JP3799428B2

JP3799428B2 - Water-soluble antifoam composition

Info

Publication number: JP3799428B2
Application number: JP07333398A
Authority: JP
Inventors: 芳和五藤
Original assignee: San Nopco Ltd
Current assignee: San Nopco Ltd
Priority date: 1998-03-05
Filing date: 1998-03-05
Publication date: 2006-07-19
Anticipated expiration: 2018-03-05
Also published as: JPH11244608A

Description

【０００１】
【発明の属する技術分野】
本発明は消泡剤に関する。さらに詳しくは発泡性の水溶液を取り扱う諸工業、例えば合成樹脂製造工業、合成ゴム製造工業、繊維加工工業、染料工業、染色工業、醗酵工業、各種排水処理工業、紙パルプ製造工業、建築工業、塗料製造および塗装工業などの各種工程で、発泡性水溶液中に均一に溶解して白濁や油膜状の浮遊物等を生じることがなく、かつ発生する気泡に対し優れた消泡性を発揮す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、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。
【０００３】
従来、ポリエーテル系消泡剤としては、１〜８価のアルコール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、ソルビタンおよび蔗糖などにアルキレンオキシドを付加したものや、その末端を脂肪酸でエステル化したもの（特公昭４５−３０１８９号、特公昭４７−４０３９４号、特公昭４９−３８９２３号、特開昭５０−２２７８８号、特開昭５４−１３３４８４号、特開昭５４−１３５２９８号、特公昭６１−７８４７号、特開平２−２１９０５号および特開平２−２１９０７号各公報等）、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、特開昭５５−９２１１０号公報等）、またプロピレングリコール脂肪酸モノエステル（特開昭５２−９７３８５号公報）などが知られている。また、水溶性を示すポリエーテル系消泡剤としては例えば特開昭５６−４８２１０号公報、特開平４−２９７３５号公報等が知られている。
【０００４】
一般にポリエーテル系消泡剤は水溶液中で白濁し始める温度、曇点を持ち、この曇点以上でないと十分な消泡性が得られない性質を持っていた。よって透明に溶解するという水溶性と消泡性とは両立し難く、前述の水溶性を示す消泡剤も消泡性が十分でなかった。また１〜８価のアルコールにアルキレンオキシドを付加したもの、アルキルフェノールのアルキレンオキシド付加物、プロピレングリコール脂肪酸モノエステル等は水溶性が十分でないという欠点があった。
【０００５】
【発明が解決しようとする課題】
一般にポリエーテル系消泡剤は水溶性と消泡性が両立しないという欠点があった。よって本発明の目的は水溶性を示しながら消泡性に優れるポリエーテル系消泡剤を提供することである。
【０００６】
【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、特定の糖類にアルキレンオキシドを付加重合させた化合物が優れた水溶性と良好な消泡効果を示すことを見いだし本発明に達した。すなわち本発明は、還元性糖類を炭素数１〜８、価数１〜３のアルコールにより化学修飾することにより得られる非還元性糖類に、炭素数２〜４のアルキレンオキシドを平均１５〜６５モル付加重合させた化合物からなる水溶性消泡剤組成物である。
【０００７】
【発明の実施の形態】
本発明において還元性糖類とは糖類のうちヘミアセタール水酸基が分子内に残っている糖類のことで、単糖類ではブドウ糖、果糖等が、二糖類では、麦芽糖、乳糖、ソホロース、セロビオースおよびゲンチオビオース等が、三糖類ではゲンチアノース、ラフィノース等が挙げられる。これらのうち好ましくは単糖類、二糖類であり、特に好ましくはブドウ糖、麦芽糖である。
【０００８】
本発明において炭素数が１〜８である価数１〜３のアルコールとは分子内に１〜３個の水酸基を持ち、かつ炭素数が１〜８の有機化合物であり、例えば直鎖または分岐のアルキル基、アルケニル基等を持つ脂肪族アルコール、アルキレン基を持つグリコール類、フェノール基を持つアルキルフェノール類、ベンジル基等を持つ芳香族アルコール類および脂環式アルコール等であり、例えばメタノール、エタノール、イソプロパノール、ブタノール、オクチルアルコール、イソオクチルアルコール、アリルアルコール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、グリセリン、トリメチロールプロパン、フェノール、シクロヘキサノールおよびベンジルアルコール等が挙げられる。これらのうち好ましくは脂肪族アルコールおよびグリコール類である。
【０００９】
本発明において化学修飾法とは還元性糖類とアルコールを酸触媒の存在下で加熱するフイッシャー法および特開昭６３−８４６３７号公報、特開平１−４７７９６号公報、特開平１−７１８９７号公報等に見られるフイッシャー法の改良法等が挙げられる。化学修飾した非還元性糖類としては、例えば高級アルコールとブドウ糖、麦芽糖等からのアルキル変成糖類、各種二価アルコールと上記糖類による縮合変成物等が挙げられる。これらは単独でまたは併用して本発明に使用できる。
【００１０】
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）、イソブチレンオキシド、１，２−ブチレンオキシド（以下、ＢＯと略記）およびテトラヒドロフラン（以下、ＴＨＦと略記）等が挙げられる。これらのうち好ましいのはＥＯ、ＰＯおよびＢＯである。
【００１１】
本発明において該糖類へのアルキレンオキシドの平均付加モル数は１５〜６５であり、好ましくは２０〜６０である。１５モルより低い場合は消泡性が低下する。また６５モルを越える場合は消泡性、水溶性性が低下する。また、アルキレンオキシド中に占めるＰＯの割合は７５モル％以上、好ましくは８０モル％以上である。７５モル％未満の場合、例えばＢＯ、ＴＨＦ等の割合が大きくなると水溶性が低下し、またＥＯの割合が大きくな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、また重合形式もブロック、ランダム等何れでもよい。
【００１２】
本発明において該化合物の分子量の分散度（重量平均分子量／数平均分子量、以下、分散度と略記）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により求められる。ＧＰＣ分析装置はＨＬＣ−８０２０［ＴｏｙｏＳｏｄａ（株）製］、カラムはＴＳＫｇｅｌＧ４０００ＨＸＬ＋Ｇ３０００ＨＸＬ＋Ｇ２０００ＨＸＬ［ＴｏｙｏＳｏｄａ（株）製］、溶媒は精製ＴＨＦ、分子量の検量線作成用の標準物質にはＴＳＫ標準ポリエチレンオキシド［ＴｏｙｏＳｏｄａ（株）製］等を用いた。
【００１３】
本発明において該化合物の分散度は１．２以下であり、好ましくは１．１５以下である。１．２を越える場合には、比較的低分子量の副反応生成物（ポリプロピレングリコールまたはアリルアルコール／ＰＯ付加物等）がかなり多量（例えば１例として分散度が１．３の場合約３０％程度）に混在し、このため消泡力が低下する。また、たとえば該糖類へのアルキレンオキシドの高モル付加物と低モル付加物とを混合した場合、分散度は２．０を越えることがあるが、この場合にも消泡力が大幅に低下する。
【００１４】
本発明において、アルキレンオキシドの付加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、また重合度に応じて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等、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、およびトリメチルアミン等であり、特に好ましくは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０．０５〜２．０重量％の範囲であり、好ましくは０．１〜１．０重量％である。
【００１５】
本発明において、付加重合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８０〜１３０℃である。また、重合中の最高圧力（ゲージ圧）は８ｋｇ／ｃｍ²、好ましくは６ｋｇ／ｃｍ²である。また反応に要する時間は通常４〜１２時間である。
【００１６】
本発明において、重合により得られる該重合物からの触媒除去の方法としては、例えば特公昭４７−３７４５号公報に記載のように、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、特開昭５３−１２３４９９号公報のアルカリ吸着剤を用いる方法、特公昭４９−１４３５９号公報の溶媒に溶かして水洗する方法、特開昭５１−２３２１１号公報のイオン交換樹脂を用いる方法、特公昭５２−３３０００号公報の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、無機酸により中和する方法、または酸性触媒の場合はいったんアルカリ成分により弱アルカリ性とした後上記方法にて除去する場合等があるが、そのいずれを用いても差し支えない。
【００１７】
本発明の消泡剤は予め適正な濃度に希釈した水溶液の状態で添加しても、またそのままで添加してもよく、またその添加量は発泡性水溶液に対して通常、１〜１０，０００ｐｐｍであり、好ましくは５〜５，０００ｐｐｍ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、水溶性等の試験結果は表１〜３記載した。尚、実施例、試験方法などにおける部は重量部を意味する。
【００１９】
［消泡性試験方法１］
下記組成の試験液を作成し、特公平６−４５９１６号公報に記載されている方法に準拠して次の通りに実施した。まず試験液１５０部を３００ｃｃのガラスビンにとり、消泡剤０．０４５部（消泡剤濃度３００ｐｐｍ）を投入しマグネチックスターラーにて４０℃に温調して３０分間撹拌する。次いで３０℃の雰囲気下にて＃４フォードカップを用いた１ｍ自然落下による発泡量（ｍｌ）を５分間にわたって観察した。評価結果は表１に記載。
［試験液組成］
クラレポバールＰＶＡ−７０６（ケン化度約９２モル％）にイオン交換水を加えて、固形分濃度を２．５％に調整して作成した。
【００２０】
［水溶性試験方法１］
上記の消泡性試験に使用した試験液を１０ｍｍのガラスセルに入れ、イオン交換水を対照として、波長４３０ｎｍの可視光線の透過率（％）を分光光度計により測定した。評価は、消泡剤無添加の試験液を１００とする相対評価とした。評価結果は表１に記載。
【００２１】
［消泡性試験方法２］
ガラス製発泡管に下記試験液５００ｍｌ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３０００ｍｌ／分で循環しながら、発泡管上部（高さは一定に設定）より約２０ｃｍ下の試験液水面に落下させることにより試験水を発泡させる。泡高さが１００ｍｍに達したとき消泡剤１０ＰＰＭ（対試験水）を添加し、最も泡面が低下するのに要した時間（秒、小さいほど分散性が良いことを表す）その泡高さ（ｍｍ、小さいほど初期破泡性が良いことを表す）および循環を持続して５分間後の泡高さ（ｍｍ、小さいほど抑泡持続性が良いことを表す）をもって消泡性を評価比較した。評価結果は表２に記載。
【００２２】

