JP2004506073A - Novel fluorinated copolymers, their use as coating and impregnating agents on substrates and the resulting substrates - Google Patents

Novel fluorinated copolymers, their use as coating and impregnating agents on substrates and the resulting substrates Download PDF

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JP2004506073A
JP2004506073A JP2002518331A JP2002518331A JP2004506073A JP 2004506073 A JP2004506073 A JP 2004506073A JP 2002518331 A JP2002518331 A JP 2002518331A JP 2002518331 A JP2002518331 A JP 2002518331A JP 2004506073 A JP2004506073 A JP 2004506073A
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fluorinated copolymer
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トンブ　ズュディ，ドゥニ
ルグラン，イヴォン
ジュユー，ディディエ
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Arkema France SA
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Atofina SA
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Abstract

１００重量部当たり５〜９２部のポリフッ化モノマー（Ｉ）、０．１０〜２５部のモノマー（ＩＩ）、（ＩＩＩ）または（ＶＩ）、０〜２０部の陰イオン性モノマー、０〜２５部のビニルモノマー（Ｖ）、０〜６０部のモノマー（ＶＩ）、０〜１０部のフッ素化コポリマーを架橋可能なモノマー、０〜２５部のモノマー（ＶＩＩ）を含むモノマー組成物から得られる陽イオン性フッ素化コポリマー。
【化１】

Figure 2004506073

（Ｒ１、Ｒ２＝ＨまたはＣ１〜Ｃ４アルキル基、Ａ＝Ｏ、ＳまたはＮ原子を有する二価結合基、Ｒｆ＝Ｃ２〜Ｃ２０パーフルオロ；Ｒ３、Ｒ６、Ｒ８、Ｒ１２＝Ｈまたは−ＣＨ３；Ｒ４、Ｒ５、Ｒ７、Ｒ９、Ｒ１０＝Ｈ、Ｃ１−Ｃ１８アルキル、ベンジルまたはヒドロキシエチル；Ｘ１−、Ｘ２−＝一価の陰イオン；Ｒ１１＝Ｃ１−Ｃ１８アルキルカルボキシレート；Ｒ１３＝Ｃ１−Ｃ６アルキレン；Ｒ１４＝Ｃ１−Ｃ３２アルキルまたはシクロアルキル；Ｒ１５＝ＨまたはＣ１−Ｃ４アルキル；Ａ２＝Ｃ１−Ｃ４アルキル；Ｒ１６、Ｒ１７＝Ｈ、Ｃ１−Ｃ１８アルキル、ヒドロキシエチルまたはベンジル）5 to 92 parts per 100 parts by weight of polyfluorinated monomer (I), 0.10 to 25 parts of monomer (II), (III) or (VI), 0 to 20 parts of anionic monomer, 0 to 25 parts A cation obtained from a monomer composition comprising a vinyl monomer (V), 0 to 60 parts of a monomer (VI), 0 to 10 parts of a monomer capable of crosslinking a fluorinated copolymer, and 0 to 25 parts of a monomer (VII) Fluorinated copolymer.
Embedded image
Figure 2004506073

(R 1, R 2 = H or C 1 -C 4 alkyl group, A = O, a divalent linking group having the S or N atom, R f = C 2 ~C 20 perfluoroalkyl; R 3, R 6, R 8, R 12 = H or -CH 3; R 4, R 5 , R 7, R 9, R 10 = H, C 1 -C 18 alkyl, benzyl or hydroxyethyl; X 1-, X 2- = monovalent R 11 ＣC 1 -C 18 alkyl carboxylate; R 13 ＣC 1 -C 6 alkylene; R 14 ＣC 1 -C 32 alkyl or cycloalkyl; R 15 ＨH or C 1 -C 4 alkyl A 2 = C 1 -C 4 alkyl; R 16 , R 17 = H, C 1 -C 18 alkyl, hydroxyethyl or benzyl)

Description

【０００１】
【発明の分野】
本発明は、新規なフッ素化コポリマーと、各種基材（例えば織物、革、木材、不織布、金属、コンクリート、特に紙およびその類似品および繊維）に疎油性および疎水性を付与するための被覆および含浸剤としてのその使用と、こうして氏よりされた基材とに関するものである。
【０００２】
【従来の技術】
上記用途では下記の３種類を含む多くの陽イオン性フッ化誘導体が提案されている：
（１）ラテックスまたはエマルション（界面剤で安定化させたポリマー粒子の水中分散液）、
（２）水／溶剤混合物中の溶液
（３）上記（２）の溶剤を除去して得られる水性分散液
【０００３】
【特許文献１】欧州特許第ＥＰ−Ｂ−０，２３４，６０１号
上記文献には下記（ａ）〜（ｅ）を共重合して得られるラテックスまたはエマルション状態の陽イオン性フッ素化コポリマーが開示されている：
（ａ）下記式のアクリレートフルオロモノマー　６０〜８０重量％
【化１１】

Figure 2004506073
（ここで、Ｒ（０） ｆは３〜２０個の炭素原子を有する脂肪族のパーフルオロラジカル、Ａ（０）は二価の結合基）、
【０００４】
（ｂ）下記の（ｉ）または（ｉｉ）　１〜３０重量％
（ｉ）下記式のアルキルまたはアルコキシアルキル（メタ）アクリレートモノマー：
【化１２】
Figure 2004506073
（ここで、Ｒ（１）はＨまたはメチル、Ｒ（２）はＣ１−Ｃ６アルキレン基、Ｒ（３）はＣ１−Ｃ２０アルキル基またはシクロアルキル基、ｍは０または１、ｎは０〜１０、ただし、ｎが０の場合、Ｒ（３）はＣ１−Ｃ１６アルキル基またはシクロアルキル基）
【０００５】
（ｉｉ）下記式のハロゲン化アルキルまたはアルコキシアルキルアクリレートモノマー：
【化１３】
Figure 2004506073
（ここで、Ｒ（４）はＣ１−Ｃ６アルキレン基またはハロアルキレン基、Ｒ（５）はＣ１−Ｃ２０アルキル基、シクロアルキル基、ハロアルキル基またはハロシクロアルキル基で、少なくとも１つのＲ（４）基またはＲ（５）基はハロゲン原子を含み、ｐは０または１、ｑは０〜１０、ただし、ｑが０の場合、Ｒ（５）はＣ１−Ｃ１６ハロアルキル基またはハロシクロアルキル基）
【０００６】
（ｃ）下記式モノマー　２〜１０重量％（コポリマーがモノマー（ｉ）由来の単位を有する場合）または１〜１５重量％（コポリマーが（ｉｉ）由来の単位を有する場合）：
【化１４】
Figure 2004506073
（ここでＲ（６）はＨまたはメチル）
【０００７】
（ｄ）下記式の陽イオンモノマー　１〜６重量％
【化１５】
Figure 2004506073
（ここで、Ｒ（７）はＨまたはメチル、Ｚ（０）はラジカル重合を活性化する電子吸引性の二価の基、Ｙ（０）＋は陽イオン性の一価の基、Ｘ（０）−は陰イオン）
（ｅ）０〜２０重量％の塩化ビニリデン。
【０００８】
【特許文献２】国際特許出願第ＷＯ９８／２３６５７号
上記文献には下記（ａ）〜（ｄ）を共重合して得られる水／溶剤（Ｎ−ビニルピロリドン）混合物中の溶液状の陽イオン性フッ素化コポリマーが記載されている：
（ａ）下記一般式のポリフルオロモノマー　５０〜９２重量％
【化１６】
Figure 2004506073
（ここで、Ａ（１０）は炭素原子を介してＯに結合され且つ１つまたは複数の酸素原子、硫黄原子および／または窒素原子を有することができる二価の結合基、Ｒ（１０）の一方は水素原子、他方は水素原子または１〜４個の炭素原子を有するアルキル基、Ｒｆは２〜２０個、好ましくは４〜１６個の炭素原子を含む直鎖または分岐鎖のパーフルオロ基）
【０００９】
（ｂ）下記一般式のモノマー　１〜２５重量％
【化１７】
Figure 2004506073
（ここで、Ｒ（１１）は水素原子または１〜４個の炭素原子を含むアルキル基、Ａ（１１）は１〜４個の炭素原子を含む直鎖または分岐鎖のアルキレン基、Ｒ（１２）およびＲ（１３）は水素原子、１〜１８個の炭素原子を含む直鎖または分岐鎖のアルキル基またはヒドロキシエチル基またはベンジル基を表し、互いに同一でも異なっていてもよく、さらには、Ｒ（１２）とＲ（１３）とがそれらが結合している窒素原子と一緒にモルフォリン基、ピペラジン基またはピロリジン−１−イル基を形成することもできる）
【００１０】
（ｃ）下記一般式のビニル誘導体　１〜２５重量％
ＣＨ２＝ＣＨ−Ｒ（１４）
（ここで、Ｒ（１４）は１〜１８個の炭素原子を含むアルキルカルボキシレートまたはアルキルエーテル基）
（ｄ）上記３つのモノマー以外の任意のモノマー　０〜１０重量％
【００１１】
