JP4458396B2 - Method for producing high-purity hydrophilic organic solvent-dispersed silica sol, high-purity hydrophilic organic solvent-dispersed silica sol obtained by the method, method for producing high-purity organic solvent-dispersed silica sol, and high-purity organic solvent-dispersed silica sol obtained by the method - Google Patents
Method for producing high-purity hydrophilic organic solvent-dispersed silica sol, high-purity hydrophilic organic solvent-dispersed silica sol obtained by the method, method for producing high-purity organic solvent-dispersed silica sol, and high-purity organic solvent-dispersed silica sol obtained by the method Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は高純度親水性有機溶媒分散シリカゾルの製造方法及びその方法で得られる高純度親水性有機溶媒分散シリカゾル並びに高純度有機溶媒分散シリカゾルの製造方法及びその方法で得られる高純度有機溶媒分散シリカゾルに係り、主たる目的は高純度が必要とされる電子材料、膜材料、有機面の研磨材などの素材となる高純度親水性有機溶媒分散シリカゾルの製造方法及びその方法で得られる高純度親水性有機溶媒分散シリカゾル並びに高純度有機溶媒分散シリカゾルの製造方法及びその方法で得られる高純度有機溶媒分散シリカゾルを提供することにある。
尚、本発明においてｐＨの中性とはｐＨ６〜８の範囲をいう。
【０００２】
【従来の技術】
従来、シリカゾルは分散媒が水であるため有機物との混合分散性が悪く、有機溶媒と十分に混合又は反応させることが困難であった。従って、シリカゾルを広く有機工業に利用するためには、その分散媒を水から有機溶媒に変えた有機溶媒分散シリカゾルを製造することが必要である。
有機溶媒分散シリカゾルは、以下のような方法により製造されている。例えば、珪酸ナトリウムを原料として作られた酸性水性シリカゾルを濃縮し、ＩＰＡなどのアルコールを添加して混合有機溶媒分散シリカゾルを得て、これにシランカップリング剤を添加してシリル化後、ＭＥＫ等の疎水溶媒に溶媒置換する方法（特開平１１−４３３１９）、珪酸ナトリウムを原料とするアルカリ性水性シリカゾルをイオン交換樹脂で脱イオン化し、このゾルを限外濾過で濃縮後、過熱しつつイソプロパノール蒸気を吹き込む方法（特開平８−１６９７０９）などが挙げられる。
【０００３】
【発明が解決しようとする課題】
しかしながら、上述した珪酸ナトリウムを原料とする製造方法では有機溶媒分散シリカゾル中にナトリウム等の金属不純物が残留し、純度が低かった。このため、高純度が必要な半導体や液晶の素材として使用するには不十分であった。また、高純度シリカ粉末をシランカップリング剤によって表面処理後、有機溶媒に分散させる方法は、微粒子の凝集の問題があり、特に粒子径がサブミクロンのサイズのものを製造することは困難であった。
また、このゾルをさまざまな素材の原料として供給する場合、長期の保存安定性が必要となる。
【０００４】
本発明は上記した問題点を解決するためになされたものであって、ナトリウム等の金属不純物含有量が１．０ｐｐｍ以下で且つ水と任意の割合で混合できる高純度親水性有機溶媒分散シリカゾル及びその製造方法、並びに該高純度親水性有機溶媒分散シリカゾルを表面改質し有機溶媒に安定に分散可能にした高純度有機溶媒分散シリカゾル及びその製造方法を創出しようとするものである。
【０００５】
【課題を解決するための手段】
すなわち本発明のうち請求項１に係る発明は、以下の（ａ）〜（ｄ）の各工程からなることを特徴とする高純度親水性有機溶媒分散シリカゾルの製造方法。：（ａ）アルコキシシラン類をアルコール水溶液中で加水分解する第一の工程，（ｂ）加水分解により得られるシリカゾル溶液を濃縮する第二の工程，（ｃ）シランカップリング剤を添加してカップリング処理を施した後、シリカゾル溶液のｐＨを中性に調整する第三の工程，（ｄ）親水性有機溶媒でシリカゾル溶液の水分を置換する第四の工程、に関する。
【０００６】
請求項２に係る発明は、前記シランカップリング剤の、前記シリカゾル濃縮液への添加量が、シリカゾル溶液中のシリカ重量に対して０．１〜２０％の範囲であることを特徴とする請求項１に記載の高純度親水性有機溶媒分散シリカゾルの製造方法に関する。
【０００７】
請求項３に係る発明は、シリカ微粒子が親水性有機溶媒に分散してなる高純度親水性有機溶媒分散シリカゾルであって、該シリカ微粒子の金属不純物含有量が１．０ｐｐｍ以下、且つ中性であることを特徴とする高純度親水性有機溶媒分散シリカゾルに関する。
請求項４に係る発明は、請求項１又は２に記載の方法で得られる高純度親水性有機溶媒分散シリカゾルであって、シリカ微粒子が親水性有機溶媒に分散し、該シリカ微粒子の金属不純物含有量が１．０ｐｐｍ以下で、且つ中性であることを特徴とする高純度親水性有機溶媒分散シリカゾルに関する。
【０００８】
請求項５に係る発明は、３ヶ月以上安定分散することを特徴とする請求項３又は４に記載の高純度親水性有機溶媒分散シリカゾルに関する。
【０００９】
請求項６に係る発明は、以下の（ａ）、（ｂ）の各工程からなることを特徴とする高純度有機溶媒分散シリカゾルの製造方法。
（ａ）請求項１又は２で得られる高純度親水性有機溶媒分散シリカゾルをシランカップリング剤で表面改質する第一の工程，
（ｂ）有機溶媒でシリカゾル溶液の水分並びに親水性有機溶媒を置換する第二の工程、に関する。
【００１０】
請求項７に係る発明は、前記シランカップリング剤の前記高純度親水性有機溶媒分散シリカゾルへの添加量が、次式
【式１】
【００１１】
請求項８に係る発明は、請求項４に記載の中性親水性有機溶媒分散シリカゾルを再度シランカップリング剤で処理することにより、シリカ微粒子が３ヶ月以上安定して有機溶媒に分散し、且つ該シリカ微粒子の水分含有量が５．０ｗｔ％以下であることを特徴とする高純度有機溶媒分散シリカゾルに関する。
