JP4053184B2 - Glue - Google Patents
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- JP4053184B2 JP4053184B2 JP17395699A JP17395699A JP4053184B2 JP 4053184 B2 JP4053184 B2 JP 4053184B2 JP 17395699 A JP17395699 A JP 17395699A JP 17395699 A JP17395699 A JP 17395699A JP 4053184 B2 JP4053184 B2 JP 4053184B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、浴中に投じたときの分散性にも優れ、衣類へのむら付きの少ない繊維製品の糊剤に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来、糊剤の主成分として、カルボキシメチルセルロース、澱粉、ポリビニルアルコール等の水溶性の高分子化合物が用いられてきたが、これらがもつ硬い紙のような風合いが、衣料用の糊剤としては不向きであり、また、これら高分子化合物の水溶液は低濃度でも粘度が高く、洗濯槽に添加した際に分散し難く、むら付きなどの欠点を有していた。
近年では、酢酸ビニル系ポリマーを主基剤とした乳液型糊料が使用されてきており、該糊料に関して、繊維への吸着性を高める方法等が提案されている（例えば、特開平７−１５７９７３号、特開平７−２２９０６７号、特開平１０−１９５７７２号）。
しかしながら、依然として、浴中に投じたときの分散性が不十分なものであった。
【０００３】
【課題を解決するための手段】
本発明は、酢酸ビニル由来の構造を構成骨格の一部として有する重合体（以下、酢酸ビニル重合体と略称する）を含有し、ブルックフィールド型単一円筒回転粘度計を用いてローターＮｏ．２で測定した該糊剤の３０℃での粘度が、１２ｒ/ ｍｉｎにおいて１５０〜３５０ｍＰａ・ｓ、３０ｒ/ ｍｉｎにおいて１００〜２５０ｍＰａ・ｓであり、且つ糊剤中の該重合体の濃度（但し、カチオン化澱粉、カチオン化セルロース、加工澱粉、ポリビニルアルコール、ポリビニルピロリドン及び／又は水溶性セルロース誘導体を含有する場合は、これらを含めた濃度）が２５〜３５重量％であるエマルジョン型糊剤により課題を解決をするものである。
ここで言う粘度は、ローターＮｏ．２を使用し、試料を温度３０℃で１時間静置恒温すること、及び回転時間を１分間とすること以外の条件はＪＩＳ Ｋ７１１７に記載されている方法に従う。
【０００４】
【発明の実施の形態】
本発明の糊剤は、３０ｒ/ ｍｉｎにおける粘度が、１２ｒ/ ｍｉｎにおける粘度の７０％以上を示すことが好ましい。
前記の粘度規定は、本糊剤のチキソトロピー性（揺変性）の程度を示すものである。１２ｒ/ ｍｉｎにおける粘度と、３０ｒ/ ｍｉｎにおける粘度の差が大きいほど、その溶液のチキソトロピー性は大きいこととなる。チキソトロピー性が大きいと、計量キャップ等での液切れ性が悪く、また浴中に投じたときの分散性も悪くなる。本発明が示す範囲内にあれば、これら問題点は改善される。
【０００５】
酢酸ビニル重合体は、酢酸ビニルと、酢酸ビニル以外のモノマーとの共重合体であっても差し支えない。
かかるモノマーとしては、カチオン性モノマー、不飽和カルボン酸、不飽和カルボン酸の低級アルコールエステル及び不飽和カルボン酸アミドが挙げられる。
カチオン性モノマーとしては、下記一般式（１）〜（７）のカチオン性モノマー化合物等が挙げられ、これらのうち特に一般式（３）〜（５）のものが好ましい。
【０００６】
【化１】
【化２】
カチオン性モノマーは、酢酸ビニル重合体の重合に用いる全モノマー混合物中に好ましくは０．１〜２重量％、より好ましくは０．３〜１．５重量％の割合で用いられる。
不飽和カルボン酸としては、特にアクリル酸、メタクリル酸、クロトン酸が好ましい。
また、不飽和カルボン酸の低級アルコールエステルとしては、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチルが好ましい。
このような不飽和カルボン酸または不飽和カルボン酸の低級アルコールエステルは、酢酸ビニル重合体の重合に用いる全モノマー混合物中に好ましくは１〜３０重量％、より好ましくは２〜２０重量％の割合で配合され重合される。
不飽和カルボン酸アミドとしては、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎージメチルメタクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ，Ｎ−ジエチルメタクリルアミド、Ｎ−プロピルアクリルアミド、Ｎ−ヒドロキシエチルメタクリルアミド、ダイアセトンイソアクリルアミドが好ましい。
不飽和カルボン酸アミドは、酢酸ビニル重合体の重合に用いる全モノマー混合物中に好ましくは０．１〜３０重量％、より好ましくは１〜２０重量％の割合で配合され重合される。
【０００９】
本発明の酢酸ビニル重合体は酢酸ビニルモノマーを最も多く反応させることによって得られる重合体であり、酢酸ビニルモノマーの割合は、前記の重合に供せられる全モノマー重量当たり、７５〜９９．８重量％、好ましくは８２〜９９重量％の割合で用いられる。
【００１０】
本発明では、高浴比における繊維への吸着促進、及び保存安定性向上を目的に、カチオン化澱粉及び／又はカチオン化セルロース（以下、陽イオン性高分子化合物と略称する）を酢酸ビニル重合体の重合時又は重合後に添加することが好ましい。これらは、最終的な糊剤中に０．５〜６．０重量％配合することが好ましい。
【００１１】
本発明では、エマルジョンの貯蔵安定性をさらに向上させるために、ポリビニルアルコール、ポリビニルピロリドン、化工澱粉、水溶性セルロース誘導体から選ばれる一種以上（以下、非イオン性高分子化合物と略称する）を併用することが好ましい。非イオン性高分子化合物は、ポリエチレングリコールを標準物質とした時の重量平均分子量が１０，０００〜２００，０００であるものが好ましい。非イオン性高分子化合物は、糊剤中に、０．１〜１０重量％含有することが好ましく、１〜４重量％含有することがより好ましい。
【００１２】
本発明の糊剤中の酢酸ビニル重合体の濃度（但し、カチオン化澱粉、カチオン化セルロース、加工澱粉、ポリビニルアルコール、ポリビニルピロリドン及び／又は水溶性セルロース誘導体を含有する場合は、これらを含めた濃度）は２５〜３５重量％である。この濃度範囲と特定の粘度を満たすことにより、水への分散性に優れ、衣類へのむら付きを抑制することができ、また使い勝手にも優れる糊剤を得ることができる。
【００１３】
酢酸ビニル重合体を得るための重合反応に際しては、乳化剤として界面活性剤が用いられる。本発明に用いられる界面活性剤としては、非イオン性界面活性剤、陰イオン性界面活性剤、陽イオン性界面活性剤が挙げられる。具体的には、特開平１０−１９５７７２号公報の７欄４３行〜８欄４０行に記載されたものを用いることができる。特に非イオン性界面活性剤として、炭素数７〜２２の飽和または不飽和アルコールのエチレンオキサイド付加物（エチレンオキサイドの付加モル数９〜１００）、陰イオン性界面活性剤として高級脂肪酸アルコール硫酸塩、陽イオン性界面活性剤として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が好ましい。
【００１４】
本発明の糊剤を得るための好適な手段として、次の条件（Ｉ）ないし（III)で示される条件を全て満たす調製方法が挙げられる。
条件（Ｉ）
酢酸ビニル重合体の重合反応時に加える界面活性剤量を、酢酸ビニル重合体量（但し、前記の陽イオン性高分子化合物及び／又非イオン性高分子化合物を配合する場合はこれらを加えた量）１００重量部に対して、０．１〜１．５重量部とする。
【００１５】
条件（II）
酢酸ビニル重合体の合成時に用いるカチオン性モノマーの含有量を全モノマー混合物中、０．１〜２重量％、好ましくは０．３〜１．５重量％の割合で共重合させるか、あるいはカチオン置換度０．０２〜１．０の陽イオン性高分子化合物を用い、その含有量を糊料基剤中２〜１７重量％とする。
ここで、カチオン置換度とはグルコース単位当りのカチオン化度であり、澱粉またはセルロースを構成している水酸基の数はグルコース単位あたり３個であり、これが総てカチオン置換されている場合を３．０とする時の値である。
【００１６】
本発明の最終的な糊剤は、重合後のエマルジョンにその他の任意成分を配合することによって得られるが、本発明では、糊剤と分けて説明するために、重合後のエマルジョン溶液を糊料基剤とする。
【００１７】
条件（III)
得られた糊料基剤を、イオン交換水やその他任意成分で酢酸ビニル重合体濃度（但し、前記の陽イオン性高分子化合物及び／又非イオン性高分子化合物を配合する場合はこれらを加えた濃度）が２５〜３５重量％の糊剤に希釈・調製する。
【００１８】
上記条件より、本発明の粘度を有し、良好な糊付け効果と分散性に優れ、使い勝手に優れる糊剤を得ることができる。
【００１９】
また、本発明のエマルジョン型糊剤のエマルジョンの平均粒径は０．５〜１．２μm が好ましい。これは酢酸ビニル重合体の重合時のモノマー混合物の滴下を３〜８時間で行う方法に加えて、反応温度、攪拌速度を調整することによって得ることができる。
【００２０】
本発明の最も好ましい製法は、陽イオン性高分子化合物、非イオン界面活性剤、及び非イオン性高分子化合物の存在下で、酢酸ビニル由来の構造を構成骨格の一部として有する重合体を重合する方法である。
【００２１】
詳しい製造条件、任意成分及び使用方法については、常法、例えば特開平１０−１９５７７２号公報の６頁９欄８行〜同頁１０欄１２行に記載と同様でよいが、本発明の糊剤には、特にその他成分としてジブチルフタレート、ジブチルアジペート、ジオクチルアジペート又はトリアセチンなどのような可塑剤、エチレングリコール、プロピレングリコール又はエタノールなどの凍結防止剤、殺菌剤、プロキセル等の防黴・防菌剤、安定な香料などを添加することが好ましく、糊剤中の濃度調整の為に水等の希釈剤も追加的に配合することができる。
【００２２】
【発明の効果】
