JPS6364911A - Production of silica sol containing silica particle having large particle size - Google Patents
Production of silica sol containing silica particle having large particle sizeInfo
- Publication number
- JPS6364911A JPS6364911A JP20563286A JP20563286A JPS6364911A JP S6364911 A JPS6364911 A JP S6364911A JP 20563286 A JP20563286 A JP 20563286A JP 20563286 A JP20563286 A JP 20563286A JP S6364911 A JPS6364911 A JP S6364911A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- silica particles
- silica sol
- silicic acid
- silica
- 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 136
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002245 particle Substances 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000377 silicon dioxide Substances 0.000 title abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 53
- 230000002378 acidificating effect Effects 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 37
- 239000002612 dispersion medium Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 abstract description 47
- 238000009826 distribution Methods 0.000 abstract description 17
- 229910052681 coesite Inorganic materials 0.000 abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000003703 image analysis method Methods 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
ユ服９且■方！
本発明は、シリカゾルの製造方法に関し、ざらに詳しく
は、ビルドアップ法による、粒度分布が均一であって、
しかも真球状の形状を有する大粒径のシリカ粒子を含む
シリカゾルの製造方法に関する。[Detailed description of the invention] 9 ways to wear clothes! The present invention relates to a method for producing silica sol, and more specifically, a build-up method is used to produce a silica sol, the particle size distribution is uniform,
Moreover, the present invention relates to a method for producing a silica sol containing large-sized silica particles having a true spherical shape.
発明の技術的背景ならびにその問題点
シリカゾルは、従来、プラスチック改質剤あるいは各種
バインダーとして、ざらにはプラスデックなどの透明基
材へのコート剤などとしての用途が期待されている。Technical background of the invention and its problems Silica sol has conventionally been expected to be used as a plastic modifier or various binders, and as a coating agent for transparent substrates such as Plasdec.
ところで、アルカリ性の低分子母シリカゾルをシード（
核）とし、これに酸性ケイ酸液を添加して、シリカ粒子
を成員させて所定粒径のシリカ粒子を含むシリカゾルを
得る、いわゆるビルドアップ法によるシリカゾルの製造
法はよく知られており、既に各種の方法が提案されてい
る。By the way, alkaline low molecular weight mother silica sol is seeded (
A method for manufacturing silica sol by the so-called build-up method, in which a silica sol is obtained by adding an acidic silicic acid solution to the core and forming silica particles to form a silica sol containing silica particles of a predetermined particle size, is well known and has already been reported. Various methods have been proposed.
たとえば、米国特許第３，４４０，１７４号明細書ある
いは同第３，５３８，０１５号明細書には、粒子径１０
ｍμ以上のシリカ粒子を含むアルカリ性シリカゾルに、
酸性シリカゾルを添加して４５〜１００ｍμあるいはそ
れ以上の粒子径を有するシリカ粒子を含むシリカゾルの
製造方法が開示されている。また、特公昭４６−２Ｏ１
３７号公報には、５００Å以上の粒子径を有するシリカ
粒子が分散したアルカリ全屈ケイ酸塩水溶液に、酸性の
水性コロイド溶液を添加して、大粒径のシリカ粒子が分
散されてなるシリカゾルの製造方法が開示されている。For example, U.S. Pat. No. 3,440,174 or U.S. Pat. No. 3,538,015 states that
Alkaline silica sol containing silica particles of mμ or more,
A method for producing a silica sol containing silica particles having a particle size of 45 to 100 mμ or more by adding an acidic silica sol is disclosed. In addition, special public service No. 46-2O1
No. 37 discloses that an acidic aqueous colloidal solution is added to an aqueous alkaline total silicate solution in which silica particles having a particle size of 500 Å or more are dispersed, thereby producing a silica sol in which large silica particles are dispersed. A manufacturing method is disclosed.
ところが上記のようなシリカゾルのｌＪａ方法では、酸
性シリカゾルの添加速度をシリカ粒子の成員に合せて変
化させなければならなかったり、あるいは酸性シリカゾ
ルを添加する過程で同時に水を連続的に蒸発させながら
シリカ粒子の成員を行なわせなければならなかったりす
るため、ビルドアップ操作が複雑になったり、あるいは
反応液中に存在するシリカ粒子の凝集が起りやすく、シ
ードである核粒子に酸性ケイ酸液中のシリカを均一に沈
着させて、均一な粒径を有する真球状粒子が分散媒中に
分散されてなるシリカゾルを得ることが困難であるとい
う問題点があった。しかもこれらの方法では、５００ｍ
μを越えるような大きな平均粒子径を有し、しかも粒度
分布が均一であって、その上真球状の形状を有するシリ
カ粒子が分散されてなるシリカゾルを得ることは難しか
った。However, in the lJa method of silica sol as described above, the addition rate of acidic silica sol must be changed depending on the members of the silica particles, or the silica sol must be added while continuously evaporating water during the process of adding acidic silica sol. The build-up operation becomes complicated, or the silica particles present in the reaction solution tend to aggregate, and the seed core particles are There has been a problem in that it is difficult to uniformly deposit silica and obtain a silica sol in which true spherical particles having a uniform particle size are dispersed in a dispersion medium. Moreover, with these methods, the distance of 500 m
It has been difficult to obtain a silica sol in which silica particles having a large average particle size exceeding μ, a uniform particle size distribution, and a perfectly spherical shape are dispersed.
また、特開昭６０−２５１１９号明ＩＩＩ書には、アル
カリ性金属ケイ酸塩水溶液に酸性ケイ酸液を添加して４
０〜１２Ｏｍμのシリカ粒子が分散媒中に分散されてな
るシリカゾルを調製した復、これに酸を添加して熟成す
ることにより、シリカゾルを製造する方法が開示されて
いる。ところがこの方法では、酸による熟成工程が必要
となるなど工程が複雑であるという問題点があった。In addition, JP-A No. 60-25119 Mei III discloses that an acidic silicate solution is added to an aqueous alkaline metal silicate solution.