【００１２】
【発明の実施の形態】
以下、本発明に係る高純度親水性有機溶媒分散シリカゾル及びその製造方法並びに高純度有機溶媒分散シリカゾル及びその製造方法について説明する。
本発明に係る高純度親水性有機溶媒分散シリカゾルは、シリカ微粒子の金属不純物含有量が１．０ｐｐｍ以下で且つ長期安定であることを特徴とする。また、本発明に係る高純度有機溶媒分散シリカゾルは、該高純度親水性有機溶媒分散シリカゾルを表面改質して得ることができ、シリカ微粒子の水分含有量が５．０％以下、金属不純物含有量が１．０ｐｐｍ以下で且つ長期安定であることを特徴とする。
本発明に係る高純度有機溶媒分散シリカゾルは、その純度が高く、好適に電子材料、膜材料、有機面の研磨材などの素材として使用することができる。
【００１３】
次に、本発明に係る高純度親水性有機溶媒分散シリカゾル及び高純度有機溶媒分散シリカゾルの製造方法について説明する。
まず、高純度親水性有機溶媒分散シリカゾルの製造方法について説明する。
本発明に係る高純度親水性有機溶媒分散シリカゾルを得るには、まず、アルコキシシラン類を出発原料とするゾルゲル法による反応でシリカゾル溶液を作製し、このゾルを濃縮し、シランカップリング剤添加による部分的な疎水化処理、ｐＨ調整によって未反応物の削減を行い、その後親水性有機溶媒での置換により得られる。
【００１４】
用いられるアルコキシシラン類は、特に限定はされないが、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシランなどを例示することができる。これらを単独で用いても良く、また、二種以上を混合して使用することもできる。
【００１５】
ゾルゲル法とは、金属の有機化合物溶液を出発原料として、溶液中の化合物の加水分解・重縮合によって溶液を金属の酸化物あるいは、水酸化物の微粒子が溶解したゾルとし、更に反応を進ませてゲル化してできた非晶質ゲルを得る方法であり、本発明においては前記アルコキシシラン類をアルコール水溶液中で加水分解してシリカゾル溶液を得る。
アルコール水溶液中のアルコールは、特に限定されないが、例えば、メタノール、エタノール、イソプロパノール、エチレングリコール、プロピレングリコールなどが用いられ、好ましくは加水分解で副生するものと同一のアルコールを使用する。また、これらを単独で用いても良く、また、二種以上を混合して使用することもできる。
加水分解の条件としては、特に限定されないが、反応液全量に対する水濃度が３〜１２ｍｏｌ／Ｌ、アンモニア濃度が０．１〜２．５ｍｏｌ／Ｌ、アルコキシシラン類濃度が０．３〜１．５ｍｏｌ／Ｌとなるようにし、反応温度は０℃以上で溶媒の沸点以下の温度で反応させる。
【００１６】
次に、上記で得たシリカゾル溶液を濃縮する。濃縮する条件としては、常圧下又は減圧下で加熱濃縮を行う。
【００１７】
得られた濃縮液にシランカップリング剤を添加し、疎水化処理をし、アンモニア除去等の処理を行うことによってｐＨを調節する。
使用されるシランカップリング剤としては特に限定されないが、例えば、メチルトリメトキシシラン，ジメチルジメトキシシラン，トリメチルメトキシシラン，メチルトリエトキシシラン，ジメチルジエトキシシラン，トリメチルエトキシシラン，フェニルトリメトキシシラン，ベンジルトリエトキシシラン，プロピルトリメトキシシラン，プロピルトリエトキシシラン，ジエトキシメチルフェニルシラン，アリルトリエトキシシラン，ビニルトリエトキシシラン，アミノプロピルトリエトキシシラン，アミノプロピルトリメトキシシラン等の分子中に一種又は二種以上の置換アルキル基、フェニル基、ビニル基等を有するアルコキシシラン類；トリメチルクロロシラン、ジエチルジクロロシラン等のクロロシラン類などが挙げられ、好ましくは、メチルメトキシシラン、メチルエトキシシランを使用する。
【００１８】
カップリング剤の添加量としては、ゾル中のシリカ重量に対して０．１〜２０％、好ましくは１．０〜２．５％を添加する。０．１％より少ないと凝集沈降物が発生するので好ましくなく、２０％より多く添加すると製造する高純度親水性有機溶媒分散シリカゾルのコストが高くなりすぎるため好ましくない。
前記シランカップリング剤を加えた後、ゾル溶液のｐＨを中性になるよう調整を行う。ｐＨ調整方法としては特に限定されないが、例えば、常圧下で加熱蒸留を行い、留出液をイオン交換塔に通してアンモニアを除去した後、ゾル溶液中に戻す操作を、ゾル溶液のｐＨが中性付近、例えばｐＨ６〜８になるまで行うような処理方法が挙げられる。
ｐＨを調整する理由は、ゾル溶液を中性にすることで未反応物の削減を行い、親水性有機溶媒に長期間安定に分散させるためである。
【００１９】
その後、親水性有機溶媒で水分を置換し、高純度親水性有機溶媒分散シリカゾルを得る。親水性有機溶媒で置換を行う目的は、親水性有機溶媒での置換によりシリカゾル溶液が安定に分散し、且つ金属不純物の少ない高純度親水性有機溶媒分散シリカゾルを得ることができるからである。使用する親水性有機溶媒としては特に限定されないが、メタノール、エタノール、イソプロパノール、エチレングリコール、プロピレングリコールなどが挙げられ、好ましくはアルコキシシランの加水分解で副生するものと同一のアルコールを使用する。これは溶媒を回収、再利用する上で工業的に優位なことになる。
親水性有機溶媒で置換を行う条件としては、常圧下で、溶媒置換を行う。好ましくはゾル溶液の水分が５．０％以下となるまで置換を行う。ゾル溶液の水分を５．０％以下とする理由は、水分が多すぎると樹脂等の有機物への馴染み、分散性が悪いためである。
【００２０】
次に、本発明に係る高純度有機溶媒分散シリカゾルの製造方法について説明する。
まず、上記の方法で得られた高純度親水性有機溶媒分散シリカゾルをシランカップリング剤で表面改質後、有機溶媒に置換することで高純度有機溶媒分散シリカゾルが得られる。表面改質する目的は、従来親水性であるシリカゾルを疎水性溶媒にて安定に分散させるためである。
高純度親水性有機溶媒分散シリカゾルを表面改質するシランカップリング剤としては特に限定されないが、前述のシランカップリング剤を好適に使用することができ、好ましくはメチルトリメトキシシラン、ジメチルジメトキシシランを使用する。
高純度親水性有機溶媒分散シリカゾルを表面改質するシランカップリング剤の添加量としては、次式
【式３】
【００２１】