【００２３】
［水溶性試験方法２］
下記の試験液を作成し、水溶性試験法１と同様にして評価した。評価結果は表２に記載。

【００２４】
［鮮鋭度試験２］
下記の条件にてポリエステル布を染色したのち還元洗浄を行う。次いで乾燥後肉眼にて鮮鋭度を評価した。（評価は５段階とし、消泡剤無添加系を最良の５とした。）評価結果は表２に記載。
【００２５】

【００２６】
［消泡性試験方法３］
消泡性試験方法２に準じて、下記のように実施した。ガラス製発泡管に発泡性試験水（製紙工場排水）５００ｍｌを入れ、３０℃に温調した。次いでポンプを用いて発泡管の底部から試験水を３０００ｍｌ／分で循環しながら、発泡管上部より約２０ｃｍ下の試験液水面に落下させることにより試験水を発泡させた。泡高さが１００ｍｍに達したとき消泡剤５０ＰＰＭを添加し、最も泡面が低下するのに要した時間、その泡高さ、および循環を持続して５分間後の泡高さをもって消泡性を評価比較した。評価結果は表３に記載。
【００２７】
［水溶性試験方法３］
上記の消泡性を評価した発泡性試験液を用いて水溶性試験法１と同様にして評価した。評価結果は表３に記載。
【００２８】
実施例１
撹拌、温度調節可能な耐圧容器に、メチルグリコシド（理論分子量１９４）１９４部、４０％トリメチルアミン水溶液（以下、ＴＭＡと略記）３．０部を加えた。次いで１００〜１１０℃にて８８部のＥＯと１７４部のＰＯの混合アルキレンオキシドを付加重合させた。所要反応時間は約６時間であった。次いで水酸化カリウム（試薬特級、以下同じ）３．０部を加え、１３０℃にて減圧下脱水の後、８７０部のＰＯを１００〜１１０℃にて付加重合させた。所要反応時間は約１２時間であった。次いで９０℃にてイオン交換水２．５部を加えた後、キョーワード６００［協和化学工業（株）製］５０部を加え、同温度にて１時間撹拌した。次いで同温度にてＮｏ．２濾紙［東洋濾紙（株）製］を用いて濾過して触媒を吸着除去しさらに減圧下１２０℃にて脱水処理して、メチルグリコシド／ＥＯ２モル／ＰＯ１８モル付加物、分散度１．０５の化合物を得て消泡性試験等に供した。
【００２９】
実施例２
特開昭６３−８４６３７号公報記載の改良フィッシャー法にて２モルのブドウ糖と１モルのエチレングリコール（ＥＧ）を脱水縮合させ、２つのピラノース環がエーテル結合を介してエチレン基で繋がったＥＧ変成ブドウ糖（理論分子量３８６）を得た。次いで撹拌、温度調節可能な耐圧容器に上記変成体３８６部、ＴＭＡ４．０部を加えた。次いで１００〜１１０℃にて２９０部のＰＯを付加重合させた。所要反応時間は約１０時間であった。次いで水酸化セシウム１２．０部［ケメタルジャパン（株）製、５０％水溶液品、以下同じ］を加え、１３０℃にて減圧下脱水の後、１４５０部のＰＯを１００〜１１０℃にて付加重合させた。さらに１４４部のＢＯ［大日本インキ化学工業（株）製］を１２０〜１３０℃にて付加重合させた。所要反応時間は約１２時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、ＥＧ変成ブドウ糖／ＰＯ３０モル／ＢＯ２モル付加物、分散度１．１３の化合物を得て消泡性試験等に供した。
【００３０】
実施例３
撹拌、温度調節可能な耐圧容器に実施例２で得たＥＧ変成ブドウ糖３８６部、ＴＭＡ４．０部を加えた。次いで１００〜１１０℃にて２２０部のＥＯを付加重合させた。所要反応時間は約５時間であった。次いで水酸化セシウム２０．０部を加え、１３０℃にて減圧下脱水の後、３１９０部のＰＯを１００〜１１０℃にて付加重合させた。所要反応時間は約１３時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、ＥＧ変成ブドウ糖／ＥＯ５モル／ＰＯ５５モル付加物、分散度１．１９の化合物を得て消泡性試験等に供した。
【００３１】
実施例４
実施例２と同様な方法にて３モルのブドウ糖と１モルのトリメチロールプロパン（ＴＰ）を脱水縮合させ、３つのピラノース環がエーテル結合を介してトリメチロールプロパン残基で繋がったＴＰ変成ブドウ糖（理論分子量６２０）を得た。次いで撹拌、温度調節可能な耐圧容器に上記変成体６２０部、ＴＭＡ４．０部を加えた。次いで１００〜１１０℃にて５８０部のＰＯを付加重合させた。所要反応時間は約１１時間であった。次いで水酸化セシウム２０．０部を加え、１３０℃にて減圧下脱水の後、２０３０部のＰＯを１００〜１１０℃にて付加重合させた。さらに１４４部のＢＯを１２０〜１３０℃にて付加重合させた。所要反応時間は約１５時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、ＴＰ変成ブドウ糖／ＰＯ４５モル／ＢＯ２モル付加物、分散度１．１７の化合物を得て消泡性試験等に供した。
【００３２】
実施例５
