JP3841164B2 - Water-soluble surfactant composition - Google Patents

Description

（式中、Ｒ¹及びＲ²はそれぞれ炭素数１〜５のアルキル基を示す。）
で表されるアセチレングリコール及び下記式（２）
【化４】

（式中、Ｒ¹及びＲ²はそれぞれ炭素数１〜５のアルキル基を示し、ｍ及びｎはそれぞれ０．５〜２５の正数であり、ｍ＋ｎは１〜４０である。）
で表されるアセチレングリコールのエトキシル化体から選ばれる１種又は２種以上 ２０〜８０重量％
（Ｂ）下記式（３）
Ｒ³Ｏ（Ｃ₃Ｈ₆Ｏ）_w（Ｃ₂Ｈ₄Ｏ）_x（Ｃ₃Ｈ₆Ｏ）_Y（Ｃ₂Ｈ₄Ｏ）_zＨ （３）
（式中、Ｒ³は炭素数１〜２０のアルキル基を示し、Ｗは１〜２０の正数であり、Ｘ、Ｙ、Ｚはそれぞれ０又は１〜２０の正数である。）
で表されるＨＬＢが９〜１８のポリオキシアルキレンアルキルエーテルの１種又は２種以上 ２０〜８０重量％
を含有し、その０．１重量％水溶液の滴下３０秒後の接触角が６０度以下、１Ｈｚ及び１０Ｈｚ時の動的表面張力がそれぞれ５０ｍＮ／ｍ以下であることを特徴とする水溶性界面活性剤組成物を提供する。
【００１３】
以下、本発明についてさらに詳しく説明する。
本発明の水溶性界面活性剤組成物の成分（Ａ）は、上述したように、下記式（１）で示されるアセチレングリコール及び下記式（２）で示されるアセチレングリコールのエトキシル化体から選ばれる１種又は２種以上のアセチレングリコール類である。
【００１４】
【化５】