また、分散安定性を向上させるために、界面活性剤を使用することもできる。界面活性剤としてはアルキル第四級アンモニウム塩類のカチオン性界面活性剤が好適に使用できる。カチオン性界面活性剤を使用する理由は、アニオン性界面活性剤では対イオンにナトリウム等の金属イオンが使用されているため金属不純物が混入する問題があり、非イオン性界面活性剤は分散安定性の効果が小さいためである。界面活性剤を使用する場合はシリカ重量に対して５０〜１５０ｐｐｍ添加する。
【００２２】
その後、有機溶媒により置換する。使用する有機溶媒としては特に限定されないが、飽和または不飽和の脂肪族炭化水素、芳香族炭化水素及びそれらのハロゲン化物、一価及び二価以上のアルコール化合物、エーテル化合物、エステル化合物、アミン類等の含窒素化合物、アルデヒド、ケトン類等のカルボニル化合物、カルボン酸化合物、あるいは単糖類、多糖類等の炭水化物等の有機化合物などが挙げられる。
置換する条件としては、塔頂温が、置換する有機溶媒の沸点に達し、且つ水分含有量が５．０％以下、好ましくは０．１〜１．０％になるまで置換する。ゾル溶液の水分を５．０％以下とする理由は、水分が多すぎると樹脂等の有機物への馴染み、分散性が悪いためである。
【００２３】
以下、本発明の実施例を記載することにより、この発明の効果をより明確なものとするが、本発明はこれらの実施例に何ら限定されるものではない。尚、配合量は重量％である。
【００２４】
【実施例】
（実施例１−１：高純度親水性有機溶媒分散シリカゾルの調製）
純水７８７．９ｇ、２６％アンモニア水７８６．０ｇ、メタノール１２９２４．０ｇの混合液に、テトラメトキシシラン１５２２．２ｇ、メタノール４１３．０ｇの混合液を、液温を３５℃に保ちつつ５５分かけて滴下し、シリカゾル溶液を得た。このゾル溶液を常圧下にて、２９００ｍｌまで加熱濃縮を行った。この濃縮液に、シランカップリング剤としてメチルトリメトキシシラン６．０ｇを加え、常圧下にて加熱蒸留を行い、留出液をイオン交換塔（オルガノ製アンバーライトＩＲ１２０Ｂ（Ｈ）−ＡＧ）に通してアンモニアを除去後、ゾル溶液中に戻す操作を、ゾル溶液のｐＨが８以下になるまで行った。その後、水分が５％以下になるまでメタノールを滴下しつつ蒸留を続け、室温まで冷却後、３μメンブランフィルターを用いて精密濾過を行い、メタノール分散シリカゾルを得た。
【００２５】
（実施例１−２：高純度有機溶媒分散シリカゾルの調製）
実施例１−１で得たメタノール分散シリカゾル５００ｇにシランカップリング剤としてメチルトリメトキシシランを１５．４ｇ添加し、室温にて１時間攪拌後、２時間全還流を行った。その後、常圧下、加熱蒸留しつつ、メチルエチルケトンを、容量を一定に保ちつつ滴下し、塔頂温が７９℃に達し且つ水分が１．０％以下になったのを確認した時点で終了し、室温まで冷却後、３μメンブランフィルターを用いて精密濾過を行い、メチルエチルケトン分散シリカゾルを得た。
【００２６】
（実施例２：高純度親水性有機溶媒分散シリカゾルの調製）
実施例１−１において、各仕込量は同様にしてゾルゲル反応、濃縮、表面処理、ｐＨ調整を同様に行い、置換する親水性有機溶媒をメタノールからイソプロパノールに変更して、ゾル溶液中の水分が１．０％以下になるまで溶媒置換を行い、室温まで冷却後、３μメンブランフィルターを用いて精密濾過を行い、イソプロパノール分散シリカゾルを得た。
【００２７】
（比較例１）
実施例１−１において、濃縮液にシランカップリング剤を添加せずに加熱蒸留した後、ｐＨを調整せずにメタノール分散シリカゾルを作製したところ、凝集沈降物が発生し、不安定なゾルが得られた。
【００２８】
（比較例２）
実施例１−１において、水分が１０％のところでメタノール滴下をやめてメタノール分散シリカゾルを得た。
【００２９】
（比較例３）
実施例１−２において、高純度親水性溶媒分散シリカゾルへ、シランカップリング剤を添加せずにメチルエチルケトン分散シリカゾルを得た。
【００３０】
【試験例】
（試験例１）
得られた実施例１−１、１−２、２及び比較例１〜３の親水性有機溶媒分散シリカゾル又は有機溶媒分散シリカゾルのシリカ粒子の比表面積、粒子径、シリカ濃度、水分、凝集の有無、不純物量をそれぞれ測定した。その結果を表１及び表２に示す。
なお、比表面積はシリカゾルを乾燥、焼成した粉末をＢＥＴ法で測定し、粒子径はシリカゾルをそのまま光子相関法により測定し、水分はカールフィッシャー水分計を用いて測定した。また、金属不純物量は原子吸光測定装置を用いて測定した。
【００３１】
【表１】
【表２】
（試験例２）
実施例１−１及び実施例２で得られたメタノール分散ゾル及びイソプロパノール分散ゾル各５０ｍｌに、それぞれ純水５０ｍｌを混合し、分散安定性の確認と粒子径の測定を行った。その結果を表３に示す。
【００３４】
【表３】
上記の結果より、本発明に係る製造方法のように、アルコキシシランを原料とするシリカゾルは金属不純物の含有量が少なく１．０ｐｐｍ以下であることがわかる。また、シランカップリング剤を添加せず且つ中性に調整しない場合は凝集沈降物が発生してしまうため、目的とする、溶媒に安定分散したシリカゾルを得ることができず、また、水分を５％以下まで削減しても親水性溶媒分散シリカゾルは安定している。さらに、本発明により製造した高純度親水性有機溶媒分散シリカゾル又は高純度有機溶媒分散シリカゾルは、比較例と比べて粒子径の上昇が見られず、且つ凝集も見られないため、分散安定性、保存安定性において優れていることがわかった。また、親水性有機溶媒分散ゾルと水を混合させても凝集せず安定であることがわかった。
【００３６】
【発明の効果】
以上詳述した如く、本発明に係る高純度親水性有機溶媒分散シリカゾルは、金属不純物の少ない親水性溶媒に分散したシリカゾルからなる高純度親水性有機溶媒分散シリカゾルであり、シリカ微粒子の金属不純物量が１．０ｐｐｍ以下で且つ長期安定である。また、本発明に係る高純度有機溶媒分散シリカゾルは、該高純度親水性有機溶媒分散シリカゾルを表面改質して得られる有機溶媒分散シリカゾルであり、シリカ微粒子の水分含有量が５．０％以下、金属不純物量が１．０ｐｐｍ以下で且つ長期安定である。
該高純度親水性有機溶媒分散シリカゾル及び該高純度有機溶媒分散シリカゾルは、高純度であり、且つそれぞれの溶媒に長期間安定に分散するので、電子材料や膜材料、有機面の研磨材などの素材として、好適に使用することができる。また、該高純度親水性有機溶媒分散シリカゾルは水と任意の割合で混合できる。
【００３７】