本発明は、従来の糊剤の欠点であった浴中での分散性の悪さを改善し、むら付きを改善するものである。また、本発明は、計量キャップへの残留の問題が少なく使い勝手に優れるものであり、その上、近年、省資源やプラスチックゴミなどの問題に対応した薄いプラスチックフィルム製の小袋に詰めた詰め替え用としても、移し替えが容易であることから、最適である。
【００２３】
【実施例】
＜糊剤の調製＞
・調製例１
重合反応槽（セパラブルフラスコ、以下略）に、イオン交換水５０重量部、水溶性のカチオン化澱粉（カチオン置換度０．０９）６０重量部とポリビニルアルコール（ＰＶＡ 鹸化度８０％、重量平均分子量６６，０００）１５重量部の混合水溶液４２５重量部、非イオン性界面活性剤（ポリオキシエチレンラウリルエーテル、エチレンオキサイド平均付加モル数４０）７．２重量部、リン酸３ナトリウム３．０重量部、酢酸ビニル１６重量部、及び２，２'-アゾビス（２−アミジノプロパン）塩酸塩１．４重量部を仕込み、窒素ガスを吹き込みながら７５℃に昇温した。
これに、酢酸ビニルとメタクリル酸の最終重量比が９７．５：２．５（但し、酢酸ビニルは、先に添加した１６重量部との合計量である）となるように予め混合しておいたもの５００重量部を６時間かけて滴下し乳化重合を行った。また、モノマーの滴下開始１時間後から滴下終了まで、２，２'-アゾビス（２−アミジノプロパン）塩酸塩１．０重量部を加えた１９０重量部の水溶液を順次滴下した。滴下終了後、そのまま１時間攪拌してから、室温まで冷却し、１０重量％炭酸ナトリウム溶液を用いて、得られたエマルジョン（糊料基剤）のｐＨを５．０に調整した。
最終的に、酢酸ビニル、メタクリル酸、カチオン化澱粉、ポリビニルアルコールの合計重量が３１重量％になるようイオン交換水で調製し、糊剤を得た。前記測定法による本糊剤の粘度は、１２ｒ/ ｍｉｎで２５０ｍＰａ・ｓ、３０ｒ/ ｍｉｎでは１８８ｍＰａ・ｓであった。これを本発明品１とする。
【００２４】
・調製例２
調製例１と同様に、重合反応槽に、イオン交換水５０重量部、カチオン化セルロース（カチオン置換度０．０６）６０重量部とポリビニルアルコール（ＰＶＡ鹸化度８０％、重量平均分子量６６，０００）１５重量部の混合水溶液４２５重量部、非イオン性界面活性剤（ポリオキシエチレンラウリルエーテル、エチレンオキサイド平均付加モル数４０）６．６重量部、リン酸３ナトリウム３．０重量部、酢酸ビニル１６重量部、及び２，２'-アゾビス（２−アミジノプロパン）塩酸塩１．４重量部を仕込み、窒素ガスを吹き込みながら７５℃に昇温した。
これに、酢酸ビニルとアクリル酸、及びメタクリル酸エチルの最終重量比が９４．５：２．５：３．０（但し、酢酸ビニルは、先に添加した１６重量部との合計量である）となるように予め混合しておいたもの５００重量部を６時間かけて滴下し乳化重合を行った。後は調製例１と同様に調製しエマルジョン（糊料基剤）を得た。
最終的に、酢酸ビニル、アクリル酸、メタクリル酸エチル、カチオン化セルロース、ポリビニルアルコールの合計重量が３１重量％になるようイオン交換水で調整し、糊剤を得た。これを本発明品２とする。
【００２５】
・調製例３
調製例１と同様に、重合反応槽に、混合水溶液、非イオン性界面活性剤、リン酸３ナトリウム、酢酸ビニル、及び２，２'-アゾビス（２−アミジノプロパン）塩酸塩を仕込み、窒素ガスを吹き込みながら７５℃に昇温した。
これに、酢酸ビニルとメタクリル酸、及びＮ，Ｎ−ジメチルアクリルアミドの最終重量比が９４．５：２．５：３．０（但し、酢酸ビニルは、先に添加した１６重量部との合計量である）となるように予め混合しておいたもの５００重量部を６時間かけて滴下し乳化重合を行った。後は調製例１と同様に調製しエマルジョン（糊料基剤）を得た。
最終的に、酢酸ビニル、メタクリル酸、Ｎ，Ｎ−ジメチルアクリルアミド、カチオン化澱粉、ポリビニルアルコールの合計重量が３１重量％になるようイオン交換水で調整し、糊剤を得た。これを本発明品３とする。
【００２６】
・調製例４
調製例１と同様に、重合反応槽に、混合水溶液、非イオン性界面活性剤、リン酸３ナトリウム、酢酸ビニル、及び２，２'-アゾビス（２−アミジノプロパン）塩酸塩を仕込み、窒素ガスを吹き込みながら７５℃に昇温した（但し、非イオン性界面活性剤の量は３．６重量部とした）。
これに、酢酸ビニルとメタクリル酸、及びＮ，Ｎ−ジメチルアクリルアミドの最終重量比が９４．５：２．５：３．０（但し、酢酸ビニルは、先に添加した１６重量部との合計量である）となるように予め混合しておいたもの５００重量部を６時間かけて滴下し乳化重合を行った。後は調製例１と同様に調製しエマルジョン（糊料基剤）を得た。
最終的に、酢酸ビニル、メタクリル酸、Ｎ，Ｎ−ジメチルアクリルアミド、カチオン化澱粉、ポリビニルアルコールの合計重量が３３重量％になるようイオン交換水で調整し、糊剤を得た。これを本発明品４とする。
【００２７】
・調製例５
調製例１と同様に、重合反応槽に、混合水溶液、非イオン性界面活性剤、リン酸３ナトリウム、酢酸ビニル、及び２，２'-アゾビス（２−アミジノプロパン）塩酸塩を仕込み、窒素ガスを吹き込みながら７５℃に昇温した（但し、非イオン性界面活性剤の量は１４．４重量部とした）。
これに、酢酸ビニルとメタクリル酸の最終重量比が９７．５：２．５（但し、酢酸ビニルは、先に添加した１６重量部との合計量である）となるように予め混合しておいたもの５００重量部を６時間かけて滴下し乳化重合を行った。後は調製例１と同様に調製しエマルジョン（糊料基剤）を得た。
