JP3575043B2 - Method for producing fluorine-based copolymer and water / oil repellent - Google Patents
Method for producing fluorine-based copolymer and water / oil repellent Download PDFInfo
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Description
【０００１】
【産業上の利用分野】
本発明はフッ素系撥水撥油剤等に利用可能なパーフルオロアルキル基含有共重合体、詳しくは低温架橋性に優れるフッ素系共重合体水性分散液の製造方法に関する。
【０００２】
【従来の技術】
パーフルオロアルキル基含有エチレン性不飽和単量体を主構成単位とするフッ素系共重合体は種々知られており、フッ素系撥水撥油剤などとして利用されている。
【０００３】
フッ素系撥水撥油剤として、撥水、撥油機能の耐久性を得る目的で、パーフルオロアルキル基含有エチレン性不飽和単量体とジアセトンアクリルアミドとの共重合体（特公昭４９−２６０７４号公報）、アミニミド基含有単量体との共重合体（特公昭６４−１０５５６号公報）などが知られている。
【０００４】
【発明が解決しようとする課題】
しかしながら、上記公報に記載されたフッ素系共重合体からなる撥水撥油剤は、低温キュアー性（低温架橋性）に乏しく、低温処理での耐久性が不十分であるばかりでなく、初期性能も不十分であった。
【０００５】
このため、上記撥水撥油剤は、紙、ポリプロピレンなど高温の熱処理が困難な素材、染色摩擦堅牢度の観点より低温での熱処理が好ましい新合成繊維に対しては十分な効果が得られないという欠点があった。
【０００６】
【課題を解決するための手段】
本発明者らは前記問題点に鑑み鋭意検討を重ねたところ、アセトアセチル基含有エチレン性不飽和単量体とパーフルオロアルキル基含有エチレン性不飽和単量体を必須構成単位とするフッ素系共重合体が低温架橋性に優れることを見い出し、本発明を完成するに至った。
【０００７】
即ち本発明は、アセトアセチル基含有エチレン性不飽和単量体（Ａ）、パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）とを界面活性剤の存在下に水性媒体中で乳化重合させ、次いで得られるフッ素系共重合体の水性分散液のｐＨを５〜１２の範囲に調整することを特徴とするフッ素系共重合体水性分散液の製造方法であり、またアセトアセチル基含有エチレン性不飽和単量体（Ａ）、パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）とこれらと共重合可能なエチレン性不飽和単量体（Ｃ）とを界面活性剤の存在下に水性媒体中で乳化重合させ、次いで得られるフッ素系共重合体の水性分散液のｐＨを５〜１２の範囲に調整することを特徴とするフッ素系共重合体水性分散液の製造方法を提供するものである。
【０００８】
本発明のフッ素系共重合体は低温架橋性に優れるものである。
本発明に係わるアセトアセチル基含有エチレン性不飽和単量体としては、アセトアセトキシエチルアクリレート、アセトアセトキシエチルメタクリレート、アセトアセトキシエチルクロトナート、アセトアセトキシプロピルアクリレート、アセトアセトキシプロピルメタクリレート、アセトアセトキシプロピルクロトナート、２−シアノアセトアセトキシエチルメタクリレート、Ｎ−（２−アセトアセトキシエチル）アクリルアミド、Ｎ−（２−アセトアセトキシエチル）メタクリルアミド、アセト酢酸アリル、アセト酢酸ビニルなどが挙げられる。このうち特に、アセトアセトキシエチルアクリレート、アセトアセトキシエチルメタクリレートが好ましい。
【０００９】
本発明のアセトアセチル基含有エチレン性不飽和単量体は、一般には、官能基含有エチレン性不飽和単量体にジケテンを反応させたり、あるいは、該単量体にアセトアセトキシアルキルエステルをエステル交換することによって製造される。
【００１０】
本発明に係わるパーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）は、特に限定されるものではなく公知慣用のものがいずれも使用可能である。
単量体（Ｂ）としては、例えば、一般式（Ｉ）
【００１１】
【化３】
［但し、Ｒｆ は炭素原子数４〜２０のパーフルオロアルキル基、Ｒ１ は−Ｈあるいは−ＣＨ３ 、Ａは−Ｑ−、−ＣＯＮ（Ｒ２）−Ｑ−、−ＳＯ２ Ｎ（Ｒ２）−Ｑ−、（但し、−Ｑ−は炭素原子数１〜１０のアルキレン基、Ｒ２ は炭素原子数１〜４のアルキル基である。）］で示される化合物が挙げられる。
【００１３】
具体的には、
Ｂ−１ ： ＣＦ３（ＣＦ２）ｎＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
（ｎ＝５−１１， ｎの平均＝９）
Ｂ−２ ： ＣＦ３（ＣＦ２）７ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２