また、本発明に係る高純度親水性有機溶媒分散シリカゾルの製造方法は、アルコキシシラン類をアルコール水溶液中で加水分解して得られるシリカゾル溶液を濃縮し、シランカップリング剤を添加後、ゾル溶液のｐＨ調整後、親水性溶媒で置換を行って得ることができる。また、高純度有機溶媒分散シリカゾルの製造方法は、前記で得られた高純度親水性有機溶媒分散シリカゾルにシランカップリング剤を添加して表面改質し、最後に、常圧もしくは減圧下にて有機溶媒で置換して得られる。従って、金属不純物の含有量が１．０ｐｐｍ以下で且つ長期安定である高純度親水性有機溶媒分散シリカゾル又は高純度有機溶媒分散シリカゾルを製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a high-purity hydrophilic organic solvent-dispersed silica sol, a high-purity hydrophilic organic solvent-dispersed silica sol obtained by the method, a method for producing a high-purity organic solvent-dispersed silica sol, and a high-purity organic solvent-dispersed silica sol obtained by the method The main purpose is to produce a high-purity hydrophilic organic solvent-dispersed silica sol that is used as a raw material for electronic materials, film materials, and organic surface abrasives that require high purity, and high-purity hydrophilicity obtained by the method. An object is to provide an organic solvent-dispersed silica sol, a method for producing a high-purity organic solvent-dispersed silica sol, and a high-purity organic solvent-dispersed silica sol obtained by the method.
In the present invention, neutral pH means a range of pH 6-8.
[0002]
[Prior art]
Conventionally, since silica sol is water as a dispersion medium, it is difficult to mix and disperse with organic substances, and it is difficult to sufficiently mix or react with an organic solvent. Therefore, in order to widely use the silica sol in the organic industry, it is necessary to produce an organic solvent-dispersed silica sol in which the dispersion medium is changed from water to an organic solvent.
The organic solvent-dispersed silica sol is manufactured by the following method. For example, an acidic aqueous silica sol made from sodium silicate as a raw material is concentrated, an alcohol such as IPA is added to obtain a mixed organic solvent-dispersed silica sol, a silane coupling agent is added thereto, silylation, MEK, etc. The solvent was replaced with a hydrophobic solvent (Japanese Patent Laid-Open No. 11-43319), an alkaline aqueous silica sol using sodium silicate as a raw material was deionized with an ion exchange resin, the sol was concentrated by ultrafiltration, and isopropanol vapor was then heated while being heated. A blowing method (Japanese Patent Laid-Open No. 8-169709) is exemplified.
[0003]
[Problems to be solved by the invention]
However, in the production method using sodium silicate as a raw material, metal impurities such as sodium remain in the organic solvent-dispersed silica sol, and the purity is low. For this reason, it was inadequate to use as a raw material for semiconductors or liquid crystals that require high purity. In addition, the method of dispersing a high purity silica powder with a silane coupling agent and then dispersing it in an organic solvent has a problem of agglomeration of fine particles, and in particular, it is difficult to produce a product having a particle size of submicron. It was.