（式中、Ｒ¹及びＲ²はそれぞれ炭素数１〜５のアルキル基を示し、ｍ及びｎはそれぞれ０．５〜２５の正数であり、ｍ＋ｎは１〜４０である。）
【００１５】
上記式（１）のアセチレングリコールとしては、例えば、
２，５，８，１１−テトラメチル−６−ドデシン−５，８−ジオール、
５，８−ジメチル−６−ドデシン−５，８−ジオール、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオール、
４，７−ジメチル−５−デシン−４，７−ジオール、
８−ヘキサデシン−７，１０−ジオール、
７−テトラデシン−６，９−ジオール、
２，３，６，７−テトラメチル−４−オクチン−３，６−ジオール、
３，６−ジエチル−４−オクチン−３，６−ジオール、
３，６−ジメチル−４−オクチン−３，６−ジオール、
２，５−ジメチル−３−ヘキシン−２，５−ジオール
等を挙げることができ、式（２）のアセチレングリコールのエトキシル化体としては、上記アセチレングリコールのエチレンオキサイド誘導体を挙げることができ、そのアセチレングリコール中のエチレンオキサイド単位の付加モル数は各０．５〜２５モルであり、総数は１〜４０モルである。エチレンオキサイドの付加モル数が４０モルを超えた場合、静的及び動的表面張力が大きくなり、濡れ剤としての効果がなくなる。
【００１６】
これらのアセチレングリコール類［成分（Ａ）］は、その１種を単独で又は２種以上を混合して使用することができ、本発明の界面活性剤組成物を調製する際に用いられる量は、２０〜８０重量％であり、好ましくは２５〜７５重量％である。２０重量％未満だと動的表面張力が上昇し、高速印刷時のハジキ発生の原因になるし、８０重量％を超えると水への溶解性が悪くなり、配合した際に凝集物が発生し、表面張力低下効果が得られず、ハジキが発生したり低温放置安定性が著しく低下し配合困難になる。
【００１７】
成分（Ａ）のアセチレングリコール類に配合する成分（Ｂ）のポリオキシアルキレンアルキルエーテルは、下記式（３）で表されるものである。
Ｒ³Ｏ（Ｃ₃Ｈ₆Ｏ）_w（Ｃ₂Ｈ₄Ｏ）_x（Ｃ₃Ｈ₆Ｏ）_Y（Ｃ₂Ｈ₄Ｏ）_zＨ （３）
（式中、Ｒ³は炭素数１〜２０のアルキル基を示し、Ｗは１〜２０の正数であり、Ｘ、Ｙ、Ｚはそれぞれ０又は１〜２０の正数である。）
【００１８】
この場合、Ｒ³は好ましくは炭素数５〜２０、さらに好ましくは１０〜１８のアルキル基であり、また、Ｗ＋Ｘ＋Ｙ＋Ｚは５〜３０、特に５〜２５であることが好ましい。
【００１９】
式（３）のポリオキシアルキレンアルキルエーテルとしては、式（３）で表されるポリオキシアルキレンアルキルエーテルであればよいが、具体的には、
Ｃ₁₆Ｈ₃₃Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）Ｈ、
Ｃ₁₆Ｈ₃₃Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）₁₀Ｈ、
Ｃ₁₆Ｈ₃₃Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）₂₀Ｈ、
Ｃ₁₆Ｈ₃₃Ｏ（Ｃ₃Ｈ₆Ｏ）₈（Ｃ₂Ｈ₄Ｏ）₂₀Ｈ、
Ｃ₁₀Ｈ₂₁Ｏ（Ｃ₃Ｈ₆Ｏ）₂₀Ｈ、
Ｃ₁₈Ｈ₃₇Ｏ（Ｃ₃Ｈ₆Ｏ）₂₀（Ｃ₂Ｈ₄Ｏ）_1.5Ｈ、
Ｃ₁₆Ｈ₃₃Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）₁₀（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）₁₀Ｈ、
Ｃ₁₆Ｈ₃₃Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）₁₀（Ｃ₃Ｈ₆Ｏ）₄Ｈ
等を挙げることができ、その１種を単独で又は２種以上を混合して使用することができる。尚、これら成分（Ｂ）のＨＬＢは９〜１８、特に９〜１７であることが好ましく、ＨＬＢが９未満では疎水性が増し、水への溶解度が低下し、十分な水溶性が得られなくなるし、１８を超えた場合は動的表面張力が大きいため、印刷時の滲みの原因になる。
【００２０】
本発明の界面活性剤組成物を調製する際に用いられる成分（Ｂ）の量は２０〜８０重量％であり、好ましくは２０〜７５重量％である。２０重量％未満だと成分（Ａ）のアセチレングリコール類の十分な可溶化が行われず、凝集物の発生が生じるし、８０重量％を超えると配合時の泡立ちが多くなり、吐出不良による印字不良又はピンホールやムラなどの塗工不良が発生する。
【００２１】
本発明では、上記２成分の合計が１００重量％になるように用いるのが好ましいが、さらに第三成分［成分（Ｃ）］として、イオン交換水、あるいはエチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、グリセリンなどの水溶性有機溶剤を併用しても良く、本界面活性剤組成物の特性を損なわない限り、０〜２５重量％、好ましくは５〜２０重量％の量で用いることができる。
【００２２】
本発明の界面活性剤は、例えば、上記各成分をプロペラ式攪拌機などの公知の混合調製方法によって混合することにより得られる。また、常温にて固体の成分については、必要により加温して混合するものである。
【００２３】
ここで、得られた水溶性界面活性剤組成物は、その０．１重量％水溶液の接触角が６０度以下、好ましくは１０〜６０度、さらに好ましくは２５〜６０度、さらに動的表面張力が５０ｍＮ／ｍ以下、好ましくは１０〜５０ｍＮ／ｍ、さらに好ましくは２５〜５０ｍＮ／ｍであることが必要である。なお、接触角は接触角計ＣＡ−Ｄ型（協和界面科学社製）を用いて０．１重量％水溶液の滴下３０秒後の値を測定したものであり、動的表面張力はバブルプレッシャー型動的表面張力計クルスＢＰ−２（ＫＲＵＳＳ社製）を用いて０．１重量％水溶液の１Ｈｚ及び１０Ｈｚ時の値を測定したものである。
【００２４】
０．１重量％界面活性剤組成物水溶液の滴下３０秒後の接触角が６０度を超えると、インキに配合した際にハジキの発生や吸収性が悪くなるためインキの滲みが発生するし、同じく０．１重量％水溶液の１Ｈｚ及び１０Ｈｚ時の動的表面張力が５０ｍＮ／ｍを超えると、プリンターなどの印刷機で印刷などを行った際、ハジキや浸透力不足による滲みが発生する。
【００２５】
