JP4096044B2 - Emulsion type antifoaming agent - Google Patents

Description

【００７３】
スルホン化ポリスチレンのアルカリ金属塩としては、商品名：ケミスタットＳＡ−９（三洋化成工業株式会社製）等が挙げられる。
スルホ基含有ポリビニルアルコールとしては、商品名：ゴーセラン Ｌ−３２６６（日本合成化学工業株式会社製）、クラレポバールＳＫ−５１０２（株式会社クラレ製）」等が挙げられる。
【００７４】
カルボキシ基含有（共）重合体（ｄ３）としては、ポリ（メタ）アクリル酸及び（メタ）アクリル酸−マレイン酸共重合体｛（メタ）アクリル酸：マレイン酸の重量比９９〜７０：１〜３０｝等が挙げられる。なお、（メタ）アクリル酸は、アクリル酸及び／又はメタクリル酸を意味する。（ｄ３）としては、商品名：ノプコサントＲ、ＳＮディスパーサント５０３４、ＳＮシックナー９２０、ＳＮシックナー９２４、ＳＮシックナー９２６、ＳＮシックナー９２８及びＳＮシックナー９２９（サンノプコ株式会社製）等が挙げられる。
【００７５】
カルバモイル基含有（共）重合体（ｄ４）としては、ポリ（メタ）アクリルアミド及び（メタ）アクリル酸−（メタ）アクリルアミド共重合体｛（メタ）アクリル酸：（メタ）アクリルアミドの重量比１０〜５０：９０〜５０｝等が挙げられる。（ｄ４）としては、商品名：サンフロックＮＯＰ、サンフロックＡＨ−２００Ｐ及びサンフロックＡＨ−３３０Ｐ（三洋化成工業株式会社製）等が挙げられる。
【００７６】
ヒドロキシ基含有（共）重合体（ｄ５）としては、部分ケン化ポリビニルアルコール及び完全ケン化ポリビニルアルコール等が挙げられる。（ｄ５）としては、商品名：クラレポバールＰＶＡ−２０３、同ＰＶＡ−２０５、同ＰＶＡ−２１７、同ＰＶＡ−２２４、同ＰＶＡ−２２８、同ＰＶＡ−２３５、同ＰＶＡ−４２４Ｈ（以上、部分ケン化ポリビニルアルコール）、クラレポバールＰＶＡ−１０５、同ＰＶＡ−１１７、同ＰＶＡ−１２４、同ＰＶＡ−１２６Ｈ（以上、完全ケン化ポリビニルアルコール）（株式会社クラレ製）等が挙げられる。
【００７７】
天然水溶性高分子（Ｄ２）としては、プルラン、アラビアガム、グアーガム、グルコマンナン、キサンタンガム、トラガントガム、ローカストビーンガム、アガロース、グリコーゲン、アルギン酸ナトリウム及びセルロース等が挙げられる。
半合成水溶性高分子（Ｄ３）としては、天然水溶性高分子を化学修飾したもの等が使用でき、セルロース変性体（ヒドロキシメチルセルロース、ヒドロキエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキエチルメチルセルロース、カルボキシメチルセルロース、カルボキシエチルメチルセルロース、メチルセルロース、エチルセルロース及び酢酸フタル酸セルロース等）及びデンプン変性体（酸化デンプン等）等が挙げられる。
【００７８】
合成水溶性高分子（Ｄ１）と、天然水溶性高分子又は／及び半合成水溶性高分子（Ｄ２）との組合せのうち、オキシエチレン基含有（共）重合体（ｄ１）と天然水溶性高分子（Ｄ２）との組合せ、オキシエチレン基含有（共）重合体（ｄ１）と半合成水溶性高分子（Ｄ３）との組合せ、スルホ基含有（共）重合体（ｄ２）と天然水溶性高分子（Ｄ２）との組合せ、スルホ基含有（共）重合体（ｄ２）と半合成水溶性高分子（Ｄ３）との組合せ、カルボキシ基含有（共）重合体（ｄ３）と天然水溶性高分子（Ｄ２）との組合せ、カルボキシ基含有（共）重合体（ｄ３）と半合成水溶性高分子（Ｄ３）との組合せ、カルバモイル基含有（共）重合体（ｄ４）と天然水溶性高分子（Ｄ２）との組合せ、ヒドロキシ基含有（共）重合体（ｄ５）と天然水溶性高分子（Ｄ２）との組合せ、及びヒドロキシ基含有（共）重合体（ｄ５）と半合成水溶性高分子（Ｄ３）との組合せが好ましく、さらに好ましくは（ｄ１）と（Ｄ２）との組合せ、（ｄ２）と（Ｄ２）との組合せ、（ｄ３）と（Ｄ２）との組合せ、（ｄ４）と（Ｄ２）との組合せ、及び（ｄ５）と（Ｄ２）との組合せ、特に好ましくは（ｄ１）と（Ｄ２）との組合せ、及び（ｄ２）と（Ｄ２）との組合せ、最も好ましくは（ｄ２）と（Ｄ２）との組合せである。
【００７９】
合成水溶性高分子（Ｄ１）と、天然水溶性高分子（Ｄ２）及び／又は半合成水溶性高分子（Ｄ３）の含有重量比率｛Ｄ１／（Ｄ２＋Ｄ３）｝は、０．０１〜９９が好ましく、さらに好ましくは０．６〜９、特に好ましくは１．５〜４である。すなわち、含有重量比率｛Ｄ１／（Ｄ２＋Ｄ３）｝は、０．０１以上が好ましく、さらに好ましくは０．６以上、特に好ましくは１．５以上であり、また９９以下が好ましく、さらに好ましくは９以下、特に好ましくは４以下である。この範囲であると、さらに適度な増粘作用を発揮し、本発明の消泡剤の安定性をさらに増すことができる。
【００８０】
天然水溶性高分子（Ｄ２）及び半合成水溶性高分子（Ｄ３）を含有する場合、（Ｄ２）及び（Ｄ３）の含有重量比率（Ｄ２／Ｄ３）は、０．０１〜９９が好ましく、さらに好ましくは０．６〜９、特に好ましくは１．５〜４である。すなわち、この場合、含有重量比率（Ｄ２／Ｄ３）は、０．０１以上が好ましく、さらに好ましくは０．６以上、特に好ましくは１．５以上であり、また、９９以下が好ましく、さらに好ましくは９以下、特に好ましくは４以下である。この範囲であると、さらに適度な増粘作用を発揮し、本発明の消泡剤の安定性をさらに増すことができる。
【００８１】
次に水（Ｅ）について説明する。
水（Ｅ）としては、蒸留水、イオン交換水、水道水、工業用水、井戸水、涌き水、河川水及び雨水等が使用できるが、イオン交換水、水道水及び工業用水等の軟水が好ましい。
【００８２】
脂肪酸部分エステル（Ａ）の含有量（重量％）は、（Ａ）、ポリオキシアルキレン化合物（Ｂ）、乳化剤（Ｃ）、増粘剤（Ｄ）及び水（Ｅ）の合計重量に基づいて、２０〜３０が好ましく、さらに好ましくは２１〜２９、特に好ましくは２２〜２８である。すなわち、（Ａ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、２０以上が好ましく、さらに好ましくは２１以上、特に好ましくは２２以上であり、また３０以下が好ましく、さらに好ましくは２９以下、特に好ましくは２８以下である。この範囲であると、消泡性能及び流動性がさらに良好となる。
【００８３】
ポリオキシアルキレン化合物（Ｂ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、４〜１０が好ましく、さらに好ましくは５〜９、特に好ましくは６〜８である。すなわち、（Ｂ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、４以上が好ましく、さらに好ましくは５以上、特に好ましくは６以上であり、また１０以下が好ましく、さらに好ましくは９以下、特に好ましくは８以下である。この範囲であると、粘度、消泡性能及び本発明の消泡剤が添加される被添加物の耐水性がさらに良好となる。
【００８４】
乳化剤（Ｃ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、０．３〜５が好ましく、さらに好ましくは０．４〜４、特に好ましくは０．５〜３である。すなわち、（Ｃ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、０．３以上が好ましく、さらに好ましくは０．４以上、特に好ましくは０．５以上であり、また、５以下が好ましく、さらに好ましくは４以下、特に好ましくは３以下である。この範囲であると、粘度及び消泡性能がさらに良好となる。
【００８５】
増粘剤（Ｄ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、０．０１〜５が好ましく、さらに好ましくは０．１〜４、特に好ましくは０．５〜３である。すなわち、（Ｄ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、０．０１以上が好ましく、さらに好ましくは０．１以上、特に好ましくは０．５以上であり、５以下が好ましく、さらに好ましくは４以下、特に好ましくは３以下である。この範囲であると、粘度及び安定性がさらに良好となる。
【００８６】
水（Ｅ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、５０〜７５が好ましく、さらに好ましくは５５〜７３、特に好ましくは６０〜７０である。すなわち、（Ｅ）の含有量（重量％）は、（Ａ）〜（Ｅ）の合計重量に基づいて、５０以上が好ましく、さらに好ましくは５５以上、特に好ましくは６０以上であり、また、７５以下が好ましく、さらに好ましくは７３以下、特に好ましくは７０以下である。この範囲であると、粘度及び安定性がさらに良好となる。
【００８７】
本発明のエマルション型消泡剤には、無機化合物及び／又は有機化合物からなる緩衝剤（Ｆ）を含ませることができる。緩衝剤（Ｆ）は、本発明のエマルション型消泡剤のｐＨを６．０〜８．５に調整することができ、このｐＨであると、本発明のエマルション型消泡剤の分解を抑制することができる。
無機化合物としては、リン酸水素二ナトリウム、リン酸二水素カリウム、水酸化ナトリウム、塩酸、塩化カリウム及びほう酸等が挙げられる。
有機化合物としては、トリス（ヒドロキシメチル）アミノメタン及びフタル酸水素カリウム等が挙げられる。
【００８８】
緩衝剤（Ｆ）を使用する場合、通常、水（Ｅ）に溶解させて、水（Ｅ）と同じように扱うことが好ましい。緩衝剤（Ｆ）のｐＨとしては、例えば、リン酸二水素カリウム及び水酸化ナトリウムから作成される緩衝水溶液、並びにリン酸水素二ナトリウム及び水酸化ナトリウムから作成される緩衝水溶液を使用すると、ｐＨを６．０〜８．５にすることができる。
【００８９】
市場から入手できる緩衝剤としては、Ｃｌａｒｋ−Ｌｕｂｓの緩衝液（ｐＨ：１．０〜１０．０）、Ｋｏｌｔｈｏｆｆの緩衝液（ｐＨ：２．２〜１２．０）、Ｍｉｃｈａｅｌｉｓの緩衝液（ｐＨ：１．４〜１１．０）、Ｇｏｍｏｒｉの緩衝液（ｐＨ：６．４〜９．７）及びＢａｔｅｓ−ＢｏｗｅｒのＴｒｉｓ緩衝液（ｐＨ：７．０〜９．０）等が挙げられる。
【００９０】
緩衝剤（Ｆ）を使用する場合、この含有量（重量％）は、水（Ｅ）の重量に基づいて、０．０１〜３．０が好ましく、さらに好ましくは０．０５〜２．５、特に好ましくは０．１〜２．０である。すなわち、この場合、（Ｆ）の含有量（重量％）は、水（Ｅ）の重量に基づいて、０．０１以上が好ましく、さらに好ましくは０．０５以上、特に好ましくは０．１以上であり、また、３．０以下が好ましく、さらに好ましくは２．５以下、特に好ましくは２．０以下である。この範囲であると、さらに良好なｐＨに調製しやすい。
【００９１】
本発明のエマルション型消泡剤は、必要に応じてさらに、その他の成分を含有させることができる。
その他の成分としては、脂肪酸及びこの塩、アミド、動植物油、炭化水素油、シリコーン、疎水性シリカ及び親水性シリカの他、防黴剤、防腐剤、防錆剤、酸化防止剤及び皮張り防止剤等が含まれる。
【００９２】
脂肪酸としては、直鎖飽和脂肪酸及び直鎖不飽和脂肪酸等が含まれ、上記のもの等が使用でき、好ましい範囲も同じである。この塩としては、上記の直鎖飽和脂肪酸、直鎖モノ不飽和脂肪酸、又はジ−若しくはトリ−不飽和脂肪酸のアンモニウム塩、ナトリウム塩、カルシウム塩、マグネシウム塩、アルミニウム塩、モノエタノールアミン塩及びジエタノールアミン塩等が挙げられる。アミドとしては、脂肪酸モノアミド及び脂肪酸ジアミド等が含まれる。脂肪酸モノアミドとしては、炭素数１９〜４４の脂肪酸モノアミド等が使用でき、ステアリン酸ラウリルモノアミド、オレイン酸ラウリルモノアミド、ステアリン酸オレイルモノアミド及びオレイン酸オレイルモノアミド等が挙げられる。脂肪酸ジアミドとしては、炭素数２６〜４６の脂肪酸ジアミド等が使用でき、Ｎ，Ｎ’−エチレンビスステアリン酸アミド、Ｎ，Ｎ’−エチレンビスオレイン酸アミド及びＮ，Ｎ’−エチレンビスラウリン酸アミド等が挙げられる。動植物油としては、天然植物油、天然動物油及びこれらの変性油等が使用でき、牛脂、豚脂、鯨油、魚油、菜種油、大豆油、落花生油及びこれらの水素添加油等が挙げられる。炭化水素油としては、４０℃の動粘度（ｍｍ²／ｓ）が５〜４０である鉱物油等が使用でき、スタノール３５（エッソ石油株式会社）及びＭＣオイルＰ２２（出光興産株式会社）等が挙げられる。シリコーンとしては、２５℃の動粘度（ｍｍ²／ｓ）が５０〜１０，０００であるジメチルポリシロキサン及び変性ジメチルポリシロキサン等が使用でき、変性ジメチルポリシロキサンとしては、ＳＨ２００−１００ＣＳ（東レ・ダウコーニング・シリコーン株式会社）、ＳＨ２００−１０００ＣＳ（東レ・ダウコーニング・シリコーン株式会社）及びＳＨ２００−５０００ＣＳ（東レ・ダウコーニング・シリコーン株式会社）等が挙げられる。疎水性シリカとしては、二酸化ケイ素を疎水化剤で処理して得られるシリカを意味する。疎水化剤としては、炭素数１２〜２４の脂肪酸（ステアリン酸等）、炭素数１２〜３６の高級アルコール（ステアリルアルコール等）、炭素数１２〜２２の脂肪族アミン（ステアリルアミン等）、炭素数２４〜３６の脂肪酸アミド（オレイン酸ラウリルモノアミド、Ｎ，Ｎ’−エチレンビスステアリルアミド等）及びシリコーン（ポリジメチルシロキサン及びアルキル基変性ポリポリジメチルシロキサン、水酸基変性ポリポリジメチルシロキサン、アミノ基変性ポリポリジメチルシロキサン及びアルキル基変性ハイドロジエンポリジメチルシロキサン等の反応性シリコーン等）等が用いられる。二酸化ケイ素としては、沈殿法で製造したシリカ、ゲル法で製造したシリカ、乾式法で製造したシリカ等が用いられる。二酸化ケイ素の粒子径（μｍ）は０．１〜１０が好ましく、さらに好ましくは０．５〜５、特に好ましくは０．７〜３である。親水性シリカとしては、上記の二酸化ケイ素等が使用できる。
【００９３】
防黴剤としては、ニトリル系、アルデヒド系、フェノール系、ナフタリン系、ナフテン酸金属塩系又は有機スズ系の防黴剤等が使用でき、２，３，５，６−テトラクロルイソフタロニトリル、ホルムアルデヒド、グルタルアルデヒド、ペンタクロルフェニルラウレート、ｏ−クロルナフタリン、ナフテン酸銅、ナフテン酸亜鉛及びパラヒドロキシ安息香酸メチルエステル等が挙げられる。防腐剤としては、イソチアゾリン系、ベンツチアゾ−ル系、ベンゾチアゾ−ル系、第４級アンモニウム塩系又はジチオカルバメート系の防腐剤等が使用でき、１，２−べンゾイソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、２−（４−チアゾリル）ベンツチアゾ−ル、２−（チオシアノメチルチオ）ベンゾチアゾ−ル、テトラデシルジメチルベンジルアンモニウムクロリド及びテトラメチルチウラムジスルフィド等が挙げられる。防錆剤としては、脂肪酸金属塩、脂肪酸アミン塩、脂肪酸エステル、スルホン酸塩、リン酸エステル及びアミン誘導体等が使用でき、ナフテン酸ナトリウム、アビエチン酸シクロヘキシルアミン塩、ソルビタンモノオレエート、石油スルホネート及びシクロヘキシルアミンエチレンオキシド１０モル付加物等が挙げられる。酸化防止剤としては、フェノール系、アミン系、硫黄系又はリン系の酸化防止剤等が使用でき、２，６−ジターシャリーブチル−４−メチルフェノール、ブチル化ヒドロキシアニソール、２，２’−メチレンビス（４−メチル−６−t−ブチルフェノール、ジラウリル３，３’−チオジプロピオネート及びトリフェニルホスファィト等が挙げられる。皮張り防止剤としては、ポリエーテル系、ケトオキシム系又は高級アルコール系の革張り防止剤等が使用でき、エチレンオキシド２０モル付加物、メチルエチルケトオキシム及びセチルアルコールエチレンオキシド２モル付加物等が挙げられる。
【００９４】
脂肪酸及びこの塩、アミド、動植物油、炭化水素油並びに／又はシリコーンを使用する場合、これらの合計含有量（重量％）は、部分エステル（Ａ）及びポリオキシアルキレン化合物（Ｂ）の重量に基づいて、０．１〜１０が好ましく、さらに好ましくは０．３〜８、特に好ましくは０．５〜５である。防黴剤、防腐剤、防錆剤、酸化防止剤及び／又は皮張り防止剤を使用する場合、これらの合計含有量（重量％）は、水（Ｅ）の重量に基づいて、０．００１〜１が好ましく、さらに好ましくは０．０１〜０．８、特に好ましくは０．０５〜０．５である。その他の成分は、エマルション型消泡剤の調整後、調整中及び／又は調整前のいずれでも添加できる。
【００９５】
本発明のエマルション消泡剤は、▲１▼部分エステル（Ａ）、ポリオキシアルキレン化合物（Ｂ）及び乳化剤（Ｃ）を溶融混合した後、増粘剤（Ｄ）、水（Ｅ）及び必要により緩衝剤（Ｆ）の混合水溶液を添加しながら攪拌混合してエマルション化する方法、▲２▼（Ｄ）、（Ｅ）及び必要により（Ｆ）の混合水溶液に、（Ａ）、（Ｂ）及び（Ｃ）の混合物を添加しながら攪拌混合してエマルション化する方法、▲３▼（Ａ）を▲１▼又は▲２▼と同様にして調製したエマルションと、（Ｂ）を▲１▼又は▲２▼と同様にして調製したエマルションとを混合する方法、▲４▼（Ｅ）の一部｛（Ｄ）を含まない｝を用いて、▲１▼〜▲３▼と同様にして高濃度エマルションを調製した後、これに残りの（Ｅ）、（Ｄ）及び必要により（Ｆ）の混合水溶液を添加する方法、並びに▲５▼（Ｅ）の一部｛（Ｄ）を含まない｝を用いて、▲１▼〜▲３▼と同様にして高濃度エマルションを調製した後、これを残りの（Ｅ）、（Ｄ）及び必要により（Ｆ）の混合水溶液に添加する方法等が挙げられ、いずれの方法でもよい。なお、乳化剤（Ｃ）、増粘剤（Ｄ）及び必要により緩衝剤（Ｆ）は、全量を部分エステル（Ａ）及び／又はポリオキシアルキレン化合物（Ｂ）と混合しておいてもよく、水（Ｅ）と混合しておいてもよい。また、（Ｃ）、（Ｄ）及び必要により（Ｆ）の一部を（Ａ）及び／又は（Ｂ）と混合し、残りを（Ｅ）と混合しておいてもよい。これらのうち、▲１▼、▲２▼又は▲３▼の方法が好ましく、さらに好ましくは▲１▼又は▲２▼の方法、特に好ましくは▲１▼の方法である。
【００９６】
エマルション化温度（℃）としては、４５〜９５が好ましく、さらに好ましくは５０〜９０、特に好ましくは５５〜８０である。すなわち、エマルション化温度（℃）としては、４５以上が好ましく、さらに好ましくは５０以上、特に好ましくは５５以上であり、また、９５以下が好ましく、さらに好ましくは９０以下、特に好ましくは８０以下である。エマルション化時間としては、バッチ（回分）生産又は連続生産や生産量により異なってくるが、例えば生産量１トンでバッチで行う場合、０．１〜２４時間程度であり、好ましくは０．５〜５時間、さらに好ましくは１〜３時間である。
【００９７】
本発明のエマルション型消泡剤中のエマルション粒子の体積平均粒子径（μｍ）は、０．１〜５０が好ましく、さらに好ましくは０．５〜２０、特に好ましくは１〜１０である。すなわち、エマルション粒子の体積平均粒子径（μｍ）は、０．１以上が好ましく、さらに好ましくは０．５以上、特に好ましくは１以上であり、また、５０以下が好ましく、さらに好ましくは２０以下、特に好ましくは１０以下である。この範囲であると、エマルション型消泡剤の安定性がさらに良好となる。
【００９８】
なお、体積平均粒子径は、レーザー回折式粒度分析計[例えば、Leeds＆Northrup Co.製Microtrac Model No.9320-X100（レーザー光波長：780nm)]を用い、電気伝導度０．１ｍＳ／ｍ以下の水１０００重量部と重量平均分子量５０万〜２０００万のポリアクリルアミド｛例えば、サンフロックＮＯＰ、三洋化成工業株式会社製]０．２重量部部との水溶液に、測定試料濃度０．１重量％となるように測定試料を添加して、測定温度２５±１０℃で測定される（レーザー回折式粒度分布測定法により５０％積算体積平均粒子径）。なお、循環液（水）の屈折率１．３３、エマルション粒子の屈折率１．４６を用いる。
【００９９】
攪拌混合装置としては、プロペラ型攪拌機、ディゾルバー、ホモミキサー、ボールミル、サンドミル、超音波分散機、ニーダー及びラインミキサー等が使用でき、これらの２種以上の設備を組合せて使用することができる。これらのうち、プロペラ型攪拌機、ディゾルバー及びホモミキサーが好ましく、さらに好ましくはプロペラ型攪拌機及びホモミキサー、特に好ましくはプロペラ型攪拌機である。乳化分散装置としては、通常の乳化分散機等が使用でき、高圧噴射式乳化分散機（ガウリンホモジナイザー、マイクロフルイダイザ−及びナノマイザー等）、超音波式乳化分散機（ディスパーソニック及びウルトラジェッター等）、加圧ノズル式乳化機（ホモジナイザー）、高速回転高せん断型攪拌乳化分散機（ホモミキサー、コーレスミキサー、ディスパーミル、ディスクキャビテーションミキサー及びステイターローラー等）及び摩砕式乳化分散機（サンドグラインダー、アジテーターミル、ボールミル、サンドミル、コロイドミル及びアトライター等）等が使用できる。これらの２種以上の設備を組合せて使用することができ、また、攪拌混合装置と乳化分散装置を組合せて使用することができる。これらのうち、高圧噴射式乳化分散機、高速回転高せん断型攪拌乳化分散機及び摩砕式乳化分散機が好ましく、さらに好ましくは高圧噴射式乳化分散機、摩砕式乳化分散機及び高速回転高せん断型攪拌乳化分散機、特に好ましくは高圧噴射式乳化分散機及び高速回転高せん断型攪拌乳化分散機である。
【０１００】
体積平均粒子径は、高圧噴射式乳化分散機の場合吐出圧力を変化させることにより、超音波式乳化分散機の場合超音波出力を変化させることにより、加圧ノズル式乳化機の場合液の循環速度を変化させることにより、高速回転高せん断型攪拌乳化分散機の場合回転翼の回転数及び／又はクリアランスを変化させてせん断力を変化させることにより、摩砕式乳化分散機の場合メディアの種類、大きさ及び回転速度を変化させることにより、調整することができる。
【０１０１】
本発明のエマルション型消泡剤は、合成及び／又は天然の発泡性界面活性剤を含む液体（以下、発泡液体：パルプ、電子基板、金属部品及び繊維等の洗浄水、醗酵液、抄造白水、抄紙白水、工業排水、屎尿処理水、水系塗料、水系インク、モノマーストリッピング液体、都市下水及びセラミックスラリー等）に対して、優れた消泡効果（抑泡、破泡、脱気及び整泡等）を発揮するが、特に無機粉体を含む発泡液体に対して好適であり、水硬性無機質建築材料の製造工程（特に抄造工程）における抄造スラリー及び抄造白水に対して最適である。
【０１０２】
無機粉体としては、シリカ、炭酸カルシウム、タルク、クレー、カオリン、珪酸カルシウム、二酸化チタン、酸化マグネシウム、炭酸マグネシウム、塩化マグネシウム、塩化アルミニウム及び珪酸アルミニウム等が含まれるが、これらに限定されるものではない。
【０１０３】
本発明のエマルション型消泡剤は、連続添加、断続添加、泡測定器と消泡剤添加装置とを連動させた方法及びこららの組合せのいずれでもよく、１ヶ所添加又は多点添加のいずれでもよい。また、添加に際しては、適当な水溶性溶剤又は水等で希釈してもよく、他の消泡剤と併用することもできる。
本発明のエマルション型消泡剤の使用量は、発泡液体の種類、温度、濃度及び処理量等（発泡の程度等）により適宜増減することができるが、発泡液体の重量に基づいて、１０^-5〜１重量％が好ましく、さらに好ましくは１０^-4〜０．５重量％、特に好ましくは１０^-3〜０．２重量％である。
なお、水硬性無機質建築材料の抄造スラリーの場合、本発明のエマルション型消泡剤の使用量（重量％）は、含有する無機粉体の重量に基づいて、０．０００１〜１が好ましく、さらに好ましくは０．００１〜０．５、特に好ましくは０．００２５〜０．０５である。
また、水硬性無機質建築材料の抄造白水の場合、本発明のエマルション型消泡剤の使用量（重量％）は、白水の重量に基づいて、０．０００１〜０．５が好ましく、さらに好ましくは０．００１〜０．１、特に好ましくは０．００２５〜０．０５である。
【０１０４】
本発明のエマルション型消泡剤は、特に、水硬性無機質建築材料（建材ボード）製造の抄造工程での使用に好適である。本発明のエマルション型消泡剤を水硬性無機質建築材料製造の抄造工程に用いると、極めて優れた耐水性及び消泡性能を発揮する。水硬性無機質建築材料としては、石綿・セメント板、無石綿・セメント板、珪酸カルシウム板、外装材、内装材及び瓦等の無機建材ボード、畳等の有機建材ボードが挙げられる。
無機建材ボードは、無機粉末（セメント、珪酸カルシウム、酸化マグネシウム、炭酸カルシウム及びシリカ等）、繊維補強材（未晒しパルプ、晒しパルプ及び古紙等のパルプ繊維等）、石綿、ガラス繊維、合成繊維及び水等の混合スラリーを抄造ドラムに付着させることによって抄造し、ろ過・脱水（ここまでが抄造工程）、乾燥、硬化させて製造することができる。有機建材ボードは、繊維補強剤、合成繊維、有機バインダー（フェノール樹脂、メチルセルロース、ポリビニルアルコール、エチレン酢酸ビニル共重合体及びポリエチレンオキサイド等）、無機粉末（セメント、珪酸カルシウム、酸化マグネシウム、炭酸カルシウム及びシリカ等）及び水等の混合スラリーを抄造ドラムに付着させることによって抄造し、ろ過・脱水（ここまでが抄造工程）、乾燥、硬化させて製造することができる。
抄造ドラムには、丸網抄造法及び長網抄造法等があり、いずれも使用できる。硬化は、自然硬化法、水蒸気養生法及びオートクレーブ養生法等があり、いずれも使用できる。
抄造工程での泡は、主にスラリー混合撹拌時、抄造ドラムでのろ過・脱水時に多く発生しやすい。したがって、これらの工程又はこれらの工程前に、本発明のエマルション型消泡剤を添加することが好ましい。
【０１０５】
【実施例】
次に、実施例により本発明を詳細に説明するが、本発明は以下の実施例により限定されるものではない。なお、部は重量部を、％は重量％を表す。また、水酸基価、融点及び酸価の測定結果を表１に示した。曇点及び¹Ｈ−ＮＭＲの測定結果を表２に示した。重量平均分子量の測定結果を表３及び表４に示した。また、体積平均粒子径、安定性、消泡性能及び耐水性の評価結果を表６に示した。
【０１０６】
＜水酸基価（ｍｇＫＯＨ／ｇ）＞ＪＩＳ Ｋ−００７０−１９９２に準拠して測定した。
＜融点（℃）＞ＪＩＳ Ｋ−００６４−１９９２に準拠して測定した。
＜酸価（ｍｇＫＯＨ／ｇ）＞ＪＩＳ Ｋ−００７０−１９９２に準拠して測定した。
＜曇点（℃）＞ＩＳＯ−１０６５−１９７５に準拠して測定した。
＜¹Ｈ−ＮＭＲ＞溶媒：重クロロホルム、濃度：０．５％、装置：ＶＡＲＩＡＮ社製３００ＭＨｚ超電導ＮＭＲ（機種：ＸＬ−３００）で測定した。
【０１０７】
＜重量平均分子量＞分子量既知のエチレンオキシドを標準物質として、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した。
装置：ＨＬＣ−８１２０ＧＰＣ、東ソー株式会社、
ＧＰＣカラム：型式ＴＳＫｇｅｌＧ５０００ＰＷＸＬと型式ＴＳＫｇｅｌＧ３０００ＰＷＸＬ各々１本を直列接続、
溶離液：電気伝導度０．１ｍＳ／ｍ以下の水１０００部と試薬特級の無水リン酸二水素ナトリウム（和光純薬工業株式会社）７．０部及び試薬特級の無水リン酸水素ニナトリウム（和光純薬工業株式会社）７．１部との水溶液、
溶離液流速：０．８０ｍＬ／分、
カラム温度：４０℃、
検出器：ＲＩ（屈折）検出器、
試料濃度：０．４％溶離液溶液、
試料溶液注入量：５０μＬ、
標準物質：東ソー株式会社製ＴＳＫ標準ポリエチレンオキシド（ＳＥ−１５０：重量平均分子量９２０，０００、ＳＥ−７０：重量平均分子量５４０，０００、ＳＥ−３０：重量平均分子量２５０，０００、ＳＥ−１５：重量平均分子量１４０，０００、ＳＥ−８：重量平均分子量１０７，０００、ＳＥ−５：重量平均分子量５０，０００）、和光純薬工業株式会社製和光規格１級合格品ポリエチレングリコール６０００（重量平均分子量７，５００）、及び和光純薬工業株式会社製試薬特級エチレングリコール（分子量６２）、住友精化株式会社製ポリエチレンオキシド（ＰＥＯ−１８、重量平均分子量４，５００，０００）
【０１０８】
＜エマルション粒子の体積平均粒子径（μｍ）＞
エマルション粒子の体積平均粒子径は、レーザー回折式粒度分析計｛Leeds&Northrup Co.製Microtrac Model No．９３２０−Ｘ１００(レーザー光波長：780nm｝を用いて、循環液：電気伝導度０．１ｍＳ／ｍ以下の水１０００部とサンフロックＮＯＰ（三洋化成工業株式会社製）０．２部との水溶液、測定試料濃度：１％（循環液で希釈）、ＦＬＯＷ：６０％（循環液装置ＭＡＸ１００％に対する値）、ＰＯＷＥＲ：４０、測定温度：２５±１０℃で、３０秒間循環させて測定した。
なお、体積平均粒子径は循環液の屈折率１．３３、エマルション粒子の屈折率１．４６を使用して日機装製データ処理装置により計算した。
【０１０９】
＜安定性＞
（１）分離安定性
内径５０ｍｍの２２５ｃｃガラス瓶に８０ｍｍの高さまで測定試料（消泡剤）を入れ密閉し、２５±３℃で１ヶ月静置後、上層及び／又は下層に生じた水層の高さの合計Ｗ（ｍｍ）を測定し、次式（４）から分離安定性（％）を算出した。
【数３】
分離安定性（％）＝（Ｗ／８０）×１００ （４）
【０１１０】
（２）粘度安定性
分離安定性を評価した後、続けて粘度測定し、この粘度（Ｎ１）と製造直後の粘度（Ｎ０）とから次式（５）から粘度安定性（％）を算出した。
なお、粘度は、Ｂ型粘度計型式ＴＶＢ−20Ｌ（株式会社トキメック）により（２５±１℃、ローター回転数６０ＲＰＭ、１分値）測定した。
【数４】
粘度安定性（％）＝｛（Ｎ１）−（Ｎ０）｝×１００／（Ｎ０） （５）
【０１１１】
（３）安定性判定
測定試料（消泡剤）の安定性は次の評価基準で判定した。
○：分離安定性が０〜２％、かつ粘度安定性が０〜５０％
△：分離安定性が３〜５％、かつ粘度安定性が５０〜１００％
×：分離安定性が５％以上、かつ／又は粘度安定性が１００％以上
【０１１２】
＜消泡性能（ｍｍ）＞
（１）水硬化性無機質建築材料スラリーに対する消泡性能１
無石綿・セメント板抄造工程白水（三菱マテリアル建材株式会社九州工場）９３部、ポルトランドセメント６部、未晒しパルプ（縦１ｃｍ、横１ｃｍの四角に切断したもの）（兵庫パルプ株式会社）１部をジューサーミキサー（機種：ナショナルミキサーＭＸ−１５１Ｓ、松下電工製）に入れ、２５℃で１００Ｖの定電圧で３分間撹拌混合しスラリーを調製した。
このスラリー１００ｇ（２５℃）を内径５０ｍｍ×高さ３５０ｍｍのガラス製メスシリンダーに入れ、測定試料（消泡剤）１μｌを添加し、ＪＩＳ Ｋ２５１８−１９９０年の泡立ち試験に準じて、デフューザーストーンをスラリー底部まで挿入して空気を４０００ｍＬ／分で通気し、通気開始から３分後のスラリーと泡との合計高さ（ｍｍ）を測定した。なお、消泡剤なしのブランクについても測定した。
【０１１３】
（２）水硬化性無機質建築材料抄造白水に対する消泡性能２
無石綿・セメント板抄造工程白水（三菱マテリアル建材株式会社九州工場（２５℃）１００ｇを内径５０ｍｍ×高さ３５０ｍｍのガラス製メスシリンダーに入れ、測定試料（消泡剤）１μｌを添加し、ＪＩＳ Ｋ ２５１８−１９９０年の泡立ち試験に準じて、デフューザーストーンを白水底部まで挿入して空気を４０００ｍＬ／分で通気し、通気開始から３分後の泡の高さ（ｍｍ）を測定した。なお、消泡剤なしのブランクについても測定した。
【０１１４】
＜耐水性１＞
無石綿・セメント板抄造工程白水（三菱マテリアル建材株式会社九州工場）９３０ｇ、ポルトランドセメント６０ｇ、未晒しパルプ（縦１ｃｍ、横１ｃｍの四角に切断したもの）（兵庫パルプ株式会社）１０ｇをジューサーミキサー（機種：ナショナルミキサーＭＸ−１５１Ｓ、松下電工製）に入れ、１００Ｖの定電圧下で３分間攪拌混合した。さらに、測定試料（消泡剤）を０．７０ｇ加え、１００Ｖの定電圧下で１０秒間攪拌混合した。次いで、このスラリーを、ヌッチェ及び直径１１ｃｍ円型のＮｏ．２濾紙（アドバンテック東洋株式会社）を用いて、減圧濾過（真空圧６，７００Ｐａ）して、含水した水硬化性無機質建築材料（含水したボード）を作成した。なお、濾過の終点は濾過残表面上に水の層が目認できなくなる点とした。
含水したボード（水硬化性無機質建築材料）を、飽和水蒸気を発生できる９０℃の恒温槽に入れ、４８時間放置し硬化し硬化ボードを調製した。
なお、測定試料（消泡剤）を添加しないこと以外は上記と同様にしてブランクのボードを作製した（このボードの耐水性について、表５のブランクの欄に表示した。）。
この硬化ボードを２５±１℃、相対湿度４０±５％の恒温恒湿室内で８時間放置後の重量（Ｗ１）を測定した。引き続き、この硬化ボードを２５±１℃の脱イオン水１０００ｍｌ中に８時間浸漬した後、２５±１℃、相対湿度４０±５％の恒温恒湿室内で８時間放置後の重量（Ｗ２）を測定した。そして、耐水性は式（６）から算出した。
【数５】
耐水性（％）＝（Ｗ２−Ｗ１）×１００／Ｗ１ （６）
【０１１５】
＜耐水性２＞
測定試料（消泡剤）を０．７０ｇから０．２５ｇに変更した以外は、耐水性１と同様にして耐水性試験を行った。
【０１１６】
＜合成例ａ１＞
オクタデカン酸２８４部（１モル部）、エチレングリコール６２部（１モル部）及びパラトルエンスルホン酸２．５部を反応容器に仕込んだ後、撹拌しながら１４０℃に昇温して１００ｍｌ／分の流量の窒素を３時間、液中通気した。窒素を液中通気しながら１５０〜１６０℃に昇温して、この温度で１０時間反応させて、オクタデカン酸エチレングリコール部分エステル（ａ１）を得た。（ａ１）の酸価は８、水酸基価は１６２ｍｇＫＯＨ／ｇ、融点は５８℃であった。
【０１１７】
＜合成例ａ２〜ａ１３＞
オクタデカン酸２８４部（１モル部）及びエチレングリコール６２部（１モル部）を表１に示した成分及びモル比に変更した以外、合成例ａ１と同様にして、部分エステル（ａ２）〜（ａ１３）を得た。（ａ２）〜（ａ１３）の酸価、水酸基価及び融点は表１に示した。
【０１１８】
＜比較合成例ａ×１及びａ×２＞
オクタデカン酸２８４部（１モル部）及びエチレングリコール６２部（１モル部）を表１に示した成分及びモル比に変更した以外、合成例ａ１と同様にして、比較例に使用するエステル（ａ×１）及び（ａ×２）を得た。エステル（ａ×１）及び（ａ×２）の酸価、水酸基価及び融点は表１に示した。
【０１１９】
【表１】

