JPH0421515A - Production of mono-dispersed silica particle - Google Patents
Production of mono-dispersed silica particleInfo
- Publication number
- JPH0421515A JPH0421515A JP2122403A JP12240390A JPH0421515A JP H0421515 A JPH0421515 A JP H0421515A JP 2122403 A JP2122403 A JP 2122403A JP 12240390 A JP12240390 A JP 12240390A JP H0421515 A JPH0421515 A JP H0421515A
- Authority
- JP
- Japan
- Prior art keywords
- silicic acid
- water
- dispersion
- silica particles
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000377 silicon dioxide Substances 0.000 title abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 54
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052681 coesite Inorganic materials 0.000 abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 210000002858 crystal cell Anatomy 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 125000006850 spacer group Chemical group 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 47
- 235000019441 ethanol Nutrition 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
鏝肌ｐ腹ｆ遺１
本発明は、粒度分布がシャープであり、かつ単分散され
たシリカ粒子の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing silica particles having a sharp particle size distribution and being monodispersed.
日の技術的背景
粒度分布がシャープなシリカ粒子は、セラミック原料、
樹脂用フィラー 液晶セル用スペーサなどにその用途が
期待されている。特に、粒径が０．１μｍ以上と大きく
、しかもその粒度分布がシャープであるシリカ粒子は液
晶セル用のスペーサとしての用途が期待されている。Technical Background Silica particles with a sharp particle size distribution are ceramic raw materials,
It is expected to find use in fillers for resins and spacers for liquid crystal cells. In particular, silica particles, which have a large particle size of 0.1 μm or more and a sharp particle size distribution, are expected to be used as spacers for liquid crystal cells.
上記のようなシリカ粒子を製造するには、従来水−アル
コール系溶媒中でアルコキシシランなどをアルカリ触媒
の存在下で加水分解させる方法が知られている。In order to produce the above-described silica particles, a conventional method is known in which an alkoxysilane or the like is hydrolyzed in a water-alcoholic solvent in the presence of an alkali catalyst.
このような方法として、たとえば本発明者らは、特開昭
６２−２７５００５号公報において、粒子成長の核とな
るシードが分散された水−アルコール系溶媒中で、アル
コキシシラン等の金属アルコキシドを加水分解させ、加
水分解物をこのシード上に付着させて粒子を成長させる
ことにより、粒径が大きく、しかも単分散された粒子を
得る方法を開示している。As such a method, for example, the present inventors have disclosed in Japanese Unexamined Patent Publication No. 62-275005 that a metal alkoxide such as an alkoxysilane is hydrated in a water-alcohol solvent in which seeds that serve as nuclei for particle growth are dispersed. A method is disclosed for obtaining monodispersed particles with a large particle size by decomposing the seeds and depositing a hydrolyzate on the seeds to grow the particles.
この方法によれば、粒径が０．１〜１０μｍ程度と大き
く、かつ粒度分布がシャープな単分散されたシリカ粒子
が得られる。According to this method, monodispersed silica particles having a large particle size of about 0.1 to 10 μm and a sharp particle size distribution can be obtained.
ところで上記のような方法では、粒子の成長過程または
生成粒子が沈降したとき粒子の一部が凝集することがあ
る。もしこのように凝集した粒子が生成すると、超音波
等で分散処理を施しても再分散が困難となり、得られる
粒子は粒径が不均一になりやすくなる。このため粒子の
成長過程あるいは生成粒子が沈降したときに粒子が凝集
することがなく、より均一でしかも安定であり、かつ単
分散された粒子の製造方法の出現が望まれている。However, in the above method, some of the particles may aggregate during the growth process of the particles or when the produced particles settle. If such agglomerated particles are generated, it becomes difficult to redisperse them even if a dispersion treatment is performed using ultrasonic waves or the like, and the resulting particles tend to have non-uniform particle sizes. Therefore, it is desired to develop a method for producing particles that are more uniform, stable, and monodispersed without agglomeration during the particle growth process or when the produced particles settle.
兄」用ｐ□叫庇
本発明は上記のような従来技術に鑑みてなされたもので
あって、粒度分布がシャープであり、かつ単分散された
シリカ粒子を製造しうるようなシリカ粒子の製造方法を
提供することを目的としている。The present invention has been made in view of the above-mentioned conventional technology, and is directed to the production of silica particles that have a sharp particle size distribution and can produce monodispersed silica particles. The purpose is to provide a method.
発」トλ欅−叉
本発明に係る単分散されたシリカ粒子の製造方法は、金
属酸化物あるいは金属水酸化物がシードとして分散され
た水−アルコール系分散液に、該分散液をアルカリ性に
保ちながらテトラアルコキシシランおよびケイ酸液を添
加して、テトラアルコキシシラン加水分解生成物および
ケイ酸重合物を前記シード上に付着させ粒子成長を行な
わせることを特徴としている。The method for producing monodispersed silica particles according to the present invention involves adding a water-alcohol dispersion in which a metal oxide or metal hydroxide is dispersed as a seed, and making the dispersion alkaline. It is characterized in that tetraalkoxysilane and silicic acid liquid are added while maintaining the temperature, so that the tetraalkoxysilane hydrolysis product and silicic acid polymer are deposited on the seeds and particles are grown.