Ｂ−３ ： ＣＦ３（ＣＦ２）５ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２
Ｂ−４ ： （ＣＦ３）２ＣＦ（ＣＦ２）６（ＣＨ２）３ＯＣＯＣＨ＝ＣＨ２
Ｂ−５ ： （ＣＦ３）２ＣＦ（ＣＦ２）１０（ＣＨ２）３ＯＣＯＣＨ＝ＣＨ２
Ｂ−６ ： ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ３Ｈ７）ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
Ｂ−７ ： ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（ＣＨ３）ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２
Ｂ−８ ： ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（ＣＨ３）ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
Ｂ−９ ： ＣＦ３（ＣＦ２）７（ＣＨ２）４ＯＣＯＣＨ＝ＣＨ２
Ｂ−１０： ＣＦ３（ＣＦ２）６ＣＯＯＣＨ＝ＣＨ２
Ｂ−１１： ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ４Ｈ９）（ＣＨ２）４ＯＣＯＣＨ＝ＣＨ２
Ｂ−１２： ＣＦ３（ＣＦ２）７ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＣＯＣＨ＝ＣＨ２
Ｂ−１３： ＣＦ３（ＣＦ２）５ＣＯＮ（Ｃ３Ｈ７）ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２
Ｂ−１４： ＣＦ３（ＣＦ２）７ＣＯＮ（Ｃ２Ｈ５）ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２
等の単量体が例示される。
【００１４】
アセトアセチル基含有エチレン性不飽和単量体（Ａ）、パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）と共重合可能なエチレン性不飽和単量体（Ｃ）としては、例えばエチレン、プロピレン、塩化ビニル、塩化ビニリデン、スチレン、α−メチルスチレン、酢酸ビニル、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボロニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、メチルビニルエーテル、プロピルビニルエーテル、オクチルビニルエーテル、ブタジエン、イソプレン、クロロプレン、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸、（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、３−クロロ−２−ヒドロキシ（メタ）アクリレート、ジアセトンアクリルアミド等の単量体が挙げられる。
【００１５】
尚、上記の共重合可能なエチレン性不飽和単量体（Ｃ）の中、カルボキシル基、アミノ基、アミド基、ウレタン基の如き官能基を有するものは、それらの官能基がアセトアセチル基含有エチレン性不飽和単量体（Ａ）のアセトアセチル基と反応し重合中ゲル化したり、貯蔵中に反応が進行し製品ライフが短くなるなど好ましくないが、極少量ならば共重合することも可能である。
【００１６】
繊維処理剤として要求される優れた撥水撥油性とソフト風合いを満足させる目的には一般式（ＩＩ）で表される炭素数１４〜２４の直鎖状又は分岐状のアルキル基含有（メタ）アクリレートを使用することが好ましい。
【００１７】
【化４】
（但し、Ｒ１は−Ｈ、−ＣＨ３、Ｒ２は炭素数１４〜２４の直鎖状または分岐状アルキル基である。）
炭素数１４〜２４の直鎖状又は分岐状のアルキル基含有（メタ）アクリレートの具体例としては、例えばｎ−セチル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、ｎ−ベヘニル（メタ）アクリレート、ｉｓｏ−ステアリル（メタ）クリレート等が挙げられる。
【００１９】
勿論、共重合可能なエチレン性不飽和単量体（Ｃ）として、これらの２種以上を併用してもよい。
本発明に係る共重合体を得るためには種々の重合反応や条件が任意に選択できるが、塊状重合、溶液重合、乳化重合、懸濁重合、放射線重合、光重合など各種の重合方式のいずれをも採用できる。
【００２０】
乳化重合によって、エマルジョン型あるいはエアゾール型の上記フッ素系共重合体と水とからなる撥水撥油剤を直接製造できる。このうち、特に本発明で得られたフッ素系共重合体を水に分散してなる撥水撥油剤が好ましい。
【００２１】
乳化重合を採用する場合、例えば共重合しようとする単量体の混合物を、界面活性剤の存在下に水に乳化させ、攪拌下に共重合すれば本発明に係わる共重合体水性分散液、すなわち撥水撥油剤を容易に製造することができる。