【０１２０】
＜合成例ｂ１＞
オクタデカノール２７１部（１モル部）、水酸化カリウム（試薬特級、和光純薬株式会社）０．５部を攪拌式オートクレーブに仕込み、窒素置換しながら１００℃に昇温後、減圧下（０．０１３ＭＰａ以下）で１時間脱水した。次いで、１５０℃に昇温し、この温度でエチレンオキシド１３２部（３モル部）を連続滴下し（０．１〜１ＭＰａ）、同温度にさらに２時間保った。その後、１３０℃に調製し、この温度でプロピレンオキシド２９０部（５モル部）を連続滴下し（０．１〜１ＭＰａ）、同温度でさらに３時間保った。そして、この反応生成物にマグネシウムシリケート（キョウワード６００、協和化学株式会社）１０部を添加して、１００℃で１時間撹拌処理し、その後、減圧濾過により、このマグネシウムシリケートを除去して、ポリオキシアルキレン化合物（ｂ１）を得た。¹Ｈ−ＮＭＲにより、（ｂ１）が組成平均値として、一般式（１）において、Ｒ：オクタデシル、ＸＯ：オキシプロピレン、ｍ：３、ｎ：５、ｍ＋ｎ：８であることを確認した。また、（ｂ１）の曇点は６１．７℃であった。
【０１２１】
＜合成例ｂ２〜ｂ１０＞
合成例ｂ１と同様にして、ポリオキシアルキレン化合物（ｂ２）〜（ｂ１０）を得た。¹Ｈ−ＮＭＲにより、（ｂ２）〜（ｂ１０）が組成平均値として、一般式（１）において、Ｒ、ＸＯ、ｍ、ｎ、ｍ＋ｎが表２に示すものであることを確認した。また、曇点を測定し表２に示した。
【０１２２】
＜比較合成例ｂ×１〜ｂ×５＞
合成例ｂ１と同様にして、比較例で使用するポリオキシアルキレン化合物（ｂ×１）〜（ｂ×５）を得た。¹Ｈ−ＮＭＲにより、（ｂｘ１）〜（ｂｘ５）が組成平均値として、一般式（１）において、Ｒ、ＸＯ、ｍ、ｎ、ｍ＋ｎが表２に示すものであることを確認した。また、曇点を測定し表２に示した。
【０１２３】
【表２】