In addition, when this sol is supplied as a raw material for various materials, long-term storage stability is required.
[0004]
The present invention has been made to solve the above-mentioned problems, and has a high-purity hydrophilic organic solvent-dispersed silica sol having a metal impurity content such as sodium of 1.0 ppm or less and capable of being mixed with water in an arbitrary ratio. An object of the present invention is to create a production method thereof, a high-purity organic solvent-dispersed silica sol in which the high-purity hydrophilic organic solvent-dispersed silica sol is surface-modified and stably dispersed in an organic solvent, and a production method thereof.
[0005]
[Means for Solving the Problems]
That is, the invention according to claim 1 of the present invention comprises the following steps (a) to (d), and a method for producing a high purity hydrophilic organic solvent-dispersed silica sol. (A) a first step of hydrolyzing alkoxysilanes in an aqueous alcohol solution, (b) a second step of concentrating the silica sol solution obtained by hydrolysis, (c) a cup added with a silane coupling agent It relates to a third step of adjusting the pH of the silica sol solution to neutral after the ring treatment and (d) a fourth step of substituting the water in the silica sol solution with a hydrophilic organic solvent.
[0006]
The invention according to claim 2 is characterized in that the amount of the silane coupling agent added to the silica sol concentrate is in the range of 0.1 to 20% with respect to the weight of silica in the silica sol solution. Item 2. A method for producing a high purity hydrophilic organic solvent-dispersed silica sol according to Item 1.
[0007]
The invention according to claim 3 is a high-purity hydrophilic organic solvent-dispersed silica sol in which silica fine particles are dispersed in a hydrophilic organic solvent, and the metal impurity content of the silica fine particles is 1.0 ppm or less and is neutral . The present invention relates to a high-purity hydrophilic organic solvent-dispersed silica sol.
The invention according to claim 4 is a high purity hydrophilic organic solvent-dispersed silica sol obtained by the method according to claim 1 or 2, wherein the silica fine particles are dispersed in the hydrophilic organic solvent, and the silica fine particles contain metal impurities. The present invention relates to a high purity hydrophilic organic solvent-dispersed silica sol having an amount of 1.0 ppm or less and neutral.
[0008]
The invention according to claim 5 relates to the high-purity hydrophilic organic solvent-dispersed silica sol according to claim 3 or 4, wherein the dispersion is stably dispersed for 3 months or more.
[0009]
The invention according to claim 6 is a method for producing a high-purity organic solvent-dispersed silica sol, comprising the following steps (a) and (b).
(A) a first step of surface-modifying the high-purity hydrophilic organic solvent-dispersed silica sol obtained in claim 1 or 2 with a silane coupling agent;
(B) It relates to a second step of replacing the water of the silica sol solution and the hydrophilic organic solvent with an organic solvent.
[0010]
In the invention according to claim 7 , the amount of the silane coupling agent added to the high purity hydrophilic organic solvent-dispersed silica sol is represented by the following formula:
[0011]
In the invention according to claim 8, by treating the neutral hydrophilic organic solvent-dispersed silica sol according to claim 4 with a silane coupling agent again, the silica fine particles are stably dispersed in the organic solvent for 3 months or more, and The present invention relates to a high-purity organic solvent-dispersed silica sol, wherein the silica fine particles have a water content of 5.0 wt% or less.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the high-purity hydrophilic organic solvent-dispersed silica sol according to the present invention and the production method thereof, and the high-purity organic solvent-dispersed silica sol and the production method thereof will be described.
The high-purity hydrophilic organic solvent-dispersed silica sol according to the present invention is characterized in that the metal impurity content of the silica fine particles is 1.0 ppm or less and is stable for a long period of time. Further, the high purity organic solvent-dispersed silica sol according to the present invention can be obtained by surface modification of the high purity hydrophilic organic solvent-dispersed silica sol. The water content of the silica fine particles is 5.0% or less and contains metal impurities. The amount is 1.0 ppm or less and is stable for a long time.
The high-purity organic solvent-dispersed silica sol according to the present invention has high purity, and can be suitably used as a material such as an electronic material, a film material, and an organic surface abrasive.
[0013]
Next, the high purity hydrophilic organic solvent dispersed silica sol and the method for producing the high purity organic solvent dispersed silica sol according to the present invention will be described.
First, a method for producing a high purity hydrophilic organic solvent-dispersed silica sol will be described.
In order to obtain a high purity hydrophilic organic solvent-dispersed silica sol according to the present invention, first, a silica sol solution is prepared by a sol-gel method reaction using alkoxysilanes as a starting material, the sol is concentrated, and a silane coupling agent is added. Unreacted substances are reduced by partial hydrophobization treatment and pH adjustment, and then obtained by substitution with a hydrophilic organic solvent.
[0014]
The alkoxysilanes used are not particularly limited, and examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. These may be used alone or in combination of two or more.
[0015]
In the sol-gel method, a metal organic compound solution is used as a starting material, and the solution is converted into a sol in which fine particles of metal oxide or hydroxide are dissolved by hydrolysis and polycondensation of the compound in the solution. In this invention, the alkoxysilanes are hydrolyzed in an aqueous alcohol solution to obtain a silica sol solution.
The alcohol in the aqueous alcohol solution is not particularly limited. For example, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, or the like is used. Preferably, the same alcohol as a by-product generated by hydrolysis is used. Moreover, these may be used independently and can also be used in mixture of 2 or more types.
The hydrolysis conditions are not particularly limited, but the water concentration is 3 to 12 mol / L, the ammonia concentration is 0.1 to 2.5 mol / L, and the alkoxysilane concentration is 0.3 to 1.5 mol with respect to the total amount of the reaction solution. The reaction temperature is 0 ° C. or higher and the boiling point of the solvent or lower.