【００２２】
具体的には、本発明の撥水撥油剤は、アセトアセチル基含有エチレン性不飽和単量体（Ａ）とパーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）とを、界面活性剤の存在下に水性媒体中で乳化重合させるか、あるいはアセトアセチル基含有エチレン性不飽和単量体（Ａ）とパーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）とこれらと共重合可能なエチレン性不飽和単量体（Ｃ）とを、界面活性剤の存在下に水性媒体中で乳化重合させることにより製造することができる。
【００２３】
重合開始源は、特に制限されないが、例えばアゾ化合物、有機過酸化物の如き各種重合開始剤、更には、紫外線あるいはγ−線などの電離性放射線などが採用され得る。
【００２４】
また界面活性剤は、特に制限されないが、例えば陰イオン性、陽イオン性あるいは非イオン性の炭化水素系、シリコーン系、フッ素系等の各種乳化剤が使用可能である。
【００２６】
本発明に係る共重合体における、アセトアセトキシ基含有エチレン性不飽和単量体（Ａ）とパーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）との共重合割合は特に制限されるものではないが、アセトアセトキシ基含有エチレン性不飽和単量体（Ａ）とパーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）との２成分系の場合は、アセトアセトキシ基含有エチレン性不飽和単量体（Ａ）１〜３０重量％、パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）７０〜９９重量％が好ましい。またアセトアセトキシ基含有エチレン性不飽和単量体（Ａ）とパーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）とこれらと共重合可能なエチレン性不飽和単量体（Ｃ）との３成分系の場合には、２成分系の場合と同様に重合割合に制限はないが、アセトアセトキシ基含有エチレン性不飽和単量体（Ａ）１〜３０重量％、パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）４０〜８０重量％、共重合可能なエチレン性不飽和単量体（Ｃ）１０〜５０重量％が好ましい。
【００２７】
撥水撥油性能、架橋性能の点では、２成分系の場合は勿論、単量体（Ａ）と単量体（Ｂ）とその他の共重合可能なエチレン性不飽和単量体（Ｃ）との共重合体を製造する場合においても、アセトアセトキシ基含有エチレン性不飽和単量体（Ａ）とパーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）との共重合割合が特に重要である。
【００２８】
これらの単量体の中、好ましいものとしては上記したとおりであるが、原料の入手性、撥水撥油性などの点より、アセトアセトキシ基含有エチレン性不飽和単量体（Ａ）としては、アセトアセトキシエチルアクリレート及び／又はアセトアセトキシエチルメタクリレート、パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ）としては、パーフルオロアルキル基含有（メタ）アクリレート、共重合可能なエチレン性不飽和単量体（Ｃ）としては、炭素数１４〜２４の直鎖状又は分岐状のアルキル基含有（メタ）アクリレートが好ましい。
【００２９】
本発明に係わる共重合体を水性分散液として調整し、例えば布帛の撥水撥油処理の目的に使用する場合には、低温キュアー性と耐久性を共に得るためには、フッ素系共重合体の水性分散液のｐＨが８〜１１にあることが好ましい。
【００３０】
本発明の製造方法により得られるフッ素系共重合体水性分散液は、フッ素系撥水撥油剤としてそのまま利用され得る。被処理物の種類または調整形態などに応じて、任意の方法で被処理物に適応され得る。例えば、必要に応じて希釈を行ない浸漬塗布あるいはスプレー等の如き被覆加工の既知の方法で被処理物の表面に付着させ熱処理する方法が採用される。
【００３１】
この際の熱処理の条件は特に限定されるものではなく、通常の熱処理条件、例えば加熱オーブン中８０〜１２０℃×３０秒〜３分で予備乾燥した後１３０〜１８０℃×３０秒〜３分キュアリングする条件が採用され得る。勿論、本発明の共重合体の特徴を生かし、より低温で乾燥することも可能である。
【００３２】
本発明の低温架橋性に優れるフッ素系共重合体水性分散液は、特に限定なく種々の物品を単独で処理することができ撥水撥油性、防汚性等を付与することができる。物品としては、例えば、繊維、紙、皮革、毛皮、プラスチックなどがある。
【００３３】
繊維としては、綿、麻、絹、羊毛などの天然繊維、ポリアミド、ポリエステル、ポリアクリロニトリル、ポリプロピレン等の合成繊維、レーヨン、アセテート等の半合成繊維、あるいはこれらの混紡・交織織物が挙げられる。
【００３４】