【０１２４】
＜実施例１＞
オクタデカン酸エチレングリコール部分エステル（ａ１）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）（ＨＬＢ１５．３）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）（重量平均分子量１．２万、商品名：ゴーセランＬ−３２６６、日本合成化学工業株式会社）０．４部、キサンタンガム（ｄ２１）（商品名：ケルザン、三昌株式会社）０．１部及び脱イオン水（ｅ１）（電気伝導度０．０５ｍＳ／ｍ）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で１時間撹拌して均一混合した。次に、高圧噴射式乳化分散機：ガウリンホモジナイザー（装置名：マントンガウリン、メーカー：ガウリン社、条件：温度：６０〜７０℃、圧力：９ＭＰa、時間：３ｋｇの乳化物を循環せずに１パス）を通した後直ちに熱交換器を通して２０℃以下に冷却してエマルション化した。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し本発明の消泡剤１を得た。消泡剤１のエマルション粒子径は５μｍ、粘度は４４０ｍＰａ・ｓであった。
【０１２５】
＜実施例２＞
オクタデカン酸グリセリン部分エステル（ａ２）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で１時間撹拌して均一混合した。次に、高速回転高せん断型撹拌乳化分散機：ホモミキサー（装置名：Ｔ．Ｋ．ホモミキサーＭＡＲＫII２．５型、メーカー：特殊機化工業株式会社、条件：温度：６０〜７０℃、回転数：１分間に１０，０００回、時間：１Ｌビーカーに乳化物５００ｇ入れ２０分間回転）で分散した直後に熱交換器を通して２０℃以下に冷却してエマルション化した。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し本発明の消泡剤２を得た。消泡剤２のエマルション粒子径は１０μｍ、粘度は３３０ｍＰａ・ｓであった。
【０１２６】
＜実施例３＞
オクタデカン酸グリセリン部分エステル（ａ３）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で１時間撹拌して均一混合した後、熱交換器を通して３０〜４０℃に冷却後、磨砕式乳化分散機：アトライター（装置名：アトライター型式：ＭＡ−１ＳＥ、メーカー：三井三池製作所、条件：温度：３０〜４０℃、ガラスビーズ（直径１ｍｍ）２０００部／乳化物：１０００部、回転数：１分間に３００回転）で処理後さらに冷却し、１０〜３０℃にした。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し本発明の消泡剤３を得た。消泡剤３のエマルション粒子径は８μｍ、粘度は３１０ｍＰａ・ｓであった。
【０１２７】
＜実施例４＞
オクタデカン酸グリセリン部分エステル（ａ４）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で１時間撹拌して均一混合した。次に、加圧ノズル式乳化機超音波式乳化分散機（装置名：ウルトラソーニックジェネレーター、modelＵＳ−５０、メーカー：株式会社日本精機製作所、条件：温度：６０〜７０℃、出力：１００Ｖ、５０Ｗ、２８ｋＨｚ）を乳化物液中にセットし３０分間超音波分散した直後に熱交換器を通して２０℃以下に冷却してエマルション化した。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し本発明の消泡剤４を得た。消泡剤４のエマルション粒子径は５μｍ、粘度は４５０ｍＰａ・ｓであった。
【０１２８】
＜実施例５＞
オクタデカン酸グリセリン部分エステル（ａ５）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で１時間撹拌して均一混合した。次に、高速回転高せん断型撹拌乳化分散機：コーレス型ミキサー（装置名：ＴＫホモジナイザーＡＭ−２０、メーカー：特殊機化工業株式会社、条件：温度：６０〜７０℃、回転数：１分間に１５，０００回転、時間：１Ｌビーカーに乳化物５００ｇを仕込み３０分間回転）で分散した直後、熱交換器を通して、１０〜２０℃に冷却してエマルション化した。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し本発明の消泡剤５を得た。消泡剤５のエマルション粒子径は１μｍ、粘度は５６０ｍＰａ・ｓであった。
【０１２９】
＜実施例６＞
オクタデカン酸グリセリン部分エステル（ａ６）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で５時間撹拌して均一混合した。次に、高速回転高せん断型攪拌乳化分散機：ホモミキサー（装置名：ハイフレックスディスパーザー型式ＨＧ９２、メーカー：株式会社エスエムテー、条件：温度：６５〜７５℃、回転数：１分間に１５，０００回、回転時間：３０分間、１Ｌビーカーに乳化物を５００ｇ入れ、ジェネレーターシャフト（対流型シャフト）を液に浸漬して液を循環する。）を通した直後に２０℃以下に冷却してエマルション化した。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し本発明の消泡剤６を得た。消泡剤６のエマルション粒子径は５μｍ、粘度は４７０ｍＰａ・ｓであった。
【０１３０】
＜実施例７＞
９−オクタデセン酸グリセリン部分エステル（ａ７）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で５時間撹拌して均一混合した。次に、高速回転高せん断型攪拌乳化分散機（装置名：ディスパーミル、メーカー：ホソカワミクロン株式会社、条件：温度：６５〜７５℃、回転数：１分間に３，０００回、クリアランス：２ｍｍ、時間：１回パス）ディスパーミルを通過後熱交換器を通して、１０〜２０℃に冷却しエマルションを得た。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し本発明の消泡剤７を得た。消泡剤７のエマルション粒子径は５μｍで、粘度は４８０ｍＰａ・ｓであった。
【０１３１】
＜実施例８〜２２＞
実施例１のオクタデカン酸エチレングリコール部分エステル（ａ１）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部を表３に示した成分及び含有量に変更した以外、実施例１と同様にして、本発明の消泡剤８〜２２を得た。消泡剤８〜２２のエマルション粒子径及び粘度は表５に示した。
【０１３２】
＜比較例１＞
オクタデカン酸グリセリン部分エステル（ａ×１）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部をプロペラ撹拌装置に仕込み７５℃に昇温後、１０％水酸化ナトリウム水溶液を添加しｐＨを８．０にした後、この温度で５時間撹拌して均一混合した。次に、高圧噴射式乳化分散機：ガウリンホモジナイザー（装置名：マントンガウリン、メーカー：ガウリン社、条件：温度：６０〜７０℃、圧力：９ＭＰa、時間：循環せず１パス）を通した後直ちに熱交換器を通して２０℃以下に冷却してエマルション化した。その後、１０％水酸化ナトリウム水溶液又は５％塩酸水溶液でｐＨを８．０に調整し比較の消泡剤２３を得た。消泡剤２３のエマルション粒子径は５μｍ、粘度は４４０ｍＰａ・ｓであった。
【０１３３】
＜比較例２〜９＞
オクタデカン酸グリセリン部分エステル（ａ×１）２５部、ポリオキシアルキレン化合物（ｂ３）７部、オレイルアルコールエチレンオキシド２０モル付加物（ｃ１）２部、スルホン化ポリビニルアルコールナトリウム塩（ｄ１１）０．４部、キサンタンガム（ｄ２１）０．１部及び脱イオン水（ｅ１）６５．５部を表４に示した成分及び含有量に変更した以外、比較例１と同様にして、比較の消泡剤２４〜３１を得た。消泡剤２４〜３１のエマルション粒子径及び粘度は表５に示した。
【０１３４】
＜比較例１０＞
オクタデカノール２７１部（１モル部）、水酸化カリウム（試薬特級、和光純薬株式会社）０．５部を攪拌式オートクレーブに仕込み、窒素置換しながら１００℃に昇温後、減圧下（０．０１３ＭＰａ以下）で１時間脱水した。次いで、１５０℃に昇温し、この温度でプロピレンオキシド１５６６部（２７モル部）を連続滴下し（０．１〜１ＭＰａ）、同温度にさらに２時間保った。その後、１３０℃に調製し、この温度でエチレンオキシド１３２部（３モル部）を連続滴下し（０．１〜１ＭＰａ）、同温度でさらに３時間保った。そして、この反応生成物にマグネシウムシリケート（キョウワード６００、協和化学株式会社）１０部を添加して、１００℃で１時間撹拌処理し、その後、減圧濾過により、このマグネシウムシリケートを除去して、比較の消泡剤３２を得た。この化合物は、¹Ｈ−ＮＭＲにより、組成平均値として、オクタデカノールのプロピレンオキシド２７モル・エチレンオキシド３モルブロック付加物であることを確認した。
【０１３５】
＜比較例１１＞
オクタデカノール２７１部（１モル部）、水酸化カリウム（試薬特級、和光純薬株式会社）０．５部を攪拌式オートクレーブに仕込み、窒素置換しながら１００℃に昇温後、減圧下（０．０１３ＭＰａ以下）で１時間脱水した。次いで、１５０℃に昇温し、この温度でプロピレンオキシド１７４０部（３０モル部）を連続滴下し（０．１〜１ＭＰａ）、同温度にさらに２時間保った。その後、１３０℃に調製し、同温度でさらに３時間保った。そして、この反応生成物にマグネシウムシリケート（キョウワード６００、協和化学株式会社）１０部を添加して、１００℃で１時間撹拌処理し、その後、減圧濾過により、このマグネシウムシリケートを除去して、比較の消泡剤３２を得た。この化合物は、¹Ｈ−ＮＭＲにより、組成平均値として、オクタデカノールのプロピレンオキシド３０モル付加物であることを確認した。
【０１３６】
＜比較例１２＞
９−オクタデセン酸５６４部（２モル部）、ニューポールＰＥ−６２（三洋化成工業株式会社）２１００部（１．０モル部）及びパラトルエンスルホン酸２．５部を反応容器に仕込んだ後、撹拌しながら１４０℃に昇温して１００ｍｌ／分の流量の窒素を３．０時間、液中通気した。窒素を液中通気しながら１５０〜１６０℃に昇温して、この温度で１０時間反応させて、ニューポールＰＥ−６２のオクタデセン酸のジエステルを得た。このジエステルの酸価は１０、水酸基価は３ｍｇＫＯＨ／ｇ、凝固点は−５℃であった。
【０１３７】
【表３】

【０１３８】
ｃ１：オレイルアルコールエチレンオキシド２０モル付加物（ＨＬＢ１５．３）
ｄ１１：スルホン化ポリビニルアルコールナトリウム塩（商品名：ゴーセランＬ−３２６６、重量平均分子量：１．２万、日本合成化学工業株式会社）
ｄ１２：ポリビニルアルコール（商品名：ＰＶＡ−２０５、重量平均分子量：１．１万、クラレ株式会社）
ｄ１３：ポリエチレンオキシド（商品名：ＰＥＯ−８、重量平均分子量：２００万、住友精化株式会社）
ｄ２１：キサンタンガム（商品名：ケルザン、三昌株式会社）
ｅ１：脱イオン水（電気伝導度：０．０５ｍＳ／ｍ）
【０１３９】
【表４】

