JPH03217230A - Modified metallic oxide sol and its production - Google Patents

Abstract

PURPOSE:To obtain this stable sol having high refractive index by preparing such a sol incorporating 2-50wt.% modified metallic oxide particles prepared by covering the surface of cores composed of specified metallic oxide colloid particles with specified colloid particles. CONSTITUTION:The metallic oxide sol having 4-50mu particle size and 3, 4, or 5 valences, by 100 pts.wt. in terms of the metallic oxide incorporated in this sol, and tungsten oxide-tin oxide composite sol having 2-7mu particle size and 0.5-2 WO3/SnO2 by 2-100 pts.wt. are mixed to prepare the stable sol of modified metal oxide colloid particles. The obtd. sol consists of modified metal oxide colloid particles of 4.5-60mu particle size, incorporating 2-50wt.% of all metallic oxide.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a method for treating the surface of colloidal particles of trivalent to pentavalent metal oxides by
formed by coating with colloidal particles of 2-7 millimicrons tungsten oxide-tin oxide composite.
The present invention relates to a sol of modified colloidal particles of trivalent to pentavalent metal oxides having a particle size of approximately 4.5 to 60 millimicrons, and a method for producing the same.

The sol of the present invention can be used as a component of a hard coating agent applied to the surface of a plastic lens, and for various other purposes.

(The best conventional technology) Sols of various metal oxides are already known.

Is this surface used to alter the masculine appearance of plastic lenses, which have become widely used in recent years? A metal oxide sol with a high refractive index is used as a component of the hard coating agent used. For example, in Japanese Patent Publication No. 63-37142, AI2,
1 to 3 of metal oxides such as Ti, Zr, Sn, Sb, etc.
A hard coating agent containing 0.00 mm particles has been described6. Although a stable sol of tungsten oxide alone is not yet known, WO3 obtained by adding silicate: Si
A sol in which the molar ratio of o■:MzO (M represents an alkali metal atom or an ammonium group) is 4 to 5:2 to 5:1 has been proposed in JP-A-5452686. In addition, in Japanese Patent Publication No. 50-40119, Si:Sn
A silicic acid-stannic acid composite sol having a molar ratio of 2 to 1[10[]:1 has been proposed.

(Problem to be solved by the invention) However, when these conventional metal oxide sols, especially cationic metal oxide sols, are used as a component of a hard coating agent, the stability of the obtained hard coating agent is sufficient. In addition, the cured film of this hard coating agent has insufficient transparency, adhesion, weather resistance, etc. In addition, when using SbzOs sol as a hard coating agent component, Sb20s
Since the refractive index of the sb2o. Sol does not sufficiently improve the refractive index of the cured film.

The tungsten oxide sol described in JP-A-54-52686 is obtained by adding a silicate to a tungstic acid aqueous solution obtained by decationizing a tungstate aqueous solution. It is stable only under strong acidity, and when used as a component of a hard coating agent, it has little effect on improving the refractive index of the coating film.

The silicic acid monostannic acid composite sol described in Japanese Patent Publication No. 50-40119 is obtained by decationizing a mixed aqueous solution of an alkali silicate and an alkali stannate. When used as a component of a coating agent, the effect of improving the refractive index of the coating film is small.

The present invention aims to provide a stable sol of colloidal particles of a metal oxide having a high refractive index, particularly a refractive index of 1.7 or higher. Still another object of the present invention is to provide a metal oxide sol that can be mixed into a hard coat paint and used as a component for improving the performance of a hard coat film applied to the surface of a plastic lens.

(Means for Solving the Problems) The metal oxide sol of the present invention has colloidal particles of a metal oxide with a valence of 3, 4, or 5 having a particle size of 4 to 50 millimicrons as a core, and the surface thereof is W03. /SnO■ Particle size 4.5-60 formed by coating with colloidal particles of tungsten oxide-tin oxide composite having a weight ratio of 0.5-100 and a particle size of 2-7 millimicrons.
Made of millimicron modified metal oxide colloid particles,
And does it contain 2 to 50% by weight of all these metal oxides? It is a fixed sol.

The sol of colloidal particles of a modified metal oxide with a particle size of 4.5 to 60 millimicrons whose surface is coated with colloidal particles of a tungsten oxide-tin oxide composite of the present invention is: 0
．． A sol of colloidal particles of the metal oxide having a valence 3, 4 or 5 metal oxide concentration of 5 to 50% by weight and a particle size of 4 to 50 millimicrons is used as the metal oxide.
0 parts by weight, particle size of 2-7 millimicrons and 0.5-1
W03/SnOz weight ratio of 00 and 0.5-40% by weight
By mixing a sol of colloidal particles consisting of a tungsten oxide-tin oxide composite having a total concentration of WO3 and SnO2 at a ratio of 2 to 100 parts by weight as the total concentration of W03 and SnO2 at 0 to 100 °C, or as required. Then, it can be obtained by concentrating the sol obtained by this mixing.

Examples of water-soluble tungstates and water-soluble stannates used in the production of the tungsten oxide-tin oxide composite sol of the present invention include tankstates and stannates of alkali metals, ammonium, or water-soluble amines. It will be done.

Preferred examples of these alkali metals, ammonium and amines include Li, Na, K, Rb, CS,
NH4 + Alkylamines such as ethylamine, triethylamine, isobrobylamine, n-probylamine, isobutylamine, diisobutylamine, di(2-ethylhexyl)amine; aralkylamines such as benzylamine; alicyclic amines such as viveridine: mono Examples include alkanolamines such as ethanolamine and triethanolamine. In particular, sodium tungstate NaJ
O4- 2H20 and sodium stannate NazSnO3
-3H20 is preferred. Furthermore, tungsten oxide, tungstic acid, stannic acid, etc. dissolved in an aqueous solution of an alkali metal hydroxide can also be used.

The hydrogen type cation exchanger used may be any conventional one, and hydrogen type cation exchange resins are conveniently available as commercial products. Are alkali metal hydroxides, ammonium hydroxide, amines, etc. used in some cases commercially available? It can be a product. Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like.

The aqueous solution of tungstic acid to be used can be easily obtained by treating the aqueous solution of the tungstate salt with the cation exchange resin at a temperature below 100°C, preferably at room temperature to about 60°C. This aqueous solution of tungstic acid is
Because it has colloidal properties, it tends to gel, so it is convenient to use it before gelation. The aqueous solution of the tungstate salt used to prepare the aqueous solution of tungstic acid is W03 of 0.1 to
A W03 concentration of 15% by weight is preferable, and even as an aqueous solution of tungstic acid, the W03 concentration is 0.1 to 15% by weight.
degree is preferred.

The aqueous solution of stannate used has a SnO concentration of 0.
．． It is preferably about 1 to 30% by weight, but it may be higher than this. In some cases, solid stannate salts can also be used.