上記国際特許出願に記載されたフッ素化コポリマーは水に混和性を有する有機溶剤または溶剤混合物の溶液中で共重合反応を実施した後に、無機酸または有機酸の水溶液で稀釈して得られる。この稀釈段階は過酸化水素の存在下で実施するか、稀釈後に過酸化水素水溶液を用いて行う。この稀釈段階後に真空蒸留や窒素等の不活性ガスを流す操作で揮発性化合物を除去して、被加工基材に塗布可能な組成物の商品を得る必要がある。
しかし、この国際特許出願に記載の溶剤は高価なＮ−メチレンピロリドンをベースとする混合物である。この溶剤は沸点が高いため蒸留操作では完全に除去できず、かなりの量が商品の組成物中に残っている。
この商品の組成物は水／溶剤（Ｎ−メチレンピロリドン）混合物中の溶液の形にする。そうすることによって安定し、輸送および貯蔵が有利になる。しかし、用途、特に食品包装の分野で用いられる紙またはその類似製品の加工では、食品と接触する際に有機溶剤の存在が欠点となる。
【００１２】
【特許文献３】国際特許出願第ＷＯ９８／２３６５７号
上記文献（第５頁、第１４〜１５行参照）では軽質溶剤を用いて蒸留後に有機溶剤を全く含まない組成物すなわち水性コポリマー分散液を得ている。この文献に記載の陽イオン性フッ素化コポリマーの製造で用いられる第３または第４アミノモノマーは１つの分子当たり１つの第３アミノ基または１つの第４アミノ基を有する。
【００１３】
【発明が解決しようとする課題】
本発明者は、上記公知の構造とは違って、２つの第３アミノ基または２つの第４アミノ基または１つの第３アミノ基と第４アミノ基との組合せを含む他のモノマーを用いることによって、各種基材、特に紙および織物に疎水性および疎油性を与えることができるということ、さらに、水性組成物、特にラテックス、エマルションまたは分散液の形または水／溶剤混合物中の溶液の形をした新規な陽イオン性フッ素化コポリマーを調製することができるということを見出した。
【００１４】
【課題を解決するための手段】
本発明の対象は、１００重量部当たり下記（Ａ）〜（Ｇ）を含むモノマー組成物から得られる陽イオン性フッ素化コポリマーにある：
（Ａ）　少なくとも１種の下記式（Ｉ）のポリフッ化モノマー　５〜９２重量部、好ましくは４０〜９０重量部：
【００１５】
【化１８】
Figure 2004506073
【００１６】
（ここで、
Ｒ１とＲ２は共に水素原子を表すか、一方が水素原子を表し、もう一方がＣ１〜Ｃ４アルキル基を表し、
Ａ１は炭素原子を介してＯに結合され、一つまたは複数の酸素原子および／または硫黄原子および／または窒素原子を有することができる二価の結合基を表し、
Ｒｆは直鎖または分岐鎖のＣ２〜Ｃ２０パーフルオロ基を表す）
（Ｂ）　下記式（ＩＩ）、（ＩＩＩ）および（ＶＩ）のモノマーの中から選択される少なくとも１種のモノマー　０．１０〜２５重量部、好ましくは１〜１８重量部：
【００１７】
【化１９】
Figure 2004506073
【００１８】
（ここで、
Ｒ３はＨまたは−ＣＨ３を表し、
Ｒ４およびＲ５はＨ、Ｃ１−Ｃ１８アルキル、ベンジルまたはヒドロキシエチルを表し、互いに同一または異なっており、
Ｘ１−は一価の陰イオンを表す）、
【００１９】
【化２０】
Figure 2004506073
（ここで、
Ｒ６はＨまたは−ＣＨ３を表し、
Ｒ７はＨ、Ｃ１−Ｃ１８アルキル、ベンジルまたはヒドロキシエチルを表す）
【００２０】
【化２１】
Figure 2004506073
【００２１】
（ここで、
Ｒ８はＨまたは−ＣＨ３を表し、
Ｒ９およびＲ１０は水素、Ｃ１−Ｃ１８アルキル、ベンジルまたはヒドロキシエチルを表し、互いに同一または異なっており、
Ｘ２−は一価の陰イオンを表す）
（Ｃ）　少なくとも一種の陰イオン性モノマーまたはｐＨを変えることによって陰イオンになり得るモノマー　０〜２０重量部、好ましくは１〜１０重量部
（Ｄ）　一般式（Ｖ）の少なくとも一種のビニルモノマー　０〜２５重量部、好ましくは２〜１０重量部：
【００２２】
【化２２】
Figure 2004506073
（ここで、
Ｒ１１はＣ１−Ｃ１８アルキルまたはアルキルカルボキシレートまたはアルキルエーテル基を表す）
（Ｅ）　一般式（ＶＩ）の少なくとも一種のモノマー　０〜６０重量部：
【００２３】
【化２３】
Figure 2004506073
【００２４】
（ここで、
Ｒ１２はＨまたは−ＣＨ３を表し、
ｍは０または１であり、
Ｒ１３は少なくとも１つのハロゲンで置換されていてもよいＣ１−Ｃ６アルキレン残基を表し、
ｎは０であるか、１〜１１の整数（両端を含む）であり、
Ｒ１４は少なくとも１つのハロゲンで置換されていてもよいＣ１−Ｃ３２アルキル残基、または少なくとも１つのハロゲンで置換されていてもよいシクロアルキル残基を表す）
（Ｆ）　フッ素化コポリマーを基材上に被覆する間または被覆後にフッ素化コポリマーを架橋できるようにする少なくとも１種のモノマー　０〜１０重量部
（Ｇ）　一般式（ＶＩＩ）の少なくとも１種のモノマー　０〜２５重量部：
【００２５】
【化２４】
Figure 2004506073
【００２６】
（ここで、
Ｒ１５は水素原子または１〜４個の炭素原子を含むアルキル基を表し、
Ａ２は１〜４個の炭素原子を含む直鎖または分岐したアルキレン基を表し、
Ｒ１６およびＲ１７は水素原子、１〜１８個の炭素原子を含む直鎖または分岐したアルキル基或いはヒドロキシエチルまたはベンジル基を表し、互いに同一または異なっており、或いは、Ｒ１６およびＲ１７がこれらが結合している窒素原子と一緒にモルフォリン、ピペリジンまたはピロリジン−１−イル基を形成する）
【００２７】
【実施の態様】
式（Ｉ）のモノマー（Ａ）は特にＲｆがＣ４−Ｃ１６パーフルオロアルキル基であるモノマーである。式（Ｉ）のモノマーは下記式（Ｉａ）のモノマーから選択されるのが好ましい：
【００２８】
【化２５】
Figure 2004506073
（ここで、ＲｆはＣ４−Ｃ１６パーフルオロアルキル基を表す）
【００２９】
式（ＩＩ）のモノマー（Ｂ）は特に下記の中から選択される：
Ｒ３がＨを表し、
Ｒ４が−ＣＨ３を表し、
Ｒ５が−ＣＨ３またはベンジルを表し、
Ｘ１−がＣｌ−を表す。
式（ＩＩＩ）のモノマー（Ｂ）は特に、Ｒ６がＨを表し、Ｒ７が−ＣＨ３を表すモノマーから選択される。
式（ＩＶ）のモノマー（Ｂ）は特に、Ｒ８がＨを表し、Ｒ９が−ＣＨ３を表し、Ｒ１０が−ＣＨ３またはベンジルを表し、Ｘ２−がＣｌ−を表すモノマーから選択される。
【００３０】
本発明コポリマーがエマルション状態で得られる場合には、化合物（Ｂ）として化合物（ＩＩ）（Ｒ３＝Ｈ、Ｒ４＝−ＣＨ３、Ｒ５＝−ＣＨ３または−ＣＨ２−Ｃ６Ｈ５、Ｘ１−＝Ｃｌ−、および／または、化合物（ＩＶ）（Ｒ８＝Ｈ、Ｒ９＝−ＣＨ３、Ｒ１０＝−ＣＨ３または−ＣＨ２−Ｃ６Ｈ５、Ｘ２−＝Ｃｌ−）を用いるのが好ましい。
本発明コポリマーが溶液状態で得られる場合には、化合物（Ｂ）として化合物（ＩＩＩ）（Ｒ６＝Ｈ、Ｒ７＝−ＣＨ３）、および／または、化合物（ＩＶ）（Ｒ８＝Ｈ、Ｒ９＝−ＣＨ３、Ｒ１０＝−ＣＨ３または−ＣＨ２−Ｃ６Ｈ５、Ｘ２−＝Ｃｌ−）を用いるのが好ましい。
【００３１】
陰イオン性モノマーまたはｐＨを変えることによって陰イオンになり得るモノマー（モノマーＣ）は、エチレン性不飽和カルボン酸およびその塩と、エチレン性不飽和スルホン化モノマーおよびその塩の中から選択するのが好ましい。
エチレン性不飽和カルボン酸はメタクリル酸が好ましく、エチレン性不飽和スルホン化モノマーは２−アクリルアミド−２−メチルプロパン−スルホン酸およびその塩との中から選択するのが好ましい。モノマー（Ｃ）としてメタクリル酸を用いるのが好ましい。
モノマー（Ｄ）は酢酸ビニルにするのが好ましい。
モノマー（Ｅ）はベヘニルアクリレート、ステアリルメタクリレート、メトキシエチルアクリレートおよびメトキシエチルメタクリレートの中から選択するのが好ましい。
【００３２】
フッ素化コポリマーを基材上に被覆する間または被覆後に上記コポリマーを架橋できるようにするモノマー（Ｆ）は下記の中から選択するのが好ましい：
（Ｆ１）　エチレン性不飽和シランモノマー、
（Ｆ２）　２−ヒドロキシ−３−クロロプロピル（メタ）アクリレート、
（Ｆ３）　エポキシ基を有する（メタ）アクリレート
（Ｆ４）　下記式（ＶＩＩＩ）のモノマー：
【００３３】
【化２６】
Figure 2004506073
（ここで、Ｒ１８はＨまたは−ＣＨ３を表し、Ｒ１９およびＲ２０はそれぞれ別々にＨまたは必要に応じて複数のＯＨ基を有していてもよいＣ１−Ｃ５アルキル、または（Ｃ１−Ｃ５）アルコキシ−（Ｃ１−Ｃ５）アルキルを表し、互いに同一または異なっている）
【００３４】
（Ｆ５）　下記式（ＩＸ）のモノマー：
【化２７】
Figure 2004506073
（ここで、Ｒ２１はＨまたは−ＣＨ３を表し、Ｒ２２、Ｒ２３およびＲ２４はそれぞれＨまたはＣ１−Ｃ４アルキルを表し、互いに同一または異なっている）
【００３５】
モノマー（Ｆ４）はＮ−メチロールアクリルアミドであるのが好ましい。
式（ＩＸ）のモノマー（Ｆ５）はＲ２１とＲ２２がそれぞれＨを表し、Ｒ２３とＲ２４がそれぞれ−ＣＨ３を表すモノマーであるのが好ましい。
モノマー（Ｇ）はジメチルアミノエチルメタクリレートであるのが好ましい。
本発明のフッ素化コポリマーは、ポリマーの最終調整状態に応じて、２つの重合方法すなわち乳化重合（ラテックス状またはエマルション状のポリマーを得る場合）および溶液重合（水／溶剤混合物中の溶液または溶剤除去後の水性分散液状のポリマーを得る場合）を用いてモノマーをラジカル共重合することによって製造できる。
【００３６】
乳化重合
乳化重合の場合には単数または複数の水混和性の有機溶剤を用いなければならない。本発明では、引火点が１００℃以上の製品となる水／溶剤混合物の組成物になる。
