JPH052607B2 - - Google Patents
Info
- Publication number
- JPH052607B2 JPH052607B2 JP63273170A JP27317088A JPH052607B2 JP H052607 B2 JPH052607 B2 JP H052607B2 JP 63273170 A JP63273170 A JP 63273170A JP 27317088 A JP27317088 A JP 27317088A JP H052607 B2 JPH052607 B2 JP H052607B2
- Authority
- JP
- Japan
- Prior art keywords
- stirring
- particle size
- silica particles
- solution
- reynolds number
- 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 - Fee Related
Links
- 238000003756 stirring Methods 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- BINKQJJWJHNOSQ-UHFFFAOYSA-N tetrabenzyl silicate Chemical compound C=1C=CC=CC=1CO[Si](OCC=1C=CC=CC=1)(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 BINKQJJWJHNOSQ-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
Description
［産業上の利用分野］
本発明は、粒径の揃つた真球状シリカ粒子を製
造する方法に関する。
［従来の技術］
アルコキシシランを水、アンモニア及びアルコ
ール溶液中で加水分解することによつて0.05〜1μ
ｍの比較的粒径の揃つたシリカ球状粒子を得る方
法が知られている（W.Sto¨ber，A.Fink and E.
Bohn；J.Colloid Interface Sci.，26，p62
（1968））。
このとき、生成するシリカ粒子の粒子径は、反
応溶液中のアンモニア濃度、アルコキシシランの
種類や濃度等によつてコントロールできる。
しかしながら、攪拌力が不十分な場合には、生
成粒子の平均粒径及び粒度分布は攪拌条件によつ
ても左右される。特に、粒子成長が進み、粒子径
が1μｍに近づくにつれ、粒子間に凝集が進んで
大きな粒子となつたり、ついには、溶液が粘稠に
なつてゲル化を起す場合もある。また、粒子径が
大きくなるにつれ、単分散性も失われていく。
ところで、近年、PETフイルムの滑剤として
のフイラーや液晶パネルのギヤツプ剤等として、
単分散性の高い粒子が要求されることもあり、前
述の方法で製造される粒子では必ずしも満足でき
ない場合がある。
［発明が解決しようとする課題］
本発明者らは、このような問題点を解決するた
め研究を行つた結果、アルコキシシラン類を供給
する際に、単位体積当りの攪拌所要動力が
0.02kw／m3以上であつて、レイノルズ数が5000
以上の条件で反応溶液を攪拌することにより、生
成粒子の単分散性が向上することを見い出し、本
発明を完成した。
従つて、本発明の目的は、真球状であつて、
0.1〜2μｍ程度の大きさで、粒径の揃つた粒子を
製造することができるシリカ粒子の製造方法を提
供することにある。
［課題を解決するための手段］
すなわち、本発明は、アルコキシシラン類を水
とアンモニアあるいはこれらにアルコールを加え
た混合溶液中で加水分解するに際し、単位体積当
りの攪拌所要動力0.02kw／m3以上及びレイノル
ズ数5000以上の攪拌条件で反応混合物を攪拌する
シリカ粒子の製造方法である。
本発明で使用するアルコキシシラン類として
は、例えばテトラメトキシシラン、テトラエトキ
シシラン、テトラプロポキシシラン、テトラブト
キシシラン、テトラフエノキシシラン、テトラベ
ンジルオキシシラン等を挙げることができ、アル
コキシシラン類であればいかなるものでもよい
が、好ましくは、炭素数１〜４のアルコキシ基を
有するものであり、加水分解反応の際の反応速度
の大きいテトラメトキシシランやテトラエトキシ
シランが特に好ましい。
本発明では、アルコキシシラン類の加水分解を
水とアンモニアの溶液あるいはこれらにアルコー
ルを加えた溶液を使用して行うものであり、この
際に使用するアルコールとしては、メチルアルコ
ール、エチルアルコール、プロピルアルコール、
ブチルアルコール、フエノール、ベンジルアルコ
ール等がある。
アルコキシシラン類の加水分解はアンモニア存
在下で水と接触することにより可能である。具体
的には、例えば、上記の混合溶液を十分に攪拌し
ながらテトラアルコキシシラン類を滴下する方法
がある。加水分解時の液温については、必要に応