A method for manufacturing a silica sol is disclosed by preparing a silica sol in which silica particles of 0 to 12 Omμ are dispersed in a dispersion medium, and then adding an acid to the sol and aging it. However, this method has a problem in that the process is complicated, such as the need for a ripening process using acid.
発明の目的
本発明は、上記のような従来技術に伴なう問題点を解決
しようとするものであって、粒度分布が均一であり、そ
の上真珠に近いような形状を有する大粒径のシリカ粒子
が分散媒中に分散されたシリカゾルの′！ＡＭ方法を提
供することを目的としている。Purpose of the Invention The present invention aims to solve the above-mentioned problems associated with the prior art. ′! of silica sol in which silica particles are dispersed in a dispersion medium! The aim is to provide an AM method.
発明の概要
本発明に係る大粒径のシリカ粒子を含むシリカゾルの製
造方法は、以下の工程（ａ）および工程（ｂ）からなっ
ている。Summary of the Invention The method for producing a silica sol containing large-sized silica particles according to the present invention comprises the following steps (a) and (b).
（ａ）比較的小さな粒子径を有するシリカ粒子が分散媒
中に分散されてなるシリカゾルと、ケイ酸アルカリ水溶
液および／またはアルカリ水溶液とを混合して、混合液
の全Ｓ ！ ０２ ／ Ｍ２Ｏ （Ｍはアルカリ全屈）
のモル比を１０〜７０に調整してシード液を調製する工
程、
（ｂ）このシード液を７０℃以上に保持しながら、酸性
ケイ酸液を下記の速度式を満足するような添加速度で添
加して、小さな粒子径を有するシリカ粒子の粒子径を成
員させるビルドアップ工程ｔｏｇＷ≦−３，５Ｘ１０−
３Ｄ＋０．７Ｗ：！性ケイ酸液の添加速度
［酸性ケイ酸液５１０２ｇ数／時・シード液中の初期シ
リカゾルＳｉＯ２９］
Ｄ二シード液中の酸性ケイ酸液を添加する前のシリカ粒
子の平均粒径（ｍμ）。(a) A silica sol in which silica particles having a relatively small particle size are dispersed in a dispersion medium is mixed with an aqueous alkali silicate solution and/or an aqueous alkali solution, and the total S of the mixed liquid is reduced. 02 / M2O (M is full alkali)
A step of preparing a seed liquid by adjusting the molar ratio of 10 to 70, (b) While maintaining this seed liquid at 70°C or higher, add the acidic silicic acid liquid at a rate that satisfies the following rate formula. Build-up step togW≦-3,5X10- in which the particle size of silica particles having a small particle size is increased by adding togW≦-3,5X10-
3D+0.7W:! Addition rate of acidic silicic acid liquid [acidic silicic acid liquid 5102 g/hour/initial silica sol SiO29 in seed liquid] D2 Average particle size (mμ) of silica particles in seed liquid before adding acidic silicic acid liquid.
本発明に係る大粒径のシリカ粒子を含むシリカゾルの製
造方法は、（ａ）特定の条件でシード液を調製する工程
と、（ｂ）このシード液に酸性ケイ酸液を特定の添加速
度で添加して、シード液中のシリカ粒子の粒子径を成員
させる工程とからなっているので、シード液中のシリカ
粒子を、大きな平均粒子径を有し、しかも粒度分布が均
一であり、その上真珠に近いような形状を有するシリカ
粒子とすることができ、したがって大きな平均粒子径を
有し、しかも粒度分布が均一であり、その上真球に近い
ような形状を有するシリカ粒子が分散媒中に分散されて
なるシリカゾルを得ることができる。The method for producing a silica sol containing large-sized silica particles according to the present invention includes (a) preparing a seed liquid under specific conditions, and (b) adding an acidic silicic acid solution to the seed liquid at a specific rate. The method consists of a step of adding the silica particles in the seed liquid to increase the particle size of the silica particles in the seed liquid, so that the silica particles in the seed liquid have a large average particle size, a uniform particle size distribution, and a The silica particles can be made to have a shape similar to a pearl, have a large average particle diameter, have a uniform particle size distribution, and have a shape similar to a perfect sphere in the dispersion medium. A silica sol can be obtained in which silica sol is dispersed in
発明の詳細な説明
以下本発明に係る粒子径が成員されたシリカ粒子を含む
シリカゾルの製造方法について具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION A method for producing a silica sol containing silica particles having a certain particle size according to the present invention will be specifically described below.
本発明に係るシリカツルの製造方法は、（ａ＞特定の条
件でシード液を調製する工程と、（ｂ）このシード液に
酸性ケイ酸液を特定の添加速度で添加して、シード液中
のシリカ粒子の粒子径を成員させる工程とからなってい
るが、以下に、工程（ａ）および工程（ｂ）について説
明する。The method for producing silica vine according to the present invention includes (a) the step of preparing a seed liquid under specific conditions, and (b) adding an acidic silicic acid solution to the seed liquid at a specific addition rate to increase the Step (a) and step (b) will be explained below.
（ａ）シード液の調製
本発明で用いられるシード液は、（ｉ）比較的小さな粒
子径を有するシリカ粒子が分散媒中に分散されてなるシ
リカゾルと、（ｉｉ ）ケイ酸アルカリ水溶液またはア
ルカリ水溶液あるいはこの両者とを混合して、混合液の
全Ｓ ｉ Ｏ２／ Ｍ ２Ｏ （Ｍはアルカリ金属）の
モル比を１０〜７０好ましくは１２〜６０に調整するこ
とによって得られる。(a) Preparation of seed liquid The seed liquid used in the present invention is composed of (i) a silica sol in which silica particles having a relatively small particle size are dispersed in a dispersion medium, and (ii) an aqueous alkali silicate solution or an aqueous alkali solution. Alternatively, it can be obtained by mixing both of them and adjusting the molar ratio of total SiO2/M2O (M is an alkali metal) in the mixed liquid to 10 to 70, preferably 12 to 60.
ここで「比較的小さな」粒子径を有するシリカ粒子とは
、原料となるシリカ粒子の粒子径が、後述するピルドア
ツプ工程を経て得られるシリカ粒子の粒子径と比較して
小さいという意味で用いられており、この比較的小さな
粒子径を有するシリカ粒子は後の工程であるビルドアッ
プ工程によってその粒子径が成員せしめられ、大きな粒
子径を有するシリカ粒子とされる。この比較的小さな粒
子径を有するシリカ粒子としては、本発明では、約２Ｏ
ｍμ以上の粒径のものが用いられる。したがって、たと
えば２（ｌｔμの平均粒子径を有するシリカ粒子を、後
述するピルドアツプ工程により、５０ｍμの平均粒子径
を有するシリカ粒子とする場合には、２Ｏｍμの平均粒
子径を有するシリカ粒子が「比較的小さな粒子径を有す
る」シリカ粒子となるが、次にこのようにして得られた
５０ｍμの平均粒子径を有するシリカ粒子を、後）ホす
るビルドアップ工程によって７０ｍμの平均粒子径を有
するシリカ粒子とする場合には、５０ ｍμの平均粒子
径を有するシリカ粒子が「比較的小さな粒子径を有する
」シリカ粒子となる。Here, silica particles having a "relatively small" particle size are used to mean that the particle size of the silica particles used as a raw material is smaller than the particle size of the silica particles obtained through the pill-up process described below. The silica particles having a relatively small particle size are made to have a larger particle size in a subsequent build-up process, and are made into silica particles having a large particle size. In the present invention, the silica particles having a relatively small particle size are about 2O
Particles having a particle size of mμ or more are used. Therefore, for example, when silica particles having an average particle diameter of 2 (ltμ) are made into silica particles having an average particle diameter of 50 mμ by the pill-up process described below, the silica particles having an average particle diameter of 20 mμ are Next, the silica particles with an average particle diameter of 50 mμ obtained in this way are transformed into silica particles with an average particle diameter of 70 mμ through a subsequent build-up process. In this case, silica particles having an average particle size of 50 mμ become silica particles having a "relatively small particle size."
このような比較的小さな粒子径を有するシリカ粒子が分
散媒中に分散されてなるシリカゾルは、本出願人が昭和
６１年８月１３日に特許出願した「シリカゾルの製造方
法」に記載された方法に従って得られたものであること
が好ましいが、従来公知の方法で得られたシリカゾルを
用い得ることももらろんできる。A silica sol in which silica particles having such a relatively small particle size are dispersed in a dispersion medium can be produced by the method described in "Method for producing silica sol" for which the applicant filed a patent application on August 13, 1988. Although it is preferable that the silica sol be obtained according to the method described above, it is of course possible to use a silica sol obtained by a conventionally known method.
この「シリカゾルの製造方法」に記載された方法では、
下記のような工程（イ）および工程（ロ）によりシリカ
ゾルが得られる。In the method described in this "method for producing silica sol",
A silica sol is obtained by the following steps (a) and (b).
（イ）ケイ酸アルカリ水溶液および／またはアルカリ水
溶液と、酸性ケイ酸液とを混合し、混合液の５ｉＯ７／
Ｍ、２Ｏ （Ｍはアルカリ金属）のモル比を２．８〜１
０に調整したのち、６０℃以上の温度で熟成して、シー
ド液を調製する工程、（ロ）上記のようにして得られた
シード液を６０℃以上に保持しながら、酸性ケイ酸液を
下記の速度式以下の速度で添加する工程、
ｌｏｇ ｙ≦２．３−３．６１０Ｃ］ ｘｙ：添加速度
［添加酸性ケイ酸液ＳｉＯ２ＳＪ数／分・シード液中の
酸性ケイ酸液
ＳｉＯ２ｇ数］
Ｘ：シード液の全ＳｉＯ２／Ｍ２Ｏモル比。(a) Mix an alkali silicate aqueous solution and/or an alkaline aqueous solution with an acidic silicate solution, and mix the 5iO7/
The molar ratio of M and 2O (M is an alkali metal) is 2.8 to 1.
0 and then ripening at a temperature of 60°C or higher to prepare a seed liquid. (b) While maintaining the seed liquid obtained as above at 60°C or higher, add an acidic silicic acid liquid. A step of adding at a rate equal to or less than the rate formula below, log y≦2.3-3.610C] : Total SiO2/M2O molar ratio of seed liquid.
本発明では、粒度分布が均一であり、しかも真球に近い
ような形状を有する大粒径のシリカ粒子が含まれたシリ
カゾルを得るには、シード液を調製する際に用いられる
比較的小さな粒子径を有するシリカ粒子も、また、でき
るだけ均一な粒子径を有していることが好ましい。この
意味で、上記のような本出願人により昭和６１年８月３
日に特許出願された「シリカゾルの製造方法」に記載さ
れた方法により得られたシリカゾルが好ましく用いられ
る。In the present invention, in order to obtain a silica sol containing large silica particles having a uniform particle size distribution and a shape close to a true sphere, relatively small particles used when preparing a seed liquid are required. It is also preferred that the silica particles have a particle size that is as uniform as possible. In this sense, on August 3, 1986 by the applicant as mentioned above,
A silica sol obtained by the method described in ``Method for producing silica sol'', which was patented in 1999, is preferably used.
なお、本発明に係る方法で得られたシリカゾルをシード
液の原料として用いることもできる。この方法では、た
とえば２Ｏｍμ前後の粒子径を有するシリカ粒子が分散
媒中に分散されてなるシリカゾルを出発原料として用い
て本発明の方法で５０ｍμ程度の粒子径を有するシリカ
粒子が分散媒中に分散されてなるシリカゾルを得た後、
次いでこれを原料として、ざらに粒径の大きいシリカゾ
ルを１ｑるというように順次くり返して大粒径のシリカ
粒子が分散されたシリカゾルを得ることができる。Note that the silica sol obtained by the method according to the present invention can also be used as a raw material for the seed liquid. In this method, for example, a silica sol in which silica particles having a particle size of about 20 mμ are dispersed in a dispersion medium is used as a starting material, and in the method of the present invention, silica particles having a particle size of about 50 mμ are dispersed in the dispersion medium. After getting the silica sol,
Next, using this as a raw material, 1 quart of silica sol with a large particle size is added, and the process is repeated in order to obtain a silica sol in which silica particles with a large particle size are dispersed.
