JP4117947B2 - Cationic glue base, process for producing the same, and liquid glue composition containing the glue base - Google Patents
Cationic glue base, process for producing the same, and liquid glue composition containing the glue base Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、特に家庭で洗濯時に衣料などにのり付けするのに好適な液体糊組成物に配合することができるカチオン性糊剤基体、その製造方法及び該基体を含有する液体糊組成物に関する。
【０００２】
【従来の技術】
現在、衣料用に使用する液体糊は、糊基剤としてポリ酢酸ビニルを主成分とする合成高分子エマルジョンが主流となっている。このポリ酢酸ビニルは衣類に適度の硬さと触感を付与することができて好ましいが、ポリ酢酸ビニルは水不溶性のため、衣類に付着した糊剤が洗濯によってほとんど落ちることが無く、くり返し使用すると衣類が硬くなりすぎる欠点があった。そこで酢酸ビニルに不飽和カルボン酸を共重合させたコポリマーを糊基剤として使用することにより、洗濯時の糊落ち性を改善することが提案されている（特公昭５７−３３３９８号公報、同５７−２９４８３号公報、同５７−３６２８４号公報、同５８−１２９５９号公報、同６０−７０７０号公報及び特公平１−１５６２５号公報など）。
しかしながら、実用的な洗濯時の糊落ち性、さらには綿繊維への吸着率を向上させるには、不十分であって未だ問題がある。
【０００３】
【発明が解決しようとする課題】
本発明は、洗濯時の糊落ち性が改善され、かつ綿繊維への吸着性の良好なカチオン性糊剤基体及び該基体を含有する液体糊組成物を提供することを目的とする。
本発明は、又、該カチオン性糊剤基体の効率的な製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明は、水性媒体中で、カチオン性モノマー及び／又はカチオン性重合体の共存下に低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステルを特定の割合で用いて乳化重合し、反応が完結後、そこにさらに低級脂肪酸ビニルエステルを乳化重合させると、上記課題を解決できるとの知見に基づいてなされたのである。
すなわち、本発明は、水性媒体中で、１種以上のカチオン性モノマー及び／又はカチオン性重合体の共存下に、低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステルを、低級脂肪酸ビニルエステル１００重量部当たり不飽和カルボン酸を２０〜４０重量部及び不飽和カルボン酸アルキルエステルを１３０〜３００重量部用いて乳化重合して得たカチオン性ポリマーエマルジョン粒子の存在下で、低級脂肪酸ビニルエステルが重合されていることを特徴とするカチオン性糊剤基体を提供する。
【０００５】
本発明は、又、水性媒体中で、１種以上のカチオン性モノマー及び／又はカチオン性重合体の共存下に、低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステルを、低級脂肪酸ビニルエステル１００重量部当たり不飽和カルボン酸を２０〜４０重量部及び不飽和カルボン酸アルキルエステルを１３０〜３００重量部用いて乳化重合し、反応が完結後、さらに低級脂肪酸ビニルエステルを乳化重合させることを特徴とするカチオン性糊剤基体の製造方法を提供する。
本発明は、又、上記カチオン性糊剤基体を含有する液体糊剤組成物を提供する。
【発明の実施の形態】
本発明では、カチオン性モノマー又はカチオン性重合体の単独使用、又はカチオン性モノマーとカチオン性重合体の併用があげられるが、カチオン性モノマーの単独使用が好ましい。
本発明に用いられるカチオン性モノマーとしては、以下に示すものがあげられる。
【０００６】
【化１】
【化２】
（式中、Ｒ1 は水素原子又はメチル基、Ｒ2 、Ｒ3 及びＲ4 は独立して水素原子又はＣ1 〜Ｃ4 のアルキル基、Ｒ5 、Ｒ6 及びＲ7 は独立して水素原子又はＣ1 〜Ｃ2 のアルキル基、Ｘ- は一価の陰イオンを表す。）
本発明で用いられるカチオン性重合体としては、上記モノマーの重合体、又は上記モノマーと低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステルの少なくとも一種、好ましくは３種とのコポリマーがあげられる。
このようなカチオン性モノマー及び／又はカチオン性重合体は、糊基剤中に１〜１０重量％（以下、％と略称する）となるように含有させるのが好ましい。
上記モノマーの単独重合体は、例えば、一般に用いられるノニオン性、アニオン性、カチオン性の乳化剤を適宜使用して重合し、エマルジョンとして得ることが好ましい。
【０００９】