また、本発明で得られたフッ素系共重合体水性分散液を樹脂溶液に添加し塗布あるいは成形することにより樹脂成分の撥水性、撥油性、防汚性、非粘着性、離型性、吸水防止性、潤滑性等の性能を改質することができる。
【００３５】
【実施例】
つぎに、本発明を実施例及び比較例により具体的に説明するが、部および％は特に断わりのない限りはすべて重量基準であるものとする。また、用いた単量体は、上記発明の詳細な説明に示した呼称をそのまま援用した。
【００３６】
合成例１
ガラス製反応容器中（内容積５００ｍｌ）に、Ｂ−１ ８０．０ｇ、アセトアセトキシエチルメタクリレート ２０．０ｇ、ドデシルメルカプタン ０．８ｇ、脱酸素した純水 ３５４．７ｇ、アセトン ４０．０ｇ、Ｃ１６Ｈ３３Ｎ（ＣＨ３）３Ｃｌ １．０ｇ及びＣ８Ｈ１７Ｃ６Ｈ４Ｏ（ＣＨ２ＣＨ２Ｏ）ｎＨ（ｎ＝８）３．０ｇを入れ、アゾビスイソブチルアミジン二塩酸塩０．５ｇを加え、窒素雰囲気下で攪拌しつつ６０℃で１０時間共重合反応せしめた。得られた共重合体エマルジョンは固型分濃度 ２０．６％であった。以下、この共重合体エマルジョンを（Ｆ−１）という。
【００３７】
合成例２
ガラス製反応容器中（内容積５００ｍｌ）に、Ｂ−１ ５５．０ｇ、ステアリルアクリレート ２５．０ｇ、アセトアセトキシエチルアクリレート ２０．０ｇ、ドデシルメルカプタン ０．８ｇ、脱酸素した純水 ３５４．７ｇ、アセトン ４０．０ｇ、Ｃ１６Ｈ３３Ｎ（ＣＨ３）３Ｃｌ １．０ｇ及びＣ８Ｈ１７Ｃ６Ｈ４Ｏ（ＣＨ２ＣＨ２Ｏ）ｎＨ
（ｎ＝８）３．０ｇを入れ、アゾビスイソブチルアミジン二塩酸塩０．５ｇを加え、窒素雰囲気下で攪拌しつつ６０℃で１０時間共重合反応せしめた。得られた共重合体エマルジョンは固型分濃度 ２０．６％であった。以下、この共重合体エマルジョンを（Ｆ−２）という。
【００３８】
同様な方法で本発明に係わる共重合体エマルジョン（Ｆ−３）〜（Ｆ−４）、および本発明に係わらない共重合体エマルジョン（Ｆ−５）〜（Ｆ−７）を合成しその共重合割合を合成例における共重合割合とともに表１に示した。
【００３９】
尚、表中ＡＡＥＡはアセトアセトキシアクリレート、ＡＡＥＭはアセトアセトキシメタクリレート、ＳＴＡはステアリルアクリレート、ＳＭＡはステアリルメタアクリレート、ＥＨＡは２−エチルヘキシルアクリレート、ＤＡＡＭはジアセトンアクリルアミド、ＶＣは塩化ビニル、Ｎ−ＭＡＭはＮ−メチロールアクリルアミド、ＯＴＡは２−ヒドロキシエチルアクリレート／ ２．４−トルエンジイソシアネート／メチルエチルケトキシム＝１／１／１（モル比）の付加体を示す。
【００４０】
【表１】
尚、撥水性（ＷＲ）はＪＩＳ Ｌ−１０９２のスプレー法により評価し、撥油性（ＯＲ）はＡＡＴＣＣ法（ハイドロカーボンレジスタンステスト）により評価した。また、洗濯はＪＩＳ Ｌ−０２１７・１０３法に準じ自然乾燥した。
【００４３】
実施例１〜３及び比較例１
共重合体エマルジョンＦ−４を水で希釈して固形分濃度０．６％の処理浴を調整し、必要に応じてアンモニア、水、塩酸により所定のｐＨとした後、ポリエステル織物を該処理浴に５秒間浸漬しマングルにより絞り、ウェットピックアップを６０％とした。次いで、所定の乾燥条件で乾燥することにより撥水撥油処理した。
【００４４】
ｐＨ調整をしない以外は同様に共重合体エマルジョンＦ−６により処理した。かくして得られた撥水撥油処理布について加工上りおよび１０回洗濯後（１０ＨＬ後）の撥水性能を評価した。
尚、実施例１〜３の処理布は、比較例１のそれに比べて低温乾燥時の撥水撥油性に優れ（低温キュアー性あるいは低温架橋性に優れ）、撥水撥油性の耐洗濯性（耐久性）にも優れていた。
【００４５】
【表３】
【発明の効果】
本発明で得られるフッ素系共重合体水性分散液は低温架橋性に優れ、撥水撥油剤として用いた場合に格別顕著な効果を奏するものである。[0001]
[Industrial applications]
The present invention relates to a method for producing a perfluoroalkyl group-containing copolymer which can be used as a fluorine-based water / oil repellent or the like, and more particularly to a method for producing an aqueous dispersion of a fluorine-based copolymer having excellent low-temperature crosslinkability .
[0002]
[Prior art]
Various fluorine-based copolymers containing a perfluoroalkyl group-containing ethylenically unsaturated monomer as a main constituent unit are known, and are used as fluorine-based water and oil repellents.