本発明の界面活性剤組成物を用いてインキを製造したり、紙コート剤の水性濡れ剤として使用する場合、インキ全量又は紙コート剤全量に対して好ましくは０．０５〜１０重量％、より好ましくは０．０５〜５重量％の添加量で使用することが望ましい。
【００２６】
【実施例】
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、例中の部及び％はそれぞれ重量部と重量％を示す。
【００２７】
［実施例１］
７０℃に加温した２，４，７，９−テトラメチル−５−デシン−４，７−ジオール（エアプロダクツ社製、商品名サーフィノール１０４）５５部をプロペラ式攪拌機付容器に投入後、攪拌しながらポリオキシアルキレンアルキルエーテル（日光ケミカルズ社製、商品名ニッコールＰＢＣ−３３、ＨＬＢ１０．５）４５部を徐々に投入混合し、２時間連続攪拌後、室温まで冷却した。冷却後、２００メッシュ濾布にて濾過し、界面活性剤組成物（以下、これをＭ−１という）を得た。
さらに、組成物Ｍ−１の０．１部をイオン交換水１００部に加え、マグネチックスタラーにて攪拌して０．１％水溶液とし、これを用いて水溶液の外観、接触角、動的表面張力、静的表面張力を測定した。その結果を表２に示す。
【００２８】
また、この界面活性剤組成物を用いて下記の配合処方によりインキ及び紙コート剤を作製し、インキ配合物の場合は、印字濃度、ドット径、印字画像の解像度、インキ吸収性を測定し、その結果を表３に、紙コート剤の場合は、ハジキ、起泡性を測定し、その結果を同じく表３に示した。
【００２９】
〈インキ配合〉
染料（商品名Ｃｉｂａｆｉｘダイレクトブラック１９、日本チバガイギー社製）５部をイオン交換水７０部にプロペラ式攪拌機で攪拌しながら徐々に添加した後、界面活性剤組成物Ｍ−１を１部、ポリエチレングリコールを１０部、グリセリンを１５部添加し、１時間攪拌して、ブラック（Ｂ）インキ（以下、このインキをイ−１という）を得た。
さらに、上記染料の代わりに、それぞれＣｉｂａｆｉｘダイレクトレッド９、Ｃｉｂａｆｉｘダイレクトブルー８６、Ｃｉｂａｆｉｘダイレクトイエロー２３を用いて上記と同様の方法により、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）インキを作製した。
【００３０】
〈紙コート剤配合〉
紙コート剤用エマルジョン（日信化学社製、商品名ビニブラン２７５０）１００部に対して界面活性剤組成物Ｍ−１を１部添加し、プロペラ式攪拌機で３０分間攪拌した後、紙コート剤（以下これをコ−１という）を得た。
【００３１】
なお、各特性の測定は下記のようにして行った。
【００３２】
《界面活性剤組成物水溶液の評価》
１）水溶液の外観
上記界面活性剤組成物の０．１％水溶液の外観、及び不溶解物の有無の確認を下記の基準により行った。
○：水溶液が透明で、不溶解物が認められない。
△：水溶液が白濁しているが、不溶解物は認められない。
×：一部不溶解物が認められる。
××：ほとんど溶解せず。
２）接触角
界面活性剤組成物の０．１％水溶液を、協和界面科学社製接触角計ＣＡ−Ｄ型を用いて、滴下３０秒後の接触角を測定した。
３）動的表面張力
ＫＲＵＳＳ社製バブルプレッシャー型動的表面張力計クルスＢＰ−２を用いて、界面活性剤組成物の０．１％水溶液の１Ｈｚ及び１０Ｈｚ時における動的表面張力を測定した。
４）静的表面張力
協和界面科学社製表面張力計ＥＳＢ−Ｖ型を用いて、界面活性剤組成物の０．１％水溶液の静的な表面張力を測定した。
【００３３】
《インキの評価》
１）印字濃度
キャノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）インキを用いて印字したドットについて、サクラマイクロデンシトメーターＰＤＭ−５型（サクラ製機社製）でドットの濃度を測定した。
２）ドット径
キャノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）インキを用いて印字し、１００倍に拡大してドット径を測定した。
３）印字画像の解像度
キャノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）インキをベタ印刷し、マクベス濃度計ＲＤ−９１８型（マクベス社製）で測定した。また、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）インキについても同様の方法により測定した。
４）インキ吸収性
キャノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）インキを同時に同一場所に噴射し、１秒後に紙押さえ板でこすり、インキによる汚れを下記の基準により測定した。
○：白色部分に汚れのないもの。
△：微かに汚れるもの。
×：汚れがひどいもの。
【００３４】
《紙コート剤の評価》
１）ハジキ
日商グラビア社製印刷適正試験機（ＧＲＡＶＯ−ＰＲＯＯＦ）にて、紙コート剤を５０ｍ／分の塗工速度で塗工し、印刷面のハジキなどを目視にて下記の基準により確認した。
○：ハジキ及びピンホールが認められない。
△：一部ハジキ及びピンホールが認められる。
×：ハジキ及びピンホールが多く認められる。
２）起泡性
紙コート剤をコート剤／水＝１／２の比率で希釈し、サンプルとした。このサンプル２０ｍｌを１００ｍｌメスシリンダーに入れ、１８０回往復／分のシェーカーで１分間振盪し、振盪終了５分後の泡のｍｌ数を測定した。
【００３５】
［実施例２〜５、比較例１〜５］
実施例１と同様にして表１に示される配合物の種類及び配合量（％）で攪拌混合し、界面活性剤組成物（Ｍ−２〜Ｍ−１０）を得た。なお、実施例１については、配合物の配合量を％で再記した。
上記界面活性剤を用いて実施例１と同様にして０．１％水溶液を作り、同様にして水溶液の評価を行って、その結果を表２に示した。さらに、実施例１と同様にしてインキ（イ−２〜イ−１０）及び紙コート剤（コ−２〜コ−１０）を作製し、同様にしてインキ及び紙コート剤の評価を行って、その結果を表３に示した。
また、固体のものについては、５０℃に加温し、成分を混合した。
【００３６】
［比較例６］
界面活性剤組成物として、市販品：ダプロＷ−７７（エレメンティス・ジャパン社製商品名、サクシネート系界面活性剤）を用いて、実施例１と同様の評価を行い、その結果を表２，表３に示した。
【００３７】
【表１】

