JP2590428B2 - Method for producing spherical hollow porous silica particles - Google Patents
Method for producing spherical hollow porous silica particlesInfo
- Publication number
- JP2590428B2 JP2590428B2 JP5328794A JP5328794A JP2590428B2 JP 2590428 B2 JP2590428 B2 JP 2590428B2 JP 5328794 A JP5328794 A JP 5328794A JP 5328794 A JP5328794 A JP 5328794A JP 2590428 B2 JP2590428 B2 JP 2590428B2
- Authority
- JP
- Japan
- Prior art keywords
- silica particles
- spherical hollow
- hollow porous
- porous silica
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Silicon Compounds (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、徐放性粒子、化粧品等
無機物充填剤として使用される球状中空シリカの製造法
に関するものであり、特に、ゾル・ゲル法による球状中
空多孔質シリカ粒子の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing sustained-release particles and spherical hollow silica used as an inorganic filler for cosmetics, and more particularly to a method for producing spherical hollow porous silica particles by a sol-gel method. It relates to a manufacturing method.
【0002】[0002]
【従来の技術】中空多孔質粒子の製造法には水ガラスと
界面活性剤のベンゼン溶液からなるw/oエマルジョン
とアルカリ土類金属水溶液からw/o/wエマルジョン
を形成した後、ケイ酸塩の反応によるものがある。しか
しながら、この方法では不純物の除去が難しく、高純度
の中空多孔質粒子の製造は困難であった。2. Description of the Related Art A method for producing hollow porous particles involves forming a w / o / w emulsion comprising a water glass and a benzene solution of a surfactant and an aqueous alkaline earth metal solution and then forming a silicate. There is a reaction. However, it is difficult to remove impurities by this method, and it is difficult to produce high-purity hollow porous particles.
【0003】[0003]
【発明が解決しようとする課題】従来の球状中空シリカ
粒子およびその製造方法は水ガラスを用いてw/o/w
エマルジョンを調整する方法であり、安定性、生成時間
および生成粒子の純度において問題があった。本発明は
ゾル・ゲル法を用いて部分加水分解後、乳化するという
手法で、これらの技術課題を解決しようとするものであ
る。Conventional spherical hollow silica particles and a method for producing the same are based on w / o / w using water glass.
This is a method for preparing an emulsion, and has problems in stability, formation time, and purity of formed particles. The present invention is intended to solve these technical problems by a method of emulsifying after partial hydrolysis using a sol-gel method.
【0004】[0004]
【課題を解決するための手段】本発明は、オルトケイ酸
テトラエチルに、アルコール、水および酸触媒を加えて
部分加水分解を行わせた後、フタル酸ジブチルを添加
し、この溶液を界面活性剤を含んだアンモニア水溶液中
で混合攪拌・乳化し、重縮合反応によって球状中空多孔
質シリカ粒子を製造する方法である。According to the present invention, a partial hydrolysis is carried out by adding alcohol, water and an acid catalyst to tetraethyl orthosilicate, and then dibutyl phthalate is added. In this method, spherical hollow porous silica particles are produced by mixing, stirring and emulsifying in a contained ammonia aqueous solution, and performing a polycondensation reaction.
【0005】本発明をさらに、詳細に説明する。オルト
ケイ酸テトラエチル(TEOS)を塩酸等の酸触媒で加
水分解すると求電子反応で反応が進行するためアルコキ
シドのアルコール基の一つが水酸基に置換すると、アル
コール基の負電荷部分の減少のため引き続く加水分解速
度は遅く、完全に加水分解することはない。その作用の
ためシリカアルコキシドには疎水性のアルコール基と親
水性の水酸基とが存在することになる。このような部分
加水分解反応を確実に進行させるためには酸触媒を用い
ることおよびTEOS1モルに対してアルコール6モ
ル、水4モル以下で反応を行わせることである。また、
1モル程度のアルコールがないと部分加水分解中に固体
が生成するために抑制剤として必要となる。最適な反応
条件としては、TEOS1モルに対してアルコール1〜
5モル、水1〜2モル程度が適当であった。The present invention will be described in further detail. When tetraethyl orthosilicate (TEOS) is hydrolyzed with an acid catalyst such as hydrochloric acid, the reaction proceeds by an electrophilic reaction. When one of the alcohol groups of the alkoxide is replaced with a hydroxyl group, the subsequent hydrolysis is performed due to a decrease in the negatively charged portion of the alcohol group. The rate is slow and there is no complete hydrolysis. Due to this effect, the silica alkoxide has a hydrophobic alcohol group and a hydrophilic hydroxyl group. In order to ensure that such a partial hydrolysis reaction proceeds, it is necessary to use an acid catalyst and to carry out the reaction with 6 mol of alcohol and 4 mol or less of water per 1 mol of TEOS. Also,
Without about 1 mole of alcohol, a solid is formed during the partial hydrolysis and is required as an inhibitor. Optimum reaction conditions are as follows: 1 mole of TEOS and 1 mole of alcohol.
About 5 moles and about 1 to 2 moles of water were appropriate.
【0006】この部分加水分解したアルコキシド溶液に
フタル酸ジブチルを添加し、アンモニア水溶液中に加え
るとともに乳化機等を用いて強く攪拌するとアルコキシ
ドの疎水基は有機溶媒側に親水基は水溶液側に向いたo
/wエマルジョンを形成する。アンモニアの塩基触媒で
部分加水分解したアルコキシドの加水分解・重縮合反応
は主にo/wエマルジョンの界面より進行する。エマル
ジョンの油滴中には添加した反応不活性なフタル酸ジブ
チルが存在するため油滴中の中心部分はシリカ粒子には
なり難い。反応終了後、これら有機溶媒は中空多孔質の
壁により簡単に洗浄除去できるため、球状中空多孔質シ
リカ粒子が製造できる。また、水溶液の攪拌速度を変え
ることで、生成粒子の平均粒径を調整でき、このように
して平均粒径2〜8μmの球状中空多孔質シリカ粒子が
製造できる。When dibutyl phthalate is added to the partially hydrolyzed alkoxide solution, added to an aqueous ammonia solution and vigorously stirred using an emulsifier or the like, the hydrophobic group of the alkoxide is directed toward the organic solvent and the hydrophilic group toward the aqueous solution. o
/ W form an emulsion. The hydrolysis / polycondensation reaction of the alkoxide partially hydrolyzed by the base catalyst of ammonia mainly proceeds from the interface of the o / w emulsion. Since the reaction-inactive dibutyl phthalate added is present in the oil droplets of the emulsion, the central portion in the oil droplets is unlikely to become silica particles. After completion of the reaction, these organic solvents can be easily washed and removed by the hollow porous walls, so that spherical hollow porous silica particles can be produced. Further, by changing the stirring speed of the aqueous solution, the average particle size of the produced particles can be adjusted, and thus spherical hollow porous silica particles having an average particle size of 2 to 8 μm can be produced.
【0007】[0007]
【実施例】オルトケイ酸テトラエチル(TEOS)20
mlを用い、部分加水分解反応はTEOS:エタノール:
水:塩酸で1:2:1:0.03のモル比で添加し、9
0分の反応時間で行ったものを用意した。これにフタル
酸ジブチル5ml加えて、0.003%の界面活性剤(Twe
en-80)を含んだ1.75%のアンモニア水溶液300ml
中に乳化機で攪拌(4000回転/分)しながら粒子生
成させる。その後、約1日静置し、メンブランフイルタ
ーで加圧濾過し、アルコール洗浄でシリカ粒子を得た。
その粒子を50℃で真空乾燥した特性を表1に示す。比
較として、通常のゾル・ゲル法により調整したシリカ粒
子(平均粒径約0.5μm)の嵩比重は0.77g/m
l、比表面積は20m2/gであり、本法のシリカ粒子
は多孔質粒子であることが分かる。また、研磨した粒子
断面を電子顕微鏡で観察した結果、このものはシリカの
球状中空粒子であることを確認した。EXAMPLE Tetraethyl orthosilicate (TEOS) 20
ml, using TEOS: ethanol:
Water: hydrochloric acid was added at a molar ratio of 1: 2: 1: 0.03, and 9
A sample that had a reaction time of 0 minutes was prepared. To this was added 5 ml of dibutyl phthalate, and a 0.003% surfactant (Twe
300 ml of 1.75% aqueous ammonia solution containing en-80)
Particles are formed therein while stirring with an emulsifier (4000 revolutions / minute). Thereafter, the mixture was allowed to stand for about 1 day, filtered under pressure through a membrane filter, and washed with alcohol to obtain silica particles.
The properties of the particles vacuum dried at 50 ° C. are shown in Table 1. As a comparison, the bulk specific gravity of silica particles (average particle size of about 0.5 μm) prepared by a usual sol-gel method is 0.77 g / m 2.
1, the specific surface area is 20 m 2 / g, which indicates that the silica particles of the present method are porous particles. Further, as a result of observing the polished particle cross section with an electron microscope, it was confirmed that this was a spherical hollow particle of silica.
【0008】[0008]
【表1】 [Table 1]
【0009】[0009]
【発明の効果】本発明によれば、高純度の球状中空多孔
質シリカ粒子を工業的に有利に得ることができる。According to the present invention, high-purity spherical hollow porous silica particles can be industrially advantageously obtained.
Claims (1)
ル、水および酸触媒を加えて部分加水分解を行わせた
後、フタル酸ジブチルを添加し、この溶液を界面活性剤
を含んだアンモニア水溶液中で混合攪拌し、乳化し、重
縮合反応させることにより球状中空多孔質シリカ粒子を
製造する方法。1. An alcohol, water and an acid catalyst are added to tetraethyl orthosilicate to cause partial hydrolysis, and then dibutyl phthalate is added. This solution is mixed and stirred in an aqueous ammonia solution containing a surfactant. , Emulsification and polycondensation reaction to produce spherical hollow porous silica particles.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5328794A JP2590428B2 (en) | 1994-02-25 | 1994-02-25 | Method for producing spherical hollow porous silica particles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5328794A JP2590428B2 (en) | 1994-02-25 | 1994-02-25 | Method for producing spherical hollow porous silica particles |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0891821A JPH0891821A (en) | 1996-04-09 |
JP2590428B2 true JP2590428B2 (en) | 1997-03-12 |
Family
ID=12938518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5328794A Expired - Lifetime JP2590428B2 (en) | 1994-02-25 | 1994-02-25 | Method for producing spherical hollow porous silica particles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2590428B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010037150A (en) * | 2008-08-05 | 2010-02-18 | Kao Corp | Method for producing hollow silica particle |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6004525A (en) * | 1997-10-06 | 1999-12-21 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Hollow oxide particle and process for producing the same |
JP4211115B2 (en) * | 1999-02-05 | 2009-01-21 | Jsr株式会社 | Method for producing hollow particles |
KR19990073271A (en) * | 1999-06-29 | 1999-10-05 | 정상옥 | Hollowness silica and manufacturing method thereof |
KR100392194B1 (en) * | 2000-07-19 | 2003-07-22 | 이종협 | Preparation of Ceramic Hollow Sphere |
JP4923372B2 (en) * | 2001-09-25 | 2012-04-25 | セイコーエプソン株式会社 | Method for producing spherical oxide particles |
JP4636869B2 (en) | 2004-12-21 | 2011-02-23 | 日揮触媒化成株式会社 | Method for producing porous silica-based particles and porous silica-based particles obtained from the method |
JP2007075660A (en) * | 2005-09-09 | 2007-03-29 | Nagoya Institute Of Technology | Method for producing hollow particle |
KR100679356B1 (en) * | 2005-11-01 | 2007-02-05 | 한국화학연구원 | Hollow silica particles with controllable holes in their surfaces and manufacturing method thereof |
CN101823719B (en) * | 2010-05-18 | 2011-08-31 | 南京大学 | Two-step preparation method of hollow silica particles |
FR2965807B1 (en) * | 2010-10-11 | 2012-12-21 | Centre Nat Rech Scient | PROCESS FOR PREPARING ALVEOLAR INORGANIC MONOLITHIC MATERIALS AND USES THEREOF |
SG11201402731RA (en) * | 2011-12-01 | 2014-06-27 | Innovations Materium | Silica microcapsules, process of making the same and uses thereof |
JP6092839B2 (en) * | 2012-02-13 | 2017-03-08 | 株式会社トクヤマシルテック | Silica balloon material with novel characteristic profile |
CN108221367A (en) * | 2018-03-21 | 2018-06-29 | 青岛纳博科环保科技有限公司 | Hydrophobic modifier for activated carbon fibre and preparation method thereof, hydrophobic active Carbon fibe and preparation method thereof |
-
1994
- 1994-02-25 JP JP5328794A patent/JP2590428B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010037150A (en) * | 2008-08-05 | 2010-02-18 | Kao Corp | Method for producing hollow silica particle |
Also Published As
Publication number | Publication date |
---|---|
JPH0891821A (en) | 1996-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2590428B2 (en) | Method for producing spherical hollow porous silica particles | |
EP0805781B1 (en) | Process for the production of modified aerogels | |
US5246624A (en) | Aqueous colloidal dispersion of fumed silica, acid and stabilizer | |
WO2007122930A1 (en) | Core-shell silica and method for producing same | |
TWI389845B (en) | Method for the production of glassy monoliths via the sol-gel process | |
JPH0350112A (en) | Aqueous colloid dispersion liquid for fumed silica and manufacture thereof | |
JPWO2009001905A1 (en) | Spherical organic polymer-silicon compound composite particles, hollow particles and methods for producing them | |
JPH0360420A (en) | Aqueous colloid dispersion liquid for fumed silica | |
JP2001518835A (en) | Method for producing low-density gel structure | |
JPS62180300A (en) | Glass forming slurry solidifying nuclear waste and solidifying method | |
JP2007182341A (en) | Mesoporous silica precursor solution, its production method, and mesoporous silica | |
JPH09278485A (en) | Alkali resistant spherical glass and its production | |
JP5431120B2 (en) | Method for producing colloidal silica | |
JP2000109312A (en) | Amorphous silicic acid and metallic silicate having narrow mesopore radius distribution produced by precipitation method, their production, method for modifying silicic acid and metallic silicate and their use | |
JP2021187692A (en) | Porous metal oxide powder and method for producing the same | |
JPH0826716A (en) | Production of porous spherical silica particle | |
JPH06279589A (en) | Production of fine spherical silicone particles | |
JP5905767B2 (en) | Dispersion stabilization method of neutral colloidal silica dispersion and neutral colloidal silica dispersion excellent in dispersion stability | |
JP2001002411A (en) | Production of aqueous silica sol | |
JP2000226453A (en) | Hollow particle and preparation thereof | |
JP2722627B2 (en) | Method for growing silica core particles | |
JP3123652B2 (en) | Method for producing spherical silica | |
JP2003313024A (en) | Surface modified porous silica and method for manufacturing the same | |
JP3338720B2 (en) | Method for producing composite oxide sol | |
JP2003520181A (en) | Sol-gel method for producing synthetic silica glass |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EXPY | Cancellation because of completion of term |