最終的に、酢酸ビニル、メタクリル酸、カチオン化澱粉、ポリビニルアルコールの合計重量が３１重量％になるようイオン交換水で調整し、糊剤を得た。これを比較品１とする。
【００２８】
・調製例６
調製例１と同様に、重合反応槽に、混合水溶液、非イオン性界面活性剤、リン酸３ナトリウム、酢酸ビニル、及び２，２'-アゾビス（２−アミジノプロパン）塩酸塩を仕込み、窒素ガスを吹き込みながら７５℃に昇温した。
これに、酢酸ビニルとメタクリル酸、及びＮ，Ｎ−ジメチルアクリルアミドの最終重量比が９４．５：２．５：３．０（但し、酢酸ビニルは、先に添加した１６重量部との合計量である）となるように予め混合しておいたもの５００重量部を６時間かけて滴下し乳化重合を行った。後は調製例１と同様に調製しエマルジョン（糊料基剤）を得た。
最終的に、酢酸ビニル、メタクリル酸、Ｎ，Ｎ−ジメチルアクリルアミド、カチオン化澱粉、ポリビニルアルコールの合計重量が４３重量％になるようイオン交換水で調整し、糊剤を得た。これを比較品２とする。
【００２９】
実施例１〜４、比較例１〜２
上記で調製した糊剤（本発明品１〜４、比較品１〜２）について、以下の評価を行った。各糊剤の粘度等とともに結果を表１に示す。
＜評価方法＞
・糊付け効果試験
ターゴトメーター型洗浄試験機を使用した。水道水５００ｍｌ、上記で調製した糊剤１．３ｇを洗浄槽（内容積１０００ｍｌ）に入れ良く分散した後、６０＃木綿ブロード布２０ｇを入れ １００ｒ/ ｍｉｎの攪拌速度で３分間糊付けした。その後１分間脱水してから、２０℃、６５％相対湿度の恒温恒湿室に一昼夜乾燥した。
上記方法により糊付けした木綿布から５ｃｍ幅の小片を作製し、１０枚を１組として、純曲げ試験機（カトーテック株式会社製）を用いて、２０℃、６５％相対湿度の恒温恒湿室において曲げ剛性を測定した。０．２２以上を合格とする。
・分散性評価試験
上記で調製した糊剤３０ｍｌを４リットルの水道水の入った洗い桶に投入し、その分散性を目視にて判定した。結果を表１に示した。○が合格である。
判定基準：
すばやく分散・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・ ○
すばやく分散するが、若干、洗い桶底部に沈殿・・・・・ △
ほとんど分散せず、洗い桶底部に沈殿・・・・・・・・・・・・・ ×
・液切れ性試験
ポリプロピレン製円柱状カップ（直径２８ｍｍ、高さ４０ｍｍ）に、調製した各糊剤を３０ｇ入れ、次に９０度に傾け、糊料を排出（１５秒間）した後の液残量から液切れ性を評価した。結果を表１に合わせて示した。○が合格である。
残留率（％）＝（糊料排出後重量−カップ重量）／３０×１００（％）
評価基準：
残留率が５％未満・・・・・・・・・・○
残留率が５〜１０％・・・・・・・・△
残留率が１０％を超える・・・・×
【００３０】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to a paste for a textile product that is excellent in dispersibility when thrown into a bath and has less unevenness on clothing.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, water-soluble polymer compounds such as carboxymethyl cellulose, starch, and polyvinyl alcohol have been used as the main component of the paste, but the texture like a hard paper is unsuitable as a paste for clothing. In addition, the aqueous solutions of these polymer compounds have a high viscosity even at a low concentration, and are difficult to disperse when added to the washing tub, and have disadvantages such as unevenness.
In recent years, an emulsion type paste based on a vinyl acetate polymer has been used, and a method for increasing the adsorptivity to fibers has been proposed for the paste (for example, JP-A-7- No. 157773, JP-A-7-229067, JP-A-10-195572).
However, the dispersibility was still insufficient when cast in a bath.
