9. (Hereinafter referred to as FA) 3013 g, 55.8 g of dodecyl mercaptan, 155 g of polyoxyethylene secondary alkyl ether as a nonionic emulsifier, 15.5 g of alkyldimethylamine acetate as a cationic emulsifier, and 5032 g of water were pre-dispersed with a homogenizer. Then, using a high-pressure homogenizer (Emulsifier manufactured by Manton Gourin), 400 kg / cm²To obtain an emulsion.
[0062]
7000 g of the emulsion was placed in a 10 liter stainless steel autoclave, 39.8 g of azobisisobutyronitrile was added, and the atmosphere was replaced with nitrogen. After raising the temperature to 60 ° C., polymerization was carried out for 8 hours (solid content: 38.8% (polymerization yield: 97.0%)). In a 10 liter stainless steel autoclave, 5000 g (solid content 1940 g; 100 parts by weight) of the above polymer dispersion (solid content concentration 38.8%), F349 g (60 parts by weight) of A, 175 g (30 parts by weight) of cyclohexyl methacrylate, and 58.2 parts by weight (10 parts by weight) of glycidyl methacrylate were charged.
[0063]
Further, 252 g of dipropylene glycol monomethyl ether and 359 g of water were added to adjust the total solid content to 40% by weight. After the mixture was stirred, 25.0 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added, and after nitrogen substitution, polymerization was performed at 60 ° C for 15 hours. After cooling, the dispersion was taken out. The solid content concentration was 38.2% by weight. When the emulsion particles were observed with a transmission electron microscope, the obtained particles were fine particles having a core-shell structure and a particle diameter of about 0.2 μm. Further, the zeta potential of the emulsion of the pH 6 aqueous solution was +16 mV. The solid content concentration of the obtained dispersion was adjusted to 20% by weight to prepare a treating agent 2 stock solution.
[0064]
[Reference Example 2] Production example of water repellent latex having a negative zeta potential
Alkyldimethylamine acetate as the cationic emulsifier used in Reference Example 1Instead of, Except for using anionic emulsifier sodium polyoxyethylene lauryl sulfate,A perfluoroalkyl group-containing aqueous dispersion was obtained in the same manner as in Reference Example 1 to prepare a water repellent latex. The resulting emulsion had a zeta potential of -6 mV at pH 7.
[0065]
[Reference Example 3] Treatment agent 2'Example of manufacturing
3100 g of FA, 1650 g of stearyl acrylate, 165 g of 2-hydroxyethyl methacrylate, 85 g of N-methylol acrylamide, 13 g of dodecyl mercaptan, 300 g of polyoxyethylene secondary alkyl ether, 30 g of alkyldimethylamine acetate, 2000 g of dipropylene glycol monomethyl ether, 5000 g of water,60 ° CInAfter pre-dispersing with a homogenizer, using a high-pressure homogenizer (emulsifier manufactured by Manton Gourin), 60 ° C., 400 kg / cm²To obtain a white emulsion.
[0066]
7000 g of the emulsified liquid was placed in a 10 liter stainless steel autoclave, 25.0 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added, and the atmosphere was replaced with nitrogen. After raising the temperature to 60 ° C., polymerization was carried out for 12 hours (solid content 40.9% (polymerization yield 94%). After cooling, the dispersion liquid was taken out. When the emulsion particles were observed with a transmission electron microscope, they were obtained. The obtained particles were fine particles having a particle diameter of about 0.15 μm, and the zeta potential of the emulsion of pH 6 aqueous solution showed +20 mV The solid content concentration of the obtained dispersion was adjusted to 20% by weight with ion-exchanged water. Treatment agent 2'The stock solution was used.
[0067]
[Example 1]
(Processing step 1)
0.27 g of a hydrophilic compound (a compound in which n is 2 to 5 in the above formula (1) and m is 1 and the average molecular weight is 1800) and 300 g of ion-exchanged water are placed in a 500 ml beaker, where wool tropical A cloth (cloth weight 10.0 g) was dipped and attached to a water bath (the weight of the hydrophilic compound is 2.7% by weight with respect to the cloth weight 100, the bath ratio is about 1:30, the hydrophilic compound in the processing bath) Concentration of 0.09%). The bath temperature was raised to 70 ° C. and kept for 15 minutes with slow stirring, and then the fabric was taken out, thoroughly washed with ion-exchanged water, and air-dried.
[0068]
(Processing step 2)
Treatment agent 2 stock solution prepared in Reference Example 1 (solid content concentration 20%) 8%, melamine resin (Sumitex Resin M3 manufactured by Sumitomo Chemical Co., Ltd.) 0.3%, catalyst (Sumitex Accelerator ACX manufactured by Sumitomo Chemical Co., Ltd.) 0 Prepare a processing bath aqueous solution containing 3% isopropanol and 1.5% isopropanol, immerse the wool tropical cloth of processing step 1 in this, squeeze the cloth between two rubber rollers, and set the wet pickup to 60% by weight. (Immersion and squeezing were repeated twice each). Next, the treated cloth was dried at 110 ° C. for 90 seconds and further heat treated at 150 ° C. for 60 seconds to obtain a test cloth. When the water and oil repellency of the obtained test cloth was measured, the water repellency number was 100 and the oil repellency number was 6.