Tungsten oxide-tin oxide complex according to the present invention? The sol is produced by mixing the tungstic acid aqueous solution and the stannate aqueous solution. This mixing is preferably carried out under sufficient stirring at a temperature higher than the temperature at which the liquid freezes and below 100°C, preferably from room temperature to about 60°C. The amount of liquid to be mixed is W03/SnO■ weight ratio of 0.5.
It is preferably about 100 to 100, particularly preferably 2 to 100. This mixing can be completed in about 5 to 100 minutes, preferably about 30 to 60 minutes. By this mixing, the resulting mixed solution usually contains the alkali metal ions, ammonium ions, amines, and the like. When these alkali metal atoms, NH4 or amine molecules are represented by M, the ratio of the number of moles of M20 contained to the total number of moles of W03 and SnO in the obtained mixed solution is M20/(WO3+S
nOz) is approximately 0.01 to 0.44. In order to obtain a highly stable tungsten oxide-tin oxide composite sol, M20/(
It is preferable to adjust the W03+Sn021 molar ratio to about 0.02 to 0.7. Obtained by the above mixture? The above molar ratio in the liquid can also be increased by adding an alkali metal oxide, ammonium hydroxide, amine, etc. to this mixed liquid, but it is also possible to increase the above molar ratio in the liquid by treating the above mixed liquid with a hydrogen type cation exchange resin. After that, M20/ (WO3 +
This can be carried out by adding an alkali metal hydroxide, ammonium hydroxide, amine, etc. so that the SnOzl molar ratio is 0.02 to 0.7.

W0 contained in the tungsten oxide-tin oxide composite sol after the above-mentioned mixing or after the above-mentioned molar ratio adjustment
Colloidal particles consisting of a complex of 3 and SnO can be observed using an electron microscope, and their size is usually 7.
The particle size of the sol is preferably 2 to 5 millimicrons.

When it is desired to increase the concentration of the tungsten oxide-tin oxide composite sol obtained by the above method, the concentration of the sol can be increased by a conventional concentration method, such as an evaporation method or an ultrafiltration method.

In particular, ultrafiltration is preferred. Even in this concentration, the temperature of the sol is preferably maintained at about 100°C or less, particularly 60°C or less. However, it is best to avoid concentrating the total concentration of WO3 and SnOz to more than 40% by weight, as this will result in poor sol stability. Practically preferred concentration is 2% by weight or more, particularly preferably about 10 to 30% by weight.

The preferred aqueous sol of the tungsten oxide-tin oxide complex obtained as described above usually exhibits a pH of 1 to 9,
It is a colorless, clear or nearly clear liquid. The sol is stable for more than 3 months at room temperature and for more than 1 month at 60°C, and no sediment is formed in this sol. Also, this sol does not thicken or gel. .

By replacing the water in the aqueous sol with a hydrophilic organic solvent, a hydrophilic organic solvent sol called an organosol can be obtained. Examples of hydrophilic organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, and isobrobyl alcohol. ;dimethylformamide, N,N'-
Linear amides such as dimethylacetamide; N-methyl-
Cyclic amides such as 2-pyrrolidone; ethyl cellosolve,
Examples include glycols such as butyl cellosolve and ethylene glycol.

The above-mentioned replacement of water with a hydrophilic organic solvent can be easily carried out by a conventional method, for example, a distillation replacement method, an ultrafiltration method, or the like. When the pH of the aqueous sol is high, before or at the same time as the above substitution, add oxycarboxylic acid such as lactic acid, tartaric acid, citric acid, gluconic acid, malic acid, or glycolic acid to the aqueous sol based on the total amount of W03 and SnOz. It is preferable to add 30% by weight or less. Regardless of the presence or absence of this oxycarponic acid, the temperature of the sol is preferably maintained at about 100° C. or lower, particularly 60° C. or lower, even during the replacement of the sol medium.

The colloidal particles of the tungsten oxide-tin oxide composite sol obtained as described above are mixed with an oxide of another metal having a valence of 3, 4 or 5, such as AI2aOs. Y203,
SbzOa, Ing03, Bi2e3, Tie■, Z
rOz. SnOz, CeOz, Tera, SbzOs,
By binding to the surface of a colloidal particle of a sol such as NbzOs+TazOs and coating the surface with the colloidal particle of the tungsten oxide-tin oxide composite, the surface becomes a tungsten oxide-tin oxide composite with the colloidal particle as a core. Colloidal particles of the above-mentioned metal oxide having a valence of 3 to 5 can be produced, and the modified colloidal particles can be obtained as a sol in which the modified colloidal particles are stably dispersed in a liquid medium.

The colloidal particles of the trivalent to pentavalent metal oxide used are prepared by known methods such as ion exchange method, peptization method, hydrolysis method, reaction method, etc. to about 4 to 50 millimicrons. It can be easily produced in the form of a sol of colloidal particles having a particle size of .

Examples of the above ion exchange methods include a method in which acidic salts of the above metals are treated with a hydrogen-type cation exchange resin, or methods in which basic salts of the above metals are treated with a hydroxyl group-type anion resin. Waru. Examples of the peptizing method include neutralizing the acid salt of the metal with a base, or washing the gel obtained by neutralizing the basic salt of the metal with an acid,
Examples include a method of peptizing with an acid or a base. Examples of the above-mentioned hydrolysis methods include a method of hydrolyzing an alkoxide of the above-mentioned metal, or a method of hydrolyzing a basic salt of the above-mentioned metal under heating and then removing unnecessary acid. An example of the above reaction method is a method of reacting the above metal powder with an acid. The medium for these metal oxide sols may be either water or a hydrophilic organic solvent, but aqueous sols in which the medium is water are preferred. The pH of these sols should preferably be a value that makes the sol stable, and is usually about 1 to 9. As long as the purpose of the present invention is achieved, these metal oxide sols may contain optional ingredients, such as alkaline substances for stabilizing the sol,
Acidic substances, carboxylic acids, etc. may be included.

) l1lt and 1,τ of the metal oxide sol used.
All M drunk 1? 'JI1+3- 1.7 n F+~F+1
1t tatami? However, the lower the concentration, the better, and preferably 1 to 30% by weight. Furthermore, a mixture of two or more of the above-mentioned sols can also be used as long as a stable sol of the present invention can be obtained.

The sol of colloidal particles of these tri- to S-valent metal oxides modified by the colloidal particles of the tungsten oxide-tin oxide composite contains 100 parts by weight of these tri- to penta-valent metal oxide sol as the metal oxide. , the above tungsten oxide-tin oxide composite sol was combined with W03 of this sol and SnO
It is obtained by mixing in a total ratio of 2 to 100 parts by weight, preferably under strong stirring. This mixing is preferably carried out at a temperature of 0 to 100°C, preferably room temperature to 60°C. This mixing takes about 5 to 10 minutes.
Preferably, the process can be completed in about 30 to 60 minutes. The modified colloidal particle sol to be obtained by this mixing is composed of the trivalent to pentavalent metal oxide, NO3 and SnO.
The concentration of the tungsten oxide-tin oxide composite sol and the trivalent to pentavalent metal oxide sol used in the above mixing are selected before the above mixing so that the sol contains a total of 2 to 40% by weight of Preferably, both sols are mixed. However, when it is desired to further increase the concentration of the sol obtained by this mixing, it can be increased up to a maximum of about 50% by weight using a conventional method, for example,
It can be concentrated by evaporation, ultrafiltration, etc.

The modified colloidal particles in the sol obtained by the above mixing can be observed with an electron microscope and have a particle size of approximately 4.5 to 60 millimicrons. The sol obtained by the above mixing has pi{approximately 1 to 9 and is stable. When you want to adjust the pH of the sol, the pH should be approximately 1.
This can be carried out by adding the hydroxides of alkali metals, ammonium, etc., the amines, xycarboxylic acid, etc. to the sol after the above mixing or after the above concentration. In particular, a sol in which the total concentration of the metal oxide, W03, and Sn02 is 10 to 40% by weight is practically preferable.

