JP5608845B2 - 消泡剤 - Google Patents
消泡剤 Download PDFInfo
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- JP5608845B2 JP5608845B2 JP2012006624A JP2012006624A JP5608845B2 JP 5608845 B2 JP5608845 B2 JP 5608845B2 JP 2012006624 A JP2012006624 A JP 2012006624A JP 2012006624 A JP2012006624 A JP 2012006624A JP 5608845 B2 JP5608845 B2 JP 5608845B2
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- Prior art date
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- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Degasification And Air Bubble Elimination (AREA)
Description
しかしながら、このものは、50℃以上の温度では消泡性能が低いという欠点がある。
そこで、50℃以上の温度においても良好な消泡性を発揮させるべく、高級アルコール10〜90重量%、及びグリコール類又はグリコール類のアルキレンオキシド付加物構造を有する化合物10〜90重量%よりなる消泡剤組成物が提案されている(特許文献2)。
すなわち、本発明の消泡剤の特徴は、炭素数12〜30のアルコール(A)と、鉱物油、動・植物油、脂肪酸エステル、ポリオルガノシロキサン及びポリエーテル化合物からなる群より選ばれる少なくとも1種であって、アルコール(A)の融点よりも低い融点又は流動点をもつ疎水性成分(B)とを必須成分として構成される粒子(X)を水に分散した分散体(Z)と、
脂肪酸金属塩、脂肪酸アミド、ワックス、疎水性金属酸化物及び合成樹脂からなる群より選ばれる少なくとも1種の核剤(C)と、ポリエーテル化合物(D)とを必須成分として構成される核剤入りポリエーテル(Y)とを含み、
分散体(Z)及び核剤入りポリエーテル(Y)の重量に基づいて、分散体(Z)の重量が65〜95重量%、核剤入りポリエーテル(Y)の重量が5〜35重量%であることを要旨とする。
炭素数1〜25の活性水素含有化合物としては、水酸基(−OH)、イミノ基(−NH−)、アミノ基(−NH2)及び/又はカルボキシル基(−COOH)を少なくとも1個含む化合物が含まれ、アルコール、アミド、アミン、カルボン酸、ヒドロキシカルボン酸及びアミノカルボン酸が含まれる。
市場から入手できる疎水性金属酸化物としては、商品名として、Nipsil SS−10、SS−40、SS−50及びSS−100(疎水性シリカ、東ソー・シリカ株式会社、「Nipsil」は東ソー・シリカ株式会社 の登録商標である。)、AEROSIL R972、RX200及びRY200(疎水性シリカ、日本アエロジル株式会社、「AEROSIL」はエボニック デグサ ゲーエムベーハーの登録商標である。 )、SIPERNAT D10、D13及びD17(疎水性シリカ、デグサジャパン株式会社、「SIPERNAT」はエボニック デグサ ゲーエムベーハーの登録商標である。 )、TS−530、TS−610、TS−720(疎水性シリカ、キャボット コーポレーション)、AEROSIL R202,R805及びR812(疎水性シリカ、デグサジャパン株式会社)、REOLOSIL MT−10、DM−10及びDM−20S (疎水性シリカ、株式会社トクヤマ、「REOLOSIL」は同社の登録商標である。)、SYLOPHOBIC100、702、505及び603(疎水性シリカ、富士シリシア化学株式会社、「SYLOPHOBIC」は同社の登録商標である。)、MT−100Z(疎水性チタニア、テイカ株式会社)、MTY−700BS(疎水性チタニア、テイカ株式会社)、MZY−303S(疎水性酸化亜鉛、テイカ株式会社)並びにSpectrAl TA−78(疎水性アルミナ、キャボット コーポレーション、「SpectrAl」は同社の登録商標である。)等が挙げられる。
イオン交換水をフローセルに入れて循環(循環強度5)しながら、ブランク測定を行う。100mLガラスビーカーにイオン交換水を約10mL入れ、測定試料(分散体(Z))を数滴加えて均一になるまで混合して分散液を作成する。この分散液をフローセルに少しずつ加えて、適切な透過光強度(青色LEDの透過光強度が80〜90%又は赤色LEDの透過光強度が70〜90%)に調整して測定を行う。
なお、測定値はブランク測定の値が差し引かれて算出される。
水(E)としては、水道水、工業用水、脱イオン水及び蒸留水等が挙げられる。
非イオン型界面活性剤としては、HLB3.5〜20のものが使用でき、好ましくはHLB3.6〜19.5のもの、さらに好ましくはHLB3.7〜19のもの、最も好ましくはHLB4〜18.5のものである。
塩としては特に制限されないが、アルカリ金属(ナトリウム、カリウム等)塩、アルカリ土類金属(カルシウム、マグネシウム等)塩、アンモニウム塩及び炭素数1〜18のアミン塩(トリエタノールアミン、トリメチルアミン、プロピルアミン等)等が含まれる(以下同じ)。
また、これらの粒子の粒径を均一化するために分級を行い、得られた分級粒子を用いてもよい。
アルティフロー FS−7301(三洋化成工業(株)製、エチレン性不飽和モノマー共重合物のポリエーテル分散体、「アルティーフロー」は同社の登録商標である)、ダイミックビーズ UCN−8070CMクリヤー(大日精化工業(株)製、ポリウレタンビーズ、「ダイミックビーズ」は同社の登録商標である)、タフチック F−120、F−167(東洋紡(株)製、エチレン性不飽和モノマー共重合物の水分散体;「タフチック」は同社の登録商標である)
脂肪酸金属塩、脂肪酸アミド及び/又はワックスと、ポリエーテル化合物(D)の一部とを加熱攪拌しながら、脂肪酸金属塩、脂肪酸アミド及び/又はワックスを溶解させて溶解液を得る溶解工程(p11)、
また、ポリエーテル化合物(D)の残部の温度は、消泡性の観点等から、0〜60℃に保つことが好ましく、さらに好ましくは0〜50℃、特に好ましくは0〜45℃、最も好ましくは0〜40℃である。すなわち、0〜60℃に冷却したポリエーテル化合物(D)の残部を攪拌しながら、この残部の温度を0〜60℃を保ちながら溶解液を少量ずつ投入して混合物を得ることが好ましい。
脂肪酸金属塩と、ポリエーテル化合物(D)とを加熱攪拌しながら、脂肪酸金属塩を溶解させて溶解液を得る溶解工程(p21)、
溶解液を冷却した後、攪拌混合して脂肪酸金属塩の分散液を得る分散工程(p22)を含む方法。
疎水性金属酸化物及び/又は合成樹脂とポリエーテル化合物(D)と攪拌混合して分散液を得る分散工程(p31)を含む方法、又は
疎水性金属酸化物及び/又は合成樹脂とポリエーテル化合物(D)と攪拌混合して混合液を得る混合工程(p32)、並びに
混合物を均質化処理して、疎水性金属酸化物及び/又は合成樹脂の分散液を得る分散工程(p33)を含む方法。
これらのうち、各種製造工程用消泡剤、排水処理用消泡剤として適しており、抄紙工程用消泡剤として最適である。
加熱、攪拌、冷却の可能な容器内で、アルコール(a1){炭素数16〜26のアルコール混合物、NAFOL20+A、SASOL社製、融点58℃}250部及び疎水性成分(b1){牛脂脂肪酸メチルエステル、新日本理化株式会社製、融点15℃}50部を70℃に加熱し、攪拌混合して溶解液(ab1)を得た。
溶解液(ab1)の組成を表1に記載した組成に変更したこと、及び水相(1)の組成を表2に記載した組成に変更したこと以外、製造例1{分散体(z1)の作成例}と同様にして、分散体(z2)〜(z7)を作成した。
疎水性成分(b3):ポリオキシプロピレン(40モル)グリコールモノブチルエーテルのオレイン酸エステル、流動点−30℃
疎水性成分(b4):ジメチルシリコーンオイル(動粘度10(mm2/s、25℃))、KF−96−10CS、信越化学工業株式会社製、流動点−65℃
疎水性成分(b5):グリセリンのプロピレンオキシド(43モル)付加体、サンニックスGP−3000、三洋化成工業株式会社製、流動点−35℃;「サンニックス」は同社の登録商標である。
疎水性成分(b6):食用菜種油、ニッコー製油株式会社製、流動点−5℃
疎水性成分(b7):精製牛脂、ITR、ミヨシ油脂製、融点45℃
疎水性成分(b8):鉱物油、コスモSP−10、コスモ石油ルブリカンツ株式会社製、流動点−12℃
加熱、攪拌、冷却の可能な容器内で、アルコール(a1)235部、疎水性成分(b1)50部及びをワックス(1){アルコール変性ワックス、OX−3405、日本精鑞(株)製}10部を110℃に加熱し、攪拌混合して溶解液(ab8)を得た。
加熱、攪拌、冷却の可能な容器内で、アルコール(a3){ベヘニルアルコール、コノール2265、新日本理化株式会社製、融点73℃}39部、疎水性成分(b1)61部、疎水性成分(b7)200部及びをワックス(2){酸化ポリエチレンワックス、エポレンE−10、イーストマンケミカル社製}20部を110℃に加熱し、攪拌混合して溶解液(ab9)を得た。
加熱、攪拌、冷却の可能な容器内で、アルコール(a3)94部、疎水性成分(b1)15部及び疎水性成分(b7)15部を90℃に加熱し、攪拌混合して溶解液(ab10)を得た。
加熱、攪拌、冷却の可能な容器内で、核剤(c1){エチレンビスステアリルアミド、アルフローH−50S、日油株式会社製}30部、ポリエーテル化合物(d1){ブタノールポリオキシプロピレン(40モル)付加体、ニューポールLB−1715、三洋化成工業株式会社製}200部及びポリエーテル化合物(d2){ポリオキシエチレン(5モル)ポリオキシプロピレン(30モル)、ニューポールPE−61、三洋化成工業株式会社製)}100部を加熱攪拌しながら150℃まで昇温し、この温度にてさらに15分間加熱攪拌を続けて均一混合液(cd1)を得た。
混合液(cd1)の組成及び加熱温度を表4に記載した組成及び加熱温度に変更したこと、並びに受け液(1)の組成及び冷却温度(混合液投入中の受け液の最高温度)を表5に記載した組成及び冷却温度に変更したこと以外、製造例11{核剤入りポリエーテル(y1)の作成例}と同様にして、核剤入りポリエーテル(y2)〜(y7)を作成した。
核剤(c3):酸化ポリエチレンワックス、エポレンE−10、イーストマンケミカル社製
核剤(c4):アルコール変性ワックス、OX−3405、日本精鑞(株)製
核剤(c5):ステアリン酸アルミニウム、SA−1500、堺化学工業(株)製
核剤(c6):カルナウバワックス、カルナウバワックス1号、株式会社加藤洋行製
核剤(c7):マレイン酸変性酸化ポリエチレンワックス、PED−136、日本精鑞(株)製
ポリエーテル化合物(d5):ポリオキシプロピレン(40モル)グリコールモノブチルエーテルのオレイン酸エステル
ポリエーテル化合物(d6):ポリプロピレングリコール(34モル)、ニューポールPP−2000、三洋化成工業株式会社製
ポリエーテル化合物(d7):ポリオキシエチレン(5モル)ポリオキシプロピレン(30モル)のステアリン酸ジエステル
ポリエーテル化合物(d9):ポリオキシプロピレン(34モル)グリコール200部と、ポリオキシエチレン(3モル)ポリオキシプロピレン(14モル)ミリスチルエーテル231部と、ヘキサメチレンジイソシアネート16.8部とを反応させて得たポリエーテル化合物
ポリエーテル化合物(d10):グリセリンのプロピレンオキシド(9モル)付加体、ニューポールGP−600、三洋化成工業株式会社製
ポリエーテル化合物(d11):蔗糖ポリオキシプロピレン80モル付加物
攪拌の可能な容器内で、核剤(c8){疎水性シリカ、SIPERNAT D10、デグサジャパン株式会社製}30部、ポリエーテル化合物(d5)900部及びポリエーテル化合物(d10)70部を15分間攪拌し、核剤分散体(cd8)を得た。
攪拌の可能な容器内で、特開2009−7506号公報の実施例1に準じて作成したポリマーポリオール[核剤(c9){(スチレン)/(アクリロニトリル)/(ジビニルベンゼン)/(グリセリンのプロピレンオキシド付加物と2−ヒドロキシエチルメタクリレートとをトリレンジイソシアネート(TDI)でジョイントして得られる反応性分散剤)/(アリルアルコールにプロピレンオキシド(PO)を付加させたポリオキシアルキレンエーテル)を構成単位とする共重合物(粒子径0.7μm)}52%、ポリエーテル化合物(d11){ペンタエリスリトールにプロピレンオキシド−エチレンオキシド(エチレンオキシドの割合12重量%)の順にアルキレンオキシドをブロック付加させたポリオール、HLB=2.5}45%及びポリエーテル化合物(d12){特開2000−344881号公報に準じて作成したグリセリンプロピレンオキシド付加体、HLB=0.3}3%の混合液]153部、ポリエーテル化合物(d1)300部、ポリエーテル化合物(d3)300部及びポリエーテル化合物(d7)247を15分間攪拌し、核剤入りポリエーテル(y9)を得た。
攪拌の可能な容器内で、分散体(z1)800部及び核剤入りポリエーテル(y1)200部を15分間攪拌混合し、本発明の消泡剤(1)を得た。
分散体(z1)及び核剤入りポリエーテル(y1)を、表7に記載した種類及び使用量に変更したこと以外、実施例1と同様にして、本発明の消泡剤(2)〜(24)を得た。
分散体(z1)〜(z10)を比較用の消泡剤(H1)〜(H10)として用いた。
分散体(z1)の使用量を表8に記載した量に変更したこと、核剤入りポリエーテル(y1)を、表8に記載した核剤又はポリエーテル化合物に変更したこと以外、実施例1と同様にして、比較用の消泡剤(H11)〜(H13)を得た。
エレミノールMON−2(ドデシルジフェニルエーテルジスルホン酸ナトリウム50.3重量%水溶液;三洋化成工業株式会社、「エレミノール」は同社の登録商標である。)0.172gを500mlのメスシリンダーに加え、上水60mLを加えて均一に混合した後、消泡剤を有効成分(水以外の成分)が0.006gになるように添加して試験液を作成した。
なお、消泡剤を添加しないこと以外、上記と同様にして、ブランク用の試験液を調製した。
試験液60mlの入った500mLのメスシリンダーの底部に木下式ガラスボールフィルターを沈め、試験液及び試験装置(メスシリンダー、木下式ガラスボールフィルター等)を25℃に調節した。続いて木下式ガラスボールフィルターを用いてシリンダーの底部から窒素ガスを20m3/分で1分間通気した後の液容積(mL)を読み取り、25℃での消泡性の値とした。液容積が小さいほど泡が破壊されており消泡性に優れているといえる。
試験液60mlの入った500mLのメスシリンダーの底部に木下式ガラスボールフィルターを沈め、試験液及び試験装置(メスシリンダー、木下式ガラスボールフィルター等)を60℃に調節した。続いて木下式ガラスボールフィルターを用いてシリンダーの底部から窒素ガスを20m3/分で1分間通気した後の液容積(mL)を読み取り、60℃での消泡性の値とした。液容積が小さいほど泡が破壊されており消泡性に優れているといえる。
Claims (8)
- 炭素数12〜30のアルコール(A)と、鉱物油、動・植物油、脂肪酸エステル、ポリオルガノシロキサン及びポリエーテル化合物からなる群より選ばれる少なくとも1種であって、アルコール(A)の融点よりも低い融点又は流動点をもつ疎水性成分(B)とを必須成分として構成される粒子(X)を水に分散した分散体(Z)と、
脂肪酸金属塩、脂肪酸アミド、ワックス、疎水性金属酸化物及び合成樹脂からなる群より選ばれる少なくとも1種の核剤(C)と、ポリエーテル化合物(D)とを必須成分として構成される核剤入りポリエーテル(Y)とを含み、
分散体(Z)及び核剤入りポリエーテル(Y)の重量に基づいて、分散体(Z)の重量が65〜95重量%、核剤入りポリエーテル(Y)の重量が5〜35重量%であることを特徴とする消泡剤。 - 粒子(X)の体積平均粒子径が、1〜50μmである請求項1に記載の消泡剤。
- アルコール(A)及び疎水性成分(B)の重量に基づいて、アルコール(A)の含有量が10〜90重量%、疎水性成分(B)の含有量が10〜90重量%である請求項1又は2に記載の消泡剤。
- 核剤(C)の融点が60〜2000℃である請求項1〜3のいずれかに記載の消泡剤。
- 分散体(Z)の重量に基づいて、粒子(X)の含有量が10〜60重量%、分散体(Z)中の水(E)の含有量が40〜90重量%である請求項1〜4のいずれかに記載の消泡剤。
- ポリエーテル化合物(D)が、一般式(1)で表されるポリエーテル化合物(D1)、一般式(2)で表されるポリエーテル化合物(D2)、一般式(3)で表されるポリエーテル化合物(D3)、一般式(4)で表されるポリエーテル化合物(D4)及び一般式(5)で表されるポリエーテル化合物(D5)からなる群より選ばれる少なくとも1種である請求項1〜5のいずれかに記載の消泡剤。
R1は炭素数1〜25の活性水素化合物の反応残基、R2及びR3は炭素数1〜24の1価の有機基、R4は炭素数1〜24の2価の有機基、R5は水酸基又は炭素数1〜24の1価の有機基、AO及びOAは炭素数2〜18のオキシアルキレン基又は、グリシドール、炭素数4〜18のアルキルグリシジルエーテル若しくはアルケニルグリシジルエーテルの反応残基を表し、(OA)n又は(AO)nのうち、オキシエチレン基の占める割合は0〜20重量%であり、nは1〜100の整数で一分子中に複数のnが存在する場合、それぞれ同じでも異なっていてもよく、sは1〜10の整数、pは0〜10の整数、qは0〜9の整数、rは0〜9の整数、mは0〜9の整数、p+rは1〜10の整数、p+q+rは1〜10の整数、p+q+r+mは2〜10である。 - 核剤(C)及びポリエーテル化合物(D)の重量に基づいて、核剤(C)の重量が0.1〜10重量%、ポリエーテル化合物(D)の重量が90〜99.9重量%である請求項1〜6のいずれかに記載の消泡剤。
- 核剤入りポリエーテル(Y)中の核剤(C)の個数平均粒子径が0.05〜20μmである請求項1〜7のいずれかに記載の消泡剤。
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