マタ、仝Ｓ ！ ０２ ／ Ｍ２Ｏ （７） モ／Ｌ／
比が１０〜７０の範囲に調整された後のシード液中の仝
ＳｉＯ２濃度は、１０重ω％以下、好ましくは０．５〜
７．０重Ｍ％の範囲であることが望ましい。全Ｓ ｉ
Ｏ２濃度が０．５Ｍ８％未満であると、最終的に得られ
るシリカゾル中のＳ ｉ ０２１度がうずくなり、濃縮
操作などに多大のエネルギーを必要とするので好ましく
ない。一方、１０重量％を越えると、シリカ粒子の凝集
が起こりやすくなり、均一な粒子の生成が困難になるた
め好ましくない。Mata, you S! 02/M2O (7) Mo/L/
After the ratio is adjusted to a range of 10 to 70, the SiO2 concentration in the seed liquid is 10% by weight or less, preferably 0.5 to 70.
The range is preferably 7.0% by weight. All S i
If the O2 concentration is less than 0.5M8%, the S i 021 degree in the silica sol finally obtained will be low, and a large amount of energy will be required for the concentration operation, which is not preferable. On the other hand, if it exceeds 10% by weight, silica particles tend to aggregate, making it difficult to produce uniform particles, which is not preferable.
シード液の全３＋０２／Ｍ２Ｏのモル比はまた、最終的
に得られるシリカゾルの品質に大きな影響を及ぼす因子
である。ＳｉＯ２／Ｍ２Ｏモル比が１０未満であると、
シード液中のシード粒子同士が凝集したり、粒子が成員
の途中で凝集したりして、いわゆるダルマ状の粒子が生
成するなどして、１７られるシリカ粒子の粒度分布がブ
ロードになったり、あるいは真球状でない粒子が得られ
たりするため好ましくない。The total 3+02/M2O molar ratio of the seed liquid is also a factor that greatly influences the quality of the silica sol finally obtained. When the SiO2/M2O molar ratio is less than 10,
The particle size distribution of the 17 silica particles becomes broad due to the seed particles in the seed liquid coagulating with each other or the particles agglomerating in the middle of membership, producing so-called daruma-shaped particles, or This is not preferable because particles that are not perfectly spherical may be obtained.
また、このモル比が７０を越えると、ビルドアップ工程
中に新たなシードが発生し、得られるシリカ粒子の粒度
分布がブロードとなるため好ましくない。Moreover, if this molar ratio exceeds 70, new seeds will be generated during the build-up process and the particle size distribution of the obtained silica particles will become broad, which is not preferable.
このようにして調製されたシード液は、直ちに次のビル
ドアップ工程で用いられるが、場合によっては、調製さ
れたシード液を６０℃以上の温度で加熱熟成した後に、
ビルドアップ工程に用いることもできる。The seed liquid prepared in this way is immediately used in the next build-up process, but in some cases, the prepared seed liquid is heated and aged at a temperature of 60°C or higher, and then
It can also be used in a build-up process.
（ｂ）ビルドアップ工程
上記のようにして調製されたシード液を７０’Ｃ以上の
温度に保らながら、このシード液に、酸性ケイ酸液を徐
々に添加して、シリカ粒子を成員させる。添加する酸性
ケイ酸液は、ケイ酸アルカリ水溶液を陽イオン交換樹脂
で処理することによってアルカリを除去するなど常法に
従って容易に得ることができる、ケイ酸の低重合物の溶
液である。(b) Build-up step While maintaining the seed liquid prepared as described above at a temperature of 70'C or higher, an acidic silicic acid solution is gradually added to the seed liquid to form silica particles. The acidic silicic acid solution to be added is a solution of a low polymer of silicic acid that can be easily obtained by a conventional method such as treating an aqueous alkali silicate solution with a cation exchange resin to remove alkali.
この酸性ケイ酸液は、通常そのｐＨが４を越えると、ま
たｓ ｒ ０２濃度が高くなると不安定になり、増粘ま
たはゲル化を起こすことが知られている。It is known that this acidic silicic acid solution usually becomes unstable when its pH exceeds 4 or when its s r 02 concentration increases, causing thickening or gelation.
したがって、本発明で用いられる酸性ケイ酸液は、ＤＨ
は２〜４であり、５ｉ０２濃度は約７重量％以下である
ことが好ましい。Therefore, the acidic silicic acid solution used in the present invention is DH
is between 2 and 4, and the 5i02 concentration is preferably about 7% by weight or less.
シード液に酸性ケイ酸液を徐々に添加する際のシード液
の温度は７０’Ｃ以上であるが、シード液の温度がシー
ド液の沸点以上である場合には、シード液中の水などの
蒸発を抑えるためビルドアップ工程をオートクレーブな
どを用いて加圧下で行なうことが好ましい。The temperature of the seed liquid when gradually adding the acidic silicic acid liquid to the seed liquid is 70'C or higher, but if the temperature of the seed liquid is higher than the boiling point of the seed liquid, water etc. in the seed liquid may In order to suppress evaporation, the build-up step is preferably carried out under pressure using an autoclave or the like.