使用するノニオン性乳化剤としては、Ｃ1 〜Ｃ11の飽和又は不飽和アルコールのエチレンオキサイド付加物（付加モル数９〜100 ）、Ｃ1 〜Ｃ11アルキル基と９〜３０またはそれ以上のエチレンオキサイド単位を持つアルキルフェノールエトキシレート、例えばポリオキシエチレンヘプチルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンメチルオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル等があげられる。特にＨＬＢが１２〜２０のものが好ましく、より好ましくはＨＬＢ１５〜１８である。アニオン乳化剤としては、ラウリル硫酸ナトリウムやカリウムなどのＣ8 〜Ｃ18アルコールの硫酸エステル塩、Ｃ8 〜Ｃ18の脂肪酸塩（例えば、ナトリウム塩、カリウム塩、トリエタノールアミンのようなエタノールアミン塩（具体的には、オレイン酸トリエタノールアミン、ステアリン酸トリエタノールアミンなど）やスルホン化アルキルアリール化合物があげられる。カチオン乳化剤としては、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルエチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩、アルキルピリジニウム塩、アルキルキノリウム塩、アルキルイソキノリウム塩、ステアリルアミドメチルピリジニウム塩、アシルアミノエチルメチルジエチルアンモニウム塩、アシルアミノエチルピリジニウム塩、アルコキシメチルピリジニウム塩、１−メチル−１−アシルアミノエチル−２−アルキルイミダゾリン、ジアシルアミノプロピルジメチルアンモニウム塩、ジアシルアミノエチルジメチルアンモニウム塩、ジアルキルジ（ポリオキシエチレン）アンモニウム塩、ジアルキルメチルポリオキシエチレンアンモニウム塩などがあげられる。
【００１０】
又、上記カチオン性モノマーと低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステルとのコポリマーは、低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステルの重合の際に、上記カチオン性モノマーを共存させることにより容易に行うことができる。
本発明に用いられる低級脂肪酸ビニルエステルとしては、炭素数が４〜６のものが好ましく、例えば、酢酸ビニル、酪酸ビニルやプロピオン酸ビニル等が例示される。これらは、１種又は２種以上の混合物を使用することができる。
本発明に用いられる、不飽和カルボン酸としては、炭素数３〜１０の不飽和モノカルボン酸及び不飽和ポリカルボン酸があげられる。具体的には、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、アコニチン酸、ソルビン酸、ケイ皮酸、α−クロロソルビン酸、シトラコン酸、ｐ−ビニル安息香酸等があげられる。又、イタコン酸、マレイン酸、フマル酸のような不飽和カルボン酸のアルキル半エステル、部分エステル又は部分アミドも使用することができる。具体的には、イタコン酸モノメチル、イタコン酸モノブチル、フマル酸モノメチル、フマル酸モノブチル、マレイン酸モノブチル等の炭素数１〜６の低級アルキル半エステルが挙げられる。これらの不飽和カルボン酸のうちアクリル酸、メタクリル酸、クロトン酸が好ましい。上記不飽和カルボン酸は、一種又は二種以上の混合物を使用することができる。
【００１１】
本発明で用いる不飽和カルボン酸アルキルエステルとしては、(a) 炭素数３〜６の不飽和モノカルボン酸のアルキルエステル（アルキル基の炭素数１〜４）、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル等のようなアクリル酸、メタクリル酸のアルキルエステル、(b) 炭素数４〜７のα，β−エチレン性不飽和ジカルボン酸のジエステル（アルキル基の炭素数１〜４）、例えば、ジブチルマレエート、ジエチルマレエート、フマレート、イタコネート、シトラコネートなど、上記低級脂肪酸ビニルエステルと不飽和カルボン酸及び不飽和カルボン酸アルキルエステルに加えこれらと共重合可能なモノマーを用いたポリマーも使用することができる。このような共重合可能なモノマーとしては、(A) エチレンなどのアルケン及びスチレン、(B) 塩化ビニルなどのハロゲン化ビニルや塩化ビニリデンなどのハロゲン化ビニリデン、(C) アクリルアミド及びＮ−メチロールアミドなどのα，β−エチレン性不飽和カルボン酸アミド及びそのＮ−アルキロール誘導体などがあげられる。これらのうち、(A) にあげたモノマーが好ましい。
【００１２】
本発明では、先ず、水性媒体中で、１種以上のカチオン性モノマー及び／又はカチオン性重合体の共存下に、低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステルを乳化重合させる。乳化重合は任意の方法で行うことができるが、１種以上のカチオン性モノマー及び／又はカチオン性重合体を予め加えた反応器に、低級脂肪酸ビニルエステル、不飽和カルボン酸及び不飽和カルボン酸アルキルエステル、並びに重合触媒を加えて初期重合し、ついでここに低級脂肪酸ビニルエステル、不飽和カルボン酸、不飽和カルボン酸アルキルエステル及び重合触媒を含む混合液を滴下して、乳化重合を継続するのが好ましい。
本発明で行う重合には種々の重合開始剤を用いることができる。例えば、２，２′−アゾビス（２−アミジノプロパン）、過酸化水素、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｔ−ブチルパーオキサイド、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、過酢酸、過安息香酸、過硫酸カリウム等があげられる。重合は、４０〜１２０℃、好ましくは５０〜９０℃であり、重合時のpHは３〜９、好ましくは４〜８の範囲とするのがよい。
【００１３】