【００３８】
〈成分Ａ〉
Ｓ−８２：サーフィノール８２（エアプロダクツ社製商品名、３，６−ジメチル−４−オクチン−３，６−ジオール）
Ｓ−１０４：サーフィノール１０４（エアプロダクツ社製商品名、２，４，７，９−テトラメチル−５−デシン−４，７−ジオール）
Ｓ−４４０：サーフィノール４４０（エアプロダクツ社製商品名、２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体、エチレンオキサイドの付加モル数３．５）
Ｓ−４６５：サーフィノール４６５（エアプロダクツ社製商品名、２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体、エチレンオキサイドの付加モル数１０）
ＤＦ−１１０：サーフィノールＤＦ−１１０（エアプロダクツ社製商品名、２，５，８，１１−テトラメチル−６−ドデシン−５，８−ジオール）
【００３９】
〈成分Ｂ〉
ＮＰ−１：ニッコールＰＢＣ−３３（日光ケミカルズ社製商品名、ＣＨ₃（ＣＨ₂）₁₄ＣＨ₂Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）₁₀Ｈ、ＨＬＢ１０．５）
ＮＰ−２：ニッコールＰＢＣ−３１（日光ケミカルズ社製商品名、ＣＨ₃（ＣＨ₂）₁₄ＣＨ₂Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）Ｈ、ＨＬＢ９．５）
ＮＰ−３：ニッコールＰＢＣ−３４（日光ケミカルズ社製商品名、ＣＨ₃（ＣＨ₂）₁₄ＣＨ₂Ｏ（Ｃ₃Ｈ₆Ｏ）₄（Ｃ₂Ｈ₄Ｏ）₂₀Ｈ、ＨＬＢ１６．５）
ＮＰ−４：ニッコールＰＥＮ４６１２（日光ケミカルズ社製商品名、Ｃ₂₄Ｈ₄₉Ｏ（Ｃ₃Ｈ₆Ｏ）₆（Ｃ₂Ｈ₄Ｏ）₁₂Ｈ、ＨＬＢ８．５）
ＮＰ−５：ニッコールＰＥＮ４６２０（日光ケミカルズ社製商品名、Ｃ₂₄Ｈ₄₉Ｏ（Ｃ₃Ｈ₆Ｏ）₆（Ｃ₂Ｈ₄Ｏ）₂₀Ｈ、ＨＬＢ１１．０）
ＮＰ−６：ニッコールＰＥＮ４６３０（日光ケミカルズ社製商品名、Ｃ₂₄Ｈ₄₉Ｏ（Ｃ₃Ｈ₆Ｏ）₆（Ｃ₂Ｈ₄Ｏ）₃₀Ｈ、ＨＬＢ１２．０）
【００４０】
【表２】

市販品：ダプロＷ−７７（エレメンティス・ジャパン社製商品名、サクシネート系界面活性剤）
【００４１】
【表３】

【００４２】
【発明の効果】
本発明の水溶性界面活性剤組成物は、滴下直後の接触角が小さく、動的表面張力も低いため、インキなどに添加した際、基材への濡れ性、浸透性及び消泡性を発揮し、高速印刷及び高速塗工にも対応でき、しかも環境問題にも適合した優れた界面活性剤組成物である。この特性により、本発明の水溶性界面活性剤は実用的に極めて有利である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a water-soluble surfactant composition, and particularly exhibits excellent wettability, penetrability and antifoaming property when blended in an ink or paper coating agent because of its low dynamic surface tension. In addition, the present invention relates to a water-soluble surfactant composition that can cope with high-speed printing and high-speed coating, and is also suitable for recent environmental problems.
[0002]
[Prior art and problems to be solved by the invention]
In recent years, the ratio of recording methods using water-based ink has been increasing in printers for office automation equipment such as personal computers, and the demand for ink has been increasing along with that. On the other hand, print quality, saturation, In order to further improve the appearance and image, inks having higher properties have been demanded.
[0003]
Also in the printing industry and the papermaking industry, it is always necessary to cope with the high speed accompanying the improvement of productivity, and the performance improvement of ink and paper coating agent corresponding to high speed printing and high speed coating is required.
[0004]
Against this background, the ink and water-based paint industries require a surfactant that imparts excellent surface tension lowering ability for wetting and penetrating the substrate. When a surfactant is selected, the static surface tension is low when the system is in a static state, and the dynamic surface tension is high when used at a high speed due to the necessity of increasing the printing speed due to the aforementioned productivity improvement. Low is very important.
[0005]
Acetylene glycol-based surfactants such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol and ethoxylated derivatives thereof have the ability to reduce static surface tension and dynamic surface tension. As it is balanced, it has almost no negative points of conventional nonionic and anionic surfactants, and also has antifoaming properties, so as a wetting agent for inks, paints, dispersion aids, etc. Have been used.
[0006]
However, since acetylene glycol surfactants have low solubility in water or have problems such as solids at room temperature, polyethylene glycol or polyoxyethylene nonylphenyl ether is used in combination as a solubilizing agent. And self-emulsifying property when added to paper coating agents.
[0007]
Japanese Patent Application Laid-Open No. 2000-290549 describes an example in which polyethylene glycol or the like is used in combination with an acetylene glycol surfactant for water-based ink. However, it is possible to use a method such as dissolving or dispersing both in advance. Polyethylene glycol used as a solubilizing agent was extracted into water, and there was a problem that aggregates of acetylene glycol surfactants were generated.
[0008]
Due to environmental issues in recent years, the use of PRTR substances and environmental hormone-related substances is feared, and legal regulations are becoming stricter. Under such circumstances, there is a need for environmentally friendly surfactants. And many companies offer alternatives to polyoxyethylene nonylphenyl ether.
[0009]
However, some of these alternatives have the same static surface tension, but have a large effect on the dynamic surface tension and a large contact angle. As a solubilizer for acetylene glycol surfactants When blended, the same performance as the conventional product was not necessarily obtained.
[0010]
The present invention was made in order to improve the above circumstances, and has a low dynamic surface tension, and therefore exhibits excellent wettability, penetration and defoaming to the substrate during printing or coating. An object of the present invention is to provide a water-soluble surfactant composition that can be used for high-speed printing and that is also water soluble and environmentally friendly.
[0011]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used an acetylene glycol surfactant and a polyoxyalkylene alkyl ether in the range of a specific HLB to obtain an ink or paper coat. When used as an additive, it has excellent wettability, permeability, and defoaming properties due to low dynamic surface tension, and is suitable for environmental problems. It has been found that it has been obtained, and has led to the invention.
[0012]
That is, the present invention
(A) The following formula (1)
[Chemical 3]

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms.)
And acetylene glycol represented by the following formula (2):
[Formula 4]

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number of 0.5 to 25, and m + n is 1 to 40.)
One or more selected from ethoxylated acetylene glycol represented by the formula: 20 to 80% by weight
(B) Following formula (3)
R ³ O (C ₃ H ₆ O) _w (C ₂ H ₄ O) _x (C ₃ H ₆ O) _Y (C ₂ H ₄ O) _z H (3)
(In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, W is a positive number of 1 to 20, and X, Y, and Z are each 0 or a positive number of 1 to 20).
One or more polyoxyalkylene alkyl ethers having an HLB of 9 to 18 represented by 20 to 80% by weight
A water-soluble surfactant having a contact angle after 60 seconds of dropping a 0.1% by weight aqueous solution thereof of 60 ° or less and dynamic surface tension at 1 Hz and 10 Hz of 50 mN / m or less, respectively. An agent composition is provided.
[0013]
Hereinafter, the present invention will be described in more detail.
As described above, the component (A) of the water-soluble surfactant composition of the present invention is selected from acetylene glycol represented by the following formula (1) and ethoxylated acetylene glycol represented by the following formula (2). One or more acetylene glycols.
[0014]
[Chemical formula 5]