[0003]
As a fluorine-based water and oil repellent, a copolymer of a perfluoroalkyl group-containing ethylenically unsaturated monomer and diacetone acrylamide for the purpose of obtaining durability of water repellency and oil repellency (JP-B-49-26074) And a copolymer with an aminimide group-containing monomer (Japanese Patent Publication No. 64-10556).
[0004]
[Problems to be solved by the invention]
However, the water- and oil-repellent comprising the fluorocopolymer described in the above-mentioned publication has poor low-temperature curing properties (low-temperature crosslinking properties), not only insufficient durability at low-temperature treatment, but also initial performance. It was not enough.
[0005]
For this reason, the water- and oil-repellent agent does not provide a sufficient effect on a paper, a material such as polypropylene which is difficult to heat-treat at a high temperature, and a new synthetic fiber which is preferably heat-treated at a low temperature from the viewpoint of dyeing friction fastness. There were drawbacks.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in view of the above problems, and found that a fluorine-based copolymer having an acetoacetyl group-containing ethylenically unsaturated monomer and a perfluoroalkyl group-containing ethylenically unsaturated monomer as essential constitutional units. The inventors have found that the polymer has excellent low-temperature crosslinking properties, and have completed the present invention.
[0007]
That is, the present invention provides emulsion polymerization of an acetoacetyl group-containing ethylenically unsaturated monomer (A) and a perfluoroalkyl group-containing ethylenically unsaturated monomer (B) in an aqueous medium in the presence of a surfactant. is, then a method for producing a fluorine-based copolymer aqueous dispersion and adjusting the pH of the aqueous dispersion of the resulting fluorine-based copolymer in the range of 5-12, also acetoacetyl group-containing ethylene The ethylenically unsaturated monomer (A), the perfluoroalkyl group-containing ethylenically unsaturated monomer (B) and the ethylenically unsaturated monomer (C) copolymerizable therewith in the presence of a surfactant A process for producing an aqueous dispersion of a fluorine-based copolymer , which comprises emulsion-polymerizing in an aqueous medium and then adjusting the pH of the resulting aqueous dispersion of a fluorine-based copolymer to a range of 5 to 12. To do.
[0008]
The fluorine-based copolymer of the present invention is excellent in low-temperature crosslinkability.
As the acetoacetyl group-containing ethylenically unsaturated monomer according to the present invention, acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl crotonate, Examples include 2-cyanoacetoacetoxyethyl methacrylate, N- (2-acetoacetoxyethyl) acrylamide, N- (2-acetoacetoxyethyl) methacrylamide, allyl acetoacetate, and vinyl acetoacetate. Of these, acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate are particularly preferred.
[0009]
The acetoacetyl group-containing ethylenically unsaturated monomer of the present invention is generally obtained by reacting a functional group-containing ethylenically unsaturated monomer with diketene or transesterifying an acetoacetoxyalkyl ester with the monomer. It is manufactured by doing.
[0010]
The perfluoroalkyl group-containing ethylenically unsaturated monomer (B) according to the present invention is not particularly limited, and any known and commonly used one can be used.
As the monomer (B), for example, a compound represented by the general formula (I)
[0011]
Embedded image
[However, R f is a perfluoroalkyl group having 4 to 20 carbon atoms, R 1 is -H or -CH 3 , A is -Q-, -CON (R 2 ) -Q-, -SO 2 N (R 2) -Q -, (where, -Q- is an alkylene group having 1 to 10 carbon atoms, R 2 can be mentioned compounds represented by a) an alkyl group having 1 to 4 carbon atoms..
[0013]
In particular,
B-1: CF 3 (CF 2 ) n CH 2 CH 2 OCOCH = CH 2
(N = 5-11, average of n = 9)
B-2: CF 3 (CF 2 ) 7 CH 2 CH 2 OCOC (CH 3 ) = CH 2
B-3: CF 3 (CF 2) 5 CH 2 CH 2 OCOC (CH 3) = CH 2
B-4: (CF 3 ) 2 CF (CF 2 ) 6 (CH 2 ) 3 OCOCH = CH 2
B-5: (CF 3 ) 2 CF (CF 2 ) 10 (CH 2 ) 3 OCOCH = CH 2
B-6: CF 3 (CF 2 ) 7 SO 2 N (C 3 H 7 ) CH 2 CH 2 OCOCH ＝ CH 2
B-7: CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2
B-8: CF 3 (CF 2 ) 7 SO 2 N (CH 3 ) CH 2 CH 2 OCOCH ２CH 2
B-9: CF 3 (CF 2 ) 7 (CH 2 ) 4 OCOCH = CH 2
B-10: CF 3 (CF 2 ) 6 COOCH = CH 2
B-11: CF 3 (CF 2) 7 SO 2 N (C 4 H 9) (CH 2) 4 OCOCH = CH 2
B-12: CF 3 (CF 2 ) 7 CH 2 CH (OH) CH 2 OCOCH = CH 2
B-13: CF 3 (CF 2 ) 5 CON (C 3 H 7 ) CH 2 CH 2 OCOC (CH 3 ) = CH 2
B-14: CF 3 (CF 2 ) 7 CON (C 2 H 5 ) CH 2 CH 2 OCOCH ＝ CH 2
And the like.