実施例２と同様にしてｎ−ブタノールと麦芽糖からブチル変成麦芽糖（理論分子量３９８）を得た。次いで撹拌、温度調節可能な耐圧容器に上記変成体３９８部、ＴＭＡ４．０部を加えた。次いで１００〜１１０℃にて４０６部のＰＯを付加重合させた。所要反応時間は約１０時間であった。次いで水酸化セシウム１７．０部を加え、１３０℃にて減圧下脱水の後、１９１４部のＰＯを１００〜１１０℃にて付加重合させた。さらに１４４部のＢＯを１２０〜１３０℃にて付加重合させた。所要反応時間は約１２時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、ブチル変成麦芽糖／ＰＯ４０モル／ＢＯ２モル付加物、分散度１．１６の化合物を得て消泡性試験等に供した。
【００３３】
実施例６
実施例２と同様にして２−エチルヘキサノールと麦芽糖からオクチル変成麦芽糖（理論分子量４５４）を得た。次いで撹拌、温度調節可能な耐圧容器に上記変成体４５４部、ＴＭＡ４．０部を加えた。次いで１００〜１１０℃にて４６４部のＰＯを付加重合させた。所要反応時間は約１０時間であった。次いで水酸化セシウム１４．０部を加え、１３０℃にて減圧下脱水の後、１５６６部のＰＯを１００〜１１０℃にて付加重合させた。所要反応時間は約１２時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、オクチル変成麦芽糖／ＰＯ３５モル付加物、分散度１．１２の化合物を得て消泡性試験等に供した。
【００３４】
比較例１
消泡剤無添加で消泡性試験等を実施した。
【００３５】
比較例２
撹拌、温度調節可能な耐圧容器にオレイルアルコール２６８部、水酸化カリウム５．０部を加え、１２０℃にて減圧下脱水の後、１７４０部のＰＯを１００〜１１０℃にて付加重合させた。次いで２２０部のＥＯを１２０〜１３０℃にて付加重合させた。所要反応時間は約１７時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、オレイルアルコール／ＰＯ３０モル／ＥＯ５モル付加物、分散度１．２０の化合物を得て消泡性試験等に供した。
【００３６】
比較例３
撹拌、温度調節可能な耐圧容器にオレイルアルコール２６８部、水酸化カリウム３．５部を加え、１２０℃にて減圧下脱水の後、８８０部のＥＯを１００〜１１０℃にて付加重合させた。次いで２９０部のＰＯを１００〜１１０℃にて付加重合させた。所要反応時間は約１１時間であった。次いで空気冷却管を取り付けた後アジピン酸７３ｇを加え、液中に窒素を少量通気させながら次第に昇温し１５０℃とする。その後次第に減圧とし、徐々に２３０℃まで昇温、水の留出が観察されなくなるまで同温度に保った。冷却後実施例１と同様にして触媒除去、脱水処理して、オレイルアルコール／ＥＯ２０モル／ＰＯ５モル付加物のアジピン酸ジエステル化物、分散度１．２２の化合物を得て消泡性試験等に供した。
【００３７】
比較例４
撹拌、温度調節可能な耐圧容器に１１１．５部のソルビトールおよび２．５部の水酸化カリウムを加え、１３０℃にて減圧下脱水の後、８８８．５部のＰＯを１００〜１１０℃にて付加重合させた。所要反応時間は約１４時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、ソルビトール／ＰＯ２５モル付加物、分散度１．１３の化合物を得て消泡性試験等に供した。
【００３８】
比較例５
撹拌、温度調節可能な耐圧容器に、メチルグリコシド１９４部、ＴＭＡ３．０部を加えた。次いで１００〜１１０℃にて１７６部のＥＯを付加重合させた。所要反応時間は約６時間であった。次いで水酸化カリウム２．０部を加え、１３０℃にて減圧下脱水の後、５８０部のＰＯを１００〜１１０℃にて付加重合させた。所要反応時間は約１２時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、メチルグリコシド／ＥＯ４モル／ＰＯ１０モル付加物、分散度１．１０の化合物を得て消泡性試験等に供した。
【００３９】
比較例６
撹拌、温度調節可能な耐圧容器にブチル変成麦芽糖３９８部、ＴＭＡ４．０部を加えた。次いで１００〜１１０℃にて４４０部のＥＯを付加重合させた。所要反応時間は約６時間であった。次いで水酸化セシウム２２．０部を加え、１３０℃にて減圧下脱水の後、３４８０部のＰＯを１００〜１１０℃にて付加重合させた。所要反応時間は約１６時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、ブチル変成麦芽糖／ＥＯ１０モル／ＰＯ６０モル付加物、分散度１．２１の化合物を得て消泡性試験等に供した。
【００４０】
比較例７
撹拌、温度調節可能な耐圧容器にブチル変成麦芽糖３９８部、ＴＭＡ４．０部を加えた。次いで１００〜１１０℃にて４０６部のＰＯを付加重合させた。所要反応時間は約１０時間であった。次いで水酸化カリウム５．０部を加え、１３０℃にて減圧下脱水の後、１９１４部のＰＯを１００〜１１０℃にて付加重合させた。さらに１４４部のＢＯを１２０〜１３０℃にて付加重合させた。所要反応時間は約１２時間であった。次いで実施例１と同様にして触媒除去、脱水処理して、ブチル変成麦芽糖／ＰＯ４０モル／ＢＯ２モル付加物、分散度１．２９の化合物を得て消泡性試験等に供した。
【００４１】
【表１】