本発明によれば、粒径が大きく、しかも粒度分布がシャ
ープであり、かつ単分散されたシリカ粒子を効率よく得
ることができる。さらに反応系中の酸化物換算の粒子濃
度を高めることができるため、粒子の製造コストを低下
させることができるという効果も得られる。According to the present invention, it is possible to efficiently obtain monodispersed silica particles that have a large particle size, a sharp particle size distribution, and are monodispersed. Furthermore, since the concentration of particles in terms of oxides in the reaction system can be increased, it is also possible to reduce the manufacturing cost of the particles.
日の、体的説明
以下本発明に係る単分散されたシリカ粒子の製造方法に
ついて具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION The method for producing monodispersed silica particles according to the present invention will be specifically described below.
本発明では、まず金属酸化物あるいは金属水酸化物がシ
ードとして分散された水−アルコール系分散液（以下ヒ
ールゾルと称することがある）を調製する。In the present invention, first, a water-alcohol dispersion (hereinafter sometimes referred to as heel sol) in which metal oxides or metal hydroxides are dispersed as seeds is prepared.
本発明ではシードとして、金属酸化物粒子あるいは金属
水酸化物粒子が用いられる。このようなシードとしては
、 目的とするシリカ粒子の粒径より若干小さく均一な
粒径を有するＳｉＯ２，Ａｌ２Ｏ。In the present invention, metal oxide particles or metal hydroxide particles are used as seeds. Such seeds include SiO2 and Al2O, which have a uniform particle size slightly smaller than the target silica particle size.
Ｔｉｏ、 Ｚｒｏ２などの粒子を用いることができる
。Particles such as Tio and Zro2 can be used.
また、場合によっては金属酸化物粒子、金属水酸化物粒
子以外の粒径の揃った粒子を用いることもできる。Further, depending on the case, particles other than metal oxide particles and metal hydroxide particles with a uniform particle size can also be used.
このようなシードが分散された水−アルコール系分散液
（ヒールゾル）は、水−アルコール系混合溶液にシード
を添加して調製してもよく、また水−アルコール系混合
液中でシードとなる粒子を生成させて調製してもよい。A water-alcohol dispersion (heal sol) in which such seeds are dispersed may be prepared by adding seeds to a water-alcohol mixed solution, or particles serving as seeds in a water-alcohol mixed solution may be prepared. It may also be prepared by producing.
このうち後者によるヒールゾルが好ましく用いら汰 た
とえば水−アルコール系混合液中で、アルコキシシラン
などの金属アルコキシドを常法に従って加水分解するこ
とによって得られるシリカ粒子などの金属酸化物粒子を
、シードとして分散させた水−アルコール系分散液が好
ましく用いられる。シードの生成方法は、たとえば「粉
体及び粉体冶金Ｊ２３．（４）１９〜２４ （１９７６
）などに記載されている。Among these, the latter type of heel sol is preferably used. For example, metal oxide particles such as silica particles obtained by hydrolyzing a metal alkoxide such as alkoxysilane according to a conventional method in a water-alcohol mixture are dispersed as seeds. Preferably, a water-alcoholic dispersion solution containing water is used. Seed generation methods are described, for example, in "Powder and Powder Metallurgy J23. (4) 19-24 (1976
) etc.
このようにして得られるヒールゾルは、シードが凝集す
るのを防ぐため、ｐＨをアルカリ性にする方が好ましい
。It is preferable that the pH of the heel sol obtained in this manner be alkaline in order to prevent the seeds from aggregating.
ヒールゾル中でのアルコール濃度は３５〜９７重量％で
あることが好ましい。ここで用いられるアルコールとし
ては、メタノール、エタノール、ｎ−プロパツール、
イソプロパツール、ｎ−ブタノール、イソブタノールな
どの低級アルコールが挙げられる。これらは単独で、ま
たはこれらの混合溶媒として用いることができる。The alcohol concentration in the heel sol is preferably 35 to 97% by weight. Alcohols used here include methanol, ethanol, n-propanol,
Examples include lower alcohols such as isopropanol, n-butanol, and isobutanol. These solvents can be used alone or as a mixed solvent.
また、水−アルコール系分散液として、水およびアルコ
ールに加えて、他の有機溶媒を用いることもできる。こ
のような有機溶媒としては、水およびアルコールと相溶
性がよく、しかもテトラアルコキシシランおよびケイ酸
液との相溶性がよいものが用いられる。In addition to water and alcohol, other organic solvents can also be used as the water-alcohol dispersion. As such an organic solvent, one is used that has good compatibility with water and alcohol, and also has good compatibility with tetraalkoxysilane and silicic acid liquid.
ヒールゾル中でのシードの濃度は、酸化物換算濃度で
０．０５〜２０重量％であることが好ましい。シードの
酸化物換算濃度が０．０５重量％未満であると、後述す
る粒子を成長させる過程で、新たなシードが発生するこ
とがあり、得られるシリカ粒子の粒径が不均一になりや
すい。一方シードの酸化物換算濃度が２０重量％を超え
ると、粒子成長過程で粒子同士が凝集しやすくなり、粒
径の均一性に影響を及ぼすようになる。The concentration of seeds in the heel sol is expressed as an oxide concentration.
