JPH02120221A - Production of silica particle - Google Patents
Production of silica particleInfo
- Publication number
- JPH02120221A JPH02120221A JP63273170A JP27317088A JPH02120221A JP H02120221 A JPH02120221 A JP H02120221A JP 63273170 A JP63273170 A JP 63273170A JP 27317088 A JP27317088 A JP 27317088A JP H02120221 A JPH02120221 A JP H02120221A
- Authority
- JP
- Japan
- Prior art keywords
- stirring
- ammonia
- particle diameter
- silica particles
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 title abstract description 33
- 239000000377 silicon dioxide Substances 0.000 title description 2
- 238000003756 stirring Methods 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 239000012798 spherical particle Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000013459 approach Methods 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
- 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
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、粒径の揃った真球状シリカ粒子を製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing truly spherical silica particles having uniform particle sizes.
［従来の技術１
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って０．０５〜１１ＪＲの比
較的粒径の揃ったシリカ球状粒子を得る方法が知られて
いる（Ｗ、 ５ｔ５ｂｅｒ、 Ａ、 Ｆｉｎｋ ａｎｄ
Ｅ、 Ｂｏｈｎ； Ｊ、 Ｃｏ１１ｏｉｄ Ｉｎｔｅｒ
ｆａｃｅ Ｓｃｉ、、 ２６． ｐ６２（１９６８））
。[Prior art 1] A method is known in which silica spherical particles with a relatively uniform particle size of 0.05 to 11 JR are obtained by hydrolyzing alkoxysilane in a water, ammonia and alcohol solution (W, 5t5ber, A, Fink and
E, Bohn; J, Co11oid Inter
face 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１１度等
によってコントロールできる。At this time, the particle size of the silica particles produced can be controlled by the ammonia concentration in the reaction solution, the type of alkoxysilane, 11 degrees, etc.
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っても左右される
。特に、粒子成長が進み、粒子径が１虜に近づくにつれ
、粒子間に凝集が進んで大きな粒子となったり、ついに
は、溶液が粘稠になっ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
。However, when the stirring power is insufficient, the average particle size and particle size distribution of the produced particles are also influenced by the stirring conditions. In particular, as particle growth progresses and the particle size approaches a single particle size, aggregation between particles may progress to form large particles, or the solution may eventually become viscous and cause gelation. Furthermore, as the particle size increases, monodispersity also decreases.
ところで、近年、ＰＥ丁フィルムの滑剤としてのフィラ
ーや液晶パネルのギャップ剤等として、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。Incidentally, in recent years, particles with high monodispersity have been required for use as fillers as lubricants in PE films, gap agents in liquid crystal panels, etc., and particles produced by the above-mentioned method may not always be sufficient. .
［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
行った結果、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／ｉ３以上であ
って、レイノルズ数が５．０００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。[Problems to be Solved by the Invention] As a result of research conducted by the present inventors to solve such problems, the power required for stirring per unit volume when supplying alkoxysilanes was 0.02 kW. /i3 or more and the Reynolds number is 5.000 or more, it was discovered that the monodispersity of the produced particles was improved, and the present invention was completed.
従って、本発明の目的は、真球状であって、０゜１〜２
虜程度の大きさで、粒径の揃った粒子を製造することが
できるシリカ粒子の！Ｉ！造方法を提供することにある
。Therefore, the object of the present invention is to have a true spherical shape with an angle of 0°1 to 2
Silica particles that are about the same size and have uniform diameter can be produced! I! The goal is to provide a method for creating
［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５，０００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。[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 a mixed solution of water and ammonia or an alcohol added thereto, while reducing the stirring power required per unit volume to 0.
This is a method for producing silica particles in which a reaction mixture is stirred under stirring conditions of 0.02 kw/m3 or more and a Reynolds number of 5,000 or more.
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、テトラフェ
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。Examples of the alkoxysilanes used in the present invention include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane. However, it is preferable to have 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 preferable.
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おり、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、フェノール、ベ
ンジルアルコール等がある。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 alcohols used at this time include methyl alcohol, ethyl alcohol, and propyl alcohol. , butyl alcohol, phenol, benzyl alcohol, etc.
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。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.
この加水分解により、平均粒径が０．０５〜２゜０ｔｓ
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
（゛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って制御可能であるが、一方で、溶
液の攪拌状態によっても、その粒径ヤ粒度分布が影響を
受ける。Through this hydrolysis, the average particle size is reduced to 0.05~2゜0ts.
It is possible to obtain a sol containing monodispersed spherical silica particles in the range of This can be controlled by controlling the dropping rate, reaction temperature, etc., but on the other hand, the particle size and particle size distribution are also influenced by the stirring state of the solution.
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＝に／Ｒｅ （但し、Ｋは定数）の関係を有し
、このレイノルズ数が５゜０００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。従って、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５５，０００以上、好ましくは１０，
０００以上の領域である必要がある。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, when Reynolds number is Re and particle size is R.
Generally, there is a relationship of R=/Re (where K is a constant), and when this Reynolds number is less than 5.000, the average particle size of the produced silica particles largely depends 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, regarding the Reynolds number, change in stirring conditions has little effect on the average particle size, that is, 55,000 or more, preferably 10,
It must be in an area of 000 or more.
また、レイノルズ数が１０，０００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。従って、単位体積当りの
攪拌所要動力は０．０２ｋｗ／ＴｒＬ３以上にする必要
がある。Furthermore, even if the Reynolds number is 10,000 or more, if the required stirring power per unit volume is small, the monodispersity will deteriorate;
Aggregation between particles is likely to occur. Therefore, the power required for stirring per unit volume needs to be 0.02 kw/TrL3 or more.
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、種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、回転数のアップや、邪魔板の取
付等等の手段が有効であり、また、チューブ式反応器で
は、例えば流速を速くする方法等の手段が有効である。In the case of a seed reactor, methods for increasing the required stirring power per unit volume include, for example, the shape of the stirring blades,
Measures such as changing blade conditions such as width and number of stages, increasing the number of revolutions, and installing baffles are effective, and in the case of a tube reactor, measures such as increasing the flow rate are effective.
［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。[Examples] The present invention will be specifically described below based on Examples and Comparative Examples.
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３８１１ｍ
部を１００分間かけて溶液中に滴下し、ざらに滴下終了
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。Examples 1 to 3 and Comparative Example 1.2 180 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, 3811 m of tetramethoxysilane was added.
was dropped into the solution over 100 minutes, and after the dropwise addition was completed, 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.
［発明の効果］
本発明方法によれば、真球状であって、凝集が少なく単
分散性に優れた０、１〜２μｓ程度の大きざで粒径の揃
った球状シリカ粒子を製造することができる。[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 μs, and have low agglomeration and excellent monodispersity. can.
特許出願人 新日鐵化学株式会社Patent applicant: Nippon Steel Chemical Co., Ltd.
Claims (2)
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／ｍ＾
３以上及びレイノルズ数５，０００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。(1) When hydrolyzing alkoxysilanes in a mixed solution of water and ammonia or alcohol added to these, the required stirring power per unit volume is 0.02 kw/m^
A method for producing silica particles, which comprises stirring a reaction mixture under stirring conditions of 3 or more and a Reynolds number of 5,000 or more.
記載のシリカ粒子の製造方法。(2) Claim 1 whose Reynolds number is 10,000 or more
A method for producing the described silica particles.
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 true JPH02120221A (en) | 1990-05-08 |
| JPH052607B2 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070163A (en) * | 2005-09-07 | 2007-03-22 | Tokuyama Corp | Method for producing silica-based oxide particle |
| JP2011089069A (en) * | 2009-10-23 | 2011-05-06 | Nippon Shokubai Co Ltd | Method for producing organic-inorganic composite particle |
| JP2011116864A (en) * | 2009-12-03 | 2011-06-16 | Nippon Shokubai Co Ltd | Method for producing fine particle |
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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070163A (en) * | 2005-09-07 | 2007-03-22 | Tokuyama Corp | Method for producing silica-based oxide particle |
| JP2011089069A (en) * | 2009-10-23 | 2011-05-06 | Nippon Shokubai Co Ltd | Method for producing organic-inorganic composite particle |
| JP2011116864A (en) * | 2009-12-03 | 2011-06-16 | Nippon Shokubai Co Ltd | Method for producing fine particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH052607B2 (en) | 1993-01-12 |
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