【００４２】
【表２】

【００４３】
【表３】

【００４４】
【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工業、例えば合成樹脂製造工業、合成ゴム製造工業、繊維加工工業、染料工業、染色工業、醗酵工業、各種排水処理工業、紙パルプ製造工業、建築工業、塗料製造および塗装工業などの各工程において、発泡性水溶液の透明性を保ちつつ従来にない良好な消泡効果を示すので最終製品の品質の向上に、環境の保全、美観の保護等に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antifoaming agent. More specifically, various industries that handle foamable aqueous solutions, such as synthetic resin manufacturing industry, synthetic rubber manufacturing industry, textile processing industry, dye industry, dyeing industry, fermentation industry, various wastewater treatment industries, paper pulp manufacturing industry, construction industry, paints A new product that does not dissolve in foamable aqueous solution even in various processes such as manufacturing and coating industries, and does not produce white turbidity or oily film-like suspended matter, etc. The present invention relates to an antifoam composition.
[0002]
[Prior art]
Conventionally, for these industrial applications, polyether-based antifoaming agents that have no adverse effects such as oil spots, pinholes, repellency, and oil floating in the final product, and that hardly generate scum or precipitates have been preferred. It is used.
[0003]
Conventionally, polyether antifoaming agents include 1 to 8 valent alcohols such as stearyl alcohol, dipropylene glycol, glycerin, sorbitan and sucrose added with alkylene oxide, and those whose ends are esterified with fatty acids ( JP-B-45-30189, JP-B-47-40394, JP-B-49-38923, JP-A-50-22788, JP-A-54-133484, JP-A-54-135298, JP-B-61-7847 , JP-A-2-21905 and JP-A-2-21907, etc.), alkylphenol added with alkylene oxide (JP-B-47-32511, JP-A-55-92110, etc.), and propylene Glycol fatty acid monoester (Japanese Patent Laid-Open No. 52-97385) is known It has been. Moreover, as a polyether type antifoamer which shows water solubility, Unexamined-Japanese-Patent No. 56-48210, Unexamined-Japanese-Patent No. 4-29735, etc. are known, for example.
[0004]
In general, a polyether-based antifoaming agent has a temperature and a clouding point at which it starts to become cloudy in an aqueous solution, and a sufficient defoaming property cannot be obtained unless the clouding point is exceeded. Therefore, it is difficult to achieve both water solubility and antifoaming property to dissolve transparently, and the above-mentioned antifoaming agent exhibiting water solubility is also insufficient in antifoaming property. Moreover, the thing which added the alkylene oxide to the 1-8 valent alcohol, the alkylene oxide addition product of alkylphenol, propylene glycol fatty acid monoester, etc. had the fault that water solubility was not enough.
[0005]
[Problems to be solved by the invention]
In general, polyether-based antifoaming agents have a drawback that water solubility and antifoaming properties are not compatible. Accordingly, an object of the present invention is to provide a polyether antifoaming agent that exhibits water solubility and is excellent in antifoaming properties.
[0006]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor has found that a compound obtained by addition polymerization of an alkylene oxide to a specific saccharide exhibits excellent water solubility and a good defoaming effect, and has reached the present invention. That is, the present invention provides an average of 15 to 65 moles of an alkylene oxide having 2 to 4 carbon atoms to a non-reducing sugar obtained by chemically modifying a reducing saccharide with an alcohol having 1 to 8 carbon atoms and 1 to 3 carbon atoms. A water-soluble antifoaming agent composition comprising an addition-polymerized compound.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the reducing saccharide refers to a saccharide in which a hemiacetal hydroxyl group remains in the molecule among saccharides, and monosaccharides include glucose, fructose, etc., and disaccharides include maltose, lactose, sophorose, cellobiose, and gentiobiose. Examples of trisaccharides include gentianose and raffinose. Of these, monosaccharides and disaccharides are preferable, and glucose and maltose are particularly preferable.
[0008]
The alcohol valence 1 to 3 carbon is 1-8 in the present invention has 1 to 3 hydroxyl groups in the molecule, and an organic compound with a carbon number 1-8, for example, linear or branched An aliphatic alcohol having an alkyl group, an alkenyl group or the like, a glycol having an alkylene group, an alkylphenol having a phenol group, an aromatic alcohol having a benzyl group or the like, and an alicyclic alcohol, for example, methanol, ethanol, Isopropanol, butanol, octyl alcohol, isooctyl alcohol, Allyl alcohol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, Glycerin, trimethylolpropane, phenol, Examples include cyclohexanol and benzyl alcohol. Of these, aliphatic alcohols and glycols are preferred.
[0009]
In the present invention, the chemical modification method refers to a Fischer method in which reducing saccharides and alcohol are heated in the presence of an acid catalyst, JP-A-63-84737, JP-A-1-47796, JP-A-1-71897, and the like. For example, an improvement of the Fischer method. Examples of chemically modified non-reducing saccharides include alkyl-modified saccharides from higher alcohols and glucose, maltose and the like, and condensation-modified products of various dihydric alcohols and saccharides. These may be used alone or in combination in the present invention.
[0010]
In the present invention, the alkylene oxide having 2 to 4 carbon atoms includes ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), isobutylene oxide, 1,2-butylene oxide (hereinafter abbreviated as BO) and Tetrahydrofuran (hereinafter abbreviated as THF) and the like can be mentioned. Of these, EO, PO and BO are preferred.
[0011]
In this invention, the average addition mole number of the alkylene oxide to this saccharide is 15-65, Preferably it is 20-60. When it is lower than 15 mol, the antifoaming property is lowered. On the other hand, when it exceeds 65 mol, the defoaming property and water solubility are lowered. The proportion of PO in the alkylene oxide is 75 mol% or more, preferably 80 mol% or more. In the case of less than 75 mol%, for example, when the proportion of BO, THF or the like increases, the water solubility decreases, and when the proportion of EO increases, the defoaming property decreases. The order of addition polymerization of alkylene oxide is not particularly limited, and the polymerization mode may be any of block, random and the like.