酸性ケイ酸液を添加する場合、この酸性ケイ酸液中のシ
リカがシード液中のシードに確実に沈着して、新たなシ
ードを発生しないようにしなければならない。このため
シード液中への酸性ケイ酸液の添加速度は、最終製品の
シリカ粒子の粒径、粒度分布、形状に大きな影響を与え
る。この点についても本発明者らは研究を重ねた結果、
シード液中への酸性ケイ酸液の添加速度を、シードとな
るシード液中の酸性ケイ酸液を添加する前のシリカ粒子
の粒径を考慮して決定すれば、大きな平均粒子径を有し
、しかも粒度分布が均一であり、その上真球に近いよう
な形状を有する、大粒径のシリカ粒子が得られることを
見出した。すなわち、シードの粒径が小さい場合には、
酸性ケイ酸液の添加速度を大きくできるが、シードの粒
径が大きい場合には、酸性ケイ酸液の添加速度を小さく
しなければならない。この点についてざらに検討したと
ころ、下記式で表わされる速度式に従って、シード液に
酸性ケイ酸液を添加すれば、目的とする、大きな平均粒
子径を有し、しかも粒度弁イｆｉが均一であり、その上
真珠に近いような形状を有するようなシリカ粒子が分散
媒中に分散されてなるシリカゾルを得ることができる。When adding an acidic silicic acid solution, it is necessary to ensure that the silica in the acidic silicic acid solution is deposited on the seeds in the seeding solution to prevent new seeds from being generated. Therefore, the rate of addition of the acidic silicic acid liquid into the seed liquid has a large effect on the particle size, particle size distribution, and shape of the silica particles in the final product. As a result of repeated research by the present inventors regarding this point,
If the rate of addition of the acidic silicic acid liquid to the seed liquid is determined by considering the particle size of the silica particles in the seed liquid before adding the acidic silicic acid liquid, it is possible to determine the rate of addition of the acidic silicic acid liquid into the seed liquid. Furthermore, it has been found that large-sized silica particles having a uniform particle size distribution and a shape close to a true sphere can be obtained. In other words, if the seed particle size is small,
Although the rate of addition of the acidic silicic acid liquid can be increased, if the particle size of the seeds is large, the rate of addition of the acidic silicic acid liquid must be decreased. After a rough study of this point, we found that if the acidic silicic acid solution is added to the seed liquid according to the rate equation shown below, the desired large average particle size can be obtained, and the particle size valve i is uniform. Furthermore, it is possible to obtain a silica sol in which silica particles having a shape similar to a pearl are dispersed in a dispersion medium.
１０（］ ］Ｗ≦−３．５ｘ１０−３Ｄ十０．７〜■酸
性ケイ酸液の添加速度
［酸性ケイ酸液５１０２ｇ数／時・シード液中の初期シ
リカゾル５ｉ０２ｙ］
Ｄ二シード液中の酸性ケイ酸液を添加する前のシリカ粒
子の平均粒径（ｍμ）。10(] ]W≦-3.5x10-3D10.7~■ Addition rate of acidic silicic acid liquid [acidic silicic acid liquid 5102g/hour・Initial silica sol in seed liquid 5i02y] D2 Acidity in seed liquid Average particle size (mμ) of silica particles before adding silicic acid liquid.
酸性ケイ酸液の添加速度を上記式以下として、酸性ケイ
酸液をシード液に添加していけば、シードへのシリカの
沈着が確実にしかも均一に起り、真球状でしかも粒径の
そろった、大粒径のシリカ粒子を得ることができる。こ
れに対して、酸性ケイ酸液の添加速度が上記式で示され
る値を越えると、添加される酸性ケイ酸液中のシリカが
シードに確実に沈着せず、新たなシードが生成したりし
て、結果的に１ｑられるシリカゾル中に大粒径のシリカ
粒子および小粒径のシリカ粒子が混在してしまうことに
なる。If the acidic silicic acid liquid is added to the seed liquid at a rate equal to or less than the above formula, the silica will be deposited reliably and uniformly on the seeds, and the particles will be perfectly spherical and have a uniform particle size. , large-sized silica particles can be obtained. On the other hand, if the addition rate of the acidic silicic acid solution exceeds the value shown by the above formula, the silica in the added acidic silicic acid solution will not be reliably deposited on the seeds, and new seeds may be generated. As a result, large-sized silica particles and small-sized silica particles are mixed in 1q of silica sol.
酸性ケイ酸液の添加速度は、前述の式以下であれば、基
本的にはどんなに遅くても本発明の目的は達せられる。Basically, the objective of the present invention can be achieved no matter how slow the addition rate of the acidic silicic acid liquid is, as long as it is equal to or less than the above-mentioned formula.
しかしながら、あまり遅くなると、目的とする粒径を有
する粒子を得るのに、たとえば数カ月を要することにも
なり、したがって約０．００１ｇ／時、９以上の速度で
酸性ケイ酸液を添加することが実用的である。However, if it is too slow, it may take several months, for example, to obtain particles with the desired particle size. Therefore, it is recommended to add the acidic silicic acid solution at a rate of about 0.001 g/hour, 9 or more. It's practical.
上記のような添加速度で酸性ケイ酸液をシード液に添加
しながら、シード液中のシリカ粒子の粒径の成員すなわ
ちビルドアップを行う際には、シード液の温度を７０’
Ｃ以上、好ましくは８０〜２Ｏ０’Ｃの範囲の一定温度
に保持することが好ましい。シード液の温度が７０’Ｃ
未満では、添加された酸性ケイ酸液中のケイ酸の溶解速
度および溶解されたシリカのシード上への沈着速度など
が遅くなり、このため酸性ケイ酸液の添加速度を遅くし
なければならないことから好ましくない。一方シード液
の温度を高くすれば、前述の溶解速度および沈着速度を
速くすることができるので有利であるが、粒径を制御す
ることが困難になることから２Ｏ０’Ｃ以下であること
が好ましい。While adding the acidic silicic acid solution to the seed solution at the above-mentioned addition rate, when building up the size of the silica particles in the seed solution, the temperature of the seed solution should be kept at 70'.
It is preferable to maintain the temperature at a constant temperature of C or higher, preferably in the range of 80 to 200'C. Seed liquid temperature is 70'C
If less than undesirable. On the other hand, raising the temperature of the seed liquid is advantageous because it can increase the aforementioned dissolution rate and deposition rate, but since it becomes difficult to control the particle size, it is preferably below 2O0'C. .
上記のような方法で得られた大粒径のシリカ粒子が分散
媒中に分散されてなるシリカゾルは、このままでも各種
の用途に供し得るが、通常はＳｉＯ２濃度を約３０〜７
０重ａ％程度にまで濃縮して使用する。濃縮方法は、限
外濾過法、蒸発法等公知の方法が広く用い得る。The silica sol obtained by dispersing large-sized silica particles in a dispersion medium obtained by the method described above can be used as is for various purposes, but usually the SiO2 concentration is adjusted to about 30 to 7.
