JP3868831B2 - Reactive surfactant - Google Patents

Description

【０００９】
［式中、Ａ₁は炭素数５〜１８の直鎖又は分岐鎖アルキレン基、あるいは式(III)
【００１０】
【化６】

【００１１】
（式中、Ｒは炭素数４〜１８の直鎖又は分岐鎖アルキル基を示す。）
で表されるアルコキシメチルエチレン基、Ａ₂は炭素数２〜４の直鎖又は分岐鎖アルキレン基、ｎは０〜２００の数、Ｍはカチオンを示す。］
また、本発明は、式（IV）又は式（Ｖ）
【００１２】
【化７】

【００１３】
〔式中、Ｒ、Ａ₂及びｎは前記の意味を示す。〕
で表される化合物とアミド硫酸を、アミド化合物（スルホン酸アミド化合物は除く）又はアミン化合物の存在下で反応させる、式（Ｉ−１）又は式（II−１）で表される化合物の製造法を提供する。
【００１４】
【化８】

【００１５】
〔式中、Ｒ、Ａ₂、ｎ及びＭは前記の意味を示す。〕
【００１６】
【発明の実施の形態】
前記の式（Ｉ）又は式（II）において、Ａ₁で示される炭素数５〜１８の直鎖又は分岐鎖アルキレン基としては、ブチルエチレン、オクチルエチレン、デシルエチレン、ドデシルエチレン、テトラデシルエチレン、ヘキサデシルエチレン等が挙げられる。式(III)においてＲで示される炭素数４〜１８の直鎖又は分岐鎖アルキル基としては、ブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等が挙げられる。
【００１７】
これらのＡ₁及びＲの中では、Ａ₁がアルキレン基のときはその総炭素数が、また、Ａ₁が式(III)で表されるアルコキシメチルエチレン基のときはＲの炭素数が、式（VI）を満足する数が特に好ましい。
【００１８】
８≦（炭素数）≦１８ （VI）
前記の式（Ｉ）又は式（II）において、Ａ₂で示される炭素数２〜４の直鎖又は分岐鎖アルキレン基としては、エチレン、プロピレン、エチルエチレン、ジメチルエチレン等が挙げられる。また、ｎ個のＡ₂は２種以上の混合基であってもよいが、そのうち、エチレン基の割合が７０モル％以上のものが好ましく、９０モル％以上のものがより好ましく、１００モル％のものが特に好ましい。
【００１９】
ｎはＡ₂Ｏで示されるオキシアルキレン基の平均付加モル数を示し、０〜２００、好ましくは１〜５０、特に好ましくは１〜３０の範囲である。Ｍで示されるカチオンとしては、ナトリウム、カリウム等のアルカリ金属イオン、カルシウム、マグネシウム等のアルカリ土類金属イオン、アンモニウムイオン、炭素数１〜４のアルキル基で置換されたアンモニウムイオン等が挙げられる。
【００２０】
本発明の反応性界面活性剤は、式（Ｉ）で表される化合物の方が、式(II)で表される化合物より塗膜の耐水性が特に向上するので好ましい。
【００２１】
本発明の式（Ｉ）又は式（II）で表される化合物は、公知の方法を用いて製造することができ、例えば、３−メチル−３−ブテン−１−オールに触媒存在下、アルキルグリシジルエーテルあるいはα−オレフィンエポキサイドを付加して、１−Ｏ−アルキル−３−Ｏ−（３−メチル−３−ブテニル）グリセリン又はオレフィンエポキサイドの３−メチル−３−ブテン−１−オールへの１モル付加体を得、得られた化合物に炭素数２〜４のアルキレンオキサイドを常法に従って付加するか、又は３−メチル−３−ブテン−１−オールに炭素数２〜４のアルキレンオキサイドを付加した後、この付加体１モルに対し、アルキルグリシジルエーテルあるいはα−オレフィンエポキサイドを１モル付加するかしてエーテルアルコールを得、これを硫酸化剤により硫酸化し、塩基性物質で中和することによって得られる。硫酸化剤としては、クロロスルホン酸、無水硫酸、アミド硫酸が挙げられるが、二重結合基への硫酸基の付加反応、二重結合基の異性化等の副反応を少なくする観点からアミド硫酸の使用が好ましい。
【００２２】
上記式（IV）又は式（Ｖ）で表される化合物を硫酸エステル化する際に、アミド化合物（スルホン酸アミド化合物は除く）、又はアミン化合物の存在下において、アミド硫酸を温度６０〜１４０℃で反応させることにより、二重結合基は充分に保護され、末端二重結合基の内部二重結合基への異性化、二重結合基への硫酸基付加等の副反応をほぼ完全に防止することができ、これにより式（Ｉ−１）又は(II−１)で表される高純度の末端不飽和化合物硫酸エステル塩を製造することができる。
【００２３】
本発明に用いられるアミド化合物としては、尿素、あるいはメチル尿素、１，１−ジメチル尿素、エチル尿素、ブチル尿素、アセチル尿素等の尿素誘導体、あるいはアセトアミド、ホルムアミド、プロピオン酸アミド、ブチルアミド、ジアセトアミド、コハク酸アミド等の酸アミド化合物を挙げることができる。
【００２４】
しかし、トルエンスルホン酸アミド等のスルホン酸アミド化合物は二重結合基の異性化、スルホン酸基の二重結合基への付加に対して防止する効果がないので本発明では用いることができない。
【００２５】
本発明に用いられるアミン化合物としては、モルホリン、トリエチルアミン、トリブチルアミン、イソプロピルアミン、ジイソプロピルアミン等が挙げられる。本発明に用いられるアミド化合物、及びアミン化合物は、分子量が小さい場合には少量使用で効果があり、分子量としては１５０以下、好ましくは１００以下である。
【００２６】
アミド化合物又はアミン化合物の使用量は、式（IV）又は式（Ｖ）で表される化合物に対して１〜５０モル％が好ましく、更に３〜３０モル％が好ましく、特に５〜２０モル％が好ましい。
【００２７】
本発明において使用するアミド硫酸は市販品を使用することができる。式（IV）又は式（Ｖ）で表される化合物とアミド硫酸の仕込み比（モル比）は特に限定されないが、硫酸エステル化度を高める観点からは、１／１〜１／１．３の範囲が好ましく、特に１／１〜１／１．１の範囲にあることがさらに好ましい。
【００２８】
アミド硫酸による硫酸エステル化では、原料中に水分が混入しているとアミド硫酸を分解して硫酸エステル化度の低下、及び副反応の増加を招くので、式（IV）又は式（Ｖ）で表される化合物中に含まれる水分は反応に先立って減圧脱水等の方法で完全に除去しておくことが望ましい。