ここで、本発明では、低級脂肪酸ビニルエステル１００重量部当たり不飽和カルボン酸を２０〜４０重量部（好ましくは、２５〜４０重量部）及び不飽和カルボン酸アルキルエステルを１３０〜３００重量部（好ましくは２００〜３００重量部）用いて乳化重合する。この１段目の重合は、次の重合工程に進む前にモノマーが反応し終わっていることが好ましい。そのため、モノマーの滴下終了後１５分〜２４時間、好ましくは３０分〜３時間重合を継続させるのが好ましい。これは、連続的に次の重合工程に移ると、２段目に供給する低級脂肪酸ビニルエステルが１段目の共重合体に付加して重合が進行し、いわゆるコア／シェル型の粒子が形成されず、本来コアに存在すべきカルボキシル基が、親水性のため粒子表面付近に配向して粒子表面のカチオンのカチオン度を打ち消し、ゼータ電位が低くなり、繊維への吸着力が弱まるからである。
本発明では、２段目として、さらに低級脂肪酸ビニルエステルを乳化重合させる。具体的には、１段目で合成したカチオン性ポリマーエマルジョンに対して、低級脂肪酸ビニルエステルと重合触媒（上記重合触媒を用いることができる）を滴下して重合を行うのがよい。重合は、４０〜１２０℃（好ましくは５０〜９０℃）であり、ｐＨ３〜９、好ましくは４〜８で行うのがよい。
このような多段重合により、本発明のカチオン性糊剤基体を得ることができる。
【００１４】
本発明では、得られるカチオン性糊剤基体である最終エマルジョン中の低級脂肪酸ビニルエステル１００重量部に対し、不飽和カルボン酸１〜１０重量部、不飽和カルボン酸アルキルエステル１０〜５０重量部（より好ましくは３０〜５０重量部）含有するのが好ましい。
本発明の液体糊剤組成物は、上記カチオン性糊剤基体自体から形成することができるが、他の成分、例えば、糊剤組成物の分散安定性を高める目的で水溶性高分子を含有させることができる。このような水溶性高分子としては、カチオン性セルロース、カチオン性でんぷんカチオン性ビニル重合体等のカチオン性高分子、ＰＶＡ、ヒドロキシエチルでんぷん、ヒドロキシプロピル化でんぷんの如き加工でんぷん、ヒドロキシエチルセルロース等のノニオン性高分子があげられる。これらは、液体糊組成物中に、0.１〜５％含有させるのが好ましい。
本発明の液体糊組成物には、さらに、必要に応じて一般の高分子エマルジョン用の添加剤、例えばジブチルフタレート、ジブチルアジペートのような可塑剤、エチレングリコール、プロピレングリコールのような凍結防止剤、その他香料、蛍光剤、抗菌剤、顔料、色素等を添加することもできる。
本発明の液体糊組成物の粘度は限定されないが、４００〜８００ｃｐ（２５℃）程度がよく、ｐＨは３〜６程度がよい。
【００１５】
【発明の効果】
本発明によれば、洗濯時の糊落ち性が改善され、かつ綿繊維への吸着性の良好なカチオン性糊剤基体、及びその効率的な製造方法が提供される。従って、該カチオン性糊剤基体を含有する液体糊剤組成物は、家庭用の糊剤組成物として好適に使用することができる。
次に実施例により本発明を説明する。
【００１６】
【実施例】
実施例１
攪拌機、滴下ロート、温度計、還流冷却器を取り付けたセパラブルフラスコに、水６０重量部、２−ヒドロキシ−３−メタクリルオキシプロピルトリメチルアンモニウムクロライドの５０％水溶液１４重量部及びエタノール5.０重量部を仕込み７０℃まで加熱した。これに酢酸ビニル0.７重量部、エチルアクリレート1.２重量部、メタクリル酸0.１９重量部を加え、重合開始剤として２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩の５％水溶液8.０重量部を加え初期重合を開始した。初期重合開始後６０分より２時間かけて酢酸ビニル１4.３重量部、エチルアクリレート２3.８重量部、メタクリル酸3.８１重量部及び２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩の５％水溶液2.０重量部を連続添加した。滴下終了後３０分間熟成した。次に酢酸ビニル６０重量部及び２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩の５％水溶液6.０重量部を４時間かけて連続滴下し、滴下終了後１時間熟成し反応を完結させた。反応後、添加剤及び水を加えて、不揮発分を５０重量％に調整した。
得られた組成物は、均一透明な乳白色の液体で、粘度６００ｍＰa ・s 、平均粒子径0.５μｍ（島津製作所（株）製、遠心沈降式ＳＰ−ＣＰ３型）であつた。
【００１７】
実施例２
攪拌機、滴下ロート、温度計、還流冷却器を取り付けたセパラブルフラスコに、水５０重量部及びカチオン性セルロース（ライオン株式会社製、レオガードＧ）の３％水溶液7.０重量部を仕込み７０℃まで加熱した。これに２−ヒドロキシ−３−メタクリルオキシプロピルトリメチルアンモニウムクロライドの５０％水溶液１４重量部、酢酸ビニル0.７重量部、エチルアクリレート1.２重量部、メタクリル酸0.１９重量部を加え、エタノール5.０重量部、重合開始剤として２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩の５％水溶液8.０重量部を加え初期重合を開始した。初期重合開始後６０分より２時間かけて酢酸ビニル１4.３重量部、エチルアクリレート２3.８重量部、メタクリル酸3.８１重量部及び２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩の５％水溶液2.０重量部を連続滴下した。滴下終了後３０分間熟成した。次に酢酸ビニル６０重量部及び２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩の５％水溶液6.０重量部を４時間かけて連続滴下し、滴下終了後１時間熟成し反応を完結させた。反応後、添加剤及び水を加えて、不揮発分を５０重量％に調整した。
得られた組成物は、均一な乳白色の液体で、粘度８００ｍＰa ・s 、平均粒子径0.４μｍであつた。
【００１８】
実施例３