ｃ１、ｄ１１、ｄ２１及びｅ１は、表３に同じである。
【０１４０】
【表５】

【０１４１】
【発明の効果】
本発明のエマルション型は、消泡性能の非常に優れており、特に無機粉体を含む発泡液体に対して極めて優れた消泡性能を発揮する。さらに、消泡剤自身の安定性が高く、分離や増粘が極めて低い。また、水硬化性無機質建築材料の抄造工程に使用しても、この建築材料の耐水性の低下が極めて低い。
従って、本発明のエマルション型消泡剤は、合成及び／又は天然の発泡性界面活性剤を含む発泡性の液体、例えば、パルプ、電子基板、金属部品及び繊維等の洗浄水、醗酵液、抄造白水、抄紙白水、工業排水、屎尿処理水、水系塗料、水系インク、モノマーストリッピング液体、都市下水、セラミックスラリー、その他の酸性〜アルカリ性の発泡性液体等に対して、優れた消泡効果（抑泡、破泡及び整泡等）を発揮する。特に無機粉体を含む発泡液体に対して好適であり、水硬性無機質建築材料の製造工程（特に抄造工程）における抄造スラリー及び抄造白水に対して最適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an emulsion type antifoaming agent. More specifically, the present invention relates to an emulsion-type antifoaming agent suitable for a foaming liquid containing inorganic powder (particularly, a process for making a hydraulic inorganic building material).
[0002]
[Prior art]
An antifoaming agent for papermaking composed of an emulsion type antifoaming agent composed of a fatty acid ester or the like and a polyoxyalkylene type antifoaming agent is known (Patent Document 1).
An emulsion type antifoaming agent composition for wastewater treatment by an aerobic treatment method containing a higher fatty acid ester and a polyoxyalkylene compound is known (Patent Document 2).
An emulsion antifoaming agent containing a polyoxyalkylene surfactant in which both ends of a fatty acid ester having a melting point of 40 to 100 ° C. and a polyalkylene glycol are blocked with acyl or alkoxy is known (Patent Document 3).
[0003]
[Patent Document 1]
JP-A-8-113891
[Patent Document 2]
JP-A-11-503
[Patent Document 3]
JP 2002-191906 A
[0004]
[Problems to be solved by the invention]
Conventional antifoaming agents may have insufficient antifoaming performance. In particular, defoaming performance may be insufficient for foaming liquids containing inorganic powder (for example, paper making process for hydraulic inorganic building materials), and the amount of antifoaming agent used to improve defoaming performance There is a problem that the water resistance decreases when the amount is increased. That is, an object of the present invention is to provide an antifoaming agent having excellent water resistance and antifoaming performance (in particular, having excellent water resistance and antifoaming performance for foaming liquids containing inorganic powder).
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor has found that the above object can be achieved by using a specific ester, a specific polyoxyalkylene compound, and a specific thickening agent. Reached.
That is, the emulsion type antifoaming agent of the present invention is characterized by a fatty acid partial ester (A) of a 2-6 valent alcohol, a polyoxyalkylene compound (B) represented by the general formula (1), an emulsifier (C), and a weight. Thickener comprising a synthetic water-soluble polymer (D1) having an average molecular weight (Mw) of 5,000 to 5,000,000, a natural water-soluble polymer (D2) and / or a semi-synthetic water-soluble polymer (D3) (D) and an emulsion type antifoaming agent comprising water (E),
(1) The hydroxyl value of (A) is 50 to 400 mgKOH / g,
(2) The cloud point by the 25 wt% butyl diglycol aqueous solution method of (B) is 43 to 70 ° C,
(3) Based on the total weight of (A), (B), (C), (D) and (E), the content of (A) is 20 to 30% by weight, and the content of (B) is 4 -10 wt%, (C) content is 0.3-5 wt%, (D) content is 0.01-5 wt%, (E) content is 50-75 wt%,
(4) The gist is that the volume average particle diameter of the emulsion particles is 0.1 to 50 μm.
[0006]
[Chemical 2]
R-O (C ₂ H _Four O) m (XO) n-H (1)
In the formula, R is a linear or branched alkyl or alkenyl group having 8 to 28 carbon atoms, XO is an oxyalkylene group having 3 to 4 carbon atoms, m is an integer of 3 to 10, and n is an integer of 5 to 40. , M + n is an integer of 8-50.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The fatty acid partial ester (A) of a 2-6 hydric alcohol is demonstrated.
2-12 are preferable, as for carbon number of 2-6 alcohol, More preferably, it is 2-5, Most preferably, it is 3 or 5. Within this range, the defoaming performance is further improved.
Examples of the dihydric alcohol include aliphatic diols having 2 to 8 carbon atoms, alicyclic diols having 8 to 15 carbon atoms, and dihydric phenols having 6 to 15 carbon atoms.
Aliphatic diols include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylpropanediol, hydroxyoctadecenyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylpentanediol and di (hydroxy And ethyl) thioether.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol, 4,4′-dihydroxydicyclohexane and dihydroxydicyclohexyldimethylmethane.
Examples of the dihydric phenol include catechol, hydroquinone, bisphenol (such as bisphenol A, bisphenol F, and bisphenol S) and 1,4-dihydroxynaphthalene.
[0008]
Examples of the trihydric alcohol include an aliphatic triol having 3 to 6 carbon atoms, an alicyclic triol having 6 to 15 carbon atoms, and a trihydric phenol having 6 to 15 carbon atoms.
Aliphatic triols include glycerin, trimethylol ethane, trimethylol propane, trimethylol octane and hexane triol. Examples of the alicyclic triol include trihydroxycyclohexane, trihydroxydicyclohexane, and trihydroxydicyclohexyldimethylmethane.
Examples of the trivalent phenol include trihydroxybenzene, trihydroxybiphenyl, and trihydroxydiphenyldimethylmethane.
[0009]
Examples of the tetravalent alcohol include aliphatic tetraols having 5 to 12 carbon atoms, alicyclic tetraols having 6 to 15 carbon atoms, and tetravalent phenols having 6 to 15 carbon atoms. Examples of the aliphatic tetraol include diglycerin, pentaerythritol, ditrimethylolpropane, and sorbitan.
Examples of the alicyclic tetraol include tetrahydroxycyclohexane, tetrahydroxydicyclohexane, and tetrahydroxydicyclohexyldimethylmethane.
Examples of tetrahydric phenols include hitetrahydroxybenzene, tetrahydroxybiphenyl, and tetrahydroxydiphenyldimethylmethane.
[0010]
The pentahydric alcohol includes aliphatic pentaols having 6 to 12 carbon atoms, and examples thereof include hydroquinone-β-D-glucoside.
Examples of the hexavalent alcohol include aliphatic hexaols having 6 to 12 carbon atoms, and include sorbitol, tetraglycerin, dipentaerythritol, and the like. Of these, dihydric alcohols, trihydric alcohols and tetrahydric alcohols are preferable, aliphatic diols, aliphatic triols and aliphatic tetraols are more preferable, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, Glycerin, trimethylolpropane, pentaerythritol and sorbitan, more particularly preferably ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and sorbitan, most preferably glycerin, trimethylolpropane and pentaerythritol.
[0011]
12-36 are preferable, as for carbon number of a fatty acid, More preferably, it is 14-28, Most preferably, it is 16-22. Within this range, the defoaming performance is further improved. Examples of fatty acids include linear saturated fatty acids and linear unsaturated fatty acids. In addition, branched fatty acid, aromatic carboxylic acid and alicyclic carboxylic acid are not preferable from the viewpoint of defoaming performance.
[0012]
The linear saturated fatty acids include dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid Examples include acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid, hentriacontanoic acid, dotriacontanoic acid, tetratriacontanoic acid and hexatriacontanoic acid.
[0013]
As the linear unsaturated fatty acid, those having one unsaturated bond include 2-dodecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 11-dodecenoic acid, 2-tridecenoic acid, 12-tridecenoic acid, 4- Tetradecenoic acid, 5-tetradecenoic acid, 9-tetradecenoic acid, 14-pentadecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 3-octadecenoic acid, 4-octadecenoic acid, 6-octadecenoic acid, 7-octadecenoic acid, 8 -Octadecenoic acid, 9-octadecenoic acid, 10-octadecenoic acid, 11-octadecenoic acid, 12-octadecenoic acid, 15-octadecenoic acid, 16-octadecenoic acid, 17-octadecenoic acid, 9-eicosenoic acid, 13-docosenoic acid and 15 -Tetracosenoic acid and the like, and those having 2 to 4 unsaturated bonds, Dienoic acid, 9,11,13-octadecatrienoic acid, 9,12,15-octadecatrienoic acid, 10,12,14-octadecatrienoic acid, 9,11,13,15-octadecatetraenoic acid, etc. Is mentioned.
[0014]
Of these, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid 4-tetradecenoic acid, 5-tetradecenoic acid, 9-tetradecenoic acid, 14-pentadecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 3-octadecenoic acid, 4-octadecenoic acid, 6-otadecenoic acid, 7-octadecene Acid, 8-octadecenoic acid, 9-octadecenoic acid, 10-octadecenoic acid, 11-octadecenoic acid, 12-octadecenoic acid, 15-octadecenoic acid, 16-octadecenoic acid, 17-octadecenoic acid, 9-eicosenoic acid, 9,12 -Octadecadienoic acid, 9,11,13-o Tadecatrienoic acid and 9,12,15-octadecatrienoic acid are preferred, more preferably hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid Acid, hexacosanoic acid, heptacosanoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 3-octadecenoic acid, 4-octadecenoic acid, 6-octadecenoic acid, 7-octadecenoic acid, 8-octadecenoic acid, 9-octadecenoic acid 10-octadecenoic acid, 11-octadecenoic acid, 12-octadecenoic acid, 15-octadecenoic acid, 16-octadecenoic acid and 17-octadecenoic acid, particularly preferably heptadecanoic acid, octadecanoic acid and 9-octadecenoic acid.
[0015]
The fatty acid partial ester (A) of a divalent to hexavalent alcohol is a partial ester in which a part of the hydroxyl group remains. And the hydroxyl value (mgKOH / g) of the fatty acid partial ester (A) of a 2-6 hydric alcohol has preferable 50-400, More preferably, it is 80-350, Especially preferably, it is 100-300. That is, the hydroxyl value (mgKOH / g) of (A) is preferably 50 or more, more preferably 80 or more, particularly preferably 100 or more, and preferably 400 or less, more preferably 350 or less, particularly preferably. 300 or less. Within this range, the defoaming performance is further improved.
[0016]
In addition, when the fatty acid partial ester (A) of a 2-6 hydric alcohol is normally produced from esterification reaction (including transesterification reaction), for example, in the case of a tetrahydric alcohol, monoester, diester, triester, tetraester and It becomes a mixture of statistical distribution (random distribution: see the examples of JP-A-9-117609 or JP-A-9-253405) containing raw material alcohol, etc., and natural products are also mixtures. In the invention, it may be a mixture or a purified product (hereinafter, the reaction product may have any of these meanings). From the viewpoint of price and the like, a mixture is preferable.
[0017]
As a method for adjusting the hydroxyl value to the above range, the blending ratio of the 2-6 alcohol and the fatty acid may be adjusted, and the fatty acid is 0.33-0. It can be obtained by reacting a divalent to hexavalent alcohol and a fatty acid at a ratio of 8 equivalents (preferably 0.4 to 0.7 equivalents, particularly preferably 0.43 to 0.63 equivalents).
[0018]
As melting | fusing point (degreeC) of fatty-acid partial ester (A), 45-95 are preferable, More preferably, it is 51-85, Most preferably, it is 55-77. That is, the melting point (° C.) of (A) is preferably 45 or more, more preferably 51 or more, particularly preferably 55 or more, and preferably 95 or less, more preferably 85 or less, particularly preferably 77 or less. It is. Within this range, the defoaming performance is further improved.
[0019]
The melting point of the divalent to hexahydric alcohol and the fatty acid partial ester (A) tends to increase as the alcohol valence and carbon number increase, and as the fatty acid carbon number increases, the melting point tends to increase. Also, the fatty acid molar ratio to alcohol tends to decrease as the fatty acid molar ratio increases, and it tends to decrease as the unsaturated bond of fatty acid increases.
[0020]
As the partial ester (A), a linear saturated fatty acid ester (A1) of a 2-6 valent alcohol, a linear unsaturated (1 unsaturated bond) fatty acid ester (A2) of a 2-6 valent alcohol, and a 2-6 valent alcohol. The unsaturated (unsaturated bond 2-4) fatty acid ester (A3) etc. of alcohol are contained. Among these, preferable partial esters are exemplified below.
[0021]
(1) Linear saturated fatty acid ester (A1) of divalent to hexavalent alcohol
Examples of linear saturated fatty acid esters of dihydric alcohol include a reaction product of 1 mol of ethylene glycol and 1 mol of octadecanoic acid (melting point: 58 ° C.), a reaction product of 1 mol of ethylene glycol and 1.5 mol of octadecanoic acid (melting point: 67 ° C. ), 1 mol of ethylene glycol and 0.5 mol of octadecanoic acid (melting point: 49 ° C.), 1 mol of ethylene glycol and 1 mol of hexadecanoic acid (melting point: 48 ° C.), 1 mol of ethylene glycol and 1 docosanoic acid Molar (melting point: 75 ° C.) reactant and the like.
[0022]
As a linear saturated fatty acid ester of a trihydric alcohol, a reaction product of 1 mol of glycerin and 0.8 mol of octadecanoic acid (melting point: 51 ° C.), a reaction product of 1 mol of glycerin and 1 mol of octadecanoic acid (melting point: 79 ° C.), Reaction product of 1 mol of glycerin and 1.5 mol of octadecanoic acid (melting point: 75 ° C), reaction product of 1 mol of glycerin and 2 mol of octadecanoic acid (melting point: 71 ° C), reaction of 1 mol of glycerin and 2.3 mol of octadecanoic acid Product (melting point: 69 ° C.), reaction product of 1 mol of glycerin and 1 mol of dodecanoic acid (melting point: 60 ° C.), reaction product of 1 mol of glycerin and 1 mol of tetradecanoic acid (melting point: 66 ° C.), 1 mol of glycerin and hexadecanoic acid 1 mol of reactant (melting point: 72 ° C.), 1 mol of glycerin and 1 mol of eicosanoic acid (melting point: 85 ° C.) and 1 mol of glycerin and 1 mol of docosanoic acid Reactant (mp: 92 ° C.), and the like.
[0023]
As linear saturated fatty acid esters of tetrahydric alcohol, a reaction product of 1 mol of pentaerythritol and 1 mol of octadecanoic acid (melting point: 81 ° C.), a reaction product of 1 mol of pentaerythritol and 2 mol of octadecanoic acid (melting point: 74 ° C.) and 1 mol of pentaerythritol and 3 mol of octadecanoic acid (melting point: 71 ° C.), reaction product of 1 mol of pentaerythritol and 1 mol of dodecanoic acid (melting point: 63 ° C.), reaction product of 1 mol of pentaerythritol and 2 mol of dodecanoic acid (melting point: 66 ° C.), 1 mol of pentaerythritol and 1 mol of tetradecanoic acid (melting point: 70 ° C.), 1 mol of pentaerythritol and 2 mol of tetradecanoic acid (melting point: 63 ° C.), 1 mol of pentaerythritol and 1 mol of hexadecanoic acid Moles of reactant (melting point: 76 ° C.), 1 mole of pentaerythritol and hexadecane 2 mol of reactant (melting point: 69 ° C.), 1 mol of pentaerythritol and 1 mol of eicosanoic acid (melting point: 88 ° C.), 1 mol of pentaerythritol and 2 mol of eicosanoic acid (melting point: 81 ° C.), Reaction product of 1 mol of pentaerythritol and 1 mol of docosanoic acid (melting point: 95 ° C), reaction product of 1 mol of pentaerythritol and 2 mols of docosanoic acid (melting point: 88 ° C), reaction of 1 mol of pentaerythritol and 2 mols of triacontanoic acid Product (melting point: 93 ° C.) and a reaction product (melting point: 85 ° C.) of 1 mol of pentaerythritol and 3 mol of triacontanoic acid.
[0024]
As a linear saturated fatty acid ester of pentavalent alcohol, a reaction product of 1 mol of hydroquinone-β-D-glucoside and 2 mol of octadecanoic acid (melting point: 82 ° C.), 1 mol of hydroquinone-β-D-glucoside and 3 mol of octadecanoic acid And a reaction product (melting point: 68 ° C.) of 1 mol of hydroquinone-β-D-glucoside and 4 mol of octadecanoic acid.
[0025]
As the linear saturated fatty acid ester of hexavalent alcohol, a reaction product of 1 mol of dipentaerythritol and 2 mol of octadecanoic acid (melting point: 85 ° C.), a reaction product of 1 mol of dipentaerythritol and 3 mol of octadecanoic acid (melting point: 78 ° C. And a reaction product (melting point: 72 ° C.) of 1 mol of dipentaerythritol and 4 mol of octadecanoic acid.
[0026]
(2) 2- to 6-valent alcohol linear unsaturated (one unsaturated bond) fatty acid ester (A2)
As the linear unsaturated fatty acid ester of a dihydric alcohol, a reaction product of 1 mol of ethylene glycol and 1 mol of 9-octadecenoic acid (melting point: 49 ° C.) and a reaction product of 1 mol of ethylene glycol and 1.5 mol of 9-octadecenoic acid (Melting point: 45 ° C.).
[0027]
As the linear unsaturated fatty acid ester of trihydric alcohol, 1 mol of glycerin and 1 mol of 9-octadecenoic acid (melting point: 51 ° C.), 1 mol of glycerin and 1.5 mol of 9-octadecenoic acid (melting point) : 48 ° C) and a reaction product of 1 mol of glycerin and 2 mol of 9-octadecenoic acid (melting point: 45 ° C).
[0028]
The linear unsaturated fatty acid ester of tetrahydric alcohol includes a reaction product of 1 mol of pentaerythritol and 1 mol of 9-octadecenoic acid (melting point: 55 ° C.), a reaction product of 1 mol of pentaerythritol and 2 mol of 9-octadecenoic acid (melting point). : 49 ° C) and a reaction product of 1 mol of pentaerythritol and 3 mol of 9-octadecenoic acid (melting point: 46 ° C).
[0029]
The linear unsaturated fatty acid ester of pentahydric alcohol includes a reaction product of 1 mol of hydroquinone-β-D-glucoside and 2 mol of 9-octadecenoic acid (melting point: 51 ° C.) and 1 mol of hydroquinone-β-D-glucoside and 9 -A reaction product of a reaction product (melting point: 45 ° C) of 3 moles of octadecenoic acid.
[0030]
As the linear unsaturated fatty acid ester of hexavalent alcohol, a reaction product of 1 mol of dipentaerythritol and 2 mol of 9-octadecenoic acid (melting point: 54 ° C.), a reaction product of 1 mol of dipentaerythritol and 3 mol of 9-octadecenoic acid (Melting point: 48 ° C.) and a reaction product of 1 mol of dipentaerythritol and 4 mol of 9-octadecenoic acid (melting point: 45 ° C.).
[0031]
(3) Unsaturated (unsaturated bond 2-4) fatty acid ester (A3) of 2-6 hydric alcohol
Examples of unsaturated fatty acid esters of dihydric alcohol include a reaction product of 1 mol of ethylene glycol and 1 mol of 9,12-octadecadienoic acid (melting point: 47 ° C.), and 1 mol of ethylene glycol and 9,11,13-octadecateriene. A reaction product of 1 mol of acid (melting point: 45 ° C.) can be mentioned.
[0032]
As unsaturated fatty acid ester of trihydric alcohol, 1 mol of glycerol and 1 mol of 9,12-octadecadienoic acid (melting point: 50 ° C.), 1 mol of glycerol and 2 mol of 9,12-octadecadienoic acid Reaction product (melting point: 47 ° C.), reaction product of 1 mol of glycerine and 1 mol of 9,11,13-octadecatrienoic acid (melting point: 48 ° C.) and reaction product of 1 mol of glycerin and 9,11,13-octadecatrienoic acid 2 Molar reactants (melting point: 46 ° C.) and the like.
[0033]
The unsaturated fatty acid ester of tetrahydric alcohol includes a reaction product of 1 mol of pentaerythritol and 1 mol of 9,12-octadecadienoic acid (melting point: 53 ° C.), 1 mol of pentaerythritol and 9,12-octadecadienoic acid 2 Molar reactant (melting point: 50 ° C.), 1 mole of pentaerythritol and 9,11,13-octadecadienoic acid 1 mole (melting point: 48 ° C.) and 1 mole of pentaerythritol and 9,11,13-octa Examples include a reaction product of 2 mol of decadienoic acid (melting point: 46 ° C.).
[0034]
As unsaturated fatty acid ester of pentahydric alcohol, 1 mol of hydroquinone-β-D-glucoside and 2 mol of 9,12-octadecadienoic acid (melting point: 52 ° C.), 1 mol of hydroquinone-β-D-glucoside And a reaction product of 3 mol of 9,12-octadecadienoic acid (melting point: 49 ° C.), a reaction product of 1 mol of hydroquinone-β-D-glucoside and 2 mol of 9,11,13-octadecadienoic acid (melting point: 49 And a reaction product (melting point: 46 ° C.) of 1 mol of hydroquinone-β-D-glucoside and 3 mol of 9,11,13-octadecadienoic acid.
[0035]
Unsaturated fatty acid esters of hexahydric alcohol include a reaction product of 1 mol of dipentaerythritol and 2 mol of 9,12-octadecadienoic acid (melting point: 56 ° C.), 1 mol of dipentaerythritol and 9,12-octadecadiene. 3 mol of a reaction product (melting point: 53 ° C.), 1 mol of dipentaerythritol and 4 mol of 9,11,13-octadecatrienoic acid (melting point: 48 ° C.), and 1 mol of dipentaerythritol and 9,11 , 13-octadecatrienoic acid 3 mol reactant (melting point: 52 ° C.) and the like.
[0036]
Among these, a linear saturated fatty acid ester (A1) of a 2-6 valent alcohol and a linear unsaturated (one unsaturated bond) fatty acid ester (A2) of a 2-6 valent alcohol are preferable, and a trivalent alcohol is more preferable. Linear saturated fatty acid ester of tetravalent alcohol, linear saturated fatty acid ester of trivalent alcohol, linear unsaturated of trivalent alcohol (one unsaturated bond) fatty acid ester and linear unsaturated of tetrahydric alcohol (one unsaturated bond) Fatty acid ester, more preferably a reaction product of 1 mol of glycerin and 1 mol of octadecanoic acid, a reaction product of 1 mol of glycerin and 1.5 mol of octadecanoic acid, a reaction product of 1 mol of glycerol and 2 mol of octadecanoic acid, 1 mol of pentaerythritol A reaction product of 1 mol of octadecanoic acid, a reaction product of 1 mol of pentaerythritol and 2 mol of octadecanoic acid, pentaerythritol Reactant of 1 mol of diol and 3 mol of octadecanoic acid, 1 mol of dipentaerythritol and 4 mol of octadecanoic acid, 1 mol of dipentaerythritol and 3 mol of octadecanoic acid, 1 mol of dipentaerythritol and 4 mol of octadecanoic acid 1 mol of glycerol, 1 mol of 9-octadecenoic acid, 1 mol of glycerol and 1.5 mol of 9-octadecenoic acid, 1 mol of glycerol and 2 mol of 9-octadecenoic acid, penta 1 mol of erythritol and 1 mol of 9-octadecenoic acid, 1 mol of pentaerythritol and 2 mol of 9-octadecenoic acid, 1 mol of pentaerythritol and 3 mol of 9-octadecenoic acid, 1 mol of dipentaerythritol 9-octadecenoic acid 2 mol reactant, dipentaerythritol 1 mol and 9 A reaction product of 3 moles of octadecenoic acid and a reaction product of 1 mole of dipentaerythritol and 4 moles of 9-octadecenoic acid, particularly preferably a reaction product of 1 mole of glycerin and 1.5 moles of octadecanoic acid, 1 mole of glycerin and octadecanoic acid 2 1 mol of pentaerythritol, 2 mol of octadecanoic acid, 1 mol of pentaerythritol and 3 mol of octadecanoic acid, 1 mol of dipentaerythritol and 4 mol of octadecanoic acid, 1 mol of dipentaerythritol And a reaction product of 3 mol of octadecanoic acid, a reaction product of 1 mol of dipentaerythritol and 4 mol of octadecanoic acid, a reaction product of 1 mol of glycerin and 1.5 mol of 9-octadecenoic acid, 1 mol of glycerin and 2 mol of 9-octadecenoic acid. Reactant, 1 mol of pentaerythritol and 9-octadecenoic acid 2 moles of reactant and 1 mole of dipentaerythritol and 3 moles of 9-octadecenoic acid, more particularly preferably a reactant of 1 mole of glycerin and 1.5 moles of octadecanoic acid, 1 mole of pentaerythritol and octadecanoic acid 2 1 mol of dipentaerythritol and 3 mol of octadecanoic acid, 1 mol of glycerin and 1.5 mol of 9-octadecenoic acid, and 1 mol of pentaerythritol and 3 mol of 9-octadecenoic acid. And most preferably a reaction product of 1 mol of glycerin and 1.5 mol of octadecanoic acid, a reaction product of 1 mol of pentaerythritol and 2 mol of octadecanoic acid, and a reaction product of 1 mol of glycerin and 1.5 mol of 9-octadecenoic acid.
[0037]
The production method of the fatty acid partial ester (A) is as follows: (1) a method of reacting a fatty acid with a divalent to hexavalent alcohol in the presence of an acid catalyst or an alkali catalyst, and (2) in the presence of an acid catalyst or an alkali catalyst. , A method of reacting an acid anhydride of a fatty acid or an acid halide of a fatty acid with a divalent to hexavalent alcohol, (3) in the presence of an acid catalyst or an alkali catalyst, a lower alcohol (1 to 4 carbon atoms: methanol, ethanol, A method of reacting a fatty acid ester (such as propanol and butanol) with a divalent to hexavalent alcohol (a transesterification reaction) can be applied.
[0038]
As the acid catalyst, a known esterification acid catalyst or the like can be used, and examples include paratoluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid, boron trifluoride, and an acidic ion exchange resin.
When an acid catalyst is used, the amount used (% by weight) is preferably from 0.01 to 3, more preferably from 0.1 to 1, particularly preferably based on the total weight of the fatty acid and the 2-6 alcohol. 0.2-0.8.
[0039]
As the alkali catalyst, a known esterified alkali catalyst or the like can be used. Alkali metal alkoxide (sodium methylate, potassium ethylate, etc.), ammonia, amine having 3 to 8 carbon atoms (pyridine, triethylamine, etc.), aluminum alkoxide (aluminum) Methylate, etc.) and alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.).
When an alkali catalyst is used, the amount used (% by weight) is preferably 0.01 to 5, more preferably 0.1 to 2, particularly preferably based on the total weight of the fatty acid and the 2-6 alcohol. 0.3 to 1.5.
[0040]
As reaction temperature (degreeC), 110-180 are preferable, More preferably, it is 120-160.
In the esterification reaction, a reaction solvent can be used as necessary.
The reaction solvent can be used without limitation as long as it does not chemically react with the divalent to hexavalent alcohol and the fatty acid and dissolves them, and examples thereof include toluene, xylene, and benzene.
When a reaction solvent is used, the amount used (% by weight) is preferably 10 to 500 based on the total weight of the fatty acid and the 2-6 hexahydric alcohol.
[0041]
Next, the polyoxyalkylene compound (B) represented by the general formula (1) will be described.
In the general formula (1), R (a linear or branched alkyl group or alkenyl group having 8 to 28 carbon atoms) includes a linear alkyl group, a linear alkenyl group, a branched alkyl group, a branched alkenyl group, and the like. It is.
[0042]
Examples of the linear alkyl group include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl and octacosyl.
Examples of the straight-chain alkenyl group include octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicenyl, dococenyl, tetracocenyl, hexacosenyl and octacocenyl.
Examples of the branched alkyl group include 2-ethylhexyl, 1-methylheptadecyl and 1-hexylheptyl.
[0043]
Examples of the branched alkenyl group include 2-ethylhexenyl, 1-methylheptadecenyl, 1-hexylheptenyl and the like.
Of these, a linear alkyl group, a linear alkenyl group, and a branched alkyl group are preferable, a linear alkyl group and a linear alkenyl group are more preferable, and a linear alkyl group is particularly preferable. In addition, as for carbon number of an alkyl group and an alkenyl group, 8-28 are preferable, More preferably, it is 12-24, Especially preferably, it is 14-22. Within this range, the defoaming performance is further improved.
[0044]
Examples of XO (oxyalkylene group having 3 to 4 carbon atoms) include oxypropylene and oxybutylene, and oxypropylene is preferable.
m is preferably an integer of 3 to 10, more preferably an integer of 4 to 9, and particularly preferably an integer of 5 to 8. Within this range, the defoaming performance is further improved.
n is preferably an integer of 5 to 40, more preferably an integer of 7 to 30, and particularly preferably an integer of 10 to 25. Within this range, the defoaming performance is further improved.
m + n is preferably an integer of 8 to 50, more preferably an integer of 11 to 39, and particularly preferably an integer of 15 to 33. Within this range, the defoaming performance is further improved.
(XO) n represents a polyoxyalkylene group, and when two or more types of oxyalkylene groups are present, any of a block shape, a random shape, and a combination thereof may be used. From the viewpoint of defoaming performance, a block shape is preferable.
(C ₂ H _Four O) m represents a polyoxyalkylene group, and H represents a hydrogen atom.
(C ₂ H _Four O) m (XO) n is (C ₂ H _Four O) m and (XO) n are bonded in a block form.
[0045]
The cloud point (° C.) of the polyoxyalkylene compound (B) by the 25 wt% butyl diglycol aqueous solution method is preferably 43 to 70, more preferably 50 to 65, and particularly preferably 52 to 62. That is, the cloud point (° C.) of (B) is preferably 43 or more, more preferably 50 or more, particularly preferably 52 or more, and preferably 70 or less, more preferably 65 or less, particularly preferably 62 or less. It is. Within this range, the defoaming performance is further improved.
[0046]
In addition, a cloud point means the physical-property value used as the scale of hydrophilicity / hydrophobicity of surfactant, and it represents that hydrophilic property is so large that a cloud point is high. In the present invention, the cloud point is measured according to “Measurement method B” in ISO 1065-1975 (E), “Ethylene oxide nonionic surfactant-cloud point measurement method”. That is, a sample is put into a 25% by weight aqueous solution of butyl diglycol (3,6-oxadecyl alcohol: butanol ethylene oxide 2 mol adduct) so as to have a concentration of 10% by weight and dissolved uniformly (usually at 25 ° C. If it does not dissolve, cool it until it becomes a clear liquid). Next, about 5 cc of this sample solution is taken into a test tube having an outer diameter of 18 mm, a total length of 165 mm, and a wall thickness of about 1 mm, and a thermometer with a diameter of about 6 mm, a length of about 250 mm, and a half degree scale is placed in the sample solution. While stirring, the sample solution is made cloudy by raising the temperature at 1.0 ± 0.2 ° C./min. Thereafter, while stirring, it is cooled at 1.0 ± 0.5 ° C./min to read the temperature at which the sample solution becomes transparent, and this is taken as the cloud point.
[0047]
The cloud point of the polyoxyalkylene compound (B) tends to decrease when the carbon number of R in the general formula (1) is increased, and the cloud point increases when the ratio of m / (m + n) is increased. Tend. Further, when the number of carbon atoms in XO is 3, the cloud point tends to be higher than 3. R tends to have a lower cloud point in the branched chain than in the straight chain, and a higher cloud point in the alkenyl group than in the alkyl group.
[0048]
Examples of the polyoxyalkylene compound (B) include compounds represented by the following formulae. N-C _{twenty two} H ₄₅ O represents n-docosyloxy, n-C ₁₈ H ₃₇ O represents n-octadecyloxy, n-C ₁₈ H ₃₅ O represents n-octadecenyloxy, n-C ₁₆ H ₃₃ O represents n-hexadecyloxy, n-C ₁₄ H ₂₉ O represents n-tetradecyloxy, n-C ₁₂ H _{twenty five} O represents n-dodecyloxy, 2-EHO represents 2-ethylhexyloxy, EO represents oxyethylene, PO represents oxypropylene, BO represents oxybutylene, and H represents a hydrogen atom.
[0049]
[Chemical 3]
1) n-C ₁₈ H ₃₇ O- (EO) _Three (PO) _Five -H (cloud point: 61.7 ° C)
2) n-C ₁₈ H ₃₇ O- (EO) _Five (PO) _Ten -H (cloud point: 65.5 ° C)
3) n-C ₁₈ H ₃₇ O- (EO) ₆ (PO) ₁₅ -H (cloud point: 61.0 ° C)
4) n-C ₁₈ H ₃₇ O- (EO) ₇ (PO) ₂₀ -H (cloud point: 57.8 ° C)
5) n-C ₁₈ H ₃₇ O- (EO) ₈ (BO) ₁₅ -H (cloud point: 58.7 ° C)
6) n-C ₁₈ H ₃₇ O- (EO) ₈ (PO) _{twenty five} -H (cloud point: 55.7 ° C)
7) n-C ₁₈ H ₃₇ O- (EO) _Ten (PO) ₄₀ -H (cloud point: 44.8 ° C)
8) n-C ₁₆ H ₃₃ O- (EO) _Three (PO) _Five -H (cloud point: 62.2 ° C)
9) n-C ₁₆ H ₃₃ O- (EO) _Five (PO) _Ten -H (cloud point: 66.0 ° C)
10) n-C ₁₆ H ₃₃ O- (EO) ₆ (PO) ₁₅ -H (cloud point: 61.5 ° C)
11) n-C ₁₆ H ₃₃ O- (EO) ₇ (PO) ₂₀ -H (cloud point: 58.3 ° C)
12) n-C ₁₆ H ₃₃ O- (EO) ₈ (BO) ₁₅ -H (cloud point: 59.2 ° C)
13) n-C ₁₆ H ₃₃ O- (EO) ₈ (PO) _{twenty five} -H (cloud point: 56.2 ° C)
14) n-C ₁₄ H ₂₉ O- (EO) _Three (PO) _Five -H (cloud point: 62.7 ° C)
15) n-C ₁₄ H ₂₉ O- (EO) _Five (PO) _Ten -H (cloud point: 66.5 ° C)
16) n-C ₁₄ H ₂₉ O- (EO) ₆ (PO) ₁₅ -H (cloud point: 62.0 ° C)
17) n-C ₁₄ H ₂₉ O- (EO) ₇ (PO) ₂₀ -H (cloud point: 58.8 ° C)
18) n-C ₁₄ H ₂₉ O- (EO) ₈ (BO) ₁₅ -H (cloud point: 59.7 ° C)
19) n-C ₁₄ H ₂₉ O- (EO) ₈ (PO) _{twenty five} -H (cloud point: 56.7 ° C)
20) n-C ₁₂ H _{twenty five} O- (EO) _Three (PO) _Five -H (cloud point: 63.2 ° C)
[0050]
[Formula 4]
21) n-C ₁₂ H _{twenty five} O- (EO) _Five (PO) _Ten -H (cloud point: 67.0 ° C)
22) n-C ₁₂ H _{twenty five} O- (EO) ₆ (PO) ₁₅ -H (cloud point: 62.5 ° C)
23) n-C ₁₂ H _{twenty five} O- (EO) ₇ (PO) ₂₀ -H (cloud point: 59.3 ° C)
24) n-C ₁₂ H _{twenty five} O- (EO) ₈ (BO) ₁₅ -H (cloud point: 60.2 ° C)
25) n-C ₁₂ H _{twenty five} O- (EO) ₈ (PO) _{twenty five} -H (cloud point: 57.2 ° C)
26) 2-EHO- (EO) ₈ (PO) _{twenty five} (Cloud point: 58.5 ° C)
27) n-C _{twenty two} H ₄₅ O- (EO) _Three (PO) _Five -H (cloud point: 60.4 ° C)
28) n-C _{twenty two} H ₄₅ O- (EO) _Five (PO) _Ten -H (cloud point: 64.2 ° C)
29) n-C _{twenty two} H ₄₅ O- (EO) ₆ (PO) ₁₅ -H (cloud point: 59.7 ° C)
30) n-C _{twenty two} H ₄₅ O- (EO) ₇ (PO) ₂₀ -H (cloud point: 56.5 ° C)
31) n-C _{twenty two} H ₄₅ O- (EO) ₈ (BO) ₁₅ -H (cloud point: 57.4 ° C)
32) n-C _{twenty two} H ₄₅ O- (EO) ₈ (PO) _{twenty five} -H (cloud point: 54.4 ° C)
33) n-C ₁₈ H ₃₅ O- (EO) _Three (PO) _Five -H (Cloud point: 62.1 ° C)
34) n-C ₁₈ H ₃₅ O- (EO) _Five (PO) _Ten -H (cloud point: 65.9 ° C)
35) n-C ₁₈ H ₃₅ O- (EO) ₆ (PO) ₁₅ -H (cloud point: 61.4 ° C)
36) n-C ₁₈ H ₃₅ O- (EO) ₇ (PO) ₂₀ -H (cloud point: 58.2 ° C)
37) n-C ₁₈ H ₃₅ O- (EO) ₈ (BO) ₁₅ -H (cloud point: 59.1 ° C)
38) n-C ₁₈ H ₃₅ O- (EO) ₈ (PO) _{twenty five} -H (cloud point: 56.1 ° C)
39) n-C ₁₈ H ₃₅ O- (EO) _Ten (PO) ₄₀ -H (cloud point: 45.2 ° C)
[0051]
Among these, the compounds represented by any one of 1), 3) to 6), 8), 10) to 14), 16) to 20), 22) to 33) and 35) to 38) are preferable, More preferably, it is a compound represented by any one of 3) to 6), 10) to 13), 16) to 19), 23) to 27), 29) to 32) and 35) to 38).
[0052]
The polyoxyalkylene compound (B) can be produced by a known alkylene oxide addition reaction. That is, it can be obtained by addition reaction of alcohol and ethylene oxide and then addition reaction of propylene oxide and / or butylene oxide.
As the alcohol, a compound (alcohol) named by adding an alcohol after the linear or branched alkyl group or alkenyl group exemplified above can be used.
[0053]
The addition reaction is carried out in the presence of an alkali catalyst or an acid catalyst. As the alkali catalyst or acid catalyst, a known catalyst can be used as it is, and an alkali metal or alkaline earth metal hydroxide (sodium hydroxide, potassium hydroxide). , Rubidium hydroxide, cesium hydroxide, calcium hydroxide and magnesium hydroxide), alkali metal or alkaline earth metal alcoholates (sodium methylate, potassium methylate, cesium methylate and calcium methylate, etc.), alkali metals or Alkaline earth metal carbonates (sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, etc.), tertiary amines having 3 to 24 carbon atoms (trimethylamine, trioctylamine, triethylenediamine, tetramethylethylenediamine, etc.), and Lewis acid (salt Stannic and boron trifluoride, etc.) and the like. Of these, alkali metal hydroxides and tertiary amines are preferable, and potassium hydroxide, cesium hydroxide, and trimethylamine are more preferable.
When using an alkali catalyst or an acid catalyst, the amount used (% by weight) is preferably 0.05 to 2, more preferably 0.1 to 1, particularly preferably based on the total weight of the alcohol and the alkylene oxide. 0.2-0.6. The catalyst is preferably removed from the reaction product {containing the polyoxyalkylene compound (B)}. As the method, an alkali adsorbent such as a synthetic aluminosilicate [for example, trade name: Kyoward 700, Kyowa Chemical Industries, Ltd.] (Japanese Patent Laid-Open No. 53-123499), a method of dissolving in a solvent such as xylene or toluene and washing with water (Japanese Patent Publication No. 49-14359), a method using an ion exchange resin And a method of filtering a carbonate formed by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000). As the end point of catalyst removal, the CPR (Controlled Polymerization Rate) value described in JIS K1557-1970 is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. As the addition reaction apparatus, it is preferable to use a pressure resistant reaction vessel capable of heating, cooling and stirring. As the reaction atmosphere, it is preferable that the inside of the reaction apparatus is under vacuum before introducing alkylene oxide into the reaction system, or an atmosphere of a dry inert gas (argon, nitrogen, carbon dioxide, etc.). Moreover, as reaction temperature (degreeC), 80-150 are preferable, More preferably, it is 90-130. The reaction pressure (gauge pressure: MPa) is preferably 0.8 or less, and more preferably 0.5 or less. The end point of the reaction can be confirmed by the following method. That is, when the reaction temperature is kept constant for 15 minutes, the reaction end point is set when the decrease in the reaction pressure (gauge pressure) is 0.001 MPa or less. The required reaction time is usually 4 to 12 hours.
[0054]
Next, the emulsifier (C) will be described.
Examples of the emulsifier (C) include a nonionic surfactant (C1) and an anionic surfactant (C2).
6-19 are preferable, as for HLB (hydrophilic-hydrophobic balance) of a nonionic surfactant (C1), More preferably, it is 10-18, Most preferably, it is 12-16. That is, the HLB of (C1) is preferably 6 or more, more preferably 10 or more, particularly preferably 12 or more, and is preferably 19 or less, more preferably 18 or less, and particularly preferably 16 or less. Within this range, the defoaming performance is further improved.
[0055]
In addition, HLB of nonionic surfactant (C1) is a value calculated by Formula (2) (new surfactant introduction, page 129, Takehiko Fujimoto, Sanyo Chemical Industries, Ltd.).
[0056]
[Expression 1]
HLB = E / 5 (2)
Here, E shows the ratio (weight%) of the oxyethylene group with respect to the weight of an oxyalkylene group.
[0057]
As nonionic surfactant (C1), polyoxyethylene sorbitan fatty acid ester (C11), polyoxyalkylene fatty acid monoester (C12), polyoxyalkylene fatty acid diester (C13), polyoxyalkylene alkyl ether (C14) and polyoxyethylene Oxyalkylene alkylphenol ether (C15) and the like can be used.
[0058]
Examples of the polyoxyethylene sorbitan fatty acid ester (C11) include sorbitan octadecanoic acid monoester ethylene oxide 4 mol adduct (HLB 9.6), sorbitan 9-octadecenoic acid monoester ethylene oxide 5 mol adduct (HLB 10.0), sorbitan 9-octadecene. Acid triester ethylene oxide 20 mol adduct (HLB11.0), sorbitandodecanoic acid monoester ethylene oxide 4 mol adduct (HLB13.3), sorbitan octadecanoic acid monoester ethylene oxide 20 mol adduct (HLB14.9), sorbitan 9-octadecene Acid monoester ethylene oxide 20 mol adduct (HLB15.0), sorbitan hexadecanoic acid monoester ethylene oxide 20 mol adduct (HLB15.6) and Sorbitan dodecanoic acid monoester of ethylene oxide 20 mol adduct (HLB16.7), and the like.
[0059]
As polyoxyalkylene fatty acid monoester (C12), 9-octadecenoic acid monoester ethylene oxide 4.5 mol adduct (HLB8.4), octadecanoic acid monoester ethylene oxide 9 mol adduct (HLB11.9), dodecanoic acid monoester Ethylene oxide 9 mol adduct (HLB13.1), dodecanoic acid monoester ethylene oxide 13.6 mol adduct (HLB14.8), 9-octadecenoic acid monoester ethylene oxide 23 mol adduct (HLB15.7), octadecanoic acid monoester ethylene oxide 23 mol adduct (HLB15.8), dodecanoic acid monoester ethylene oxide 23 mol adduct (HLB16.5), etc. are mentioned.
[0060]
As polyoxyalkylene fatty acid diester (C13), dodecanoic acid diester ethylene oxide 4.5 mol adduct (HLB 6.6), 9-octadecenoic acid diester ethylene oxide 9 mol adduct (HLB8.4), dodecanoic acid diester ethylene oxide 9 mol addition Product (HLB9.8), 9-octadecenoic acid diester ethylene oxide 13.6 mol addition product (HLB10.4), octadecanoic acid diester ethylene oxide 13.6 mol addition product (HLB10.5), dodecanoic acid diester ethylene oxide 13.6 mol addition Product (HLB11.8), octadecanoic acid diester ethylene oxide 23 mol adduct (HLB13.0), dodecanoic acid diester ethylene oxide 23 mol adduct (HLB14.1), 9-octadecenoic acid die Ether of ethylene oxide 35 mol adduct (HLB14.7), octadecanoic acid diester of ethylene oxide 35 mol adduct (HLB14.8), dodecanoic acid diester of ethylene oxide 35 mol adduct (HLB15.7), and the like.
[0061]
As polyoxyalkylene alkyl ether (C14), lauryl alcohol ethylene oxide 5 mol adduct (HLB10.8), lauryl alcohol ethylene oxide 10 mol adduct (HLB14.1), lauryl alcohol ethylene oxide 23 mol adduct (HLB16.9), Oleyl alcohol ethylene oxide 10 mol adduct (HLB12.4), oleyl alcohol ethylene oxide 20 mol adduct (HLB15.3), stearyl alcohol ethylene oxide 25 mol adduct (HLB16.0), oleyl alcohol ethylene oxide 30 mol adduct (HLB16.6) ) And oleyl alcohol ethylene oxide 40 mol adduct (HLB17.3).
[0062]
Examples of the polyoxyalkylene alkylphenol ether (C15) include nonylphenol ethylene oxide 4 mol adduct (HLB8.9), nonylphenol ethylene oxide 6 mol adduct (HLB10.9), nonylphenol ethylene oxide 10 mol adduct (HLB13.3), nonylphenol ethylene oxide 14 Mole adduct (HLB14.8), nonylphenol ethylene oxide 20 mol adduct (HLB16.0), nonylphenol ethylene oxide 40 mol adduct (HLB17.8), and the like.
[0063]
10-50 are preferable, as for HLB (hydrophilic-hydrophobic balance) of an anionic surfactant (C2), More preferably, it is 15-45, Most preferably, it is 18-42. That is, the HLB of (C2) is preferably 10 or more, more preferably 15 or more, particularly preferably 18 or more, 50 or less, more preferably 45 or less, and particularly preferably 42 or less. Within this range, the defoaming performance is further improved.
In addition, HLB is a value calculated by Formula (3) (Davis method; introduction of new surfactant, page 133, Takehiko Fujimoto, Sanyo Chemical Industries, Ltd.).
[0064]
[Expression 2]
HLB = Σ (number of hydrophilic groups) −Σ (number of hydrophobic groups) +7 (3)
[0065]
Examples of the anionic surfactant (C2) include alkyl sulfate (C21), fatty acid salt (C22), dialkyl sulfosuccinate (C23), lignin sulfonate (C24), and alkyl aromatic sulfonate (C25). And α-olefin sulfonate (C26) and the like can be used. Examples of the salt include alkali metal (such as lithium, sodium and potassium) salts, alkaline earth metal (such as calcium and magnesium) salts and ammonium salts.
[0066]
Examples of the alkyl sulfate (C21) include sodium lauryl sulfate (HLB41) and sodium oleyl sulfate (HLB38).
Examples of the fatty acid salt (C22) include sodium laurate (HLB21) and sodium oleate (HLB) 18.
Examples of the dialkylsulfosuccinate (C23) include sodium dioctylsulfosuccinate (HLB42).
Examples of lignin sulfonate (C24) include sodium lignin sulfonate (HLB44).
Examples of the alkyl aromatic sulfonate (C25) include sodium alkylbenzenesulfonate {sodium dodecylbenzenesulfonate (HLB37)} and sodium alkylnaphthalenesulfonate {sodium monopropylnaphthalenesulfonate (HLB40)}.
Examples of the α-olefin sulfonate (C26) include sodium α-olefin sulfonate (HLB38).
[0067]
As the emulsifier (C), a nonionic surfactant (C1) and an anionic surfactant (C2) may be used alone, or these may be used in combination.
Of these, the nonionic surfactant (C1) is preferable, more preferably polyoxyethylene sorbitan fatty acid ester (C11), polyoxyalkylene fatty acid monoester (C12) and polyoxyalkylene fatty acid diester (C13), particularly preferably (C11) and (C12), most preferably (C11).
[0068]
Next, the thickener (D) will be described.
The weight average molecular weight (Mw) of the synthetic water-soluble polymer (D1) is preferably from 5,000 to 5,000,000, more preferably from 8,000 to 4,500,000, particularly preferably from 10,000 to 4 , 000,000. That is, (Mw) of (D1) is preferably 5,000 or more, more preferably 8,000 or more, particularly preferably 10,000 or more, and preferably 5,000,000 or less, more preferably It is 4,500,000 or less, particularly preferably 4,000,000 or less. Within this range, a moderate thickening effect can be exhibited, and the stability of the antifoaming agent of the present invention can be further increased.
[0069]
The synthetic water-soluble polymer (D1) includes oxyethylene group-containing (co) polymer (d1), sulfo group-containing (co) polymer (d2), carboxy group-containing (co) polymer (d3), carbamoyl group The containing (co) polymer (d4) and the hydroxy group-containing (co) polymer (d5) are included.
[0070]
Examples of the oxyethylene group-containing (co) polymer (d1) include polyethylene glycol, polyoxyethylene / polyoxypropylene copolymer (polyoxyalkylene / polyoxypropylene weight ratio 99/1 to 80/20), alcohol Examples include ethylene oxide adduct, alkyl ether or alkenyl ether of alcohol ethylene oxide adduct, and fatty acid monoester or diester of polyethylene glycol. Examples of the alcohol include linear or branched saturated alcohols having 1 to 22 carbon atoms, and unsaturated (unsaturated bond numbers 1 to 3) alcohols having 18 to 22 carbon atoms. Alkyl has 1 to 22 carbon atoms, and alkenyl has 18 to 22 carbon atoms. Examples of fatty acids include linear or branched saturated fatty acids having 1 to 22 carbon atoms, and unsaturated (unsaturated bonds 1 to 3) fatty acids having 18 to 22 carbon atoms.
[0071]
Examples of the sulfo group-containing (co) polymer (d2) include an alkali metal salt of sulfonated polystyrene and a sulfo group-containing polyvinyl alcohol (copolymer having a unit represented by the following formula in the main chain skeleton of polyvinyl alcohol). Coalescence, etc .; M can be a hydrogen atom, ammonium or alkali metal (sodium, potassium, etc.)} etc.
[0072]
[Chemical formula 5]