【００２９】
アミド硫酸による硫酸エステル化反応は、酸化防止、着色防止の観点から窒素ガス等の不活性ガスの雰囲気下で行うことが好ましく、アミド化合物又はアミン化合物の存在下、温度６０〜１４０℃、好ましくは９０〜１２０℃で行う。反応終了後、余剰のアミド硫酸やアミド化合物等の反応系に溶解していない物質は濾過により取り除くことができる。
【００３０】
アミド硫酸による硫酸エステル化物はアンモニウム塩となっているが、必要に応じて、水酸化ナトリウム水溶液を添加する等の方法でアンモニウム塩を他の塩に置換することも可能である。
【００３１】
本発明のポリマーエマルションの製造法は、本発明の反応性界面活性剤を乳化剤として用いビニル系モノマーを乳化重合する方法である。本発明のポリマーエマルションの製造法では、乳化剤として他の陰イオン界面活性剤あるいは非イオン界面活性剤を併用することもできるが、本発明に係わる反応性界面活性剤の割合は乳化剤総量に対し５〜１００重量％が好ましく、２０〜１００重量％がより好ましい。本発明に係わる乳化重合において、乳化剤の使用量は、ビニル系モノマーの総量に対して０．１〜１０重量％が好ましい。
【００３２】
本発明で用いられるビニル系モノマーとしては、スチレン、α−メチルスチレン、クロロスチレン等の芳香族ビニルモノマー；（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル等の（メタ）アクリル酸エステル；（メタ）アクリル酸；塩化ビニル、臭化ビニル、塩化ビニリデン等のハロゲン化ビニル及びハロゲン化ビニリデン類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；（メタ）アクリロニトリル等のニトリル類；ブタジエン、イソプレン等の共役ジエン類が挙げられ、これらのモノマーは、単独で重合させても、２種以上を共重合させても良い。ビニル系モノマーの使用量は、全系に対して４０〜６０重量％が好ましい。
【００３３】
本発明において乳化重合に用いる開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過酸化水素等の無機過酸化物、ｔ−ブチルパーオキサイド、クメンヒドロキシパーオキサイド、パラメンタンパーオキサイド等の有機過酸化物、アゾビスジイソブチルニトリル、２，２’−アゾビス（２−アミジノプロパン）ジハイドロクロライド等のアゾ系化合物が挙げられるが、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩が好ましい。また、重合促進剤として、亜硫酸水素ナトリウム、硫酸第１鉄アンモニウム等を用いることもできる。
【００３４】
モノマーの添加方法は、モノマー滴下法、モノマー一括仕込み法、あるいはプレエマルション法等を用いることができるが、重合安定性からプレエマルション法が好ましい。滴下時間は１〜８時間、熟成時間は１〜５時間が好ましい。重合温度は、開始剤の分解温度により調整されるが、過硫酸塩の場合は７０〜８０℃が好ましい。
【００３５】
上記のような方法で得られた本発明のポリマーエマルションの平均粒径は用途によって異なるが、３０〜５００ｎｍが好ましく、８０〜３００ｎｍが更に好ましい。また、粘度は、５００００〜１０ｍＰａ・ｓが好ましく、１００００〜５０ｍＰａ・ｓが更に好ましい。ここで、ポリマーエマルションの平均粒径及び粘度は、下記の実施例に示す方法で測定した値である。
【００３６】
本発明のポリマーエマルションから調製されたポリマー塗膜は耐水性に優れ、塗料、特に水性塗料分野や、粘着製品分野に好ましく用いることができる。
【００３７】
本発明のポリマー塗膜の調製方法は用途により異なる。例えば、粘着用途では、本発明の反応性界面活性剤を用いた乳化重合によって、アクリル酸２−エチルヘキシル、アクリル酸ｎ−ブチル等のポリマーＴｇの低い本発明のポリマーエマルジョンを製造する。この本発明のポリマーエマルジョンに必要に応じて増粘剤、粘着付与剤等を配合したものを紙やフィルム等の基材に塗工し、熱風乾燥して厚さ２０μｍ程度のポリマー塗膜を形成させると耐水性、及び粘着性能に優れた粘着製品を得ることができる。
【００３８】
また、塗料用途では、本発明の反応性活性剤を用いた乳化重合によって、アクリル酸ｎ−ブチル／メタクリル酸メチル共重合体等の本発明のポリマーエマルジョンを製造する。この本発明のポリマーエマルジョンに必要に応じて成膜助剤、顔料等を配合したものを建築壁材等に乾燥膜厚が１００μｍ程度になるように塗工し、これを自然乾燥、又は熱風乾燥することにより、耐水性、耐候性に優れた塗膜を得ることができる。
【００３９】
【実施例】
例中の％は、特記しない限り重量％である。
【００４０】
製造例１
攪拌機、温度計、滴下漏斗、還流管を備えた反応容器に３−メチル−３−ブテン−１−オール２５８３ｇ（３０モル）、粉末ナトリウムメトキサイド１０．８ｇ（０．２モル）を仕込み、窒素雰囲気下８５℃でｎ−ブチルグリシジルエーテル３９０ｇ（３モル）を２時間かけて滴下し、この温度で８時間熟成した。この反応物にリン酸を加えてナトリウムメトキサイドを中和した後、減圧下で未反応の３−メチル−３−ブテン−１−オールを除去し、反応物中に含まれるリン酸ナトリウム塩を濾過により除去した。この反応物を減圧蒸留精製して１−Ｏ−ｎ−ブチル−３−Ｏ−（３−メチル−３−ブテニル）グリセリン４６０ｇを得た。この蒸留精製品４３２．２ｇ（２モル）とＫＯＨ ３．４ｇをオートクレーブに仕込み、１２０℃、０．３ＭＰａの条件でエチレンオキサイド８８１ｇ（２０モル）を付加した。次に、このエチレンオキサイド付加物３２８．３ｇ（０．５モル）、アミド硫酸５１．５ｇ（０．５３モル）、尿素３ｇを攪拌機、温度計を備えた反応容器に仕込み、窒素雰囲気下１１０℃で４時間反応させて硫酸化を行った後、未反応のアミド硫酸を加圧濾過により除去し、下記式で表される反応性界面活性剤［Ａ−１］を得た。得られた反応性界面活性剤［Ａ−１］の¹Ｈ−ＮＭＲスペクトルを図１に示す。
【００４１】
【化９】