[0016]
Next, the silica sol solution obtained above is concentrated. As a condition for concentration, heating and concentration are performed under normal pressure or reduced pressure.
[0017]
The pH is adjusted by adding a silane coupling agent to the obtained concentrated liquid, hydrophobizing it, and removing ammonia.
The silane coupling agent used is not particularly limited. For example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, phenyltrimethoxysilane, benzyltrisilane. One or more of ethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, diethoxymethylphenylsilane, allyltriethoxysilane, vinyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane Preferred examples include alkoxysilanes having a substituted alkyl group, phenyl group, vinyl group, etc .; chlorosilanes such as trimethylchlorosilane and diethyldichlorosilane. Uses methyl silane, methyl silane.
[0018]
The addition amount of the coupling agent is 0.1 to 20%, preferably 1.0 to 2.5%, based on the weight of silica in the sol. If the amount is less than 0.1%, aggregated precipitates are generated, which is not preferable. If the amount is added more than 20%, the cost of the high purity hydrophilic organic solvent-dispersed silica sol to be produced is excessively high.
After adding the silane coupling agent, the pH of the sol solution is adjusted to be neutral. The pH adjustment method is not particularly limited. For example, the operation of performing distillation under heating at normal pressure, passing the distillate through an ion exchange column to remove ammonia, and then returning the distillate to the sol solution results in the pH of the sol solution being medium. And a treatment method that is performed until the pH is about 6 to 8, for example.
The reason for adjusting the pH is to reduce the amount of unreacted substances by neutralizing the sol solution and stably disperse it in the hydrophilic organic solvent for a long period of time.
[0019]
Thereafter, water is replaced with a hydrophilic organic solvent to obtain a high-purity hydrophilic organic solvent-dispersed silica sol. The purpose of substitution with a hydrophilic organic solvent is that a silica sol solution can be stably dispersed by substitution with a hydrophilic organic solvent, and a high-purity hydrophilic organic solvent-dispersed silica sol with few metal impurities can be obtained. Although it does not specifically limit as a hydrophilic organic solvent to be used, Methanol, ethanol, isopropanol, ethylene glycol, propylene glycol etc. are mentioned, Preferably the same alcohol used as a by-product by hydrolysis of alkoxysilane is used. This is industrially advantageous in recovering and reusing the solvent.
As conditions for substitution with a hydrophilic organic solvent, solvent substitution is carried out under normal pressure. Preferably, the substitution is performed until the water content of the sol solution is 5.0% or less. The reason why the water content of the sol solution is 5.0% or less is that, if the water content is too much, it is difficult to adjust to organic substances such as resins and dispersibility.
[0020]
Next, the manufacturing method of the high purity organic solvent dispersion | distribution silica sol which concerns on this invention is demonstrated.
First, a high purity organic solvent-dispersed silica sol obtained by the above method is subjected to surface modification with a silane coupling agent and then replaced with an organic solvent to obtain a high purity organic solvent-dispersed silica sol. The purpose of the surface modification is to stably disperse the conventionally hydrophilic silica sol with a hydrophobic solvent.
The silane coupling agent for modifying the surface of the high-purity hydrophilic organic solvent-dispersed silica sol is not particularly limited, but the above-mentioned silane coupling agent can be suitably used, and preferably methyltrimethoxysilane or dimethyldimethoxysilane is used. use.
The amount of the silane coupling agent that modifies the surface of the high-purity hydrophilic organic solvent-dispersed silica sol is as follows:
[0021]
A surfactant can also be used to improve the dispersion stability. As the surfactant, cationic surfactants of alkyl quaternary ammonium salts can be preferably used. The reason for using cationic surfactants is that anionic surfactants use metal ions such as sodium as counter ions, so there is a problem of contamination by metal impurities, and nonionic surfactants have dispersion stability. This is because the effect is small. When using a surfactant, it is added in an amount of 50 to 150 ppm based on the weight of silica.
[0022]
Then, it substitutes with an organic solvent. The organic solvent to be used is not particularly limited, but saturated or unsaturated aliphatic hydrocarbons, aromatic hydrocarbons and their halides, monovalent and divalent alcohol compounds, ether compounds, ester compounds, amines, etc. And organic compounds such as carbonyl compounds such as aldehydes and ketones, carboxylic acid compounds, and carbohydrates such as monosaccharides and polysaccharides.
Substitution conditions are such that the tower top temperature reaches the boiling point of the organic solvent to be substituted, and the water content is 5.0% or less, preferably 0.1 to 1.0%. The reason why the water content of the sol solution is 5.0% or less is that, if the water content is too much, it is difficult to adjust to organic substances such as resins and dispersibility.
[0023]
Hereinafter, the effects of the present invention will be clarified by describing examples of the present invention, but the present invention is not limited to these examples. In addition, a compounding quantity is weight%.
[0024]
【Example】
(Example 1-1: Preparation of high-purity hydrophilic organic solvent-dispersed silica sol)
A mixture of 787.9 g of pure water, 786.0 g of 26% ammonia water, and 12924.0 g of methanol was mixed with 1522.2 g of tetramethoxysilane and 413.0 g of methanol over 55 minutes while maintaining the liquid temperature at 35 ° C. To obtain a silica sol solution. This sol solution was heated and concentrated to 2900 ml under normal pressure. To this concentrated liquid, 6.0 g of methyltrimethoxysilane as a silane coupling agent was added, heated and distilled under normal pressure, and the distillate was passed through an ion exchange tower (Amberlite IR120B (H) -AG made by Organo). Then, after removing ammonia, the operation of returning to the sol solution was performed until the pH of the sol solution became 8 or less. Thereafter, distillation was continued while dropping methanol until the water content was 5% or less, and after cooling to room temperature, microfiltration was performed using a 3 μ membrane filter to obtain a methanol-dispersed silica sol.