It is preferably 0.05 to 20% by weight. If the oxide concentration of the seeds is less than 0.05% by weight, new seeds may be generated in the process of growing particles, which will be described later, and the particle size of the obtained silica particles tends to be non-uniform. On the other hand, if the oxide concentration of the seeds exceeds 20% by weight, the particles tend to aggregate together during the particle growth process, which affects the uniformity of particle size.
次に、上記のようにして得られたヒールゾルをアルカリ
性に保ちながら、テトラアルコキシシランおよびケイ酸
液を添加する。Next, tetraalkoxysilane and silicic acid solution are added to the heel sol obtained as described above while keeping it alkaline.
本発明で用いられるテトラアルコキシシランは、一般式
５ｉ（ＯＲ）、で表わすことができる。The tetraalkoxysilane used in the present invention can be represented by the general formula 5i(OR).
式中、Ｒは炭素数１〜７のアルキル基であり、好ましく
は炭素数１〜４のアルキル基である。このようなテトラ
アルコキシシランとしては、具体的に、テトラメトキシ
シラン（メチルシリケート）、テトラエトキシシラン（
エチルシリケート）、テトライソプロポキシシラン、テ
トラブトキシシランなどが挙げられる。In the formula, R is an alkyl group having 1 to 7 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Specifically, such tetraalkoxysilanes include tetramethoxysilane (methyl silicate), tetraethoxysilane (
(ethyl silicate), tetraisopropoxysilane, tetrabutoxysilane, etc.
テトラアルコキシシランはそのまま用いてもよく、また
アルコールなどで希釈して用いてもよい。Tetraalkoxysilane may be used as it is, or may be diluted with alcohol or the like.
また本発明で用いられるケイ酸液は、ケイ酸低重合物の
水溶液であり、具体的には、たとえばケイ酸ナトリウム
などのアルカリケイ酸塩水溶液を、陽イオン交換樹脂な
どで脱アルカリして得られる。Furthermore, the silicic acid liquid used in the present invention is an aqueous solution of a low polymerized silicic acid, and specifically, it is obtained by dealkalizing an aqueous alkali silicate solution such as sodium silicate with a cation exchange resin or the like. It will be done.
ケイ酸液は、５１０２濃度として約 ０．１−１０重量
％のものが好ましく用いられる。The silicic acid solution preferably has a 5102 concentration of about 0.1-10% by weight.
本発明において、上記のようなテトラアルコキシシラン
とケイ酸液とを前記のヒールゾルに添加するに際しては
、■両者を同時に添加する方法、■数回にわたって両者
を交互に添加する方法、■当初テトラアルコキシシラン
のみを添加して粒子成長を行わせ最後にケイ酸液を添加
する方法など任意の方法を採用することができる。In the present invention, when adding the above-described tetraalkoxysilane and silicic acid liquid to the heel sol, there are two methods: (1) adding both at the same time, (2) adding both alternately several times, (2) initially Any method can be used, such as adding only silane to cause particle growth and finally adding silicic acid solution.
これらのうち、両者を別々に添加する方法が好ましく、
■交互に添加する方法が好ましく用いらＬ 分散液およ
び生成粒子が安定性よく得られる。Among these, the method of adding both separately is preferred;
(2) A method in which L is added alternately is preferably used, whereby the dispersion and the resulting particles can be obtained with good stability.
■の方法が用いられるときは、それぞれの１回の添加量
は特に制限なく、任意の量を交互に添加することができ
る。When method (2) is used, there is no particular restriction on the amount of each addition at one time, and arbitrary amounts can be added alternately.
本発明においては、最終的に得られるシリカ粒子の最外
層が、ケイ酸重合物で形成されることが好ましく、最終
添加時はケイ酸液を用いることが好ましい。In the present invention, it is preferable that the outermost layer of the silica particles finally obtained is formed of a silicic acid polymer, and it is preferable to use a silicic acid liquid at the time of final addition.
上記のような方法で、ヒールゾルにテトラアルコキシシ
ランおよびケイ酸液を添加すると、テトラアルコキシシ
ランの加水分解反応とケイ酸の重合反応が起こり、これ
らの反応物がシード上に沈着し、粒子の成長が行われる
。また、このとき反応系のｐＨが低下して中性に近づく
と、粒子の凝集が起こりやすくなるだけでなく新たなシ
ードが生成しやすくなるので、最終的に得られる粒子は
粒径が不均一になりやすい。このため、テトラアルコキ
シシランおよびケイ酸液を添加するに際しては、分散液
のｐＨ値を９〜１４好ましくは１０〜１３に保持するこ
とが好ましい。分散液のｐＨ値は、上記の範囲内でなる
べく変動しない方が好ましい。When tetraalkoxysilane and silicic acid liquid are added to Heal Sol using the method described above, a hydrolysis reaction of the tetraalkoxysilane and a polymerization reaction of silicic acid occur, and these reactants are deposited on the seeds, causing particle growth. will be held. In addition, when the pH of the reaction system decreases and approaches neutrality, not only does particle aggregation become more likely to occur, but also new seeds are more likely to be generated, so the final particles have non-uniform particle sizes. easy to become. Therefore, when adding the tetraalkoxysilane and the silicic acid liquid, it is preferable to maintain the pH value of the dispersion liquid at 9 to 14, preferably 10 to 13. It is preferable that the pH value of the dispersion liquid does not fluctuate as much as possible within the above range.