【００４２】
製造例２
製造例１と同様の反応容器に３−メチル−３−ブテン−１−オール１９３７ｇ（２２．５モル）、粉末ナトリウムメトキサイド８．１ｇ（０．１５モル）を仕込み、窒素雰囲気下８５℃で２−エチルヘキシルグリシジルエーテル２７９．４ｇ（１．５モル）を２時間かけて滴下し、この温度で８時間熟成した。この反応物にリン酸を加えてナトリウムメトキサイドを中和した後、減圧下で未反応の３−メチル−３−ブテン−１−オールを除去し、反応物中に含まれるリン酸ナトリウム塩を濾過により除去した。この反応物を減圧蒸留精製して１−Ｏ−（２−エチルヘキシル）−３−Ｏ−（３−メチル−３−ブテニル）グリセリン３０４ｇを得た。この蒸留精製品２９９．６ｇ（１．１モル）とＫＯＨ １．８５ｇをオートクレーブに仕込み、１２０℃、０．３ＭＰａの条件でエチレンオキサイド４８４．５ｇ（１１モル）を付加した。次に、このエチレンオキサイド付加物２００ｇ（０．２８モル）、アミド硫酸３２．７ｇ（０．３３６モル）、尿素１．６８ｇを攪拌機、温度計を備えた反応容器に仕込み、窒素雰囲気下１１０℃で４時間反応させて硫酸化を行った後、未反応のアミド硫酸を加圧濾過により除去し、下記式で表される反応性界面活性剤［Ａ−２］を得た。
【００４３】
【化１０】

【００４４】
製造例３
ｎ−ブチルグリシジルエーテルの代わりに、ｎ−オクチルグリシジルエーテルとｎ−デシルグリシジルエーテルの混合体３９８ｇ（２モル）を用いる以外は製造例１と同様にして、１−Ｏ−ｎ−オクチル−３−Ｏ−（３−メチル−３−ブテニル）グリセリンと１−Ｏ−ｎ−デシル−３−Ｏ−（３−メチル−３−ブテニル）グリセリンの混合体（５０．２ｗｔ％／４７．８ｗｔ％）５１７ｇを得た。この蒸留精製品４６５．６ｇ（１．６モル）とＫＯＨ ２．６９ｇをオートクレーブに仕込み、１２０℃、０．３ＭＰａの条件でエチレンオキサイド７０４．８ｇ（１６モル）を付加した。次に、このエチレンオキサイド付加物２００ｇ（０．２７３モル）、アミド硫酸２９．２ｇ（０．３モル）、尿素１．６９ｇを攪拌機、温度計を備えた反応容器に仕込み、窒素雰囲気下１０５℃で３時間反応させて硫酸化を行った後、未反応のアミド硫酸を加圧濾過により除去し、下記式で表される反応性界面活性剤［Ａ−３］を得た。
【００４５】
【化１１】

【００４６】
製造例４
エチレンオキサイドを１０５７ｇ（２４モル）付加した以外は製造例３と同様の方法で、１−Ｏ−ｎ−オクチル−３−Ｏ−（３−メチル−３−ブテニル）グリセリンと１−Ｏ−ｎ−デシル−３−Ｏ−（３−メチル−３−ブテニル）グリセリンの混合体（５０．２ｗｔ％／４７．８ｗｔ％）のエチレンオキサイド１５モル付加物を得た。次に、このエチレンオキサイド付加物２００ｇ（０．２１０１モル）、アミド硫酸２２．５ｇ（０．２３１モル）、尿素１．２６ｇを攪拌機、温度計を備えた反応容器に仕込み、窒素雰囲気下１０５℃で３時間反応させて硫酸化を行った後、未反応のアミド硫酸を加圧濾過により除去し、下記式で表される反応性界面活性剤［Ａ−４］を得た。
【００４７】
【化１２】

【００４８】
製造例５
製造例１と同様の反応容器に３−メチル−３−ブテン−１−オール８６１ｇ（１０モル）、粉末ナトリウムメトキサイド３．１１ｇ（０．０５７６モル）を仕込み、窒素雰囲気下１３０℃で炭素数１２、１４のα−オレフィンエポキサイド（ＡＯＥ Ｘ２４、ダイセル化学工業（株）製）２３６．７ｇ（１．１５モル）を４時間かけて滴下し、この温度で１２時間熟成した。この反応物にリン酸を加えてナトリウムメトキサイドを中和した後、減圧下で未反応の３−メチル−３−ブテン−１−オールを除去し、反応物中に含まれるリン酸ナトリウム塩を濾過により除去した。この反応物を減圧蒸留精製し、下記式(VII)で表されるのオレフィンエポキサイドの３−メチル−３−ブテン−１−オール付加体２６５ｇを得た。
【００４９】
【化１３】

【００５０】
上記のオレフィンエポキサイドの３−メチル−３−ブテン−１−オール付加体(VII)２５０ｇ（０．８５６モル）、ＫＯＨ １．４４ｇをオートクレーブに仕込み、１３０℃、０．３ＭＰａの条件でエチレンオキサイド５６５．６ｇ（１２．８４モル）を付加した。次に、得られた反応混合物の一部２００ｇ（０．２１モル）、アミド硫酸２２．４５ｇ（０．２３１モル）、尿素１．２６ｇを攪拌機、温度計を備えた反応容器に仕込み、窒素雰囲気下１１５℃で４時間反応させて硫酸化を行った後、未反応のアミド硫酸を加圧濾過により除去し、下記式で表される反応性界面活性剤［Ａ−５］を得た。
【００５１】
【化１４】

【００５２】
製造例６
ｎ−ブチルグリシジルエーテルの代わりに、ｎ−ドデシルグリシジルエーテル７２６ｇ（３モル）を用いる以外は製造例１と同様にして１−Ｏ−ｎ−ドデシル−３−Ｏ−（３−メチル−３−ブテニル）グリセリン６９７ｇを得た。この蒸留精製品６５６．２ｇ（２モル）に、製造例１と同様にしてエチレンオキサイド８８１ｇ（２０モル）を付加し、次に、このエチレンオキサイド付加物３８４．３ｇ（０．５モル）を同様に硫酸化し、下記式で表される反応性界面活性剤［Ａ−６］を得た。
【００５３】
【化１５】

【００５４】
製造例７
ｎ−ブチルグリシジルエーテルの代わりに、ｎ−テトラデシルグリシジルエーテル８１０ｇ（３モル）を用いる以外は製造例１と同様にして、１−Ｏ−ｎ−テトラデシル−３−Ｏ−（３−メチル−３−ブテニル）グリセリン７３５ｇを得た。この蒸留精製品７１２．２ｇ（２モル）に、製造例１と同様にしてエチレンオキサイド８８１ｇ（２０モル）を付加し、次に、このエチレンオキサイド付加物３９８．３ｇ（０．５モル）を同様に硫酸化し、下記式で表される反応性界面活性剤［Ａ−７］を得た。
【００５５】
【化１６】