[0069]
Also, the post-friction rain test was obtained aboveTest clothAs a result, the water repellency number was 90. Further, this test cloth was repeatedly dry-cleaned five times by the same method, then dried at 90 ° C. for 60 seconds and subjected to a rainfall test after friction. As a result, the water repellency number was maintained at 80.
[0070]
[Example 2]
Hydrophilic compoundThingProcess step 1 as in Example 1 except that the amount used is 0.54 g (the weight of the hydrophilic compound is 5.4% by weight with respect to the fabric weight of 100, the bath ratio is about 1:30, the hydrophilic compound in the processing bath is (Concentration 0.18%), and then through treatment step 2, a test cloth was obtained. The obtained test fabric had initial water repellency, oil repellency, and water repellency after the rain test after friction were 100, 6, and 100-, respectively. Further, after 5 times of dry cleaning, after drying at 90 ° C. for 60 seconds, a post-friction rain test was conducted.sexThe number was 80.
[0071]
[Example 3]
Treatment agent 2 produced in Reference Example 3 as treatment agent 2 stock solution'Same as Example 1 except using stock solutionBy operationA test cloth was obtained. When the water and oil repellency of the obtained test cloth was measured, the water repellency number was 100 and the oil repellency number was 6.
[0072]
Also, the post-friction rain test was obtained aboveTest clothAs a result, the water repellency number was 80-. Further, this test cloth was repeatedly dry-cleaned five times by the same method, then dried at 90 ° C. for 60 seconds, and subjected to a rainfall test after friction. As a result, the water repellency number was 70.
[0073]
[Example 4]
The same as Example 2 except that the treated cloth is changed to nylon taffetaoperationBytestI got a cloth. When the water and oil repellency of the obtained test cloth was measured, the water repellency number was 100 and the oil repellency number was 7.
[0074]
Also, the post-friction rain test was obtained abovetestThe water repellency number was 100 when run on the fabric. Further, this test cloth was repeatedly washed 10 times in the same manner, then dried at room temperature and subjected to a rainfall test after friction. As a result, the water repellency number was 80.
[0075]
[Comparative Example 1] Example in which processing step 1 is omitted
A test cloth was obtained by the same operation except that the treatment step 1 was not performed in Example 1. The test fabric had an initial water repellency number of 100 and an oil repellency number of 3. When the rainfall test after friction was carried out, the water repellency number was 50.
[0076]
[Comparative Example 2]
Treatment step 1 as in Example 1 except that 2.0 g of the same compound as Example 1 is used as the hydrophilic compound (weight of hydrophilic compound is 20% by weight with respect to fabric weight of 100, bath ratio is about 1:30, processing The concentration of the hydrophilic compound in the bath was 0.66%), and then through the treatment step 2, a test cloth was obtained. The obtained test cloth had initial water repellency, oil repellency, and water repellency after the rain test after friction of 80 and 3, respectively.
[0077]
[Comparative Example 3] Example using treatment agent with negative zeta potential
Treatment agent 2 stock solution in treatment step 2 of Example 1Instead ofA test cloth was obtained in the same manner as in Example 1 except that the water repellent latex produced in Reference Example 2 was used. The initial water repellency number of the test cloth is 70, oil repellencysexThe number was 4. When the rainfall test was conducted after friction, the water repellency number was 0.
[0078]
【The invention's effect】
Of the present inventionfiberAccording to the treatment method, excellent water and oil repellency can be imparted to fibers and textiles. In addition, the present inventionofAccording to the method, excellent friction durability, which is a practically important performance, and water repellency against rainfall can be imparted. The friction durability can be exhibited even after dry cleaning. In addition, there is also an advantage that excellent performance can be imparted to polyamide fibers such as wool fibers, which have been difficult to impart these performances, and the fiber products.
Moreover, since all the processing agents used by this invention are aqueous processing agents, it is advantageous also from the point of handling or environmental protection.

Claims (1)

A polyamide-based fiber treatment method, wherein a fiber is treated in the following treatment step 2 after the following treatment step 1.
Treatment step 1: A hydrophilic compound having one or more anionic residues and two or more benzene rings and an aqueous medium are contained, and the amount of the hydrophilic compound is 1.0 with respect to 100 parts by weight of the fiber. The process processed using the processing agent 1 which is -15.0 weight part.
Treatment Step 2: Fine particles containing a polyfluoroalkyl group-containing compound having a zeta potential of 0 or more in an aqueous medium and an aqueous medium, and the fine particles are polymerized with a polyfluoroalkyl group-containing polymerizable monomer unit Ri Ah with fine particles of two or more polymers containing, and, in the fine particle shell, the more hydrophilic polymer sites, the particles within the shell, there is a more hydrophobic polymer parts treating with Oh Ru treatment agent 2 in core-shell particles. However, the fine particles contain two or more different polymers.