[0012]
In the present invention, the molecular weight dispersity (weight average molecular weight / number average molecular weight, hereinafter abbreviated as dispersity) of the compound is determined by gel permeation chromatography (GPC). The GPC analyzer is HLC-8020 [manufactured by Toyo Soda Co., Ltd.], the column is TSKgel G4000HXL + G3000HXL + G2000HXL [manufactured by Toyo Soda Co., Ltd.], the solvent is purified THF, and the standard substance for preparing a molecular weight calibration curve is TSK standard polyethylene oxide [Toyo Soda Co., Ltd.] and the like were used.
[0013]
In the present invention, the degree of dispersion of the compound is 1.2 or less, preferably 1.15 or less. If it exceeds 1.2, a relatively large amount of by-products (such as polypropylene glycol or allyl alcohol / PO adduct) having a relatively low molecular weight (for example, about 30% when the dispersity is 1.3 as an example) ) And defoaming power is reduced. For example, when a high molar adduct and a low molar adduct of alkylene oxide to the saccharide are mixed, the degree of dispersion may exceed 2.0. In this case, however, the defoaming power is greatly reduced. .
[0014]
In the present invention, examples of the polymerization method used for addition of alkylene oxide include anionic polymerization, cationic polymerization, and coordination anionic polymerization. These polymerization formats may be used alone or in combination depending on the degree of polymerization. Catalysts include alkali or alkaline earth metal hydroxides, alcoholates or carbonates, trialkylamines, Lewis acid catalysts such as stannic chloride and boron trifluoride, mineral acids, etc. A composite metal cyano complex found in Japanese Patent No. 63-277236 or an organic aluminum porphyrin complex found in Japanese Patent Publication No. 5-14734 is used. Of these, potassium hydroxide, cesium hydroxide, trimethylamine and the like are preferable, and cesium hydroxide is particularly preferable. The amount of the catalyst used is in the range of 0.05 to 2.0% by weight, preferably 0.1 to 1.0% by weight, based on the weight of the compound at the end of the polymerization.
[0015]
In the present invention, the addition polymerization reaction may be carried out under ordinary conditions. For example, the temperature is 70 to 150 ° C, preferably 80 to 130 ° C. The maximum pressure (gauge pressure) during the polymerization is 8 kg / cm ² , preferably 6 kg / cm ² . The time required for the reaction is usually 4 to 12 hours.
[0016]
In the present invention, as a method for removing the catalyst from the polymer obtained by polymerization, for example, as described in Japanese Patent Publication No. 47-3745, the alkaline catalyst is neutralized with an acidic component, and the resulting salt is removed by filtration. A method using an alkali adsorbent disclosed in JP-A-53-123499, a method of dissolving in a solvent disclosed in JP-B-49-14359, and a method of washing with water, a method using an ion-exchange resin disclosed in JP-A-51-23211 The method of neutralizing the alkaline catalyst of Japanese Patent Publication No. 52-33000 with carbon dioxide and filtering the resulting carbonate, and the method of neutralizing with various organic acids and inorganic acids, or in the case of an acidic catalyst, once an alkaline component However, any of these may be used.
[0017]
The antifoaming agent of the present invention may be added in the form of an aqueous solution diluted to an appropriate concentration in advance, or may be added as it is, and the addition amount is usually 1 to 10,000 ppm with respect to the foaming aqueous solution. And preferably 5 to 5,000 ppm.
[0018]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Test results such as antifoaming property and water solubility are shown in Tables 1 to 3. In addition, the part in an Example, a test method, etc. means a weight part.
[0019]
[Defoaming test method 1]
A test solution having the following composition was prepared and carried out as follows in accordance with the method described in JP-B-6-45916. First, 150 parts of the test solution is placed in a 300 cc glass bottle, 0.045 part of antifoaming agent (antifoaming concentration: 300 ppm) is added, the temperature is adjusted to 40 ° C. with a magnetic stirrer, and the mixture is stirred for 30 minutes. Subsequently, the amount of foaming (ml) by natural fall using a # 4 Ford cup using a # 4 Ford cup was observed over 5 minutes in an atmosphere of 30 ° C. The evaluation results are shown in Table 1.
[Test solution composition]
It was prepared by adding ion exchange water to Kuraray Poval PVA-706 (degree of saponification of about 92 mol%) to adjust the solid content concentration to 2.5%.
[0020]
[Water solubility test method 1]
The test solution used for the defoaming test was placed in a 10 mm glass cell, and the transmittance (%) of visible light having a wavelength of 430 nm was measured with a spectrophotometer using ion-exchanged water as a control. Evaluation was made into the relative evaluation which sets the test liquid without an antifoamer to 100. The evaluation results are shown in Table 1.
[0021]
[Defoaming test method 2]
500 ml of the following test solution is put into a glass foam tube, and the temperature is adjusted to 40 ° C. Next, while circulating the test water from the bottom of the foaming tube at 3000 ml / min using a pump, the test water is foamed by dropping it onto the surface of the test solution approximately 20 cm below the top of the foaming tube (the height is set constant). . When the foam height reaches 100 mm, the defoaming agent 10PPM (vs. test water) is added, and the time required for the foam surface to fall most (second, smaller indicates that the dispersibility is better) (The smaller the diameter, the better the initial foam breaking property) and the foam height after 5 minutes of continuous circulation (the smaller the mm, the better the defoaming sustainability). did. The evaluation results are shown in Table 2.
[0022]

