JP4457497B2 - 撥水撥油剤水性分散液 - Google Patents

撥水撥油剤水性分散液 Download PDF

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JP4457497B2
JP4457497B2 JP2000589643A JP2000589643A JP4457497B2 JP 4457497 B2 JP4457497 B2 JP 4457497B2 JP 2000589643 A JP2000589643 A JP 2000589643A JP 2000589643 A JP2000589643 A JP 2000589643A JP 4457497 B2 JP4457497 B2 JP 4457497B2
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water
polymer
weight
aqueous dispersion
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雅之 山名
司 阿賀
正弘 宮原
正樹 福森
良輔 原
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Daikin Industries Ltd
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Description

技術分野
本発明は、パーフルオロアルキル基もしくはパーフルオロアルケニル基およびアクリル酸基もしくはメタクリル酸基を有する重合性化合物の重合体を成分とする、各種の繊維に撥水撥油性を付与する撥水撥油剤水性分散液に関する。
関連技術
パーフルオロアルキル基もしくはパーフルオロアルケニル基およびアクリル酸基もしくはメタクリル酸基を有する重合性化合物の重合体が繊維織物の撥水撥油剤として有用であることは知られており、特に該重合体を乳化剤により水性媒体中に分散せしめた水性分散液が工業的に広く使用されている。しかし、従来の一般的な水性分散液によって処理された繊維織物の撥水撥油性は、摩擦などの物理的な作用に対する抵抗性、すなわち、耐久性において不満足である。さらに、従来の水性分散液は、耐久性のある撥水撥油性を有するものであっても、優れた貯蔵安定性を有していない。
発明の要旨
本発明の目的は、耐久性のある撥水撥油性および優れた貯蔵安定性を有する撥水撥油剤水性分散液を提供することにある。
本発明は、
（Ａ）パーフルオロアルキル基もしくはパーフルオロアルケニル基およびアクリル酸基もしくはメタクリル酸基を有する重合性化合物の少なくとも１種のホモ重合体もしくは共重合体またはそれらと共重合可能な重合性化合物との共重合体、
（Ｂ）トリプロピレングリコールである有機溶剤、および
（Ｃ）界面活性剤
を含有してなる撥水撥油剤水性分散液を提供する。
発明の詳細な説明
重合体（Ａ）において、パーフルオロアルキル基もしくはパーフルオロアルケニル基およびアクリル酸基もしくはメタクリル酸基を有する重合性化合物と共重合可能な他の重合性化合物との共重合体の場合では、前者が少なくとも共重合体中２５重量％であり、好ましくは少なくとも４０重量％である。
パーフルオロアルキル基もしくはパーフルオロアルケニル基およびアクリル酸基もしくはメタクリル酸基を有する重合性化合物の例として、式：
Figure 0004457497
［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、Ｒ１は水素または炭素数１〜１０のアルキル基、Ｒ２は炭素数１〜１０のアルキレン基、Ｒ３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。
さらに具体的には、
Figure 0004457497
Figure 0004457497
を例示することができる。
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、グリシジルエステル、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。
本発明における有機溶剤（Ｂ）は、トリプロピレングリコール
Ｈ［ＯＣＨ２ＣＨ（ＣＨ３）］３ＯＨである。
有機溶剤（Ｂ）の量は重合体（Ａ）１００重量部当たり５〜２００重量部、例えば１０〜１００重量部、特に２０〜６０重量部であってよい。
重合体および有機溶剤を分散するために使用される界面活性剤（Ｃ）は、陽イオン性、陰イオン性または非イオン性乳化剤である。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（陽イオン性乳化剤と非イオン性乳化剤との好ましい重量比は１：９〜９：１である）であるのが望ましい。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、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。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（Ｃ１２−Ｃ１６）チオール、ソルビタンモノ脂肪酸（Ｃ７−Ｃ１９）またはアルキル（Ｃ１２−Ｃ１８）アミンなどとの縮合生成物が包含される。
界面活性剤（Ｃ）の重量は重合体（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。
本発明の分散液を製造するには、界面活性剤（Ｃ）の存在下で重合性化合物を、有機溶剤（Ｂ）を加えた水中で乳化重合して、重合体（Ａ）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。
本発明の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。
本発明の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を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。
発明の好ましい態様
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０．０８重量％になるよう水で希釈して処理液を調製する。ポリエステル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６５％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。