有機溶剤は少なくとも部分的に水で稀釈可能な化合物、例えばプロピレングリコール、エチレングリコール、エチルグリコール、メトキシプロパノール、エチレンカーボネート、プロピレンカーボネート、エチレングリコールジエチルエーテル、プロピレングリコールメチルエーテル、Ｎ−メチルピロリドン、アセトン、メチルエチルケトン、酢酸、プロピオン酸、テトラヒドロフラン、ジアセトンアルコール、メチルアルコール、エチルアルコール、イソプロピルアルコールおよびγ−ブチロラクトン等である。
【００３７】
水／溶剤混合物の水は４０〜９０重量％、溶剤混合物は５〜６０重量％にすることができる。
下記溶剤を用いるのが好ましい：
（ａ）プロピレングリコール、Ｎ−メチルピロリドン、プロピレングリコールメチルエーテルまたは酢酸；この場合、溶剤混合物が０〜１００℃の引火点にならないため重合の後に蒸留を実施しない。
（ｂ）アセトン；水／アセトン混合物は引火点が０〜１００℃になる。この場合、蒸留を実施してエマルションから溶剤を除去する。
【００３８】
乳化共重合は陽イオン性界面活性剤（モノマー混合物に対して１〜１０重量％の非イオン界面活性剤と組み合わせても、組み合わせなくてもよい）の存在下で実施する。反応混合物（水／溶剤／モノマー／界面活性剤）中のモノマーの合計濃度は１５〜７０重量％、好ましくは３０〜７０重量％である。
モノマー混合物に対して０．０１〜０．５重量％のメルカプタン等の連鎖移動剤を用いるか、モノマー導入方法を調節して分子量を調整する。
【００３９】
共重合は過酸化型（例えば過酸化水素）または過酸塩（過硫酸塩）またはアゾ型、例えば４，４’−アゾビス（４−シアノペンタン酸）またはアゾビス（アミニジノプロパン）塩酸塩等の開始剤を用いて２０〜１５０℃で開始できる。開始剤はモノマー混合物に対して０．１〜４重量％用いる。
水混和性溶剤の量は幅広い範囲で可変であり、一般に全モノマー１００重量部に対して１０〜８０重量部にする。モノマーの乳化には超音波すなわちＭａｎｔｏｎ−Ｇａｕｌｉｎ型のホモジナイザー等の高エネルギー乳化手段を用いることができる。
重合段階の後に溶剤を蒸留する段階を実施して有機溶剤を含まない水性乳化剤（ｅｍｕｌｓｉｏｎ ｉｎ ｗａｔｅｒ）を得ることができる。
【００４０】
溶液重合
この溶液重合は重合終了時に酸によって四級化または塩（Ｓａｌｉｆｉｅ）になる少なくとも１種の第３アミノ基を有するコポリマーの場合に用いられる。この溶液重合は水混和性を有する有機溶剤または溶剤混合物中で実施する。水と混合した蒸留可能な溶剤を用いて溶剤を含まない生成物を得るのが好ましい。次いで、反応媒体を無機酸または有機酸の存在下で希釈して高分子を塩にする。
本発明の好ましい変形例ではこの稀釈段階を過酸化水素の存在下で実施するか、稀釈段階後に過酸化水素水溶液を用いて処理する。
【００４１】
共重合を実施する水との混合物としての蒸留可能な水と混和性のある水混和性有機溶剤の例としては、ケトン（例えばアセトンおよびメチルエチルケトン）、アルコール（例えばイソプロパノル）およびエーテル（メチルエーテル）等が挙げられる。本発明では溶剤としてメチルイソブチルケトンまたはメチルエチルケトン、或いはこれらのケトンとアセトンとの混合物を用いるのが好ましい。
水と混和性があり且つ蒸留ができない水混和性有機溶剤（この中で共重合を実施する）の例としてはＮ−ビニルピロリドンが挙げられる。
有機溶剤または有機溶剤混合物中のモノマー濃度の合計は１５〜７０重量％、好ましくは３０〜６０重量％の範囲にできる。
【００４２】
共重合は、モノマーの全重量に対して０．１〜２重量％の少なくとも１種の開始剤の存在下で実施する。開始剤としては過酸化物、例えば過酸化ベンゾイル、過酸化ラウロイル、過酸化スクシニルおよびペルピヴァリン酸ター−ブチルまたはアゾ化合物、例えば２、２’−アゾビス（イソブチロニトリル）、４‐４’−アゾビス（４−シアノペンタン）酸およびアゾビス（アミジノプロパン）を用いることができる。４０℃から反応混合物の沸点までの温度で共重合を実施する。６０〜９０℃で実施するのが好ましい。
【００４３】
稀釈段階では強酸〜やや強酸の有機酸または無機酸の水溶液（すなわち解離定数または第１解離定数が１０−５以上の酸）をコポリマーの有機溶液に添加する。酸の例としては塩酸、臭化水素酸、硫酸、硝酸、燐酸、酢酸、ホルム酸、ピロピオン酸およびラクト酸が挙げられる。酢酸を用いるのが好ましい。用いる水溶液の量および酸濃度は、式（ＩＩＩ）、（ＩＶ）および（ＶＩＩ）のモノマーのアミン官能基を完全に塩にし且つ５〜３０重量％、好ましくは２０〜３０重量％の固体含有量を有する最終コポリマー溶液を得るのに十分なものでなければならない。アミン官能基を完全に塩にするには酸の当量を式（ＩＩＩ）、（ＩＶ）および（ＶＩＩ）のモノマーに対して０〜５当量、好ましくは１〜２当量にするのが有利である。
【００４４】
用いる過酸化水素の量はモノマーの初期全重量に対して０〜１０重量％、好ましくは０．５〜４重量％にする。２５〜１００℃、好ましくは７０〜８５℃で処理する。
本発明フッ素化コポリマーのエマルションまたは溶液は各種基材、例えば革、不織布、建材、紙および厚紙等に塗布できる。特に、本発明コポリマーは各種の方法（サイズプレスや材料全体に添加）で織物または紙に塗布でき、それによって、他の添加剤無しで、基材に優れた疎水性および疎油性を与えることができる。
【００４５】
本発明の他の対象は、上記に定義の本発明の少なくとも１種のフッ素化コポリマーを含む固体基材にある。
本発明化合物で疎油性および疎水性を付与できる基材としては紙、厚紙およびその類似製品が挙げられる。例えば、セルロースまたは再生セルロース、天然繊維、人工繊維または合成繊維、例えば綿、アセチル・セルロース、ウール、絹、ポリアミド、ポリエステル、ポリオレフィン、ポリウレタンまたはポリアクリロニトリル等の繊維をベースにした織物または非織物、革、プラスチック、ガラス、木材、金属、磁器および塗装面等の各種材料に用いることができる。コンクリート、石、レンガおよびタイル等の建築材料を本発明化合物で処理するのも有利である。
【００４６】
本発明のフッ素化コポリマーを含む組成物は基本的に水性媒体または水と溶剤との混合物中に稀釈して周知の方法、例えば被覆、含浸、浸漬、噴霧、刷毛塗り、たんぽ刷りまたはフィルムコーティング等で塗布することができる。
本発明化合物の水溶液は紙に塗布することができ、基材の表面上に（好ましくは紙の重量の０．０５〜０．２重量％のフッ素量で）塗布するか、素材本体内に添加すなわち製紙用パルプ中に添加（好ましくはパルプ重量の０．２〜０．４％のフッ素量で添加）することができる。
【００４７】
得られた処理済み基材は室温または高温で乾燥した後、必要に応じて基材の種類に応じた２００℃以下の範囲に加熱することが十分な疎油性および疎水性を示す。
本発明のフッ素化コポリマーを塗布する基材に対する接着性を十分にし、さらに本発明の特定の効果を得るために、適当なの添加剤、ポリマー、熱縮合可能な化合物および基材との架橋を促進可能な触媒を混合するのが有利である。例としては尿素ホルムアルデヒドまたはメラミンホルムアルデヒド縮合物または初期縮合物、ジグリシジルグリセロール、ポリアミン−エピクロロヒドリン樹脂等のエポキシ誘導体、グリオキサールとその誘導体、ポリビニルアルコールおよび陽イオン性澱粉、酸化澱粉および両性澱粉等が挙げられる。
【００４８】
本発明のフッ素化コポリマーを１種または複数の非イオン性および／または陽イオン性界面活性剤と混合して基材との濡れ性を改良することもできる。この界面活性剤の量はコポリマーの総量に対して０〜１００％にすることができる。
本発明で処理した基材の性能評価は以下テストで行った。
【００４９】
耐油度テストまたはキット番号（ Ｋｉｔ Ｖａｌｕｅ ）
このテストは「ＴＡＰＰＩ，Ｖｏｌ．５０， Ｎｏ．１０の第１５２Ａ頁、第１５３Ａ頁」と規格ＲＣ３３８およびＵＭ５１１に記載されており、キャスターオイル、トルエンおよびヘプタンの混合物を用いて基材の耐油度を測定する。各混合物は３種類の化合物を下記比率で含んでいる：
【００５０】
【表１】
Figure 2004506073
【００５１】
テストでは処理した紙上に上記の混合物の液滴を静かに置く。液滴を紙上に１５秒間放置してから、紙または厚紙の外観を観察し、表面の褐変によって濡れまたは浸透性を記録する。紙に浸透しない（または紙を濡らさない）混合物のヘプタン比率が最大の混合物に対応する「番号」がその紙のキット番号となり、処理した紙の疎油度を表す。キット番号が高い程、紙の耐油性は良い。
【００５２】
ＣＯＢＢ テスト
Ｃｏｂｂテスト［規格ＮＦ ＥＮ ２０５３５−ＩＳＯ ５３５ （１９９４）］は、高さ１ｃｍの水柱を支持する１ｍ２の紙が１分間に吸収する水の量（ｇ単位）を測定するものである。
【００５３】
耐油テスト
耐油性は、「ＡＡＴＣＣ Ｔｅｃｈｎｉｃａｌ Ｍａｎｕａｌ、Ｔｅｓｔ Ｍｅｔｈｏｄ １１８‐１９７２」に記載の方法を用いて所定の基材上で測定した。このテストでは下記の１〜８の番号を付けた一連のオイルを用いて基材の非湿潤性を測定する：
Ｎｏ．１：　流動パラフィン
Ｎｏ．２：　流動パラフィン／ｎ−ヘキサデカン（６４／３５）
Ｎｏ．３：　ｎ−ヘキサデカン
Ｎｏ．４：　ｎ−テトラデカン
Ｎｏ．５：　ｎ−ドデカン
Ｎｏ．６：　ｎ−デカン
Ｎｏ．７：　ｎ−オクタン
Ｎｏ．８：　ｎ−ヘプタン
このテストでは処理済の基材の上に上記オイル滴を置き、３０秒接触させた後の影響を観察する。基材に浸透したり、濡らしたりしなかった最後のオイルの番号で評価する。
【００５４】
耐水 （ 疎水性 ） テスト
「噴霧テスト」とよばれるこのテストは、ＡＡＴＣＣ ２２−１９８９規格に記載されている。このテストでは４５℃に傾けた支持体に固定した処理済の織物の上に約２０秒間、約１５ｃｍの高さからスプリンクラーを取付けた漏斗から２５０ｍｌの水を注ぐ。このテストでは視覚で読取り、０（完全に濡れた織物）〜１００（完全に乾いた織物）で評価する。
【００５５】
【実施例】
以下、本発明の実施例を説明するが、本発明が下記実施例に限定されるものではない。
部および比率（％）は特に表示が無ければ重量単位である。
略号は以下のものを表す：
Ｓ‐ＡＤＡＮＱＵＡＴ ２ＢＺ：　下記式の化合物
【００５６】
【化２８】
Figure 2004506073
【００５７】
実施例１および２では下記式のポリフッ化アクリレートの混合物を用いた：
【化２９】
Figure 2004506073
（ここで、ｐは８、１０、１２および１４（それぞれ重量比６３／２５／１０／２に対応する）である）
【００５８】
実施例１
サーモスタット付きジャケットで加熱された固定撹拌器と還流凝縮器とが取り付けられた１０００容量部の反応器に、下記を導入した：
３８３重量部の脱塩水、
１４０重量部のアセトン、
３．７５重量部のトリメチルオレイル塩化アンモニウム、
３．４３重量部のエトキシ化アルキルフェノール混合物（ＨＬＢ＝１５）、
１７６．９重量部の上記定義のポリフッ化アクリレートの混合物
４３．２重量部のメトキシエチルアクリレート、
２５重量部の４８％Ｎ−メチロールアクリルアミド水溶液、
１２．８重量部の７５％Ｓ−ＡＤＡＭＱＵＡＴ ２ＢＺ水溶液、
０．４８重量部のｎ−ドデシルメルカプタン。
【００５９】
窒素で不活性化し、７０℃に加熱してから、８重量部の水に溶解した１．２重量部のアゾビス（アミジノプロパン）塩酸塩を用いて重合を開始した。７０℃で２時間重合した後、固形分が３０．２％の７９６重量部のエマルションを得る。
次に、９０℃でアセトンを蒸留し、固形分３６％のラテックスを得る。これを水で稀釈して固形分２５％の完全に安定したエマルションにする。この生成物は密閉カップテスト（Ｓｅｔａｆｌａｓｈ ＮＦ．Ｔ．３００．５０を用いた）で０〜１００℃の間に引火点を有していなかった。
【００６０】
実施例２
サーモスタット付きジャケットで加熱された固定撹拌器と還流凝縮器とを取り付けた１０００容量部の反応器に下記を導入した：
２５７．４重量部の脱塩水、
９１．８重量部のアセトン、
８．９８重量部のトリメチルオレイル塩化アンモニウム、
８．２２重量部のエトキシ化アルキルフェノール混合物（ＨＬＢ＝１５）、
１１８．７重量部の上記定義のポリフッ化アクリレートの混合物
５０．３重量部のメトキシエチルアクリレート、
５．７４重量部の４８％Ｎ−メチロールアクリルアミド水溶液、
７．３０重量部の下記式モノマーの５０％溶液：
【００６１】
【化３０】
Figure 2004506073
２．８０重量部の７５％Ｓ−ＡＤＡＭＱＵＡＴ ２ＢＺ水溶液、
８．４５重量部のメチルアクリレート、
０．１８重量部のｎ−ドデシルメルカプタン。
【００６２】
窒素で不活性化し、７０℃に加熱してから、９重量部の水に溶解した０．９重量部のアゾビス（アミジノプロパン）塩酸塩を用いて重合を開始した。７０℃で２時間重合した後、固形分が３６％の５７３重量部のエマルションを得た。
次に、９０℃でアセトンを蒸留して固形分４０％のラテックスを得た。これを水で稀釈して固形分２０％の完全に安定したエマルションにした。この生成物は密閉カップテスト（Ｓｅｔａｆｌａｓｈ ＮＦ．Ｔ．３００．５０を用いた）で０〜１００℃の間に引火点を有していなかった。
【００６３】
実施例３
実施例１で得られたエマルションを１６ｇ／ｌ含むサイズプレス浴（ｓｉｚｅ−ｐｒｅｓｓ ｂａｔｈ）を調製した。
この組成物をサイズプレスで漂白パルプから成る７０ｇ／ｍ２の紙に塗布した。塗布率は約７０％であった。１２０℃で１分乾燥した後、処理した紙を室温で１日貯蔵し、各種テストを実施した。
結果は［表２］に示す。
【００６４】
【表２】
Figure 2004506073
本発明の陽イオン性フッ素化コポリマーで処理した紙は優れた疎油性および疎水性を示す。
【００６５】
実施例４
実施例２で得られたエマルションを２０ｇ／ｌと水中に１．５ｇ／ｌの酢酸を含む水溶液とのバジング浴（ｐａｄｄｉｎｇ ｂａｔｈ）を室温で調製した。ポリエステル織物を４０％に圧搾しながらこの浴中でパッド（ｆｏｕｌａｒｄｅ）する。乾燥後、織物をＢＥＮＺ型ヒートセッタ内で１６０℃で１分間ヒートセットした。
織物の疎水性および疎油性をテストし、結果を［表３］に示す。
【００６６】
【表３】
Figure 2004506073
本発明の陽イオン性フッ素化コポリマーで処理した織物が優れた疎油性および疎水性を有することが分かる。[0001]
FIELD OF THE INVENTION
The present invention relates to novel fluorinated copolymers and coatings for imparting oleophobicity and hydrophobicity to various substrates, such as textiles, leather, wood, nonwovens, metals, concrete, especially paper and the like and fibers. It relates to its use as an impregnating agent and to the substrates thus made.
[0002]
[Prior art]
A number of cationic fluorinated derivatives have been proposed for the above uses, including the following three:
(1) latex or emulsion (dispersion in water of polymer particles stabilized by surfactant),
(2) A solution in a water / solvent mixture (3) An aqueous dispersion obtained by removing the solvent of the above (2)
[Patent Document 1] EP-B-0,234,601 The above document discloses a cationic fluorinated copolymer in latex or emulsion state obtained by copolymerizing the following (a) to (e). Has been:
(A) 60-80% by weight of acrylate fluoromonomer of the following formula
Embedded image
Figure 2004506073
(Where R (0) f is an aliphatic perfluoro radical having 3 to 20 carbon atoms, A (0) is a divalent linking group),
[0004]
(B) The following (i) or (ii) 1 to 30% by weight
(I) an alkyl or alkoxyalkyl (meth) acrylate monomer of the formula:
Embedded image
Figure 2004506073
(Where R (1) is H or methyl, R (2) is a C 1 -C 6 alkylene group, R (3) is a C 1 -C 20 alkyl group or a cycloalkyl group, m is 0 or 1, n Is 0 to 10, provided that when n is 0, R (3) is a C 1 -C 16 alkyl group or a cycloalkyl group)
[0005]
(Ii) a halogenated alkyl or alkoxyalkyl acrylate monomer of the formula:
Embedded image
Figure 2004506073
(Where R (4) is a C 1 -C 6 alkylene group or a haloalkylene group, R (5) is a C 1 -C 20 alkyl group, a cycloalkyl group, a haloalkyl group or a halocycloalkyl group, and at least one The R (4) group or the R (5) group contains a halogen atom, p is 0 or 1, q is 0 to 10, provided that when q is 0, R (5) is a C 1 -C 16 haloalkyl group or Halocycloalkyl group)
[0006]
(C) 2 to 10% by weight (when the copolymer has units derived from monomer (i)) or 1 to 15% by weight (when the copolymer has units derived from (ii)):
Embedded image
Figure 2004506073
(Where R (6) is H or methyl)
[0007]
(D) 1 to 6% by weight of a cationic monomer of the following formula
Embedded image
Figure 2004506073
(Where R (7) is H or methyl, Z (0) is an electron-withdrawing divalent group that activates radical polymerization, Y (0) + is a cationic monovalent group, X ( 0) -is an anion)
(E) 0 to 20% by weight of vinylidene chloride.
[0008]
[Patent Document 2] International Patent Application No. WO98 / 23657 The above-mentioned document discloses a cationic solution in a water / solvent (N-vinylpyrrolidone) mixture obtained by copolymerizing the following (a) to (d). Fluorinated copolymers have been described:
(A) 50 to 92% by weight of a polyfluoro monomer represented by the following general formula
Embedded image
Figure 2004506073
Wherein A (10) is a divalent linking group bonded to O via a carbon atom and can have one or more oxygen, sulfur and / or nitrogen atoms, R (10) One is a hydrogen atom, the other is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R f is a linear or branched perfluoro group containing 2 to 20, preferably 4 to 16 carbon atoms. )
[0009]
(B) Monomers of the following general formula: 1 to 25% by weight
Embedded image
Figure 2004506073
(Where R (11) is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, A (11) is a linear or branched alkylene group containing 1 to 4 carbon atoms, R (12 ) And R (13) represent a hydrogen atom, a linear or branched alkyl group containing 1 to 18 carbon atoms or a hydroxyethyl group or a benzyl group, which may be the same or different from each other; (12) and R (13) together with the nitrogen atom to which they are attached can also form a morpholine, piperazine or pyrrolidin-1-yl group)
[0010]
(C) 1 to 25% by weight of a vinyl derivative represented by the following general formula
CH 2 = CH-R (14 )
(Where R (14) is an alkyl carboxylate or alkyl ether group containing 1 to 18 carbon atoms)
(D) Any monomer other than the above three monomers 0 to 10% by weight
[0011]
The fluorinated copolymer described in the above-mentioned international patent application is obtained by carrying out a copolymerization reaction in a solution of an organic solvent or a solvent mixture miscible with water, and then diluting with an aqueous solution of an inorganic acid or an organic acid. This dilution step is carried out in the presence of hydrogen peroxide or after dilution with an aqueous solution of hydrogen peroxide. After this dilution step, it is necessary to remove volatile compounds by vacuum distillation or an operation of flowing an inert gas such as nitrogen to obtain a product of a composition that can be applied to a substrate to be processed.
However, the solvents described in this international patent application are expensive N-methylenepyrrolidone based mixtures. This solvent cannot be completely removed by the distillation operation due to its high boiling point, and a considerable amount remains in the commercial composition.
The commercial composition is in the form of a solution in a water / solvent (N-methylenepyrrolidone) mixture. Doing so provides stability and transportation and storage advantages. However, in the application, in particular in the processing of paper or similar products used in the field of food packaging, the presence of organic solvents when in contact with food is disadvantageous.
[0012]
[Patent Document 3] International Patent Application No. WO 98/23657 In the above-mentioned document (see page 5, lines 14 to 15), a composition containing no organic solvent after distillation using a light solvent, that is, an aqueous copolymer dispersion is obtained. ing. The tertiary or quaternary amino monomers used in the preparation of the cationic fluorinated copolymers described in this document have one tertiary or one quaternary amino group per molecule.
[0013]
[Problems to be solved by the invention]
The present inventor has proposed that, unlike the above known structure, use of another monomer containing two tertiary amino groups or two quaternary amino groups or a combination of one tertiary amino group and quaternary amino group Can impart hydrophobic and oleophobic properties to various substrates, especially paper and textiles, and furthermore to form aqueous compositions, especially latexes, emulsions or dispersions or solutions in water / solvent mixtures. It has been found that new cationic fluorinated copolymers can be prepared.
[0014]
[Means for Solving the Problems]
The subject of the present invention is a cationic fluorinated copolymer obtained from a monomer composition comprising the following (A) to (G) per 100 parts by weight:
(A) at least one polyfluorinated monomer of the following formula (I): 5 to 92 parts by weight, preferably 40 to 90 parts by weight:
[0015]
Embedded image
Figure 2004506073
[0016]
(here,
R 1 and R 2 both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a C 1 -C 4 alkyl group;
A 1 represents a divalent linking group bonded to O via a carbon atom and capable of having one or more oxygen atoms and / or sulfur atoms and / or nitrogen atoms;
R f represents a linear or branched C 2 -C 20 perfluoro group)
(B) 0.10 to 25 parts by weight, preferably 1 to 18 parts by weight, of at least one monomer selected from monomers of the following formulas (II), (III) and (VI):
[0017]
Embedded image
Figure 2004506073
[0018]
(here,
R 3 represents H or —CH 3 ;
R 4 and R 5 represent H, C 1 -C 18 alkyl, benzyl or hydroxyethyl and are the same or different from each other;
X 1 represents a monovalent anion),
[0019]
Embedded image
Figure 2004506073
(here,
R 6 represents H or —CH 3 ;
R 7 represents H, C 1 -C 18 alkyl, benzyl or hydroxyethyl)
[0020]
Embedded image
Figure 2004506073
[0021]
(here,
R 8 represents H or —CH 3 ,
R 9 and R 10 represent hydrogen, C 1 -C 18 alkyl, benzyl or hydroxyethyl and are the same or different from each other;
X 2-represents a monovalent anion)
(C) at least one anionic monomer or a monomer that can become an anion by changing pH 0 to 20 parts by weight, preferably 1 to 10 parts by weight (D) at least one vinyl monomer of the general formula (V) 0 ２５25 parts by weight, preferably 2-10 parts by weight:
[0022]
Embedded image
Figure 2004506073
(here,
R 11 represents a C 1 -C 18 alkyl or alkyl carboxylate or alkyl ether group)
(E) at least one monomer of the general formula (VI): 0 to 60 parts by weight:
[0023]
Embedded image
Figure 2004506073
[0024]
(here,
R 12 represents H or —CH 3 ,
m is 0 or 1,
R 13 represents a C 1 -C 6 alkylene residue optionally substituted with at least one halogen,
n is 0 or an integer of 1 to 11 (including both ends);
R 14 represents a C 1 -C 32 alkyl residue optionally substituted with at least one halogen, or a cycloalkyl residue optionally substituted with at least one halogen)
(F) at least one monomer that allows the fluorinated copolymer to crosslink during or after coating the fluorinated copolymer on the substrate 0 to 10 parts by weight (G) at least one monomer of general formula (VII) 0 to 25 parts by weight:
[0025]
Embedded image
Figure 2004506073
[0026]
(here,
R 15 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
A 2 represents a linear or branched alkylene group containing 1 to 4 carbon atoms,
R 16 and R 17 represent a hydrogen atom, a linear or branched alkyl group containing 1 to 18 carbon atoms or a hydroxyethyl or benzyl group, which are the same or different from each other, or R 16 and R 17 are Forms a morpholine, piperidine or pyrrolidin-1-yl group together with the nitrogen atom to which it is attached)
[0027]
Embodiment
The monomers (A) of the formula (I) are especially those in which R f is a C 4 -C 16 perfluoroalkyl group. Preferably, the monomer of formula (I) is selected from monomers of formula (Ia):
[0028]
Embedded image
Figure 2004506073
(Where R f represents a C 4 -C 16 perfluoroalkyl group)
[0029]
The monomers (B) of the formula (II) are in particular selected from:
R 3 represents H;
R 4 represents —CH 3 ,
R 5 represents —CH 3 or benzyl;
X 1- represents Cl − .
The monomers (B) of the formula (III) are in particular selected from monomers in which R 6 represents H and R 7 represents —CH 3 .
The monomers (B) of the formula (IV) are in particular selected from monomers in which R 8 represents H, R 9 represents —CH 3 , R 10 represents —CH 3 or benzyl and X 2- represents Cl −. Is done.
[0030]
When the copolymers of the invention is obtained by emulsion state, the compound (B) as the compound (II) (R 3 = H , R 4 = -CH 3, R 5 = -CH 3 or -CH 2 -C 6 H 5 , X 1- = Cl -, and / or compound (IV) (R 8 = H , R 9 = -CH 3, R 10 = -CH 3 or -CH 2 -C 6 H 5, X 2- = Cl - ) Is preferably used.
When the copolymer of the present invention is obtained in a solution state, compound (III) (R 6 H, R 7 −—CH 3 ) and / or compound (IV) (R 8 ＨH, R 9 = -CH 3, R 10 = -CH 3 or -CH 2 -C 6 H 5, X 2- = Cl -) preferably used.
[0031]
The anionic monomer or a monomer that can become an anion by changing the pH (monomer C) is selected from ethylenically unsaturated carboxylic acids and salts thereof and ethylenically unsaturated sulfonated monomers and salts thereof. preferable.
The ethylenically unsaturated carboxylic acid is preferably methacrylic acid, and the ethylenically unsaturated sulfonated monomer is preferably selected from 2-acrylamido-2-methylpropane-sulfonic acid and salts thereof. It is preferable to use methacrylic acid as the monomer (C).
The monomer (D) is preferably vinyl acetate.
The monomer (E) is preferably selected from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and methoxyethyl methacrylate.
[0032]
The monomers (F) which enable the copolymer to be crosslinked during or after the coating of the fluorinated copolymer on the substrate are preferably selected from:
(F1) an ethylenically unsaturated silane monomer,
(F2) 2-hydroxy-3-chloropropyl (meth) acrylate,
(F3) Epoxy-containing (meth) acrylate (F4) Monomer of the following formula (VIII):
[0033]
Embedded image
Figure 2004506073
(Where R 18 represents H or —CH 3 , and R 19 and R 20 are each independently H or C 1 -C 5 alkyl optionally having a plurality of OH groups, or ( Represents a C 1 -C 5 ) alkoxy- (C 1 -C 5 ) alkyl, which are the same or different from each other)
[0034]
(F5) a monomer of the following formula (IX):
Embedded image
Figure 2004506073
(Where R 21 represents H or —CH 3 and R 22 , R 23 and R 24 each represent H or C 1 -C 4 alkyl, which are the same or different from each other)
[0035]
The monomer (F4) is preferably N-methylolacrylamide.
The monomer (F5) of the formula (IX) is preferably a monomer wherein R 21 and R 22 each represent H, and R 23 and R 24 each represent -CH 3 .
The monomer (G) is preferably dimethylaminoethyl methacrylate.
The fluorinated copolymers of the present invention can be prepared by two polymerization methods, depending on the final preparation of the polymer: emulsion polymerization (when a latex or emulsion polymer is obtained) and solution polymerization (solution or solvent removal in a water / solvent mixture). (In the case where a polymer in the form of an aqueous dispersion later is obtained), it can be produced by radical copolymerization of a monomer.
[0036]
Emulsion polymerization In the case of emulsion polymerization, one or more water-miscible organic solvents must be used. In the present invention, the composition of the water / solvent mixture is a product having a flash point of 100 ° C. or higher.
The organic solvent is at least partially dilutable with water, such as propylene glycol, ethylene glycol, ethyl glycol, methoxypropanol, ethylene carbonate, propylene carbonate, ethylene glycol diethyl ether, propylene glycol methyl ether, N-methylpyrrolidone, acetone, Methyl ethyl ketone, acetic acid, propionic acid, tetrahydrofuran, diacetone alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, and γ-butyrolactone.
[0037]
The water of the water / solvent mixture can be 40-90% by weight and the solvent mixture can be 5-60% by weight.
It is preferred to use the following solvents:
(A) propylene glycol, N-methylpyrrolidone, propylene glycol methyl ether or acetic acid; in this case, no distillation is carried out after the polymerization, since the flash point of the solvent mixture does not reach 0-100 ° C.
(B) Acetone; The flash point of the water / acetone mixture is 0-100 ° C. In this case, distillation is performed to remove the solvent from the emulsion.
[0038]
The emulsion copolymerization is carried out in the presence of a cationic surfactant, which may or may not be combined with 1 to 10% by weight of the nonionic surfactant, based on the monomer mixture. The total concentration of the monomers in the reaction mixture (water / solvent / monomer / surfactant) is between 15 and 70% by weight, preferably between 30 and 70% by weight.
The molecular weight is adjusted by using a chain transfer agent such as mercaptan in an amount of 0.01 to 0.5% by weight based on the monomer mixture, or by adjusting the monomer introduction method.
[0039]
The copolymerization may be carried out using a peroxide type (eg, hydrogen peroxide) or a persalt (persulfate) or an azo type, such as 4,4′-azobis (4-cyanopentanoic acid) or azobis (aminidinopropane) hydrochloride. It can be started at 20-150 ° C. with an initiator. The initiator is used in an amount of 0.1 to 4% by weight based on the monomer mixture.
The amount of water-miscible solvent can vary over a wide range and generally ranges from 10 to 80 parts by weight per 100 parts by weight of total monomers. For emulsification of the monomer, high-energy emulsifying means such as ultrasonic waves, a Manton-Gaulin type homogenizer, or the like can be used.
After the polymerization step, a step of distilling the solvent can be performed to obtain an aqueous emulsifier in water free of an organic solvent.
[0040]
Solution polymerization This solution polymerization is used in the case of copolymers having at least one tertiary amino group which is quaternized or salified by acid at the end of the polymerization. The solution polymerization is carried out in a water-miscible organic solvent or solvent mixture. It is preferred to obtain a solvent-free product using a distillable solvent mixed with water. The polymer is then salted by diluting the reaction medium in the presence of an inorganic or organic acid.
In a preferred variant of the invention, this dilution step is carried out in the presence of hydrogen peroxide or after the dilution step it is treated with an aqueous hydrogen peroxide solution.
[0041]
Examples of water-miscible organic solvents which are miscible with water, which are miscible with the water in which the copolymerization is carried out, include ketones (eg acetone and methyl ethyl ketone), alcohols (eg isopropanol) and ethers (methyl ether) and the like. Is mentioned. In the present invention, it is preferable to use methyl isobutyl ketone or methyl ethyl ketone or a mixture of these ketones and acetone as the solvent.
An example of a water-miscible organic solvent that is miscible with water and cannot be distilled (in which copolymerization is performed) is N-vinylpyrrolidone.
The sum of the monomer concentrations in the organic solvent or organic solvent mixture can range from 15 to 70% by weight, preferably 30 to 60% by weight.
[0042]
The copolymerization is carried out in the presence of from 0.1 to 2% by weight, based on the total weight of the monomers, of at least one initiator. Initiators include peroxides such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and ter-butyl perpivalate or azo compounds such as 2,2'-azobis (isobutyronitrile), 4-4'-azobis (4-Cyanopentane) acid and azobis (amidinopropane) can be used. The copolymerization is carried out at a temperature between 40 ° C. and the boiling point of the reaction mixture. It is preferably carried out at 60 to 90 ° C.
[0043]
In the dilution step, an aqueous solution of a strong acid to a slightly strong organic or inorganic acid (ie, an acid having a dissociation constant or a first dissociation constant of 10 −5 or more) is added to the organic solution of the copolymer. Examples of acids include hydrochloric, hydrobromic, sulfuric, nitric, phosphoric, acetic, formic, propionic, and lactoic acids. Preferably, acetic acid is used. The amount of aqueous solution used and the acid concentration are such that the amine functions of the monomers of the formulas (III), (IV) and (VII) are completely salted and the solids content is 5 to 30% by weight, preferably 20 to 30% by weight. Must be sufficient to obtain a final copolymer solution having In order to completely salt the amine function, the acid equivalents are advantageously from 0 to 5 equivalents, preferably from 1 to 2 equivalents, relative to the monomers of formulas (III), (IV) and (VII). .
[0044]
The amount of hydrogen peroxide used is 0 to 10% by weight, preferably 0.5 to 4% by weight, based on the total initial weight of the monomers. The treatment is performed at 25 to 100 ° C, preferably 70 to 85 ° C.
The emulsion or solution of the fluorinated copolymer of the present invention can be applied to various substrates such as leather, nonwoven fabric, building materials, paper and cardboard. In particular, the copolymers according to the invention can be applied to textiles or papers in various ways (size press or addition to the whole material), thereby giving the substrate excellent hydrophobic and oleophobic properties without other additives. it can.
[0045]
Another subject of the invention is a solid substrate comprising at least one fluorinated copolymer of the invention as defined above.
Substrates to which the compounds of the present invention can impart oleophobicity and hydrophobicity include paper, cardboard and similar products. For example, woven or non-woven, leather based fibers such as cellulose or regenerated cellulose, natural fibers, artificial fibers or synthetic fibers such as cotton, acetyl cellulose, wool, silk, polyamide, polyester, polyolefin, polyurethane or polyacrylonitrile , Plastic, glass, wood, metal, porcelain and painted surfaces. It is also advantageous to treat building materials such as concrete, stone, brick and tile with the compounds of the present invention.
[0046]
The composition comprising the fluorinated copolymer of the present invention is basically diluted in an aqueous medium or a mixture of water and a solvent and is coated in a known manner, such as coating, impregnating, dipping, spraying, brushing, dandelion or film coating. Can be applied.
The aqueous solution of the compound of the present invention can be applied to paper and applied on the surface of the substrate (preferably with a fluorine content of 0.05 to 0.2% by weight of the paper) or added to the base material. That is, it can be added to papermaking pulp (preferably with a fluorine content of 0.2 to 0.4% of the pulp weight).
[0047]
The treated substrate obtained shows sufficient oleophobicity and hydrophobicity to be dried at room temperature or high temperature and then heated to a temperature of 200 ° C. or less depending on the type of the substrate as necessary.
In order to ensure sufficient adhesion to the substrate to which the fluorinated copolymer of the present invention is applied and further to obtain the specific effects of the present invention, appropriate additives, polymers, heat-condensable compounds, and crosslinking with the substrate are promoted. It is advantageous to mix possible catalysts. Examples include urea formaldehyde or melamine formaldehyde condensates or precondensates, diglycidyl glycerol, epoxy derivatives such as polyamine-epichlorohydrin resin, glyoxal and its derivatives, polyvinyl alcohol and cationic starch, oxidized starch and amphoteric starch, etc. Is mentioned.
[0048]
The fluorinated copolymers of the present invention can also be mixed with one or more nonionic and / or cationic surfactants to improve wettability with the substrate. The amount of this surfactant can be from 0 to 100% based on the total amount of the copolymer.
The performance of the substrate treated in the present invention was evaluated by the following tests.
[0049]
Oil resistance test or kit number ( Kit Value )
This test is described in “TAPPI, Vol. 50, No. 10, pp. 152A, 153A” and Standards RC338 and UM511. The oil resistance of the substrate is determined using a mixture of caster oil, toluene and heptane. Measure. Each mixture contains the three compounds in the following proportions:
[0050]
[Table 1]
Figure 2004506073
[0051]
In the test, drops of the above mixture are gently placed on the treated paper. The droplets are left on the paper for 15 seconds before observing the appearance of the paper or cardboard and recording the wetting or penetration by browning of the surface. The "number" corresponding to the mixture with the highest heptane ratio of the mixture that does not penetrate (or wet) the paper is the kit number for that paper and represents the oleophobicity of the treated paper. The higher the kit number, the better the oil resistance of the paper.
[0052]
COBB Test The Cobb test [Standard NF EN 20535-ISO 535 (1994)] measures the amount of water (in g) that 1 m 2 of paper supporting a 1 cm high water column absorbs in one minute.
[0053]
Oil Resistance Test Oil resistance was measured on a given substrate using the method described in "AATCC Technical Manual, Test Method 118-1972". This test measures the non-wetting properties of a substrate using a series of oils numbered 1-8 below:
No. 1: Liquid paraffin No. 1 2: Liquid paraffin / n-hexadecane (64/35)
No. 3: n-hexadecane No. 3: 4: n-tetradecane No. 5: n-dodecane No. 5 6: n-decane No. 6 7: n-octane No. 7 8: n-heptane In this test, the oil drop is placed on the treated substrate and the effect after 30 seconds of contact is observed. Evaluate by the number of the last oil that did not penetrate or wet the substrate.
[0054]
Water resistance ( hydrophobicity ) test This test, called the "spray test", is described in the AATCC 22-1989 standard. In this test, 250 ml of water are poured from a funnel fitted with a sprinkler from a height of about 15 cm on a treated fabric fixed on a support inclined at 45 ° C. for about 20 seconds. This test is read visually and rated from 0 (completely wet fabric) to 100 (completely dry fabric).
[0055]
【Example】
Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.
Parts and ratios (%) are by weight unless otherwise indicated.
Abbreviations represent:
S-ADANQUAT 2BZ: a compound of the following formula:
Embedded image
Figure 2004506073
[0057]
Examples 1 and 2 used a mixture of polyfluorinated acrylates of the formula:
Embedded image
Figure 2004506073
(Where p is 8, 10, 12 and 14 (corresponding to a weight ratio of 63/25/10/2 respectively))
[0058]
Example 1
The following were introduced into a 1000-volume reactor equipped with a fixed stirrer and a reflux condenser heated by a thermostated jacket:
383 parts by weight of demineralized water,
140 parts by weight of acetone,
3.75 parts by weight of trimethyl oleyl ammonium chloride,
3.43 parts by weight of an ethoxylated alkylphenol mixture (HLB = 15),
173.9 parts by weight of a mixture of polyfluorinated acrylates as defined above, 43.2 parts by weight of methoxyethyl acrylate,
25 parts by weight of a 48% aqueous solution of N-methylolacrylamide,
12.8 parts by weight of a 75% S-ADAMQUAT 2BZ aqueous solution,
0.48 parts by weight of n-dodecyl mercaptan.