【００５６】
製造例８
製造例１と同様の反応容器に３−メチル−３−ブテン−１−オール２５８３ｇ（３０モル）、粉末ナトリウムメトキサイド８．１ｇ（０．１５モル）を仕込み、窒素雰囲気下８５℃でｎ−オクタデシルグリシジルエーテル６５２．０ｇ（２モル）を２時間かけて滴下し、この温度で８時間熟成した。この反応物にリン酸を加えてナトリウムメトキサイドを中和した後、減圧下で未反応の３−メチル−３−ブテン−１−オールを除去し、反応物中に含まれるリン酸ナトリウム塩を濾過により除去した。この反応物を減圧蒸留精製して１−Ｏ−ｎ−オクタデシル−３−Ｏ−（３−メチル−３−ブテニル）グリセリン５２６ｇを得た。この蒸留精製品４１２．１ｇ（１モル）とＫＯＨ １．７ｇをオートクレーブに仕込み、１２０℃、０．３ＭＰａの条件でエチレンオキサイド４４０．５ｇ（１０モル）を付加した。次に、このエチレンオキサイド付加物３４１．０ｇ（０．４モル）、アミド硫酸４２．８ｇ（０．４４モル）、尿素２．４ｇを攪拌機、温度計を備えた反応容器に仕込み、窒素雰囲気下１１０℃で４時間反応させて硫酸化を行った後、未反応のアミド硫酸を加圧濾過により除去し、下記式で表される反応性界面活性剤［Ａ−８］を得た。
【００５７】
【化１７】

【００５８】
製造例９
オートクレーブに３−メチル−３−ブテン−１−オール３４４．４ｇ（４モル）にＫＯＨ ６．７３ｇ（０．１２モル）を仕込み、１２０℃、０．３ＭＰａの条件でエチレンオキサイド８８１ｇ（２０モル）を付加した。攪拌機、温度計、滴下漏斗、還流管を備えた反応容器に、このエチレンオキサイド付加物６１２．７ｇ（２モル）を仕込み、窒素雰囲気下８５℃でｎ−ドデシルグリシジルエーテル２４２ｇ（１モル）を２時間かけて滴下し同温度で８時間熟成した。この反応物をリン酸で中和した後、スミス式分子蒸留機を用いて蒸留精製し、下記式(VIII)で表される化合物を得た。
【００５９】
【化１８】

【００６０】
次に、この化合物(VIII）１３７．１ｇ（０．２５モル）、アミド硫酸２６．２ｇ（０．２７モル）、尿素１．５ｇを攪拌機、温度計を備えた反応容器に仕込み、窒素雰囲気下１１５℃で４時間反応させて硫酸化を行った後、未反応のアミド硫酸を加圧濾過により除去し、下記式で表される反応性界面活性剤［Ａ−９］を得た。
【００６１】
【化１９】

【００６２】
実施例１〜１２及び比較例１〜３
製造例１〜９で得られた本発明の反応性界面活性剤、及び表１に示す従来型陰イオン界面活性剤を乳化剤として用い、下記の方法で乳化重合を行い、下記方法で性能を評価した。結果を表１に示す。
【００６３】
＜乳化重合法＞
ビーカーに秤取ったイオン交換水１０４．１ｇに、乳化剤５．８３ｇ、過硫酸カリウム０．３９ｇを溶解し、アクリル酸２．４ｇ、アクリル酸ブチル１２０．３ｇ及びメタクリル酸メチル１２０．３ｇを加え、ホモミキサーにて５０００ｒ／ｍｉｎ×１０分間乳化し、モノマー乳化物を得た。セパラブルフラスコにイオン交換水１７８．６ｇ、乳化剤１．３５ｇ、過硫酸カリウム０．０９ｇ、及び上記モノマー乳化物１６．４ｇを仕込み、窒素気流中で１５分間撹拌した。次に、窒素気流中で撹拌しながら、水浴でフラスコの内温が、８０℃になるまで昇温し、３０分間重合反応した後、上記モノマー乳化物３１０．８ｇを滴下漏斗から３時間かけて滴下し、１時間熟成後、室温まで冷却してポリマーエマルションを得た。滴下及び熟成の間、フラスコ内の温度は８０±２℃に保った。また、滴下するモノマー乳化物が滴下漏斗内で分離する場合には、小型の攪拌機を滴下漏斗内に挿入し均一性を維持した。
【００６４】
＜性能評価法＞
（１）重合安定性
ポリマーエマルションを２００メッシュのステンレス製金網で濾過し、重合後の反応器壁や撹拌羽根等に付着した凝集物も集めて同様に濾過し、水洗後２６．６ｋＰａ、１０５℃で２時間乾燥・秤量して、凝集物量を求めた。使用したモノマーの総量に対する凝集物の重量％で、重合安定性を表した。重合安定性はこの数値が小さいほど良く、０．１５％以下の場合に特に良好であると判断される。
【００６５】
（２）機械的安定性
２５％アンモニア水で中和したポリマーエマルション５０ｇをマロン安定試験器にて１０ｋｇｆ、１０００ｒ／ｍｉｎの条件で５分間回転させ、生成した凝集物を２００メッシュのステンレス製金網で濾過し、濾過残渣を水洗後に２６．６ｋＰａ、１０５℃で乾燥・秤量して、ポリマーに対する重量％で表示した。重合安定性はこの数値が小さいほど良く、０．３５％以下、特に０．１５％以下の場合に良好であると判断される。
【００６６】
（３）平均粒径
ベックマン・コールター社製の動的光散乱法粒径測定装置コールターＮ4 Plusを使用して、２５％アンモニア水で中和したポリマーエマルション粒子の平均粒径を測定した。
【００６７】
（４）粘度
Ｂ型粘度計を使用して、２５％アンモニア水で中和したポリマーエマルションの粘度を温度２５℃、回転数１２ｒ／ｍｉｎで測定した。
【００６８】
（５）ポリマーフィルムの耐水性
２５％アンモニア水で中和したポリマーエマルションを、透明アクリル板上にアプリケーターを使用して、乾燥膜厚が１５０μｍとなるよう塗工し、熱風乾燥機で１００℃、１０分間乾燥した。このアクリル板を６０℃の温水に１６時間浸漬した後、ヘイズメーターを使用して、ポリマーフィルムのヘイズ値を測定した。耐水性はヘイズ値が小さい程良く、ヘイズ値が１５％以下の場合には特に良好と判断される。
【００６９】
【表１】