[0014]
Examples of the ethylenically unsaturated monomer (C) copolymerizable with the acetoacetyl group-containing ethylenically unsaturated monomer (A) and the perfluoroalkyl group-containing ethylenically unsaturated monomer (B) include, for example, ethylene , Propylene, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (Meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate , Isostearyl (meth) Acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl vinyl ether, propyl vinyl ether, octyl vinyl ether, butadiene, isoprene, Monomers such as chloroprene, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, 3-chloro-2-hydroxy (meth) acrylate, and diacetone acrylamide Is mentioned.
[0015]
Among the above copolymerizable ethylenically unsaturated monomers (C), those having a functional group such as a carboxyl group, an amino group, an amide group, or a urethane group have those functional groups containing an acetoacetyl group. It is not desirable that it reacts with the acetoacetyl group of the ethylenically unsaturated monomer (A) to cause gelation during polymerization, or the reaction proceeds during storage to shorten the product life, but copolymerization is possible if the amount is extremely small. It is.
[0016]
For the purpose of satisfying the excellent water / oil repellency and soft feeling required as a fiber treatment agent, a linear or branched alkyl group containing 14 to 24 carbon atoms represented by the general formula (II) (meth) It is preferred to use acrylates.
[0017]
Embedded image
(However, R 1 is —H, —CH 3 , and R 2 is a linear or branched alkyl group having 14 to 24 carbon atoms.)
Specific examples of the linear or branched alkyl group-containing (meth) acrylate having 14 to 24 carbon atoms include, for example, n-cetyl (meth) acrylate, n-stearyl (meth) acrylate, and n-behenyl (meth) acrylate. , Iso-stearyl (meth) acrylate and the like.
[0019]
Of course, two or more of these may be used in combination as the copolymerizable ethylenically unsaturated monomer (C).
To obtain the copolymer according to the present invention, various polymerization reactions and conditions can be arbitrarily selected, and any of various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, radiation polymerization, and photopolymerization can be used. Can also be adopted.
[0020]
By emulsion polymerization, a water- and oil-repellent comprising the emulsion-type or aerosol-type fluorine-based copolymer and water can be directly produced. Among them, a water- and oil-repellent obtained by dispersing the fluorine-based copolymer obtained in the present invention in water is particularly preferable.
[0021]
When emulsion polymerization is employed, for example, a mixture of monomers to be copolymerized is emulsified in water in the presence of a surfactant, and the copolymer is dispersed under stirring, and the copolymer aqueous dispersion according to the present invention, That is, a water and oil repellent can be easily produced.
[0022]
Specifically, the water- and oil-repellent agent of the present invention comprises a surfactant containing an ethylenically unsaturated monomer containing an acetoacetyl group (A) and an ethylenically unsaturated monomer containing a perfluoroalkyl group (B). Emulsion polymerization in an aqueous medium in the presence of acetic acid, or copolymerizable with ethylenically unsaturated monomer containing acetoacetyl group (A) and ethylenically unsaturated monomer containing perfluoroalkyl group (B) It can be produced by subjecting an ethylenically unsaturated monomer (C) to emulsion polymerization in an aqueous medium in the presence of a surfactant.
[0023]
Although the polymerization initiation source is not particularly limited, for example, various polymerization initiators such as azo compounds and organic peroxides, and further, ionizing radiation such as ultraviolet rays or γ-rays may be employed.
[0024]
The surfactant is not particularly limited, but various emulsifiers such as anionic, cationic or nonionic hydrocarbons, silicones and fluorines can be used.
[0026]
In the copolymer according to the present invention, the copolymerization ratio between the acetoacetoxy group-containing ethylenically unsaturated monomer (A) and the perfluoroalkyl group-containing ethylenically unsaturated monomer (B) is particularly limited. However, in the case of a two-component system composed of an ethylenically unsaturated monomer containing an acetoacetoxy group (A) and an ethylenically unsaturated monomer containing a perfluoroalkyl group (B), an ethylenically unsaturated monomer containing an acetoacetoxy group is used. The saturated monomer (A) is preferably 1 to 30% by weight, and the perfluoroalkyl group-containing ethylenically unsaturated monomer (B) is preferably 70 to 99% by weight. Also, an ethylenically unsaturated monomer containing an acetoacetoxy group (A), an ethylenically unsaturated monomer containing a perfluoroalkyl group (B) and an ethylenically unsaturated monomer copolymerizable therewith (C) In the case of a three-component system, the polymerization ratio is not limited as in the case of the two-component system. However, 1 to 30% by weight of an acetoacetoxy group-containing ethylenically unsaturated monomer (A) and a perfluoroalkyl group-containing ethylene The unsaturated unsaturated monomer (B) is preferably 40 to 80% by weight, and the copolymerizable ethylenically unsaturated monomer (C) is preferably 10 to 50% by weight.