[0073]
Examples of the alkali metal salt of sulfonated polystyrene include trade name: Chemistat SA-9 (manufactured by Sanyo Chemical Industries, Ltd.).
Examples of the sulfo group-containing polyvinyl alcohol include trade names: Gocelan L-3266 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and Kuraray Poval SK-5102 (manufactured by Kuraray Co., Ltd.).
[0074]
As the carboxy group-containing (co) polymer (d3), poly (meth) acrylic acid and (meth) acrylic acid-maleic acid copolymer {(meth) acrylic acid: maleic acid weight ratio 99-70: 1- 30} and the like. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid. Examples of (d3) include trade names: Nopco Santo R, SN Dispersant 5034, SN thickener 920, SN thickener 924, SN thickener 926, SN thickener 928 and SN thickener 929 (manufactured by San Nopco Co., Ltd.).
[0075]
As the carbamoyl group-containing (co) polymer (d4), poly (meth) acrylamide and (meth) acrylic acid- (meth) acrylamide copolymer {(meth) acrylic acid: (meth) acrylamide weight ratio of 10 to 50 : 90-50} and the like. Examples of (d4) include trade names: Sanflock NOP, Sanflock AH-200P, and Sanflock AH-330P (manufactured by Sanyo Chemical Industries).
[0076]
Examples of the hydroxy group-containing (co) polymer (d5) include partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol. As (d5), trade names: Kuraray Poval PVA-203, PVA-205, PVA-217, PVA-224, PVA-228, PVA-235, PVA-235, and PVA-424H (above, partially saponified) Polyvinyl alcohol), Kuraray Poval PVA-105, PVA-117, PVA-124, PVA-126H (above, completely saponified polyvinyl alcohol) (manufactured by Kuraray Co., Ltd.) and the like.
[0077]
Examples of the natural water-soluble polymer (D2) include pullulan, gum arabic, guar gum, glucomannan, xanthan gum, tragacanth gum, locust bean gum, agarose, glycogen, sodium alginate and cellulose.
As the semi-synthetic water-soluble polymer (D3), those obtained by chemically modifying a natural water-soluble polymer can be used, and modified cellulose (hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, carboxy) Methyl cellulose, carboxyethyl methyl cellulose, methyl cellulose, ethyl cellulose, cellulose acetate phthalate, etc.) and starch modified products (oxidized starch, etc.).
[0078]
Among the combinations of the synthetic water-soluble polymer (D1) and the natural water-soluble polymer or / and the semi-synthetic water-soluble polymer (D2), the oxyethylene group-containing (co) polymer (d1) and the natural water-soluble polymer Combination with molecule (D2), combination of oxyethylene group-containing (co) polymer (d1) and semisynthetic water-soluble polymer (D3), sulfo group-containing (co) polymer (d2) and natural water-soluble polymer Combination with molecule (D2), Combination with sulfo group-containing (co) polymer (d2) and semi-synthetic water-soluble polymer (D3), Carboxy group-containing (co) polymer (d3) and natural water-soluble polymer (D2), carboxy group-containing (co) polymer (d3) and semi-synthetic water-soluble polymer (D3), carbamoyl group-containing (co) polymer (d4) and natural water-soluble polymer ( D2), hydroxy group-containing (co) polymer (d5) and natural A combination with a soluble polymer (D2) and a combination of a hydroxy group-containing (co) polymer (d5) and a semi-synthetic water-soluble polymer (D3) are preferred, more preferably (d1) and (D2). Combinations, combinations of (d2) and (D2), combinations of (d3) and (D2), combinations of (d4) and (D2), and combinations of (d5) and (D2), particularly preferably A combination of (d1) and (D2), a combination of (d2) and (D2), and most preferably a combination of (d2) and (D2).
[0079]
The content weight ratio {D1 / (D2 + D3)} of the synthetic water-soluble polymer (D1), the natural water-soluble polymer (D2) and / or the semi-synthetic water-soluble polymer (D3) is preferably 0.01 to 99. More preferably, it is 0.6-9, Most preferably, it is 1.5-4. That is, the content weight ratio {D1 / (D2 + D3)} is preferably 0.01 or more, more preferably 0.6 or more, particularly preferably 1.5 or more, and preferably 99 or less, more preferably 9 or less. Particularly preferably, it is 4 or less. Within this range, a moderate thickening effect can be exhibited, and the stability of the antifoaming agent of the present invention can be further increased.
[0080]
When the natural water-soluble polymer (D2) and the semi-synthetic water-soluble polymer (D3) are contained, the weight ratio (D2 / D3) of (D2) and (D3) is preferably 0.01 to 99, Preferably it is 0.6-9, Most preferably, it is 1.5-4. That is, in this case, the content weight ratio (D2 / D3) is preferably 0.01 or more, more preferably 0.6 or more, particularly preferably 1.5 or more, and preferably 99 or less, more preferably 9 or less, particularly preferably 4 or less. Within this range, a moderate thickening effect can be exhibited, and the stability of the antifoaming agent of the present invention can be further increased.
[0081]
Next, water (E) will be described.
As water (E), distilled water, ion exchange water, tap water, industrial water, well water, water for spraying, river water, rain water and the like can be used, but soft water such as ion exchange water, tap water and industrial water is preferable.
[0082]
The content (% by weight) of the fatty acid partial ester (A) is based on the total weight of (A), the polyoxyalkylene compound (B), the emulsifier (C), the thickener (D), and water (E). 20-30 are preferable, More preferably, it is 21-29, Most preferably, it is 22-28. That is, the content (% by weight) of (A) is preferably 20 or more, more preferably 21 or more, particularly preferably 22 or more, and 30 or less based on the total weight of (A) to (E). Is preferable, more preferably 29 or less, and particularly preferably 28 or less. Within this range, the defoaming performance and fluidity are further improved.
[0083]
The content (% by weight) of the polyoxyalkylene compound (B) is preferably 4 to 10, more preferably 5 to 9, particularly preferably 6 to 8, based on the total weight of (A) to (E). is there. That is, the content (% by weight) of (B) is preferably 4 or more based on the total weight of (A) to (E), more preferably 5 or more, particularly preferably 6 or more, and 10 or less. Is preferable, more preferably 9 or less, and particularly preferably 8 or less. Within this range, the viscosity, antifoaming performance, and water resistance of the additive to which the antifoaming agent of the present invention is added are further improved.
[0084]
The content (% by weight) of the emulsifier (C) is preferably 0.3 to 5, more preferably 0.4 to 4, particularly preferably 0.5, based on the total weight of (A) to (E). ~ 3. That is, the content (% by weight) of (C) is preferably 0.3 or more, more preferably 0.4 or more, particularly preferably 0.5 or more, based on the total weight of (A) to (E). Moreover, 5 or less is preferable, More preferably, it is 4 or less, Most preferably, it is 3 or less. Within this range, the viscosity and defoaming performance are further improved.
[0085]
The content (% by weight) of the thickener (D) is preferably 0.01 to 5, more preferably 0.1 to 4, particularly preferably 0, based on the total weight of (A) to (E). .5-3. That is, the content (% by weight) of (D) is preferably 0.01 or more, more preferably 0.1 or more, particularly preferably 0.5 or more, based on the total weight of (A) to (E). And is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less. Within this range, the viscosity and stability are further improved.
[0086]
The content (% by weight) of water (E) is preferably 50 to 75, more preferably 55 to 73, particularly preferably 60 to 70, based on the total weight of (A) to (E). That is, the content (% by weight) of (E) is preferably 50 or more based on the total weight of (A) to (E), more preferably 55 or more, particularly preferably 60 or more, and 75 The following is preferable, more preferably 73 or less, and particularly preferably 70 or less. Within this range, the viscosity and stability are further improved.
[0087]
The emulsion antifoaming agent of the present invention can contain a buffer (F) made of an inorganic compound and / or an organic compound. The buffer (F) can adjust the pH of the emulsion type antifoaming agent of the present invention to 6.0 to 8.5, and at this pH, the decomposition of the emulsion type antifoaming agent of the present invention is suppressed. can do.
Examples of the inorganic compound include disodium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydroxide, hydrochloric acid, potassium chloride, and boric acid.
Examples of the organic compound include tris (hydroxymethyl) aminomethane and potassium hydrogen phthalate.
[0088]
When the buffer (F) is used, it is usually preferable to dissolve it in water (E) and handle it in the same manner as water (E). As the pH of the buffer (F), for example, a buffer aqueous solution prepared from potassium dihydrogen phosphate and sodium hydroxide, and a buffer aqueous solution prepared from disodium hydrogen phosphate and sodium hydroxide are used. It can be set to 6.0 to 8.5.
[0089]
Commercially available buffers include Clark-Lubs buffer (pH: 1.0 to 10.0), Kolthoff buffer (pH: 2.2 to 12.0), Michaelis buffer (pH: 1.4 to 11.0), Gomori's buffer (pH: 6.4 to 9.7), and Bates-Bower's Tris buffer (pH: 7.0 to 9.0).
[0090]
When the buffer (F) is used, the content (% by weight) is preferably 0.01 to 3.0, more preferably 0.05 to 2.5, based on the weight of water (E). Most preferably, it is 0.1-2.0. That is, in this case, the content (% by weight) of (F) is preferably 0.01 or more, more preferably 0.05 or more, particularly preferably 0.1 or more, based on the weight of water (E). In addition, it is preferably 3.0 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. Within this range, it is easy to adjust to a better pH.
[0091]
The emulsion antifoaming agent of the present invention can further contain other components as necessary.
Other ingredients include fatty acids and their salts, amides, animal and vegetable oils, hydrocarbon oils, silicones, hydrophobic silicas and hydrophilic silicas, as well as antifungal agents, antiseptics, rust inhibitors, antioxidants and skin prevention. Agents and the like.
[0092]
Examples of fatty acids include linear saturated fatty acids and linear unsaturated fatty acids. The above-mentioned ones can be used, and preferred ranges are also the same. Examples of the salt include the above-mentioned linear saturated fatty acid, linear monounsaturated fatty acid, or ammonium salt, sodium salt, calcium salt, magnesium salt, aluminum salt, monoethanolamine salt and diethanolamine of di- or tri-unsaturated fatty acid. Examples include salts. Examples of amides include fatty acid monoamides and fatty acid diamides. As the fatty acid monoamide, a fatty acid monoamide having 19 to 44 carbon atoms can be used, and examples thereof include lauryl stearate monoamide, lauryl monooleate, oleyl monoamide stearate, and oleyl monoamide oleate. As the fatty acid diamide, a fatty acid diamide having 26 to 46 carbon atoms can be used, and N, N'-ethylenebisstearic acid amide, N, N'-ethylenebisoleic acid amide and N, N'-ethylenebislauric acid amide Etc. As animal and vegetable oils, natural vegetable oils, natural animal oils and modified oils thereof can be used, and examples thereof include beef tallow, lard, whale oil, fish oil, rapeseed oil, soybean oil, peanut oil, and hydrogenated oils thereof. As hydrocarbon oil, kinematic viscosity (mm ² Mineral oil or the like having a / s) of 5 to 40 can be used, and examples include stanol 35 (Esso Oil Co., Ltd.) and MC oil P22 (Idemitsu Kosan Co., Ltd.). Silicone has a kinematic viscosity of 25 ° C (mm ² Dimethylpolysiloxane and modified dimethylpolysiloxane having a / s) of 50 to 10,000 can be used. Examples of the modified dimethylpolysiloxane include SH200-100CS (Toray Dow Corning Silicone Co., Ltd.) and SH200-1000CS (Toray). -Dow Corning Silicone Co., Ltd.) and SH200-5000CS (Toray Dow Corning Silicone Co., Ltd.). Hydrophobic silica means silica obtained by treating silicon dioxide with a hydrophobizing agent. Examples of the hydrophobizing agent include fatty acids having 12 to 24 carbon atoms (such as stearic acid), higher alcohols having 12 to 36 carbon atoms (such as stearyl alcohol), aliphatic amines having 12 to 22 carbon atoms (such as stearyl amine), and carbon numbers. 24-36 fatty acid amides (such as lauryl oleate monoamide, N, N′-ethylenebisstearylamide) and silicones (polydimethylsiloxane and alkyl group-modified polypolydimethylsiloxane, hydroxyl group-modified polypolydimethylsiloxane, amino group-modified polypolydimethylsiloxane, and A reactive silicone such as alkyl group-modified hydrodiene polydimethylsiloxane). As silicon dioxide, silica produced by a precipitation method, silica produced by a gel method, silica produced by a dry method, and the like are used. The particle diameter (μm) of silicon dioxide is preferably 0.1 to 10, more preferably 0.5 to 5, particularly preferably 0.7 to 3. As the hydrophilic silica, the above silicon dioxide or the like can be used.
[0093]
As the antifungal agent, a nitrile type, aldehyde type, phenol type, naphthalene type, naphthenic acid metal salt type or organotin type antifungal agent can be used, and 2,3,5,6-tetrachloroisophthalonitrile, Examples include formaldehyde, glutaraldehyde, pentachlorophenyl laurate, o-chloronaphthalene, copper naphthenate, zinc naphthenate, and methyl parahydroxybenzoate. As preservatives, isothiazoline, benzthiazol, benzothiazol, quaternary ammonium salt or dithiocarbamate preservatives can be used, such as 1,2-benzoisothiazoline-3-one, 2 -N-octyl-4-isothiazolin-3-one, 2- (4-thiazolyl) benzthiazol, 2- (thiocyanomethylthio) benzothiazol, tetradecyldimethylbenzylammonium chloride and tetramethylthiuram disulfide . As rust preventives, fatty acid metal salts, fatty acid amine salts, fatty acid esters, sulfonates, phosphate esters and amine derivatives can be used, such as sodium naphthenate, cyclohexylamine salt of abietic acid, sorbitan monooleate, petroleum sulfonate and Examples include cyclohexylamine ethylene oxide 10 mol adduct. As the antioxidant, phenol-based, amine-based, sulfur-based or phosphorus-based antioxidants can be used. 2,6-ditertiary butyl-4-methylphenol, butylated hydroxyanisole, 2,2′-methylenebis (Examples include 4-methyl-6-tert-butylphenol, dilauryl 3,3′-thiodipropionate, and triphenyl phosphite. Examples of the anti-skinning agent include polyether-based, ketoxime-based, and higher alcohol-based leathers. Anti-tensioning agents and the like can be used, and examples include ethylene oxide 20 mol adduct, methyl ethyl ketoxime and cetyl alcohol ethylene oxide 2 mol adduct.
[0094]
When fatty acids and salts thereof, amides, animal and vegetable oils, hydrocarbon oils and / or silicones are used, their total content (% by weight) is based on the weight of the partial ester (A) and the polyoxyalkylene compound (B). 0.1-10 is preferable, More preferably, it is 0.3-8, Most preferably, it is 0.5-5. When using antifungal agents, antiseptics, rust inhibitors, antioxidants and / or anti-skinning agents, their total content (% by weight) is 0.001 based on the weight of water (E). ˜1 is preferable, more preferably 0.01 to 0.8, and particularly preferably 0.05 to 0.5. Other components can be added either after adjustment of the emulsion type antifoaming agent, during adjustment and / or before adjustment.
[0095]
The emulsion antifoaming agent of the present invention comprises: (1) a partial ester (A), a polyoxyalkylene compound (B) and an emulsifier (C) after melt mixing, and then a thickener (D), water (E) and, if necessary, (2) (D), (E) and, if necessary, the mixed aqueous solution of (F), (A), (B) and (3) A method of stirring and mixing while adding the mixture of (C), (3) (A) an emulsion prepared in the same manner as (1) or (2), and (B) of (1) or A method of mixing with an emulsion prepared in the same manner as 2), using a part of {4} (E) {not including (D)}, and a high-concentration emulsion in the same manner as in 1) to 3) Is prepared, and the remaining (E), (D) and, if necessary, (F) are mixed. Using the method of adding an aqueous solution and part of {5} (E) {not including (D)}, a high-concentration emulsion was prepared in the same manner as in {circle over (1)} to {circle around (3)}. (E), (D), and a method of adding to the mixed aqueous solution of (F) if necessary. The emulsifier (C), the thickener (D) and, if necessary, the buffer (F) may be mixed with the partial ester (A) and / or the polyoxyalkylene compound (B), and water. You may mix with (E). Further, (C), (D) and, if necessary, a part of (F) may be mixed with (A) and / or (B), and the rest may be mixed with (E). Of these, the method (1), (2) or (3) is preferred, the method (1) or (2) is more preferred, and the method (1) is particularly preferred.
[0096]
The emulsification temperature (° C.) is preferably 45 to 95, more preferably 50 to 90, and particularly preferably 55 to 80. That is, the emulsification temperature (° C.) is preferably 45 or higher, more preferably 50 or higher, particularly preferably 55 or higher, 95 or lower, more preferably 90 or lower, particularly preferably 80 or lower. . The emulsification time varies depending on batch (batch) production or continuous production or production amount. For example, in the case of batch production with 1 ton of production, it is about 0.1 to 24 hours, preferably 0.5 to 5 hours, more preferably 1 to 3 hours.
[0097]
0.1-50 are preferable, as for the volume average particle diameter (micrometer) of the emulsion particle | grains in the emulsion type antifoamer of this invention, More preferably, it is 0.5-20, Most preferably, it is 1-10. That is, the volume average particle diameter (μm) of the emulsion particles is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, and preferably 50 or less, more preferably 20 or less, Particularly preferably, it is 10 or less. Within this range, the stability of the emulsion type antifoaming agent is further improved.
[0098]
The volume average particle size was measured using a laser diffraction particle size analyzer [for example, Microtrac Model No. 9320-X100 (laser light wavelength: 780 nm) manufactured by Leeds & Northrup Co.] and water having an electric conductivity of 0.1 mS / m or less. A sample concentration of 0.1% by weight is obtained in an aqueous solution of 1000 parts by weight and 0.2 parts by weight of polyacrylamide having a weight average molecular weight of 500,000 to 20 million {eg, Sanfloc NOP, Sanyo Chemical Industries, Ltd.] Thus, a measurement sample is added and measured at a measurement temperature of 25 ± 10 ° C. (50% cumulative volume average particle diameter by laser diffraction particle size distribution measurement method). The refractive index of the circulating fluid (water) is 1.33 and the refractive index of the emulsion particles is 1.46.
[0099]
As the stirring and mixing device, a propeller type stirrer, a dissolver, a homomixer, a ball mill, a sand mill, an ultrasonic disperser, a kneader, a line mixer, and the like can be used, and these two or more types of equipment can be used in combination. Among these, a propeller type stirrer, a dissolver and a homomixer are preferable, a propeller type stirrer and a homomixer are more preferable, and a propeller type stirrer is particularly preferable. As the emulsifying and dispersing device, an ordinary emulsifying and dispersing device can be used, a high-pressure jet type emulsifying and dispersing device (gaulin homogenizer, microfluidizer, nanomizer, etc.), and an ultrasonic emulsifying disperser (dispersonic, ultra jetter, etc.). , Pressurized nozzle type emulsifier (homogenizer), high-speed rotation high shear type agitated emulsifier disperser (homomixer, coreless mixer, disper mill, disc cavitation mixer, status roller, etc.) and grinding type emulsifier disperser (sand grinder, An agitator mill, a ball mill, a sand mill, a colloid mill, an attritor, etc.) can be used. These two or more types of equipment can be used in combination, and a stirring and mixing device and an emulsifying and dispersing device can be used in combination. Among these, a high-pressure injection type emulsification disperser, a high-speed rotation high shear type stirring emulsification disperser, and a grinding type emulsification disperser are preferable, and a high-pressure injection type emulsification disperser, a grinding type emulsification disperser, and a high-speed rotation height A shear type agitation emulsification disperser, particularly preferably a high-pressure jet type emulsification disperser and a high-speed rotation high shear type agitation emulsification disperser.
[0100]
Volume average particle size is determined by changing the discharge pressure in the case of a high-pressure injection type emulsifying disperser, changing the ultrasonic output in the case of an ultrasonic emulsifying disperser, and circulating liquid in the case of a pressure nozzle type emulsifying machine. By changing the speed, in the case of a high-speed rotating high shear type agitated emulsifying disperser, by changing the rotational force and / or clearance of the rotating blades and changing the shearing force, in the case of a grinding type emulsifying disperser, the type of media It can be adjusted by changing the size and rotation speed.
[0101]
The emulsion type antifoaming agent of the present invention is a liquid containing a synthetic and / or natural foaming surfactant (hereinafter referred to as foaming liquid: washing water for pulp, electronic substrate, metal parts and fibers, fermentation liquid, paper white water, Excellent defoaming effect (foam suppression, foam breakage, degassing, foam control, etc.) for papermaking white water, industrial wastewater, manure treated water, water-based paint, water-based ink, monomer stripping liquid, municipal sewage, ceramic slurry, etc. However, it is suitable for foaming liquid containing inorganic powder, and is most suitable for papermaking slurry and papermaking white water in the manufacturing process (particularly papermaking process) of hydraulic inorganic building materials.
[0102]
Examples of inorganic powders include silica, calcium carbonate, talc, clay, kaolin, calcium silicate, titanium dioxide, magnesium oxide, magnesium carbonate, magnesium chloride, aluminum chloride, and aluminum silicate. Absent.
[0103]
The emulsion-type antifoaming agent of the present invention may be any of continuous addition, intermittent addition, a method in which a foam measuring device and an antifoaming agent adding device are linked, and a combination thereof. But you can. Further, upon addition, it may be diluted with a suitable water-soluble solvent or water, etc., and can be used in combination with other antifoaming agents.
The amount of the emulsion-type antifoaming agent of the present invention can be appropriately increased or decreased depending on the type, temperature, concentration and treatment amount (foaming degree, etc.) of the foaming liquid, but 10 based on the weight of the foaming liquid. ^-Five -1% by weight is preferred, more preferably 10%. ^-Four ~ 0.5% by weight, particularly preferably 10 ^-3 ~ 0.2 wt%.
In addition, in the case of the papermaking slurry of a hydraulic inorganic building material, the usage-amount (weight%) of the emulsion type antifoamer of this invention is preferably 0.0001-1 based on the weight of the inorganic powder to contain, Furthermore, Preferably it is 0.001-0.5, Most preferably, it is 0.0025-0.05.
Moreover, in the case of the papermaking white water of a hydraulic inorganic building material, the usage-amount (weight%) of the emulsion type antifoamer of this invention has preferable 0.0001-0.5 based on the weight of white water, More preferably 0.001 to 0.1, particularly preferably 0.0025 to 0.05.
[0104]
The emulsion type antifoaming agent of the present invention is particularly suitable for use in a papermaking process for producing a hydraulic inorganic building material (building material board). When the emulsion type antifoaming agent of the present invention is used in a papermaking process for producing a hydraulic inorganic building material, it exhibits extremely excellent water resistance and antifoaming performance. Examples of hydraulic inorganic building materials include asbestos / cement board, non-asbestos / cement board, calcium silicate board, exterior materials, interior construction materials and inorganic construction material boards such as tiles, and organic construction material boards such as tatami mats.
Inorganic building material boards are made of inorganic powder (cement, calcium silicate, magnesium oxide, calcium carbonate, silica, etc.), fiber reinforcement (unbleached pulp, bleached pulp, pulp fiber, etc.), asbestos, glass fiber, synthetic fiber, Paper can be made by adhering a mixed slurry of water or the like to a paper making drum, filtered and dehydrated (so far, the paper making process), dried and cured. Organic building material board is made of fiber reinforcing agent, synthetic fiber, organic binder (phenol resin, methylcellulose, polyvinyl alcohol, ethylene vinyl acetate copolymer, polyethylene oxide, etc.), inorganic powder (cement, calcium silicate, magnesium oxide, calcium carbonate and silica) Etc.) and a mixed slurry of water or the like is made to adhere to a papermaking drum, and can be produced by filtration, dehydration (up to here the papermaking process), drying and curing.
As the papermaking drum, there are a round netting method and a long netting method, and any of them can be used. Curing includes a natural curing method, a steam curing method, an autoclave curing method, and the like, and any of them can be used.
Bubbles in the papermaking process are likely to be generated mainly during slurry mixing and stirring and during filtration and dewatering with a papermaking drum. Therefore, it is preferable to add the emulsion type antifoaming agent of this invention before these processes or these processes.
[0105]
【Example】
EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited by a following example. In addition, a part represents a weight part and% represents weight%. Further, Table 1 shows the measurement results of the hydroxyl value, melting point and acid value. Cloud point and ¹ The measurement results of H-NMR are shown in Table 2. The measurement results of the weight average molecular weight are shown in Tables 3 and 4. Table 6 shows the evaluation results of the volume average particle diameter, stability, defoaming performance and water resistance.
[0106]
<Hydroxyl value (mgKOH / g)> Measured according to JIS K-0070-1992.
<Melting point (° C.)> Measured according to JIS K-0064-1992.
<Acid Value (mgKOH / g)> Measured according to JIS K-0070-1992.
<Cloud point (° C.)> Measured according to ISO-1065-1975.
< ¹ H-NMR> solvent: deuterated chloroform, concentration: 0.5%, apparatus: 300 MHz superconducting NMR (model: XL-300) manufactured by VARIAN.
[0107]
<Weight average molecular weight> It was measured by gel permeation chromatography (GPC) using ethylene oxide having a known molecular weight as a standard substance.
Equipment: HLC-8120GPC, Tosoh Corporation,
GPC column: model TSKgelG5000PWXL and model TSKgelG3000PWXL, one each connected in series,
Eluent: 1000 parts of water having an electric conductivity of 0.1 mS / m or less, 7.0 parts of reagent-grade anhydrous sodium dihydrogen phosphate (Wako Pure Chemical Industries, Ltd.) and reagent-grade grade of disodium hydrogen phosphate anhydrous (sum Kojun Pharmaceutical Co., Ltd.) 7.1 parts aqueous solution,
Eluent flow rate: 0.80 mL / min,
Column temperature: 40 ° C
Detector: RI (refraction) detector,
Sample concentration: 0.4% eluent solution,
Sample solution injection volume: 50 μL,
Standard substances: TSK standard polyethylene oxide (SE-150: weight average molecular weight 920,000, SE-70: weight average molecular weight 540,000, SE-30: weight average molecular weight 250,000, SE-15: weight manufactured by Tosoh Corporation Average molecular weight 140,000, SE-8: weight average molecular weight 107,000, SE-5: weight average molecular weight 50,000), Wako Pure Chemical Industries, Ltd. Wako standard first grade polyethylene glycol 6000 (weight average molecular weight 7) , 500), and Wako Pure Chemical Industries, Ltd., reagent grade ethylene glycol (molecular weight 62), Sumitomo Seika Co., Ltd. polyethylene oxide (PEO-18, weight average molecular weight 4,500,000)
[0108]
<Volume average particle diameter of emulsion particles (μm)>
The volume average particle diameter of the emulsion particles is determined by a laser diffraction particle size analyzer {Microtrac Model No. manufactured by Leeds & Northrup Co. 9320-X100 (laser light wavelength: 780 nm), circulating liquid: aqueous solution of 1000 parts of water having an electric conductivity of 0.1 mS / m or less and 0.2 part of Sanfloc NOP (manufactured by Sanyo Chemical Industries), Measurement sample concentration: 1% (diluted with circulating fluid), FLOW: 60% (value with respect to circulating fluid device MAX100%), POWER: 40, measuring temperature: 25 ± 10 ° C., circulating for 30 seconds.
The volume average particle diameter was calculated by a Nikkiso data processor using a refractive index of the circulating fluid of 1.33 and a refractive index of the emulsion particles of 1.46.
[0109]
<Stability>
(1) Separation stability
The measurement sample (antifoaming agent) was put in a 225 cc glass bottle with an inner diameter of 50 mm up to a height of 80 mm, sealed, left to stand at 25 ± 3 ° C. for 1 month, and then the total height W of the aqueous layer formed in the upper layer and / or the lower layer ( mm) was measured, and the separation stability (%) was calculated from the following equation (4).
[Equation 3]
Separation stability (%) = (W / 80) × 100 (4)
[0110]
(2) Viscosity stability
After evaluating the separation stability, the viscosity was continuously measured, and the viscosity stability (%) was calculated from the following formula (5) from this viscosity (N1) and the viscosity immediately after production (N0).
The viscosity was measured with a B-type viscometer model TVB-20L (Tokimec Co., Ltd.) (25 ± 1 ° C., rotor rotational speed 60 RPM, 1 minute value).
[Expression 4]
Viscosity stability (%) = {(N1) − (N0)} × 100 / (N0) (5)
[0111]
(3) Stability judgment
The stability of the measurement sample (antifoaming agent) was determined according to the following evaluation criteria.
○: Separation stability is 0 to 2% and viscosity stability is 0 to 50%
Δ: Separation stability is 3 to 5%, and viscosity stability is 50 to 100%.
X: Separation stability is 5% or more and / or viscosity stability is 100% or more
[0112]
<Defoaming performance (mm)>
(1) Defoaming performance for water-curable inorganic building material slurry 1
Asbestos / cement board making process 93 parts of white water (Mitsubishi Materials Building Materials Co., Ltd. Kyushu Factory), 6 parts of Portland cement, 1 part of unbleached pulp (cut into 1 cm long and 1 cm wide squares) (Hyogo Pulp Co., Ltd.) The mixture was placed in a juicer mixer (model: National Mixer MX-151S, manufactured by Matsushita Electric Works), and stirred and mixed at 25 ° C. and a constant voltage of 100 V for 3 minutes to prepare a slurry.
100 g (25 ° C.) of this slurry is placed in a glass graduated cylinder having an inner diameter of 50 mm and a height of 350 mm, 1 μl of a measurement sample (antifoaming agent) is added, and the diffuser stone is slurried according to the foaming test of JIS K2518-1990. It inserted to the bottom part, air was ventilated at 4000 mL / min, and the total height (mm) of the slurry and foam 3 minutes after the start of aeration was measured. In addition, it measured also about the blank without an antifoamer.
[0113]
(2) Defoaming performance for water-curable inorganic building material paper-making white water 2
Non-asbestos / cement board making process White water (Mitsubishi Materials Building Materials Co., Ltd. Kyushu Factory (25 ° C) 100g is placed in a glass graduated cylinder with an inner diameter of 50mm x height of 350mm, and 1μl of measurement sample (antifoam) is added. According to the foaming test of 2518-1990, a diffuser stone was inserted to the bottom of white water and air was ventilated at 4000 mL / min, and the foam height (mm) was measured 3 minutes after the start of aeration. It was also measured for blanks without foam.
[0114]
<Water resistance 1>
Non-asbestos / cement board making process White water (Mitsubishi Materials Building Materials Co., Ltd. Kyushu Factory) 930g, Portland cement 60g, unbleached pulp (cut 1cm in length and 1cm in width) (Hyogo Pulp Co., Ltd.) 10g in juicer mixer ( (Model: National Mixer MX-151S, manufactured by Matsushita Electric Works) and stirred and mixed for 3 minutes under a constant voltage of 100V. Further, 0.70 g of a measurement sample (antifoaming agent) was added and stirred and mixed for 10 seconds under a constant voltage of 100V. Next, this slurry was mixed with a Nutsche and a circular No. 11 cm diameter. Using 2 filter paper (Advantech Toyo Co., Ltd.), vacuum filtration (vacuum pressure 6,700 Pa) was performed to prepare a water-containing water-curable inorganic building material (water-containing board). In addition, the end point of filtration was made into the point from which the layer of water cannot be recognized on the filtration residual surface.
The water-containing board (water-curable inorganic building material) was placed in a constant temperature bath at 90 ° C. capable of generating saturated water vapor and allowed to stand for 48 hours to prepare a cured board.
A blank board was produced in the same manner as described above except that the measurement sample (antifoaming agent) was not added (the water resistance of this board was indicated in the blank column of Table 5).
The weight (W1) of this cured board after standing for 8 hours in a constant temperature and humidity room at 25 ± 1 ° C. and a relative humidity of 40 ± 5% was measured. Subsequently, after immersing this cured board in 1000 ml of deionized water at 25 ± 1 ° C. for 8 hours, the weight (W2) after standing for 8 hours in a constant temperature and humidity room at 25 ± 1 ° C. and relative humidity of 40 ± 5% is obtained. It was measured. And water resistance was computed from Formula (6).
[Equation 5]
Water resistance (%) = (W2-W1) × 100 / W1 (6)
[0115]
<Water resistance 2>
A water resistance test was performed in the same manner as in the water resistance 1, except that the measurement sample (antifoaming agent) was changed from 0.70 g to 0.25 g.
[0116]
<Synthesis Example a1>
After charging 284 parts (1 mole part) of octadecanoic acid, 62 parts (1 mole part) of ethylene glycol and 2.5 parts of paratoluenesulfonic acid to the reaction vessel, the temperature was raised to 140 ° C. while stirring and 100 ml / min. A flow of nitrogen was bubbled through the solution for 3 hours. The temperature was raised to 150 to 160 ° C. while aeration of nitrogen in the liquid, and the reaction was carried out at this temperature for 10 hours to obtain octadecanoic acid ethylene glycol partial ester (a1). The acid value of (a1) was 8, the hydroxyl value was 162 mgKOH / g, and the melting point was 58 ° C.
[0117]
<Synthesis Examples a2 to a13>
Partial esters (a2) to (a13) were synthesized in the same manner as in Synthesis Example a1 except that 284 parts (1 mole part) of octadecanoic acid and 62 parts (1 mole part) of ethylene glycol were changed to the components and molar ratios shown in Table 1. ) The acid value, hydroxyl value and melting point of (a2) to (a13) are shown in Table 1.
[0118]
<Comparative Synthesis Examples a × 1 and a × 2>
Esters (a) used in the comparative examples in the same manner as in Synthesis Example a1 except that 284 parts (1 mol part) of octadecanoic acid and 62 parts (1 mol part) of ethylene glycol were changed to the components and molar ratios shown in Table 1. * 1) and (a * 2) were obtained. The acid value, hydroxyl value and melting point of the esters (a × 1) and (a × 2) are shown in Table 1.
[0119]
[Table 1]