[0023]
[Water solubility test method 2]
The following test solutions were prepared and evaluated in the same manner as in the water solubility test method 1. The evaluation results are shown in Table 2.

[0024]
[Sharpness test 2]
After the polyester cloth is dyed under the following conditions, reduction cleaning is performed. Subsequently, the sharpness was evaluated with the naked eye after drying. (Evaluation was made into 5 steps, and the best antifoam additive-free system was taken as 5.) The evaluation results are shown in Table 2.
[0025]

[0026]
[Defoaming property test method 3]
According to the antifoaming property test method 2, it carried out as follows. 500 ml of foaming test water (paper mill wastewater) was placed in a glass foam tube, and the temperature was adjusted to 30 ° C. Next, the test water was foamed by dropping it onto the surface of the test solution approximately 20 cm below the top of the foaming tube while circulating the test water at 3000 ml / min from the bottom of the foaming tube using a pump. When the foam height reaches 100 mm, the antifoaming agent 50 PPM is added, and the foam removal time is as long as it takes 5 minutes to maintain the foam height and the foam height, and the foam height after 5 minutes. Sex was evaluated and compared. The evaluation results are shown in Table 3.
[0027]
[Water solubility test method 3]
Evaluation was performed in the same manner as in the water solubility test method 1 using the above-described foamability test solution for which defoaming property was evaluated. The evaluation results are shown in Table 3.
[0028]
Example 1
194 parts of methyl glycoside (theoretical molecular weight 194) and 3.0 parts of 40% trimethylamine aqueous solution (hereinafter abbreviated as TMA) were added to a pressure-resistant vessel capable of stirring and temperature adjustment. Subsequently, a mixed alkylene oxide of 88 parts EO and 174 parts PO was subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 6 hours. Next, 3.0 parts of potassium hydroxide (special reagent grade, the same applies hereinafter) was added, and after dehydration at 130 ° C. under reduced pressure, 870 parts of PO was subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 12 hours. Next, 2.5 parts of ion-exchanged water was added at 90 ° C., and then 50 parts of KYOWARD 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] was added and stirred at the same temperature for 1 hour. Next, at the same temperature, no. Using 2 filter paper [manufactured by Toyo Filter Paper Co., Ltd.], the catalyst was adsorbed and removed, and further dehydrated at 120 ° C. under reduced pressure to give methylglycoside / EO 2 mol / PO 18 mol adduct, dispersity 1.05. The compound was obtained and subjected to an antifoaming test or the like.
[0029]
Example 2
EG modification in which 2 mol of glucose and 1 mol of ethylene glycol (EG) are dehydrated and condensed by an improved Fischer method described in JP-A-63-84637, and two pyranose rings are linked by an ethylene group via an ether bond Glucose (theoretical molecular weight 386) was obtained. Next, 386 parts of the above-mentioned modified body and 4.0 parts of TMA were added to a pressure vessel capable of stirring and temperature adjustment. Subsequently, 290 parts of PO were subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 10 hours. Next, 12.0 parts of cesium hydroxide [manufactured by Kemetal Japan Co., Ltd., 50% aqueous solution product, the same applies below] was added, dehydrated under reduced pressure at 130 ° C., and 1450 parts of PO were added at 100 to 110 ° C. Polymerized. Furthermore, 144 parts of BO [manufactured by Dainippon Ink & Chemicals, Inc.] was subjected to addition polymerization at 120 to 130 ° C. The required reaction time was about 12 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain an EG-modified glucose / PO 30 mol / BO 2 mol adduct, a compound having a dispersity of 1.13, and subjected to an antifoaming test or the like.
[0030]
Example 3
386 parts of EG-modified glucose obtained in Example 2 and 4.0 parts of TMA were added to a pressure-resistant container capable of stirring and temperature adjustment. Subsequently, 220 parts of EO was addition-polymerized at 100-110 degreeC. The required reaction time was about 5 hours. Next, 20.0 parts of cesium hydroxide was added, and after dehydration at 130 ° C. under reduced pressure, 3190 parts of PO was subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 13 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain an EG-modified glucose / EO 5 mol / PO 55 mol adduct, a compound having a dispersity of 1.19, and subjected to an antifoaming test or the like.
[0031]
Example 4
In the same manner as in Example 2, 3 mol of glucose and 1 mol of trimethylolpropane (TP) were subjected to dehydration condensation, and TP-modified glucose in which three pyranose rings were connected by trimethylolpropane residues via an ether bond ( The theoretical molecular weight 620) was obtained. Next, 620 parts of the above-mentioned modified product and 4.0 parts of TMA were added to a pressure vessel capable of stirring and temperature adjustment. Subsequently, 580 parts of PO was addition-polymerized at 100-110 degreeC. The required reaction time was about 11 hours. Next, 20.0 parts of cesium hydroxide was added, and after dehydration at 130 ° C. under reduced pressure, 2030 parts of PO was subjected to addition polymerization at 100 to 110 ° C. Further, 144 parts of BO was subjected to addition polymerization at 120 to 130 ° C. The required reaction time was about 15 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain a compound having a TP-modified glucose / PO 45 mol / BO 2 mol adduct and a dispersity of 1.17, which was subjected to an antifoaming test and the like.
[0032]
Example 5