じて適当な温度を選択することができるが、常温
でも可能である。
この加水分解により、平均粒径が0.05〜2.0μｍ
の範囲の単分散球状シリカ粒子を含むゾルを得る
ことができる。このシリカ粒子の粒径は、加水分
解に使用する溶液中の水とアンモニアの濃度、ア
ルコキシシランの種類や濃度、アルコキシシラン
の滴下速度、反応温度等を制御することによつて
制御可能であるが、一方で、溶液の攪拌状態によ
つても、その粒径や粒度分布が影響を受ける。
攪拌が不十分な場合には粒径が大きくなり、分
布がブロードになる傾向がある。また、レイノル
ズ数と粒径の関係は、レイノルズ数をReとし、
粒径をＲとしたとき、概ねＲ＝Ｋ／Re（但し、Ｋ
は定数）の関係を有し、このレイノルズ数が5000
未満では生成するシリカ粒子の平均粒径が攪拌条
件に大きく依存する。それ故、反応途中の固形分
濃度、溶液組成、温度等の変化につれて必然的に
溶液の粘度が変化し、この溶液の粘度の変化によ
り攪拌条件が変化すると生成するシリカ粒子の平
均粒径も変化することになる。従つて、レイノル
ズ数については、攪拌条件の変化が平均粒径に及
ぼす影響の少ない領域、すなわち5000以上、好ま
しくは10000以上の領域である必要がある。
また、レイノルズ数が10000以上でも、単位体
積当りの攪拌所要動力が小さいと、単分散性が悪
くなり、粒子間の凝集が起り易くなる。従つて、
単位体積当りの攪拌所要動力は0.02kw／m3以上
にする必要がある。
そして、単位体積当りの攪拌所要動力を大きく
する方法としては、槽型反応器の場合には、例え
ば攪拌翼の形、巾、段数等の翼条件や、回転数の
アツプや、邪魔板の取付等等の手段が有効であ
り、また、チユーブ式反応器では、例えば流速を
速くする方法等の手段が有効である。
［実施例］
以下、実施例及び比較例に基づいて、本発明を
具体的に説明する。
実施例１〜３及び比較例１，２
水180重量部、アンモニア54重量部及びメタノ
ール416重量部を丸底反応槽に仕込み、第１表に
示す攪拌条件で混合しながら、テトラメトキシシ
ラン381重量部を100分間かけて溶液中に滴下し、
さらに滴下終了後60分間攪拌を続けてシリカ粒子
を製造した。得られたシリカ粒子について、その
粒度分布を光透過式粒度分布計により測定した。
結果を第１表に示す。
[Industrial Field of Application] The present invention relates to a method for producing truly spherical silica particles with uniform particle sizes. [Prior art] By hydrolyzing alkoxysilane in water, ammonia and alcohol solution,
A method for obtaining silica spherical particles of relatively uniform particle size of m is known (W. Sto¨ber, A. Fink and E.
Bohn; J. Colloid Interface Sci., 26 , p62
(1968)). At this time, the particle size of the silica particles produced can be controlled by the ammonia concentration, the type and concentration of alkoxysilane, etc. in the reaction solution. However, if the stirring force is insufficient, the average particle size and particle size distribution of the produced particles also depend on the stirring conditions. In particular, as particle growth progresses and the particle diameter approaches 1 μm, aggregation between particles may progress to form larger particles, and the solution may eventually become viscous and cause gelation. Furthermore, as the particle size increases, monodispersity also decreases. By the way, in recent years, fillers have been used as lubricants for PET films, gapping agents for liquid crystal panels, etc.
