JP3744034B2 - Water-dispersed water- and oil-repellent composition with excellent foreign matter stability - Google Patents

Description

【００３０】
ただし、界面活性剤（ｃ）の具体例中におけるＲ¹ 〜Ｒ³ 、［Ｘ］^- 、Ａ、Ｂ、Ｑ、ｋ、ｍ、ｎ、ｐ、およびｑ〜ｖは、以下の意味を示す。
Ｒ¹ ：炭素数６〜２２のアルキル基、炭素数６〜２２のアルケニル基、炭素数６〜２２のアシル基、アルキル基（炭素数６〜２２）が結合したフェニル基、または、アルケニル基（炭素数６〜２２）が結合したフェニル基。
Ｒ² 、Ｒ³ ：同一であっても異なっていてもよく、それぞれ、水素原子、メチル基、エチル基、またはベンジル基。
【００３１】
［Ｘ］^- ：１価のアニオンを示し、塩素イオン、ＨＳＯ₄ ^-、ＮＯ₃ ^-、ＣＨ₃ ＣＯＯ^- 、ＣＨ₃ ＣＨ₂ ＣＯＯ^- 、ＨＣＯＯ^- 、または、Ｃ₂ Ｈ₅ ＳＯ₄ ^-等が好ましい。
Ａ：オキシエチレン基。
Ｂ：オキシプロピレン基［−ＣＨ₂ ＣＨ（ＣＨ₃ ）Ｏ−または−ＣＨ（ＣＨ₃ ）ＣＨ₂ Ｏ−］。オキシプロピレン基が窒素原子と結合している場合には、窒素原子と−ＣＨ₂ または−ＣＨで結合しているのが好ましい。
Ｑ：−（ＣＨ₂ ） _ｗ −（ｗは０〜５の整数。）で表される２価の結合基を示す。ｗが０の場合は単結合であることを示し、窒素原子と窒素原子が直接結合している。
【００３２】
ｋ、ｍ、ｎ、ｐ：それぞれ、０〜２０の整数であり、ｋ＋ｍ＋ｎ＋ｐの平均値は５〜４０である。ｋ、ｍ、ｎ、ｐは、オキシエチレン単位またはオキシプロピレン単位の個数を示す。入手容易な界面活性剤（ｃ）におけるオキシエチレン単位および／またはオキシプロピレン単位の個数は、通常の場合、ｋ、ｍ、ｎ、およびｐの組み合わせの異なる２種以上であり、その場合においてもｋ＋ｍ＋ｎ＋ｐの平均値は５〜４０であり、１０〜３５が好ましい。また、ｍとｎのいずれもが０である場合には、窒素原子と水素原子が直接結合していることを示す。他の場合においても同様の意味を示す。
【００３３】
ｑ、ｒ、ｓ、ｔ、ｕ、ｖ：それぞれ、０〜２０の整数を示し、ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖの平均値は５〜４０である。ｑ、ｒ、ｓ、ｔ、ｕ、ｖは、オキシエチレン単位またはオキシプロピレン単位の個数を示す。入手容易な界面活性剤（ｃ）におけるオキシエチレン単位および／またはオキシプロピレン単位の個数は、通常の場合、ｑ、ｒ、ｓ、ｔ、ｕ、およびｖの組み合わせの異なる２種以上であり、その場合においてもｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖの平均値は５〜４０であり、１０〜３５が好ましい。ｑとｒのいずれもが０である場合には、窒素原子と水素原子が直接結合していることを示す。他の場合においても同様の意味を示す。
【００３４】
さらに、該界面活性剤（ｃ）が、上記の式（１）〜（４）のいずれかである場合、入手容易な界面活性剤（ｃ）は、通常は２種以上の混合物であり、Ｒ¹ の種類および炭素数の異なる混合物等である。たとえば、Ｒ¹ が、アルキル基を主成分とするアルキル基およびアルケニル基の混合基（ヤシ油アルキル基）、アルキル基およびアルケニル基の混合基（牛脂アルキル基）、大部分がアルキル基である基（硬化牛脂アルキル基）等であるものが挙げられる。
【００３５】
上記の界面活性剤（ｃ）分子中における、オキシエチレン基またはオキシプロピレン基の割合が少ないと、本発明の主目的である充分な加工処理浴安定性が得られないおそれがあり、一方、多すぎる場合には親水性が増加し充分な撥水性を得ることができないおそれがある。
【００３６】
界面活性剤（ｃ）のうち、式（１）で表される界面活性剤は、市販されており、たとえば、以下のものが挙げられる。
ポリオキシエチレンヤシ油アルキルモノメチルアンモニウムクロリド（オキシエチレン基の平均個数１５）［商品名：エソガードＣ／２５（ライオンアクゾ社製）］。
ポリオキシエチレンラウリルモノメチルアンモニウムクロリド（オキシエチレン基の平均個数７）［商品名：カチオンＬ−２０７（日本油脂社製）］。
【００３７】
また、式（１）で表される界面活性剤は、下式（５）で表される界面活性剤と塩酸、硫酸、硝酸等の鉱酸、ギ酸、酢酸、プロピオン酸等の有機酸、塩化メチル、塩化ベンジル、ジエチル硫酸、ジメチル硫酸等との反応によっても合成できる。なお、式（５）におけるＲ¹ 、Ａ、Ｂ、ｋ、ｍ、ｎ、およびｐは、上記と同じ意味を示す。
【００３８】
【化３】

【００３９】
式（５）で表される界面活性剤は市販されており、たとえば、以下のものが挙げられる。
ポリオキシエチレンステアリルアミン（オキシエチレン基の平均個数１５）［商品名：ナイミーンＳ−２１５（日本油脂社製）］。ナイミーンＳ−２１５の構造を式（６）に示す。式（６）におけるａは０〜１５の整数、ｂは０〜１５の整数であり、ａ＋ｂの平均値は１５であり、Ｒはステアリル基を示す。
【００４０】
【化４】

【００４１】
ポリオキエチレンヤシ油アルキルアミン（オキシエチレン基の平均個数１５）［商品名：エソミンＣ／２５（ライオンアクゾ社製）］。
ポリオキシエチレンオレイルアミン（オキシエチレン基の平均個数１０）［商品名：エソミンＯ／２０（ライオンアクゾ社製）］。
ポリオキシエチレンポリオキシプロピレンヤシ油アルキルアミン（オキシエチレンオキシプロピレン基の平均個数１６）［商品名：エソプロポミンＣ／１８ー１８（ライオンアクゾ社製）］。
【００４２】
また、界面活性剤（ｃ）のうち式（２）で表される界面活性剤は、式（７）で表される界面活性剤の１当量に対して、塩酸、硫酸、硝酸等の鉱酸、ギ酸、酢酸、プロピオン酸等の有機酸、塩化メチル、塩化ベンジル、ジエチル硫酸、ジメチル硫酸等を２当量反応させることによって合成できる。ただし、式（７）におけるＲ¹ 、Ａ、Ｂ、およびｑ〜ｖは、上記と同じ意味を示す。
【００４３】
【化５】