[0003]
[Means for Solving the Problems]
The present invention contains a polymer having a vinyl acetate-derived structure as a part of the constituent skeleton (hereinafter, abbreviated as vinyl acetate polymer), and a rotor No. using a Brookfield type single cylinder rotational viscometer. The viscosity at 30 ° C. of the paste measured in 2 is 150 to 350 mPa · s at 12 r / min, 100 to 250 mPa · s at 30 r / min, and the concentration of the polymer in the paste (however, In the case of containing cationized starch, cationized cellulose, modified starch, polyvinyl alcohol, polyvinylpyrrolidone and / or a water-soluble cellulose derivative, the emulsion type paste having a concentration of 25 to 35% by weight) It is a solution.
The viscosity said here is the rotor No. No. 2 is used, and the sample is allowed to stand at a temperature of 30 ° C. for 1 hour and the rotation time is set to 1 minute. The conditions described in JIS K7117 are followed.
[0004]
DETAILED DESCRIPTION OF THE INVENTION
In the paste of the present invention, the viscosity at 30 r / min preferably represents 70% or more of the viscosity at 12 r / min.
The above-mentioned viscosity regulation indicates the degree of thixotropic property (thixotropic property) of the present glue. The greater the difference between the viscosity at 12 r / min and the viscosity at 30 r / min, the greater the thixotropic property of the solution. If the thixotropy is large, liquid drainage with a measuring cap or the like is poor, and dispersibility when thrown into a bath is also poor. If the present invention is within the range indicated, these problems are improved.
[0005]
The vinyl acetate polymer may be a copolymer of vinyl acetate and a monomer other than vinyl acetate.
Such monomers include cationic monomers, unsaturated carboxylic acids, lower alcohol esters of unsaturated carboxylic acids and unsaturated carboxylic acid amides.
Examples of the cationic monomer include cationic monomer compounds of the following general formulas (1) to (7), and among these, those of general formulas (3) to (5) are particularly preferable.
[0006]
[Chemical 1]
[Chemical 2]
The cationic monomer is preferably used in a proportion of 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight in the total monomer mixture used for the polymerization of the vinyl acetate polymer.
As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, and crotonic acid are particularly preferable.
Moreover, as a lower alcohol ester of unsaturated carboxylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate are preferable.
The unsaturated carboxylic acid or the lower alcohol ester of the unsaturated carboxylic acid is preferably 1 to 30% by weight, more preferably 2 to 20% by weight in the total monomer mixture used for the polymerization of the vinyl acetate polymer. Blended and polymerized.
As unsaturated carboxylic acid amides, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-propylacrylamide, N-hydroxyethylmethacrylamide, Diacetone isoacrylamide is preferred.
The unsaturated carboxylic acid amide is preferably blended and polymerized in a proportion of 0.1 to 30% by weight, more preferably 1 to 20% by weight, in the total monomer mixture used for the polymerization of the vinyl acetate polymer.
[0009]
The vinyl acetate polymer of the present invention is a polymer obtained by reacting the most vinyl acetate monomer, and the ratio of the vinyl acetate monomer is 75 to 99.8 wt.% Based on the total monomer weight to be subjected to the polymerization. %, Preferably 82-99% by weight.
[0010]
In the present invention, a cationized starch and / or a cationized cellulose (hereinafter abbreviated as a cationic polymer compound) is a vinyl acetate polymer for the purpose of promoting adsorption to fibers at a high bath ratio and improving storage stability. It is preferably added during or after the polymerization. These are preferably blended in an amount of 0.5 to 6.0% by weight in the final paste.
[0011]
In the present invention, in order to further improve the storage stability of the emulsion, one or more selected from polyvinyl alcohol, polyvinyl pyrrolidone, modified starch, and water-soluble cellulose derivative (hereinafter abbreviated as nonionic polymer compound) are used in combination. It is preferable. The nonionic polymer compound preferably has a weight average molecular weight of 10,000 to 200,000 when polyethylene glycol is used as a standard substance. The nonionic polymer compound is preferably contained in the paste in an amount of 0.1 to 10% by weight, and more preferably 1 to 4% by weight.
[0012]
Concentration of vinyl acetate polymer in the paste of the present invention (however, in the case of containing cationized starch, cationized cellulose, modified starch, polyvinyl alcohol, polyvinyl pyrrolidone and / or water-soluble cellulose derivative) ) Is 25 to 35% by weight. By satisfying this concentration range and a specific viscosity, it is possible to obtain a paste that is excellent in water dispersibility, can suppress unevenness in clothing, and is excellent in usability.
[0013]
In the polymerization reaction for obtaining the vinyl acetate polymer, a surfactant is used as an emulsifier. Examples of the surfactant used in the present invention include nonionic surfactants, anionic surfactants, and cationic surfactants. Specifically, what was described in 7th column 43 line-8th column 40 line of Unexamined-Japanese-Patent No. 10-195572 can be used. In particular, as a nonionic surfactant, an ethylene oxide adduct of a saturated or unsaturated alcohol having 7 to 22 carbon atoms (addition mole number of ethylene oxide 9 to 100), a higher fatty acid alcohol sulfate as an anionic surfactant, Alkyltrimethylammonium salts and dialkyldimethylammonium salts are preferred as the cationic surfactant.
[0014]
As a suitable means for obtaining the paste of the present invention, a preparation method that satisfies all the conditions indicated by the following conditions (I) to (III) can be mentioned.