分散液をアルカリ性に保つには、反応系にアルカリを添
加すればよく、具体的には、アンモニアガス、アンモニ
ア木 アミン瓜 アルカリ金属水酸化物、第４級アンモ
ニウム塩などが単独あるいは組合せて用いられる。To keep the dispersion alkaline, it is sufficient to add an alkali to the reaction system. Specifically, ammonia gas, ammonia wood, alkali metal hydroxide, quaternary ammonium salt, etc. are used alone or in combination. .
また、粒子成長過程における反応系温度は、特に限定さ
れないが、水またはアルコールの沸点以上の温度で行わ
れる場合には、溶液が液相を保持できるように加圧する
ことが好ましい。Further, the temperature of the reaction system during the particle growth process is not particularly limited, but when the reaction is carried out at a temperature equal to or higher than the boiling point of water or alcohol, it is preferable to apply pressure so that the solution can maintain a liquid phase.
本発明において、反応系中でのアルコール濃度は、 ３
５〜９７重量％であることが好ましい。アルコール濃度
が３５重量％未満であると、テトラアルコキシシランと
の相溶性が低下しヒールゾルがエマルジョン化しやすく
、シードが凝集したりあるいは球状でない不定形生成分
を生じやすくなる。一方アルコール溶液が９７重量％を
越えるとテトラアルコキシシランの加水分解速度が遅く
なる。In the present invention, the alcohol concentration in the reaction system is 3
It is preferably 5 to 97% by weight. When the alcohol concentration is less than 35% by weight, the compatibility with the tetraalkoxysilane decreases, the heel sol tends to emulsify, and the seeds tend to aggregate or form amorphous components that are not spherical. On the other hand, if the alcohol solution exceeds 97% by weight, the rate of hydrolysis of the tetraalkoxysilane becomes slow.
反応系中のアルコール濃度は、反応系中に水およびアル
コールを添加することにより調節するが、このときそれ
ぞれの添加量は、テトラアルコキシシラン（Ｓｉｎ２換
算）１モルに対し、水２．０〜２４．０モル、アルコー
ル０．４−１．１モルの量で添加されることが望ましい
。The alcohol concentration in the reaction system is adjusted by adding water and alcohol to the reaction system, and at this time, the amount of each added is 2.0 to 24 Preferably, the alcohol is added in an amount of 0.4-1.1 moles.
このようにして得られる水−アルコール系分散媒に分散
されたシリカ粒子は、金属酸化物または金属水酸化物を
核としたテトラアルコキシシランの加水分解縮合物とケ
イ酸重合物からなり、両者が混在した構造、両者の層が
交互に積層した構造またはアルコキシシラン加水分解縮
合物からなる粒子の最外層がケイ酸重合物の層で被覆さ
れた構造を有することができる。本発明においては、上
記いずれの構造の場合もその最外層はケイ酸重合物から
なる層であることが好ましい。The silica particles dispersed in the water-alcohol dispersion medium obtained in this manner are composed of a hydrolyzed condensate of tetraalkoxysilane with a metal oxide or metal hydroxide as the core, and a silicic acid polymer, and both are It may have a mixed structure, a structure in which both layers are alternately laminated, or a structure in which the outermost layer of particles made of an alkoxysilane hydrolysis condensate is coated with a layer of silicic acid polymer. In the present invention, in any of the above structures, the outermost layer is preferably a layer made of a silicic acid polymer.
上記のようなシリカ粒子は、球状で、かつ粒度分布がシ
ャープであり、分散媒中で凝集せずに単分散されている
。また、平均粒径が約０．０１μｍの小粒径から１０μ
ｍ以上の大粒径まで任意の粒径を有する粒子を得ること
ができる。分散媒中の粒子の濃度は、５ｉ０２換算で約
２Ｑ、０重量％の高濃度とすることが可能であり、従
来の製造方法と比較して著しく高くすることが可能であ
る。したがってシリカ粒子の製造効率を高めることがで
き、製造コストの低減を図ることもできる。The silica particles described above are spherical and have a sharp particle size distribution, and are monodispersed without agglomerating in a dispersion medium. In addition, the average particle size ranges from about 0.01μm to 10μm.
Particles having any size up to a large particle size of m or more can be obtained. The concentration of particles in the dispersion medium can be as high as about 2Q or 0% by weight in terms of 5i02, and can be significantly higher than in conventional production methods. Therefore, the production efficiency of silica particles can be increased, and production costs can also be reduced.
また本発明によって得られたシリカ粒子が単分散された
分散液は、さらに濃縮することによって、粒子の濃度を
約 ６０．０重量％まで高めることができる。Further, by further concentrating the monodispersed silica particles obtained by the present invention, the particle concentration can be increased to about 60.0% by weight.
本発明により得られた分散液に単分散されたシリカ粒子
の安定性をさらに高めるには、得られた分散液中に、ア
ルカリなとの安定剤を添加することができ、このように
熟成処理を施こすことにより長期間にわたって分散液中
の粒子が凝集したりすることがない。また分散液中のア
ルコールヲ別の有機溶媒に置換することもできる。In order to further increase the stability of the silica particles monodispersed in the dispersion obtained according to the present invention, an alkaline stabilizer can be added to the dispersion obtained, and the aging treatment is performed in this way. This prevents the particles in the dispersion from agglomerating over a long period of time. Further, the alcohol in the dispersion can also be replaced with another organic solvent.
１更辺羞遇
本発明で得られるシリカ粒子は、テトラアルコキシシラ
ンの加水分解縮合物とケイ酸重合物が混在あるいは交互
に積層した構造であり、特に最外層がケイ酸重合物の層
がらなっていることが好ましい。1. Further Disapproval The silica particles obtained in the present invention have a structure in which a hydrolyzed condensate of tetraalkoxysilane and a silicic acid polymer are mixed or alternately laminated, and in particular, the outermost layer is composed of a silicic acid polymer layer. It is preferable that
従って、従来の方法で得られたシリカ粒子と比較して、
粒子の凝集が少なく単分散度が一層向上したシリカ粒子
が得られる。Therefore, compared to silica particles obtained by conventional methods,
Silica particles with less particle aggregation and further improved monodispersity can be obtained.
さらに、本発明の単分散されたシリカ粒子は、乾燥して
用いても乾燥粒子相互の凝集力が弱く、静電気を帯びに
くく、粉体としての流動性に優れている。このため、た
とえば乾式散布等に好適な粉体が得られる。Furthermore, even when the monodispersed silica particles of the present invention are used after drying, the cohesive force between the dry particles is weak, they are not easily charged with static electricity, and they have excellent fluidity as a powder. Therefore, a powder suitable for, for example, dry spraying can be obtained.
以下本発明を実施例により説明するが、本発明はこれら
実施例に限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.
矢廠旦１
エチルアルコール４８７ｇ、２８％アンモニア水２５６
ｇおよび水２０５ｇからなる混合溶液を３５℃に保ちな
がら攪拌し、これにエチルシリケト（Ｓ１０２として２
８重量％）を １７．５ ｇを加えた その後、 ２時
間攪拌を続け、５１０２として ０．５重量％に相当す
るシリカ粒子が分散したヒールゾルを得へ
このヒールゾル９７４ｇを３５℃に保ちながら攪拌し
これにまずケイ酸液（Ｓ１０２としての濃度は ５．０
重量％）２ｇを徐々に添加し 次いでエチルアルコール
／水混合溶液（重量比１．Ｏｌｏ、８）４７ｇおよびエ
チルシリケート（ＳｉＯ２として２８重量％） １０
．５ｇを同時に徐々に添加した。この際、反応液のｐＨ
をアンモニアガスによって１１，５に維持した
上記添加操作を繰り返し、得られるシリカ粒子の最外層
がケイ酸液による重合物の層となるようにして、 １９
時間かけて所定量を添加し八 それぞれの全添加量は、
ケイ酸液１１７ｇ、エチルアルコール／水混合液 ２６
９８．５ｇおよびエチルシリケート６０６ｇであった
全量添加終了後、反応液に１重量％のＮａＯＨ水溶液２
０４ｇを加え、７０℃で２時間保持し、シリカ粒子が単
分散された分散液を得ｆ。Yahagi Dan 1 ethyl alcohol 487g, 28% ammonia water 256
A mixed solution consisting of g and 205 g of water was stirred while keeping it at 35°C, and to this was added ethyl silicate (205 g as S102).
After that, stirring was continued for 2 hours to obtain a heel sol in which silica particles equivalent to 0.5 wt% as 5102 were dispersed. 974 g of this heel sol was stirred while keeping it at 35 °C.
First, add silicic acid liquid (concentration as S102 is 5.0
Then 47 g of ethyl alcohol/water mixed solution (weight ratio 1.Olo, 8) and ethyl silicate (28 wt% as SiO2) were gradually added 10
．． 5g were added slowly at the same time. At this time, the pH of the reaction solution
By repeating the above addition operation in which the amount of silica particles was maintained at 11.5 with ammonia gas, the outermost layer of the obtained silica particles became a layer of polymerized silicic acid solution, and 19
The total amount of each addition is as follows:
117g of silicic acid liquid, ethyl alcohol/water mixture 26
After completing the addition of 98.5 g of ethyl silicate and 606 g of ethyl silicate, 1% by weight NaOH aqueous solution 2
04g was added and held at 70°C for 2 hours to obtain a dispersion in which silica particles were monodispersed f.