[0059]
After inerting with nitrogen and heating to 70 ° C., polymerization was initiated using 1.2 parts by weight of azobis (amidinopropane) hydrochloride dissolved in 8 parts by weight of water. After polymerization for 2 hours at 70 ° C., 796 parts by weight of an emulsion having a solids content of 30.2% are obtained.
Next, acetone is distilled at 90 ° C. to obtain a latex having a solid content of 36%. This is diluted with water to a completely stable emulsion with 25% solids. The product did not have a flash point between 0 and 100 ° C. in a closed cup test (using Setaflash NF.T. 300.50).
[0060]
Example 2
The following were introduced into a 1000 volume reactor equipped with a thermostated jacketed fixed stirrer and a reflux condenser:
257.4 parts by weight of demineralized water,
91.8 parts by weight of acetone,
8.98 parts by weight of trimethyl oleyl ammonium chloride,
8.22 parts by weight of an ethoxylated alkylphenol mixture (HLB = 15),
118.7 parts by weight of a mixture of polyfluorinated acrylates as defined above, 50.3 parts by weight of methoxyethyl acrylate,
5.74 parts by weight of a 48% aqueous solution of N-methylolacrylamide,
7.30 parts by weight of a 50% solution of a monomer of the formula:
[0061]
Embedded image
Figure 2004506073
2.80 parts by weight of a 75% S-ADAMQUAT 2BZ aqueous solution,
8.45 parts by weight of methyl acrylate,
0.18 parts by weight of n-dodecyl mercaptan.
[0062]
After inerting with nitrogen and heating to 70 ° C., polymerization was initiated using 0.9 parts by weight of azobis (amidinopropane) hydrochloride dissolved in 9 parts by weight of water. After polymerization at 70 ° C. for 2 hours, 573 parts by weight of an emulsion having a solid content of 36% was obtained.
Next, acetone was distilled at 90 ° C. to obtain a latex having a solid content of 40%. This was diluted with water to a completely stable emulsion with 20% solids. The product did not have a flash point between 0 and 100 ° C. in a closed cup test (using Setaflash NF.T. 300.50).
[0063]
Example 3
A size-press bath containing 16 g / l of the emulsion obtained in Example 1 was prepared.
This composition was applied on a size press to 70 g / m 2 paper of bleached pulp. The coating rate was about 70%. After drying at 120 ° C. for 1 minute, the treated paper was stored at room temperature for 1 day and various tests were performed.
The results are shown in [Table 2].
[0064]
[Table 2]
Figure 2004506073
Paper treated with the cationic fluorinated copolymer of the present invention exhibits excellent oleophobicity and hydrophobicity.
[0065]
Example 4
A padding bath of 20 g / l of the emulsion obtained in Example 2 and an aqueous solution containing 1.5 g / l acetic acid in water was prepared at room temperature. The polyester fabric is foularded in this bath while squeezing to 40%. After drying, the fabric was heat set at 160 ° C. for 1 minute in a BENZ type heat setter.
The fabric was tested for hydrophobicity and oleophobicity and the results are shown in Table 3.
[0066]
[Table 3]
Figure 2004506073
It can be seen that the fabric treated with the cationic fluorinated copolymer of the present invention has excellent oleophobicity and hydrophobicity.

Claims (23)

１００重量部当たり下記（Ａ）〜（Ｇ）を含むモノマー組成物から得られる陽イオン性フッ素化コポリマー：
（Ａ）　少なくとも１種の下記式（Ｉ）のポリフッ化モノマー　５〜９２重量部：
Figure 2004506073
（ここで、
Ｒ１とＲ２は共に水素原子を表すか、一方が水素原子を表し、もう一方がＣ１〜Ｃ４アルキル基を表し、
Ａ１は炭素原子を介してＯに結合され、一つまたは複数の酸素原子および／または硫黄原子および／または窒素原子を有することができる二価結合基を表し、
Ｒｆは直鎖または分岐鎖のＣ２〜Ｃ２０パーフルオロ基を表す）
（Ｂ）　下記式（ＩＩ）、（ＩＩＩ）および（ＶＩ）のモノマーの中から選択される少なくとも１種のモノマー　０．１０〜２５重量部：
Figure 2004506073
（ここで、
Ｒ３はＨまたは−ＣＨ３を表し、
Ｒ４およびＲ５はＨ、Ｃ１−Ｃ１８アルキル、ベンジルまたはヒドロキシエチルを表し、互いに同一または異なっており、
Ｘ１−は一価の陰イオンを表す）、
Figure 2004506073
（ここで、
Ｒ６はＨまたは−ＣＨ３を表し、
Ｒ７はＨ、Ｃ１−Ｃ１８アルキル、ベンジルまたはヒドロキシエチルを表す）
Figure 2004506073
（ここで、
Ｒ８はＨまたは−ＣＨ３を表し、
Ｒ９およびＲ１０は水素、Ｃ１−Ｃ１８アルキル、ベンジルまたはヒドロキシエチルを表し、互いに同一または異なっており、
Ｘ２−は一価の陰イオンを表す）
（Ｃ）　少なくとも一種の陰イオン性モノマーまたはｐＨを変えることによって陰イオンになり得るモノマー　０〜２０重量部、
（Ｄ）　一般式（Ｖ）の少なくとも一種のビニルモノマー　０〜２５重量部：
Figure 2004506073
（ここで、
Ｒ１１はＣ１−Ｃ１８アルキルまたはアルキルカルボキシレートまたはアルキルエーテル基を表す）
（Ｅ）　一般式（ＶＩ）の少なくとも一種のモノマー　０〜６０重量部：
Figure 2004506073
（ここで、
Ｒ１２はＨまたは−ＣＨ３を表し、
ｍは０または１であり、
Ｒ１３は少なくとも１つのハロゲンで置換されていてもよいＣ１−Ｃ６アルキレン残基を表し、
ｎは０であるか、１〜１１の整数（両端を含む）であり、
Ｒ１４は少なくとも１つのハロゲンで置換されていてもよいＣ１−Ｃ３２アルキル残基、または少なくとも１つのハロゲンで置換されていてもよいシクロアルキル残基を表す）
（Ｆ）　フッ素化コポリマーを基材上に被覆する間または被覆後にフッ素化コポリマーを架橋できるようにする少なくとも１種のモノマー　０〜１０重量部
（Ｇ）　一般式（ＶＩＩ）の少なくとも１種のモノマー　０〜２５重量部：
Figure 2004506073
（ここで、
Ｒ１５は水素原子または１〜４個の炭素原子を含むアルキル基を表し、
Ａ２は１〜４個の炭素原子を含む直鎖または分岐したアルキレン基を表し、
Ｒ１６およびＲ１７は水素原子、１〜１８個の炭素原子を含む直鎖または分岐したアルキル基或いはヒドロキシエチルまたはベンジル基を表し、互いに同一または異なっており、或いは、Ｒ１６およびＲ１７がこれらが結合している窒素原子と一緒にモルフォリン、ピペリジンまたはピロリジン−１−イル基を形成する）Cationic fluorinated copolymer obtained from a monomer composition containing the following (A) to (G) per 100 parts by weight:
(A) 5 to 92 parts by weight of at least one polyfluorinated monomer of the following formula (I):
Figure 2004506073
 (here,
R 1 and R 2 both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a C 1 -C 4 alkyl group;
A 1 represents a divalent linking group bonded to O via a carbon atom, which may have one or more oxygen atoms and / or sulfur atoms and / or nitrogen atoms,
R f represents a linear or branched C 2 -C 20 perfluoro group)
(B) 0.10 to 25 parts by weight of at least one monomer selected from monomers of the following formulas (II), (III) and (VI):
Figure 2004506073
 (here,
R 3 represents H or —CH 3 ;
R 4 and R 5 represent H, C 1 -C 18 alkyl, benzyl or hydroxyethyl and are the same or different from each other;
X 1 represents a monovalent anion),
Figure 2004506073
 (here,
R 6 represents H or —CH 3 ;
R 7 represents H, C 1 -C 18 alkyl, benzyl or hydroxyethyl)
Figure 2004506073
 (here,
R 8 represents H or —CH 3 ,
R 9 and R 10 represent hydrogen, C 1 -C 18 alkyl, benzyl or hydroxyethyl and are the same or different from each other;
X 2-represents a monovalent anion)
(C) 0 to 20 parts by weight of at least one anionic monomer or a monomer capable of becoming an anion by changing pH;
(D) at least one vinyl monomer of the general formula (V): 0 to 25 parts by weight:
Figure 2004506073
 (here,
R 11 represents a C 1 -C 18 alkyl or alkyl carboxylate or alkyl ether group)
(E) at least one monomer of the general formula (VI): 0 to 60 parts by weight:
Figure 2004506073
 (here,
R 12 represents H or —CH 3 ,
m is 0 or 1,
R 13 represents a C 1 -C 6 alkylene residue optionally substituted with at least one halogen,
n is 0 or an integer of 1 to 11 (including both ends);
R 14 represents a C 1 -C 32 alkyl residue optionally substituted with at least one halogen, or a cycloalkyl residue optionally substituted with at least one halogen)
(F) at least one monomer that allows the fluorinated copolymer to crosslink during or after coating the fluorinated copolymer on the substrate 0 to 10 parts by weight (G) at least one monomer of general formula (VII) 0 to 25 parts by weight:
Figure 2004506073
 (here,
R 15 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
A 2 represents a linear or branched alkylene group containing 1 to 4 carbon atoms,