Condition (I)
The amount of surfactant added during the polymerization reaction of the vinyl acetate polymer is the amount of the vinyl acetate polymer (however, in the case where the cationic polymer compound and / or the nonionic polymer compound are blended) ) 0.1 to 1.5 parts by weight per 100 parts by weight.
[0015]
Condition (II)
The cationic monomer content used in the synthesis of the vinyl acetate polymer is copolymerized at a ratio of 0.1 to 2% by weight, preferably 0.3 to 1.5% by weight in the total monomer mixture, or cationic substitution. A cationic polymer compound having a degree of 0.02 to 1.0 is used, and the content thereof is 2 to 17% by weight in the paste base.
Here, the degree of cation substitution is the degree of cationization per glucose unit, the number of hydroxyl groups constituting the starch or cellulose is 3 per glucose unit, and the case where all of these are cation-substituted. This is the value when 0 is set.
[0016]
The final paste of the present invention can be obtained by blending other optional components with the emulsion after polymerization. In the present invention, in order to explain separately from the paste, the emulsion solution after polymerization is used as a paste. Use as a base.
[0017]
Condition (III)
The resulting paste base is added with ion-exchanged water or other optional components to a vinyl acetate polymer concentration (however, when these cationic polymer compounds and / or nonionic polymer compounds are added, these are added. Dilute and prepare to a paste of 25 to 35% by weight.
[0018]
From the above conditions, it is possible to obtain a paste having the viscosity of the present invention, excellent in a good pasting effect and dispersibility, and excellent in usability.
[0019]
The average particle size of the emulsion-type paste of the present invention is preferably 0.5 to 1.2 μm. This can be obtained by adjusting the reaction temperature and the stirring speed in addition to the method of dropping the monomer mixture during polymerization of the vinyl acetate polymer in 3 to 8 hours.
[0020]
The most preferable production method of the present invention is to polymerize a polymer having a structure derived from vinyl acetate as a part of a skeleton in the presence of a cationic polymer compound, a nonionic surfactant, and a nonionic polymer compound. It is a method to do.
[0021]
Detailed manufacturing conditions, optional components, and methods of use may be the same as those described in conventional methods, for example, JP 10-195572, page 6, column 9, line 8 to column 10, line 12; In particular, as other components, plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate or triacetin, antifreezing agents such as ethylene glycol, propylene glycol or ethanol, fungicides, antifungal agents such as proxel, It is preferable to add a stable fragrance or the like, and a diluent such as water can be additionally blended for adjusting the concentration in the paste.
[0022]
【The invention's effect】
The present invention improves the poor dispersibility in a bath, which is a drawback of conventional glues, and improves unevenness. In addition, the present invention is excellent in usability with few problems of remaining on the measuring cap, and moreover, in recent years, for refilling packed in a thin plastic film sachet corresponding to problems such as resource saving and plastic garbage. However, it is optimal because it is easy to transfer.
[0023]
【Example】
<Preparation of paste>
Preparation Example 1
In a polymerization reactor (separable flask, hereinafter abbreviated), ion-exchanged water 50 parts by weight, water-soluble cationized starch (cation substitution degree 0.09) 60 parts by weight and polyvinyl alcohol (PVA saponification degree 80%, weight average molecular weight) 66,000) 15 parts by weight of mixed aqueous solution 425 parts by weight, nonionic surfactant (polyoxyethylene lauryl ether, ethylene oxide average added mole number 40) 7.2 parts by weight, trisodium phosphate 3.0 parts by weight Then, 16 parts by weight of vinyl acetate and 1.4 parts by weight of 2,2′-azobis (2-amidinopropane) hydrochloride were charged, and the temperature was raised to 75 ° C. while blowing nitrogen gas.
This was mixed in advance so that the final weight ratio of vinyl acetate and methacrylic acid was 97.5: 2.5 (wherein vinyl acetate is the total amount of 16 parts by weight added previously). 500 parts by weight of the soup was added dropwise over 6 hours to carry out emulsion polymerization. In addition, 190 parts by weight of an aqueous solution in which 1.0 part by weight of 2,2′-azobis (2-amidinopropane) hydrochloride was added was sequentially added dropwise from 1 hour after the start of monomer addition until the end of addition. After completion of dropping, the mixture was stirred as it was for 1 hour, then cooled to room temperature, and the pH of the obtained emulsion (glue base) was adjusted to 5.0 using a 10 wt% sodium carbonate solution.
Finally, it was prepared with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, cationized starch and polyvinyl alcohol was 31% by weight to obtain a paste. The viscosity of the glue according to the measurement method was 250 mPa · s at 12 r / min and 188 mPa · s at 30 r / min. This is product 1 of the present invention.
[0024]
Preparation Example 2
In the same manner as in Preparation Example 1, 50 parts by weight of ion exchange water, 60 parts by weight of cationized cellulose (cation substitution degree 0.06) and polyvinyl alcohol (PVA saponification degree 80%, weight average molecular weight 66,000) were added to the polymerization reaction tank. 15 parts by weight of mixed aqueous solution 425 parts by weight, nonionic surfactant (polyoxyethylene lauryl ether, ethylene oxide average added mole number 40) 6.6 parts by weight, trisodium phosphate 3.0 parts by weight, vinyl acetate 16 Part by weight and 1.4 parts by weight of 2,2′-azobis (2-amidinopropane) hydrochloride were charged, and the temperature was raised to 75 ° C. while blowing nitrogen gas.