Particles with high monodispersity may be required, and particles produced by the above-mentioned method may not always be sufficient. [Problems to be Solved by the Invention] As a result of research to solve these problems, the present inventors have found that the power required for stirring per unit volume when supplying alkoxysilanes has been determined.
0.02kw/ m3 or more and Reynolds number 5000
The present invention was completed based on the discovery that stirring the reaction solution under the above conditions improves the monodispersity of the produced particles. Therefore, the object of the present invention is to have a truly spherical shape,
The object of the present invention is to provide a method for producing silica particles that can produce particles with a uniform particle size of about 0.1 to 2 μm. [Means for Solving the Problems] That is, the present invention provides a method for hydrolyzing alkoxysilanes in a mixed solution of water and ammonia or alcohol added thereto, using a stirring power of 0.02 kw/m 3 per unit volume. This is a method for producing silica particles in which a reaction mixture is stirred under the above stirring conditions and a Reynolds number of 5000 or more. Examples of the alkoxysilanes used in the present invention include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane. Any type of silane may be used, but it is preferably one having an alkoxy group having 1 to 4 carbon atoms, and tetramethoxysilane and tetraethoxysilane, which have a high reaction rate during a hydrolysis reaction, are particularly preferred. In the present invention, the hydrolysis of alkoxysilanes is carried out using a solution of water and ammonia or a solution in which alcohol is added to these, and the alcohol used at this time includes methyl alcohol, ethyl alcohol, and propyl alcohol. ,
Examples include butyl alcohol, phenol, and benzyl alcohol. Hydrolysis of alkoxysilanes is possible by contacting them with water in the presence of ammonia. Specifically, for example, there is a method in which tetraalkoxysilanes are added dropwise to the above-mentioned mixed solution while sufficiently stirring it. Regarding the liquid temperature during hydrolysis, an appropriate temperature can be selected as required, but room temperature is also possible. This hydrolysis results in an average particle size of 0.05 to 2.0 μm.
A sol can be obtained containing monodisperse spherical silica particles in the range of . The particle size of the silica particles can be controlled by controlling the concentrations of water and ammonia in the solution used for hydrolysis, the type and concentration of alkoxysilane, the dropping rate of alkoxysilane, the reaction temperature, etc. On the other hand, the particle size and particle size distribution are also affected by the stirring state of the solution. If stirring is insufficient, the particle size tends to increase and the distribution tends to become broad. In addition, the relationship between Reynolds number and particle size is as follows, where Reynolds number is Re.
When the particle size is R, approximately R=K/Re (however, K
is a constant), and this Reynolds number is 5000
If it is less than this, the average particle size of the silica particles produced will largely depend on the stirring conditions. Therefore, the viscosity of the solution inevitably changes as the solid content concentration, solution composition, temperature, etc. change during the reaction, and when the stirring conditions change due to the change in the viscosity of the solution, the average particle size of the silica particles produced also changes. I will do it. Therefore, the Reynolds number needs to be in a range where changes in stirring conditions have little effect on the average particle size, that is, 5,000 or more, preferably 10,000 or more. Furthermore, even if the Reynolds number is 10,000 or more, if the required stirring power per unit volume is small, monodispersity deteriorates and aggregation between particles is likely to occur. Therefore,
The power required for stirring per unit volume must be 0.02kw/m 3 or more. In the case of a tank-type reactor, methods for increasing the required stirring power per unit volume include, for example, changing the blade conditions such as the shape, width, and number of stages of the stirring blade, increasing the rotation speed, and installing baffles. For example, in a tube reactor, methods such as increasing the flow rate are effective. [Examples] The present invention will be specifically described below based on Examples and Comparative Examples. Examples 1 to 3 and Comparative Examples 1 and 2 180 parts by weight of water, 54 parts by weight of ammonia and 416 parts by weight of methanol were charged into a round bottom reaction tank, and while mixing under the stirring conditions shown in Table 1, 381 parts by weight of tetramethoxysilane was added. dropwise into the solution over 100 minutes,
Furthermore, after the completion of the dropwise addition, stirring was continued for 60 minutes to produce silica particles. The particle size distribution of the obtained silica particles was measured using a light transmission type particle size distribution meter.
The results are shown in Table 1.
【表】
［発明の効果］
本発明方法によれば、真球状であつて、凝集が
少なく単分散性に優れた0.1〜2μｍ程度の大きさ
で粒径の揃つた球状シリカ粒子を製造することが
できる。[Table] [Effects of the Invention] According to the method of the present invention, it is possible to produce spherical silica particles that are perfectly spherical, have a uniform particle size of about 0.1 to 2 μm, and have low agglomeration and excellent monodispersity. I can do it.
Claims (1)
はこれらにアルコールを加えた混合溶液中で加水
分解するに際し、単位体積当りの攪拌所要動力
0.02kw／m3以上及びレイノルズ数5000以上の攪
拌条件で反応混合物を攪拌することを特徴とする
シリカ粒子の製造方法。 ２ レイノルズ数が10000以上である請求項１記
載のシリカ粒子の製造方法。[Scope of Claims] 1. Power required for stirring per unit volume when hydrolyzing alkoxysilanes in a mixed solution of water and ammonia or alcohol added thereto.
A method for producing silica particles, characterized by stirring a reaction mixture under stirring conditions of 0.02 kw/m 3 or more and a Reynolds number of 5000 or more. 2. The method for producing silica particles according to claim 1, wherein the Reynolds number is 10,000 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63273170A JPH02120221A (en) | 1988-10-31 | 1988-10-31 | Production of silica particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63273170A JPH02120221A (en) | 1988-10-31 | 1988-10-31 | Production of silica particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02120221A JPH02120221A (en) | 1990-05-08 |
| JPH052607B2 true JPH052607B2 (en) | 1993-01-12 |
Family
ID=17524074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63273170A Granted JPH02120221A (en) | 1988-10-31 | 1988-10-31 | Production of silica particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02120221A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4895556B2 (en) * | 2005-09-07 | 2012-03-14 | 株式会社トクヤマ | Method for producing silica-based oxide particles |
| JP5704740B2 (en) * | 2009-10-23 | 2015-04-22 | 株式会社日本触媒 | Method for producing organic-inorganic composite particles |
| JP5558796B2 (en) * | 2009-12-03 | 2014-07-23 | 株式会社日本触媒 | Method for producing fine particles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5841810A (en) * | 1981-09-07 | 1983-03-11 | Tokuyama Soda Co Ltd | Composite reparative material |
| JPS6272514A (en) * | 1985-09-25 | 1987-04-03 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Spherical sio2 particle |
| JPS62207356A (en) * | 1986-03-07 | 1987-09-11 | Nippon Shokubai Kagaku Kogyo Co Ltd | Method of improving slipperiness |
| JPS6374911A (en) * | 1986-09-19 | 1988-04-05 | Shin Etsu Chem Co Ltd | Production of fine spherical silica |
-
1988
- 1988-10-31 JP JP63273170A patent/JPH02120221A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5841810A (en) * | 1981-09-07 | 1983-03-11 | Tokuyama Soda Co Ltd | Composite reparative material |
| JPS6272514A (en) * | 1985-09-25 | 1987-04-03 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Spherical sio2 particle |
| JPS62207356A (en) * | 1986-03-07 | 1987-09-11 | Nippon Shokubai Kagaku Kogyo Co Ltd | Method of improving slipperiness |
| JPS6374911A (en) * | 1986-09-19 | 1988-04-05 | Shin Etsu Chem Co Ltd | Production of fine spherical silica |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02120221A (en) | 1990-05-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |