JP3743206B2

JP3743206B2 - Antifoam composition

Info

Publication number: JP3743206B2
Application number: JP11241299A
Authority: JP
Inventors: 芳和五藤
Original assignee: San Nopco Ltd
Current assignee: San Nopco Ltd
Priority date: 1999-04-20
Filing date: 1999-04-20
Publication date: 2006-02-08
Anticipated expiration: 2019-04-20
Also published as: JP2000300907A

Description

【０００１】
【発明の属する技術分野】
本発明はポリエーテル系の消泡剤に関する。さらに詳しくは発泡性水溶液を取り扱う諸工業、例えば紙パルプの製造工業やその抄紙工程、建築工業やその抄造工程、染料工業および染色工業、発酵工業、合成樹脂製造工業、合成ゴム製造工業、インキ、塗料工業および繊維加工工業などの各工程、またそれらの排水処理工程で発生する気泡に対して優れた消泡性を発揮し、かつ抄紙などの工程を経て得られた最終製品である紙などに耐水性を保持させることのできる新規な消泡剤組成物に関するものである。
【０００２】
【従来の技術】
従来からこれらの工業用としては、水分散性が良好で最終製品にオイルスポット、ピンホールやはじき、油浮き等の弊害が少なく、またスカムや沈殿物の発生が殆ど見られないポリエーテル系の消泡剤が好んで用いられている。例えばステアリルアルコール、ジプロピレングリコール、グリセリンおよびソルビタンなどの１価〜多価のアルコールにアルキレンオキシドを付加したもの（特公昭４５−３０１８９号、特公昭４９−３８９２３号、特開昭５４−１３３４８４号、および特公昭６１−７８４７号公報など）や、アルキルフェノールにアルキレンオキシドを付加したもの（特公昭４７−３２５１１号公報）またはこれらの末端水酸基をエステル化したもの（特開昭５２−９７３８５号公報、特開昭５６−４８２１０号各公報等）などが知られている。
【０００３】
前述のポリエーテル系消泡剤を抄紙工程で使用して得た紙は、例えば高級アルコールを乳化したエマルション系消泡剤を用いた場合に較べて耐水性が大幅に劣るという問題があった。また従来からポリエーテル系消泡剤に長鎖脂肪酸のアルカリ土類金属塩などの有機固形物を加え（特開平１０−３２３５０５など）たり、高級脂肪酸を加え（特開平９−３０８８０４など）て消泡性の改良を図ったり、または脂肪酸アンモニウム塩を加え（特開平９−１１７６０８など）て消泡剤の水希釈安定性の改良を図った例はあるが、いずれの場合も耐水性を改良する効果は見られない。
【０００４】
【発明が解決しようとする課題】
このようにポリエーテル系消泡剤では最終製品の耐水性を低下させるという欠点があった。よって本発明の目的は優れた消泡性、すなわち初期消泡性および消泡持続性を維持し、かつ最終的に得られる製品の耐水性を低下させないポリエーテル系消泡剤を提供することである。
【０００５】
【課題を解決するための手段】
本発明者は鋭意検討を重ねた結果本発明に到達した。すなわち本発明は、平均炭素数１７以上の脂肪族モノアルコールと炭素数２〜４のアルキレンオキシドとの化合物［Ａ］と、平均炭素数１７以上で融点が２０℃以下の脂肪族モノカルボン酸の、ナトリウム、カリウム、セシウム、マグネシウムおよびアルミニウムの群から選ばれる金属塩［Ｂ］からなり、［Ａ］対［Ｂ］が重量比で１００：０．５〜５．０であり、ブチルジグリコール２５％水溶液法での曇点が３２〜４８℃である消泡剤組成物、
及び平均炭素数１７以上の脂肪族モノアルコールと炭素数２〜４のアルキレンオキシドとの化合物［Ａ］と、平均炭素数１７以上で融点が２０℃以下の脂肪族モノカルボン酸の、ナトリウム、カリウム、セシウム、マグネシウムおよびアルミニウムの群から選ばれる金属塩［Ｂ］からなり、［Ａ］対［Ｂ］が重量比で１００：０．５〜５．０であり、ブチルジグリコール２５％水溶液法での曇点が３２〜４８℃である消泡剤組成物を製造する方法であって、
触媒として、アルカリあるいはアルカリ土類金属の水酸化物、アルコラートまたは炭酸塩を用いて、化合物［Ａ］を得た後、
平均炭素数１７以上で融点が２０℃以下の脂肪族モノカルボン酸を加え、
さらに必要により水を加えて濃度９９〜８０重量％に希釈することを特徴とする消泡剤組成物の製造方法である。
【０００６】
【発明の実施の形態】
本発明において平均炭素数１７以上の脂肪族モノアルコールとは、ヘプタデシルアルコール、ステアリルアルコール、ノナデシルアルコール、エイコシルアルコールなどの直鎖アルキル基を持つアルコールおよびこれらを主成分とする混合アルコールさらには合成等により得られ、平均炭素数１７以上の分岐アルキル基を持つアルコールなどが挙げられる。これらは単独で、または混合物として用いることが出来る。脂肪族モノアルコールの平均炭素数が１７未満の場合消泡性が不十分となり、またサイズ度が低下する。
【０００７】
本発明において炭素数２〜４のアルキレンオキシドとしては、エチレンオキシド（以下、ＥＯと略記）、プロピレンオキシド（以下、ＰＯと略記）、１，２−ブチレンオキシド（以下、ＢＯと略記）等が挙げられる。アルコールに対する付加モル数は、ＥＯが２〜５好ましくは３〜４、ＰＯが１０〜２０好ましくは１２〜１８、ＢＯが０〜３好ましくは０〜２である。ＢＯが増加すると耐水性は改善されるが、３モルを超えると消泡性が低下する。アルキレンオキシドの付加重合の順序は特に限定されず、その重合形式もブロック、ランダム何れでもよい。
【０００８】
本発明において平均炭素数１７以上で融点が２０℃以下の脂肪族モノカルボン酸とは、例えばオレイン酸やリノール酸などの不飽和脂肪酸、分岐のアルキル基や不飽和脂環基等を持つカルボン酸およびこれらの混合物、また動植物油から得られる混合脂肪酸等が挙げられる。これらのうち特に好ましいのはオレイン酸である。ステアリン酸などの融点が２０℃以上のカルボン酸を用いると消泡剤組成物が常温で固化またはペースト化したり、凝固物を生じて不均一となることがあるので取り扱い性が低下する。さらに耐水性の改善がオレイン酸等の場合に比べて劣ることが判明した。また平均炭素数が１７未満のカルボン酸、例えば２−エチルヘキシル酸などを用いた場合は耐水性の改善が見られない。