When the modified metal oxide sol obtained by the above mixing is an aqueous sol, an organosol can be obtained by replacing the aqueous medium of this aqueous sol with a hydrophilic organic solvent. This substitution can be carried out by a conventional method such as a distillation method or an ultrafiltration method. Examples of hydrophilic organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, and isobrobyl alcohol; dimethylformamide,
Examples include linear amides such as N,N'-dimethylacetamide; cyclic amides such as N-methyl-2-pyrrolidone; and glycols such as ethyl cellosolve, butyl cellosolve, and ethylene glycol.

(Function) Both the colloidal particles of the tungsten oxide-tin oxide composite according to the present invention and the colloidal particles of the modified trivalent to pentavalent metal oxide whose surfaces are coated with these particles are negatively charged in the sol. It was found that the particles were

Excluding the colloidal particles of SbzOs, the above-mentioned examples 3 to 5
Since the surface of the colloidal particles of the valent metal oxide is positively charged, the mixing causes the negatively charged colloidal particles of the tungsten oxide-tin oxide composite to surround the positively charged colloidal particles. The colloidal particles of the tungsten oxide-tin oxide composite are electrically attracted and bonded by chemical bonds on the surface of the positively charged colloidal particles, and the surface becomes the tungsten oxide-tin oxide composite with this positively charged particle as the core. By covering the
It is thought that colloidal particles of modified trivalent to pentavalent metal oxides were produced. However, Sb. Since the OS colloidal particles are not positively charged, the sb. o. It is thought that the colloidal particles of the tungsten oxide-tin oxide composite were bonded to the surface of the colloidal particles. The fact that a stable mixed sol can be obtained without agglomeration of colloidal particles by mixing these generated negatively charged colloidal particle sols with the well-known negatively charged silica sol indicates that tungsten oxide Both the colloidal particles of the tin oxide complex and the colloidal particles of the modified trivalent to pentavalent metal oxide whose surfaces are coated with these particles must be sufficiently negatively charged colloidal particles to maintain a stable sol. It shows. However, the particle size of trivalent to pentavalent metal oxides is 4 to 50.
When mixing a sol of millimicron colloidal particles and a sol of tungsten oxide-tin oxide composite colloidal particles, the total amount of W03 and Snug is 10
If the amount is less than 2 parts by weight relative to 0 parts by weight, a stable sol cannot be obtained. This means that when the amount of colloidal particles of the tungsten oxide-tin oxide composite is insufficient, the surface of the colloidal particles of the tungsten oxide-tin oxide composite, with the metal oxide colloidal particles as the core, is insufficiently covered, and the resulting colloidal particles are It is thought that aggregation is likely to occur, making the produced sol unstable.

Therefore, the amount of tungsten oxide-tin oxide composite colloidal particles to be mixed may be less than the amount that covers the entire surface of the metal oxide colloidal particles? , the amount is at least the minimum amount necessary to produce a stable sol of modified metal oxide colloidal particles. When the amount of tungsten oxide-tin oxide composite colloidal particles exceeding the amount used for this surface coating is used for the above mixing, the resulting sol is a sol of tungsten oxide-tin oxide composite colloidal particles and a sol of the tungsten oxide-tin oxide composite colloidal particles. It is nothing more than a stable mixed sol with a sol of modified metal oxide colloid particles.

Preferably, to modify the metal oxide colloidal particles by their surface coating, the amount of colloidal particles of the tungsten oxide-tin oxide composite used is greater than the amount of WO in the composite sol.
The total of 3 and SnO2 is preferably 100 parts by weight or less per 100 parts by weight of the metal oxide.

Preferred aqueous sols of modified metal oxides according to the invention have a put~9; at pH below 1 such sols tend to become unstable. In addition, when this pH exceeds 9, tungsten oxide-acid covering the modified metal oxide colloid particles? Tin complex easily dissolves in liquid. Furthermore, when the total concentration of the metal oxide, WOs, and Sn02 in the sol of modified metal oxide colloidal particles exceeds 50% by weight, such a sol tends to become unstable. The preferred concentration as an industrial product is about 10 to 40% by weight.

When the above trivalent to pentavalent metal oxide sol and the above tungsten oxide-tin oxide composite sol are mixed, the metal oxide concentration and the total concentration of WO and SnO in these sol all exceed 50% by weight. Use of a sol is not preferred because gelation may occur during the above mixing. Rather, the concentration of the sol used should be low, but if the concentration is too low, when concentrating the sol obtained by mixing,
This results in an increase in the amount of liquid that must be removed. Furthermore, if this mixing is carried out at a high temperature of 100°C or higher, the tungsten oxide-tin oxide composite colloidal particles are susceptible to hydrolysis. As a trivalent to pentavalent metal oxide sol, SnOt sol, Zr0
2 sol, Tilt sol, sb. o. Do you use sol etc.? The sol of the present invention can be obtained which has sufficient stability, colloidal particle size, and modified metal oxide colloidal particle refractive index.

If a sol of colloidal particles of a tungsten oxide-tin oxide composite is not prepared in a preferred manner, the resulting sol will be of limited practical use. An aqueous solution of tungstic acid obtained by treating an aqueous solution of a tungstate salt with a hydrogen-type cation exchange resin and an aqueous solution of a stannate were mixed into NO.
/SnO■ The stability of the sol obtained by mixing at a weight ratio of 2 to 100 is due to the colloidal particles of tin oxide produced by this mixing and the colloidal particles of tungsten oxide or polyanidine, which is a low polymer of tungstic acid. The alkali metal introduced by the stannate into the colloidal particles of the tungsten oxide and tin oxide complex by the combination of
This is thought to be due to the fact that cations such as ammonium and amines acted as stabilizing counter ions and stable colloidal particles were produced.

However, if the weight ratio of Wow/SnO in the obtained sol is less than 0.5, the sol will be unstable when it is acidic, and if this weight ratio exceeds 100, the sol will still show no stability. . The amount of cations such as alkali metals, ammonium, amines, etc. contained in the sol is M20/(
The molar ratio of wo3+sno2) is 0. Even when the molar ratio is less than 0.7, such a sol has poor stability, and when this molar ratio exceeds 0.7, the water resistance of the dried coating film obtained using such a sol is low, making it impractical for practical use. Undesirable. Oxycarboxylic acid, which is added when producing the above organosol from a high pH aqueous sol, also contributes to stabilizing the sol, but the amount of the added amount increases the WO. and SnO. If the amount exceeds 30% by weight based on the total amount of sol, the water resistance of the dried coating film obtained using such a sol will decrease. The pH of the sol changes depending on the amount of alkali metal, ammonium, amine, carboxylic acid, etc. in the sol. When the pH of the sol is below 1, the sol is unstable, and when the pH is above 9,
Colloidal particles of a composite of tungsten oxide and tin oxide are easily dissolved in the liquid. In the sol? When the total concentration of 03 and SnO■ is as high as 40% by weight or more, the sol still has poor stability. If this concentration is too low, it is impractical, and the preferred concentration for industrial products is 10 to 30% by weight.