It is used after being concentrated to about 0% by weight. As the concentration method, a wide variety of known methods such as ultrafiltration and evaporation can be used.
なお、本発明で得られるシリカゾルの分散媒は通常水で
あるが、これをアルコール、エチレングリコール等の有
機溶媒と置換して、有機溶媒を分散媒としたシリカゾル
とすることも可能である。Note that the dispersion medium of the silica sol obtained in the present invention is usually water, but it is also possible to replace this with an organic solvent such as alcohol or ethylene glycol to obtain a silica sol using the organic solvent as the dispersion medium.
置換方法としては、たとえば濃縮後の水分散ゾルにエチ
レングリコールなどを加え、蒸昭により水を留去するな
ど公知の方法が採用される。As the substitution method, a known method may be employed, such as adding ethylene glycol or the like to the water-dispersed sol after concentration and distilling off the water.
本発明で得られるシリカゾルは、８１０２７Ｍ２Ｏのモ
ル比が７０〜２Ｏ０の範囲にあり、分散シリカ粒子の平
均粒径（ＤＡ ＞が約４０〜１、ｏｏｏｍμで、その粒
度分布は（１±０．３）［）八が全体の８０％以上とぎ
わめて均一な粒径をもっており、さらにその形状は、次
式で定義した形状係数が１．０〜１．２となり、真球状
に近い形状のシリカ粒子が７０％以上の割合で存在して
いる。The silica sol obtained in the present invention has a molar ratio of 81027M2O in the range of 70 to 2O0, an average particle diameter of dispersed silica particles (DA > about 40 to 1, ooomμ, and a particle size distribution of (1±0.3 )[)8 has an extremely uniform particle size, accounting for more than 80% of the total, and its shape has a shape factor of 1.0 to 1.2 as defined by the following formula, making it a nearly perfect spherical silica. Particles are present in a proportion of 70% or more.
形状係数＝ （ＰＭ）２／ＡＸ１／４πＰＭ：粒子の投
影面の周囲の長ざ
Ａ：粒子の投影面の面積
したがって、このシリカゾルをプラスチック等の改質剤
、あるいはハードコート剤として用いると、分散性が良
好になるとともに、表面の平滑度が向上するなど、従来
のシリカゾルに比べすぐれた効果を発揮する。Shape factor = (PM)2/AX1/4πPM: Length around the projected surface of the particle A: Area of the projected surface of the particle Therefore, when this silica sol is used as a modifier for plastics or as a hard coating agent, dispersion It exhibits superior effects compared to conventional silica sol, such as improved properties and improved surface smoothness.
なお、本発明にあけるシリカ粒子の平均粒径、粒度分布
、形状係数は、シリカ粒子の電顕写真による画像解析法
により求めた値である。Note that the average particle diameter, particle size distribution, and shape factor of the silica particles in the present invention are values determined by an image analysis method using an electron micrograph of the silica particles.
発明の効果
本発明に係る粒子径が大粒径のシリカ粒子を含むシリカ
ゾルの製造方法は、（ａ）特定の条件でシード液を調製
する工程と、（ｂ）このシード液に酸性ケイ酸液を特定
の添加速度で添加して、シード液中のシリカ粒子の粒子
径を成員させる工程とからなっているので、大きな平均
粒子径を有し、しかも粒度分布が均一であり、その上真
珠に近いような形状を有するシリカ粒子とすることがで
き、したがって大きな平均粒子径を有し、しがも粒度分
布が均一であり、その上真珠に近いような形状を有する
シリカ粒子が分散媒中に分散されてなるシリカゾルを得
ることができる。Effects of the Invention The method for producing a silica sol containing silica particles with large particle diameters according to the present invention includes (a) preparing a seed liquid under specific conditions; and (b) adding an acidic silicic acid solution to the seed liquid. The process consists of the step of adding silica particles at a specific addition rate to adjust the particle size of the silica particles in the seed liquid, so it has a large average particle size, a uniform particle size distribution, and moreover, The silica particles can have a shape similar to that of a pearl, and therefore have a large average particle size, a uniform particle size distribution, and a shape similar to a pearl in the dispersion medium. A dispersed silica sol 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.
実施例１〜４
表１に示すようなシリカゾルに、ケイ酸ナトリウム溶液
（ＳｉＯ２濃度２４重量％）および純水を混合してシー
ド液を調製した。Examples 1 to 4 Seed liquids were prepared by mixing silica sol shown in Table 1 with a sodium silicate solution (SiO2 concentration: 24% by weight) and pure water.
このシード液を還流器、攪拌装置および加熱装置を備え
た内容積５ｇのステンレス製容器に仕込んだ。これを表
１に示すような所定温度に昇温し、その温度を保持しな
がら酸性ケイ酸液を一定の速度で添加してピルドアツプ
工程を実施した。添加終了後、同一温度に約１時間保持
したのち冷却し、限外濾過装置により、所定濃度まで濃
縮して表１に示すような性状のシリカ粒子を含むシリカ
ゾルを１９だ。This seed liquid was charged into a stainless steel container with an internal volume of 5 g equipped with a refluxer, a stirring device, and a heating device. This was heated to a predetermined temperature as shown in Table 1, and while maintaining that temperature, an acidic silicic acid solution was added at a constant rate to perform a pill-up step. After the addition, the mixture was kept at the same temperature for about 1 hour, cooled, and concentrated to a predetermined concentration using an ultrafiltration device to obtain a silica sol containing silica particles having the properties shown in Table 1.
酸性ケイ酸液は、市販のケイ酸ナトリウム溶液を純水で
希釈し、これを、水素型陽イオン交換樹脂が充填された
カラムに通すことによって脱アルカリすることによって
調製した。The acidic silicic acid solution was prepared by diluting a commercially available sodium silicate solution with pure water and dealkalizing it by passing it through a column packed with a hydrogen-type cation exchange resin.
なお、実施例４では、攪拌機、加熱装置を備えたオート
クレーブを用いた。In addition, in Example 4, an autoclave equipped with a stirrer and a heating device was used.