R 16 and R 17 represent a hydrogen atom, a linear or branched alkyl group containing 1 to 18 carbon atoms or a hydroxyethyl or benzyl group, which are the same or different from each other, or R 16 and R 17 are Forms a morpholine, piperidine or pyrrolidin-1-yl group together with the nitrogen atom to which it is attached) モノマー（Ａ）が全モノマー１００重量部当たり４０〜９０重量部存在する請求項１に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to claim 1, wherein the monomer (A) is present in an amount of 40 to 90 parts by weight per 100 parts by weight of the total monomers. 式（Ｉ）のモノマー（Ａ）のＲｆがＣ４−Ｃ１６パーフルオロアルキル基である請求項１または２に記載の陽イオン性フッ素化コポリマー。Cationic fluorinated copolymer according to claim 1 or 2 R f is a C 4 -C 16 perfluoroalkyl group of the monomer of formula (I) (A). 式（ＩＩ）のモノマー（Ａ）が下記式（Ｉａ）のモノマーから選択される請求項１〜３のいずれか一項に記載の陽イオン性フッ素化コポリマー：
Figure 2004506073
（ここで、ＲｆはＣ４−Ｃ１６パーフルオロアルキル基を表す）The cationic fluorinated copolymer according to any one of claims 1 to 3, wherein the monomer (A) of the formula (II) is selected from the monomers of the following formula (Ia):
Figure 2004506073
 (Where R f represents a C 4 -C 16 perfluoroalkyl group) モノマー（Ｂ）が全モノマー１００重量部当たり１〜１８重量部存在する請求項１〜４のいずれか一項に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to any one of claims 1 to 4, wherein the monomer (B) is present in an amount of 1 to 18 parts by weight per 100 parts by weight of the total monomers. 下記（ａ）〜（ｃ）を特徴とする請求項１〜５のいずれか一項に記載の陽イオン性フッ素化コポリマー：
（ａ）　式（ＩＩ）のモノマー（Ｂ）のＲ３がＨを表し、Ｒ４が−ＣＨ３を表し、Ｒ５が−ＣＨ３またはベンジルを表し、Ｘ１−がＣｌ−を表し、
（ｂ）　式（ＩＩＩ）のモノマー（Ｂ）のＲ６がＨを表し、Ｒ７が−ＣＨ３を表し、
（ｃ）　式（ＩＶ）のモノマー（Ｂ）のＲ８がＨを表し、Ｒ９が−ＣＨ３を表し、Ｒ１０が−ＣＨ３またはベンジルを表し、Ｘ２−がＣｌ−を表す。The cationic fluorinated copolymer according to any one of claims 1 to 5, characterized by the following (a) to (c):
R 3 of monomer (B) of (a) reacting a compound of formula (II) represents H, R 4 represents -CH 3, R 5 represents -CH 3 or benzyl, X 1-is Cl - represents,
R 6 monomer (B) of (b) formula (III) represents H, R 7 represents -CH 3,
R 8 in the monomers (B) of (c) formula (IV) represents H, R 9 represents -CH 3, R 10 represents -CH 3 or benzyl, X 2-is Cl - represents a. モノマー（Ｃ）が全モノマー１００重量部当たり１〜１０重量部存在する請求項１〜６のいずれか一項に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to any one of claims 1 to 6, wherein the monomer (C) is present in an amount of 1 to 10 parts by weight per 100 parts by weight of the total monomers. モノマー（Ｃ）がエチレン性不飽和カルボン酸およびその塩と、エチレン性不飽和スルホン化モノマーおよびその塩の中から選択される請求項１〜７のいずれか一項に記載の陽イオン性フッ素化コポリマー。The cationic fluorination according to any one of claims 1 to 7, wherein the monomer (C) is selected from ethylenically unsaturated carboxylic acids and salts thereof and ethylenically unsaturated sulfonated monomers and salts thereof. Copolymer. エチレン性不飽和カルボン酸がメタクリル酸であり、エチレン性不飽和スルホン化モノマーが２−アクリルアミド−２−メチルプロパン−スルホン酸およびその塩の中から選択される請求項８に記載の陽イオン性フッ素化コポリマー。9. The cationic fluorine according to claim 8, wherein the ethylenically unsaturated carboxylic acid is methacrylic acid and the ethylenically unsaturated sulfonated monomer is selected from 2-acrylamido-2-methylpropane-sulfonic acid and salts thereof. Copolymerized. モノマー（Ｄ）が全モノマー１００重量部当たり２〜１０重量部存在する請求項１〜６のいずれか一項に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to any one of claims 1 to 6, wherein the monomer (D) is present in an amount of 2 to 10 parts by weight per 100 parts by weight of the total monomers. モノマー（Ｄ）が酢酸ビニルである請求項１〜１０のいずれか一項に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to any one of claims 1 to 10, wherein the monomer (D) is vinyl acetate. モノマー（Ｅ）がベヘニルアクリレート、ステアリルメタクリレート、メトキシエチルアクリレートおよびメトキシエチルメタクリレートの中から選択される請求項１〜１１のいずれか一項に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to any one of claims 1 to 11, wherein the monomer (E) is selected from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and methoxyethyl methacrylate. モノマー（Ｆ）が下記（Ｆ１）〜（Ｆ５）の中から選択される請求項１〜１２のいずれか一項に記載の陽イオン性フッ素化コポリマー：
（Ｆ１）　エチレン性不飽和シランモノマー、
（Ｆ２）　２−ヒドロキシ−３−クロロプロピル（メタ）アクリレート、
（Ｆ３）　エポキシ基を有する（メタ）アクリレート
（Ｆ４）　下記式（ＶＩＩＩ）のモノマー：
Figure 2004506073
（ここで、
Ｒ１８はＨまたは−ＣＨ３を表し、
Ｒ１９およびＲ２０はＨまたは一つまたは複数のＯＨ基を有していてもよいＣ１−Ｃ５アルキルまたは（Ｃ１−Ｃ５）アルコキシ−（Ｃ１−Ｃ５）アルキルを表し、互いに同一または異なっている）
（Ｆ５）　下記式（ＩＸ）のモノマー：
Figure 2004506073
（ここで、
Ｒ２１はＨまたは−ＣＨ３を表し、
Ｒ２２、Ｒ２３およびＲ２４はＨまたはＣ１−Ｃ４アルキルを表し、互いに同一または異なっている）The cationic fluorinated copolymer according to any one of claims 1 to 12, wherein the monomer (F) is selected from the following (F1) to (F5):
(F1) an ethylenically unsaturated silane monomer,
(F2) 2-hydroxy-3-chloropropyl (meth) acrylate,
(F3) Epoxy-containing (meth) acrylate (F4) Monomer of the following formula (VIII):
Figure 2004506073
 (here,
R 18 represents H or —CH 3 ,
R 19 and R 20 represent H or C 1 -C 5 alkyl or (C 1 -C 5 ) alkoxy- (C 1 -C 5 ) alkyl optionally having one or more OH groups, Same or different)
(F5) a monomer of the following formula (IX):
Figure 2004506073
 (here,
R 21 represents H or —CH 3 ,
R 22 , R 23 and R 24 represent H or C 1 -C 4 alkyl and are the same or different from each other) モノマー（Ｆ４）がＮ−メチロールアクリルアミドである請求項１３に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to claim 13, wherein the monomer (F4) is N-methylolacrylamide. 式（ＩＸ）のモノマー（Ｆ５）のＲ２１とＲ２２がＨを表し、Ｒ２３とＲ２４が−ＣＨ３を表す請求項１３に記載の陽イオン性フッ素化コポリマー。 R 21 and R 22 represent H, cationic fluorinated copolymer of claim 13, R 23 and R 24 represents -CH 3 monomers of formula (IX) (F5). 式（ＶＩＩ）のモノマー（Ｇ）がジメチルアミノエチルメタクリレートである請求項１〜１５のいずれか一項に記載の陽イオン性フッ素化コポリマー。The cationic fluorinated copolymer according to any one of claims 1 to 15, wherein the monomer (G) of the formula (VII) is dimethylaminoethyl methacrylate. 少なくとも１種の水と混和する有機溶剤中での乳化重合によって得られ、重合後に必要に応じて溶剤を蒸留して有機溶剤を含まない水性乳化剤を得る、請求項１〜１６のいずれか一項に記載の陽イオン性フッ素化コポリマー。17. An aqueous emulsifier obtained by emulsion polymerization in an organic solvent miscible with at least one water and optionally distilling the solvent after polymerization to obtain an aqueous emulsifier containing no organic solvent. 3. The cationic fluorinated copolymer according to item 1. 水と混和する有機溶剤または有機溶剤混合物中で溶液重合した後、無機酸または有機酸の水溶液で稀釈し、この稀釈段階後は必要に応じて過酸化水素の存在下で実施するか、後で過酸化水素水溶液で処理する請求項１〜１６のいずれか一項に記載の陽イオン性フッ素化コポリマー。After solution polymerization in a water-miscible organic solvent or mixture of organic solvents, it is diluted with an aqueous solution of an inorganic or organic acid, and after this dilution step it is carried out in the presence of hydrogen peroxide, if necessary, or The cationic fluorinated copolymer according to any one of claims 1 to 16, which is treated with an aqueous hydrogen peroxide solution. 請求項１〜１８のいずれか一項に記載の陽イオン性フッ素化コポリマーの、固体基材、特に紙および厚紙の疎油加工または疎水加工での使用。Use of the cationic fluorinated copolymer according to any one of claims 1 to 18 in oleophobic or hydrophobic processing of solid substrates, in particular paper and cardboard. 紙の重量に対してフッ素の量が０．０５〜０．２重量％となるように紙の表面に塗布する請求項１９に記載の使用。The use according to claim 19, wherein the amount of fluorine is applied to the surface of the paper such that the amount of fluorine is 0.05 to 0.2% by weight based on the weight of the paper. パルプの重量に対してフッ素の量が０．２〜０．４重量％となるように製紙用パルプ中に添加する請求項１９に記載の使用。The use according to claim 19, wherein the amount of fluorine is added to the papermaking pulp such that the amount of fluorine is 0.2 to 0.4% by weight based on the weight of the pulp. 請求項１〜１８のいずれか一項に記載の少なくとも１種のフッ素化コポリマーを含む固体基材。A solid substrate comprising at least one fluorinated copolymer according to any one of the preceding claims. 紙または厚紙である請求項２２に記載の固体基材。23. The solid substrate according to claim 22, which is paper or cardboard.
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