[0120]
<Synthesis Example b1>
271 parts (1 mole part) of octadecanol and 0.5 part of potassium hydroxide (special grade reagent, Wako Pure Chemical Industries, Ltd.) were charged into a stirring autoclave, heated to 100 ° C. while purging with nitrogen, and then reduced in pressure (0 And dehydrated for 1 hour. Subsequently, the temperature was raised to 150 ° C., and 132 parts (3 parts by mole) of ethylene oxide was continuously dropped at this temperature (0.1 to 1 MPa), and the temperature was further maintained for 2 hours. Then, it prepared at 130 degreeC, 290 parts (5 mol parts) of propylene oxide was continuously dripped at this temperature (0.1-1 Mpa), and also it maintained at the same temperature for 3 hours. Then, 10 parts of magnesium silicate (Kyoward 600, Kyowa Chemical Co., Ltd.) is added to the reaction product, and the mixture is stirred at 100 ° C. for 1 hour. Then, the magnesium silicate is removed by vacuum filtration, An oxyalkylene compound (b1) was obtained. ¹ By H-NMR, it was confirmed that (b1) was R: octadecyl, XO: oxypropylene, m: 3, n: 5, m + n: 8 in the general formula (1) as a composition average value. The cloud point of (b1) was 61.7 ° C.
[0121]
<Synthesis Examples b2 to b10>
In the same manner as in Synthesis Example b1, polyoxyalkylene compounds (b2) to (b10) were obtained. ¹ It was confirmed by H-NMR that (b2) to (b10) were the composition average values, and that R, XO, m, n, and m + n were those shown in Table 2 in general formula (1). The cloud point was measured and shown in Table 2.
[0122]
<Comparative Synthesis Examples b × 1 to b × 5>
In the same manner as in Synthesis Example b1, polyoxyalkylene compounds (b × 1) to (b × 5) used in Comparative Examples were obtained. ¹ It was confirmed by H-NMR that (bx1) to (bx5) are composition average values, and that R, XO, m, n, and m + n are those shown in Table 2 in general formula (1). The cloud point was measured and shown in Table 2.
[0123]
[Table 2]

[0124]
<Example 1>
Octadecanoic acid ethylene glycol partial ester (a1) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) (HLB15.3) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) ( Weight average molecular weight 12,000, trade name: GOCELAN L-3266, Nippon Synthetic Chemical Industry Co., Ltd. 0.4 part, xanthan gum (d21) (trade name: Kelzan, Sansho Co., Ltd.) 0.1 part and deionized 65.5 parts of water (e1) (electrical conductivity 0.05 mS / m) was charged into a propeller stirring device, heated to 75 ° C., 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.0, and then Stir at temperature for 1 hour to mix uniformly. Next, high-pressure injection type emulsifying disperser: Gaurin homogenizer (device name: Manton Gaurin, manufacturer: Gaurin, conditions: temperature: 60 to 70 ° C., pressure: 9 MPa, time: 1 pass without circulating 3 kg of emulsion ) And immediately after passing through a heat exchanger, the mixture was cooled to 20 ° C. or lower and emulsified. Then, pH was adjusted to 8.0 with 10% sodium hydroxide aqueous solution or 5% hydrochloric acid aqueous solution, and the antifoamer 1 of this invention was obtained. Defoamer 1 had an emulsion particle size of 5 μm and a viscosity of 440 mPa · s.
[0125]
<Example 2>
Octadecanoic acid glycerin partial ester (a2) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, xanthan gum ( d21) 0.1 part and 65.5 parts deionized water (e1) were charged into a propeller stirrer, heated to 75 ° C., 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.0, and this temperature was And stirred uniformly for 1 hour. Next, high-speed rotation high shear type stirring emulsification disperser: homomixer (device name: TK. Homomixer MARKII2.5 type, manufacturer: Tokushu Kika Kogyo Co., Ltd., conditions: temperature: 60 to 70 ° C., rotation speed Immediately after dispersion in a 1 L beaker for 10,000 minutes, 500 g of emulsion in a 1 L beaker and rotated for 20 minutes), the mixture was cooled to 20 ° C. or less through a heat exchanger to be emulsified. Thereafter, the pH was adjusted to 8.0 with 10% aqueous sodium hydroxide or 5% aqueous hydrochloric acid to obtain antifoaming agent 2 of the present invention. Defoamer 2 had an emulsion particle size of 10 μm and a viscosity of 330 mPa · s.
[0126]
<Example 3>
Octadecanoic acid glycerin partial ester (a3) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, xanthan gum ( d21) 0.1 part and 65.5 parts deionized water (e1) were charged into a propeller stirrer, heated to 75 ° C., 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.0, and this temperature was The mixture is stirred and mixed uniformly for 1 hour, cooled to 30 to 40 ° C. through a heat exchanger, and then a grinding type emulsifying disperser: Attritor (device name: Attritor type: MA-1SE, manufacturer: Mitsui Miike Seisakusho, Conditions: Temperature: 30 to 40 ° C., 2000 parts of glass beads (diameter 1 mm) / Emulsion: 1000 parts, Rotation speed: 300 revolutions per minute In further cooled after the treatment, was 10 to 30 ° C.. Thereafter, the pH was adjusted to 8.0 with a 10% aqueous sodium hydroxide solution or a 5% aqueous hydrochloric acid solution to obtain antifoaming agent 3 of the present invention. Defoamer 3 had an emulsion particle size of 8 μm and a viscosity of 310 mPa · s.
[0127]
<Example 4>
Octadecanoic acid glycerin partial ester (a4) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, xanthan gum ( d21) 0.1 part and 65.5 parts deionized water (e1) were charged into a propeller stirrer, heated to 75 ° C., 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.0, and this temperature was And stirred uniformly for 1 hour. Next, a pressure nozzle type emulsifier, an ultrasonic type emulsifying disperser (device name: Ultrasonic Generator, modelUS-50, manufacturer: Nippon Seiki Seisakusho Co., Ltd., conditions: temperature: 60 to 70 ° C., output: 100 V, 50 W) , 28 kHz) was set in the emulsion liquid and ultrasonically dispersed for 30 minutes, and then immediately cooled to 20 ° C. or less through a heat exchanger to be emulsified. Thereafter, the pH was adjusted to 8.0 with a 10% aqueous sodium hydroxide solution or a 5% aqueous hydrochloric acid solution to obtain antifoaming agent 4 of the present invention. Defoamer 4 had an emulsion particle size of 5 μm and a viscosity of 450 mPa · s.
[0128]
<Example 5>
Octadecanoic acid glycerin partial ester (a5) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, xanthan gum ( d21) 0.1 part and 65.5 parts deionized water (e1) were charged into a propeller stirrer, heated to 75 ° C., 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.0, and this temperature was And stirred uniformly for 1 hour. Next, a high-speed rotation high shear type stirring emulsification disperser: Coreless mixer (device name: TK homogenizer AM-20, manufacturer: Tokushu Kika Kogyo Co., Ltd., conditions: temperature: 60 to 70 ° C., rotation speed: 1 minute Immediately after dispersion at 15,000 rpm, time: 500 g of emulsion in a 1 L beaker and rotation for 30 minutes, the mixture was cooled to 10 to 20 ° C. through a heat exchanger and emulsified. Thereafter, the pH was adjusted to 8.0 with a 10% aqueous sodium hydroxide solution or a 5% aqueous hydrochloric acid solution to obtain antifoaming agent 5 of the present invention. Defoamer 5 had an emulsion particle size of 1 μm and a viscosity of 560 mPa · s.
[0129]
<Example 6>
Octadecanoic acid glycerin partial ester (a6) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, xanthan gum ( d21) 0.1 part and 65.5 parts deionized water (e1) were charged into a propeller stirrer, heated to 75 ° C., 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.0, and this temperature was And stirred uniformly for 5 hours. Next, high-speed rotation high shear type stirring emulsification disperser: homomixer (device name: High Flex Disperser Model HG92, manufacturer: SMT Co., Ltd., conditions: temperature: 65 to 75 ° C., rotation speed: 15,000 per minute Time, rotation time: 30 minutes, 500 g of the emulsion is put into a 1 L beaker, and immediately after passing through the generator shaft (convection type shaft), the solution is circulated. did. Then, pH was adjusted to 8.0 with 10% sodium hydroxide aqueous solution or 5% hydrochloric acid aqueous solution, and the antifoamer 6 of this invention was obtained. Defoamer 6 had an emulsion particle size of 5 μm and a viscosity of 470 mPa · s.
[0130]
<Example 7>
9-octadecenoic acid glycerin partial ester (a7) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, After adding 0.1 part of xanthan gum (d21) and 65.5 parts of deionized water (e1) to a propeller stirrer, the temperature was raised to 75 ° C., 10% aqueous sodium hydroxide was added to adjust the pH to 8.0, The mixture was stirred at this temperature for 5 hours and mixed uniformly. Next, high-speed rotation high shear type stirring emulsification disperser (device name: Disper mill, manufacturer: Hosokawa Micron Corporation, conditions: temperature: 65 to 75 ° C., rotation speed: 3,000 times per minute, clearance: 2 mm, time 1 pass) After passing through a disper mill, it was cooled to 10 to 20 ° C. through a heat exchanger to obtain an emulsion. Thereafter, the pH was adjusted to 8.0 with a 10% aqueous sodium hydroxide solution or a 5% aqueous hydrochloric acid solution to obtain antifoaming agent 7 of the present invention. Defoamer 7 had an emulsion particle size of 5 μm and a viscosity of 480 mPa · s.
[0131]
<Examples 8 to 22>
25 parts of octadecanoic acid ethylene glycol partial ester (a1), 7 parts of polyoxyalkylene compound (b3), 2 parts of oleyl alcohol ethylene oxide 20 mol adduct (c1), sulfonated polyvinyl alcohol sodium salt (d11) 0. Antifoam of the present invention in the same manner as in Example 1, except that 4 parts, 0.1 part of xanthan gum (d21) and 65.5 parts of deionized water (e1) were changed to the components and contents shown in Table 3. Agents 8 to 22 were obtained. The emulsion particle diameters and viscosities of the antifoams 8 to 22 are shown in Table 5.
[0132]
<Comparative Example 1>
Octadecanoic acid glycerin partial ester (a × 1) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, After adding 0.1 part of xanthan gum (d21) and 65.5 parts of deionized water (e1) to a propeller stirrer, the temperature was raised to 75 ° C., 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.0, The mixture was stirred at this temperature for 5 hours and mixed uniformly. Next, immediately after passing through a high-pressure injection type emulsifying disperser: Gaurin homogenizer (device name: Manton Gaurin, manufacturer: Gaurin, conditions: temperature: 60 to 70 ° C., pressure: 9 MPa, time: 1 pass without circulation) It cooled to 20 degrees C or less through the heat exchanger, and emulsified. Thereafter, the pH was adjusted to 8.0 with a 10% aqueous sodium hydroxide solution or a 5% aqueous hydrochloric acid solution to obtain a comparative antifoaming agent 23. Defoamer 23 had an emulsion particle size of 5 μm and a viscosity of 440 mPa · s.
[0133]
<Comparative Examples 2-9>
Octadecanoic acid glycerin partial ester (a × 1) 25 parts, polyoxyalkylene compound (b3) 7 parts, oleyl alcohol ethylene oxide 20 mol adduct (c1) 2 parts, sulfonated polyvinyl alcohol sodium salt (d11) 0.4 part, Comparative antifoaming agents 24-31 in the same manner as in Comparative Example 1, except that 0.1 part of xanthan gum (d21) and 65.5 parts of deionized water (e1) were changed to the components and contents shown in Table 4. Got. Table 5 shows the emulsion particle sizes and viscosities of the antifoams 24-31.
[0134]
<Comparative Example 10>
271 parts (1 mole part) of octadecanol and 0.5 part of potassium hydroxide (special grade reagent, Wako Pure Chemical Industries, Ltd.) were charged into a stirring autoclave, heated to 100 ° C. while purging with nitrogen, and then reduced in pressure (0 And dehydrated for 1 hour. Next, the temperature was raised to 150 ° C., and 1566 parts (27 mol parts) of propylene oxide was continuously added dropwise at this temperature (0.1 to 1 MPa), and the temperature was further maintained for 2 hours. Then, it adjusted at 130 degreeC, 132 parts (3 mol parts) of ethylene oxide was continuously dripped at this temperature (0.1-1 Mpa), and also it maintained at the same temperature for 3 hours. Then, 10 parts of magnesium silicate (Kyoward 600, Kyowa Chemical Co., Ltd.) was added to the reaction product, and the mixture was stirred at 100 ° C. for 1 hour, and then the magnesium silicate was removed by filtration under reduced pressure. The antifoaming agent 32 was obtained. This compound ¹ By H-NMR, it was confirmed that the composition average value was a propylene oxide 27 mol / ethylene oxide 3 mol block adduct of octadecanol.
[0135]
<Comparative Example 11>
271 parts (1 mole part) of octadecanol and 0.5 part of potassium hydroxide (special grade reagent, Wako Pure Chemical Industries, Ltd.) were charged into a stirring autoclave, heated to 100 ° C. while purging with nitrogen, and then reduced in pressure (0 And dehydrated for 1 hour. Next, the temperature was raised to 150 ° C., and 1740 parts (30 mol parts) of propylene oxide was continuously added dropwise at this temperature (0.1 to 1 MPa), and the temperature was maintained at the same temperature for 2 hours. Then, it adjusted to 130 degreeC and kept at the same temperature for further 3 hours. Then, 10 parts of magnesium silicate (Kyoward 600, Kyowa Chemical Co., Ltd.) was added to the reaction product, and the mixture was stirred at 100 ° C. for 1 hour, and then the magnesium silicate was removed by filtration under reduced pressure. The antifoaming agent 32 was obtained. This compound ¹ By H-NMR, it was confirmed that the composition average value was a 30 mol propylene oxide adduct of octadecanol.
[0136]
<Comparative Example 12>
After charging 564 parts (2 mol parts) of 9-octadecenoic acid, 2100 parts (1.0 mol parts) of New Pole PE-62 (Sanyo Chemical Industries Co., Ltd.) and 2.5 parts of paratoluenesulfonic acid, While stirring, the temperature was raised to 140 ° C. and nitrogen at a flow rate of 100 ml / min was bubbled through the solution for 3.0 hours. The temperature was raised to 150 to 160 ° C. while aeration of nitrogen in the liquid, and the reaction was carried out at this temperature for 10 hours to obtain a new ester of octadecenoic acid PE-62. This diester had an acid value of 10, a hydroxyl value of 3 mgKOH / g, and a freezing point of -5 ° C.
[0137]
[Table 3]