In the same manner as in Example 2, butyl-modified maltose (theoretical molecular weight 398) was obtained from n-butanol and maltose. Next, 398 parts of the above-mentioned modified body and 4.0 parts of TMA were added to a pressure vessel capable of stirring and temperature adjustment. Subsequently, 406 parts of PO was addition-polymerized at 100-110 degreeC. The required reaction time was about 10 hours. Next, 17.0 parts of cesium hydroxide was added, and after dehydration at 130 ° C. under reduced pressure, 1914 parts of PO were subjected to addition polymerization at 100 to 110 ° C. Further, 144 parts of BO was subjected to addition polymerization at 120 to 130 ° C. The required reaction time was about 12 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain a compound having a butyl-modified maltose / PO 40 mol / BO 2 mol adduct and a dispersity of 1.16, which was subjected to an antifoaming test and the like.
[0033]
Example 6
In the same manner as in Example 2, octyl-modified maltose (theoretical molecular weight 454) was obtained from 2-ethylhexanol and maltose. Next, 454 parts of the above-mentioned modified product and 4.0 parts of TMA were added to a pressure vessel capable of stirring and temperature control. Subsequently, 464 parts of PO were subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 10 hours. Next, 14.0 parts of cesium hydroxide was added, and after dehydration at 130 ° C. under reduced pressure, 1566 parts of PO was subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 12 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain a compound having an octyl-modified maltose / PO35 molar adduct and a dispersity of 1.12, which was subjected to an antifoaming test and the like.
[0034]
Comparative Example 1
An antifoaming property test and the like were conducted without adding an antifoaming agent.
[0035]
Comparative Example 2
268 parts of oleyl alcohol and 5.0 parts of potassium hydroxide were added to a pressure vessel capable of stirring and temperature adjustment, and after dehydration at 120 ° C. under reduced pressure, 1740 parts of PO was subjected to addition polymerization at 100 to 110 ° C. Then 220 parts of EO were addition polymerized at 120-130 ° C. The required reaction time was about 17 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain an oleyl alcohol / PO 30 mol / EO 5 mol adduct, a compound having a dispersity of 1.20, which was subjected to an antifoaming test and the like.
[0036]
Comparative Example 3
268 parts of oleyl alcohol and 3.5 parts of potassium hydroxide were added to a pressure vessel capable of stirring and temperature control, and after dehydration at 120 ° C. under reduced pressure, 880 parts of EO was subjected to addition polymerization at 100 to 110 ° C. 290 parts of PO were then addition polymerized at 100-110 ° C. The required reaction time was about 11 hours. Next, after attaching an air cooling pipe, 73 g of adipic acid is added, and the temperature is gradually raised to 150 ° C. while a small amount of nitrogen is passed through the liquid. Thereafter, the pressure was gradually reduced, and the temperature was gradually raised to 230 ° C. and kept at the same temperature until no distillation of water was observed. After cooling, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain an adipic acid diesterified product of oleyl alcohol / EO 20 mol / PO 5 mol adduct, a compound having a dispersity of 1.22, and used for an antifoaming test and the like. did.
[0037]
Comparative Example 4
Add 111.5 parts of sorbitol and 2.5 parts of potassium hydroxide to a pressure vessel with stirring and temperature control, dehydrate at 130 ° C under reduced pressure, and then add 888.5 parts of PO at 100-110 ° C. Addition polymerization was performed. The required reaction time was about 14 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain a sorbitol / PO 25 molar adduct and a compound having a dispersity of 1.13, which were subjected to a defoaming test and the like.
[0038]
Comparative Example 5
194 parts of methyl glycoside and 3.0 parts of TMA were added to a pressure-resistant container capable of stirring and temperature adjustment. Subsequently, 176 parts of EO was addition-polymerized at 100-110 degreeC. The required reaction time was about 6 hours. Next, 2.0 parts of potassium hydroxide was added, and after dehydration at 130 ° C. under reduced pressure, 580 parts of PO was subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 12 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain a methylglycoside / EO 4 mol / PO 10 mol adduct, a compound having a dispersity of 1.10, and subjected to an antifoaming test or the like.
[0039]
Comparative Example 6
398 parts of butyl-modified maltose and 4.0 parts of TMA were added to a pressure vessel capable of stirring and temperature control. Subsequently, 440 parts of EO were addition-polymerized at 100-110 degreeC. The required reaction time was about 6 hours. Next, 22.0 parts of cesium hydroxide was added, and after dehydration at 130 ° C. under reduced pressure, 3480 parts of PO was subjected to addition polymerization at 100 to 110 ° C. The required reaction time was about 16 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain a compound having a butyl-modified maltose / EO 10 mol / PO 60 mol adduct and a dispersity of 1.21, which was subjected to an antifoaming test and the like.
[0040]
Comparative Example 7
398 parts of butyl-modified maltose and 4.0 parts of TMA were added to a pressure vessel capable of stirring and temperature control. Subsequently, 406 parts of PO was addition-polymerized at 100-110 degreeC. The required reaction time was about 10 hours. Next, 5.0 parts of potassium hydroxide was added, and after dehydration at 130 ° C. under reduced pressure, 1914 parts of PO were subjected to addition polymerization at 100 to 110 ° C. Further, 144 parts of BO was subjected to addition polymerization at 120 to 130 ° C. The required reaction time was about 12 hours. Next, the catalyst was removed and dehydrated in the same manner as in Example 1 to obtain a compound having a butyl-modified maltose / PO 40 mol / BO 2 mol adduct and a dispersity of 1.29, which was subjected to an antifoaming test and the like.
[0041]
[Table 1]