[0027]
In terms of water repellency, oil repellency and cross-linking performance, the monomer (A), the monomer (B) and other copolymerizable ethylenically unsaturated monomers (C) are of course used in the case of the two-component system. In the case of producing a copolymer with styrene, the copolymerization ratio between the acetoacetoxy group-containing ethylenically unsaturated monomer (A) and the perfluoroalkyl group-containing ethylenically unsaturated monomer (B) is particularly important. It is.
[0028]
Among these monomers, preferable ones are as described above. However, from the viewpoints of availability of raw materials and water / oil repellency, the acetoacetoxy group-containing ethylenically unsaturated monomer (A) includes: As the acetoacetoxyethyl acrylate and / or acetoacetoxyethyl methacrylate, the perfluoroalkyl group-containing ethylenically unsaturated monomer (B) may be a perfluoroalkyl group-containing (meth) acrylate, a copolymerizable ethylenically unsaturated monomer. As the body (C), a linear or branched alkyl group-containing (meth) acrylate having 14 to 24 carbon atoms is preferable.
[0029]
When the copolymer according to the present invention is prepared as an aqueous dispersion, for example, when used for the purpose of water- and oil-repellent treatment of a fabric, in order to obtain both low-temperature curing property and durability, a fluorine-based copolymer is used. It is preferable that the pH of the aqueous dispersion is 8 to 11.
[0030]
The aqueous fluorine-based copolymer dispersion obtained by the production method of the present invention can be used as it is as a fluorine-based water / oil repellent. The method can be applied to the object to be processed in an arbitrary manner according to the type or the adjustment form of the object to be processed. For example, a method of diluting, if necessary, applying a known method of coating processing such as dip coating or spraying, and attaching it to the surface of the object to be treated and heat-treating it is employed.
[0031]
The conditions of the heat treatment at this time are not particularly limited, and are preliminarily dried in a heating oven at 80 to 120 ° C. for 30 seconds to 3 minutes and then cured at 130 to 180 ° C. for 30 seconds to 3 minutes. Ring conditions can be employed. Of course, it is possible to dry at a lower temperature by utilizing the characteristics of the copolymer of the present invention.
[0032]
The aqueous fluorocopolymer dispersion of the present invention, which is excellent in low-temperature crosslinkability, can treat various articles alone without particular limitation, and can impart water and oil repellency, stain resistance, and the like. Examples of the article include fiber, paper, leather, fur, and plastic.
[0033]
Examples of the fibers include natural fibers such as cotton, hemp, silk, and wool; synthetic fibers such as polyamide, polyester, polyacrylonitrile, and polypropylene; semi-synthetic fibers such as rayon and acetate;
[0034]
Further, by adding the aqueous dispersion of the fluorocopolymer obtained in the present invention to a resin solution and coating or molding the resin component, the resin component has water repellency, oil repellency, antifouling property, non-adhesiveness, mold release property, water absorption. Performance such as prevention and lubricity can be modified.
[0035]
【Example】
Next, the present invention will be specifically described with reference to Examples and Comparative Examples. All parts and percentages are by weight unless otherwise specified. As for the monomers used, the names shown in the above detailed description of the invention are used as they are.
[0036]
Synthesis Example 1
In a glass reaction vessel (internal volume: 500 ml), 80.0 g of B-1, 20.0 g of acetoacetoxyethyl methacrylate, 0.8 g of dodecyl mercaptan, 354.7 g of deoxygenated pure water, 40.0 g of acetone, and C 16 H 33 n (CH 3) 3 Cl 1.0g and C 8 H 17 C 6 H 4 O (CH 2 CH 2 O) n H (n = 8) placed 3.0 g, azobisisobutylamidine dihydrochloride 0. 5 g was added, and a copolymerization reaction was performed at 60 ° C. for 10 hours while stirring under a nitrogen atmosphere. The obtained copolymer emulsion had a solid concentration of 20.6%. Hereinafter, this copolymer emulsion is referred to as (F-1).