【０００９】
本発明において［Ｂ］の中和塩を成す金属としてナトリウム、カリウム、セシウム、マグネシウム、アルミニウムが使用でき、これらのうち好ましいのはカリウムおよびマグネシウムであり、特に好ましいのはカリウムである。リチウム、バリウムなどの金属を用いると消泡剤組成物が常温で固化または白濁したり、沈殿を生じて不均一となることがあり、充分な消泡性、耐水性が得られない。
【００１０】
本発明において［Ａ］対［Ｂ］は重量比で１００：０．５〜５．０、好ましくは１００：０．８〜４．０である。［Ｂ］が５．０を越えると消泡剤組成物の粘度が上昇することで取り扱い性が低下し、また消泡性も低下する。また、０．５未満では耐水性の改善が見られない。
【００１１】
本消泡剤組成物は、［Ａ］にカリウムやマグネシウムなどの水酸化物またはアルコラートなどを加えた後に該カルボン酸を加えて［Ａ］中で金属塩を生成させても、または該金属塩を［Ａ］に直接加えて作成してもよい。また水酸化カリウムなどを触媒として［Ａ］を重合した場合は、そのまま該カルボン酸を加えて本消泡剤組成物を作成することもできる。
【００１２】
本発明の消泡剤組成物は、水を１〜２０％（重量％、以下同じ）加えて濃度を９９〜８０％に希釈した水溶液の状態としてもよい。水で希釈する場合は、まず常温または５０℃以下にて［Ａ］に［Ｂ］を加え、または［Ａ］中で［Ｂ］を生成させて十分攪拌し、次いで水を徐々に加えて所定の濃度に調整する。水を８％程度以上加えると引火点の測定が不可能となり、消防法上の危険物に非該当となるので貯蔵保管上の簡便性が得られる。また消泡性に関しても、水を１〜２０％加えると初期消泡性の改善が見られる。水を２０％を超えて加えると粘度の上昇が顕著となり、取り扱い性に劣る。例えば水を１０％加えた場合は４００ｍＰａ・ｓ／２０℃であるが、３０％加えた場合は同温度でペースト状となる。７５％以上加えた場合は静置すると沈降分離を生ずる。消泡性に関しては、水を２０％を超えて加えた場合には初期消泡性、消泡持続性とも低下する。
【００１３】
本発明において曇点とは非イオン系界面活性剤の親水性の尺度となるもので、曇点の高い化合物ほど親水性が大きいことを表わしている。本発明での測定法はＩＳＯ１０６５−１９７５（Ｅ）、「エチレンオキシド系非イオン界面活性剤−曇り点測定法」の中の「測定法Ｂ」に準じた。すなわち、まず２５重量％のブチルジグリコール（ブタノール／ＥＯ２モル付加物）水溶液に、試料を１０重量％濃度になるように溶解する。次いでこの試料溶液約５ｃｃを試験管に採り、試験管中に温度計を入れて攪拌しながら徐々に加熱するとついには試料溶液が白濁する。次いで攪拌しながら徐々に冷却し、試料溶液が白濁から透明に転ずる温度を読みとり、これを曇点とする。本発明の組成物の曇点は３２〜４８℃、好ましくは３５〜４５℃である。曇点が４８℃を越えても、また３２℃を下廻っても親水性／疎水性のバランスが崩れて十分な消泡性が得られない。また、曇点が４８℃を越える場合は耐水性が低下する。
【００１４】
本発明において、アルキレンオキシドの反応に用いられる重合形式としてはアニオン重合、カチオン重合あるいは配位アニオン重合等が挙げられる。これらの重合形式は単独で用いられても、併用して用いられても構わない。また触媒としては、アルカリあるいはアルカリ土類金属の水酸化物、アルコラートまたは炭酸塩およびトリアルキルアミン等、塩化第二錫、トリフッ化ホウ素等のルイス酸系触媒や鉱酸等、特開昭６３−２７７２３６号公報に見られる複合金属シアノ錯体あるいは特公平５−１４７３４号公報に見られる有機アルミニゥムポルフィリン錯体等が用いられる。これらのうち好ましくは、水酸化カリウム、水酸化セシウムである。触媒の使用量は重合終了時の該化合物の重量に対して０．０５〜３．０重量％の範囲であり、好ましくは０．１〜２．０重量％である。
【００１５】
本発明において、炭素数２〜４のアルキレンオキシドの反応は通常の条件下で実施されてよく、例えば温度は７０〜１５０℃、好ましくは８０〜１４０℃である。また、重合中の圧力（ゲージ圧）は８ｋｇ／ｃｍ^２以下、好ましくは６ｋｇ／ｃｍ^２以下である。
【００１６】
本発明において、該アルコールと該アルキレンオキシドとの反応により得られる［Ａ］の触媒は除去しても、また除去せずにそのまま用いてもよい。触媒の除去方法としては、酸性成分によりアルカリ性触媒を中和し、生じた塩を濾過除去する方法、アルカリ吸着剤または酸吸着剤を用いる方法、溶媒に溶かして水洗除去する方法、イオン交換樹脂を用いる方法、アルカリ性触媒を炭酸ガスで中和して、生じた炭酸塩を濾過する方法および各種有機酸、無機酸またはアルカリ成分により中和する方法等があるが、そのいずれを用いても差し支えない。
【００１７】
本発明の消泡剤組成物は、水を加えて濃度９９〜８０％に希釈した水溶液の状態としても、また未希釈のままで発泡系に添加しても良い。また本発明の消泡剤組成物の発泡性水溶液に対する添加量は通常、０．１〜１０，０００ｐｐｍであり、好ましくは１〜１，０００ｐｐｍである。
【００１８】
【実施例】
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。消泡性および耐水性の試験結果は表１に記載した。尚、実施例、比較例における部は重量部を意味する。また特に記載のない限り、用いた原料はすべて試薬特級品を用いた。
【００１９】
［消泡性試験方法］
ガラス製シリンダー（以下、発泡管と称す）に発泡性試験水（新聞用紙抄紙白水）７５０ｍｌを入れ、４０℃に温調する。次いでポンプを用いて発泡管の底部から試験水を３，０００ｍｌ／分で循環しながら、発泡管上部より１５ｃｍ下の試験液水面に落下させる。泡高さが１００ｍｍに達した時点でマイクロピペットにて消泡剤５．０ｐｐｍ（対試験水）を添加する。循環を持続し、変化する泡高さを５分間追跡する。試験開始１分後のデータが初期消泡性を、５分後のデータが消泡持続性を示している。
【００２０】
［耐水性試験方法］
下記の試験紙作成条件により得た紙を用いてのステキヒトサイズ度試験（ＪＩＳＰ８１２２）にて全平均値（秒、値が大きいほど耐水性が良いことを表す）をもって耐水性を評価比較した。