If instead of the production method of the present invention, an aqueous solution in which tungstate and stannate are dissolved is treated with a hydrogen-type cation exchange resin, the resulting colloid particles will be too small and precipitation of tin oxide will easily occur. A method for producing a sol by adding the above-mentioned alkali metal hydroxide, ammonium hydroxide, amine, etc. to the liquid obtained by treatment with a hydrogen-type cation exchange resin is not efficient.

Further, if the W03 concentration of the aqueous solution of tungstic acid used is 0.1% by weight or less, the concentration of the obtained sol decreases, and a large amount of water must be removed during concentration, which is not efficient. On the contrary, the WO of this aqueous solution of tungstic acid. ? When the 1 degree is as high as 15% by weight or more, such an aqueous solution has poor stability and is likely to be difficult to handle.

When ultrafiltration is used for concentration, tungsten oxide polyanidine, ultrafine particles, etc. coexisting in the sol pass through the ultrafiltration membrane together with water, causing instability of the sol. Certain of these ponoanions, ultrafine particles, etc. can be removed from the sol. In an aqueous sol of colloidal particles of a tungsten oxide-tin oxide composite, at a temperature of 100°C or higher, the colloidal particles of a tungsten oxide and tin oxide composite in this sol undergo hydrolysis and dissolve, or these oxides dissolve. Because it is easy to precipitate, the temperature is kept at 100°C or less during treatment with the cation exchange resin, mixing, concentration, etc. A safe temperature that does not cause such changes is preferably 60°C or less.

(Examples) The present invention will be explained in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not limited to these Examples in any way.

Example 1 Sodium tungstate sa2WO4・2H20 (
By dissolving 550 g of 1st class reagent) in 4850 g of water? , 5400 g of an aqueous solution of sodium tungstate
I got it. This aqueous solution has a specific gravity of 1,086. pH9.
79, and the WO3 content was 7.16% by weight.

Next, the entire amount of the above aqueous solution was added to a hydrogen type cation exchange resin (
An aqueous solution of tungstic acid 5690 was prepared by passing it through a column packed with Amberlite 120B (manufactured by Organo).
I got g. This aqueous solution has a specific gravity of 1,068. pH1
．． 60, viscosity 2. Ocp. WL content 6.8% by weight, N
The aiO content was 0.04% by weight, and it was a yellow transparent liquid. Moreover, when this aqueous solution was left at room temperature, it turned into a gel-like state after 1 hour.

Separately, by dissolving sodium stannate NazSn03.3H20 (first class reagent) in water, the specific gravity is 1.244,
pH 12.8, Sno■ content 15.0% by weight, Na2
An aqueous sodium stannate solution with a content of 6.2% by weight was obtained.

Next, the aqueous solution 569 of tungstic acid immediately after the above production
0 g, 505 g of the above aqueous solution of sodium stannate,
By adding the tungsten oxide-tin oxide composite of the present invention under strong stirring at room temperature, I got a sex sol. This sol is
Although it had a slight colloidal color, it was almost colorless and transparent.

And specific gravity 1.073. pl{5.03, viscosity 1
．． 5cp, WO3 content 6.25% by weight, SnO content 1
．． 22% by weight, Na20 content was 0.54% by weight, and the colloid particle diameter was about 5 millimicrons as observed by electron microscopy. Moreover, this sol had stability for more than 3 months when left at room temperature under closed conditions. Furthermore, from the above values, WO in this sol
The value of the weight ratio WOi/SnOz of 3 and Sno■ is 5.12
, the value of the NazO/WOa+SnOa molar ratio is calculated to be 0.25, respectively.

Example 2 By passing 3100 g of the aqueous sol obtained in Example 1 through a column packed with hydrogen type cation exchange resin, the specific gravity was reduced to 1.0.
62. pH 1.53, viscosity 1.5 cp. W.O. Content 5.69% by weight, Sn02 content 1.11% by weight, Na
An aqueous sol of the invention with a zO content of 0.04% by weight was obtained. From the above values, the NazO/WOz+SnOz molar ratio of this sol is 0. It is calculated as 02.

Next item, Ko (7) pH1. 53(7) Sol 34oo
g and examples? The pH obtained at 5. 03 sol 309
The aqueous sol of the present invention was obtained by mixing 5 g at room temperature. The sol obtained here had a slight colloidal color, but was almost colorless and transparent, and had a specific gravity of 1.068. p
H2.36, viscosity 1.5cp. WOa content 5.96% by weight, Sno■ content 1.17% by weight, NaaO content 0.
28% by weight, colloid particle size approximately 5 as observed by electron microscope
It was millimicrons. It was stable for more than 3 months in a room temperature storage test. Furthermore, when calculated from the above values, WOx
/Sno■Weight ratio 5. l2, NaJ/WOs+SnO■
Molar ratio 0. It is 135.

Next, 6495 g of this pH 2.36 sol was concentrated by ultrafiltration to obtain 1840 g of highly concentrated sol. This sol also had a slight colloidal color, but was almost colorless and transparent, with a specific gravity of 1.212. pH2
．． 34, viscosity 2.5 cp. W.O. Content 17. 1% by weight, Snow content 3.93% by weight, NazO content 0.8
8% by weight, colloidal particle diameter approximately 5 millimicrons by electron microscopy, dynamic light scattering method (N4 manufactured by Coulter, USA)
particle size of 90 mm? The 6th Minister who was
The WOs/SnO■ weight ratio of this high concentration sol is 4.35,
The NaiO/WO3+SnOz molar ratio is calculated as 0.14. In addition, by the above ultrafiltration, W in the sol before filtration is
Approximately 20% of 03 has decreased. This decrease indicates that polyanidine or ultrafine particles of W03 passing through the ultrafiltration membrane were present in the sol before filtration.

Furthermore, when the above-mentioned high concentration sol was tested, it was found to have good dispersion in methanol and stability for more than 3 months at room temperature. Further, when the refractive index of light of this dried sol was measured, it was found to be 1.84.

Example 3 By passing 5,400 g of an aqueous solution of sodium tungstate with a W03 content of 7.16% by weight through a column packed with a hydrogen-type cation exchange resin, an aqueous solution of tungstic acid of 61 g was prepared.
35 g was obtained. This aqueous solution has a specific gravity of 1.062.
pH 1.48, viscosity 2.5cp. WOs content 6.16
% by weight, and the NazO content was 0.03% by weight. Therefore, the Na20/WO3 molar ratio is calculated to be 0.018. ? Then, the aqueous solution 61 of tungstic acid immediately after the above production.
35 g, 765 g of an aqueous solution of sodium stannate (SnOz content: 15.0% by weight, Na20 content: 62% by weight) was added at room temperature with strong stirring to obtain 6900 g of the aqueous sol of the present invention. This sol has a specific gravity of 1.073,
pH 6.72, viscosity 1.5 cp. WO! Content 5.60
% by weight, SnOz content 1.67% by weight, Na. O content 0
．． It was 71% by weight. By calculation, WO3/Sn02
Weight ratio 3.35, NazO/WOa+SnOz molar ratio 0
．． It is 33.

Next, the above sol was evaporated using a rotary evaporator.
When concentrated under reduced pressure, 1610 g of highly concentrated aqueous sol was obtained. This highly concentrated sol had a slight colloidal color, but was almost colorless and transparent, and had a specific gravity of 1.385.
pH 6.68, viscosity 2.6 cp. W03 content 24.0
Weight%, Snu■ content 7.14% by weight, NaaO content 3
．． 06% by weight, and the colloid particle diameter was approximately 5 mm by electron microscopy. It was also stable for more than 3 months in a room temperature storage test.