The final weight ratio of vinyl acetate, acrylic acid, and ethyl methacrylate is 94.5: 2.5: 3.0 (wherein vinyl acetate is the total amount of 16 parts by weight added previously) 500 parts by weight of a mixture previously mixed so as to be added dropwise over 6 hours was subjected to emulsion polymerization. Thereafter, an emulsion (paste material base) was obtained in the same manner as in Preparation Example 1.
Finally, the mixture was adjusted with ion-exchanged water so that the total weight of vinyl acetate, acrylic acid, ethyl methacrylate, cationized cellulose, and polyvinyl alcohol was 31% by weight to obtain a paste. This is designated as Product 2 of the present invention.
[0025]
Preparation Example 3
Similarly to Preparation Example 1, a polymerization reaction vessel was charged with a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2′-azobis (2-amidinopropane) hydrochloride, and nitrogen gas The temperature was raised to 75 ° C. while blowing.
The final weight ratio of vinyl acetate, methacrylic acid, and N, N-dimethylacrylamide was 94.5: 2.5: 3.0 (provided that vinyl acetate is the total amount of 16 parts by weight added previously. 500 parts by weight of the mixture previously mixed so as to be emulsion was added dropwise over 6 hours to carry out emulsion polymerization. Thereafter, an emulsion (paste material base) was obtained in the same manner as in Preparation Example 1.
Finally, the mixture was adjusted with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, N, N-dimethylacrylamide, cationized starch, and polyvinyl alcohol was 31% by weight to obtain a paste. This is product 3 of the present invention.
[0026]
Preparation Example 4
Similarly to Preparation Example 1, a polymerization reaction vessel was charged with a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2′-azobis (2-amidinopropane) hydrochloride, and nitrogen gas The temperature was raised to 75 ° C. while blowing (however, the amount of the nonionic surfactant was 3.6 parts by weight).
The final weight ratio of vinyl acetate, methacrylic acid, and N, N-dimethylacrylamide was 94.5: 2.5: 3.0 (provided that vinyl acetate is the total amount of 16 parts by weight added previously. 500 parts by weight of the mixture previously mixed so as to be emulsion was added dropwise over 6 hours to carry out emulsion polymerization. Thereafter, an emulsion (paste material base) was obtained in the same manner as in Preparation Example 1.
Finally, the mixture was adjusted with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, N, N-dimethylacrylamide, cationized starch, and polyvinyl alcohol was 33% by weight to obtain a paste. This is designated as Product 4 of the present invention.
[0027]
Preparation Example 5
Similarly to Preparation Example 1, a polymerization reaction vessel was charged with a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2′-azobis (2-amidinopropane) hydrochloride, and nitrogen gas The temperature was raised to 75 ° C. while blowing (however, the amount of the nonionic surfactant was 14.4 parts by weight).
This was mixed in advance so that the final weight ratio of vinyl acetate and methacrylic acid was 97.5: 2.5 (wherein vinyl acetate is the total amount of 16 parts by weight added previously). 500 parts by weight of the soup was added dropwise over 6 hours to carry out emulsion polymerization. Thereafter, an emulsion (paste material base) was obtained in the same manner as in Preparation Example 1.
Finally, the mixture was adjusted with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, cationized starch and polyvinyl alcohol was 31% by weight to obtain a paste. This is referred to as comparative product 1.
[0028]
Preparation Example 6
Similarly to Preparation Example 1, a polymerization reaction vessel was charged with a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2′-azobis (2-amidinopropane) hydrochloride, and nitrogen gas The temperature was raised to 75 ° C. while blowing.
The final weight ratio of vinyl acetate, methacrylic acid, and N, N-dimethylacrylamide was 94.5: 2.5: 3.0 (provided that vinyl acetate is the total amount of 16 parts by weight added previously. 500 parts by weight of the mixture previously mixed so as to be emulsion was added dropwise over 6 hours to carry out emulsion polymerization. Thereafter, an emulsion (paste material base) was obtained in the same manner as in Preparation Example 1.
Finally, the mixture was adjusted with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, N, N-dimethylacrylamide, cationized starch, and polyvinyl alcohol was 43% by weight to obtain a paste. This is referred to as comparative product 2.
[0029]
Examples 1-4, Comparative Examples 1-2
The following evaluation was performed about the adhesive agent prepared above (this invention products 1-4, comparative products 1-2). The results are shown in Table 1 together with the viscosity of each paste.
<Evaluation method>
-Gluing effect test A tartometer type cleaning tester was used. After 500 ml of tap water and 1.3 g of the paste prepared above were placed in a washing tank (with an internal volume of 1000 ml) and well dispersed, 20 g of 60 # cotton broad cloth was placed and glued at a stirring speed of 100 r / min for 3 minutes. Then, after dehydrating for 1 minute, it was dried overnight in a constant temperature and humidity chamber of 20 ° C. and 65% relative humidity.
A small piece with a width of 5 cm is produced from the cotton cloth glued by the above method, and a set of 10 pieces is used as a set, using a pure bending tester (manufactured by Kato Tech Co., Ltd.), a constant temperature and humidity chamber at 20 ° C. and 65% relative humidity. The bending stiffness was measured. A score of 0.22 or higher is accepted.