Figure 0004457497
Figure 0004457497
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
実施例１
５００ｃｃフラスコにＣｎＦ２ｎ＋１ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
（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、トリプロピレングリコール４０ｇ、酢酸０．３ｇ、アルキ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アルキルフェニルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。アゾビスイソブチルアミジン−２塩酸塩０．７５ｇを添加し、５時間反応させ、重合体の水性分散液を得た。
撥水撥油性および貯蔵安定性を評価した。結果を表３に示す。
実施例２
５００ｃｃフラスコにＣｎＦ２ｎ＋１ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
（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、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３０ｇ、酢酸０．３ｇ、アルキ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アルキルフェニルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。アゾビスイソブチルアミジン−２塩酸塩０．７５ｇを添加し、５時間反応させ、重合体の水性分散液を得た。
撥水撥油性および貯蔵安定性を評価した。結果を表３に示す。
実施例３
５００ｃｃフラスコにＣｎＦ２ｎ＋１ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
（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、純水２００ｇ、トリプロピレングリコール８０ｇ、酢酸０．３ｇ、アルキ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アルキルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。アゾビスイソブチルアミジン−２塩酸塩０．７５ｇを添加し、５時間反応させ、重合体の水性分散液を得た。
撥水撥油性および貯蔵安定性を評価した。結果を表３に示す。
実施例４
５００ｃｃフラスコにＣｎＦ２ｎ＋１ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
（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、ダイアセントンアクリルアミド２ｇ、純水２００ｇ、トリプロピレングリコール５０ｇ、酢酸０．３ｇ、アルキ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アルキルフェニルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。アゾビスイソブチルアミジン−２塩酸塩０．７５ｇを添加し、５時間反応させ、重合体の水性分散液を得た。
撥水撥油性および貯蔵安定性を評価した。結果を表３に示す。
実施例５
５００ｃｃフラスコにＣｎＦ２ｎ＋１ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
（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、Ｎ−メチロールアクリルアミド２ｇ、純水２００ｇ、トリプロピレングリコール６０ｇ、酢酸０．３ｇ、アルキ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アルキルエーテル１０ｇを入れ、撹拌下に６０℃で１５分間、超音波で乳化分散させた。アゾビスイソブチルアミジン−２塩酸塩０．７５ｇを添加し、５時間反応させ、重合体の水性分散液を得た。
撥水撥油性および貯蔵安定性を評価した。結果を表３に示す。
比較例１
トリプロピレングリコール４０ｇに代えてプロピレングリコール４０ｇを使用する以外は、実施例１の手順を繰り返した。
比較例２
トリプロピレングリコール４０ｇに代えてジプロピレングリコール４０ｇを使用する以外は、実施例１の手順を繰り返した。
比較例３
トリプロピレングリコール３０ｇに代えてプロピレングリコール３０ｇを使用する以外は、実施例２の手順を繰り返した。
比較例４
トリプロピレングリコール３０ｇに代えてジプロピレングリコール３０ｇを使用する以外は、実施例２の手順を繰り返した。
比較例５
トリプロピレングリコール５０ｇに代えてプロピレングリコール５０ｇを使用する以外は、実施例４の手順を繰り返した。
Figure 0004457497
注）
ＨＬ−３： ＪＩＳ Ｌ−０２１７−１０３法による洗濯３回後
ＤＣ−３： ＪＩＳ Ｌ−１０９２−３２２法によるドライクリーニング３回後
発明の効果
本発明において使用するトリプロピレングリコールは、無害性の点で優れている。本発明の水性分散液は、環境汚染の低減に有効であり、耐久性のある撥水撥油性および優れた貯蔵安定性を有している。

Claims (4)

  1. （Ａ）パーフルオロアルキル基もしくはパーフルオロアルケニル基およびアクリル酸基もしくはメタクリル酸基を有する重合性化合物の少なくとも１種のホモ重合体もしくは共重合体またはそれらと共重合可能な重合性化合物との共重合体、
    （Ｂ）トリプロピレングリコールである有機溶剤、および
    （Ｃ）陽イオン性乳化剤と非イオン性乳化剤の混合物である界面活性剤
    を含有してなり、
    有機溶剤(Ｂ)の量が重合体(Ａ)１００重量部当たり５〜２００重量部であり、重合体（Ａ）が有機溶剤（Ｂ）を加えた水中で乳化重合されたものである撥水撥油剤水性分散液。
  2. 有機溶剤(Ｂ)の量が重合体(Ａ)１００重量部当たり１０〜１００重量部である特許請求の範囲第１項記載の分散液。
  3. 界面活性剤（Ｃ）における陽イオン性乳化剤と非イオン性乳化剤との重量比が１：９〜９：１である請求項１または２に記載の分散液。
  4. 請求項１〜３のいずれかに記載の分散液を適用した繊維製品。
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