[0037]
Synthesis Example 2
In a glass reaction vessel (internal volume: 500 ml), 55.0 g of B-I, 25.0 g of stearyl acrylate, 20.0 g of acetoacetoxyethyl acrylate, 0.8 g of dodecylmercaptan, 354.7 g of deoxygenated pure water, and acetone 40 1.0 g, C 16 H 33 N (CH 3 ) 3 Cl, 1.0 g and C 8 H 17 C 6 H 4 O (CH 2 CH 2 O) n H
3.0 g of (n = 8) was added, 0.5 g of azobisisobutylamidine dihydrochloride was added, and a copolymerization reaction was carried out at 60 ° C. for 10 hours while stirring under a nitrogen atmosphere. The obtained copolymer emulsion had a solid concentration of 20.6%. Hereinafter, this copolymer emulsion is referred to as (F-2).
[0038]
In the same manner, copolymer emulsions (F-3) to (F-4) according to the present invention and copolymer emulsions (F-5) to (F-7) not related to the present invention were synthesized and their copolymers were synthesized. Table 1 shows the polymerization ratio together with the copolymerization ratio in the synthesis examples.
[0039]
In the table, AAEA is acetoacetoxy acrylate, AAEM is acetoacetoxy methacrylate, STA is stearyl acrylate, SMA is stearyl methacrylate, EHA is 2-ethylhexyl acrylate, DAAM is diacetone acrylamide, VC is vinyl chloride, and N-MAM is N. -Methylol acrylamide, OTA is an adduct of 2-hydroxyethyl acrylate / 2.4-toluene diisocyanate / methyl ethyl ketoxime = 1/1/1 (molar ratio).
[0040]
[Table 1]
The water repellency (WR) was evaluated by a spray method according to JIS L-1092, and the oil repellency (OR) was evaluated by an AATCC method (hydrocarbon resistance test). The laundry was air-dried according to JIS L-0217.103 method.
[0043]
Examples 1 to 3 and Comparative Example 1
After diluting the copolymer emulsion F-4 with water to prepare a treatment bath having a solid content of 0.6%, and adjusting the pH to a predetermined value with ammonia, water and hydrochloric acid as necessary, the polyester fabric is treated with the treatment bath. For 5 seconds and squeezed with a mangle to reduce the wet pickup to 60%. Next, water- and oil-repellent treatment was performed by drying under predetermined drying conditions.
[0044]
The same treatment was performed with the copolymer emulsion F-6 except that the pH was not adjusted. The water-repellent and oil-repellent treated cloth thus obtained was evaluated for water repellency after processing and after washing 10 times (after 10 HL).
The treated cloths of Examples 1 to 3 are excellent in water / oil repellency at low temperature drying (excellent in low temperature curing property or low temperature crosslinking property) and water / oil repellency in washing resistance ( Durability).
[0045]
[Table 3]
【The invention's effect】
The aqueous fluorocopolymer dispersion obtained in the present invention has excellent low-temperature crosslinking properties and exhibits a particularly remarkable effect when used as a water / oil repellent .
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02247194A JP3575043B2 (en) | 1994-02-21 | 1994-02-21 | Method for producing fluorine-based copolymer and water / oil repellent |
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|---|---|---|---|
| JP02247194A JP3575043B2 (en) | 1994-02-21 | 1994-02-21 | Method for producing fluorine-based copolymer and water / oil repellent |
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| Publication Number | Publication Date |
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| JPH07228638A JPH07228638A (en) | 1995-08-29 |
| JP3575043B2 true JP3575043B2 (en) | 2004-10-06 |
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| WO1997042266A1 (en) * | 1996-05-02 | 1997-11-13 | Bridgestone Corporation | Pneumatic tire |
| WO2002064696A1 (en) | 2001-01-30 | 2002-08-22 | Daikin Industries, Ltd. | Water- and oil-repellent composition, process for producing the same and use thereof |
| WO2007061329A1 (en) * | 2005-11-25 | 2007-05-31 | Pfc-Tec Llc | Method for producing a film-forming fluorine-containing component and a composition based thereon |
| JP5245834B2 (en) * | 2007-02-02 | 2013-07-24 | ダイキン工業株式会社 | Soil release agent composition |
| JP2010222382A (en) * | 2007-07-20 | 2010-10-07 | Daikin Ind Ltd | Fluorine-containing fiber processing agent having soil release property |
| US9534343B2 (en) * | 2012-10-18 | 2017-01-03 | The Chemours Company Fc, Llc | Partially fluorinated copolymer emulsions containing fatty acids and esters |
| JP6350161B2 (en) * | 2013-10-02 | 2018-07-04 | ダイキン工業株式会社 | Waterproof and moisture-proof durable coating composition |
| CN116804313A (en) * | 2023-07-31 | 2023-09-26 | 河北多维康助剂有限公司 | Low-temperature durable three-proofing finishing method for wool/cashmere fabric |
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