Dispersibility evaluation test 30 ml of the paste prepared as described above was put into a washing tub containing 4 liters of tap water, and the dispersibility was visually determined. The results are shown in Table 1. ○ is a pass.
Judgment criteria:
Disperse quickly ...
Disperses quickly, but slightly settles at the bottom of the washing bowl △
Almost no dispersion, settled at the bottom of the washing bowl ...
・ Liquid breakability test Polypropylene cylindrical cup (diameter: 28 mm, height: 40 mm) 30 g of each prepared paste was then tilted to 90 degrees and the amount of liquid remaining after discharging the paste (15 seconds) From this, the liquid breakability was evaluated. The results are shown in Table 1. ○ is a pass.
Residual rate (%) = (weight after discharging paste-cup weight) / 30 × 100 (%)
Evaluation criteria:
Residual rate is less than 5%
Residual rate is 5-10% ・ ・ ・ △△
Residual rate exceeds 10%
[0030]
[Table 1]
Claims (2)
＜条件（Ｉ）＞
酢酸ビニル重合体（Ａ）の重合反応時に、乳化剤として炭素数７〜２２の飽和または不飽和アルコールのエチレンオキサイド付加物（エチレンオキサイドの付加モル数９〜１００）を用い、該乳化剤量を、酢酸ビニル重合体（Ａ）、陽イオン性高分子化合物（Ｂ）及び非イオン性高分子化合物（Ｃ）の合計１００重量部に対して、０．１〜１．５重量部とする。
＜条件（ II ）＞
酢酸ビニル重合体（Ａ）の合成時にカチオン置換度０．０２〜１．０の陽イオン性高分子化合物（Ｂ）を用い、その含有量を糊料基剤中２〜１７重量％とする。
＜条件（ III ）＞
得られた糊料基剤を、イオン交換水やその他任意成分で、酢酸ビニル重合体（Ａ）、陽イオン性高分子化合物（Ｂ）及び非イオン性高分子化合物（Ｃ）の合計濃度が２５〜３５重量％の糊剤に希釈・調製する。 A cationic polymer compound (B) selected from a polymer (A) having a structure derived from vinyl acetate as a part of a constituent skeleton (hereinafter referred to as vinyl acetate polymer (A)), cationized starch and cationized cellulose. And a non-ionic polymer compound (C) selected from modified starch, polyvinyl alcohol, polyvinyl pyrrolidone and / or a water-soluble cellulose derivative, and using a Brookfield single cylinder rotational viscometer, rotor No. The viscosity at 30 ° C. of the paste measured in 2 is 150 to 350 mPa · s at 12 r / min, 100 to 250 mPa · s at 30 r / min, and the vinyl acetate polymer (A) in the paste , A method for producing an emulsion-type paste in which the total concentration of the cationic polymer compound (B) and the nonionic polymer compound (C) is 25 to 35% by weight , comprising the following conditions (I) and ( II ) A method for producing an emulsion type paste, wherein a paste base is prepared under the conditions shown in the following, and then the paste base is diluted with water under the conditions shown in the following conditions ( III ).
<Condition (I)>
During the polymerization reaction of the vinyl acetate polymer (A), an ethylene oxide adduct of a saturated or unsaturated alcohol having 7 to 22 carbon atoms (9 to 100 moles of added ethylene oxide) is used as an emulsifier. It is 0.1-1.5 weight part with respect to a total of 100 weight part of a vinyl polymer (A), a cationic high molecular compound (B), and a nonionic high molecular compound (C).
<Condition ( II )>
At the time of synthesizing the vinyl acetate polymer (A), the cationic polymer compound (B) having a cation substitution degree of 0.02 to 1.0 is used, and the content thereof is set to 2 to 17% by weight in the paste base.
<Condition ( III )>
The resulting paste base is made of ion-exchanged water and other optional components, and the total concentration of the vinyl acetate polymer (A), the cationic polymer compound (B) and the nonionic polymer compound (C) is 25. Dilute and prepare to ~ 35 wt% glue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17395699A JP4053184B2 (en) | 1999-06-21 | 1999-06-21 | Glue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17395699A JP4053184B2 (en) | 1999-06-21 | 1999-06-21 | Glue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001003270A JP2001003270A (en) | 2001-01-09 |
| JP4053184B2 true JP4053184B2 (en) | 2008-02-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17395699A Expired - Fee Related JP4053184B2 (en) | 1999-06-21 | 1999-06-21 | Glue |
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| JP (1) | JP4053184B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014001469A (en) * | 2012-06-15 | 2014-01-09 | Kao Corp | Paste composition for fiber product |
| CN103696246A (en) * | 2013-12-18 | 2014-04-02 | 江苏波波熊纺织品有限公司 | Slurry for sizing of polyester fiber |
| JP6779578B2 (en) * | 2017-01-25 | 2020-11-04 | 花王株式会社 | Finishing agent composition for clothing |
| JP7051202B2 (en) * | 2017-12-08 | 2022-04-11 | 花王株式会社 | Finishing agent composition for clothing |
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| JP2001003270A (en) | 2001-01-09 |
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