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number of 0.5 to 25, and m + n is 1 to 40.)
[0015]
As the acetylene glycol of the above formula (1), for example,
2,5,8,11-tetramethyl-6-dodecin-5,8-diol,
5,8-dimethyl-6-dodecin-5,8-diol,
2,4,7,9-tetramethyl-5-decyne-4,7-diol,
4,7-dimethyl-5-decyne-4,7-diol,
8-hexadecine-7,10-diol,
7-tetradecine-6,9-diol,
2,3,6,7-tetramethyl-4-octyne-3,6-diol,
3,6-diethyl-4-octyne-3,6-diol,
3,6-dimethyl-4-octyne-3,6-diol,
2,5-dimethyl-3-hexyne-2,5-diol and the like, and the ethoxylated form of acetylene glycol represented by the formula (2) can include the ethylene oxide derivative of acetylene glycol. The number of moles of ethylene oxide units added in acetylene glycol is 0.5 to 25 moles each, and the total number is 1 to 40 moles. When the added mole number of ethylene oxide exceeds 40 moles, static and dynamic surface tensions are increased, and the effect as a wetting agent is lost.
[0016]
These acetylene glycols [component (A)] can be used alone or in admixture of two or more, and the amount used when preparing the surfactant composition of the present invention is as follows. It is 20 to 80% by weight, preferably 25 to 75% by weight. If it is less than 20% by weight, the dynamic surface tension will increase, causing repelling during high-speed printing, and if it exceeds 80% by weight, the solubility in water will be poor, and aggregates will be generated when blended. The effect of lowering the surface tension cannot be obtained, repelling occurs, the low-temperature storage stability is remarkably lowered, and the blending becomes difficult.
[0017]
The polyoxyalkylene alkyl ether of component (B) to be blended with the acetylene glycols of component (A) is represented by the following formula (3).
R ³ O (C ₃ H ₆ O) _w (C ₂ H ₄ O) _x (C ₃ H ₆ O) _Y (C ₂ H ₄ O) _z H (3)
(In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, W is a positive number of 1 to 20, and X, Y, and Z are each 0 or a positive number of 1 to 20).
[0018]
In this case, R ³ is preferably an alkyl group having 5 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, and W + X + Y + Z is preferably 5 to 30, particularly 5 to 25.
[0019]
The polyoxyalkylene alkyl ether of the formula (3) may be any polyoxyalkylene alkyl ether represented by the formula (3). Specifically,
C ₁₆ H ₃₃ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) H,
C ₁₆ H ₃₃ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₀ H,
C ₁₆ H ₃₃ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₂₀ H,
C ₁₆ H ₃₃ O (C ₃ H ₆ O) ₈ (C ₂ H ₄ O) ₂₀ H,
C ₁₀ H ₂₁ O (C ₃ H ₆ O) ₂₀ H,
C ₁₈ H ₃₇ O (C ₃ H ₆ O) ₂₀ (C ₂ H ₄ O) _1.5 H,
C ₁₆ H ₃₃ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₀ (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₀ H,
C ₁₆ H ₃₃ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₀ (C ₃ H ₆ O) ₄ H
1 type can be used individually or in mixture of 2 or more types. In addition, it is preferable that HLB of these components (B) is 9 to 18, particularly 9 to 17. When HLB is less than 9, the hydrophobicity increases, the solubility in water decreases, and sufficient water solubility cannot be obtained. However, if it exceeds 18, the dynamic surface tension is large, which causes bleeding during printing.
[0020]
The amount of the component (B) used in preparing the surfactant composition of the present invention is 20 to 80% by weight, preferably 20 to 75% by weight. If it is less than 20% by weight, the acetylene glycols of the component (A) are not sufficiently solubilized and aggregates are generated. If it exceeds 80% by weight, foaming at the time of blending increases, resulting in poor printing due to ejection failure. Or coating defects such as pinholes and unevenness occur.
[0021]
In the present invention, the total of the two components is preferably 100% by weight. However, as the third component [component (C)], ion-exchanged water or ethylene glycol, diethylene glycol, triethylene glycol, tetra Water-soluble organic solvents such as ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, and glycerin may be used in combination. Unless damaged, it can be used in an amount of 0 to 25% by weight, preferably 5 to 20% by weight.
[0022]
The surfactant of the present invention can be obtained, for example, by mixing the above components by a known mixing preparation method such as a propeller type stirrer. Moreover, about a solid component at normal temperature, it heats and mixes as needed.
[0023]
Here, the obtained water-soluble surfactant composition has a contact angle of its 0.1% by weight aqueous solution of 60 degrees or less, preferably 10 to 60 degrees, more preferably 25 to 60 degrees, and further dynamic surface tension. Is 50 mN / m or less, preferably 10 to 50 mN / m, more preferably 25 to 50 mN / m. The contact angle is a value measured 30 seconds after dropping a 0.1 wt% aqueous solution using a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.), and the dynamic surface tension is a bubble pressure type. The value at 1 Hz and 10 Hz of a 0.1 wt% aqueous solution was measured using a dynamic surface tension meter Cruz BP-2 (manufactured by KRUS).
[0024]
If the contact angle after 30 seconds of dropping of the 0.1% by weight aqueous surfactant composition solution exceeds 60 degrees, the ink bleeds and absorbability worsens when blended into the ink, Similarly, when the dynamic surface tension of a 0.1 wt% aqueous solution at 1 Hz and 10 Hz exceeds 50 mN / m, bleeding due to repelling or insufficient penetration occurs when printing is performed with a printing machine such as a printer.
[0025]
When an ink is produced using the surfactant composition of the present invention or used as an aqueous wetting agent for a paper coating agent, it is preferably 0.05 to 10% by weight based on the total amount of ink or the total amount of paper coating agent. It is desirable to use it in an addition amount of 0.05 to 5% by weight.
[0026]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the part and% in an example show a weight part and weight%, respectively.
[0027]
[Example 1]
After charging 55 parts of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (trade name Surfinol 104, manufactured by Air Products) into a vessel equipped with a propeller type stirrer, While stirring, 45 parts of polyoxyalkylene alkyl ether (manufactured by Nikko Chemicals, trade name Nikkor PBC-33, HLB10.5) was gradually added and mixed, and after continuous stirring for 2 hours, it was cooled to room temperature. After cooling, the mixture was filtered through a 200 mesh filter cloth to obtain a surfactant composition (hereinafter referred to as M-1).
Further, 0.1 part of the composition M-1 was added to 100 parts of ion-exchanged water, and stirred with a magnetic stirrer to make a 0.1% aqueous solution. Using this, the appearance of the aqueous solution, the contact angle, the dynamic surface Tension and static surface tension were measured. The results are shown in Table 2.
[0028]
In addition, using this surfactant composition, an ink and a paper coating agent are prepared by the following formulation, and in the case of an ink formulation, the print density, the dot diameter, the resolution of the printed image, and the ink absorptivity are measured, The results are shown in Table 3. In the case of a paper coating agent, repellency and foaming properties were measured, and the results are also shown in Table 3.
[0029]
<Ink formulation>
After gradually adding 5 parts of a dye (trade name Cibafix Direct Black 19, manufactured by Ciba Geigy Japan Co., Ltd.) to 70 parts of ion-exchanged water while stirring with a propeller-type stirrer, 1 part of surfactant composition M-1 and polyethylene glycol 10 parts and glycerin 15 parts were added and stirred for 1 hour to obtain a black (B) ink (hereinafter, this ink is referred to as A-1).
Further, magenta (M), cyan (C), and yellow (Y) inks were prepared in the same manner as described above using Cibafix Direct Red 9, Cibafix Direct Blue 86, and Cibafix Direct Yellow 23 instead of the above dyes. did.
[0030]
<Containing paper coating agent>
One part of the surfactant composition M-1 is added to 100 parts of an emulsion for paper coating (manufactured by Nissin Chemical Co., Ltd., trade name Vinibrand 2750), and stirred for 30 minutes with a propeller-type stirrer. This is hereinafter referred to as co-1).
[0031]
Each characteristic was measured as follows.
[0032]
<< Evaluation of Surfactant Composition Aqueous Solution >>
1) Appearance of aqueous solution The appearance of a 0.1% aqueous solution of the surfactant composition and the presence or absence of insoluble matter were confirmed according to the following criteria.
○: The aqueous solution is transparent, and no insoluble matter is observed.
(Triangle | delta): Although aqueous solution is cloudy, an insoluble matter is not recognized.
X: A partly insoluble matter is recognized.
XX: hardly dissolved.
2) Contact angle The contact angle 30 seconds after dripping was measured for the 0.1% aqueous solution of surfactant composition using Kyowa Interface Science Co., Ltd. contact angle meter CA-D type.
3) Dynamic surface tension The dynamic surface tension at 1 Hz and 10 Hz of a 0.1% aqueous solution of the surfactant composition was measured using a bubble pressure type dynamic surface tension meter Cruz BP-2 manufactured by KRUS.
4) Static surface tension Static surface tension of a 0.1% aqueous solution of the surfactant composition was measured using a surface tension meter ESB-V type manufactured by Kyowa Interface Science Co., Ltd.
[0033]
<Evaluation of ink>
1) Print density For the dots printed with the Canon printer BJC455J using black (B) ink, the density of the dots was measured with a Sakura Microdensitometer PDM-5 (manufactured by Sakura Kikai Co., Ltd.).
2) Dot diameter Printing was performed with a Canon printer BJC455J using black (B) ink, and the dot diameter was measured by enlarging 100 times.
3) Resolution of printed image Black (B) ink was solid-printed with a Canon printer BJC455J and measured with a Macbeth densitometer RD-918 (manufactured by Macbeth). Further, magenta (M), cyan (C), and yellow (Y) inks were measured by the same method.
4) Black (B), magenta (M), cyan (C), and yellow (Y) inks are jetted simultaneously to the same location with an ink-absorbing Canon printer BJC455J, and rubbed with a paper presser plate after 1 second to remove stains from the ink. Measurement was performed according to the following criteria.
○: The white portion is not soiled.
Δ: Slightly dirty.
X: A thing with severe dirt.
[0034]
<Evaluation of paper coating agent>
1) Using a printing suitability tester (GRAVO-PROOF) manufactured by Hajiki Nissho Gravure Co., Ltd., coat the paper coating agent at a coating speed of 50 m / min. did.
○: No repelling or pinholes are observed.
Δ: Partial repelling and pinholes are observed.
X: Many repelling and pinholes are recognized.
2) A foamable paper coating agent was diluted at a ratio of coating agent / water = 1/2 to prepare a sample. 20 ml of this sample was placed in a 100 ml graduated cylinder, shaken for 1 minute with a shaker 180 times / minute, and the number of ml of foam 5 minutes after the end of shaking was measured.
[0035]
[Examples 2 to 5, Comparative Examples 1 to 5]
The surfactant composition (M-2 to M-10) was obtained by stirring and mixing in the same manner as in Example 1 with the types and amounts (%) of the formulations shown in Table 1. In addition, about Example 1, the compounding quantity of the compound was rewritten in%.
Using the surfactant, a 0.1% aqueous solution was prepared in the same manner as in Example 1, and the aqueous solution was evaluated in the same manner. The results are shown in Table 2. Further, ink (I-2 to i-10) and paper coating agent (co-2 to co-10) were prepared in the same manner as in Example 1, and the ink and paper coating agent were evaluated in the same manner. The results are shown in Table 3.
Moreover, about the solid thing, it heated at 50 degreeC and mixed the component.
[0036]
[Comparative Example 6]
As a surfactant composition, a commercial product: Dapro W-77 (trade name, manufactured by Elementis Japan, succinate surfactant) was used for the same evaluation as in Example 1, and the results are shown in Table 2. It is shown in Table 3.
[0037]
[Table 1]