［試験紙作成条件］
消泡剤濃度５０ＰＰＭの水溶液を作成し、上質紙［フジゼロックス（株）製ゼロックス用紙Ｌ、Ａ−４サイズ］に２．０ｇを均一に吹きかける。１５分間の風乾後、ドラムドライヤーにて１２０℃×２分間乾燥させる。
【００２１】
実施例１
２５０℃までの加熱、冷却および攪拌の可能な耐圧反応容器にステアリルアルコール１モル２７０部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１６モル９２８部を１００〜１２０℃にて約９時間で、次いでＥＯの３モル１３２部を１３０℃にて約３時間で反応させた。次いで４０℃にてオレイン酸（融点：１６℃）１２．６部を加え１時間攪拌した。次いで同温度にて１５部の水を徐々に加え、均一透明な組成物を得て消泡性試験等に供した。ブチルジグリコール２５％水溶液によるサンプル濃度１０％測定法での曇点（以下、単に曇点と記す）は３９．７℃であった。
【００２２】
実施例２
実施例１と同様な反応容器にステアリルアルコール１モル２７０部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１６モル９２８部を１００〜１２０℃にて約９時間で、次いでＥＯの３モル１３２部を１３０℃にて約３時間で反応させた。次いで９０℃にて水２０部を加え３０分間攪拌する。さらに同温度にてキョーワード６００［協和化学（株）製、触媒除去用のアルカリ吸着剤］５０部を加え、１時間攪拌する。次いで２号濾紙［東洋濾紙（株）製］を用いて濾過し、減圧下脱水した。このポリエーテル化合物（以下、ベースポリエーテルと称す）９００部にオレイン酸カリウム３０部、水７０部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３９．８℃の組成物を得て消泡性試験等に供した。
【００２３】
実施例３
実施例２で得たベースポリエーテル９００部にオレイン酸マグネシウム１０部、水９０部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３９．６℃の組成物を得て消泡性試験等に供した。
【００２４】
実施例４
実施例２で得たベースポリエーテル８５０部にリノール酸カリウム１０部（リノール酸の融点：−５℃）水１４０部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３９．５℃の組成物を得て消泡性試験等に供した。
【００２５】
実施例５
実施例２で得たベースポリエーテル９８５部に、不飽和脂環基を持ち炭素数が１８であるゴルリン酸（融点：６℃）のカリウム塩１５部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３９．４℃の組成物を得て消泡性試験等に供した。
【００２６】
実施例６
実施例１と同様な反応容器にステアリルアルコール１モル２７０部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１３モル７５４部を１００〜１２０℃にて約８時間で、次いでＥＯの３モル１３２部を１３０℃にて約３時間で、次いで同温度にてＢＯの１モル７２部を約４時間で反応させた。次いで４０℃にてオレイン酸１２．６部を加え１時間攪拌し、さらに同温度にて１４５部の水を徐々に加え均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３４．２℃の組成物を得て消泡性試験等に供した。
【００２７】
実施例７
実施例１と同様な反応容器にヘプタデシルアルコール１モル２５６部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１５モル８７０部を１００〜１２０℃にて約８時間で、次いでＥＯの３モル１３２部を１３０℃にて約３時間で付加重合させた。次いで４０℃にてオレイン酸１２．６部を加え１時間攪拌した。次いで同温度にて１４０部の水を徐々に加え均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が４５．２℃の組成物を得て消泡性試験等に供した。
【００２８】
実施例８
実施例１と同様な反応容器にエイコシルアルコール１モル２９８部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１７モル９８６部を１００〜１２０℃にて約８時間で、次いでＥＯの３．５モル１５４部を１３０℃にて約３時間で付加重合させた。次いで４０℃にてオレイン酸１２．６部を加え１時間攪拌した。次いで同温度にて１６０部の水を徐々に加え均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３６．７℃の組成物を得て消泡性試験等に供した。
【００２９】
比較例１
実施例２で得たベースポリエーテル９００部に、４０℃にて水１００部を徐々に加え均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が４０．１℃の組成物を得て消泡性試験等に供した。
【００３０】
比較例２
実施例１と同様な反応容器にペンタデシルアルコール１モル２２８部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１４．５モル８４１部を１００〜１２０℃にて約８時間で、次いでＥＯの２．５モル１１０部を１３０℃にて約３時間で付加重合させた。次いで４０℃にてオレイン酸１２．６部を加え１時間攪拌した。次いで同温度にて１３５部の水を徐々に加え均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３７．８℃の組成物を得て消泡性試験等に供した。
【００３１】
比較例３
実施例１と同様な反応容器にステアリルアルコール１モル２７０部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１０モル５８０部を１００〜１２０℃にて約８時間で、次いでＥＯの４モル１７６部を１３０℃にて約３時間で、次いで同温度にてＢＯの４モル２８８部を約４時間で付加重合させた。次いで４０℃にてオレイン酸１２．６部を加え１時間攪拌した。次いで同温度にて１４５部の水を徐々に加え均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３０．３℃の組成物を得て消泡性試験等に供した。