【００７０】
【化２０】

【００７１】
【発明の効果】
本発明の反応性界面活性剤を乳化重合用の乳化剤として用いると、重合安定性、機械的安定性に優れたポリマーエマルションが製造できる。また、このポリマーエマルションから調製されたポリマー塗膜は耐水性に優れ、塗料分野、粘着分野で優れた効果を発揮する。
【図面の簡単な説明】
【図１】 反応性界面活性剤［Ａ−１］の¹Ｈ−ＮＭＲスペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a reactive surfactant, a method for producing a polymer emulsion using the same, a polymer emulsion produced by this production method, and a polymer coating film prepared using this polymer emulsion.
[0002]
[Prior art and problems to be solved by the invention]
Polymer emulsions obtained by emulsion polymerization of vinyl monomers such as vinyl acetate and acrylate esters are widely used in the fields of paints, adhesives, paper processing, fiber processing, etc. Has been used. In the emulsion polymerization, as an emulsifier, an anionic surfactant such as alkyl sulfate ester salt, alkylbenzene sulfonate salt, polyoxyethylene alkyl ether salt, polyoxyethylene alkylphenyl ether salt, and polyoxyethylene alkyl ether, polyoxyethylene Nonionic surfactants such as alkylphenyl ethers are used.
[0003]
The emulsifier in the emulsion polymerization not only affects the initiation reaction and growth reaction of the polymerization, but also the stability of the polymer emulsion during the polymerization, and the mechanical stability, chemical stability, freezing stability of the polymer emulsion formed, Affects storage stability, and further, emulsion physical properties such as particle size, viscosity, foaming properties, etc. of polymer emulsions, and film properties such as water resistance, moisture resistance, heat resistance, adhesiveness, and tackiness when filmed It has a big influence on. In applications such as paints and adhesives, a polymer coating is formed by drying the polymer emulsion, but the emulsifier remaining in the polymer coating causes a decrease in water resistance, adhesion, weather resistance, heat resistance, etc. It is known. For example, a polymer emulsion obtained by emulsion polymerization of (meth) acrylic acid ester is used for the water-based paint, but if the water resistance of this polymer coating film is poor, the water resistance of the building outer wall or bathroom wall is required. Can not be used. Further, in the production of synthetic rubber and the like, there is a problem that an emulsifier is contained in the wastewater when the polymer is taken out from the polymer emulsion by means such as salting out, which increases the burden of wastewater treatment.
[0004]
In order to solve such drawbacks, a method using a so-called reactive surfactant having an ethylenically unsaturated bond as a polymerizable group in the molecule has been proposed. For example, JP-A-61-223011 discloses a method using a polyoxyalkylene ether sulfate having an allyl or methallyl group as a polymerizable group. In Macromolecules, 32, 5967 (1999), sodium oxyalkanesulfonate having a polymerizable group of 3-methyl-3-butenyl group, 10- (3-methyl-3-butenyloxy) decane-1 -Results of emulsion polymerization using sodium sulfonate are described.
[0005]
However, when these reactive surfactants are used alone as an emulsifier for emulsion polymerization, the stability during polymerization is often insufficient, and in this case, there is a problem that a conventional emulsifier must be used in combination. is there. Further, in the case of sodium 10- (3-methyl-3-butenyloxy) decane-1-sulfonate, there is a problem that its own production is not easy in terms of reaction temperature, yield and the like and is not economical. is there.
[0006]
An object of the present invention is to provide a reactive surfactant that gives a polymer emulsion having good polymer emulsion stability during polymerization or a polymer film having good physical properties, a method for producing a polymer emulsion using the same, and water resistance obtained thereby It is an object to provide a polymer coating film that exhibits excellent water resistance in the field of a good polymer emulsion, and further in the fields of paints, adhesive products and the like.
[0007]
[Means for Solving the Problems]
The present invention relates to a reactive surfactant comprising at least one compound represented by formula (I) or formula (II), a method for producing a polymer emulsion for carrying out emulsion polymerization using this reactive surfactant, Provided are a water-resistant polymer emulsion produced using a reactive surfactant and a polymer coating prepared using the polymer emulsion.
[0008]
[Chemical formula 5]

[0009]
[Where A ₁ Is a linear or branched alkylene group having 5 to 18 carbon atoms, or formula (III)
[0010]
[Chemical 6]

[0011]
(In the formula, R represents a linear or branched alkyl group having 4 to 18 carbon atoms.)
An alkoxymethylethylene group represented by ₂ Represents a linear or branched alkylene group having 2 to 4 carbon atoms, n represents a number of 0 to 200, and M represents a cation. ]
Further, the present invention provides a compound represented by formula (IV) or formula (V)
[0012]
[Chemical 7]

[0013]
[Where R, A ₂ And n have the above meanings. ]
Production of a compound represented by the formula (I-1) or the formula (II-1), wherein the compound represented by formula (II) is reacted with an amidosulfuric acid in the presence of an amide compound (excluding sulfonic acid amide compounds) or an amine compound. Provide law.
[0014]
[Chemical 8]

[0015]
[Where R, A ₂ , N and M have the above-mentioned meanings. ]
[0016]
DETAILED DESCRIPTION OF THE INVENTION
In the above formula (I) or formula (II), A ₁ Examples of the linear or branched alkylene group having 5 to 18 carbon atoms represented by: butylethylene, octylethylene, decylethylene, dodecylethylene, tetradecylethylene, hexadecylethylene and the like. Examples of the linear or branched alkyl group having 4 to 18 carbon atoms represented by R in the formula (III) include a butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and an undecyl group. , Dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like.
[0017]
These A ₁ And R, A ₁ When is an alkylene group, the total number of carbon atoms is ₁ Is an alkoxymethylethylene group represented by the formula (III), the number of carbon atoms of R is particularly preferably a number satisfying the formula (VI).
[0018]
8 ≦ (carbon number) ≦ 18 (VI)
In the above formula (I) or formula (II), A ₂ Examples of the linear or branched alkylene group having 2 to 4 carbon atoms represented by: ethylene, propylene, ethylethylene, dimethylethylene and the like. In addition, n A ₂ May be two or more kinds of mixed groups, and among them, the proportion of ethylene groups is preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%.
[0019]
n is A ₂ The average number of added moles of the oxyalkylene group represented by O is 0 to 200, preferably 1 to 50, particularly preferably 1 to 30. Examples of the cation represented by M include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, ammonium ions substituted with an alkyl group having 1 to 4 carbon atoms, and the like.
[0020]
As the reactive surfactant of the present invention, the compound represented by the formula (I) is preferable because the water resistance of the coating film is particularly improved as compared with the compound represented by the formula (II).
[0021]
The compound represented by the formula (I) or the formula (II) of the present invention can be produced by using a known method. For example, 3-methyl-3-buten-1-ol is alkylated in the presence of a catalyst. Add 1-O-alkyl-3-O- (3-methyl-3-butenyl) glycerin or olefin epoxide to 3-methyl-3-buten-1-ol by adding glycidyl ether or α-olefin epoxide. A molar adduct is obtained, and an alkylene oxide having 2 to 4 carbon atoms is added to the obtained compound according to a conventional method, or an alkylene oxide having 2 to 4 carbon atoms is added to 3-methyl-3-buten-1-ol. After that, 1 mol of alkyl glycidyl ether or α-olefin epoxide is added to 1 mol of this adduct to obtain ether alcohol, which is sulfated. Obtained by sulfating and neutralizing with a basic substance by. Examples of the sulfating agent include chlorosulfonic acid, anhydrous sulfuric acid, and amidosulfuric acid. Amidosulfuric acid is used from the viewpoint of reducing side reactions such as addition reaction of sulfuric acid group to double bond group and isomerization of double bond group. Is preferred.
[0022]
When the compound represented by the above formula (IV) or formula (V) is sulfated, an amide compound (excluding a sulfonic acid amide compound) or an amine compound is subjected to a temperature of 60 to 140 ° C. in the presence of an amine compound. In this reaction, the double bond group is sufficiently protected, and side reactions such as isomerization of the terminal double bond group to the internal double bond group and addition of a sulfate group to the double bond group are almost completely prevented. Thus, a highly pure terminal unsaturated compound sulfate ester salt represented by the formula (I-1) or (II-1) can be produced.
[0023]
Examples of the amide compound used in the present invention include urea, urea derivatives such as methylurea, 1,1-dimethylurea, ethylurea, butylurea, and acetylurea, or acetamide, formamide, propionic acid amide, butylamide, diacetamide, Examples thereof include acid amide compounds such as succinic acid amide.
[0024]
However, sulfonic acid amide compounds such as toluenesulfonic acid amide cannot be used in the present invention because they have no effect of preventing isomerization of double bond groups and addition of sulfonic acid groups to double bond groups.
[0025]
Examples of the amine compound used in the present invention include morpholine, triethylamine, tributylamine, isopropylamine, diisopropylamine and the like. The amide compound and amine compound used in the present invention are effective when used in a small amount when the molecular weight is small, and the molecular weight is 150 or less, preferably 100 or less.
[0026]
The amount of the amide compound or amine compound used is preferably 1 to 50 mol%, more preferably 3 to 30 mol%, particularly 5 to 20 mol%, relative to the compound represented by formula (IV) or formula (V). Is preferred.
[0027]
A commercially available product can be used for the amidosulfuric acid used in the present invention. The charging ratio (molar ratio) of the compound represented by formula (IV) or formula (V) and amidosulfuric acid is not particularly limited, but from the viewpoint of increasing the degree of sulfate esterification, it is 1/1 to 1 / 1.3. A range is preferable, and a range of 1/1 to 1 / 1.1 is particularly preferable.
[0028]
In sulfate esterification with amidosulfuric acid, if water is mixed in the raw material, the amidosulfuric acid is decomposed to cause a decrease in the degree of sulfate esterification and an increase in side reactions. Therefore, in formula (IV) or formula (V) It is desirable to completely remove the water contained in the compound represented by a method such as dehydration under reduced pressure prior to the reaction.
[0029]
The sulfate esterification reaction with amide sulfuric acid is preferably performed in an atmosphere of an inert gas such as nitrogen gas from the viewpoint of oxidation prevention and coloring prevention, and the temperature is 60 to 140 ° C. in the presence of an amide compound or an amine compound, preferably Perform at 90-120 ° C. After completion of the reaction, substances that are not dissolved in the reaction system, such as excess amide sulfuric acid and amide compound, can be removed by filtration.
[0030]
The sulfate esterified product with amidosulfuric acid is an ammonium salt, but if necessary, the ammonium salt can be replaced with another salt by adding an aqueous sodium hydroxide solution.
[0031]
The production method of the polymer emulsion of the present invention is a method of emulsion polymerization of a vinyl monomer using the reactive surfactant of the present invention as an emulsifier. In the method for producing a polymer emulsion of the present invention, other anionic surfactants or nonionic surfactants can be used in combination as an emulsifier. However, the ratio of the reactive surfactant according to the present invention is 5 to the total amount of emulsifier. -100 wt% is preferable, and 20-100 wt% is more preferable. In the emulsion polymerization according to the present invention, the use amount of the emulsifier is preferably 0.1 to 10% by weight based on the total amount of the vinyl monomer.
[0032]
Examples of the vinyl monomer used in the present invention include aromatic vinyl monomers such as styrene, α-methylstyrene, and chlorostyrene; methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. (Meth) acrylic acid ester; (meth) acrylic acid; vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide and vinylidene chloride; vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylonitrile Nitriles such as conjugated dienes such as butadiene and isoprene, and these monomers may be polymerized alone or in combination of two or more. The amount of vinyl monomer used is preferably 40 to 60% by weight based on the total system.
[0033]
Examples of the initiator used in the emulsion polymerization in the present invention include inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, and organic peroxides such as t-butyl peroxide, cumene hydroxy peroxide, and paramentane peroxide. An azo compound such as an oxide, azobisdiisobutylnitrile, or 2,2′-azobis (2-amidinopropane) dihydrochloride is exemplified, but a persulfate such as potassium persulfate or ammonium persulfate is preferable. Moreover, sodium hydrogen sulfite, ferrous ammonium sulfate, etc. can also be used as a polymerization accelerator.
[0034]
As a monomer addition method, a monomer dropping method, a monomer batch charging method, a pre-emulsion method, or the like can be used, but the pre-emulsion method is preferable from the viewpoint of polymerization stability. The dropping time is preferably 1 to 8 hours, and the aging time is preferably 1 to 5 hours. The polymerization temperature is adjusted by the decomposition temperature of the initiator, but in the case of persulfate, it is preferably 70 to 80 ° C.
[0035]
Although the average particle diameter of the polymer emulsion of the present invention obtained by the method as described above varies depending on the application, it is preferably 30 to 500 nm, and more preferably 80 to 300 nm. The viscosity is preferably 50000 to 10 mPa · s, and more preferably 10000 to 50 mPa · s. Here, the average particle diameter and viscosity of the polymer emulsion are values measured by the methods shown in the following examples.
[0036]
The polymer coating prepared from the polymer emulsion of the present invention is excellent in water resistance and can be preferably used in paints, particularly in the field of aqueous paints and adhesive products.
[0037]
The method for preparing the polymer coating film of the present invention varies depending on the application. For example, in the adhesive application, the polymer emulsion of the present invention having a low polymer Tg such as 2-ethylhexyl acrylate and n-butyl acrylate is produced by emulsion polymerization using the reactive surfactant of the present invention. This polymer emulsion of the present invention is blended with a thickener, tackifier, etc., if necessary, on a substrate such as paper or film, and dried with hot air to form a polymer coating having a thickness of about 20 μm. When it is made, the adhesive product excellent in water resistance and adhesive performance can be obtained.
[0038]
For paint applications, the polymer emulsion of the present invention such as n-butyl acrylate / methyl methacrylate copolymer is produced by emulsion polymerization using the reactive activator of the present invention. This polymer emulsion according to the present invention is blended with a film forming aid, pigment, etc., if necessary, on a building wall material etc. so that the dry film thickness is about 100 μm, and this is naturally dried or hot air dried By doing, the coating film excellent in water resistance and a weather resistance can be obtained.
[0039]
【Example】
In the examples, “%” means “% by weight” unless otherwise specified.
[0040]
Production Example 1
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube was charged with 2583 g (30 mol) of 3-methyl-3-buten-1-ol and 10.8 g (0.2 mol) of powdered sodium methoxide, and nitrogen. Under an atmosphere, 390 g (3 mol) of n-butyl glycidyl ether was added dropwise at 85 ° C. over 2 hours, and the mixture was aged at this temperature for 8 hours. After adding phosphoric acid to this reaction product to neutralize sodium methoxide, unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure, and sodium phosphate contained in the reaction product was removed. Removed by filtration. The reaction product was purified by distillation under reduced pressure to obtain 460 g of 1-On-butyl-3-O- (3-methyl-3-butenyl) glycerin. 432.2 g (2 mol) of this distilled purified product and 3.4 g of KOH were charged into an autoclave, and 881 g (20 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa. Next, 328.3 g (0.5 mol) of this ethylene oxide adduct, 51.5 g (0.53 mol) of amidosulfuric acid, and 3 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and 110 ° C. under a nitrogen atmosphere. Then, the unreacted amidosulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-1] represented by the following formula. Of the obtained reactive surfactant [A-1] ¹ The H-NMR spectrum is shown in FIG.
[0041]
[Chemical 9]

[0042]
Production Example 2
In a reaction vessel similar to Production Example 1, 1937 g (22.5 mol) of 3-methyl-3-buten-1-ol and 8.1 g (0.15 mol) of powdered sodium methoxide were charged at 85 ° C. under a nitrogen atmosphere. 279.4 g (1.5 mol) of 2-ethylhexyl glycidyl ether was added dropwise over 2 hours, followed by aging at this temperature for 8 hours. After adding phosphoric acid to this reaction product to neutralize sodium methoxide, unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure, and sodium phosphate contained in the reaction product was removed. Removed by filtration. This reaction product was purified by distillation under reduced pressure to obtain 304 g of 1-O- (2-ethylhexyl) -3-O- (3-methyl-3-butenyl) glycerin. 299.6 g (1.1 mol) of this distilled product and 1.85 g of KOH were charged into an autoclave, and 484.5 g (11 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa. Next, 200 g (0.28 mol) of this ethylene oxide adduct, 32.7 g (0.336 mol) of amidosulfuric acid and 1.68 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and the temperature was 110 ° C. under a nitrogen atmosphere. Then, the unreacted amidosulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-2] represented by the following formula.
[0043]
[Chemical Formula 10]

[0044]
Production Example 3
Instead of n-butyl glycidyl ether, 1-O-n-octyl-3-l was prepared in the same manner as in Production Example 1 except that 398 g (2 mol) of a mixture of n-octyl glycidyl ether and n-decyl glycidyl ether was used. 517 g of a mixture of O- (3-methyl-3-butenyl) glycerin and 1-On-decyl-3-O- (3-methyl-3-butenyl) glycerin (50.2 wt% / 47.8 wt%) Got. 465.6 g (1.6 mol) of this distilled product and 2.69 g of KOH were charged into an autoclave, and 704.8 g (16 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa. Next, 200 g (0.273 mol) of this ethylene oxide adduct, 29.2 g (0.3 mol) of amidosulfuric acid, and 1.69 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and were heated at 105 ° C. under a nitrogen atmosphere. Then, the unreacted amidosulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-3] represented by the following formula.
[0045]
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[0046]
Production Example 4
1-O-n-octyl-3-O- (3-methyl-3-butenyl) glycerin and 1-O-n- are prepared in the same manner as in Production Example 3, except that 1057 g (24 mol) of ethylene oxide is added. An ethylene oxide 15 mol adduct of a mixture of decyl-3-O- (3-methyl-3-butenyl) glycerin (50.2 wt% / 47.8 wt%) was obtained. Next, 200 g (0.2101 mol) of this ethylene oxide adduct, 22.5 g (0.231 mol) of amidosulfuric acid, and 1.26 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and were heated at 105 ° C. under a nitrogen atmosphere. Then, the unreacted amidosulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-4] represented by the following formula.
[0047]
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[0048]
Production Example 5
A reaction vessel similar to Production Example 1 was charged with 861 g (10 mol) of 3-methyl-3-buten-1-ol and 3.11 g (0.0576 mol) of powdered sodium methoxide, and the carbon number at 130 ° C. in a nitrogen atmosphere. 236.7 g (1.15 mol) of 12, 14 α-olefin epoxide (AOE X24, manufactured by Daicel Chemical Industries, Ltd.) was added dropwise over 4 hours, followed by aging at this temperature for 12 hours. After adding phosphoric acid to this reaction product to neutralize sodium methoxide, unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure, and sodium phosphate contained in the reaction product was removed. Removed by filtration. This reaction product was purified by distillation under reduced pressure to obtain 265 g of a 3-methyl-3-buten-1-ol adduct of olefin epoxide represented by the following formula (VII).
[0049]
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[0050]
250 g (0.856 mol) of 3-methyl-3-buten-1-ol adduct (VII) of olefin epoxide and 1.44 g of KOH were charged into an autoclave, and ethylene oxide 565 was obtained at 130 ° C. and 0.3 MPa. .6 g (12.84 mol) was added. Next, 200 g (0.21 mol) of the obtained reaction mixture, 22.45 g (0.231 mol) of amidosulfuric acid, and 1.26 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and a nitrogen atmosphere After reacting at 115 ° C. for 4 hours for sulfation, unreacted amidosulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-5] represented by the following formula.
[0051]
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[0052]
Production Example 6
1-On-dodecyl-3-O- (3-methyl-3-butenyl) was prepared in the same manner as in Production Example 1 except that 726 g (3 mol) of n-dodecyl glycidyl ether was used instead of n-butyl glycidyl ether. ) 697 g of glycerin was obtained. In the same manner as in Production Example 1, 881 g (20 mol) of ethylene oxide was added to 656.2 g (2 mol) of this distilled purified product, and then 384.3 g (0.5 mol) of this ethylene oxide adduct was similarly added. To obtain a reactive surfactant [A-6] represented by the following formula.
[0053]
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[0054]
Production Example 7
1-O-n-tetradecyl-3-O- (3-methyl-3) was prepared in the same manner as in Production Example 1 except that 810 g (3 mol) of n-tetradecyl glycidyl ether was used instead of n-butyl glycidyl ether. -Butenyl) glycerin 735 g was obtained. 881 g (20 mol) of ethylene oxide was added to 712.2 g (2 mol) of this distilled purified product in the same manner as in Production Example 1, and then 398.3 g (0.5 mol) of this ethylene oxide adduct was added in the same manner. To obtain a reactive surfactant [A-7] represented by the following formula.
[0055]
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[0056]
Production Example 8
A reaction vessel similar to Production Example 1 was charged with 2583 g (30 mol) of 3-methyl-3-buten-1-ol and 8.1 g (0.15 mol) of powdered sodium methoxide, and n- 652.0 g (2 mol) of octadecyl glycidyl ether was added dropwise over 2 hours and aged at this temperature for 8 hours. After adding phosphoric acid to this reaction product to neutralize sodium methoxide, unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure, and sodium phosphate contained in the reaction product was removed. Removed by filtration. This reaction product was purified by distillation under reduced pressure to obtain 526 g of 1-On-octadecyl-3-O- (3-methyl-3-butenyl) glycerin. 412.1 g (1 mol) of this distilled purified product and 1.7 g of KOH were charged into an autoclave, and 440.5 g (10 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa. Next, 341.0 g (0.4 mol) of this ethylene oxide adduct, 42.8 g (0.44 mol) of amidosulfuric acid, and 2.4 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and a nitrogen atmosphere was obtained. After reacting at 110 ° C. for 4 hours for sulfation, unreacted amidosulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-8] represented by the following formula.
[0057]
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[0058]
Production Example 9
In an autoclave, 344.4 g (4 mol) of 3-methyl-3-buten-1-ol was charged with 6.73 g (0.12 mol) of KOH, and 881 g (20 mol) of ethylene oxide under the conditions of 120 ° C. and 0.3 MPa. Was added. Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux tube, 612.7 g (2 mol) of this ethylene oxide adduct was charged, and 242 g (1 mol) of n-dodecylglycidyl ether was added at 85 ° C. in a nitrogen atmosphere. The solution was dropped over time and aged at the same temperature for 8 hours. The reaction product was neutralized with phosphoric acid and then purified by distillation using a Smith type molecular distillation machine to obtain a compound represented by the following formula (VIII).
[0059]
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[0060]
Next, 137.1 g (0.25 mol) of this compound (VIII), 26.2 g (0.27 mol) of amidosulfuric acid and 1.5 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and the reaction was performed under a nitrogen atmosphere. After reacting at 115 ° C. for 4 hours for sulfation, unreacted amidosulfuric acid was removed by filtration under pressure to obtain a reactive surfactant [A-9] represented by the following formula.
[0061]
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[0062]
Examples 1-12 and Comparative Examples 1-3
Using the reactive surfactant of the present invention obtained in Production Examples 1 to 9 and the conventional anionic surfactant shown in Table 1 as an emulsifier, emulsion polymerization is performed by the following method, and performance is evaluated by the following method. did. The results are shown in Table 1.
[0063]
<Emulsion polymerization method>
In 104.1 g of ion-exchanged water weighed in a beaker, 5.83 g of an emulsifier and 0.39 g of potassium persulfate are dissolved, 2.4 g of acrylic acid, 120.3 g of butyl acrylate and 120.3 g of methyl methacrylate are added, The mixture was emulsified with a homomixer at 5000 r / min × 10 minutes to obtain a monomer emulsion. A separable flask was charged with 178.6 g of ion-exchanged water, 1.35 g of an emulsifier, 0.09 g of potassium persulfate, and 16.4 g of the monomer emulsion, and stirred for 15 minutes in a nitrogen stream. Next, while stirring in a nitrogen stream, the temperature of the flask was raised to 80 ° C. in a water bath and polymerized for 30 minutes, and then 310.8 g of the monomer emulsion was added from the dropping funnel over 3 hours. After dropping and aging for 1 hour, the mixture was cooled to room temperature to obtain a polymer emulsion. During the dropping and aging, the temperature in the flask was kept at 80 ± 2 ° C. Moreover, when the monomer emulsion to be dropped was separated in the dropping funnel, a small stirrer was inserted into the dropping funnel to maintain uniformity.
[0064]
<Performance evaluation method>
(1) Polymerization stability
The polymer emulsion is filtered through a 200-mesh stainless steel wire mesh, and the agglomerates adhering to the reactor wall and stirring blade after polymerization are collected and filtered in the same manner. After washing with water, drying and weighing at 26.6 kPa and 105 ° C for 2 hours. Then, the amount of aggregate was determined. Polymerization stability was expressed in terms of the weight percent of aggregates relative to the total amount of monomers used. The smaller the numerical value, the better the polymerization stability, and it is judged that the polymerization stability is particularly good when it is 0.15% or less.
[0065]
(2) Mechanical stability
50 g of a polymer emulsion neutralized with 25% ammonia water was rotated for 5 minutes under a condition of 10 kgf and 1000 r / min with a Maron stability tester, and the resulting aggregate was filtered with a 200 mesh stainless steel wire mesh, and the filter residue was washed with water. Later, it was dried and weighed at 26.6 kPa and 105 ° C., and expressed in terms of% by weight based on the polymer. The smaller the numerical value, the better the polymerization stability, and it is judged to be good when it is 0.35% or less, particularly 0.15% or less.
[0066]
(3) Average particle size
The average particle size of the polymer emulsion particles neutralized with 25% aqueous ammonia was measured using a dynamic light scattering particle size measuring device Coulter N4 Plus manufactured by Beckman Coulter.
[0067]
(4) Viscosity
Using a B-type viscometer, the viscosity of the polymer emulsion neutralized with 25% aqueous ammonia was measured at a temperature of 25 ° C. and a rotational speed of 12 r / min.
[0068]
(5) Water resistance of polymer film
The polymer emulsion neutralized with 25% aqueous ammonia was applied onto a transparent acrylic plate using an applicator so that the dry film thickness was 150 μm, and dried with a hot air dryer at 100 ° C. for 10 minutes. The acrylic plate was immersed in warm water at 60 ° C. for 16 hours, and then the haze value of the polymer film was measured using a haze meter. The water resistance is better as the haze value is smaller, and is judged to be particularly good when the haze value is 15% or less.
[0069]
[Table 1]

[0070]
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[0071]
【The invention's effect】
When the reactive surfactant of the present invention is used as an emulsifier for emulsion polymerization, a polymer emulsion excellent in polymerization stability and mechanical stability can be produced. Moreover, the polymer coating film prepared from this polymer emulsion is excellent in water resistance, and exhibits excellent effects in the paint and adhesive fields.
[Brief description of the drawings]
FIG. 1 shows a reactive surfactant [A-1]. ¹ It is a 1 H-NMR spectrum.

Claims (4)

A reactive surfactant comprising at least one compound represented by formula (I) or formula (II).

[Wherein A ₁ is a linear or branched alkylene group having 5 to 18 carbon atoms, or a group represented by formula (III)

(In the formula, R represents a linear or branched alkyl group having 4 to 18 carbon atoms.)
A ₂ is a linear or branched alkylene group having 2 to 4 carbon atoms, n is a number from 0 to 200, and M is a cation. ] The manufacturing method of the polymer emulsion which performs the emulsion polymerization of a vinyl-type monomer using the reactive surfactant of Claim 1. A polymer emulsion produced by emulsion polymerization of a vinyl monomer using the reactive surfactant according to claim 1.   A polymer coating prepared using the polymer emulsion according to claim 3.

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