セパラブルフラスコに仕込む水を５５重量部から４５重量部に変更し、カチオン性セルロース（ライオン株式会社製、レオガードＧ）の３％水溶液7.０重量部をカチオン性澱粉（松谷化学製、ネオポジパリン）の５％水溶液１４重量部に変更した以外は実施例２と同様に反応を完結させた。
得られた組成物は、均一な乳白色の液体で、粘度５００ｍＰa ・s 、平均粒子径0.７μｍであつた。
実施例４
初期重合前に添加する酢酸ビニル0.７重量部、エチルアクリレート1.２重量部、メタクリル酸0.１９重量部を酢酸ビニル0.４８重量部、エチルアクリレート1.４重量部、メタクリル酸0.１９重量部に変更し、初期重合後に滴下する酢酸ビニル１4.３重量部、エチルアクリレート２3.８重量部、メタクリル酸3.８１重量部を酢酸ビニル9.５重量部、エチルアクリレート２8.６重量部、メタクリル酸3.８重量部（酢ビ／ＥＡ比率を変更）に変更した以外は実施例１と同様に反応を完結した。
得られた組成物は、均一な乳白色の液体で、粘度６００ｍＰa ・s 、平均粒子径0.５μｍであつた。
【００１９】
実施例５
メタクリル酸をクロトン酸に変更した以外は配合量・配合時間とも実施例１同様に反応を完結した。
得られた組成物は、均一な乳白色の液体で、粘度７００ｍＰa ・s 、平均粒子径0.６μｍであつた。
比較例１
攪拌機、滴下ロート、温度計、還流冷却器を取り付けたセパラブルフラスコに、水５重量部、カチオン性セルロース（ライオン株式会社製、レオガードＧ）の３％水溶液３０重量部を仕込み７０℃まで加熱した。これに酢酸ビニル５重量部、クロトン酸0.５重量部を加え、重合開始剤として２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩0.２重量部を５％水溶液として加え初期重合を開始した。重合開始後２０分より５時間かけて酢酸ビニル４０重量部、クロトン酸５重量部及び２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩0.２重量部を５％水溶液として連続滴下した。滴下終了後１時間熟成し反応を完結させた。反応後添加剤及び水を加えて、不揮発分を５０重量％に調整した。
得られた組成物は、均一な乳白色の液体で、粘度１０００ｍＰa ・s 、平均粒子径1.０μｍであつた。
【００２０】
比較例２
攪拌機、滴下ロート、温度計、還流冷却器を取り付けたセパラブルフラスコに、２−ヒドロキシ−３−メタクリルオキシプロピルトリメチルアンモニウムクロライドの５０％水溶液１４重量部、水２５重量部、エタノール５重量部、重合開始剤として、２．２’−アゾビス（２−アミジノシクロプロパン）塩酸塩0.２重量部を５％水溶液として加え７０℃で重合しカチオン性ポリマー水溶液を得た。これに酢酸ビニル５重量部、クロトン酸０．５重量部を加え、重合開始剤として、２．２’−アゾビス（２−アミジノシクロプロパン）塩酸塩０．２重量部を５％水溶液として加え初期重合を開始した。重合開始後２０分より５時間かけて酢酸ビニル４０重量部、クロトン酸５重量部及び２，２’−アゾビス（２−アミジノシクロプロパン）塩酸塩0.２重量部を５％水溶液として連続滴下した。滴下終了後１時間熟成し反応を完結させた。反応後、添加剤及び水を加えて、不揮発分を５０重量％に調整した。
得られた組成物は、均一な乳白色の液体で、粘度５００ｍＰa ・s 、平均粒子径0.６μｍであつた。
【００２１】
実施例１〜５及び比較例１〜２で得られた組成物の特性を次の方法で調べた。結果をまとめて表−１に示す。
糊付け方法
市販の綿ブロード＃６０を用い、市販衣料用洗剤「スーパートツプ（ライオン株式会社製）」により家庭用電気洗濯機を用いて、５０℃温水で１５分洗浄−１５分すすぎ操作を５回繰り返しこれを試験布とした。
次に大栄科学精機株式会社のラウンダーメーターを用いてステンレスポツト中に２５０ｃｃの水道水およびエマルジョン固形分を0.１ｇ添加し、均一に分散させた。この分散液中に約１２ｇの試験布を入れ３分間処理した後、３０秒脱水し、一晩風乾した。その後アイロンがけを行った。
剛軟度
上記糊付け法で処理した布をＪＩＳ−Ｌ−１０９６剛軟性 Ｅ法に基づき剛軟度を測定した。
【００２２】
ゼータ電位
糊剤を水道水（硬度４．５ＤＨ）にて希釈したものをCouter社製DELTA440SXにて測定した。
吸着率
糊付け時において、処理前後の液を採取して、６６０ｎｍにおける吸光度を測定し、下式に基づき布への吸着率を求めた。
【式１】
吸着率＝１００×〔処理前の吸光度(abs) −処理後の吸光度(abs) 〕／〔処理前の吸光度(abs) −水道水の吸光度(abs) 〕
糊除去率
糊付けした布を、市販衣料用洗剤「スーパートツプ（ライオン株式会社製）」により家庭用電気洗濯機を用いて、標準使用濃度で１０分洗浄−１５分すすぎ後これを洗浄布とした。糊除去性は下式に基づき算出した。
【式２】
糊除去率＝１００×〔糊付け時の剛軟度−洗浄後の剛軟度〕／〔糊付け時の剛軟度−糊付け前の剛軟度〕
【００２３】
【表１】
表−１
BACKGROUND OF THE INVENTION
The present invention relates to a cationic paste base material that can be blended in a liquid paste composition suitable for application to clothing and the like, particularly at home, during washing, a method for producing the same, and a liquid paste composition containing the base.