[0025]
(Example 1-2: Preparation of high-purity organic solvent-dispersed silica sol)
15.4 g of methyltrimethoxysilane as a silane coupling agent was added to 500 g of the methanol-dispersed silica sol obtained in Example 1-1, and the mixture was stirred at room temperature for 1 hour and then fully refluxed for 2 hours. Thereafter, methyl ethyl ketone was added dropwise while maintaining the volume at a constant pressure while heating and distilling under normal pressure, and when the tower top temperature reached 79 ° C. and the water content was 1.0% or less, the process was terminated. After cooling to room temperature, microfiltration was performed using a 3 μ membrane filter to obtain a methyl ethyl ketone-dispersed silica sol.
[0026]
(Example 2: Preparation of high-purity hydrophilic organic solvent-dispersed silica sol)
In Example 1-1, each charge amount was similarly subjected to sol-gel reaction, concentration, surface treatment, and pH adjustment, and the hydrophilic organic solvent to be replaced was changed from methanol to isopropanol. Solvent replacement was performed until the content became 1.0% or less, and after cooling to room temperature, microfiltration was performed using a 3 μ membrane filter to obtain an isopropanol-dispersed silica sol.
[0027]
(Comparative Example 1)
In Example 1-1, after distillation by heating without adding a silane coupling agent to the concentrate, a methanol-dispersed silica sol was prepared without adjusting the pH. Obtained.
[0028]
(Comparative Example 2)
In Example 1-1, methanol dripping was stopped when the water content was 10% to obtain a methanol-dispersed silica sol.
[0029]
(Comparative Example 3)
In Example 1-2, methyl ethyl ketone-dispersed silica sol was obtained without adding a silane coupling agent to high-purity hydrophilic solvent-dispersed silica sol.
[0030]
[Test example]
(Test Example 1)
Specific surface area, particle diameter, silica concentration, moisture, presence / absence of aggregation of the hydrophilic organic solvent-dispersed silica sols of Examples 1-1, 1-2, 2 and Comparative Examples 1-3 obtained or the organic solvent-dispersed silica sols The amount of impurities was measured. The results are shown in Tables 1 and 2.
The specific surface area was measured by drying and calcining the silica sol using the BET method, the particle size was measured by the photon correlation method using the silica sol as it was, and the water content was measured using a Karl Fischer moisture meter. Moreover, the amount of metal impurities was measured using an atomic absorption measuring device.
[0031]
[Table 1]
[Table 2]
(Test Example 2)
50 ml of pure water was mixed with 50 ml of each of the methanol dispersion sol and isopropanol dispersion sol obtained in Example 1-1 and Example 2, and confirmation of dispersion stability and measurement of particle diameter were performed. The results are shown in Table 3.
[0034]
[Table 3]
From the above results, it can be seen that silica sol using alkoxysilane as a raw material has a low content of metal impurities and is 1.0 ppm or less as in the production method according to the present invention. Further, when the silane coupling agent is not added and the neutrality is not adjusted, an aggregated precipitate is generated, so that the target silica sol stably dispersed in the solvent cannot be obtained, and the water content is 5%. The hydrophilic solvent-dispersed silica sol is stable even if it is reduced to less than or equal to%. Furthermore, since the high-purity hydrophilic organic solvent-dispersed silica sol or the high-purity organic solvent-dispersed silica sol produced according to the present invention shows no increase in particle diameter and no aggregation compared to the comparative example, the dispersion stability, It was found that the storage stability was excellent. Further, it was found that even when the hydrophilic organic solvent-dispersed sol and water were mixed, they were stable without aggregation.
[0036]
【The invention's effect】
As described above in detail, the high-purity hydrophilic organic solvent-dispersed silica sol according to the present invention is a high-purity hydrophilic organic solvent-dispersed silica sol composed of silica sol dispersed in a hydrophilic solvent with few metal impurities. Is 1.0 ppm or less and is stable for a long time. The high-purity organic solvent-dispersed silica sol according to the present invention is an organic solvent-dispersed silica sol obtained by surface modification of the high-purity hydrophilic organic solvent-dispersed silica sol, and the water content of the silica fine particles is 5.0% or less. The amount of metal impurities is 1.0 ppm or less and is stable for a long time.
Since the high-purity hydrophilic organic solvent-dispersed silica sol and the high-purity organic solvent-dispersed silica sol have high purity and are stably dispersed in each solvent for a long period of time, electronic materials, film materials, organic surface abrasives, etc. It can be suitably used as a material. The high purity hydrophilic organic solvent-dispersed silica sol can be mixed with water at an arbitrary ratio.
[0037]
The method for producing a high purity hydrophilic organic solvent-dispersed silica sol according to the present invention comprises concentrating a silica sol solution obtained by hydrolyzing alkoxysilanes in an alcohol aqueous solution, adding a silane coupling agent, After pH adjustment, it can be obtained by substitution with a hydrophilic solvent. In addition, the high purity organic solvent-dispersed silica sol is produced by adding a silane coupling agent to the high-purity hydrophilic organic solvent-dispersed silica sol obtained above to modify the surface, and finally, under normal pressure or reduced pressure. Obtained by substitution with an organic solvent. Therefore, a high-purity hydrophilic organic solvent-dispersed silica sol or a high-purity organic solvent-dispersed silica sol having a metal impurity content of 1.0 ppm or less and having a long-term stability can be produced.
Claims (8)
（ａ）アルコキシシラン類をアルコール水溶液中で加水分解する第一の工程，
（ｂ）加水分解により得られるシリカゾル溶液を濃縮する第二の工程，
（ｃ）シランカップリング剤を添加してカップリング処理を施した後、シリカゾル溶液のｐＨを中性に調整する第三の工程，
（ｄ）親水性有機溶媒でシリカゾル溶液の水分を置換する第四の工程。A method for producing a high-purity hydrophilic organic solvent-dispersed silica sol, comprising the following steps (a) to (d):
(A) a first step of hydrolyzing alkoxysilanes in an aqueous alcohol solution;
(B) a second step of concentrating the silica sol solution obtained by hydrolysis,
(C) a third step of adjusting the pH of the silica sol solution to neutral after adding a silane coupling agent and applying a coupling treatment;
(D) A fourth step of substituting the water in the silica sol solution with a hydrophilic organic solvent.
（ａ）請求項１又は２で得られる高純度親水性有機溶媒分散シリカゾルをシランカップリング剤で表面改質する第一の工程，
（ｂ）有機溶媒でシリカゾル溶液の水分並びに親水性有機溶媒を置換する第二の工程。A method for producing a high-purity organic solvent-dispersed silica sol, comprising the following steps (a) and (b):
(A) a first step of surface-modifying the high-purity hydrophilic organic solvent-dispersed silica sol obtained in claim 1 or 2 with a silane coupling agent;
(B) A second step of replacing the water in the silica sol solution and the hydrophilic organic solvent with an organic solvent.
【式１】
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| JP2002251019A JP4458396B2 (en) | 2002-08-29 | 2002-08-29 | Method for producing high-purity hydrophilic organic solvent-dispersed silica sol, high-purity hydrophilic organic solvent-dispersed silica sol obtained by the method, method for producing high-purity organic solvent-dispersed silica sol, and high-purity organic solvent-dispersed silica sol obtained by the method |
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| JP2002251019A JP4458396B2 (en) | 2002-08-29 | 2002-08-29 | Method for producing high-purity hydrophilic organic solvent-dispersed silica sol, high-purity hydrophilic organic solvent-dispersed silica sol obtained by the method, method for producing high-purity organic solvent-dispersed silica sol, and high-purity organic solvent-dispersed silica sol obtained by the method |
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| JP2004091220A JP2004091220A (en) | 2004-03-25 |
| JP4458396B2 true JP4458396B2 (en) | 2010-04-28 |
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| JP2005298226A (en) * | 2004-04-06 | 2005-10-27 | Mitsubishi Chemicals Corp | Silica sol and its manufacturing method |
| JP4544519B2 (en) * | 2004-09-10 | 2010-09-15 | 日本化薬株式会社 | Photosensitive resin composition |
| JP4641412B2 (en) * | 2004-12-01 | 2011-03-02 | 日本板硝子株式会社 | Hydrophobic organic-containing sol solution and method for producing the same |
| WO2006070846A1 (en) | 2004-12-27 | 2006-07-06 | Konishi Chemical Ind. Co., Ltd. | Organic-solvent dispersion of fine polysilsesquioxane particle, process for producing the same, aqueous dispersion of fine polysilsesquioxane particle, and process for producing the same |
| CN100372764C (en) * | 2005-05-23 | 2008-03-05 | 电子科技大学 | Nano organic solvent silicasol and preparation method thereof |
| JP2007063117A (en) * | 2005-08-02 | 2007-03-15 | Nissan Chem Ind Ltd | Silica sol dispersed in organic solvent and process for producing the same |
| US9550683B2 (en) | 2007-03-27 | 2017-01-24 | Fuso Chemical Co., Ltd. | Colloidal silica, and method for production thereof |
| EP2025381A1 (en) * | 2007-07-30 | 2009-02-18 | Nanoresins AG | Method for removing alkaline or acid compounds from a metal oxide (silica) dispersion containing solvents |
| JP5495880B2 (en) * | 2010-03-25 | 2014-05-21 | 扶桑化学工業株式会社 | Method for adjusting secondary particle size of colloidal silica |
| CN105308123B (en) | 2013-06-10 | 2019-03-29 | 日产化学工业株式会社 | The molded product of resin combination and its manufacturing method containing silica and the resin combination containing silica |
| KR102393989B1 (en) * | 2016-09-26 | 2022-05-02 | 한국전기연구원 | Hybrid thermoplastic elastomer comprising a siloxane and a method of manufacturing the same |
| CN106811957B (en) * | 2016-12-08 | 2019-08-27 | 苏州榕绿纳米科技有限公司 | A kind of preparation method of the super hydrophobic surface for lotion separation |
| CN113607788B (en) * | 2021-07-16 | 2023-04-14 | 福建师范大学 | Preparation method of sensor for detecting clenbuterol hydrochloride based on modified silica sol |
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| JPS63182204A (en) * | 1987-01-22 | 1988-07-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of monodisperse body of fine inorganic oxide particle in organic solvent |
| JPS6442314A (en) * | 1987-08-07 | 1989-02-14 | Shinetsu Chemical Co | Production of silica sol dispersed in organic solvent |
| JPH0798655B2 (en) * | 1988-09-13 | 1995-10-25 | 信越化学工業株式会社 | Method for producing surface-modified silica |
| JP2718431B2 (en) * | 1990-06-18 | 1998-02-25 | 触媒化成工業株式会社 | Silica organosol and method for producing the same |
| JP2839725B2 (en) * | 1990-12-28 | 1998-12-16 | 新日鐵化学株式会社 | Method for producing high-purity crystalline silica |
| JPH05201718A (en) * | 1992-01-27 | 1993-08-10 | Mitsubishi Kasei Corp | Production of silica glass powder and silica glass molten molding |
| JP3753192B2 (en) * | 1994-08-05 | 2006-03-08 | 日産化学工業株式会社 | Method for producing silica propanol sol |
| JP4032503B2 (en) * | 1997-05-26 | 2008-01-16 | 日産化学工業株式会社 | Method for producing hydrophobic organosilica sol |
| JP4631119B2 (en) * | 2000-01-28 | 2011-02-16 | Ｊｓｒ株式会社 | Method for producing hydrophobized colloidal silica |
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