Example 4? Specific gravity obtained in Example 2: 1.068. pH2.36
n-probylamine 2 was added to 3250 g of aqueous sol with stirring.
An aqueous sol was obtained by adding 2 g and 19 g of tartaric acid. This sol has a specific gravity of 1.067. pH 3.82,
Viscosity 1.5 cp. WO, content 5.88% by weight, SnO
■Content 1.16% by weight, Na20 content 0.28% by weight,
The amine content was 0.67% by weight, and the tartaric acid content was 0.58% by weight.

By calculation, NazO+ (amine) 20/WO3
+Sn02 molar ratio 0.31, tartaric acid/WO3+SnO
z9. It is 52% by weight.

Next, this sol was concentrated under reduced pressure using a rotary evaporator to obtain 970 g of a highly concentrated aqueous sol. Although this sol had a slight colloidal color, it was almost colorless and transparent, with a specific gravity of 1.282 and a pH of 3.68.
Viscosity 2.3 Cll). WO3 content 199% by weight, Sn
o2 content 3.93% by weight, Na20 content 095% by weight,
The amine content was 2.27% by weight, and the tartaric acid content was 1.97% by weight. This sol had good dispersibility in methanol and had stability when left at room temperature for 3 months or more.

Example 5 Specific gravity obtained in Example 2: 1.212. pH2.34
A methanol sol in which the water in the aqueous sol has been replaced with methanol is obtained by putting 215 g of the aqueous sol into a rotary evaporator and distilling off the sol medium while continuously adding methanol 3a little by little under reduced pressure. 376
I got g. This sol had a slight colloidal color, but was almost colorless and transparent, with a specific gravity of 0.932. pH3.
46 (equal weight mixture of this sol and water), viscosity 6.2c
p. WO3 content 9.78% by weight, SnO. Content 2.2
5% by weight, and water content was 7.5% by weight. This sol produced a very small amount of sediment while left standing, but the amount did not increase even if the standing period was extended and was stable.

Example 6 Regarding 300 g of the highly concentrated aqueous sol obtained in Example 4, 350 g of methanol sol was obtained by replacing the water in the medium with methanol in the same manner as in Example 5. This sol had a slight colloidal color, but was almost colorless and transparent, with a specific gravity of 0. 978,? H5. 28 (equal weight mixture of this sol and water), viscosity 4.0 CI]. W03 content 17.1% by weight, Sn02 content 337% by weight, Na20
Content 0.81% by weight, n-probylamine content 1.94
Weight%, tartaric acid content 1.69% by weight, moisture 3.5% by weight
No sediment was formed after 3 months of being left at room temperature.
It was stable.

Example 7 Sodium tungstate NaJO4.2H20-24
Aqueous solution of sodium tungstate (WO34.88% by weight) 344 by dissolving 0g in 3200g of water
This aqueous solution was then passed through a column packed with a hydrogen-type cation exchange resin to obtain 4450 g of an aqueous solution of tungstic acid (specific gravity 1.033, pH 1.03).
53) was obtained. By mixing 366 g of a separately prepared sodium stannate Na2SnOi aqueous solution with a SnO■ content of 150% by weight with 3440 g of the above tungstic acid aqueous solution, a tungsten oxide-tin oxide composite sol (■) (
Specific gravity 1.042. 3806 g of pi{7.02) was obtained. Next, this is passed through a column of hydrogen type cation exchange resin to form acidic tungsten oxide. - Tin oxide composite sol (I) (specific gravity 1,032. pH 1.82, WO
3 2.87% by weight, SnOzO. 94% by weight, W
O3/Sn02 weight ratio 3.07) 5860 g was obtained.

This acidic kungsten oxide-tin oxide composite sol (I)
5860 g of the above sodium stannate aqueous solution (SnO
■150%) By mixing 413g of tungsten oxide-tin oxide composite sol (II) (specific gravity 1.04
4. pH 7.26) 6273g was obtained. Next, this is passed through a column packed with a hydrogen-type cation exchange resin to obtain an acidic tungsten oxide-tin oxide composite sol (II
) (specific gravity 1.032. pH 2.07, VIOs 2
．． 22% by weight, Snu 1.55% by weight, WO3/Sn
02 weight ratio 1.44) 7556 g was obtained.

This acidic tungsten oxide-tin oxide composite sol (I
I) Add the above sodium stannate aqueous solution (S
15.0%) by mixing 445g of tungsten oxide-tin oxide composite sol (III) (
Specific gravity 1.040. 8001 g of pi{7.56) was obtained. Next, 22,000 g of water was added to this composite sol, and the mixture was passed through a column packed with a hydrogen type cation exchange resin. Acidic tungsten oxide-tin oxide composite sol (II
I) (specific gravity 1.013. pH 2.61, viscosity 1.
5cp, WO30.77% by weight, SnOz 0.85
% by weight, WO3/Sno (weight ratio 0.92) was obtained.

Further, 8.0 g of isobrobylamine was added to 21.7 kg of this acidic composite sol (III) to prepare tungsten oxide.
A tin oxide composite sol (TV) was obtained. This sol has a specific gravity of 1.
013. pH 4.0, viscosity 1.3cp. No.
0.77% by weight, Sno 0.85% by weight, WO3/
Sn02 1.62% by weight WO,/SnO ■ Weight ratio 0
．． 92, Isoprobylamine 0. 037% by weight, (isobrobylamine) 20/(wo3+sno21 molar ratio 0.035. Colloidal particle size by electron microscope is 5
The sol was less than mμ, had a slight colloidal color, and was almost transparent.

Example 8 In this example, Sno2 aqueous sol (Al, sb2o
．． An aqueous sol (B) and a 2rO2 aqueous sol (C) were made.

(11 Preparation of SnOsol (A) Specific gravity 1.420 obtained by reaction of metal tin powder, aqueous hydrochloric acid solution, and aqueous hydrogen peroxide solution. pH 0.40, viscosity immediately after stirring 32 cp. SnOz content 33.0% by weight.
, Hl content 2.56% by weight, spindle-shaped colloid particle size as determined by electron microscope less than 10 millimicrons, specific surface area of particles as determined by BET method 120rn''/g, converted particle diameter from this specific surface area of 7.2 millimicrons, American Coulter Co., Ltd. -Manufactured by N4
Dynamic light scattering method using a device 200 g of a pale yellow transparent aqueous tin oxide sol with a particle size of 107 mm and 1800 g of water
After dispersing the solution, 0.8 g of isobrobylamine was added thereto, and this liquid was then passed through a column packed with a hydroxyl group-type anion exchange resin to obtain 2240 g of an alkaline tin oxide aqueous sol (A). This sol (A) is stable and has a colloidal color, but is extremely transparent and has a specific gravity of 1.029. pH 8.80, viscosity 1.4
cp. Sn02 content 2.95% by weight, isobrobylamine content 0. It was 0.036% by weight.

(21 Preparation of Sb.O, Sol (B) According to the method proposed in JP-A-61-227918, using sodium antimonate as a raw material, the gel obtained by reaction with hydrochloric acid is peptized with phosphoric acid. Accordingly, the specific gravity is 1.
142. pH 1.75, viscosity 5. 6cp, Sb2
0s content l3.4% by weight, Na. An Sb20s aqueous sol (B) with an O content of 0.0017% by weight and a particle size of 5 to 15 mm as measured by an electron microscope was obtained. (31) Preparation of ZrO sol (C) A highly transparent and stable ZrO sol aqueous sol (C) was obtained by hydrolyzing an aqueous zirconium oxychloride solution. This sol had a specific gravity of 1.177 and a pH of 3. 85, viscosity 5.6 cp, ZrO content 22.1% by weight, and particle size determined by electron microscope of 5 millimicrons.

Example 9 A modified SnO■ aqueous sol was prepared.

The pH obtained in Example 1 was 2. 36 composite sol 420g
Add 500g of water to make a diluted composite sol, and add this to the above S
Modified Sno2 aqueous sol 31 with low concentration stabilized by adding to 2240g of nO ■ aqueous sol (A) under strong stirring
60g was obtained. This sol has a specific gravity of 1. 030, pH4
．． 65, viscosity 1.4cp, (WO.÷SnOz)/Sn
The Oa weight ratio is 0.45 and it has a colloidal color, but is it transparent? Particle size by electron microscope: approximately 10 mm, specific surface area: 104 m''/g, converted particle size from specific surface area: 8.7 mm, particle size by dynamic light scattering using N4 device manufactured by Coulter, USA: 108 mm. Met.

Next, 3160 g of the above low concentration modified SnO aqueous sol
was concentrated using an ultrafiltration device using an ultrafiltration membrane with a molecular weight cut off of 50,000 to obtain 517 g of a highly concentrated modified SnO2 aqueous sol. This sol has a specific gravity of 1.172. pH4.20,
Viscosity 2. 8cp, total SnOa 13.67% by weight, W
3.6% by weight of O3, 0.19% by weight of Naa0, 0.14% by weight of isobrobylamine, (WOa+SnO
■l /SnOz weight ratio was 0.35. Although this sol had a colloidal color, it was highly transparent and stable at room temperature for more than 3 months. WO before and after the above ultrafiltration
From the 3 content values, it was observed that about 20% of the original W03 from the sol passed through the ultrafiltration membrane together with the water.

This highly concentrated sol shows good dispersibility in methanol and is similar to a normal anionically charged silica sol. By mixing, a stable mixed sol can be obtained. Further, the dried film of this highly concentrated sol exhibited a refractive index of 1.84.

Example 10 A modified SnO■ aqueous sol was prepared.

Composite sol (W035) with pH 2.36 obtained in Example 1
96% by weight, SnO 1.17% by weight, WOa+Sn
Oz7. Add 500 g of water to 420 g (13% by weight) to make a diluted composite sol, and add this to 3390 g of the alkaline tin oxide aqueous sol (A) prepared in Example 8 with strong stirring, and further add 0.6 g of isobrobylamine. Low concentration modified SnO aqueous sol 4310 which is particularly stable
I got g. This sol has a specific gravity of 1.028. pH6
．． 97, viscosity 1.4cp, (WO3+SnO■l/S
The nOz weight ratio was 0.30, and although it had a colloidal color, it was highly transparent.

Next, 4310 g of this low concentration modified SnO aqueous sol
was concentrated using an ultrafiltration device using an ultrafiltration membrane with a molecular weight cut off of 50,000 to obtain 410 g of a highly concentrated modified SnO2 aqueous sol. This sol has a specific gravity of 1,325. pH? 35, viscosity 6
．． 2cp, total SnOz 25.4% by weight, W0352% by weight, tWO3+snoz) /SnO■ weight ratio 0.2
5. Isobrobylamine was 0.39% by weight. Although this sol had a colloidal color, it was highly transparent and stable at room temperature for more than 3 months. WO before and after the above ultrafiltration,
It was found from the value that about 15% by weight of the original WOs passed through the ultrafiltration membrane together with water. This sol had good dispersibility in methanol and could be stably mixed with ordinary anionically charged silica sol.

Example 11 A modified SnO■ aqueous sol was prepared.

Tungsten oxide-tin oxide composite sol (IV) obtained in Example 7 (WO3+SnO■1.62% by weight)2
370 g of alkaline tin oxide sol (A) prepared in Example 8 (SnO22.95% by weight) 86
By adding 78 g under strong stirring, 11,048 g of a stable, low concentration modified SnO2 sol was obtained. This sol has a specific gravity of 1
,026. pH 7.50, viscosity 1.4 cp, (WO
s+SnOzl/SnO ■ Weight ratio is 0.15 and exhibits colloidal color? was highly transparent.

Next, 11,048 g of this low concentration modified SnO sol was
Concentrate using an ultrafiltration membrane filtration device with a molecular weight cutoff of 50,000,
940 g of highly concentrated modified Sno2 aqueous sol was obtained. This sol has a specific gravity of 1.332. pH 7.10, viscosity 4. Oc
p. Total Snu■29.3% by weight, W031.85% by weight. (WO3+SnOz)/SnOz weight ratio 0.1
4. Isobrobylamine was 0.38% by weight. Although this sol had a colloidal color, it was highly transparent and stable at room temperature for more than 3 months. W0 before and after upper epoch ultrafiltration
From the value of 3, it was found that about 5% by weight of the original W03 passed through the ultrafiltration membrane along with the water.

This sol had good dispersibility in methanol and could be stably mixed with ordinary anionically charged silica sol.

Example 12 A modified SnO■ aqueous sol was prepared.

Add 8136 g of the alkaline tin oxide aqueous sol (A) prepared in Example 8 to 7410 g of the tungsten oxide-tin oxide composite sol (IV) obtained in Example 7? Low concentration modified Snu2 aqueous sol 1 stabilized by addition under stirring
5546 g was obtained. This sol has a specific gravity of 1. 0222
, pH 6.42, viscosity 1.4 cp, (WO3+Sn02
)/Sn02 weight ratio was 0.50, and although it exhibited a colloidal color, it was highly transparent.

Next, 15,546 g of this low concentration modified SnOz sol was concentrated using an ultrafiltration device using an ultrafiltration membrane with a molecular fraction of N50,000 to obtain 1440 g of a high concentration modified SnO2 aqueous sol. This sol has a specific gravity of 1.256. pH6.21, viscosity 6.8cp, total SnO 20.7% by weight, WO33.6
3% by weight, (W03+Sn021/Sn02 weight ratio 0.
46, and 0.35% by weight of isobrobylamine. Although this sol had a colloidal color, it was highly transparent and stable at room temperature for more than 3 months. W03 before and after the above ultrafiltration
It was confirmed from the value that about 10% by weight of the original W03 passed through the ultrafiltration membrane together with water.

This sol had good dispersibility in methanol and could be stably mixed with ordinary anionically charged silica sol.

Example 13 ? A methanol sol of SnOa was prepared.

Highly concentrated modified Snow aqueous sol 51 obtained in Example 9
The water in the aqueous sol was replaced with methanol by distilling off water from a sol containing 1.8 g of isobrobylamine and 1.8 g of tartaric acid in a rotary evaporator under reduced pressure while adding methanol 4I2 little by little. 430 g of modified SnO■ methanol sol was obtained. This sol is
Specific gravity 0.974, pH 6.29 (equal weight mixture with water), viscosity 3. Ocp, total Snu216.23% by weight, W
0. 4.27% by weight, water 2.9% by weight, isobrobylamine 0.585% by weight, and tartaric acid 0.419% by weight. This sol contained a very small amount of sediment, but
It exhibited a colloidal color and was highly transparent. Even after being left at room temperature for 3 months, there was no increase in the initial amount of sediment and the product remained stable.

Example 14 A modified SnO methanol sol was prepared.

410 g of the highly concentrated modified Sn02 aqueous sol of Example IO, 2.3 g of tartaric acid, 7.4 g of diisoptylamine, ? Foaming agent (SN Deformer 483 manufactured by San Nobuco) 1
After adding the drops, under reduced pressure in a rotary evaporator,
Modified S in which the water in the aqueous sol was replaced with methanol by distilling off the water while adding methanol 6I2 little by little.
410 g of nO■ methanol sol was obtained. This sol has a specific gravity of 1.096. pH 8.34 (equal weight mixture with water), viscosity 4.5 cp, total Snug 25.4% by weight,
WOa 5.2% by weight, WO3+SnOz 30.6% by weight, water 2.3% by weight, isoprobylamine 0.35% by weight, diisobutylamine 1.62% by weight, tartaric acid 0
．． It was 56% by weight. It should be noted that about 10% by weight of the amine was lost due to volatilization during methanol substitution.

This sol had a colloidal color, was highly transparent, and remained stable without any abnormalities such as formation of sediment, cloudiness, or thickening even after being left at room temperature for 3 months.

The refractive index of the dry product of this sol was 1.84.

Example 15 A modified SnO methanol sol was prepared.

? 940 g of the highly concentrated modified SnO aqueous sol of Example 11, 5.6 g of tartaric acid, 8.5 g of diisobutylamine, and antifoaming agent (SN Deformer-483 manufactured by San Nobuco) 1
After adding the drops, under reduced pressure in a rotary evaporator,
Modified S in which water in the aqueous sol was replaced with methanol by distilling off water while adding methanol l2β little by little
950 g of nOz methanol sol was obtained. This sol has a specific gravity of 1. 120, pH 7.10 (equal weight mixture with water),
Viscosity 7.5 cp, total SnO2 29.0% by weight, W0.
1.83% by weight, WO3+SnO■ 30.8% by weight, water 3.0% by weight, isobrobylamine 0.34% by weight,
The contents were 0.82% by weight of diisobutylamine and 0.59% by weight of tartaric acid. In addition, when the amine is replaced with methanol, about 1
O weight percent was lost due to volatilization. This sol had a colloidal color, was highly transparent, and remained stable without any abnormalities such as formation of sediment, cloudiness, or thickening even after being left at room temperature for 3 months. The refractive index of the dry product of this sol was 1.83.

Example 16 ? A methanol sol of SnO was prepared.

1440 g of highly concentrated modified SnO aqueous sol of Example 12
7.0g of tartaric acid, 12.0g of diisoptylamine, and antifoaming agent (SN Diff Saiichimer 483 manufactured by Sannopco)
After adding 2 drops, the water was distilled off using a rotary evaporator under reduced pressure while adding methanol 21I2 little by little to obtain 1160 g of a modified SnO2 methanol sol in which the water in the aqueous sol was replaced with methanol. This sol has a specific gravity of 1.118, a pH of 6.82 (equal weight mixture with water), and a viscosity of 8. 5cp, total SnO■25.7% by weight,
W0. 4.5% by weight, WO3+SnOz 30.2% by weight, water 2.5% by weight, isobrobylamine 0.37% by weight, diisobutylamine 0.93% by weight, tartaric acid 0.
It was 60% by weight. It should be noted that about 10% by weight of the amine was lost due to volatilization during methanol substitution. This sol had a colloidal color, was highly transparent, and was stable with no abnormalities such as formation of sediment, cloudiness, or thickening even after being left at room temperature for 3 months. The refractive index of the dry product of this sol was 1.84.

Example 17 A modified Sb205 aqueous sol was created.

Example 8 Sb205 aqueous sol (B) 1036g
+. :, 590 g of the pH 2.36 composite sol obtained in Example 1 was added under strong stirring, and 7.0 g of n-probylamine was added to obtain a stable low concentration of modified Sb.
1626 g of 20s aqueous sol was obtained.

Next, this low concentration sol was concentrated using an ultrafiltration membrane with a molecular weight cut off of 50,000 to obtain 890 g of a high concentration modified Sbz05 aqueous sol. This sol has a specific gravity of 1,214. p
H2.81, viscosity 2.2cp. Sb2os 15.7
% by weight, WO33.52% by weight, SnOz 0.84% by weight, Na20 0.18% by weight, n-probylamine 0.72% by weight, (WOa+SnOzl/Sbz05 weight ratio 0.28).

Although this sol had a colloidal color, it was highly transparent and stable for more than 3 months at room temperature. This sol showed good dispersibility in methanol, and the refractive index of the dry film was 1.
．． It showed 74.

Example 18 A modified Sb205 methanol sol was created.

? 250 g of the highly concentrated modified Sb 20 g aqueous sol obtained in Example 17 was added to 250 g of the aqueous sol obtained in Example 17 under reduced pressure in a rotary evaporator.
Modified Sb20s in which water in the aqueous sol was replaced with methanol by distilling off water while adding methanol at 5°C
335 g of methanol sol was obtained. This sol has a specific gravity of 0.
946. pH 3.69 (equal weight mixture with water),
Viscosity 12.8cp. Sb2051L. 8% by weight, WO
32.7% by weight, SnOz 0.62% by weight, moisture 61
% by weight, n-probylamine 0.52% by weight.

This sol had a colloidal color, but was transparent.
It was stable for more than 3 months at room temperature.

Example 19 A modified ZrOz aqueous sol was created.

1 part water to 200 g of ZrO ■ aqueous sol (C) of Example 8
300 g was added to make a dilute Zr0 2 aqueous sol.

Separately, composite sol 23 with pH 2.36 obtained in Example 1
200 g of water was added to 0 g to prepare a diluted composite sol.

Next, add 1500 g of the above diluted ZrL aqueous sol to 1500 g of the above diluted ZrL aqueous sol.
430 g of the diluted composite sol was added under strong stirring, and 3.0 g of isoprobylamine was further added to obtain 1930 g of a stable, low concentration modified 2rO2 aqueous sol.

Furthermore, this low concentration modified ZrO2 sol was concentrated under reduced pressure in a rotano evaporator to obtain 315 g of a high concentration modified ZrO2 aqueous sol.

This sol has a specific gravity of 1.184. pH 7.05, viscosity 2.4 cp. ZrO■14.0% by weight, WO34.3
5% by weight, Sn020, 85% by weight, isobrobylamine 095% by weight, (WO3+SnOzl/ZrOz weight ratio 0.37. This sol exhibited a colloidal color,
Although the transparency was low, it was stable for more than 3 months at room temperature. And this sol showed good dispersibility in methanol,
It could also be stably mixed with ordinary anionically charged silica sol. The refractive index of the dry film of this sol was 1.95.

Example 20 In this example, a hard coat agent was prepared by combining the ingredients obtained in Examples 9 to 19 above, the water-based sun plaster, and the raw materials obtained in Examples 9 to 19, and the performance of the hard coat film. was tested.

As the bangu, methyltrimethoxysilane 150
Add 400 parts by weight of Imbropanol to the parts by weight, and add 0.00 parts by weight while stirring. After dropping 12 parts by weight of IN hydrochloric acid and 50 parts by weight of water, the mixture was further stirred for 10 hours, then left at room temperature for 16 hours, and then 0.6 g of isobrobylamine was added to adjust the pH to approximately neutral. The obtained hydrolyzed solution of methyltrimethoxysilane was used.

The 11 types of hard coating agents are the above-mentioned Baingu 612.
g, 300 g of either the high concentration modified metal oxide aqueous sol or methanol sol obtained in Examples 9 to 19 above.
g, 0.2 g of a commercially available silicone surfactant, and 0.1 g of a commercially available ultraviolet absorber, and stirred for 4 hours.

As a base material, Lens C (trade name) CR-391, which is a diethylene glycol bisallyl carbonate polymer that has been thoroughly washed after alkali treatment, is prepared. .

Next, this lens was immersed in the hard coat agent, taken out, left at room temperature, and then cured at 120° C. for 2 hours to form a hard coat film on the lens. This coating adhered strongly to the lens, and its refractive index, adhesion, and transparency were also high.

Comparative Examples 1 and 2 below include an example of a tungsten oxide-tin oxide composite sol that has poor stability, Comparative Example 3 includes an example of a modified 2rO2 aqueous sol that has poor stability, and Comparative Example 4
The unmodified ZrO aqueous sol of Example 8 (
An example of forming a hard coat film using C) is shown. Comparative Example I An aqueous solution of sodium tungstate having a WOa content of 7.16% by weight was passed through a column packed with a hydrogen type cation exchange resin to obtain 1420 g of an aqueous solution of tungstic acid. This aqueous solution has a specific gravity of 1.068. pH1.60
, viscosity 2. Ocp. WO3 content 6.8% by weight, Na2
0 content was 0.04% by weight.

? Temporarily prepared SnO content: 15.0% by weight, Na20
5 g of an aqueous solution of sodium stannate with a content of 6.2% by weight,
An aqueous sol was obtained by adding it to 1420 g of the aqueous solution of tungstic acid with strong stirring, and this sol gelled after about 1 hour. Immediately after production, this sol has a specific gravity of 1.0.
68. pH 1.62, WO3 content 6.78% by weight,
Sno■ content 0.053% by weight, Na20 content 0.
062% by weight, and the WO3/SnOz weight ratio is 128
, NaiO/WOa+SnOz molar ratio is 0. It is calculated as 034.

Comparative Example 2 Specific gravity 1 obtained in Example 2. 062, put. 2100 g of aqueous sol of No. 53, SnOz content 15.0% by weight,
An aqueous sol was obtained by mixing with 300 g of an aqueous solution of sodium stannate having a Na20 content of 6.2% by weight under strong stirring. This sol has a slightly colloidal color,
It is almost colorless and transparent, and has a specific gravity of 1.079. pH8.0
2. Viscosity 1. 5cp, ■03 content 4.98% by weight, S
The nOz content was 2.85% by weight, and the Na20 content was 0.81% by weight.

Next, rotary evaporation of this sol? When the mixture was concentrated under reduced pressure, it became cloudy as the concentration progressed.

Separately, when a hydrogen-type cation exchange resin was added to the above sol under stirring to lower the pH, p}[ was approximately 5
When this was reached, the sol increased in viscosity and a stable sol could not be obtained.

Above WO3. According to each content of SnOz and NaJ,
This sol has a WOs/Sn02 weight ratio of l. 75, NazO
/WO3+SnOz molar ratio is 0.32.

Comparative Example 3 ZrO aqueous sol (C) obtained in Example 8 200
1300 g of water was added to make a diluted sol, and with strong stirring, the pH 2. 36 composite sol 10
When g was added, the mixture became cloudy and increased in volume, making it impossible to obtain a stable sol. Furthermore, when this mixture was added to ordinary anionically charged silica sol, significant gelation occurred.

In this mixture, the weight ratio of (WO3+SnO■)/2rO■ is 0. 016, and the amount of composite sol added is insufficient? Comparative Example 4 In the performance test of the hard coat film of Example 20,
Instead of the modified metal oxide sol, Zr0 according to Example 8
A hard coat film was formed in the same manner except that di-aqueous sol (C) was used, but although the film had a high refractive index, it was cloudy and had poor transparency, adhesion, and weather resistance. It was insufficient.

(Effects of the Invention) The sol of colloidal particles of a tungsten oxide-tin oxide composite obtained by the present invention is colorless and transparent, and its dry coating film exhibits a high refractive index of about 1.8 to 1.9. It also has high bonding strength and hardness, and has high water resistance and adhesion. Furthermore, antistatic properties, heat resistance, abrasion resistance, etc. are also good. The sol of colloidal particles of a trivalent to pentavalent metal oxide whose surface has been modified by the colloidal particles of this tungsten oxide-tin oxide composite is also colorless and transparent, and its dried coating film has a refraction of about 1.7 to 2.2. Insects t1;2 I
Tori hlJe le tongue co che nore k”t
ノ/-'7.卆１ノ - Shows the same excellent performance as the colloidal particle sol of the Todorokura tin composite.

These sols are stable at pH approximately 1-9,
It can also provide sufficient stability to be supplied as an industrial product.

Since the colloidal particles of these sols are negatively charged, they have good miscibility with sols made of other negatively charged colloidal particles, such as silica sol, antimony pentoxide sol, anionic or non-silica sol. It can be stably mixed with dispersions such as aqueous solutions of aqueous surfactants, polyvinyl alcohol, anionic or non-anionic resin emulsions, water glass, and aqueous solutions of aluminum phosphate.

The sol of the present invention having such properties has a refractive index for forming a hard coat film on a plastic lens,
It is particularly useful as an ingredient for improving dyeability, chemical resistance, water resistance, weather resistance, abrasion resistance, etc., but it can also be used for various other purposes.

By applying these sols to the surfaces of organic fibers, textile products, paper, etc., the flame retardancy, surface slip resistance, antistatic properties, dyeability, etc. of these materials can be improved. Further, these sols can be used as a binder for ceramic fibers, glass fibers, ceramics, etc. Furthermore, by mixing it into various paints, adhesives, etc., it is possible to improve the water resistance, chemical resistance, weather resistance, abrasion resistance, flame retardance, etc. of the cured coatings. In addition, these sols can generally be used as surface treatment agents for metal materials, ceramic materials, glass materials, plastic materials, and the like. Furthermore, it is useful as a catalyst component.

Claims (2)

[Claims] (1) Valency 3 with a particle size of 4 to 50 millimicrons
, 4 or 5 colloidal particles of a tungsten oxide-tin oxide composite whose surface has a WO_3/SnO_2 weight ratio of 0.5 to 100 and a particle size of 2 to 7 millimicrons. A stable sol consisting of modified metal oxide colloidal particles having a particle size of 4.5 to 60 millimicrons formed by coating with a metal oxide, and containing 2 to 50% by weight of the total metal oxide. (2) A metal oxide sol with a valence of 3, 4, or 5 having a particle size of 4 to 50 millimicrons, 100 parts by weight of the metal oxide contained in this sol, and a particle size of 2 to 7 millimicrons and 0. Modification according to claim 1, characterized in that a tungsten oxide-tin oxide composite sol having a WO_3/SnO_2 weight ratio of .5 to 100 is mixed in a ratio of 2 to 100 parts by weight as this composite. A method for producing a stable sol of metal oxide colloidal particles.