[0002]
[Prior art]
At present, the liquid paste used for clothing is mainly a synthetic polymer emulsion mainly composed of polyvinyl acetate as a paste base. This polyvinyl acetate is preferable because it can impart appropriate hardness and tactile sensation to clothing, but since polyvinyl acetate is insoluble in water, the adhesive attached to the clothing is hardly dropped by washing, and if used repeatedly, the clothing However, there was a drawback that it became too hard. In view of this, it has been proposed to use a copolymer obtained by copolymerizing an unsaturated carboxylic acid with vinyl acetate as a paste base to improve paste removal during washing (Japanese Patent Publication Nos. 57-33398 and 57). No. -29483, No. 57-36284, No. 58-12959, No. 60-7070 and JP-B-1-15625).
However, it is insufficient and still has a problem in improving the paste-removing property at the time of practical washing and further the adsorption rate to cotton fibers.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a cationic paste base material that has improved paste removal during washing and has good adsorptivity to cotton fibers, and a liquid paste composition containing the base material.
Another object of the present invention is to provide an efficient method for producing the cationic paste substrate.
[0004]
[Means for Solving the Problems]
The present invention emulsion-polymerizes a lower fatty acid vinyl ester, an unsaturated carboxylic acid and an unsaturated carboxylic acid alkyl ester in a specific ratio in an aqueous medium in the presence of a cationic monomer and / or a cationic polymer, After completion of the reaction, it was made based on the knowledge that the above problem can be solved by further emulsion polymerization of a lower fatty acid vinyl ester.
That is, the present invention relates to lower fatty acid vinyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid alkyl ester in the presence of one or more cationic monomers and / or cationic polymers in an aqueous medium. Lower fatty acid vinyl in the presence of cationic polymer emulsion particles obtained by emulsion polymerization using 20 to 40 parts by weight of unsaturated carboxylic acid and 130 to 300 parts by weight of unsaturated carboxylic acid alkyl ester per 100 parts by weight of vinyl ester There is provided a cationic paste substrate characterized in that an ester is polymerized.
[0005]
The present invention also provides a lower fatty acid vinyl ester, an unsaturated carboxylic acid and an unsaturated carboxylic acid alkyl ester in the presence of one or more cationic monomers and / or cationic polymers in an aqueous medium. Emulsion polymerization is carried out using 20 to 40 parts by weight of unsaturated carboxylic acid and 130 to 300 parts by weight of unsaturated carboxylic acid alkyl ester per 100 parts by weight of vinyl ester, and after completion of the reaction, the lower fatty acid vinyl ester is further emulsion polymerized. A method for producing a cationic paste substrate characterized by the above.
The present invention also provides a liquid paste composition containing the cationic paste substrate.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the cationic monomer or the cationic polymer can be used alone, or the cationic monomer and the cationic polymer can be used in combination. The cationic monomer is preferably used alone.
Examples of the cationic monomer used in the present invention include the following.
[0006]
[Chemical 1]
[Chemical formula 2]
Wherein R 1 is a hydrogen atom or a methyl group, R 2 , R 3 and R 4 are independently a hydrogen atom or a C 1 to C 4 alkyl group, R 5 , R 6 and R 7 are independently hydrogen. Atom or C 1 -C 2 alkyl group, X − represents a monovalent anion.)
Examples of the cationic polymer used in the present invention include a polymer of the above monomer, or a copolymer of the above monomer and at least one, preferably three, of lower fatty acid vinyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid alkyl ester. can give.
Such a cationic monomer and / or cationic polymer is preferably contained in the paste base so as to be 1 to 10% by weight (hereinafter abbreviated as%).
The homopolymer of the above monomer is preferably obtained as an emulsion by polymerizing, for example, a commonly used nonionic, anionic or cationic emulsifier.
[0009]
Nonionic emulsifiers used include ethylene oxide adducts of C 1 to C 11 saturated or unsaturated alcohols (addition moles 9 to 100), C 1 to C 11 alkyl groups and 9 to 30 or more ethylene oxides. Examples thereof include alkylphenol ethoxylates having units such as polyoxyethylene heptyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene methyl octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether and the like. In particular, those having an HLB of 12 to 20 are preferred, and more preferably HLB 15 to 18. Examples of anionic emulsifiers include sulfuric acid ester salts of C 8 to C 18 alcohols such as sodium lauryl sulfate and potassium, and fatty acid salts of C 8 to C 18 (for example, ethanolamine salts such as sodium salt, potassium salt, triethanolamine ( Specific examples include oleic acid triethanolamine, stearic acid triethanolamine, etc., and sulfonated alkylaryl compounds.Cationic emulsifiers include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylethylammonium salts, alkyls. Dimethylbenzylammonium salt, alkylpyridinium salt, alkylquinolium salt, alkylisoquinolium salt, stearylamidomethylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acyl Aminoethylpyridinium salt, alkoxymethylpyridinium salt, 1-methyl-1-acylaminoethyl-2-alkylimidazoline, diacylaminopropyldimethylammonium salt, diacylaminoethyldimethylammonium salt, dialkyldi (polyoxyethylene) ammonium salt, dialkylmethyl And polyoxyethylene ammonium salt.
[0010]
The copolymer of the cationic monomer and the lower fatty acid vinyl ester, the unsaturated carboxylic acid and the unsaturated carboxylic acid alkyl ester is obtained by polymerization of the lower fatty acid vinyl ester, the unsaturated carboxylic acid and the unsaturated carboxylic acid alkyl ester. This can be easily performed by allowing the cationic monomer to coexist.
The lower fatty acid vinyl ester used in the present invention preferably has 4 to 6 carbon atoms, and examples thereof include vinyl acetate, vinyl butyrate and vinyl propionate. These can use 1 type, or 2 or more types of mixtures.
As unsaturated carboxylic acid used for this invention, C3-C10 unsaturated monocarboxylic acid and unsaturated polycarboxylic acid are mention | raise | lifted. Specific examples include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, citraconic acid, p-vinylbenzoic acid and the like. It is done. Alkyl half esters, partial esters or partial amides of unsaturated carboxylic acids such as itaconic acid, maleic acid and fumaric acid can also be used. Specific examples include lower alkyl half esters having 1 to 6 carbon atoms such as monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl fumarate, monobutyl maleate and the like. Of these unsaturated carboxylic acids, acrylic acid, methacrylic acid and crotonic acid are preferred. One or a mixture of two or more of the unsaturated carboxylic acids can be used.
[0011]
The unsaturated carboxylic acid alkyl ester used in the present invention includes (a) an alkyl ester of an unsaturated monocarboxylic acid having 3 to 6 carbon atoms (1 to 4 carbon atoms of the alkyl group), for example, methyl acrylate, ethyl acrylate , Acrylic acid such as propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and the like, (b) C4-7 α, β- Diesters of ethylenically unsaturated dicarboxylic acids (alkyl group having 1 to 4 carbon atoms), for example, dibutyl maleate, diethyl maleate, fumarate, itaconate, citraconate and the like, and the lower fatty acid vinyl esters and unsaturated carboxylic acids and unsaturated carboxylic acids In addition to acid alkyl esters, use monomers copolymerizable with these Polymer can also be used. Examples of such copolymerizable monomers include (A) alkenes such as ethylene and styrene, (B) vinyl halides such as vinyl chloride and vinylidene halides such as vinylidene chloride, (C) acrylamide and N-methylolamide, etc. And α, β-ethylenically unsaturated carboxylic acid amides and N-alkylol derivatives thereof. Of these, the monomers listed in (A) are preferred.
[0012]
In the present invention, first, a lower fatty acid vinyl ester, an unsaturated carboxylic acid, and an unsaturated carboxylic acid alkyl ester are emulsion-polymerized in an aqueous medium in the presence of one or more cationic monomers and / or cationic polymers. . Emulsion polymerization can be carried out by any method, but a lower fatty acid vinyl ester, an unsaturated carboxylic acid and an unsaturated carboxylic acid alkyl are added to a reactor in which one or more cationic monomers and / or cationic polymers are added in advance. The initial polymerization is carried out by adding an ester and a polymerization catalyst, and then a mixed liquid containing a lower fatty acid vinyl ester, an unsaturated carboxylic acid, an unsaturated carboxylic acid alkyl ester and a polymerization catalyst is added dropwise to continue the emulsion polymerization. preferable.
Various polymerization initiators can be used for the polymerization carried out in the present invention. For example, 2,2'-azobis (2-amidinopropane), hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid Examples thereof include acid and potassium persulfate. The polymerization is performed at 40 to 120 ° C., preferably 50 to 90 ° C., and the pH during the polymerization is 3 to 9, preferably 4 to 8.
[0013]
Here, in the present invention, the unsaturated carboxylic acid is 20 to 40 parts by weight (preferably 25 to 40 parts by weight) and the unsaturated carboxylic acid alkyl ester is 130 to 300 parts by weight (preferably per 100 parts by weight of the lower fatty acid vinyl ester. Is 200 to 300 parts by weight). In this first stage polymerization, it is preferable that the monomer has been reacted before proceeding to the next polymerization step. Therefore, it is preferable to continue the polymerization for 15 minutes to 24 hours, preferably 30 minutes to 3 hours after completion of dropping of the monomer. This is because when the process proceeds continuously to the next polymerization step, the lower fatty acid vinyl ester supplied in the second stage is added to the copolymer in the first stage and the polymerization proceeds to form so-called core / shell type particles. This is because the carboxyl group that should originally exist in the core is hydrophilic and is oriented near the particle surface to cancel the cation degree of the cation on the particle surface, the zeta potential is lowered, and the adsorptive power to the fiber is weakened. .
In the present invention, as the second stage, a lower fatty acid vinyl ester is further emulsion polymerized. Specifically, it is preferable to perform polymerization by dropping a lower fatty acid vinyl ester and a polymerization catalyst (the above polymerization catalyst can be used) into the cationic polymer emulsion synthesized in the first stage. The polymerization is performed at 40 to 120 ° C. (preferably 50 to 90 ° C.), and pH 3 to 9, preferably 4 to 8.
The cationic paste base of the present invention can be obtained by such multistage polymerization.
[0014]
In the present invention, 1 to 10 parts by weight of unsaturated carboxylic acid and 10 to 50 parts by weight of unsaturated carboxylic acid alkyl ester (more than 100 parts by weight of the lower fatty acid vinyl ester in the final emulsion which is the resulting cationic paste base) It is preferably contained in an amount of 30 to 50 parts by weight.
The liquid paste composition of the present invention can be formed from the cationic paste substrate itself, but contains other components, for example, a water-soluble polymer for the purpose of improving the dispersion stability of the paste composition. be able to. Such water-soluble polymers include cationic polymers such as cationic cellulose and cationic starch cationic vinyl polymer, non-ionic properties such as PVA, hydroxyethyl starch, processed starch such as hydroxypropylated starch, and hydroxyethylcellulose. A polymer. It is preferable to contain 0.1 to 5% of these in the liquid paste composition.
The liquid paste composition of the present invention further contains, as necessary, additives for general polymer emulsions, for example, plasticizers such as dibutyl phthalate and dibutyl adipate, antifreezing agents such as ethylene glycol and propylene glycol, In addition, fragrances, fluorescent agents, antibacterial agents, pigments, dyes and the like can be added.
The viscosity of the liquid paste composition of the present invention is not limited, but is preferably about 400 to 800 cp (25 ° C.), and the pH is preferably about 3 to 6.
[0015]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the paste removal property at the time of washing | cleaning is improved, and the cationic paste agent base | substrate with the favorable adsorptivity to cotton fiber, and its efficient manufacturing method are provided. Therefore, the liquid paste composition containing the cationic paste substrate can be suitably used as a household paste composition.
Next, an example explains the present invention.
[0016]
【Example】
Example 1
In a separable flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser, 60 parts by weight of water, 14 parts by weight of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, and 5.0 parts by weight of ethanol Was charged and heated to 70 ° C. To this was added 0.7 parts by weight of vinyl acetate, 1.2 parts by weight of ethyl acrylate, and 0.19 parts by weight of methacrylic acid, and 5% of 2,2′-azobis (2-amidinocyclopropane) hydrochloride as a polymerization initiator. The initial polymerization was started by adding 8.0 parts by weight of the aqueous solution. Over 60 minutes from the start of initial polymerization, 14.3 parts by weight of vinyl acetate, 23.8 parts by weight of ethyl acrylate, 3.81 parts by weight of methacrylic acid, and 2,2'-azobis (2-amidinocyclopropane) hydrochloride 2.0 parts by weight of a 5% aqueous solution was continuously added. After completion of dropping, the mixture was aged for 30 minutes. Next, 60 parts by weight of vinyl acetate and 6.0 parts by weight of a 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride are continuously added dropwise over 4 hours. After completion of the addition, the reaction is aged for 1 hour. Completed. After the reaction, an additive and water were added to adjust the nonvolatile content to 50% by weight.
The resulting composition was a uniform transparent milky white liquid having a viscosity of 600 mPa · s and an average particle size of 0.5 μm (manufactured by Shimadzu Corporation, centrifugal sedimentation type SP-CP3 type).
[0017]
Example 2
A separable flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser was charged with 50 parts by weight of water and 7.0 parts by weight of a 3% aqueous solution of cationic cellulose (Leonard G, manufactured by Lion Corporation) up to 70 ° C. Heated. To this was added 14 parts by weight of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 0.7 parts by weight of vinyl acetate, 1.2 parts by weight of ethyl acrylate and 0.19 parts by weight of methacrylic acid, and ethanol 5 Initial polymerization was started by adding 8.0 parts by weight of a 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride as a polymerization initiator. Over 60 minutes from the start of initial polymerization, 14.3 parts by weight of vinyl acetate, 23.8 parts by weight of ethyl acrylate, 3.81 parts by weight of methacrylic acid, and 2,2'-azobis (2-amidinocyclopropane) hydrochloride 2.0 parts by weight of a 5% aqueous solution was continuously added dropwise. After completion of dropping, the mixture was aged for 30 minutes. Next, 60 parts by weight of vinyl acetate and 6.0 parts by weight of a 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride are continuously added dropwise over 4 hours. After completion of the addition, the reaction is aged for 1 hour. Completed. After the reaction, an additive and water were added to adjust the nonvolatile content to 50% by weight.
The resulting composition was a uniform milky white liquid with a viscosity of 800 mPa · s and an average particle size of 0.4 μm.
[0018]
Example 3
The water charged in the separable flask was changed from 55 parts by weight to 45 parts by weight, and 7.0 parts by weight of a 3% aqueous solution of cationic cellulose (Leonard G, manufactured by Lion Corporation) was added to cationic starch (Matsutani Chemical, neopositive parin). The reaction was completed in the same manner as in Example 2 except that the amount was changed to 14 parts by weight of a 5% aqueous solution.
The resulting composition was a uniform milky white liquid with a viscosity of 500 mPa · s and an average particle size of 0.7 μm.
Example 4
0.7 parts by weight of vinyl acetate, 1.2 parts by weight of ethyl acrylate, 0.19 parts by weight of methacrylic acid added before initial polymerization, 0.48 parts by weight of vinyl acetate, 1.4 parts by weight of ethyl acrylate, and 0.7% by weight of methacrylic acid. The amount was changed to 19 parts by weight, and after the initial polymerization, 14.3 parts by weight of vinyl acetate, 23.8 parts by weight of ethyl acrylate, 3.81 parts by weight of methacrylic acid, 9.5 parts by weight of vinyl acetate, 28.6 parts by weight of ethyl acrylate The reaction was completed in the same manner as in Example 1 except that the content was changed to 3.8 parts by weight of methacrylic acid (changing the vinyl acetate / EA ratio).
The resulting composition was a uniform milky white liquid with a viscosity of 600 mPa · s and an average particle size of 0.5 μm.
[0019]
Example 5
The reaction was completed in the same manner as in Example 1 except that methacrylic acid was changed to crotonic acid.
The resulting composition was a uniform milky white liquid having a viscosity of 700 mPa · s and an average particle size of 0.6 μm.
Comparative Example 1
A separable flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser was charged with 5 parts by weight of water and 30 parts by weight of a 3% aqueous solution of cationic cellulose (Leonard G, manufactured by Lion Corporation) and heated to 70 ° C. . To this was added 5 parts by weight of vinyl acetate and 0.5 parts by weight of crotonic acid, and 0.2 parts by weight of 2,2′-azobis (2-amidinocyclopropane) hydrochloride as a polymerization initiator was added as a 5% aqueous solution to perform initial polymerization. Started. Over 20 minutes after the start of polymerization, 40 parts by weight of vinyl acetate, 5 parts by weight of crotonic acid, and 0.2 parts by weight of 2,2′-azobis (2-amidinocyclopropane) hydrochloride were continuously added dropwise as a 5% aqueous solution. . After completion of the dropwise addition, the reaction was completed by aging for 1 hour. After the reaction, an additive and water were added to adjust the nonvolatile content to 50% by weight.
The resulting composition was a uniform milky white liquid with a viscosity of 1000 mPa · s and an average particle size of 1.0 μm.
[0020]
Comparative Example 2
In a separable flask equipped with a stirrer, dropping funnel, thermometer, reflux condenser, 14 parts by weight of 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 25 parts by weight of water, 5 parts by weight of ethanol, polymerization As an initiator, 0.2 part by weight of 2.2′-azobis (2-amidinocyclopropane) hydrochloride was added as a 5% aqueous solution and polymerized at 70 ° C. to obtain a cationic polymer aqueous solution. To this was added 5 parts by weight of vinyl acetate and 0.5 parts by weight of crotonic acid, and 0.2 parts by weight of 2.2′-azobis (2-amidinocyclopropane) hydrochloride was added as a 5% aqueous solution as a polymerization initiator. Polymerization was started. Over 20 minutes after the start of polymerization, 40 parts by weight of vinyl acetate, 5 parts by weight of crotonic acid, and 0.2 parts by weight of 2,2′-azobis (2-amidinocyclopropane) hydrochloride were continuously added dropwise as a 5% aqueous solution. . After completion of the dropwise addition, the reaction was completed by aging for 1 hour. After the reaction, an additive and water were added to adjust the nonvolatile content to 50% by weight.
The resulting composition was a uniform milky white liquid with a viscosity of 500 mPa · s and an average particle size of 0.6 μm.
[0021]
The characteristics of the compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were examined by the following method. The results are summarized in Table 1.
Gluing method Using commercially available cotton broad # 60, washing with a commercial laundry detergent "Super Top (Lion Corporation)" using a household electric washing machine for 15 minutes with hot water at 50C-15 minutes The operation was repeated 5 times to obtain a test cloth.
Next, 0.1 g of 250 cc of tap water and emulsion solids was added to the stainless steel pot using a rounder meter of Daiei Kagaku Seiki Co., Ltd. and dispersed uniformly. About 12 g of test cloth was placed in this dispersion and treated for 3 minutes, then dehydrated for 30 seconds and air dried overnight. I then ironed.
Bending softness The cloth treated by the gluing method was measured for bending resistance based on the JIS-L-1096 bending softness E method.
[0022]
Zeta potential A paste diluted with tap water (hardness of 4.5 DH) was measured with a DELTA440SX manufactured by Couter.
Adsorption rate At the time of gluing, the liquid before and after the treatment was collected, the absorbance at 660 nm was measured, and the adsorption rate to the cloth was determined based on the following formula.
[Formula 1]
Adsorption rate = 100 × [absorbance before treatment (abs) −absorbance after treatment (abs)] / [absorbance before treatment (abs) −absorbance of tap water (abs)]
Glue removal rate Glued fabric was washed for 10 minutes at standard use concentration with a commercial electric detergent "Super Top (Lion Co., Ltd.)" and rinsed for 15 minutes. A cleaning cloth was used. The paste removal property was calculated based on the following formula.
[Formula 2]
Glue removal rate = 100 × [bending softness-bending softness after washing] / [bending softening-bending softness before gluing]
[0023]
[Table 1]
Table-1
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| JP31489098A JP4117947B2 (en) | 1998-11-05 | 1998-11-05 | Cationic glue base, process for producing the same, and liquid glue composition containing the glue base |
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