[0042]
[Table 2]

[0043]
[Table 3]

[0044]
【The invention's effect】
The antifoaming agent according to the present invention is an industry that handles various foamable aqueous solutions, such as synthetic resin manufacturing industry, synthetic rubber manufacturing industry, fiber processing industry, dye industry, dyeing industry, fermentation industry, various wastewater treatment industries, paper pulp manufacturing industry, In each process such as building industry, paint manufacturing and painting industry, it exhibits unprecedented good defoaming effect while maintaining the transparency of foaming aqueous solution, improving the quality of the final product, protecting the environment, protecting aesthetics, etc. Useful for.

Claims

A compound obtained by subjecting a reducing sugar to a non-reducing sugar obtained by chemically modifying a reducing sugar with an alcohol having 1 to 8 carbon atoms and 1 to 3 carbon atoms to an average of 15 to 65 moles of addition-polymerized alkylene oxide having 2 to 4 carbon atoms. A water-soluble antifoam composition comprising:

The water-soluble antifoam composition according to claim 1, wherein the reducing saccharide is a monosaccharide and / or a disaccharide.

The water-soluble antifoaming composition according to claim 1, wherein the proportion of propylene oxide in the alkylene oxide is 75 mol% or more.

The water-soluble antifoam composition according to any one of claims 1 to 3, wherein the molecular weight dispersity (MW / MN) of the compound is 1.2 or less.

The water-soluble property according to any one of claims 1 to 4, wherein cesium hydroxide is used as a catalyst in the addition polymerization step of alkylene oxide, and the amount thereof is 0.05 to 2.0% by weight in the compound at the end of polymerization. Antifoam composition.

It is a defoamer for synthetic resin manufacturing processes, The water-soluble defoamer composition in any one of Claims 1-5.

It is an antifoamer for dyeing processes, The water-soluble antifoamer composition in any one of Claims 1-5.

It is a defoamer for waste water treatment processes, The water-soluble defoamer composition in any one of Claims 1-5.