実施例５
実施例２で得られた粒子径のシリカ粒子を含むシリカゾ
ルを、シード液調製用のシリカゾルとして用いた以外は
、実施例１と同様の方法で行い、表１に示すような、さ
らに粒子径が成員されたシリカ粒子を含むシリカゾルを
得た。Example 5 The same method as Example 1 was carried out except that the silica sol containing silica particles having the particle size obtained in Example 2 was used as the silica sol for preparing the seed liquid, and further preparations as shown in Table 1 were carried out. A silica sol containing silica particles having a uniform particle size was obtained.
実施例６
実施例５で得られた粒子径のシリカ粒子を含むシリカゾ
ルを、シード液調製用のシリカゾルとして用いた以外は
、実施例１と同様にして、表１に示すような、ざらに粒
子径が成員されたシリカ粒子を含むシリカゾルを得た。Example 6 In the same manner as in Example 1, except that the silica sol containing silica particles having the particle size obtained in Example 5 was used as the silica sol for preparing the seed liquid, particles as shown in Table 1 were prepared. A silica sol containing silica particles having a uniform diameter was obtained.
実施例７
実施例２で得られた粒子径のシリカ粒子を含むシリカゾ
ルを、シード液［ｊ用のシリカゾルとして用いた以外は
、実施例４と同様にして、表１に ′示すような、さら
に粒子径が成員されたシリカ粒子を含むシリカゾルを得
た。Example 7 In the same manner as in Example 4, except that the silica sol containing silica particles having the particle size obtained in Example 2 was used as the silica sol for the seed liquid [j, A silica sol containing silica particles having a uniform particle size was obtained.
叉蓋■旦
実施例７で得られた粒子径のシリカ粒子を含むシリカゾ
ルを、シード液調製用のシリカゾルとして用いた以外は
、実施例４と同様にして、表１に示すような、ざらに粒
子径が成員されたシリカ粒子を含むシリカゾルを得た。In the same manner as in Example 4, except that the silica sol containing silica particles having the particle size obtained in Example 7 was used as the silica sol for preparing the seed liquid, the coarse particles as shown in Table 1 were prepared. A silica sol containing silica particles having a uniform particle size was obtained.
実施例９
実施例８で得られた粒子径のシリカ粒子を含むシリカゾ
ルを、シード液調製用のシリカゾルとして用いた以外は
、実施例４と同様にして、表１に示すような、ざらに粒
子径が成員されたシリカ粒子を含むシリカゾルを得た。Example 9 In the same manner as in Example 4, except that the silica sol containing silica particles having the particle size obtained in Example 8 was used as the silica sol for preparing the seed liquid, particles as shown in Table 1 were prepared. A silica sol containing silica particles having a uniform diameter was obtained.
実施例１０〜１１
実施例５で１ｑられた粒子径のシリカ粒子を含むシリカ
ゾルをシード液調製用のシリカゾルとして用いた以外は
、実施例４と同様にして、表１に示すような、さらに粒
子径が成員されたシリカ粒子を含むシリカゾルを１９た
〈実施例１０）。ざらに実施例１０で得られたシリカゾ
ルをシード液ｍＷ用のシリカゾルとして用いて、実施例
４と同様にして、表１に示すような、ざらに粒子径が成
員されたシリカ粒子を含むシリカゾルを得た（実施例１
１）。Examples 10 to 11 In the same manner as in Example 4, except that the silica sol containing silica particles having the particle size of 1q in Example 5 was used as the silica sol for preparing the seed liquid, further particles as shown in Table 1 were prepared. A silica sol containing silica particles having a uniform diameter was prepared (Example 10). Using the silica sol obtained in Rarani Example 10 as a silica sol for the seed liquid mW, a silica sol containing silica particles having a particle diameter as shown in Table 1 was prepared in the same manner as in Example 4. obtained (Example 1
1).
±竺里ユ
実施例７と同一シード液を用い、添加速度を変化させた
以外は同一条件でビルドアップ操作を行った。得られた
シリカゾル中のシリカ粒子は、平均粒径、形状係数およ
び粒度分布が測定不能なほど粒径は不ぞろいであり、形
状もいびつであった。The build-up operation was performed under the same conditions except that the same seed liquid as in Example 7 was used and the addition rate was changed. The silica particles in the obtained silica sol were so irregular in average particle size, shape factor, and particle size distribution that it was impossible to measure them, and the shape was also distorted.
ル較■ｌ
実施例９において、添加速度を変化させた以外は、同一
のシード液を用いて、同一条件でビルドアップ操作を行
ったが、比較例１と同様に、得られたシリカゾル中のシ
リカ粒子は、平均粒径、形状係数および粒度分布が測定
不能なほど粒径は不ぞろいであり、形状もいびつであっ
た。Comparison ■l In Example 9, the same seed liquid was used and the build-up operation was performed under the same conditions except that the addition rate was changed. The silica particles were so irregular that the average particle size, shape factor, and particle size distribution were unmeasurable, and the shape was also distorted.
比較例３
実施例４で得られた粒子径のシリカ粒子を含むシリカゾ
ルを、シード液調製用のシリカゾルとして用い、実施例
４と同様にしてビルドアップ操作を行ったが、シード液
中の全Ｓ ｉ Ｏ７／Ｍ？０のモル比が７０を越えてい
たため、比較例１と同様に粒径、形状とも、不ぞろいで
いびつでおった。Comparative Example 3 A silica sol containing silica particles having the particle size obtained in Example 4 was used as a silica sol for preparing a seed liquid, and a build-up operation was performed in the same manner as in Example 4, but the total S in the seed liquid was i O7/M? Since the molar ratio of 0 exceeded 70, the particle size and shape were irregular and distorted as in Comparative Example 1.
比較例４
実施例２と同じシリカゾルを用いて、シード液を調製し
、ビルドアップ操作を行ったが、シード液中の全ＳｉＯ
２／Ｍ２Ｏのモル比が１０未満であったため、表１に示
すように形状係数および粒度分布に劣ったシリカゾルし
か得ることはできなかった。Comparative Example 4 A seed liquid was prepared using the same silica sol as in Example 2, and a build-up operation was performed.
Since the molar ratio of 2/M2O was less than 10, only a silica sol with poor shape coefficient and particle size distribution could be obtained as shown in Table 1.
表１続きTable 1 continued
Claims (1)
特徴とする、大粒径のシリカ粒子を含むシリカゾルの製
造方法： （ａ）比較的小さな粒子径を有するシリカ粒子が分散媒
中に分散されてなるシリカゾルと、ケイ酸アルカリ水溶
液および／またはアルカリ水溶液とを混合して、混合液
の全ＳｉＯ＿２／Ｍ＿２Ｏ（Ｍはアルカリ金属）のモル
比を１０〜７０に調整してシード液を調製する工程、 （ｂ）このシード液を７０℃以上に保持しながら、酸性
ケイ酸液を下記の速度式を満足するような添加速度で添
加して、小さな粒子径を有するシリカ粒子の粒子径を成
員させるビルドアップ工程ｌｏｇＷ≦−３．５×１０＾
−＾３Ｄ＋０．７Ｗ：酸性ケイ酸液の添加速度 ［酸性ケイ酸液ＳｉＯ＿２ｇ数／時・シード液中の初期
シリカゾルＳｉＯ＿２ｇ］ Ｄ：シード液中の酸性ケイ酸液を添加する前のシリカ粒
子の平均粒径（ｍμ）。[Claims] 1) A method for producing a silica sol containing large-sized silica particles, characterized by comprising the following steps (a) and (b): (a) having a relatively small particle size A silica sol in which silica particles are dispersed in a dispersion medium is mixed with an aqueous alkali silicate solution and/or an aqueous alkali solution, and the molar ratio of total SiO_2/M_2O (M is an alkali metal) in the mixed liquid is adjusted to 10 to 70. (b) While maintaining this seed liquid at 70°C or higher, add acidic silicic acid liquid at an addition rate that satisfies the following rate formula to reduce particle size. Build-up process to increase the particle size of silica particles logW≦-3.5×10^
-^3D+0.7W: Addition rate of acidic silicic acid solution [Number of acidic silicic acid liquid SiO_2g/hour・Initial silica sol SiO_2g in seed liquid] D: Average of silica particles in seed liquid before adding acidic silicic acid liquid Particle size (mμ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20563286A JPS6364911A (en) | 1986-09-01 | 1986-09-01 | Production of silica sol containing silica particle having large particle size |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20563286A JPS6364911A (en) | 1986-09-01 | 1986-09-01 | Production of silica sol containing silica particle having large particle size |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6364911A true JPS6364911A (en) | 1988-03-23 |
| JPH0456775B2 JPH0456775B2 (en) | 1992-09-09 |
Family
ID=16510104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20563286A Granted JPS6364911A (en) | 1986-09-01 | 1986-09-01 | Production of silica sol containing silica particle having large particle size |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6364911A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004203729A (en) * | 2002-12-12 | 2004-07-22 | Catalysts & Chem Ind Co Ltd | Method for manufacturing silica sol and silica sol |
| WO2007018069A1 (en) * | 2005-08-10 | 2007-02-15 | Catalysts & Chemicals Industries Co., Ltd. | Deformed silica sol and process for producing the same |
| JP2009083224A (en) * | 2007-09-28 | 2009-04-23 | Jgc Catalysts & Chemicals Ltd | Base material with hard coat film and coating solution for forming hard coat film |
| JP2018535178A (en) * | 2016-03-28 | 2018-11-29 | エルジー・ケム・リミテッド | Method for producing airgel blanket with low dust and high thermal insulation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3440174A (en) * | 1965-04-26 | 1969-04-22 | Nalco Chemical Co | Method of making silica sols containing large particle size silica |
| US3538015A (en) * | 1967-12-07 | 1970-11-03 | Nalco Chemical Co | Large particle silica sols and method of production |
| US3789009A (en) * | 1971-07-15 | 1974-01-29 | Du Pont | Process for the preparation of large particle silica sols |
-
1986
- 1986-09-01 JP JP20563286A patent/JPS6364911A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3440174A (en) * | 1965-04-26 | 1969-04-22 | Nalco Chemical Co | Method of making silica sols containing large particle size silica |
| US3538015A (en) * | 1967-12-07 | 1970-11-03 | Nalco Chemical Co | Large particle silica sols and method of production |
| US3789009A (en) * | 1971-07-15 | 1974-01-29 | Du Pont | Process for the preparation of large particle silica sols |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004203729A (en) * | 2002-12-12 | 2004-07-22 | Catalysts & Chem Ind Co Ltd | Method for manufacturing silica sol and silica sol |
| JP4493320B2 (en) * | 2002-12-12 | 2010-06-30 | 日揮触媒化成株式会社 | Method for producing silica sol and silica sol |
| KR101050549B1 (en) | 2002-12-12 | 2011-07-19 | 닛키 쇼쿠바이카세이 가부시키가이샤 | Preparation method of silica sol and silica sol |
| WO2007018069A1 (en) * | 2005-08-10 | 2007-02-15 | Catalysts & Chemicals Industries Co., Ltd. | Deformed silica sol and process for producing the same |
| US20110314745A1 (en) * | 2005-08-10 | 2011-12-29 | Jgc Catalysts And Chemicals Ltd. | Nodular silica sol and method of producing the same |
| JP5127452B2 (en) * | 2005-08-10 | 2013-01-23 | 日揮触媒化成株式会社 | Method for producing deformed silica sol |
| US8585791B2 (en) * | 2005-08-10 | 2013-11-19 | Jgc Catalysts And Chemicals Ltd. | Method of producing nodular silica sol |
| JP2009083224A (en) * | 2007-09-28 | 2009-04-23 | Jgc Catalysts & Chemicals Ltd | Base material with hard coat film and coating solution for forming hard coat film |
| JP2018535178A (en) * | 2016-03-28 | 2018-11-29 | エルジー・ケム・リミテッド | Method for producing airgel blanket with low dust and high thermal insulation |
| US11059262B2 (en) | 2016-03-28 | 2021-07-13 | Lg Chem, Ltd. | Method of preparing low-dust and high-insulation aerogel blanket |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0456775B2 (en) | 1992-09-09 |
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