【００３２】
比較例４
実施例１と同様な反応容器にステアリルアルコール１モル２７０部に水酸化カリウム２．５部を加え、１３０℃にて減圧下脱水の後、ＰＯの１６モル９２８部を１００〜１２０℃にて約８時間で、次いでＥＯの６モル２６４部を１３０℃にて約３時間で付加重合させた。次いで４０℃にてオレイン酸１２．６部を加え１時間攪拌した。次いで同温度にて１６５部の水を徐々に加え均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が５０．４℃の組成物を得て消泡性試験等に供した。
【００３３】
比較例５
実施例２で得たベースポリエーテル９００部に２−エチルヘキシル酸カリウム１０部、水９０部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が３９．５℃の組成物を得て消泡性試験等に供した。
【００３４】
比較例６
実施例２で得たベースポリエーテル９００部にステアリン酸ナトリウム１０部、水９０部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、常温でペースト状の曇点が３９．７℃の組成物を得て消泡性試験等に供した。
【００３５】
比較例７
実施例２で得たベースポリエーテル９００部にオレイン酸バリウム１０部、水９０部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、常温で微白濁の曇点が３９．３℃の組成物を得て消泡性試験等に供した。
【００３６】
比較例８
実施例２で得たベースポリエーテル７７０部にオレイン酸カリウム１０部、水２２０部を加え５０℃にて均一になるまで攪拌を続けたのち冷却して、均一透明な曇点が４０．３℃の組成物を得て消泡性試験等に供した。
【００３７】
【表１】

【００３８】
【発明の効果】
本発明による消泡剤は各種の発泡性水溶液を扱う産業例えば紙パルプ製造工業やその抄紙工程、建築工業やその抄造工程、染料工業および染色工業、発酵工業、合成樹脂製造工業、合成ゴム製造工業、インキ、塗料工業および繊維加工工業など、また各種工業の排水処理工程で発生する気泡に対し優れた初期消泡性および消泡持続性を示す。また最終製品に耐水性が要求される分野、例えば紙パルプ製造工業での抄紙工程に本発明による消泡剤を用いた場合、得られた紙に優れた耐水性を保持させることが出来るので有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyether-based antifoaming agent. More specifically, various industries that handle foaming aqueous solutions, such as paper pulp manufacturing industry and paper making process, construction industry and paper making process, dye industry and dyeing industry, fermentation industry, synthetic resin manufacturing industry, synthetic rubber manufacturing industry, ink, For paper such as the final product obtained through processes such as papermaking, which exhibits excellent defoaming properties against air bubbles generated in each process such as paint industry and textile processing industry, and wastewater treatment process The present invention relates to a novel antifoaming agent composition that can maintain water resistance.
[0002]
[Prior art]
Conventionally, for these industrial applications, polyether-based products with good water dispersibility, less adverse effects such as oil spots, pinholes, repellency and oil floating in the final product, and almost no occurrence of scum or precipitates. Antifoam agents are preferred. For example, monohydric to polyhydric alcohols such as stearyl alcohol, dipropylene glycol, glycerin and sorbitan added with alkylene oxide (Japanese Patent Publication No. 45-30189, Japanese Patent Publication No. 49-38923, Japanese Patent Publication No. 54-133484, And Japanese Patent Publication No. 61-7847), those obtained by adding an alkylene oxide to an alkylphenol (Japanese Patent Publication No. 47-32511), or those obtained by esterifying these terminal hydroxyl groups (Japanese Patent Laid-Open No. 52-97385). No. 56-48210, etc.) are known.