【００４４】
また、界面活性剤（ｃ）のうち式（３）および式（４）で表される界面活性剤は、前記の式（７）で表される界面活性剤の１当量に対して、塩酸、硫酸、硝酸等の鉱酸、ギ酸、酢酸、プロピオン酸等の有機酸、塩化メチル、塩化ベンジル、ジエチル硫酸、ジメチル硫酸等を１当量反応させることによって合成できる。
【００４５】
つぎに、ノニオン性界面活性剤（ｄ）について説明する。
ノニオン性界面活性剤（ｄ）としては、公知ないしは周知のノニオン性界面活性剤が採用でき、界面活性剤ハンドブックに記載される非イオン性界面活性剤のうち、ポリエチレングリコール型、および多価アルコール脂肪酸（部分）エステル型に分類される非イオン性界面活性剤が好ましい。非イオン性界面活性剤（ｄ）は１種あるいは２種以上を含ませることができる。
【００４６】
ノニオン性界面活性剤（ｄ）としては、ポリエチレングリコールエステル類、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンプロピレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレン脂肪酸エステル類、ポリオキシエチレングリセリンエステル類、ソルビタンエステル類、グリセリンエステル類、ポリオキシエチレン脂肪酸エステル類等が挙げられる。特に、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンプロピレンアルキルエーテル類が安定性が高く好ましい。
【００４７】
さらに、カチオン性界面活性剤（ｅ）について説明する。
カチオン性界面活性剤（ｅ）は、前記の界面活性剤（ｃ）以外のカチオン性界面活性剤であり、界面活性剤ハンドブックに記載される公知ないしは周知の陽イオン界面活性剤のうち第４アンモニウム塩型、または、アミン塩型に分類される界面活性剤が好ましく、特に、アルキルアンモニウム塩、または、アルキルアミンの塩が好ましい。カチオン性界面活性剤（ｅ）も１種あるいは２種以上を含ませることができる。さらに、繊維に加工した後の撥水撥油性能にカチオン性界面活性剤が悪影響を与えない等の点から、アルキルアンモニウム塩としては、式（８）で表されるものが、アルキルアミンの塩としては式（９）で表されるものが好ましい。
【００４８】
［Ｒ⁴ −Ｎ⁺ （ＣＨ₃ ）₂ Ｒ⁵ ］・［Ｘ¹ ］^- （８）
Ｒ⁴ −Ｎ（ＣＨ₃ ）Ｒ⁵ の塩 （９）
【００４９】
ただし、式（８）および（９）において、Ｒ⁴ 、Ｒ⁵ 、および［Ｘ¹ ］^- は、以下の意味を示す。
Ｒ⁴ ：炭素数６〜２２のアルキル基、炭素数６〜２２のアルケニル基、アルキル基（炭素数が６〜２２）が結合したフェニル基、または、アルケニル基（炭素数が６〜２２）が結合したフェニル基を示し、炭素数１２〜２２のアルキルまたは炭素数１２〜２２のアルケニル基が好ましい。
Ｒ⁵ ：水素原子、炭素数１〜２２のアルキル基、炭素数２〜２２のアルケニル基、アルキル基（炭素数６〜２２）が結合したフェニル基、アルケニル基（炭素数６〜２２）が結合したフェニル基、ベンジル基、または、アルケニル基（炭素数６〜２２）が結合したベンジル基を示し、水素原子、メチル基、エチル基、ベンジル基、炭素数１２〜２２のアルキル基、または炭素数１２〜２２のアルケニル基が好ましい。
【００５０】
［Ｘ¹ ］^- ：１価のアニオンを示し、塩素イオン、ＨＳＯ₄ ^-、ＮＯ₃ ^-、 ＣＨ₃ ＣＯＯ^- 、ＣＨ₃ ＣＨ₂ ＣＯＯ^- 、ＨＣＯＯ^- 、Ｃ₂ Ｈ₅ ＳＯ₄ ^-等が好ましい。
【００５１】
本発明における特定の界面活性剤（ｂ）中の界面活性剤（ｃ）、（ｄ）および（ｅ）の量比は、重量比で示した場合に以下の関係にあるのが好ましい。
（ｄ）／（ｃ）＝９９／１〜１／９９。
（ｅ）／［（ｃ）＋（ｄ）］＝１／９９〜４０／６０。
【００５２】
本発明の水分散型撥水撥油剤組成物においては、界面活性剤として上記の少なくとも３種の界面活性剤を含むことが重要である。たとえば、ノニオン界面活性剤（ｄ）だけでは夾雑物共存下の加工浴中での安定性が充分でなく、マングルへのポリマー付着（ガムアップ）が生じる問題がある。一方、界面活性剤（ｃ）だけでは、夾雑物への安定性は高くなるものの、撥水撥油性が充分でなくなる問題がある。したがって、界面活性剤としては、（ｄ）と（ｃ）を併用する必要がある。（ｄ）と（ｃ）との割合は、（ｄ）／（ｃ）＝９９／１〜１／９９間の任意の割合で混合して使用することが好ましく、（ｄ）／（ｃ）＝９５／５〜４０／６０とするのが特に好ましい。
【００５３】
さらに、本発明においては、（ｅ）成分を併用することが良好な分散安定性と高い撥水撥油性能を両立させるために重要である。しかし、（ｅ）成分の割合が高くなりすぎると分散安定性が低下するため、（ｅ）／［（ｃ）＋（ｄ）］＝１／９９〜４０／６０の範囲が好ましく、５／９５〜３５／６５が特に好ましい。
【００５４】
界面活性剤（ｂ）の総量は重合体（ａ）１００重量部に対し３〜１５重量部が好ましく、特に、５〜１３重量部が好ましい。界面活性剤（ｂ）の量が少ないとエマルションの安定性が充分でなく、多いと撥水撥油性が低下するおそれがある。
【００５５】
本発明の水分散型撥水撥油組成物には、上記の界面活性剤（ｂ）以外の他の界面活性剤を含ませてもよい。他の界面活性剤としては両性界面活性剤や上記の界面活性剤（ｃ）〜（ｅ）以外の高分子界面活性剤が挙げられ、たとえば、酢酸ベタイン類、イミダゾリニウムベタイン、アミンオキサイド類、ポリオキシエチレンアルキルエーテル酢酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリビニルアルコール等が挙げられる。
【００５６】
本発明における重合体（ａ）を得る方法としては、特に限定されないが、重合体を乳化重合法で合成する方法が効率的であり好ましい。さらに、重合体（ａ）を乳化重合法によって合成する方法を採用し、重合時に撹拌することによって自然に分散させる方法、また、乳化重合の重合開始剤を添加する前に、ホモミキサーまたは高圧乳化装置により乳化して、その後に重合を開始することによって分散させる方法が好ましい。
すなわち、本発明における重合体（ａ）を乳化重合法で得る場合、Ｒ^f 基を含有する（メタ）アクリレート、および必要に応じて他の重合性単量体を、特定の界面活性剤（ｂ）の存在下に乳化重合することにより合成する方法が好ましい。
【００５７】
乳化重合時の重合媒体としては、本発明の水分散型撥水撥油剤組成物の水系媒体と同じものを採用するのが好ましく、水のみ、または水に水溶性有機溶剤を含ませたものが挙げられる。水溶性有機溶剤としては、ケトン類、エステル類、グリコール類、グリコールエーテル類あるいはアルコール類等が挙げられる。
【００５８】
乳化重合は、通常の場合、重合開始源を作用させることによって実施する。重合開始源としては特に限定されず、有機過酸化物、アゾ化合物、過硫酸塩等の通常の重合開始剤、または、γ線のような電離性放射線等が採用できる。
【００５９】
水媒体中に分散した、Ｒ ^f 基含有（メタ）アクリレートの重合した単位を含む重合体（ａ）は、粒子状で分散しているのが好ましく、粒子系は、０．０３〜０．２５μｍ程度が好ましい。
【００６０】
本発明の水分散型撥水撥油剤組成物は、目的や用途等に応じて、任意の濃度に希釈されて、被処理物に適用される。被処理物の適用方法も、被処理物の種類により任意の方法が採用されうる。たとえば、浸漬塗布等の被覆加工の既知の方法により、被処理物の表面に付着させ乾燥する方法が採用されうる。また、必要ならば適当な架橋剤とともに適用し、キュアリングを行ってもよい。
【００６１】
本発明の水分散型撥水撥油剤組成物は、他の化合物を併用した場合においても、優れた安定性を発揮するため、必要に応じて、他の重合体ブレンダー、他の撥水剤や撥油剤あるいは防虫剤、難燃剤、帯電防止剤、染料安定剤、防シワ剤などの添加剤を併用できる。そして、他の化合物を併用した場合にも、優れた撥水撥油性能、および分散型組成物としての安定性を発揮する。
【００６２】
本発明の水分散型撥水撥油剤組成物で処理されうる物品は、特に限定なく種々の例を挙げられる。たとえば、繊維織物、ガラス、紙、木、皮革、毛皮、石綿、レンガ、セメント、金属および酸化物、窯業製品、プラスチックなどがある。
【００６３】
繊維織物としては、綿、麻、羊毛、絹などの動植物性天然繊維、ポリアミド、ポリエステル、ポリビニルアルコール、ポリアクリロニトリル、ポリ塩化ビニル、ポリプロピレン等の種々の合成繊維、レーヨン、アセテート等の半合成繊維、ガラス繊維、炭素繊維、アスベスト繊維等の無機繊維、あるいはこれらの混合繊維の織物が挙げられる。
【００６４】
【作用】
本発明の水分散型撥水撥油剤組成物が優れた安定性を示す機構は必ずしも明確ではないが、本発明の組成物においては、非イオン性界面活性剤（ｄ）の通常の安定化効果に加えて、陽イオン性の窒素原子とポリオキシアルキレン鎖を有する界面活性剤（ｃ）が、特に共存する酸またはアニオン性物質に作用することによって、共存物質が他の化合物と反応して組成物から水系媒体に不溶な化合物が生成するのを防ぐと考えられる。また、不溶性の化合物が生成したとしても、界面活性剤（ｃ）中の親水性のポリオキシアルキレン鎖の可溶化作用により組成物の安定性が向上すると考えられる。一方、このような親水性部分を有する界面活性剤（ｃ）は撥水撥油性能に悪影響を与えるおそれがあるが、その悪影響は、長鎖アルキル基等の疎水基を有するカチオン性界面活性剤（ｅ）の疎水作用により低減されると推定される。
【００６５】
【実施例】
つぎに、本発明を実施例（例１〜６）および比較例（例７〜９）によって具体的に説明するが、これらによって本発明は限定されない。なお、以下の例に示す撥水性はＪＩＳ Ｌ１０９２のスプレー法による撥水性ナンバー（下記表１参照）をもって表し、撥油性は下記表２に示す試験溶液を試料布の上、２ケ所に数滴（径約４ｍｍ）置き、３０秒後の浸透状態により判定した（ＡＡＴＣＣ−ＴＭ１１８−１９６６）。
【００６６】
【表１】

【００６７】
【表２】

【００６８】
［例１］
１リットルのガラス製オートクレーブにパーフルオロアルキルエチルアクリレート［Ｃ_n Ｆ_2n+1ＣＨ₂ ＣＨ₂ ＯＣＯＣＨ＝ＣＨ₂ であり、ｎが６〜１６の混合物で平均値は９］（１５４ｇ）、ステアリルアクリレート（９５ｇ）、（２−ヒドロキシエチル）アクリレート（７. ７ｇ）、ステアリルメルカプタン（０. ７７ｇ）、（ポリオキシエチレン）オクチルフェニルエーテル（１８. ５ｇ）、ステアリルトリメチルアンモニウムクロリド（２. ７ｇ）、Ｒ−Ｎ⁺(ＣＨ₂ Ｐｈ)[（Ｃ₂ Ｈ₄ Ｏ）₁₅Ｈ］₂ Ｃｌ^- ［Ｒは牛脂アルキル基であり、Ｐｈはフェニル基を示す。］（５. ３ｇ）、イオン交換水（３０７. ６ｇ）、ジプロピレングリコールモノメチルエーテル（ＤＰＧＭＭＥ）（１４１ｇ）、アゾビス（ジメチレンイソブチラミジン）塩酸塩（０. ５ｇ）を加えた後、オートクレーブを窒素置換した。撹拌しながら６０℃に昇温して６時間重合を行い、固形分濃度３８％、粒子径０. ０８μｍの乳白色エマルションを得た。
【００６９】
［例２〜６］
表３に示す重合性単量体および界面活性剤を、表３に示す量用いて、例１と同様に重合を行いエマルションを得た。なお、表３、表４中の略号は下記のとおりである。
【００７０】
ＦＡ：Ｃ_n Ｆ_2n+1ＣＨ₂ ＣＨ₂ ＯＣＯＣＨ＝ＣＨ₂ であり、ｎが６〜１６の混合物である。
ＳｔＡ：ステアリルアクリレート。
ＨＥＡ：（２−ヒドロキシエチル）アクリレート。
ＧＭＡ：グリシジルメタクリレート。
ＶＣｌ：塩化ビニル。
ＤＯＭ：ジオクチルマレート。
ＤＭＡＡ：ジメチルアクリルアミド。
ＰＥＰＡ：ポリオキシエチレンポリオキシプロピレンメタクリレート。
ＨＥ６Ｐ：片末端メチルエチルケトンオキシムブロック化イソホロンジイソシアナート／２−ヒドロキシエチルメタクリレート反応物。
ＥＤＭＡ：エチレングリコールジメタクリレート。
ＣＨＭＡ：シクロヘキシルメタクリレート。
ＮＭＡＭ：Ｎ−メチロールアクリルアミド。
【００７１】
ＴＢｚＰＯＥＣ：下式（１０）で示されるポリオキシエチレン牛脂アルキルベンジルアンモニウムクロリド。ただし、式（１０）において、Ｒは牛脂アルキル基であり、Ｐｈはフェニル基であり、ａは０〜３０の整数、ｂは０〜３０の整数であり、ａ＋ｂ＝３０である。
ＳＭＰＯＥＣ：下式（１１）で示されるポリオキシエチレンステアリルメチルアンモニウムクロリドであり、Ｒはステアリル基、ｃは０〜１５の整数、ｄは０〜１５の整数であり、ｃ＋ｄ＝１５である。
ＰＯＥ・ＯＰＥ：ポリオキシエチレン（オクチルフェニル）エーテルであり、オキシエチレン単位を２０個含む化合物。
ＰＯＥＬ：ポリオキシエチレンラウリルエーテルであり、オキシエチレン単位を１５個含む化合物。
ＳＴＭＡＣ：ステアリルトリメチルアンモニウムクロリド。
ＤＴＤＭＡＣ：ジ（牛脂アルキル）ジメチルアンモニウムクロリド。
【００７２】
【化６】

【００７３】
【化７】

【００７４】
【表３】

【００７５】
［例７〜９］
表４に示す重合性単量体、界面活性剤を用いて、例１と同様に重合を行い例７〜９のエマルションを得た。
【００７６】
【表４】

【００７７】
［撥水撥油性能の評価］
上記の方法で得られたエマルションを固形分濃度を２０重量％に水で調整してこれを原液とした。原液の水に対する割合が２重量％となるように希釈したものを処理液として、撥水撥油性能を測定した。
また、ナイロン用染料固着剤（フィックス剤と記す。明成化学工業社製／商品名：ディマフィックスＥＳ）を処理液に０．０５重量％添加して、アニオン性物質の存在下の撥水撥油性能および処理浴の状態を調べた。
【００７８】
撥水撥油性能の評価は、撥水撥油処理を以下に示す方法で行ったナイロンタフタ布について行った。上記で調製した処理液に試験布を浸漬し、２本のゴムローラの間で布を絞ってウェットピックアップを６０重量％とした。ついで１１０℃で９０秒間乾燥し、さらに１７０℃で６０秒間熱処理した布を得て、この布について評価した。
【００７９】
処理浴の状態は、フィックス剤添加後の処理浴を目視観察した。○は沈降の生じないもの、△は強い白濁が認められるもの、×は沈降物が認められるものを示す。結果を表５に示す。
【００８０】
【表５】

【００８１】
【発明の効果】
本発明の水分散型撥水撥油剤組成物は、優れた撥水撥油性を示す。また、併用助剤や夾雑物が存在したとしても、撥水撥油性能やエマルションの安定性の低下がないことから、実用性にも優れた水分散型撥水撥油剤組成物である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a water-dispersed water / oil repellent composition excellent in stability in a processing bath and a method for producing the same. Specifically, excellent dispersion stability and water and water repellency can be achieved even when a concomitant drug is included in the processing bath, or when foreign substances adhering to the processed cloth from the pretreatment step are mixed in the processing bath. The present invention relates to a water-dispersed water / oil repellent composition that exhibits oiliness.
[0002]
[Prior art]
A polymer containing a polymerized unit of a polymerizable compound containing a polyfluoroalkyl group such as an acrylate or methacrylate containing polyfluoroalkyl group is synthesized by emulsion polymerization, and the resulting aqueous dispersion is used as a water and oil repellent. Is widely practiced (Japanese Patent Publication No. 47-40467).
[0003]
[Problems to be solved by the invention]
However, conventional aqueous dispersions have emulsion particles due to degradation of water and oil repellency or deterioration of aqueous dispersion due to the presence of acid or anionic substances (such as dye fixing agents and acid dyes) in the processing bath. As a result, the water and oil repellency performance deteriorates, and the polymer adheres to the mangle (gum up), resulting in processing unevenness on the processed cloth.
[0004]
[Means for Solving the Problems]
As a result of repeated studies to solve the above-mentioned problems, the present inventors have included an acid or anionic property by including three kinds of surfactants having a specific combination in a water-dispersed water- and oil-repellent agent. It has been found that a water-dispersed water- and oil-repellent composition that exhibits extremely excellent dispersion stability and does not cause a decrease in water- and oil-repellency even when there are concomitant drugs such as substances and impurities can be provided. .
[0005]
That is, the present invention relates to a water-dispersed water / oil repellent comprising a polymer (a) containing a polymer unit of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium, and a surfactant (b). In the composition, the surfactant (b) contains at least three of the following surfactant (c), the following surfactant (d), and the following surfactant (e), and is a water-dispersed type A water / oil repellent composition and a method for producing the composition are provided.
[0006]
Surfactant (c): a cationic surfactant comprising a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule.
Surfactant (d): Nonionic surfactant.
Surfactant (e): Cationic surfactant other than (c).
[0007]
First, the polymer (a) will be described.
The water-dispersed water / oil repellent composition of the present invention contains a polymer (a) containing polymerized units of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium.
[0008]
In the following, the polyfluoroalkyl group is R^f It is written as a group. In addition, acrylate and methacrylate are collectively referred to as (meth) acrylate, and the same applies to other compounds. In addition, acrylates containing polyfluoroalkyl groups and methacrylates containing polyfluoroalkyl groups are collectively referred to as R^f It is described as group-containing (meth) acrylate.
[0009]
R^f R of group-containing (meth) acrylate^f The group means a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. R^f The group may contain a hydrogen atom substituted with a halogen atom other than a fluorine atom, and a chlorine atom is preferred as the other halogen atom. In addition, R^f In the group, one or more carbon atoms may be substituted with an etheric oxygen atom.
[0010]
R^f 3-20 are preferable and, as for carbon number of group, 4-16 are especially preferable. Also R^f The group preferably has a straight chain or branched structure, and preferably has a straight chain. In the case of a branched structure, the branched portion is R^f The case where it exists in the terminal part of group and carbon number is short is preferable.
[0011]
R^f The number of fluorine atoms in the group is R^f When expressed as a proportion of the number of hydrogen atoms of the corresponding alkyl group having the same carbon number as the group, 60% or more is preferable, and 80% or more is more preferable. R^f The group is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (hereinafter referred to as a perfluoroalkyl group) or an R containing a perfluoroalkyl group.^f Groups are preferred.
[0012]
R^f Group containing (The (meth) acrylate is preferably a compound represented by the formula (10). However, in Formula (10), R^f1Is a carbon number 4 ~ 16'sLinear or branchedR ^f  A perfluoroalkyl group is preferred. In the formula (10), R^f1R of group⁶ It is preferable that a fluorine atom is bonded to the carbon atom bonded to. R⁶ Represents a divalent linking group having 1 to 1 carbon atoms.ZeroA linear or branched alkylene group is preferred, and those described in the specific examples are particularly preferred. R⁷ Represents a hydrogen atom or a methyl group.
[0013]
R ^f1-R⁶ -OCOCR⁷ = CH₂         (10)
[0014]
R^f Group containing (Specific examples of (meth) acrylate are listed below, but are not limited thereto.
[0015]
CF_Three(CF₂)₇(CH₂)₂OCOCH = CH₂
CF_Three(CF₂)₇(CH₂)_ThreeOCOCH = CH₂
CF₂H (CF₂)₇(CH₂)_ThreeOCOCH = CH₂
CF_Three(CF₂)₆CH₂OCOCH = CH₂
CF_Three(CF₂)_FourCH₂OCOC (CH_Three) = CH₂
(CF_Three)₂CF (CF₂)₆(CH₂)₂OCOCH = CH₂
(CF_Three)₂CF (CF₂)_Ten(CH₂)_ThreeOCOCH = CH₂
CF_Three(CF₂)₆(CH₂)₂OCOC (CH_Three) = CH₂
[0016]
(CF_Three)₂CF (CF₂)_Four(CH₂)₂OCOCH = CH₂
CF_Three(CF₂)₇SO₂N (C_ThreeH₇) (CH₂)₂OCOCH = CH₂
CF_Three(CF₂)₇SO₂N (CH_Three) (CH₂)₂OCOC (CH_Three) = CH₂
CF_Three(CF₂)₇(CH₂)_ThreeOCOCH = CH₂
(CF_Three)₂CF (CF₂)_FourCH₂CH (OH) CH₂OCOCH = CH₂
(CF_Three)₂CF (CF₂)₆CH₂CH (OCOCH_Three) OCOC (CH_Three) = CH₂
[0017]
The present inventionInThe polymer (a) has the above R^f 1 type or 2 types or more of group containing (meth) acrylate are included. R when two or more are included^f (Meth) acrylates having different group carbon numbers are preferred.
[0018]
The polymer (a) has the above R^f Although it may be a polymer composed only of polymerized units of a group-containing (meth) acrylate, R^f A copolymer containing a polymerized unit of a polymerizable monomer other than the group-containing (meth) acrylate is preferable. Other polymerizable monomers include R^f The compound is not particularly limited as long as it is a compound copolymerizable with a (meth) acrylate containing a group. Preferable examples of other polymerizable compounds include the following compounds.
[0019]
N-methylol (meth) acrylamide, (meth) acrylamide, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, ethylene glycol di (meth) acrylate, hydroxyalkyl ( (Meth) acrylate, 3-fluoro-2-hydroxypropyl (meth)AkRelate, 3-chloro-2-hydroxypropyl (meth)AkPolymerization having a crosslinkable group such as relate, one-end methyl ethyl ketone oxime blocked isophorone diisocyanate / hydroxyethyl (meth) acrylate reaction, one-end methyl ethyl ketone oxime blocked tolylene diisocyanate / hydroxyethyl (meth) acrylate reaction Monomer.
[0020]
Vinyl chloride, ethylene, vinyl acetate, vinyl fluoride, styrene, α-methylstyrene, alkyl (meth) acrylate, benzyl (meth) acrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl (meth) acrylate, Maleic anhydride, butadiene, isoprene, chloroprene, etc.
[0021]
When the polymer (a) is a copolymer containing a polymerized unit of another polymerizable monomer, one or more kinds of other polymerizable monomers can be included.
[0022]
The present inventionInThe polymer (a) is R^f In the case of a copolymer containing a polymerized unit of a group-containing (meth) acrylate and a polymerized unit of another polymerizable monomer, R in the copolymer^f The polymerized unit of (meth) acrylate containing a group is preferably 40% by weight or more, and particularly preferably about 50 to 80% by weight in the polymer. Further, when a monomer having a crosslinkable group is included as another polymerizable monomer, the amount of the monomer may be small, and usually 0.01 to 10% by weight in the copolymer. About 0.1 to 5% by weight is particularly preferable.
[0023]
The present inventionInThe polymer (a) is dispersed in an aqueous medium. Examples of the aqueous medium include water or water containing a water-soluble organic solvent. Examples of the water-soluble organic solvent include ketones, esters, glycols, glycol ethers, and alcohols. When an aqueous medium contains a water-soluble organic solvent, it is preferable to contain about 5-50 weight part of water-soluble organic solvents with respect to 100 weight part of water.
[0024]
The water-dispersed water / oil repellent composition of the present invention is characterized by containing a specific surfactant (b) together with the aqueous medium and the polymer (a). The specific surfactant (b) is a surfactant including three specific surfactants [surfactant (c), surfactant (d), and surfactant (e)].
[0025]
Surfactant (c): a cationic surfactant comprising a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule.
Surfactant (d) is a nonionic surfactant (hereinafter referred to as nonionic surfactant (d)).
The surfactant (e) is a cationic surfactant other than (c) (hereinafter referred to as a cationic surfactant (e)).
[0026]
First, the surfactant (c) will be described. Surfactant (c) is a cationic surfactant composed of a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule. The surfactant is a component that exhibits excellent dispersion stability in an emulsion even when a concomitant drug such as an acid or an anionic substance or impurities coexist in the processing bath.
[0027]
As the oxyalkylene unit in the surfactant (c) molecule, oxyethylene and oxypropylene are preferable. The oxyalkylene unit may be one type or two or more types. Surfactant (c) is a compound containing 5 or more oxyalkylene units in the molecule, and the oxyalkylene units are present in the molecule as polyoxyalkylene chains in which 2 or more are linked. preferable. The polyoxyalkylene chain may be either a polyoxyalkylene chain in which two or more types of oxyalkylene units are continuous or a polyoxyalkylene chain in which two or more types of oxyalkylene units are continuous. Good. When two or more types of oxyalkylene units are linked, two or more oxyalkylene units may be linked in either a block or random manner. Furthermore, it is preferable that 1 to 3 polyoxyalkylene chains exist in the molecule, and 1 to 2 is particularly preferable. Furthermore, surfactant (c) can contain 1 type (s) or 2 or more types.
[0028]
The present inventionInSpecific examples of the surfactant (c) include the following. In the following formula, when the oxyethylene unit and the propylene unit are continuous, they may be connected in a block form or a random form.
[0029]
[Chemical2]

[0030]
However, R in the specific examples of the surfactant (c)¹ ~ R^Three , [X]^- , A, B, Q, k, m, n, p, and q to v have the following meanings.
R¹ : An alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an acyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group (6 to 22 carbon atoms) is bonded, or an alkenyl group (carbon number) A phenyl group to which 6-22) is bonded;
R² , R^Three : May be the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or a benzyl group.
[0031]
[X]^- : Indicates a monovalent anion, chlorine ion, HSO_Four ^-, NO_Three ^-, CH_Three COO^- , CH_Three CH₂ COO^- , HCOO^- Or C₂ H_Five SO_Four ^-Etc. are preferred.
A: Oxyethylene group.
B: Oxypropylene group [—CH₂ CH (CH_Three ) O- or -CH (CH_Three ) CH₂ O-]. When the oxypropylene group is bonded to a nitrogen atom, the nitrogen atom and —CH₂ Or it is preferable that it couple | bonds with -CH.
Q:-(CH₂ ) _w  − (wIs an integer from 0 to 5. ) Represents a divalent linking group represented by:wWhen 0 is 0, it indicates a single bond, and a nitrogen atom and a nitrogen atom are directly bonded.
[0032]
k, m, n, p: each is an integer of 0-20, and the average value of k + m + n + p is 5-40. k, m, n, and p represent the number of oxyethylene units or oxypropylene units. The number of oxyethylene units and / or oxypropylene units in the easily available surfactant (c) is usually two or more different combinations of k, m, n, and p, and even in that case, k + m + n + p Is an average value of 5 to 40, preferably 10 to 35. Further, when both m and n are 0, it indicates that a nitrogen atom and a hydrogen atom are directly bonded. The same meaning is shown in other cases.
[0033]
q, r, s, t, u, v: each represents an integer of 0-20, and the average value of q + r + s + t + u + v is 5-40. q, r, s, t, u, v represent the number of oxyethylene units or oxypropylene units. The number of oxyethylene units and / or oxypropylene units in the easily available surfactant (c) is usually two or more different combinations of q, r, s, t, u, and v. Even in this case, the average value of q + r + s + t + u + v is 5 to 40, and 10 to 35 is preferable. When both q and r are 0, it indicates that a nitrogen atom and a hydrogen atom are directly bonded. The same meaning is shown in other cases.
[0034]
Further, when the surfactant (c) is any one of the above formulas (1) to (4), the easily available surfactant (c) is usually a mixture of two or more, and R¹ These are mixtures of different types and carbon numbers. For example, R¹ Is a mixed group of an alkyl group and an alkenyl group (coconut oil alkyl group) mainly composed of an alkyl group, an alkyl group and an alkenyl groupofExamples include a mixed group (tallow alkyl group), a group (cured beef tallow alkyl group) that is mostly an alkyl group, and the like.
[0035]
When the ratio of the oxyethylene group or oxypropylene group in the surfactant (c) molecule is small, sufficient processing bath stability, which is the main object of the present invention, cannot be obtained.OsoOn the other hand, if too much, the hydrophilicity increases and sufficient water repellency cannot be obtained.OsoThere is.
[0036]
Of the surfactant (c), the surfactant represented by the formula (1) is commercially available, and examples thereof include the following.
Polyoxyethylene coconut oil alkyl monomethylammonium chloride (average number of oxyethylene groups: 15) [trade name: Esogard C / 25 (manufactured by Lion Akzo)].
Polyoxyethylene lauryl monomethyl ammonium chloride (average number of oxyethylene groups: 7) [trade name: Cation L-207 (manufactured by NOF Corporation)].
[0037]
The surfactant represented by the formula (1) includes a surfactant represented by the following formula (5), a mineral acid such as hydrochloric acid, sulfuric acid and nitric acid, an organic acid such as formic acid, acetic acid and propionic acid, and a chloride. It can also be synthesized by reaction with methyl, benzyl chloride, diethyl sulfate, dimethyl sulfate and the like. R in formula (5)¹ , A, B, k, m, n, and p have the same meaning as described above.
[0038]
[Chemical3]

[0039]
The surfactant represented by the formula (5) is commercially available, and examples thereof include the following.
Polyoxyethylene stearylamine (average number of oxyethylene groups: 15) [trade name: Naimine S-215 (manufactured by NOF Corporation)]. The structure of Naimine S-215 is shown in Formula (6). In the formula (6), a is an integer of 0-15, b is an integer of 0-15, the average value of a + b is 15, and R represents a stearyl group.
[0040]
[Chemical4]

[0041]
Polyoxyethylene coconut oil alkylamine (average number of oxyethylene groups: 15) [trade name: Esomine C / 25 (manufactured by Lion Akzo)].
Polyoxyethylene oleylamine (average number of oxyethylene groups: 10) [trade name: Esomine O / 20 (manufactured by Lion Akzo)].
Polyoxyethylene polyoxypropylene coconut oil alkylamine (average number of oxyethyleneoxypropylene groups: 16) [trade name: Esopropomin C / 18-18 (manufactured by Lion Akzo)].
[0042]
Of the surfactant (c), the surfactant represented by the formula (2) is a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid with respect to 1 equivalent of the surfactant represented by the formula (7). It can be synthesized by reacting 2 equivalents of organic acid such as formic acid, acetic acid and propionic acid, methyl chloride, benzyl chloride, diethyl sulfate, dimethyl sulfate and the like. However, R in Formula (7)¹ , A, B, and q to v have the same meaning as described above.
[0043]
[Chemical5]

[0044]
Moreover, surfactant represented by Formula (3) and Formula (4) among surfactant (c) is hydrochloric acid, with respect to 1 equivalent of surfactant represented by said Formula (7). It can be synthesized by reacting 1 equivalent of a mineral acid such as sulfuric acid and nitric acid, an organic acid such as formic acid, acetic acid and propionic acid, methyl chloride, benzyl chloride, diethyl sulfuric acid and dimethyl sulfuric acid.
[0045]
Next, the nonionic surfactant (d) will be described.
As the nonionic surfactant (d), a known or well-known nonionic surfactant can be adopted, and among the nonionic surfactants described in the surfactant handbook, polyethylene glycol type and polyhydric alcohol fatty acid Nonionic surfactants classified as (partial) ester types are preferred. Nonionic surfactant (d) can contain 1 type (s) or 2 or more types.
[0046]
Nonionic surfactants (d) include polyethylene glycol esters, polyoxyethylene alkyl ethers, polyoxyethylene propylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene glycerin. Examples thereof include esters, sorbitan esters, glycerin esters, polyoxyethylene fatty acid esters and the like. In particular, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene propylene alkyl ethers are preferable because of their high stability.
[0047]
Further, the cationic surfactant (e) will be described.
The cationic surfactant (e) is a cationic surfactant other than the surfactant (c), and is a quaternary ammonium among known or well-known cationic surfactants described in the surfactant handbook. A surfactant classified into a salt type or an amine salt type is preferable, and an alkylammonium salt or an alkylamine salt is particularly preferable. Cationic surfactant (e) can also contain 1 type, or 2 or more types. Furthermore, from the viewpoint that the cationic surfactant does not adversely affect the water and oil repellency after processing into fibers, the alkylammonium salt represented by the formula (8) is an alkylamine salt. Is preferably represented by the formula (9).
[0048]
[R^Four -N⁺ (CH_Three )₂ R^Five ] ・ [X¹ ]^- (8)
R^Four -N (CH_Three ) R^Five No salt (9)
[0049]
However, in the formulas (8) and (9), R^Four , R^Five , And [X¹ ]^- Indicates the following meanings.
R^Four : A C6-C22 alkyl group, a C6-C22 alkenyl group, a phenyl group to which an alkyl group (C6-C22) is bonded, or an alkenyl group (C6-C22) is bonded A phenyl group is shown, and an alkyl group having 12 to 22 carbon atoms or an alkenyl group having 12 to 22 carbon atoms is preferable.
R^Five : A hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a phenyl group to which an alkyl group (6 to 22 carbon atoms) is bonded, or a phenyl to which an alkenyl group (6 to 22 carbon atoms) is bonded A benzyl group to which a group, a benzyl group, or an alkenyl group (having 6 to 22 carbon atoms) is bonded, a hydrogen atom, a methyl group, an ethyl group, a benzyl group, an alkyl group having 12 to 22 carbon atoms, or a carbon atom having 12 to 22 carbon atoms 22 alkenyl groups are preferred.
[0050]
[X¹ ]^- : Indicates a monovalent anion, chlorine ion, HSO_Four ^-, NO_Three ^-, CH_Three COO^- , CH_Three CH₂ COO^- , HCOO^- , C₂ H_Five SO_Four ^-Etc. are preferred.
[0051]
The present inventionInThe amount ratio of the surfactants (c), (d) and (e) in the specific surfactant (b) is preferably in the following relationship when expressed in weight ratio.
(D) / (c) = 99/1 to 1/99.
(E) / [(c) + (d)] = 1/99 to 40/60.
[0052]
In the water-dispersed water / oil repellent composition of the present invention, it is important to contain at least three kinds of surfactants as the surfactant. For example, the nonionic surfactant (d) alone is not sufficient in stability in the processing bath in the presence of impurities, and there is a problem that polymer adhesion (gum up) occurs on the mangle. On the other hand, the surfactant (c) alone has a problem that water and oil repellency is not sufficient although stability to impurities is increased. Therefore, it is necessary to use (d) and (c) in combination as the surfactant. The ratio of (d) and (c) is preferably used by mixing at an arbitrary ratio between (d) / (c) = 99/1 to 1/99, and (d) / (c) = The ratio is particularly preferably 95/5 to 40/60.
[0053]
Furthermore, in the present invention, it is important to use the component (e) together in order to achieve both good dispersion stability and high water / oil repellency. However, when the proportion of the component (e) becomes too high, the dispersion stability is lowered. Therefore, the range of (e) / [(c) + (d)] = 1/99 to 40/60 is preferable. ~ 35/65 is particularly preferred.
[0054]
Total amount of surfactant (b)Is heavy3 to 15 parts by weight is preferable with respect to 100 parts by weight of the combined (a), and 5 to 13 parts by weight is particularly preferable. If the amount of the surfactant (b) is small, the stability of the emulsion is not sufficient, and if it is large, the water and oil repellency may be lowered.
[0055]
In the water-dispersed water / oil repellent composition of the present invention, a surfactant other than the surfactant (b) is added.IncludedIt may be allowed. Examples of other surfactants include amphoteric surfactants and polymer surfactants other than the above-described surfactants (c) to (e). For example, betaine acetates, imidazolinium betaines, amine oxides, Polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfate, polyvinyl alcohol, etc. are mentioned.
[0056]
The present inventionInThe method for obtaining the polymer (a) is not particularly limited, but a method of synthesizing the polymer by an emulsion polymerization method is efficient and preferable. Further, a method of synthesizing the polymer (a) by an emulsion polymerization method is adopted, and the polymer (a) is naturally dispersed by stirring at the time of polymerization. A method of emulsifying with an apparatus and then dispersing by starting polymerization is preferred.
That is, the present inventionInWhen the polymer (a) is obtained by an emulsion polymerization method, R^f A method of synthesizing (meth) acrylate containing a group and, if necessary, other polymerizable monomer by emulsion polymerization in the presence of a specific surfactant (b) is preferable.
[0057]
As a polymerization medium at the time of emulsion polymerization,Water dispersion typeThe same water-based medium as the water / oil repellent composition is preferably used, and examples include water alone or water containing a water-soluble organic solvent. Examples of the water-soluble organic solvent include ketones, esters, glycols, glycol ethers, and alcohols.
[0058]
Emulsion polymerization is usually carried out by allowing a polymerization initiation source to act. The polymerization initiation source is not particularly limited, and usual polymerization initiators such as organic peroxides, azo compounds and persulfates, or ionizing radiation such as γ rays can be employed.
[0059]
R dispersed in an aqueous medium ^f Group containing (The polymer (a) containing a polymerized unit of (meth) acrylate is preferably dispersed in the form of particles, and the particle system is preferably about 0.03 to 0.25 μm.
[0060]
The water-dispersed water / oil repellent composition of the present invention is diluted to an arbitrary concentration and applied to an object to be treated according to the purpose and application. As an application method of the object to be processed, any method can be adopted depending on the type of the object to be processed. For example, a method of adhering to the surface of an object to be processed and drying by a known method of coating processing such as dip coating can be employed. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured.
[0061]
The water-dispersed water / oil repellent composition of the present invention exhibits excellent stability even when other compounds are used in combination, so that other polymer blenders, other water repellents, Additives such as oil repellents or insect repellents, flame retardants, antistatic agents, dye stabilizers, and anti-wrinkle agents can be used in combination. Even when other compounds are used in combination, excellent water and oil repellency and stability as a dispersed composition are exhibited.
[0062]
Of the present inventionWater dispersion typeWater and oil repellentCompositionExamples of articles that can be treated with are not particularly limited, and various examples can be given. Examples include textile fabrics, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics and the like.
[0063]
As textile fabrics, animal and vegetable natural fibers such as cotton, hemp, wool, silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibers such as rayon and acetate, Examples thereof include inorganic fibers such as glass fibers, carbon fibers and asbestos fibers, or woven fabrics of these mixed fibers.
[0064]
[Action]
The mechanism of the excellent stability of the water-dispersed water / oil repellent composition of the present invention is not necessarily clear, but in the composition of the present invention,NonionicIn addition to the normal stabilizing effect of the surfactant (d), the surfactant (c) having a cationic nitrogen atom and a polyoxyalkylene chain acts on the coexisting acid or anionic substance. It is considered that the coexisting substances are prevented from reacting with other compounds to form insoluble compounds in the aqueous medium from the composition. Even if an insoluble compound is produced, it is considered that the stability of the composition is improved by the solubilizing action of the hydrophilic polyoxyalkylene chain in the surfactant (c). On the other hand, the surfactant (c) having such a hydrophilic part may adversely affect the water / oil repellency, but the adverse effect is having a hydrophobic group such as a long-chain alkyl group.CationicIt is presumed to be reduced by the hydrophobic action of the surfactant (e).
[0065]
【Example】
Next, the present invention will be specifically described with reference to Examples (Examples 1 to 6) and Comparative Examples (Examples 7 to 9), but the present invention is not limited thereto. The water repellency shown in the following examples is represented by the water repellency number (see Table 1 below) according to the spray method of JIS L1092, and the oil repellency is a few drops (2 drops) of the test solution shown in Table 2 below on the sample cloth ( (AATCC-TM118-1966) was determined by the penetration state after 30 seconds.
[0066]
[Table 1]

[0067]
[Table 2]

[0068]
[Example 1]
In a 1 liter glass autoclave, perfluoroalkylethyl acrylate [C_n F_{2n + 1}CH₂ CH₂ OCOCH = CH₂ N is a mixture of 6 to 16 and the average value is 9] (154 g), stearyl acrylate (95 g), (2-hydroxyethyl) acrylate (7.7 g), stearyl mercaptan (0.77 g), (polyoxy Ethylene) octylphenyl ether (18.5 g), stearyltrimethylammonium chloride (2.7 g), RN⁺(CH₂ Ph) [(C₂ H_Four O)₁₅H]₂ Cl^- [R represents a beef tallow alkyl group, and Ph represents a phenyl group. (5.3 g), ion-exchanged water (307.6 g), dipropylene glycol monomethyl ether (DPGMME) (141 g), azobis (dimethyleneisobutyridine) hydrochloride (0.5 g), and then an autoclave. Was replaced with nitrogen. While stirring, the temperature was raised to 60 ° C. and polymerization was carried out for 6 hours to obtain a milky white emulsion having a solid content concentration of 38% and a particle size of 0.08 μm.
[0069]
[Examples 2 to 6]
Using the polymerizable monomer and surfactant shown in Table 3 in the amounts shown in Table 3, polymerization was carried out in the same manner as in Example 1 to obtain an emulsion. In addition, the symbol in Table 3 and Table 4 is as follows.
[0070]
FA: C_n F_{2n + 1}CH₂ CH₂ OCOCH = CH₂ And n is a mixture of 6-16.
StA: Stearyl acrylate.
HEA: (2-hydroxyethyl) acrylate.
GMA: glycidyl methacrylate.
VCl: Vinyl chloride.
DOM: Dioctyl malate.
DMAA: dimethylacrylamide.
PEPA: polyoxyethylene polyoxypropylene methacrylate.
HE6P: One-end methyl ethyl ketone oxime blocked isophorone diisocyanate / 2-hydroxyethyl methacrylate reaction product.
EDMA: ethylene glycol dimethacrylate.
CHMA: cyclohexyl methacrylate.
NMAM: N-methylolacrylamide.
[0071]
TBzPOEC: polyoxyethylene beef tallow alkyl benzyl ammonium chloride represented by the following formula (10). However, in Formula (10), R is a beef tallow alkyl group, Ph is a phenyl group, a is an integer of 0-30, b is an integer of 0-30, and a + b = 30.
SMPOEC: Polyoxyethylene stearylmethylammonium chloride represented by the following formula (11), R is a stearyl group, c is an integer of 0 to 15, d is an integer of 0 to 15, and c + d = 15.
POE.OPE: A compound that is polyoxyethylene (octylphenyl) ether and contains 20 oxyethylene units.
POEL: Polyoxyethylene lauryl ether, a compound containing 15 oxyethylene units.
STMAC: Stearyl trimethyl ammonium chloride.
DTDMAC: Di (tallow alkyl) dimethylammonium chloride.
[0072]
[Chemical6]

[0073]
[Chemical7]

[0074]
[Table 3]

[0075]
[Examples 7 to 9]
Polymerization was carried out in the same manner as in Example 1 using the polymerizable monomers and surfactants shown in Table 4, and emulsions of Examples 7 to 9 were obtained.
[0076]
[Table 4]

[0077]
[Evaluation of water and oil repellency]
The emulsion obtained by the above method was adjusted to a solid content concentration of 20% by weight with water and used as a stock solution. The water / oil repellency performance was measured using a diluted solution so that the ratio of the stock solution to water was 2% by weight.
In addition, a dye fixing agent for nylon (referred to as a fixing agent; manufactured by Meisei Chemical Industry Co., Ltd./trade name: Dimafix ES) is added to the treatment liquid in an amount of 0.05% by weight to provide water and oil repellency in the presence of an anionic substance. Performance and treatment bath conditions were investigated.
[0078]
The water and oil repellency performance was evaluated on a nylon taffeta cloth which was subjected to the water and oil repellency treatment by the method shown below. The test cloth was immersed in the treatment liquid prepared above, and the cloth was squeezed between two rubber rollers to make the wet pickup 60 wt%. Next, a fabric which was dried at 110 ° C. for 90 seconds and further heat treated at 170 ° C. for 60 seconds was obtained and evaluated.
[0079]
Regarding the state of the treatment bath, the treatment bath after the addition of the fixing agent was visually observed. ○ indicates that sedimentation does not occur, Δ indicates that strong cloudiness is observed, and × indicates that sediment is observed. The results are shown in Table 5.
[0080]
[Table 5]

[0081]
【The invention's effect】
The water-dispersed water / oil repellent composition of the present invention exhibits excellent water / oil repellency. In addition, even if there are co-existing aids and impurities, there is no decrease in water and oil repellency and stability of the emulsion, so it is also practical.Water dispersion typeIt is a water / oil repellent composition.

Claims (5)

In a water-dispersed water / oil repellent composition comprising a polymer (a) containing a polymer unit of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium, and a surfactant (b) The water-dispersed water / oil repellent composition, wherein the agent (b) contains at least three of the following surfactant (c), the following surfactant (d), and the following surfactant (e) .
Surfactant (c): a cationic surfactant comprising a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule.
Surfactant (d): Nonionic surfactant.
Surfactant (e): Cationic surfactant other than (c). A polymer (a) is a polymer synthesized by emulsion polymerization of a polymerizable monomer containing an acrylate or methacrylate containing a polyfluoroalkyl group in an aqueous medium in the presence of a surfactant (b). The water-dispersed water / oil repellent composition according to claim 1. The water-dispersed water / oil repellent composition according to claim 1 or 2, wherein the surfactant (c) is at least one selected from surfactants represented by formulas (1) to (4).
^{However, R 1 ~R 3, [X} ] -, A, B, Q, k, m, n, p, and q~v have the following meanings.
R ¹ : an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an acyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group (6 to 22 carbon atoms) is bonded, or an alkenyl group ( A phenyl group having 6 to 22 carbon atoms bonded thereto.
R ² and R ³ may be the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or a benzyl group.
[X] ^- : a monovalent anion.
A: Oxyethylene group.
B: Oxypropylene group.
Q: a divalent linking group represented by — (CH ₂ ) _w — ( w is an integer of 1 to 5).
k, m, n, p: each is an integer of 0-20, and the average value of k + m + n + p is 5-40.
q, r, s, t, u, v: each is an integer of 0-20, and the average value of q + r + s + t + u + v is 5-40.

The water-dispersed water / oil repellent composition according to claim 1 , 2 or 3, wherein the surfactant (e) is at least one selected from surfactants represented by formula (8) or formula (9). .
[ R ⁴ −N ⁺ (CH ₃ ) ₂ R ⁵ ] · [X ¹ ] ⁻ (8)
R ⁴ —N (CH ₃ ) R ⁵ salt (9)
However, R ⁴ , R ⁵ , and [X ¹ ] ⁻ have the following meanings.
R ⁴ : an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group (having 6 to 22 carbon atoms) is bonded, or an alkenyl group (having 6 to 22 carbon atoms). A bonded phenyl group.
R ⁵ : A hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a phenyl group to which an alkyl group (6 to 22 carbon atoms) is bonded, or an alkenyl group (6 to 22 carbon atoms) is bonded. A benzyl group to which a phenyl group, a benzyl group or an alkenyl group (having 6 to 22 carbon atoms) is bonded.
[X ¹ ] ⁻ : a monovalent anion. The presence of the following surfactant (c), the following surfactant (d), and the following surfactant (e) in a water-based medium containing a polymerizable monomer containing an acrylate or methacrylate containing a polyfluoroalkyl group A method for producing a water-dispersed water- and oil-repellent composition, which comprises emulsion polymerization below.
Surfactant (c): a cationic surfactant comprising a compound containing 5 or more cationic nitrogen atoms and oxyalkylene units in the molecule.
Surfactant (d): Nonionic surfactant.
Surfactant (e): Cationic surfactant other than (c).