なおここで用いたケイ酸液は、水ガラス（ＳｉＯ２とし
て２４重量％、ＳｉＯ２／Ｎａ、、Ｏがモル比で３）を
５１０２濃度が５重量％となるように水で希釈したのち
、陽イオン交換樹脂で脱アルカリして調製した
叉１遺Ｊ
実施例１のヒールゾル９７４ｇを３５℃に保ちながら攪
拌し、まず実施例１と同じケイ酸液２ｇを徐々に添加し
た 次いで、エチルアルコール／水／アンモニア混合溶
液（重量比１．０／１．４１０．７）８２ｇと、エチル
シリケート（Ｓ ｉ Ｏ２として２８重量％） １０
．５ｇとを同時に添加したこの操作を繰り返し、最外層
がケイ酸液による重合物の層となるようにして、 １０
分間で所定量を添加した それぞれの全添加量は、ケイ
酸液１１７ｇ、 エチルアルコール／水／アンモニア
混合溶液４６７９．５ｇおよびエチルシリケート６０６
ｇであった
全量添加後、実施例１と同様に処理し シリカ粒子が単
分散された分散液を得た
叉為遣」
エチルアルコール／水混合溶液（重量比１．○１０．８
）に、Ｓ１０２濃度として ０．５重量％となるように
平均粒径８μｍの球状シリカ粒子を添加し該球状シリカ
粒子が分散されたヒールゾルを調製しｔム
このヒールゾル１９１０ｇを３５℃に保ちながら攪拌し
、まず実施例１と同じケイ酸液を３ｇを添加し、次いで
エチルアルコール／水混合溶液（重量比１．０／１．１
） ８．５ｇと、エチルシリケート（Ｓ１０２として
２８重量％）１ｇとを同時に添加した この操作をｐＨ
を１１に維持しながら、得られるシリカ粒子の最外層が
ケイ酸液による重合物の層となるようにして繰り返し、
所定量を添加した
それぞれの全添加量は、ケイ酸液６０ｇ、エチルアルコ
ール／水混合溶液１４９ ｇ、 エチルシリケート２
２ｇで、添加時間は３時間であった その後、実施例１
と同様にしてシリカ粒子が単分散された分散液を得た
大蓋ｊ」
平均粒径０．、０８ ｐ ｍ、 Ｓ １ｏ２ａ度４０
重量％のシリカゾル（ＳＩ−８０Ｐ、 触媒化成工業
製）２．５ｇ、 約０．１重量％のＮａＯＨ水溶液８
１．５ｇおよびエチルアルコール１００．５ｇを混合し
ヒールゾルを調製した
この分散液に、まず実施例１と同じ条件でエチルアルコ
ール／水混合溶液（重量比１．０１０．９）２４．５
ｇおよびエチルシリケート（８１０□ ２８重量％）７
ｇを同時に添加し、次いで実施例１と同じケイ酸液１．
５ｇを添加し八 この操作をｐＨ１１，５に維持しなが
ら得られるシリカ粒子の最外層がケイ酸液による重合物
の層となるようにして繰り返し、 １９時間で所定量を
添加し八 それぞれの全添加量は、エチルアルコール／
水混合液１４０１ｇ、エチルシリケート３９３ｇ、ケイ
酸液７６ｇであっｔム 全量添加後１重量％ＮａＯＨ水
溶液３７ｇを加え、７０℃、２時間処理して、シリカ粒
子が単分散された分散液を得ｔも夫蓋簿」
イソプロパツール４８６．５ｇ、 水２１４ｇおよび
２８％アンモニア水２５６ｇからなる混合溶液を３５℃
に保ち、これにチタニウムテトラプロポキシド １７．
５ ｇをアンモニアガスでｐＨを１１以上に維持しなが
ら２時間がけて添加した得られたＴｌｏ２粒子分散液の
一部をとり、イソプロパツールで希釈してＴ ｉ ０２
４度が０．５重量％であるシード分散液を１８４ｇ調製
しへこの分散液を３５℃、 ｐＨ１１，５に保ちながら
攪拌し、まず実施例１と同じケイ酸ｉ３ｇを添加し、次
いでイソプロパツール／水混合溶液（重量比１．０１０
．８）４７ｇおよびエチルシリケート（ＳｉＣ２として
２８重量％）１６．５ｇを同時に添加し八 この操作を
最外層がケイ酸液による重合物の層となるようにして繰
り返し、ケイ酸液 ７６ｇ、イソプロパツール／水混合
溶液１１２９．５ｇおよびエチルシリケー）３９３ｇを
４時間かけて添加しｔム その後７０℃、２時間維持し
てシリカ分散液を得た
叉羞章」
エチルアルコール３６８５．５ｇ、水１３６５ｇおよび
２８％アンモニア水９２１．５ ｇからなる混合溶液に
、平均粒径５．０μｍの球状シリカ２４９ｇを分散させ
た後、１重量％のＮａＯＨ水溶液１６１ｇを加え、超音
波処理を施してヒールゾルを調製しへ
このヒールゾルをオートクレーブに入ｔ５１Ｚｏ℃に加
熱し、この温度を保ちながら、まず実施例１と同じケイ
酸液 ４ｇを添加し、次いでエチルアルコール／水／ア
ンモニアの混合溶液（重量比１．０１０．３１０．１）
１３１．５ ｇおよびエチルシリケート２１ｇを同時に
添加した。この操作を得られるシリカ粒子の最外層がケ
イ酸液による重合物の層となるようにして繰り返し、
５時間でケイ酸液 １２０．５ｇ、 エチルアルコー
ル／水／アンモニア混合液 ３９３７．５ｇおよびエチ
ルシリケート６２５ｇを添加した 全量添加後、１重量
％のＮａＯＨ水溶液１１７ｇを加えたのち、１５０℃で
１時間保持して、シリカ粒子が単分散された分散液を得
た
失鳥遣１
実施例１で得られたヒールゾル９７４ｇを６５℃に保ち
、エチルアルコール／水／アンモニア混合溶液（重量比
１．０／２．５１０．２） １１０３ ｇおよびエチル
シリケート（Ｓ１０２として２８重量％）６２７ｇを同
時に１９時間かけて添加しへその後、 ７０℃で２時間
維持した 次いで、この分散液に実施例１のケイ酸液１
２６３ｇを、７０℃で６時間かけて添加して、単分散シ
リカ粒子分散液を得た
実施例１〜７で得られた単分散シリカ粒子の性状を表−
１に示す。それぞれの測定法は次のとおりである。The silicic acid solution used here was prepared by diluting water glass (24% by weight as SiO2, molar ratio of SiO2/Na, 3) with water so that the 5102 concentration was 5% by weight, and then diluting it with water so that the 5102 concentration was 5% by weight. 974 g of the heel sol prepared by dealkalization with a replacement resin was stirred while keeping it at 35°C, and 2 g of the same silicic acid solution as in Example 1 was gradually added.Then, ethyl alcohol/water/ 82 g of ammonia mixed solution (weight ratio 1.0/1.410.7) and ethyl silicate (28% by weight as SiO2) 10
．． Repeat this operation by adding 5g of silicic acid at the same time, so that the outermost layer becomes a layer of polymerized silicic acid solution,
The total amount added was 117 g of silicic acid liquid, 4679.5 g of ethyl alcohol/water/ammonia mixed solution, and 606 g of ethyl silicate.
