JP2737199B2 - Tungsten oxide-antimony pentoxide composite sol and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composite sol of tungsten oxide-antimony pentoxide, and more specifically, water as a dispersion medium, which is used as a refractive index improver for a hard coat agent of a lens. The present invention relates to a tungsten oxide-antimony pentoxide hydrophilic organic solvent sol using a tungsten oxide-antimony pentoxide aqueous sol and a hydrophilic organic solvent as a dispersion medium.

[Conventional technology]

At present, metal oxide sols such as antimony pentoxide, zirconium oxide, titanium oxide and tin oxide are used or studied for controlling the refractive index of the hard coat agent.

In recent years, the use of antimony pentoxide sol or the like as a refractive index improver has increased due to the increase in the refractive index of lenses, particularly plastic lenses. As the antimony pentoxide sol, a high-concentration antimony pentoxide aqueous sol stabilized with an amine, or a high-concentration antimony pentoxide hydrophilic organic sol using a dispersion medium such as methanol stabilized with an organic base and an organic acid is used. Have been.

Five colloidal antimony pentoxide antimony oxide sol _{Sb 2 O 5 (Na 2 O} ) x · nH 2 O and can be represented generally X = 0 to 0.8, a n = 2 to 4, colloidal pentoxide The refractive index of antimony varies depending on the contents of sodium, water, amine, organic acid and the like, but is approximately 1.65 to 1.68.

The refractive index of the lens, especially plastic lens substrate is 1.6
With the above, it is difficult for the antimony pentoxide sol to sufficiently increase the refractive index of the hard coat layer. Therefore, a metal oxide sol having a higher refractive index has been demanded. At the same time, it is also desired to improve the abrasion resistance, dyeability and antistatic property of the hard coat layer.

Sols such as zirconium oxide, titanium oxide and tin oxide are known as metal oxide sols having a high refractive index.
For example, JP-B-63-37142 proposes using these metal oxide sols for a transparent coating layer. The use of these sols increases the refractive index, but has the drawback that the oxide colloid generally has a chaotic property and thus impairs the stability of the hard coat treatment solution, and silica sol and antimony pentoxide sol As described above, there is a problem that it is difficult to use because of exhibiting different dyeability from the case of the anionic colloid.

Harry Bayer Weis was first published in 1935 for tungsten oxide sols.
er) by Inorganic Colloid Chemistry
Its existence is reported in Volume 2 (Inorganic Colloid Chemistry Vol II), etc., but in Modern Aspects of Inorganic Chemistry published in 1958, tungsten oxide sol contains tungstic acid. There are many unclear points such as the fact that it is present as a polyanion, and tungsten oxide alone is not produced as a stable sol.

From the above, a method for producing a stable sol in the form of a composite sol of tungsten oxide and another oxide has been proposed.
JP tungsten compound as a colloid solution of the No. 54-52686 tungsten compounds, silicon oxide compounds and contain an alkali metal ion or an ammonium ion, WO _3: S
A colloid having a molar ratio of iO ₂ : M ₂ O (M is an alkali metal or ammonium) of 4 to 15: 2 to 5: 1 is produced by a method of adding silicate to a cation exchanged aqueous solution of tungstate. It has been reported that Also, JP-A-61-2311
No. 97 describes a method of passing tungstate and molybdate through a column filled with a cation exchange resin and aging the tungstate and molybdate mixture at less than 60 ° C. It has been reported to produce mixed colloids. It has been reported that these tungsten oxide composite sols are used as a fiber treatment agent or an electrochromic film-forming agent, but no report has been made on their use as a hard coat agent.

As a composite sol of antimony pentoxide and other oxides, a silica-antimonic acid composite sol is reported in Japanese Patent Publication No. 50-40119.Since silica has a low refractive index, the refractive index of the composite colloid is pentoxide. Since it is lower than the refractive index of antimony colloid, it is not effective as a refractive index improver.
In addition, the present inventors have proposed a method of coating the surface of an antimony pentoxide colloid with a substance such as zirconium oxychloride or tin oxychloride as a positively charged antimony pentoxide sol (Japanese Patent Application Laid-Open No. 61-227919). These have a high refractive index, but are not preferred because of their cationic nature.

[Problems to be solved by the invention]

An object of the present invention is to solve the above-mentioned problems. That is, an object of the present invention is to provide an anionic oxide sol having high transparency, high refractive index, high abrasion resistance, good dyeing properties, and good antistatic properties, and its production, which are mainly used for hard coating agents such as lenses. It is to provide a method.

The present inventors have focused on tungsten oxide as an oxide having a large refractive index, and as a result, have found that antimonic acid (antimony pentoxide) can stabilize tungstic acid (tungsten oxide). The present invention has been completed.

[Means for Solving the Problems] That is, in the present invention, the weight ratio of tungsten oxide to antimony pentoxide is 0.1 to 100 in terms of WO ₃ / Sb ₂ O ₅ weight ratio, and alkali metal or ammonium is converted to M ₂ O / (WO ₃ + Sb ₂ O ₅₎ [M represents an alkali metal or ammonium. ] In a molar ratio of 0.
Tungsten oxide characterized by containing 02-0.7
The present invention relates to a tungsten oxide-antimony pentoxide composite hydrophilic organic solvent sol in which a dispersion medium of the aqueous sol is replaced by a hydrophilic organic solvent rather than water. Hereinafter, the present invention will be described in more detail.

As the method for producing the tungsten oxide-antimony pentoxide composite aqueous sol of the present invention, the following two methods are exemplified.

The first method is obtained by mixing acidic aqueous antimony pentoxide sol and tungstate in a weight ratio of WO ₃ / Sb ₂ O ₅ of 1 or less. At this time, an amine or an amine and a carboxylic acid may be further added as a stabilizer.

The antimony pentoxide sol used in the present invention is prepared by reacting antimony trioxide with potassium hydroxide to form potassium antimonate, which is deionized (Japanese Patent Publication No. 57-11 / 1982).
No. 848), a method of deionizing antimony alkali with an ion-exchange resin (US Pat. No. 4,110,247), and a method of oxidizing antimony trioxide with hydrogen peroxide at high temperature (Japanese Patent Publication No. 53-53)
No. 20479), a method of peptizing an antimony pentoxide gel obtained by reacting sodium antimonate with an inorganic acid with an amine or phosphoric acid (JP-A-60-41536, JP-A-61-227918). can get. Further, an acidic antimony pentoxide sol obtained by a method of performing cation exchange on the antimony pentoxide sol obtained by the above-mentioned amine peptization can also be used.

Antimony pentoxide produced by these methods is generally acidic (pH 1 to 6) and Sb ₂ O ₅ (Na ₂ O) _x · nH ₂ O (X = 0 to 0.
5, n = 2 to 4), and those having a small X have a property of incorporating sodium ions into the structure of antimony pentoxide. That is, colloidal antimony pentoxide is a cation exchanger and has exactly the same action as a cation exchange resin.

The acidic aqueous antimony pentoxide sol used in the present invention
The concentration of Sb ₂ O ₅ is preferably 2 to 50% by weight. 2% by weight
Smaller sols can be used but are not economical. Also, 50
Although it can be used even if it exceeds the weight percentage, it is not preferable because the reaction tends to be non-uniform when mixed with the tungstate.

As the tungstate used in the present invention, tungstates such as lithium, sodium, potassium, rubidium, cesium, ammonia, amine, quaternary ammonium, and guanidine can also be used. Among these,
As sodium (sodium tungstate), a solid such as Na ₂ WO ₄ .2H ₂ O is commercially available and easily available.
Alternatively, tungsten oxide dissolved in an aqueous solution of an alkali metal hydroxide, or ammonia water, or the like can be used.

In the present invention, by mixing a tungstate with an acidic aqueous antimony pentoxide sol, a cation such as an alkali ion or an ammonium ion of the tungstate is taken into the colloidal antimony pentoxide. Tungsten oxide is produced. Since tungsten oxide is also an ion exchanger, it is considered that tungsten oxide and antimony pentoxide form a composite colloid via alkali ions and ammonium ions.

That is, the obtained polyanion of tungstic acid or colloidal tungsten oxide forms a Sb ₂ O ₅ —M ₂ O—WO ₃ (M is an alkali metal or ammonium) bond on the surface of colloidal antimony pentoxide, and the tungsten oxide It becomes antimony oxide composite sol.

The mixing of the tungstate and the acidic aqueous antimony pentoxide sol can be performed at room temperature to 100 ° C., and the mixing ratio thereof is 1 or less, preferably 0.1 to 0.1, by weight of WO ