JP2006188545A - Aqueous dispersion of water-repelling and oil-repelling agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aqueous dispersion type water-repelling and oil-repelling agent composition more excellent in water-repelling and oil-repelling properties than those of conventional ones, and also excellent in process stability. <P>SOLUTION: This aqueous dispersion of the water-repelling and oil-repelling agent composition is characterized by containing (A) a fluorine-containing polymer, and (B) a nonionic surfactant of a copolymer having a structure that a polyoxyalkylene block (the number of carbons of the alkylene group is ≥3) is at the outside of its molecule and a polyoxyethylene block is at the inside of the molecule so that the polyoxyalkylene block presents from the polyoxyethylene block to the outside of the molecule. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

【化３】

［式中、Ｒｆは炭素数３〜２１のパーフルオロアルキル基またはパーフルオロアルケニル基、Ｒ^１は水素または炭素数１〜１０のアルキル基、Ｒ^２は炭素数１〜１０のアルキレン基、Ｒ^３は水素またはメチル基、Ａｒは置換基を有することもあるアリール基、ｎは１〜１０の整数を表わす。］
で示される（メタ）アクリレートエステルを挙げることができる。
【０００８】
さらに具体的には、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₆(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇ＳＯ₂Ｎ(Ｃ₂Ｈ₅)(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₆ＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)=ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₆ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
【化４】

を例示することができる。
【０００９】
他の共重合可能な重合性化合物には種々のものがあるが、例示すると、 （１）アクリル酸およびメタクリル酸ならびにこれらのメチル、エチル、ブチル、イソブチル、ｔ−ブチル、プロピル、２−エチルヘキシル、ヘキシル、デシル、ラウリル、ステアリル、イソボルニル、β−ヒドロキシエチル、グリシジル、フェニル、ベンジル、４−シアノフェニルエステル類、（２）酢酸、プロピオン酸、カプリル酸、ラウリル酸、ステアリン酸等の脂肪酸のビニルエステル類、（３）スチレン、α−メチルスチレン、ｐ−メチルスチレン等のスチレン系化合物、（４）フッ化ビニル、塩化ビニル、臭化ビニル、フッ化ビニリデン、塩化ビニリデン等のハロゲン化ビニルまたはビニリデン化合物類、（５）ヘプタン酸アリル、カプリル酸アリル、カプロン酸アリル等の脂肪族のアリルエステル類、（６）ビニルメチルケトン、ビニルエチルケトン等のビニルアルキルケトン類、（７）Ｎ−メチルアクリルアミド、Ｎ−メチロールメタクリルアミド等のアクリルアミド類および（８）２，３−ジクロロ−１，３−ブタジエン、イソプレン等のジエン類などを例示できる。
【００１０】
本発明の組成物は界面活性剤（Ｂ）を含む。界面活性剤（Ｂ）は、ポリオキシエチレンブロックから分子の外側に向かってポリオキシアルキレンブロックが存在するように、ポリオキシアルキレンブロック（アルキレン基の炭素数は３以上である。）が分子の外側にあり、ポリオキシエチレンブロックが分子の内側にある化学構造を有する。界面活性剤（Ｂ）において、ポリオキシエチレンブロックの数は１以上であり、ポリオキシアルキレンブロックの数は２以上である。例えば、界面活性剤（Ｂ）は、（１）分子の中央にポリオキシエチレンブロックを配置し、その両端にポリオキシアルキレンブロックを配置した構造であるトリブロック型のコポリマー、あるいは（２）分子の中央に２〜６価の有機基（例えば、４価であるエチレンジアミン基）を有し、有機基にポリオキシエチレンブロック−ポリオキシアルキレンブロックが結合したコポリマーであってよい。
【００１１】
ポリオキシエチレンブロックが親水性であり、ポリオキシアルキレンブロック（アルキレン基の炭素数は３以上である。）が疎水性である。オキシアルキレンにおける炭素数は、例えば、３〜１０であってよい。オキシアルキレンとしては、オキシプロピレン、オキシブチレン等が挙げられるが、中でも、オキシプロピレンが好ましい。
【００１２】
界面活性剤（Ｂ）の例は、式（１）：
Ａ¹¹Ｏ−(Ｒ¹¹Ｏ)_a−(ＣＨ_２ＣＨ_２Ｏ)_b−(Ｒ¹²Ｏ)_c−Ａ¹² （１）
［式中、Ａ¹¹およびＡ¹²は水素原子、炭素数１〜２２のアルキル基、炭素数２〜２２のアルケニル基またはR¹³Ｃ(＝Ｏ)−（R¹³は炭素数１〜２２のアルキル基または炭素数２〜２２のアルケニル基である。）であり、
Ｒ¹¹およびＲ¹²は炭素数３以上のアルキレン基であり、
ａ、ｂおよびｃは２以上の数であり、ｂはコポリマーに対してポリオキシエチレンブロックの重量割合が５〜８０重量％になるような数である。］
で示されるコポリマー、および
式（２）：
【化５】

［式中、Ａ²¹、Ａ²²、Ａ²³およびＡ²⁴は水素原子、炭素数１〜２２のアルキル基、炭素数２〜２２のアルケニル基またはR¹³Ｃ(＝Ｏ)−（R¹³は炭素数１〜２２のアルキル基または炭素数２〜２２のアルケニル基である。）であり、
それぞれのＲ²¹は、同一または異なって、炭素数３以上のアルキレン基であり、それぞれのｘおよびｙは、同一または異なって、２以上の数であり、ｘはコポリマーに対してポリオキシエチレンブロックの重量割合が５〜８０重量％になるような数である。］
で示されるコポリマーである。
【００１３】
界面活性剤（Ｂ）の平均分子量は、５００〜２００００、例えば１０００〜１５０００であってよい。式（１）のコポリマーの平均分子量は１０００〜１００００であることが好ましく、式（２）のコポリマーの平均分子量は平均分子量２０００〜１５０００であることが好ましい。平均分子量は、標準ポリエチレングリコール換算によるゲルパーミエーショングロマトグラフィー（ＧＰＣ）によって測定したものである。
【００１４】
界面活性剤（Ｂ）の具体例は、次のとおりである。
HO-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-H
C₁₀H₂₁O-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-HC₁₂H₂₅O-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-HC₁₆H₃₁O-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-HC₁₆H₃₃O-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-HC₁₂H₂₅O-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c- C₁₂H₂₅C₁₆H₃₁O-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c- C₁₆H₃₁C₁₆H₃₃O-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c- C₁₆H₃₃
【００１５】
【化６】

【００１６】
ポリオキシエチレンブロックの割合が界面活性剤（Ｂ）（コポリマー）の分子量に対して、下限が５重量％、例えば７重量％、特に１０重量％であり、一方、上限が８０重量％、例えば５０重量％、特に４０重量％、特別に３５重量％であるような割合であることができる。界面活性剤（Ｂ）は１種単独でも２種以上を併用することもできる。
【００１７】
界面活性剤（Ｂ）は乳化液の安定性をよくするために、モノマーを乳化する前に、あるいは乳化した後で重合する前に、あるいはモノマーを重合した後に、保護コロイドとして重合液に加えられる。界面活性剤（Ｂ）の量は重合体（Ａ）１００重量部当たり０．０１〜３０重量部、例えば１〜２０重量部であってよいが、加える量により貯蔵安定性や風合いが損なわれることはない。
【００１８】
本発明では界面活性剤（Ｂ）に加えて、界面活性剤（Ｂ）以外の界面活性剤（Ｃ）を併用することが好ましい。界面活性剤（Ｃ）としては、陽イオン性、陰イオン性または非イオン性乳化剤があげられるが、陽イオン性乳化剤または非イオン性乳化剤あるいは両者の混合物であるのが望ましい。
【００１９】
陽イオン性乳化剤には、ドデシルトリメチルアンモニウムアセテート、トリメチルテトラデシルアンモニウムクロライド、ヘキサデシルトリメチルアンモニウムブロマイド、トリメチルオクタデシルアンモニウムクロライド、（ドデシルメチルベンジル）トリメチルアンモニウムクロライド、ベンジルドデシルジメチルアンモニウムクロライド、メチルドデシルジ（ヒドロポリオキシエチレン）アンモニウムクロライド、ベンジルドデシルジ（ヒドロポリオキシエチレン）アンモニウムクロライド、ジ硬化牛脂アルキルジメチルアンモニウムクロライド、Ｎ−［２−（ジエチルアミノ）エチル］オレアミド塩酸塩が包含される。
【００２０】
非イオン性界面活性剤には、エチレンオキシドとヘキシルフェノール、イソオクタチルフェノール、ヘキサデカノール、オレイン酸、アルカン（Ｃ_１２−Ｃ_１６）チオール、ソルビタンモノ脂肪酸（Ｃ_７−Ｃ_１９）またはアルキル（Ｃ_１２−Ｃ_１８）アミンなどとの縮合生成物が包含される。
界面活性剤（Ｃ）は、モノマーを乳化する前に、あるいは乳化した後で重合する前に、あるいはモノマーを重合した後に、重合液に加えられる。
界面活性剤（Ｃ）の量は重合体（Ａ）１００重量部当たり、４０重量部以下、好ましくは０．０１〜３０重量部、例えば１〜２０重量部であってよい。
【００２１】
本発明では重合体の分散性の向上を目的とし、必要に応じて有機溶剤を加えることができる。有機溶剤の例としては、アセトン、メチルエチルケトンのごときケトン類、エチレングリコール、ポリエチレングリコールのごときエチレングリコール誘導体および、ポリエチレングリコールモノメチルエーテル、ポリエチレングリコールジメチルエーテル、ポリエチレングリコールモノブチルエーテルのごときエチレングリコール誘導体のアルキルエーテル類、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコールのごときプロピレングリコール誘導体、シクロデキストリン、デキストリンのごときポリエーテル類、酢酸メチル、酢酸エチルのごときエステル類、Ｎ−アルキルピロリドン等である。有機溶剤の量は重合体１００重量部当たり５〜２００重量部、例えば１０〜１００重量部、特に２０〜８０重量部であってよい。
【００２２】
本発明の水性分散液を製造するには、重合開始剤および必要により界面活性剤の存在下で重合性化合物を、有機溶剤を加えた水中で乳化重合して、重合体の乳濁液を得る。必要に応じて、乳濁液に、水および／または界面活性剤を加える。また必要に応じて有機酸を使用してもよい。
【００２３】
また目的に応じてさらに架橋剤、他の重合体、他の撥水剤、撥油剤、防汚剤、防虫剤、難燃剤、帯電防止剤、染料安定剤、防シワ剤、防縮剤、風合い加工剤、柔軟仕上げ剤、消泡剤等の添加剤等を含んでもよい。
【００２４】
架橋剤としては、ブロック化イソシアネート化合物、メラミン樹脂化合物、グリオキザール系樹脂化合物、尿素系樹脂化合物、架橋性単量体（Ｎ−メチロールアクリルアミド、２−イソシアネートエチルメタクリレートのブロック化体等）を必須重合単位とする重合体等が挙げられ、ブロック化イソシアネート化合物またはメラミン樹脂化合物が好ましい。ここで、ブロック化イソシアネート化合物としては、重合性不飽和基を有しない化合物であり、ポリイソシアネートのイソシアネート基をブロック化剤でブロックした構造の化合物が好ましい。メラミン樹脂化合物としては、トリメチロールメラミン、ヘキサメチロールメラミン等が挙げられる。
【００２５】
本発明の水性分散液を適用する適当な基体は、フィルム、繊維、糸、織布、カーペットならびに天然重合体物質や変性された天然重合体物質や合成重合体物質から得られたフィラメント、繊維あるいは糸で作られた製品である。基体は、繊維、糸または布の形態である繊維製品であることが好ましい。
【００２６】
基体は、ナイロン繊維単独またはナイロン繊維と他の繊維素材との混合物から構成されていることが好ましい。ナイロンはその製造方法により数種が製造販売されているが、その製造方法によらずいずれが用いられてもよい。例えば、ナイロン６、ナイロン６６、ナイロン６１０、ナイロン１２、およびこれらの製造に用いられる原料の成分を有する共重合ナイロン等があげられる。ナイロン繊維と他の繊維素材との混合物としては、例えば、ナイロンとポリエステルの混合物、ナイロンと綿の混合物、ナイロンとポリウレタンの混合物、ナイロンと綿とポリウレタンの混合物、ナイロンとウールの混合物、ナイロンとアクリルとポリウレタンの混合物、ナイロンとポリエステルと麻の混合物等が挙げられる。
【００２７】
水性分散液を基体に適用するには、塗布、浸漬、吹きつけ、パッディング、ロール被覆あるいはこれらの方法の組み合せによるのが望ましい。例えば、浴の固形分量を０．１〜１０重量％にすることによってパッド浴として使用する。基体をこの浴でパッドし、次に普通絞りロールで過剰の液を除いて乾燥吸収（基体上の乾燥重合体の重量）が基体の約０．０１〜１重量％となるようにする。次いで処理基体を１００〜２００℃に加熱するのがよい。
【００２８】
【実施例】
以下に実施例および比較例を示し、本発明を更に詳しく説明する。
特性は、次のようにして測定した。
撥水撥油性
重合体分散液を固形分濃度が０．５重量％になるよう水で希釈して処理液を調製する。ナイロンタフタ布（カネボウ製ナチュレーヌ、ナイロン６、紺色染色布）を処理液に浸漬し、マングルで絞って、ウェットピックアップ４０％とし、１００℃で２分間乾燥し、１６０℃で１分間熱処理した後に、処理布の撥水撥油性を評価する。
撥水性はＪＩＳ−Ｌ−１０９２のスプレー法による撥水性Ｎｏ．（下記表１参照）をもって表す。
撥油性はＡＡＴＣＣ−ＴＭ１１８によって下記表２に示す試験溶液を試験布上、２箇所に数滴たらし、３０秒後の浸透状態を観察し、浸漬を示さない試験溶液が与える撥油性の最高点を撥油性とする。
【００２９】
【表１】

【００３０】
【表２】

【００３１】
撥水撥油性の洗濯耐久性
JIS L-0217-103法による洗濯を３回繰り返して行い、その後の撥水撥油性を評価する(HL-3)。
【００３２】
貯蔵安定性
水性分散液（固形分３０重量％）を、４０℃で１ヶ月保存し、沈降の発生を観察する。
○： 全く沈降なし
△： わずかに沈降あり
×： 多く沈降あり
【００３３】
風合い
５％濃度の処理を施したナイロン（Ｎｙ）布を用意し、触手によりこれらの差異を以下の基準により判定した。
○：未処理布とほとんど同じ、
△：未処理布よりやや硬いが問題となる程度ではない
×：未処理布より明らかに硬い
【００３４】
実施例１
１ＬフラスコにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２（ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１００ｇ、ステアリルアクリレート５０ｇ、Ｎ−メチロールアクリルアミド２ｇ、純水２００ｇ、ジプロピレングリコールモノメチルエーテル５０ｇ、酢酸０．３ｇ、ポリオキシエチレンラウリルエーテル４ｇ、ポリオキシエチレンセチルエーテル１０ｇ、ポリオキシプロピレン−ポリオキシエチレン−ポリオキシプロピレントリブロック共重合体［HO-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-H （平均分子量３１００、オキシエチレンの割合が２０重量％）］４ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。２,２'−アゾビス（２−アミジノプロパン）２塩酸塩０．７５ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００３５】
実施例２
１ＬフラスコにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１００ｇ、ステアリルメタクリレート５０ｇ、３−クロロ−２−ヒドロキシプロピルメタクリレート２ｇ、純水２００ｇ、トリプロピレングリコール４０ｇ、酢酸０．３ｇ、オクタデシルトリメチルアンモニウムクロライド４ｇ、ポリオキシエチレンラウリルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。２,２'−アゾビス（２−アミジノプロパン）２塩酸塩０．７５ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。さらにこの水性分散液にポリオキシプロピレン−ポリオキシエチレン−ポリオキシプロピレントリブロック共重合体［HO-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-H （平均分子量３１００、オキシエチレンの割合が２０重量％）］３ｇを入れ、１時間攪拌させて水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００３６】
実施例３
１ＬフラスコにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１００ｇ、ステアリルアクリレート２５ｇ、２−エチルヘキシルメタクリレート２５ｇ、ダイアセントンアクリルアミド１．２ｇ、３−クロロ−２−ヒドロキシプロピルメタクリレート０．８ｇ、純水２００ｇ、トリプロピレングリコール８０ｇ、酢酸０．３ｇ、オクタデシルトリメチルアンモニウムクロライド４ｇ、ポリオキシエチレンセチルエーテル６ｇ、ポリオキシプロピレン−ポリオキシエチレン−ポリオキシプロピレントリブロック共重合体［HO-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-H （平均分子量２８００、オキシエチレンの割合が１０重量％）］４ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。２,２'−アゾビス（２−アミジノプロパン）２塩酸塩０．７５ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。さらにこの水性分散液にポリオキシプロピレン−ポリオキシエチレン−ポリオキシプロピレントリブロック共重合体［HO-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-H （平均分子量２８００、ポリオキシエチレンの割合が１０重量％）］３ｇを入れ、１時間攪拌させて水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００３７】
実施例４
１ＬオートクレーブにＣｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１５０ｇ、ステアリルアクリレート７５ｇ、ダイアセントンアクリルアミド３ｇ、純水３００ｇ、ジプロピレングリコールモノメチルエーテル７５ｇ、酢酸０．４５ｇ、ジ硬化牛脂アルキルジメチルアンモニウムクロライド６ｇ、ポリオキシエチレンセチルエーテル９ｇ、ポリオキシプロピレン−ポリオキシエチレン−ポリオキシプロピレントリブロック共重合体［HO-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-H （平均分子量３１００、オキシエチレンの割合が２０重量％）］６ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。乳化後ｎ−ドデシルメルカプタン１．５ｇを添加し、さらに塩化ビニル４５ｇを圧入充填した。さらに２,２'−アゾビス（２−アミジノプロパン）２塩酸塩１．１２ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００３８】
実施例５
１ＬオートクレーブにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１５０ｇ、ステアリルアクリレート３７．５ｇ、ラウリルアクリレート３７．５ｇ、Ｎ−メチロールアクリルアミド１．８ｇ、３−クロロ−２−ヒドロキシプロピルメタクリレート１．２ｇ、純水３００ｇ、トリプロピレングリコール７５ｇ、エチレングリコール１５ｇ、酢酸０．４５ｇ、ジ硬化牛脂アルキルジメチルアンモニウムクロライド６ｇ、ポリオキシエチレンラウリルエーテル１５ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。乳化後ｎ−ドデシルメルカプタン１．５ｇを添加し、さらに塩化ビニル４５ｇを圧入充填した。さらに２,２'−アゾビス（２−アミジノプロパン）２塩酸塩１．１２ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。さらにこの水性分散液にポリオキシプロピレン−ポリオキシエチレン−ポリオキシプロピレントリブロック共重合体［HO-(C₃H₆O)_a-(CH₂CH₂O)_b-(C₃H₆O)_c-H （平均分子量２８００、オキシエチレンの割合が１０重量％）］４．５ｇを入れ、１時間攪拌させて水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００３９】
比較例１
１ＬフラスコにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２（ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１００ｇ、ステアリルアクリレート５０ｇ、Ｎ−メチロールアクリルアミド１．２ｇ、３−クロロ−２−ヒドロキシプロピルメタクリレート０．８ｇ、純水２００ｇ、ジプロピレングリコールモノメチルエーテル３０ｇ、酢酸０．３ｇ、オクタデシルトリメチルアンモニウムクロライド４ｇ、ポリオキシエチレンラウリルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。２,２'−アゾビス（２−アミジノプロパン）２塩酸塩０．７５ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００４０】
比較例２
１ＬフラスコにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１００ｇ、ステアリルメタクリレート５０ｇ、３−クロロ−２−ヒドロキシプロピルメタクリレート２ｇ、純水２００ｇ、トリプロピレングリコール４０ｇ、酢酸０．３ｇ、オクタデシルトリメチルアンモニウムクロライド４ｇ、ポリオキシエチレンセチルエーテル６ｇ、ポリオキシエチレン−ポリオキシプロピレン−ポリオキシエチレントリブロック共重合体［HO-(CH₂CH₂O)_p-(C₃H₆O)_q-(CH₂CH₂O)_r-H （平均分子量２９００、ポリオキシエチレンの割合が４０重量％）］４ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。２,２'−アゾビス（２−アミジノプロパン）２塩酸塩０．７５ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００４１】
比較例３
１ＬフラスコにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１００ｇ、ステアリルアクリレート２５ｇ、２−エチルヘキシルメタクリレート２５ｇ、ダイアセントンアクリルアミド１．２ｇ、３−クロロ−２−ヒドロキシプロピルメタクリレート０．８ｇ、純水２００ｇ、トリプロピレングリコール８０ｇ、酢酸０．３ｇ、ジ硬化牛脂アルキルジメチルアンモニウムクロライド４ｇ、ポリオキシエチレンラウリルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。２,２'−アゾビス（２−アミジノプロパン）２塩酸塩０．７５ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。さらにこの水性分散液にポリオキシエチレン−ポリオキシプロピレン−ポリオキシエチレントリブロック共重合体［HO-(CH₂CH₂O)_p-(C₃H₆O)_q-(CH₂CH₂O)_r-H （平均分子量２９００、ポリオキシエチレンの割合が４０重量％）]４ｇを入れ、１時間攪拌させて水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００４２】
比較例４
１ＬオートクレーブにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１５０ｇ、ステアリルアクリレート７５ｇ、ダイアセントンアクリルアミド３ｇ、純水３００ｇ、ジプロピレングリコールモノメチルエーテル７５ｇ、酢酸０．４５ｇ、ジ硬化牛脂アルキルジメチルアンモニウムクロライド６ｇ、ポリオキシエチレンセチルエーテル１５ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。乳化後ｎ−ドデシルメルカプタン１．５ｇを添加し、さらに塩化ビニル４５ｇを圧入充填した。さらに２,２'−アゾビス（２−アミジノプロパン）２塩酸塩１．１２ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００４３】
比較例５
１ＬオートクレーブにＣ_ｎＦ_２ｎ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２ （ｎ＝６，８，１０，１２，１４（ｎの平均８）の化合物の混合物）１５０ｇ、ステアリルアクリレート３７．５ｇ、ラウリルアクリレート３７．５ｇ、Ｎ−メチロールアクリルアミド１．８ｇ、３−クロロ−２−ヒドロキシプロピルメタクリレート１．２ｇ、純水３００ｇ、トリプロピレングリコール７５ｇ、エチレングリコール１５ｇ、酢酸０．４５ｇ、ジ硬化牛脂アルキルジメチルアンモニウムクロライド６ｇ、ポリオキシエチレンラウリルエーテル１５ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。乳化後ｎ−ドデシルメルカプタン１．５ｇを添加し、さらに塩化ビニル４５ｇを圧入充填した。さらに２,２'−アゾビス（２−アミジノプロパン）２塩酸塩１．１２ｇを添加し、６０℃で５時間反応させ、重合体の水性分散液を得た。さらにこの水性分散液にポリオキシエチレン−ポリオキシプロピレン−ポリオキシエチレントリブロック共重合体［HO-(CH₂CH₂O)_p-(C₃H₆O)_q-(CH₂CH₂O)_r-H （平均分子量２９００、ポリオキシエチレンの割合が４０重量％）]６ｇを入れ、１時間攪拌させて水性分散液を得た。
水性分散液の特性を評価した。結果を表３に示す。
【００４４】
【表３】

【００４５】
【発明の効果】
本発明によれば、従来の撥水撥油剤水性分散液組成物よりも撥水撥油性、特に撥油性に優れ、かつ加工安定性に優れた水分散型の撥水撥油剤水性分散液組成物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a water-dispersed water- and oil-repellent agent and a method for producing the same, in which water and oil repellency to a synthetic fiber, in particular, imparting oil repellency to nylon is significantly improved.
[0002]
[Prior art]
It is known that a polymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group is useful as a water / oil repellent agent for a textile fabric. In particular, the polymer is used as an emulsifier. Thus, aqueous dispersions dispersed in an aqueous medium are widely used industrially. WO 00/37583 proposes a method of providing a water-dispersed water / oil repellent having a durable water / oil repellency and excellent storage stability by using a specific organic solvent. Japanese Patent Application Laid-Open No. 2002-275453 discloses a polyoxyl, which is a specific emulsifier, in order to obtain a water-dispersed water / oil repellent composition that exhibits good water / oil repellency and is excellent in production stability and product storage stability. A production method using a block copolymer in which polyoxyethylene chains are arranged at both ends of an alkylene chain and a specific polymerization initiator has been proposed. However, the water / oil repellent composition described above has not been able to provide water / oil / oil repellency, particularly oil / oil repellency, which is sufficiently satisfactory with the recent diversity of water / oil repellent processing.
[0003]
[Problems to be solved by the invention]
The present invention has been made to solve the above-mentioned problems, and is a water-dispersed repellency that is superior in water and oil repellency, in particular oil repellency, and processing stability to conventional water and oil repellent compositions. An object is to provide a water / oil repellent aqueous dispersion composition.
[0004]
[Means for Solving the Problems]
The present invention relates to (A) at least one homopolymer or copolymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group, or a polymerizable property copolymerizable therewith. A fluoropolymer that is a copolymer with the compound, and
(B) The polyoxyalkylene block (the number of carbon atoms of the alkylene group is 3 or more) is on the outside of the molecule so that the polyoxyalkylene block exists from the polyoxyethylene block to the outside of the molecule. Nonionic surfactant which is a copolymer having a structure in which an ethylene block is inside the molecule
A water- and oil-repellent aqueous dispersion composition comprising:
[0005]
The present invention relates to a method for treating a substrate, characterized by applying the water / oil repellent aqueous dispersion composition to a substrate and attaching the polymer (A) to the substrate, and the water / oil repellent aqueous dispersion composition. A treated product obtained by treating a substrate with the product is also provided.
[0006]
In the case of a copolymer with a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group in the fluoropolymer (A), The former is at least 25% by weight in the copolymer, preferably at least 40% by weight.
Examples of polymerizable compounds having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group have the formula:
[0007]
[Chemical formula 2]

[Chemical Formula 3]

[Wherein Rf is a perfluoroalkyl group or perfluoroalkenyl group having 3 to 21 carbon atoms, R¹Is hydrogen or an alkyl group having 1 to 10 carbon atoms, R²Is an alkylene group having 1 to 10 carbon atoms, R³Represents hydrogen or a methyl group, Ar represents an aryl group which may have a substituent, and n represents an integer of 1 to 10. ]
(Meth) acrylate ester shown by can be mentioned.
[0008]
More specifically,
CF_Three(CF₂)₇(CH₂) OCOCH = CH₂,
CF_Three(CF₂)₆(CH₂) OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)₆(CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₇(CH₂)₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₇(CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₇SO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₇SO₂N (C₂H_Five) (CH₂)₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)₆CH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)₆CH₂CH (OH) CH₂OCOCH = CH₂,
[Formula 4]

Can be illustrated.
[0009]
There are various other copolymerizable polymerizable compounds. Examples include (1) Acrylic acid and methacrylic acid and their methyl, ethyl, butyl, isobutyl, t-butyl, propyl, 2-ethylhexyl, Hexyl, decyl, lauryl, stearyl, isobornyl, β-hydroxyethyl, glycidyl, phenyl, benzyl, 4-cyanophenyl esters, (2) vinyl esters of fatty acids such as acetic acid, propionic acid, caprylic acid, lauric acid, stearic acid (3) Styrenic compounds such as styrene, α-methylstyrene, p-methylstyrene, (4) Vinyl halides or vinylidene compounds such as vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride (5) allyl heptanoate, allyl caprylate, cap Aliphatic allyl esters such as allyl acid, (6) vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone, (7) acrylamides such as N-methylacrylamide and N-methylolmethacrylamide, and (8) Examples include dienes such as 2,3-dichloro-1,3-butadiene and isoprene.
[0010]
The composition of the present invention contains a surfactant (B). In the surfactant (B), the polyoxyalkylene block (the number of carbon atoms of the alkylene group is 3 or more) is outside the molecule so that the polyoxyalkylene block exists from the polyoxyethylene block toward the outside of the molecule. And has a chemical structure in which the polyoxyethylene block is inside the molecule. In the surfactant (B), the number of polyoxyethylene blocks is 1 or more, and the number of polyoxyalkylene blocks is 2 or more. For example, the surfactant (B) is (1) a triblock type copolymer having a structure in which a polyoxyethylene block is arranged at the center of a molecule and polyoxyalkylene blocks are arranged at both ends thereof, or (2) It may be a copolymer having a divalent to hexavalent organic group (for example, a tetravalent ethylenediamine group) in the center and a polyoxyethylene block-polyoxyalkylene block bonded to the organic group.
[0011]
The polyoxyethylene block is hydrophilic, and the polyoxyalkylene block (the alkylene group has 3 or more carbon atoms) is hydrophobic. Carbon number in oxyalkylene may be 3-10, for example. Examples of oxyalkylene include oxypropylene and oxybutylene. Among them, oxypropylene is preferable.
[0012]
Examples of surfactants (B) are those of formula (1):
A¹¹O- (R¹¹O)_a-(CH₂CH₂O)_b-(R¹²O)_c-A¹²      (1)
[Where A¹¹And A¹²Is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or R¹³C (= O)-(R¹³Is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. ) And
R¹¹And R¹²Is an alkylene group having 3 or more carbon atoms,
a, b and c are numbers of 2 or more, and b is a number such that the weight ratio of the polyoxyethylene block to the copolymer is 5 to 80% by weight. ]
A copolymer represented by
Formula (2):
[Chemical formula 5]

[Where A^{twenty one}, A^{twenty two}, A^{twenty three}And A^{twenty four}Is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or R¹³C (= O)-(R¹³Is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. ) And
Each R^{twenty one}Are the same or different and are alkylene groups having 3 or more carbon atoms, and each x and y are the same or different and are 2 or more, and x is a weight ratio of the polyoxyethylene block to the copolymer. The number is 5 to 80% by weight. ]
It is a copolymer shown by these.
[0013]
The average molecular weight of the surfactant (B) may be 500 to 20000, for example 1000 to 15000. The average molecular weight of the copolymer of formula (1) is preferably 1000 to 10,000, and the average molecular weight of the copolymer of formula (2) is preferably 2000 to 15000. The average molecular weight is measured by gel permeation chromatography (GPC) in terms of standard polyethylene glycol.
[0014]
Specific examples of the surfactant (B) are as follows.
HO- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-H
C_TenH_{twenty one}O- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-HC₁₂H_{twenty five}O- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-HC₁₆H₃₁O- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-HC₁₆H₃₃O- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-HC₁₂H_{twenty five}O- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-C₁₂H_{twenty five}C₁₆H₃₁O- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-C₁₆H₃₁C₁₆H₃₃O- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-C₁₆H₃₃
[0015]
[Chemical 6]

[0016]
The proportion of polyoxyethylene blocks is 5% by weight, for example 7% by weight, in particular 10% by weight, with respect to the molecular weight of the surfactant (B) (copolymer), while the upper limit is 80% by weight, for example 50 It can be in proportions such as 40% by weight, in particular 40% by weight, especially 35% by weight. Surfactant (B) can be used alone or in combination of two or more.
[0017]
In order to improve the stability of the emulsion, the surfactant (B) is added to the polymerization liquid as a protective colloid before emulsifying the monomer, before emulsification, before polymerization, or after polymerization of the monomer. . The amount of the surfactant (B) may be 0.01 to 30 parts by weight, for example 1 to 20 parts by weight per 100 parts by weight of the polymer (A), but the storage stability and texture may be impaired depending on the amount added. There is no.
[0018]
In the present invention, in addition to the surfactant (B), a surfactant (C) other than the surfactant (B) is preferably used in combination. The surfactant (C) includes a cationic, anionic or nonionic emulsifier, and is preferably a cationic emulsifier or a nonionic emulsifier or a mixture of both.
[0019]
Cationic emulsifiers include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi (hydropoly). Oxyethylene) ammonium chloride, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, di-cured tallow alkyl dimethyl ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride are included.
[0020]
Nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkanes (C₁₂-C₁₆) Thiol, sorbitan mono fatty acid (C₇-C₁₉) Or alkyl (C₁₂-C₁₈) Condensation products with amines and the like are included.
Surfactant (C) is added to the polymerization solution before emulsifying the monomer, before emulsification and before polymerization, or after polymerizing the monomer.
The amount of the surfactant (C) may be 40 parts by weight or less, preferably 0.01 to 30 parts by weight, for example 1 to 20 parts by weight, per 100 parts by weight of the polymer (A).
[0021]
In the present invention, an organic solvent can be added as needed for the purpose of improving the dispersibility of the polymer. Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, ethylene glycol derivatives such as ethylene glycol and polyethylene glycol, and alkyl ethers of ethylene glycol derivatives such as polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether and polyethylene glycol monobutyl ether, Propylene glycol derivatives such as propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol, polyethers such as cyclodextrin and dextrin, esters such as methyl acetate and ethyl acetate, and N-alkylpyrrolidone. The amount of organic solvent may be 5 to 200 parts by weight, for example 10 to 100 parts by weight, in particular 20 to 80 parts by weight, per 100 parts by weight of polymer.
[0022]
To produce the aqueous dispersion of the present invention, a polymerizable compound is emulsion-polymerized in water containing an organic solvent in the presence of a polymerization initiator and, if necessary, a surfactant to obtain a polymer emulsion. . If necessary, add water and / or surfactant to the emulsion. Moreover, you may use an organic acid as needed.
[0023]
Depending on the purpose, cross-linking agents, other polymers, other water repellents, oil repellents, antifouling agents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, anti-shrink agents, texture processing An additive such as an agent, a softening finish, and an antifoaming agent may be included.
[0024]
As a crosslinking agent, a blocked isocyanate compound, a melamine resin compound, a glyoxal resin compound, a urea resin compound, a crosslinkable monomer (N-methylol acrylamide, a blocked form of 2-isocyanate ethyl methacrylate, etc.) is an essential polymerization unit. The blocked isocyanate compound or the melamine resin compound is preferable. Here, the blocked isocyanate compound is a compound having no polymerizable unsaturated group, and a compound having a structure in which the isocyanate group of polyisocyanate is blocked with a blocking agent is preferable. Examples of the melamine resin compound include trimethylol melamine and hexamethylol melamine.
[0025]
Suitable substrates to which the aqueous dispersions of the present invention are applied include films, fibers, yarns, woven fabrics, carpets and filaments, fibers or fibers obtained from natural polymeric materials, modified natural polymeric materials or synthetic polymeric materials. A product made of yarn. The substrate is preferably a textile product in the form of a fiber, yarn or fabric.
[0026]
The substrate is preferably made of nylon fibers alone or a mixture of nylon fibers and other fiber materials. Several types of nylon are manufactured and sold depending on the manufacturing method, but any of them may be used regardless of the manufacturing method. For example, nylon 6, nylon 66, nylon 610, nylon 12, and copolymer nylon having ingredients of raw materials used for production thereof can be mentioned. Mixtures of nylon fibers and other fiber materials include, for example, nylon and polyester mixtures, nylon and cotton mixtures, nylon and polyurethane mixtures, nylon and cotton and polyurethane mixtures, nylon and wool mixtures, and nylon and acrylic. And a mixture of nylon and polyester, and a mixture of nylon, polyester and hemp.
[0027]
In order to apply the aqueous dispersion to the substrate, it is desirable to use coating, dipping, spraying, padding, roll coating, or a combination of these methods. For example, it is used as a pad bath by setting the solid content of the bath to 0.1 to 10% by weight. The substrate is padded with this bath and then the excess liquid is removed with a regular squeeze roll so that the dry absorption (weight of dry polymer on the substrate) is about 0.01 to 1% by weight of the substrate. The treated substrate is then preferably heated to 100-200 ° C.
[0028]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The characteristics were measured as follows.
Water and oil repellency
A treatment liquid is prepared by diluting the polymer dispersion with water so that the solid concentration is 0.5% by weight. Nylon taffeta cloth (Kanebo Naturine, nylon 6, amber dyed cloth) is dipped in the treatment liquid, squeezed with a mangle, made 40% wet pickup, dried at 100 ° C. for 2 minutes, and heat treated at 160 ° C. for 1 minute. Evaluate the water and oil repellency of the treated fabric.
The water repellency was measured according to the water repellent No. JIS-L-1092 spray method. (See Table 1 below).
The oil repellency is the highest point of oil repellency given by the test solution shown in Table 2 below by AATCC-TM118. Is made oil-repellent.
[0029]
[Table 1]

[0030]
[Table 2]

[0031]
Water and oil repellent washing durability
Washing is repeated 3 times according to JIS L-0217-103, and the subsequent water and oil repellency is evaluated (HL-3).
[0032]
Storage stability
The aqueous dispersion (solid content 30% by weight) is stored at 40 ° C. for 1 month, and the occurrence of sedimentation is observed.
○: No sedimentation
Δ: Slightly settled
×: Many sedimentation
[0033]
Texture
Nylon (Ny) cloth subjected to 5% concentration treatment was prepared, and these differences were determined by the tentacles according to the following criteria.
○: Almost the same as untreated cloth
Δ: Slightly harder than untreated cloth, but not a problem
×: apparently harder than untreated cloth
[0034]
Example 1
C in a 1 L flask_nF_{2n + 1}CH₂CH₂OCOCH = CH₂(Mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) 100 g, stearyl acrylate 50 g, N-methylol acrylamide 2 g, pure water 200 g, dipropylene glycol monomethyl ether 50 g, acetic acid 0.3 g , Polyoxyethylene lauryl ether 4 g, polyoxyethylene cetyl ether 10 g, polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer [HO- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-H (average molecular weight 3100, oxyethylene ratio is 20% by weight)] was added, and the mixture was emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0035]
Example 2
C in a 1 L flask_nF_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of compounds of n = 6, 8, 10, 12, 14 (average of n 8)) 100 g, stearyl methacrylate 50 g, 3-chloro-2-hydroxypropyl methacrylate 2 g, pure water 200 g, tripropylene glycol 40 g, acetic acid 0.3 g, 4 g of octadecyltrimethylammonium chloride, and 10 g of polyoxyethylene lauryl ether were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. Furthermore, this aqueous dispersion was mixed with a polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer [HO- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-H (average molecular weight 3100, oxyethylene ratio is 20% by weight)] was added and stirred for 1 hour to obtain an aqueous dispersion.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0036]
Example 3
C in a 1 L flask_nF_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of compounds of n = 6, 8, 10, 12, 14 (average of n 8)) 100 g, stearyl acrylate 25 g, 2-ethylhexyl methacrylate 25 g, diaceton acrylamide 1.2 g, 3-chloro-2-hydroxy Propyl methacrylate 0.8 g, pure water 200 g, tripropylene glycol 80 g, acetic acid 0.3 g, octadecyltrimethylammonium chloride 4 g, polyoxyethylene cetyl ether 6 g, polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer [ HO- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-H (average molecular weight 2800, oxyethylene ratio is 10% by weight)] was added, and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. Furthermore, this aqueous dispersion was mixed with a polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer [HO- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-H (average molecular weight 2800, polyoxyethylene ratio is 10% by weight)] was added and stirred for 1 hour to obtain an aqueous dispersion.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0037]
Example 4
CnF in 1L autoclave_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of compounds of n = 6, 8, 10, 12, 14 (average 8 of n)) 150 g, stearyl acrylate 75 g, diaceton acrylamide 3 g, pure water 300 g, dipropylene glycol monomethyl ether 75 g, acetic acid 0.45 g , 6 g of di-cured tallow alkyl dimethyl ammonium chloride, 9 g of polyoxyethylene cetyl ether, polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer [HO- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-H (average molecular weight 3100, oxyethylene ratio is 20% by weight)] was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was press-fitted and filled. Furthermore, 1.12 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of a polymer.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0038]
Example 5
C in 1L autoclave_nF_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of n = 6, 8, 10, 12, 14 (average of n 8) compounds) 150 g, stearyl acrylate 37.5 g, lauryl acrylate 37.5 g, N-methylolacrylamide 1.8 g, 3-chloro-2 -1.2 g of hydroxypropyl methacrylate, 300 g of pure water, 75 g of tripropylene glycol, 15 g of ethylene glycol, 0.45 g of acetic acid, 6 g of di-cured tallow alkyldimethylammonium chloride and 15 g of polyoxyethylene lauryl ether are added at 60 ° C. with stirring. The mixture was emulsified and dispersed with ultrasonic waves for 15 minutes. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was press-fitted and filled. Furthermore, 1.12 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of a polymer. Furthermore, this aqueous dispersion was mixed with a polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer [HO- (C_ThreeH₆O)_a-(CH₂CH₂O)_b-(C_ThreeH₆O)_c-H (average molecular weight 2800, oxyethylene ratio is 10% by weight)] was added and stirred for 1 hour to obtain an aqueous dispersion.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0039]
Comparative Example 1
C in a 1 L flask_nF_{2n + 1}CH₂CH₂OCOCH = CH₂(Mixture of n = 6, 8, 10, 12, 14 (n average 8) compounds) 100 g, stearyl acrylate 50 g, N-methylolacrylamide 1.2 g, 3-chloro-2-hydroxypropyl methacrylate 0.8 g, 200 g of pure water, 30 g of dipropylene glycol monomethyl ether, 0.3 g of acetic acid, 4 g of octadecyltrimethylammonium chloride, and 10 g of polyoxyethylene lauryl ether were added and emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0040]
Comparative Example 2
C in a 1 L flask_nF_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of compounds of n = 6, 8, 10, 12, 14 (average of n 8)) 100 g, stearyl methacrylate 50 g, 3-chloro-2-hydroxypropyl methacrylate 2 g, pure water 200 g, tripropylene glycol 40 g, acetic acid 0.3 g, 4 g octadecyltrimethylammonium chloride, 6 g polyoxyethylene cetyl ether, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer [HO- (CH₂CH₂O)_p-(C_ThreeH₆O)_q-(CH₂CH₂O)_r-H (average molecular weight 2900, polyoxyethylene ratio 40% by weight)] was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0041]
Comparative Example 3
C in a 1 L flask_nF_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of compounds of n = 6, 8, 10, 12, 14 (average 8 of n)) 100 g, stearyl acrylate 25 g, 2-ethylhexyl methacrylate 25 g, diaceneton acrylamide 1.2 g, 3-chloro-2-hydroxy Add propyl methacrylate 0.8g, pure water 200g, tripropylene glycol 80g, acetic acid 0.3g, di-cured tallow alkyldimethylammonium chloride 4g, polyoxyethylene lauryl ether 10g, and ultrasonically at 60 ° C for 15 minutes with ultrasonic Emulsified and dispersed. 0.75 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. Further, the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer [HO- (CH₂CH₂O)_p-(C_ThreeH₆O)_q-(CH₂CH₂O)_r-H (average molecular weight 2900, polyoxyethylene ratio 40% by weight)] was added and stirred for 1 hour to obtain an aqueous dispersion.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0042]
Comparative Example 4
C in 1L autoclave_nF_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of compounds of n = 6, 8, 10, 12, 14 (average 8 of n)) 150 g, stearyl acrylate 75 g, diaceton acrylamide 3 g, pure water 300 g, dipropylene glycol monomethyl ether 75 g, acetic acid 0.45 g Then, 6 g of di-cured beef tallow alkyldimethylammonium chloride and 15 g of polyoxyethylene cetyl ether were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was press-fitted and filled. Furthermore, 1.12 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of a polymer.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0043]
Comparative Example 5
C in 1L autoclave_nF_{2n + 1}CH₂CH₂OCOCH = CH₂ (Mixture of n = 6, 8, 10, 12, 14 (average of n 8) compounds) 150 g, stearyl acrylate 37.5 g, lauryl acrylate 37.5 g, N-methylolacrylamide 1.8 g, 3-chloro-2 -1.2 g of hydroxypropyl methacrylate, 300 g of pure water, 75 g of tripropylene glycol, 15 g of ethylene glycol, 0.45 g of acetic acid, 6 g of di-cured tallow alkyldimethylammonium chloride and 15 g of polyoxyethylene lauryl ether are added at 60 ° C. with stirring. The mixture was emulsified and dispersed with ultrasonic waves for 15 minutes. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was press-fitted and filled. Furthermore, 1.12 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of a polymer. Further, the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer [HO- (CH₂CH₂O)_p-(C_ThreeH₆O)_q-(CH₂CH₂O)_r-H (average molecular weight 2900, polyoxyethylene ratio is 40% by weight)] was added and stirred for 1 hour to obtain an aqueous dispersion.
The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3.
[0044]
[Table 3]

[0045]
【The invention's effect】
According to the present invention, a water-dispersed water- and oil-repellent aqueous dispersion composition having superior water- and oil-repellency, particularly oil-repellency, and excellent processing stability, compared to conventional water- and oil-repellent aqueous dispersion compositions. Is obtained.

Claims (10)

(A) Copolymerization of at least one homopolymer or copolymer of a polymerizable compound having a perfluoroalkyl group or perfluoroalkenyl group and an acrylic acid group or methacrylic acid group or a polymerizable compound copolymerizable therewith. The fluorine-containing polymer that is a polymer, and (B) the polyoxyalkylene block (the number of carbon atoms of the alkylene group is 3 or more so that the polyoxyalkylene block exists from the polyoxyethylene block toward the outside of the molecule). A water / oil repellent aqueous dispersion composition comprising a nonionic surfactant which is a copolymer having a structure in which a polyoxyethylene block is inside the molecule and the polyoxyethylene block is inside the molecule.   The composition according to claim 1, wherein the surfactant (B) is a triblock type copolymer having a structure in which a polyoxyethylene block is arranged at the center of the molecule and polyoxyalkylene blocks are arranged at both ends thereof. Surfactant (B) has the formula (1):
^{A 11 O- (R 11 O)} a - (CH 2 CH 2 O) b - (R 12 O) c -A 12 (1)
[Wherein, A ¹¹ and A ¹² are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or R ¹³ C (═O) — (R ¹³ is an alkyl having 1 to 22 carbon atoms. Group or an alkenyl group having 2 to 22 carbon atoms).
R ¹¹ and R ¹² are alkylene groups having 3 or more carbon atoms,
a, b and c are numbers of 2 or more, and b is a number such that the weight ratio of the polyoxyethylene block to the copolymer is 5 to 80% by weight. ]
The composition of Claim 2 which is a copolymer shown by these.   The composition according to claim 1, wherein the surfactant (B) is a copolymer having a divalent to hexavalent organic group at the center of the molecule and a polyoxyethylene block-polyoxyalkylene block bonded to the organic group. Surfactant (B) has formula (2):

[Wherein A ²¹ , A ²² , A ²³ and A ²⁴ are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or R ¹³ C (═O) — (R ¹³ is carbon An alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms).
Each R ²¹ is the same or different and is an alkylene group having 3 or more carbon atoms, each x and y is the same or different and is a number of 2 or more, and x is a polyoxyethylene block relative to the copolymer The weight ratio is such that the weight ratio is 5 to 80% by weight. ]
The composition of Claim 4 which is a copolymer shown by these.   The composition according to claim 1, wherein the polyoxyalkylene block in the surfactant (B) is a polyoxypropylene block.   A method for treating a substrate, comprising applying the water / oil repellent aqueous dispersion composition according to claim 1 to a substrate and attaching the fluoropolymer (A) to the substrate.   The method according to claim 7, wherein the substrate is nylon fiber alone or a mixture of nylon fiber and other fibers.   The method according to claim 7, wherein the surfactant (B) is added to the liquid containing the fluoropolymer (A).   A treated product obtained by treating a substrate with the water / oil repellent aqueous dispersion composition according to claim 1, wherein the substrate is nylon fiber alone or a mixture of nylon fiber and other fibers. Processed product.