[0003]
Paper obtained by using the above-mentioned polyether antifoaming agent in the papermaking process has a problem that the water resistance is significantly inferior to the case of using an emulsion antifoaming agent emulsified with a higher alcohol, for example. Conventionally, an organic solid such as an alkaline earth metal salt of a long chain fatty acid is added to a polyether antifoaming agent (Japanese Patent Laid-Open No. 10-323505) or a higher fatty acid is added (Japanese Patent Laid-Open No. 9-308804). There are examples of improving the foaming property, or adding fatty acid ammonium salt (JP-A-9-117608, etc.) to improve the water dilution stability of the antifoaming agent. In either case, the water resistance is improved. No effect is seen.
[0004]
[Problems to be solved by the invention]
As described above, the polyether antifoaming agent has a drawback of reducing the water resistance of the final product. Therefore, an object of the present invention is to provide a polyether-based antifoaming agent that maintains excellent antifoaming properties, that is, initial defoaming property and antifoaming sustainability, and does not lower the water resistance of the finally obtained product. is there.
[0005]
[Means for Solving the Problems]
The inventor has reached the present invention as a result of intensive studies. That is, the present invention relates to a compound [A] of an aliphatic monoalcohol having an average carbon number of 17 or more and an alkylene oxide having 2 to 4 carbon atoms and an aliphatic monocarboxylic acid having an average carbon number of 17 or higher and a melting point of 20 ° C. or lower. , Sodium, potassium, cesium, magnesium and aluminum, [B], [A] to [B] in a weight ratio of 100: 0.5 to 5.0, butyl diglycol 25 A defoamer composition having a cloud point of 32 to 48 ° C. in an aqueous solution method,
Sodium and potassium of a compound [A] of an aliphatic monoalcohol having an average carbon number of 17 or more and an alkylene oxide having 2 to 4 carbon atoms and an aliphatic monocarboxylic acid having an average carbon number of 17 or higher and a melting point of 20 ° C. or lower. , Cesium, magnesium, and a metal salt selected from the group of aluminum [B], [A] to [B] is 100: 0.5 to 5.0 by weight, butyl diglycol 25% aqueous solution method Is a method for producing an antifoaming composition having a cloud point of 32 to 48 ° C,
After obtaining compound [A] using a hydroxide, alcoholate or carbonate of an alkali or alkaline earth metal as a catalyst,
Add an aliphatic monocarboxylic acid having an average carbon number of 17 or more and a melting point of 20 ° C. or less,
Furthermore, it is a manufacturing method of the antifoamer composition characterized by adding water if necessary and diluting to the density | concentration 99 to 80 weight%.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the aliphatic monoalcohol having an average carbon number of 17 or more is an alcohol having a linear alkyl group such as heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, and a mixed alcohol containing these as a main component. Examples include alcohols obtained by synthesis and the like and having a branched alkyl group having an average carbon number of 17 or more. These can be used alone or as a mixture. When the average carbon number of the aliphatic monoalcohol is less than 17, the defoaming property is insufficient and the sizing degree is lowered.
[0007]
Examples of the alkylene oxide having 2 to 4 carbon atoms in the present invention include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide (hereinafter abbreviated as BO) and the like. . The addition mole number with respect to alcohol is 2-5, preferably 3-4, PO is 10-20, preferably 12-18, and BO is 0-3, preferably 0-2. When BO is increased, the water resistance is improved, but when it exceeds 3 mol, the antifoaming property is lowered. The order of addition polymerization of alkylene oxide is not particularly limited, and the polymerization form may be either block or random.
[0008]
In the present invention, an aliphatic monocarboxylic acid having an average carbon number of 17 or more and a melting point of 20 ° C. or less is, for example, an unsaturated fatty acid such as oleic acid or linoleic acid, a carboxylic acid having a branched alkyl group, an unsaturated alicyclic group, or the like. And mixtures thereof, and mixed fatty acids obtained from animal and vegetable oils. Of these, oleic acid is particularly preferred. When a carboxylic acid having a melting point of 20 ° C. or higher such as stearic acid is used, the defoamer composition may be solidified or pasted at room temperature or a solidified product may be formed, resulting in non-uniformity. Furthermore, it has been found that the improvement in water resistance is inferior to that of oleic acid or the like. Further, when a carboxylic acid having an average carbon number of less than 17 such as 2-ethylhexylic acid is used, water resistance is not improved.
[0009]
In the present invention, sodium, potassium, cesium, magnesium, and aluminum can be used as the metal constituting the neutralized salt of [B]. Among these, potassium and magnesium are preferable, and potassium is particularly preferable. If a metal such as lithium or barium is used, the antifoaming agent composition may solidify or become cloudy at room temperature or may become non-uniform due to precipitation, so that sufficient antifoaming properties and water resistance cannot be obtained.
[0010]
In the present invention, the weight ratio of [A] to [B] is 100: 0.5 to 5.0, preferably 100: 0.8 to 4.0. When [B] exceeds 5.0, the viscosity of the antifoaming agent composition increases, so that the handleability is lowered and the antifoaming property is also lowered. On the other hand, if it is less than 0.5, water resistance is not improved.
[0011]
The antifoaming composition may be formed by adding a hydroxide or alcoholate such as potassium or magnesium to [A] and then adding the carboxylic acid to form a metal salt in [A], or the metal salt May be created by directly adding to [A]. In addition, when [A] is polymerized using potassium hydroxide or the like as a catalyst, the present antifoaming agent composition can be prepared by adding the carboxylic acid as it is.
[0012]
The antifoaming agent composition of the present invention may be in the form of an aqueous solution in which water is added to 1 to 20% (weight%, hereinafter the same) to dilute the concentration to 99 to 80%. When diluting with water, first add [B] to [A] at room temperature or 50 ° C. or lower, or generate [B] in [A] and stir well, and then gradually add water to the prescribed Adjust the density. If water is added in an amount of about 8% or more, the flash point cannot be measured. Regarding the antifoaming property, when 1 to 20% of water is added, the initial defoaming property is improved. When water is added in excess of 20%, the increase in viscosity becomes remarkable, and the handleability is poor. For example, when 10% of water is added, it is 400 mPa · s / 20 ° C., but when 30% is added, it becomes a paste at the same temperature. In the case where 75% or more is added, sedimentation separation occurs upon standing. Regarding the defoaming property, when water is added in excess of 20%, both the initial defoaming property and the defoaming sustainability are lowered.
[0013]
In the present invention, the cloud point is a measure of the hydrophilicity of the nonionic surfactant, and the higher the cloud point, the higher the hydrophilicity. The measurement method in the present invention was in accordance with “Measurement method B” in ISO 1065-1975 (E), “Ethylene oxide nonionic surfactant-cloud point measurement method”. That is, first, a sample is dissolved in an aqueous solution of 25% by weight of butyl diglycol (butanol / EO2 molar adduct) to a concentration of 10% by weight. Next, about 5 cc of this sample solution is put in a test tube, and a thermometer is put in the test tube and gradually heated with stirring, the sample solution eventually becomes cloudy. Next, the sample solution is gradually cooled with stirring, and the temperature at which the sample solution turns from white turbidity to transparent is read and used as the cloud point. The cloud point of the composition of this invention is 32-48 degreeC, Preferably it is 35-45 degreeC. Even when the cloud point exceeds 48 ° C. or below 32 ° C., the balance between hydrophilicity / hydrophobicity is lost and sufficient defoaming properties cannot be obtained. On the other hand, when the cloud point exceeds 48 ° C., the water resistance decreases.
[0014]
In the present invention, examples of the polymerization method used for the reaction of alkylene oxide include anionic polymerization, cationic polymerization, and coordination anionic polymerization. These polymerization formats may be used alone or in combination. Examples of the catalyst include alkali or alkaline earth metal hydroxides, alcoholates or carbonates and trialkylamines, Lewis acid catalysts such as stannic chloride and boron trifluoride, mineral acids, and the like. A composite metal cyano complex found in Japanese Patent No. 277236 or an organic aluminum porphyrin complex found in Japanese Patent Publication No. 5-14734 is used. Of these, potassium hydroxide and cesium hydroxide are preferable. The amount of the catalyst used is in the range of 0.05 to 3.0% by weight, preferably 0.1 to 2.0% by weight, based on the weight of the compound at the end of the polymerization.
[0015]
In the present invention, the reaction of an alkylene oxide having 2 to 4 carbon atoms may be carried out under ordinary conditions. For example, the temperature is 70 to 150 ° C, preferably 80 to 140 ° C. Further, the pressure (gauge pressure) during the polymerization is 8 kg / cm ² or less, preferably 6 kg / cm ² or less.
[0016]
In the present invention, the catalyst [A] obtained by the reaction between the alcohol and the alkylene oxide may be removed or may be used as it is without being removed. The catalyst removal method includes neutralizing the alkaline catalyst with an acidic component, filtering and removing the resulting salt, using an alkali adsorbent or acid adsorbent, dissolving in a solvent and washing away with water, ion exchange resin There are a method to be used, a method in which an alkaline catalyst is neutralized with carbon dioxide gas, a method in which the resulting carbonate is filtered, a method in which neutralization is performed with various organic acids, inorganic acids or alkali components, and any of them may be used. .
[0017]
The antifoaming agent composition of the present invention may be added to the foaming system as an aqueous solution diluted with water to a concentration of 99 to 80% or undiluted. Moreover, the addition amount with respect to the foaming aqueous solution of the antifoamer composition of this invention is 0.1-10,000 ppm normally, Preferably it is 1-1000 ppm.
[0018]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. The test results of antifoaming properties and water resistance are shown in Table 1. In addition, the part in an Example and a comparative example means a weight part. Unless otherwise specified, all the raw materials used were reagent-grade products.
[0019]
[Defoaming test method]
750 ml of foaming test water (newspaper white paper) is put into a glass cylinder (hereinafter referred to as a foam tube), and the temperature is adjusted to 40 ° C. Next, while circulating test water from the bottom of the foam tube at a rate of 3,000 ml / min using a pump, the test water is dropped to the surface of the test solution 15 cm below the top of the foam tube. When the foam height reaches 100 mm, 5.0 ppm of antifoaming agent (vs. test water) is added with a micropipette. Continue to circulate and follow the changing bubble height for 5 minutes. The data 1 minute after the start of the test shows the initial defoaming property, and the data after 5 minutes shows the defoaming persistence.
[0020]
[Water resistance test method]
The water resistance was evaluated and compared with the total average value (seconds, indicating that the larger the value, the better the water resistance) in the Stekkite sizing test (JIS P8122) using the paper obtained under the following test paper preparation conditions. .
[Test paper preparation conditions]
An aqueous solution having a defoamer concentration of 50 PPM is prepared, and 2.0 g is uniformly sprayed on high-quality paper [Xerox paper L, A-4 size manufactured by Fuji Xerox Co., Ltd.]. After air drying for 15 minutes, it is dried with a drum dryer at 120 ° C. for 2 minutes.
[0021]
Example 1
To a pressure-resistant reaction vessel capable of heating, cooling and stirring up to 250 ° C., 2.5 parts of potassium hydroxide is added to 270 parts of stearyl alcohol, dehydrating under reduced pressure at 130 ° C., and then 928 parts of PO 16 mol. The reaction was carried out at 100-120 ° C. for about 9 hours and then 132 parts of 3 moles of EO at 130 ° C. for about 3 hours. Next, 12.6 parts of oleic acid (melting point: 16 ° C.) was added at 40 ° C. and stirred for 1 hour. Next, 15 parts of water was gradually added at the same temperature to obtain a uniform transparent composition, which was subjected to a defoaming test or the like. The cloud point (hereinafter simply referred to as the cloud point) in a 10% sample concentration measurement method using a 25% aqueous solution of butyl diglycol was 39.7 ° C.
[0022]
Example 2
In a reaction vessel similar to Example 1, 270 parts of stearyl alcohol was added to 2.5 parts of potassium hydroxide, dehydrated under reduced pressure at 130 ° C., and 928 parts of 16 mol of PO at about 100 to 120 ° C. In 9 hours, then 132 parts of 3 moles of EO were reacted at 130 ° C. in about 3 hours. Next, 20 parts of water is added at 90 ° C. and stirred for 30 minutes. Further, 50 parts of KYOWARD 600 [manufactured by Kyowa Chemical Co., Ltd., alkali adsorbent for removing catalyst] is added at the same temperature and stirred for 1 hour. Next, it was filtered using No. 2 filter paper [manufactured by Toyo Filter Paper Co., Ltd.] and dehydrated under reduced pressure. To 900 parts of this polyether compound (hereinafter referred to as base polyether), 30 parts of potassium oleate and 70 parts of water were added, and stirring was continued until uniform at 50 ° C., followed by cooling to obtain a uniform transparent cloud point. A composition at 39.8 ° C. was obtained and subjected to an antifoaming test or the like.
[0023]
Example 3
To 900 parts of the base polyether obtained in Example 2, 10 parts of magnesium oleate and 90 parts of water were added, and stirring was continued until uniform at 50 ° C., followed by cooling to obtain a uniform transparent cloud point of 39.6 ° C. The composition was obtained and subjected to an antifoaming test or the like.
[0024]
Example 4
To 850 parts of the base polyether obtained in Example 2, 10 parts of potassium linoleate (melting point of linoleic acid: −5 ° C.) and 140 parts of water were added. A composition having a clear cloud point of 39.5 ° C. was obtained and subjected to a defoaming test or the like.
[0025]
Example 5
To 985 parts of the base polyether obtained in Example 2, 15 parts of a potassium salt of gorlic acid (melting point: 6 ° C.) having an unsaturated alicyclic group and 18 carbon atoms was added and stirred at 50 ° C. until uniform. Then, the mixture was cooled to obtain a composition having a uniformly transparent cloud point of 39.4 ° C., and was subjected to an antifoaming test or the like.
[0026]
Example 6
In a reaction vessel similar to Example 1, 270 parts of stearyl alcohol was added to 2.5 parts of potassium hydroxide, dehydrated under reduced pressure at 130 ° C., and 754 parts of PO at about 100 to 120 ° C. 8 hours, then 132 parts of 3 moles of EO were reacted at 130 ° C. for about 3 hours, and then 72 parts of 1 mole of BO at the same temperature for about 4 hours. Next, 12.6 parts of oleic acid was added at 40 ° C. and stirred for 1 hour. Further, 145 parts of water was gradually added at the same temperature, and stirring was continued until uniform, followed by cooling to obtain a uniform transparent cloud point. A composition at 34.2 ° C. was obtained and subjected to an antifoaming test or the like.
[0027]
Example 7
To a reaction vessel similar to Example 1, 2.5 parts of potassium hydroxide was added to 256 parts of 1 mole of heptadecyl alcohol, dehydrated at 130 ° C. under reduced pressure, and 870 parts of 15 moles of PO at 100 to 120 ° C. In about 8 hours, 132 parts of 3 moles of EO were then addition polymerized at 130 ° C. in about 3 hours. Next, 12.6 parts of oleic acid was added at 40 ° C. and stirred for 1 hour. Next, 140 parts of water was gradually added at the same temperature, and stirring was continued until it became uniform, followed by cooling to obtain a composition having a uniform transparent cloud point of 45.2 ° C., which was subjected to a defoaming test or the like. .
[0028]
Example 8
In a reaction vessel similar to that in Example 1, 2.5 parts of potassium hydroxide was added to 298 parts of eicosyl alcohol, dehydrated at 130 ° C. under reduced pressure, and 986 parts of PO at 100 to 120 ° C. In about 8 hours, 154 parts of 3.5 moles of EO were then addition polymerized at 130 ° C. in about 3 hours. Next, 12.6 parts of oleic acid was added at 40 ° C. and stirred for 1 hour. Next, 160 parts of water was gradually added at the same temperature, and stirring was continued until it became uniform, followed by cooling to obtain a composition having a uniform transparent cloud point of 36.7 ° C., which was subjected to an antifoaming test and the like. .
[0029]
Comparative Example 1
A composition having a uniform and transparent cloud point of 40.1 ° C. is gradually added to 900 parts of the base polyether obtained in Example 2 by gradually adding 100 parts of water at 40 ° C. and continuing to stir until uniform. To obtain an antifoaming property test.
[0030]
Comparative Example 2
In a reaction vessel similar to that in Example 1, 2.5 parts of potassium hydroxide was added to 228 parts of pentadecyl alcohol, dehydrated at 130 ° C. under reduced pressure, and 841 parts of 14.5 moles of PO were added at 100 to 120 ° C. For about 8 hours, and then 110 parts of 2.5 moles of EO were addition polymerized at 130 ° C. for about 3 hours. Next, 12.6 parts of oleic acid was added at 40 ° C. and stirred for 1 hour. Next, 135 parts of water was gradually added at the same temperature, and stirring was continued until uniform, followed by cooling to obtain a composition having a uniform transparent cloud point of 37.8 ° C., which was used for an antifoaming test and the like. .
[0031]
Comparative Example 3
In a reaction vessel similar to that in Example 1, 270 parts of stearyl alcohol was added to 2.5 parts of potassium hydroxide, dehydrated at 130 ° C. under reduced pressure, and 10 moles of 580 parts of PO were added at about 100 to 120 ° C. In 8 hours, 176 parts of 4 moles of EO were then addition polymerized at 130 ° C. for about 3 hours, and then 288 parts of 4 moles of BO at the same temperature in about 4 hours. Next, 12.6 parts of oleic acid was added at 40 ° C. and stirred for 1 hour. Next, 145 parts of water was gradually added at the same temperature, and stirring was continued until it became uniform, followed by cooling to obtain a composition having a uniform transparent cloud point of 30.3 ° C., which was subjected to a defoaming test or the like. .
[0032]
Comparative Example 4
In a reaction vessel similar to Example 1, 270 parts of stearyl alcohol was added to 2.5 parts of potassium hydroxide, dehydrated under reduced pressure at 130 ° C., and 928 parts of 16 mol of PO at about 100 to 120 ° C. In 8 hours, 264 parts of 6 moles of EO were then addition polymerized at 130 ° C. in about 3 hours. Next, 12.6 parts of oleic acid was added at 40 ° C. and stirred for 1 hour. Next, 165 parts of water was gradually added at the same temperature, and stirring was continued until it became uniform, followed by cooling to obtain a composition having a uniform transparent cloud point of 50.4 ° C., which was subjected to an antifoaming test and the like. .
[0033]
Comparative Example 5
To 900 parts of the base polyether obtained in Example 2, 10 parts of potassium 2-ethylhexylate and 90 parts of water were added and stirred at 50 ° C. until uniform. A composition at 5 ° C. was obtained and subjected to an antifoaming test or the like.
[0034]
Comparative Example 6
To 900 parts of the base polyether obtained in Example 2, 10 parts of sodium stearate and 90 parts of water were added, and stirring was continued until uniform at 50 ° C., followed by cooling. A composition at 7 ° C. was obtained and subjected to an antifoaming test or the like.
[0035]
Comparative Example 7
To 900 parts of the base polyether obtained in Example 2, 10 parts of barium oleate and 90 parts of water were added, and stirring was continued until uniform at 50 ° C., followed by cooling. A composition at 3 ° C. was obtained and subjected to a defoaming test or the like.
[0036]
Comparative Example 8
To 770 parts of the base polyether obtained in Example 2, 10 parts of potassium oleate and 220 parts of water were added, and stirring was continued until uniform at 50 ° C., followed by cooling to obtain a uniform transparent cloud point of 40.3 ° C. The composition was obtained and subjected to an antifoaming test or the like.
[0037]
[Table 1]

[0038]
【The invention's effect】
The antifoaming agent according to the present invention is used in various industries that handle foamable aqueous solutions such as the pulp and paper manufacturing industry, the paper making process, the building industry and the paper manufacturing process, the dye industry and the dyeing industry, the fermentation industry, the synthetic resin manufacturing industry, and the synthetic rubber manufacturing industry. Excellent initial antifoaming property and defoaming sustainability against bubbles generated in wastewater treatment processes of various industries such as ink, paint industry and textile processing industry. In addition, when the antifoaming agent according to the present invention is used in a field where water resistance is required for the final product, for example, in the papermaking process in the paper pulp manufacturing industry, it is useful because the obtained paper can retain excellent water resistance. It is.

Claims

A compound [A] of an aliphatic monoalcohol having an average carbon number of 17 or more and an alkylene oxide having 2 to 4 carbon atoms, an aliphatic monocarboxylic acid having an average carbon number of 17 or higher and a melting point of 20 ° C. or lower, sodium, potassium, It consists of a metal salt [B] selected from the group of cesium, magnesium and aluminum, [A] to [B] being 100: 0.5 to 5.0 by weight ratio, An antifoaming composition having a cloud point of 32 to 48 ° C.

The antifoaming agent according to claim 1, wherein [A] is a compound obtained by addition polymerization of 2 to 5 mol of ethylene oxide, 10 to 20 mol of propylene oxide, and 0 to 3 mol of butylene oxide to an aliphatic monoalcohol having an average carbon number of 17 or more. Composition.

The antifoam composition according to claim 1 or 2, wherein [B] is potassium oleate.

The antifoamer composition according to any one of claims 1 to 3 , comprising 1 to 20% by weight of water.

The defoamer composition according to any one of claims 1 to 4 , which is an antifoaming agent for a papermaking process in paper pulp manufacturing industry.

A compound [A] of an aliphatic monoalcohol having an average carbon number of 17 or more and an alkylene oxide having 2 to 4 carbon atoms, an aliphatic monocarboxylic acid having an average carbon number of 17 or higher and a melting point of 20 ° C. or lower, sodium, potassium, It consists of a metal salt [B] selected from the group of cesium, magnesium and aluminum, [A] to [B] being 100: 0.5 to 5.0 by weight ratio, A method for producing an antifoam composition having a cloud point of 32 to 48 ° C,
After obtaining compound [A] using a hydroxide, alcoholate or carbonate of an alkali or alkaline earth metal as a catalyst,
Add an aliphatic monocarboxylic acid having an average carbon number of 17 or more and a melting point of 20 ° C. or less,
Further, if necessary, water is added to dilute to a concentration of 99 to 80% by weight.