[0038]
<Component A>
S-82: Surfinol 82 (trade name, 3,6-dimethyl-4-octyne-3,6-diol, manufactured by Air Products)
S-104: Surfynol 104 (trade name, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, manufactured by Air Products)
S-440: Surfynol 440 (trade name, manufactured by Air Products, ethoxylated form of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, number of moles of ethylene oxide added 3.5)
S-465: Surfynol 465 (trade name, manufactured by Air Products, ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol, number of moles of ethylene oxide added 10)
DF-110: Surfynol DF-110 (trade name, 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, manufactured by Air Products)
[0039]
<Component B>
NP-1: Nikkor PBC-33 (trade name, manufactured by Nikko Chemicals, CH ₃ (CH ₂ ) ₁₄ CH ₂ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₀ H, HLB 10.5)
NP-2: Nikkor PBC-31 (trade name, manufactured by Nikko Chemicals, CH ₃ (CH ₂ ) ₁₄ CH ₂ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) H, HLB 9.5)
NP-3: Nikkor PBC-34 (trade name, manufactured by Nikko Chemicals, CH ₃ (CH ₂ ) ₁₄ CH ₂ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₂₀ H, HLB 16.5)
NP-4: Nikkor PEN4612 (Nikko Chemicals Co., trade _{name, C 24 H 49 O (C} 3 H 6 O) 6 (C 2 H 4 O) 12 H, HLB8.5)
NP-5: Nikkor PEN 4620 (trade name, manufactured by Nikko Chemicals, C ₂₄ H ₄₉ O (C ₃ H ₆ O) ₆ (C ₂ H ₄ O) ₂₀ H, HLB 11.0)
NP-6: Nikkor PEN 4630 (trade name, manufactured by Nikko Chemicals, C ₂₄ H ₄₉ O (C ₃ H ₆ O) ₆ (C ₂ H ₄ O) ₃₀ H, HLB 12.0)
[0040]
[Table 2]

Commercial product: Dapro W-77 (trade name, succinate surfactant, manufactured by Elementis Japan)
[0041]
[Table 3]

[0042]
【The invention's effect】
Since the water-soluble surfactant composition of the present invention has a small contact angle immediately after dropping and low dynamic surface tension, it exhibits wettability, penetrability and antifoaming property when added to ink. In addition, it is an excellent surfactant composition that can cope with high-speed printing and high-speed coating, and is also suitable for environmental problems. Due to this characteristic, the water-soluble surfactant of the present invention is extremely advantageous practically.

Claims (1)

(A) The following formula (1)

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms.)
And acetylene glycol represented by the following formula (2):

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number of 0.5 to 25, and m + n is 1 to 40.)
One or two or more selected from ethoxylated acetylene glycol represented by the formula: 20 to 80% by weight
(B) Following formula (3)
R ³ O (C ₃ H ₆ O) _w (C ₂ H ₄ O) _x (C ₃ H ₆ O) _Y (C ₂ H ₄ O) _z H (3)
(In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, W is a positive number of 1 to 20, and X, Y, and Z are each 0 or a positive number of 1 to 20).
One or more polyoxyalkylene alkyl ethers having an HLB of 9 to 18 represented by 20 to 80% by weight
A water-soluble surfactant having a contact angle after 60 seconds of dropping a 0.1% by weight aqueous solution thereof of 60 ° or less and dynamic surface tension at 1 Hz and 10 Hz of 50 mN / m or less, respectively. Agent composition.