After adding the total amount of 1.5g, the mixture was treated in the same manner as in Example 1 to obtain a dispersion in which silica particles were monodispersed.Ethyl alcohol/water mixed solution (weight ratio 1.○10.8
), spherical silica particles with an average particle size of 8 μm were added to give an S102 concentration of 0.5% by weight, and a heel sol in which the spherical silica particles were dispersed was prepared. 1910 g of this heel sol was stirred while maintaining the temperature at 35°C. First, 3 g of the same silicic acid solution as in Example 1 was added, and then an ethyl alcohol/water mixed solution (weight ratio 1.0/1.1) was added.
) and 1 g of ethyl silicate (28% by weight as S102) were simultaneously added.
While maintaining the temperature at 11, the outermost layer of the obtained silica particles becomes a layer of polymerized silicic acid solution, and the process is repeated.
The total amount of each added in the specified amount is 60 g of silicic acid liquid, 149 g of ethyl alcohol/water mixed solution, and 2 ethyl silicate.
2 g and the addition time was 3 hours. Then, Example 1
In the same manner as above, a dispersion liquid in which silica particles were monodispersed was obtained using a large lid with an average particle size of 0. , 08 p.m., S 1o2a degree 40
2.5 g of silica sol (SI-80P, Catalysts & Chemicals Co., Ltd.), approximately 0.1% by weight of NaOH aqueous solution 8
A heel sol was prepared by mixing 1.5 g of ethyl alcohol and 100.5 g of ethyl alcohol.To this dispersion, a mixed solution of ethyl alcohol/water (weight ratio 1.010.9) 24.5 g was first added under the same conditions as in Example 1.
g and ethyl silicate (810□ 28% by weight) 7
g of the same silicic acid solution as in Example 1.
Add 5g of silica and repeat this operation while maintaining the pH at 11.5 so that the outermost layer of the silica particles becomes a polymer layer of the silicic acid solution, and add the specified amount over 19 hours. The amount added is ethyl alcohol/
After adding 1401 g of water mixture, 393 g of ethyl silicate, and 76 g of silicic acid solution, 37 g of 1% by weight NaOH aqueous solution was added and treated at 70°C for 2 hours to obtain a dispersion in which silica particles were monodispersed. A mixed solution consisting of 486.5 g of isopropanol, 214 g of water, and 256 g of 28% ammonia water was heated at 35°C.
and titanium tetrapropoxide 17.
5 g was added over 2 hours while maintaining the pH at 11 or higher with ammonia gas. A portion of the resulting Tlo2 particle dispersion was taken and diluted with isopropanol to obtain Ti02.
184 g of a seed dispersion containing 0.5% by weight of 4°C was prepared and stirred while maintaining the dispersion at 35° C. and pH 11.5. First, 3 g of silicic acid i as in Example 1 was added, and then isopropyl acetate was added. Tool/water mixed solution (weight ratio 1.010
．． 8) Add 47 g of silicic acid solution and 16.5 g of ethyl silicate (28% by weight as SiC2) at the same time. Repeat this operation so that the outermost layer is a layer of polymerized silicic acid solution, and add 76 g of silicic acid solution and isopropanol. 3,685.5 g of ethyl alcohol, 1,365 g of water, and 28% After dispersing 249 g of spherical silica with an average particle size of 5.0 μm in a mixed solution consisting of 921.5 g of ammonia water, 161 g of a 1% by weight NaOH aqueous solution was added, and ultrasonication was performed to prepare a heel sol. Healsol was placed in an autoclave and heated to 51°C. While maintaining this temperature, 4g of the same silicic acid solution as in Example 1 was added, and then a mixed solution of ethyl alcohol/water/ammonia (weight ratio 1.010.310. 1)
131.5 g and 21 g of ethyl silicate were added simultaneously. Repeat this operation so that the outermost layer of the silica particles obtained is a layer of polymerized silicic acid solution,
In 5 hours, 120.5 g of silicic acid liquid, 3937.5 g of ethyl alcohol/water/ammonia mixture and 625 g of ethyl silicate were added. After all additions, 117 g of 1% by weight NaOH aqueous solution was added, and then kept at 150°C for 1 hour. 974 g of the heel sol obtained in Example 1 was kept at 65°C and mixed with an ethyl alcohol/water/ammonia mixed solution (weight ratio 1.0/2). .510.2) 1103 g and 627 g of ethyl silicate (28% by weight as S102) were added simultaneously over a period of 19 hours and then maintained at 70°C for 2 hours.Then, to this dispersion was added the silicic acid solution 1 of Example 1.
The properties of monodisperse silica particles obtained in Examples 1 to 7, in which 263g of monodisperse silica particles were added over 6 hours at 70°C to obtain monodisperse silica particle dispersions, are shown in the table below.
Shown in 1. The respective measurement methods are as follows.
（１）平均粒径
電子顕微鏡写真を画像解析装置により測定しμ（２）均
一係数
（１）で求めた平均粒径および標準偏差から次式により
算出した
σ
ＣＶ＝ ｘ １ ００
Ｄ 平均粒径
σ 標準偏差
（３）凝集状態
電子顕微鏡写真の一定視野における凝集粒子数ｎと全粒
子数Ｎとの比率（ｎ／Ｎ）を算出し九（４）安息角
円筒回転式安息角測定器（筒片理化学器機ＫＫ製）を用
いて測定した(1) Average particle size σ CV = x 1 00 D Average particle size calculated from the average particle size and standard deviation obtained from μ (2) uniformity coefficient (1) by measuring an electron micrograph using an image analyzer and using the following formula. σ Standard deviation (3) Calculate the ratio (n/N) between the number of aggregated particles n and the total number N of particles in a fixed field of view of an electron micrograph of the agglomerated state. Measured using Katari Kagakukiki KK)
Claims (2)
分散された水−アルコール系分散液に、該分散液をアル
カリ性に保ちながらテトラアルコキシシランおよびケイ
酸液を添加して、テトラアルコキシシラン加水分解生成
物およびケイ酸重合物を前記シード上に付着させ粒子成
長を行なわせることを特徴とする単分散されたシリカ粒
子の製造方法。(1) Tetraalkoxysilane and silicic acid solution are added to a water-alcohol dispersion in which metal oxides or metal hydroxides are dispersed as seeds while keeping the dispersion alkaline to hydrolyze tetraalkoxysilane. A method for producing monodispersed silica particles, which comprises depositing a product and a silicic acid polymer on the seeds to cause particle growth.
形成されていることを特徴とする請求項第１項記載の単
分散されたシリカ粒子の製造方法。(2) The method for producing monodispersed silica particles according to claim 1, wherein the outermost layer of the silica particles is formed of the silicic acid polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2122403A JPH0764548B2 (en) | 1990-05-11 | 1990-05-11 | Method for producing monodispersed silica particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2122403A JPH0764548B2 (en) | 1990-05-11 | 1990-05-11 | Method for producing monodispersed silica particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0421515A true JPH0421515A (en) | 1992-01-24 |
| JPH0764548B2 JPH0764548B2 (en) | 1995-07-12 |
Family
ID=14834935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2122403A Expired - Lifetime JPH0764548B2 (en) | 1990-05-11 | 1990-05-11 | Method for producing monodispersed silica particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764548B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6580026B1 (en) | 1999-06-30 | 2003-06-17 | Catalysts & Chemicals Industries Co., Ltd. | Photovoltaic cell |
| WO2007142047A1 (en) | 2006-06-09 | 2007-12-13 | Tokuyama Corporation | Dry-process fine silica particle |
| CN104003409A (en) * | 2014-06-11 | 2014-08-27 | 北京化工大学 | Method for preparing controllable monodisperse spherical large-particle-size nano-silicon dioxide |
| CN111470512A (en) * | 2019-03-13 | 2020-07-31 | 上海稷弘智能科技有限公司 | Method for preparing silica with high oil absorption value and large pore volume |
| CN115571887A (en) * | 2022-09-20 | 2023-01-06 | 中谱科技(福州)有限公司 | Monodisperse silicon dioxide microsphere and preparation method thereof |
-
1990
- 1990-05-11 JP JP2122403A patent/JPH0764548B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6580026B1 (en) | 1999-06-30 | 2003-06-17 | Catalysts & Chemicals Industries Co., Ltd. | Photovoltaic cell |
| US6849797B2 (en) | 1999-06-30 | 2005-02-01 | Catalysts & Chemicals Industries Co., Ltd. | Photovoltaic cell |
| WO2007142047A1 (en) | 2006-06-09 | 2007-12-13 | Tokuyama Corporation | Dry-process fine silica particle |
| US7803341B2 (en) | 2006-06-09 | 2010-09-28 | Tokuyama Corporation | Fine dry silica particles |
| CN104003409A (en) * | 2014-06-11 | 2014-08-27 | 北京化工大学 | Method for preparing controllable monodisperse spherical large-particle-size nano-silicon dioxide |
| CN104003409B (en) * | 2014-06-11 | 2016-01-20 | 北京化工大学 | A kind of preparation method of controlled monodisperse spherical Large stone nano silicon |
| CN111470512A (en) * | 2019-03-13 | 2020-07-31 | 上海稷弘智能科技有限公司 | Method for preparing silica with high oil absorption value and large pore volume |
| CN115571887A (en) * | 2022-09-20 | 2023-01-06 | 中谱科技(福州)有限公司 | Monodisperse silicon dioxide microsphere and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764548B2 (en) | 1995-07-12 |
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