[0138]
c1: oleyl alcohol ethylene oxide 20 mol adduct (HLB15.3)
d11: Sodium sulfonated polyvinyl alcohol (trade name: Gocelan L-3266, weight average molecular weight: 12,000, Nippon Synthetic Chemical Industry Co., Ltd.)
d12: Polyvinyl alcohol (trade name: PVA-205, weight average molecular weight: 11,000, Kuraray Co., Ltd.)
d13: Polyethylene oxide (trade name: PEO-8, weight average molecular weight: 2 million, Sumitomo Seika Co., Ltd.)
d21: Xanthan gum (trade name: Kelzan, Sansho Co., Ltd.)
e1: Deionized water (electric conductivity: 0.05 mS / m)
[0139]
[Table 4]

c1, d11, d21 and e1 are the same as in Table 3.
[0140]
[Table 5]

[0141]
【The invention's effect】
The emulsion type of the present invention is very excellent in defoaming performance, and particularly exhibits excellent defoaming performance for foamed liquids containing inorganic powder. Furthermore, the antifoaming agent itself is highly stable and has very low separation and thickening. Moreover, even if it uses for the papermaking process of a water-curable inorganic building material, the fall of the water resistance of this building material is very low.
Accordingly, the emulsion type antifoaming agent of the present invention is a foaming liquid containing a synthetic and / or natural foaming surfactant, for example, washing water for pulp, electronic substrates, metal parts and fibers, fermentation liquid, papermaking Excellent defoaming effect (suppression) against white water, papermaking white water, industrial wastewater, manure treated water, water-based paint, water-based ink, monomer stripping liquid, municipal sewage, ceramic slurry, and other acidic to alkaline foaming liquids Demonstrates foam, broken foam, and foam regulation. It is particularly suitable for foaming liquid containing inorganic powder, and is most suitable for papermaking slurry and papermaking white water in the manufacturing process (particularly papermaking process) of hydraulic inorganic building materials.

Claims (8)

Fatty acid partial ester (A) of 2-6 hydric alcohol, polyoxyalkylene compound (B) represented by general formula (1), emulsifier (C), weight average molecular weight (Mw) 5,000-5,000,000 A thickener (D) comprising a synthetic water-soluble polymer (D1) and a natural water-soluble polymer (D2) and / or a semi-synthetic water-soluble polymer (D3), and an emulsion-type composition comprising water (E). A foam,
(1) The hydroxyl value of (A) is 50 to 400 mgKOH / g,
(2) The cloud point by the 25 wt% butyl diglycol aqueous solution method of (B) is 43 to 70 ° C,
(3) Based on the total weight of (A), (B), (C), (D) and (E), the content of (A) is 20 to 30% by weight, and the content of (B) is 4 -10 wt%, (C) content is 0.3-5 wt%, (D) content is 0.01-5 wt%, (E) content is 50-75 wt%,
(4) The emulsion type antifoaming agent, wherein the emulsion particles have a volume average particle diameter of 0.1 to 50 μm.

In the formula, R is a linear or branched alkyl or alkenyl group having 8 to 28 carbon atoms, XO is an oxyalkylene group having 3 to 4 carbon atoms, m is an integer of 3 to 10, and n is an integer of 5 to 40. , M + n is an integer of 8-50. The emulsion type antifoaming agent according to claim 1, wherein the hydroxyl value of the fatty acid partial ester (A) of the divalent to hexavalent alcohol is 100 to 300 mgKOH / g. The emulsion type antifoaming agent according to claim 1 or 2, wherein the fatty acid partial ester (A) of a divalent to hexavalent alcohol is composed of an alcohol having 3 or 5 carbon atoms and a fatty acid having 16 to 22 carbon atoms. Furthermore, the buffer (F) which consists of an inorganic compound and / or an organic compound is 0.1-3.0 weight% based on the weight of water (E), and pH (25 degreeC) is 6.0-8. The emulsion-type antifoaming agent according to any one of claims 1 to 3, which is 5. The emulsion type antifoaming agent according to any one of claims 1 to 4, which is for foaming liquid containing inorganic powder. The emulsion type antifoaming agent according to claim 5, wherein the inorganic powder is at least one selected from the group consisting of silica, calcium carbonate, talc, clay, kaolin, calcium silicate, titanium dioxide, magnesium carbonate, and aluminum silicate. The emulsion-type antifoaming agent according to any one of claims 1 to 6, wherein the emulsion-type antifoaming agent is used for a production process of a hydraulic inorganic building material. The manufacturing of the hydraulic inorganic building material characterized by including the process of making paper using 0.0001-1 weight% of emulsion type antifoamers in any one of Claims 1-7 based on the weight of inorganic powder Method.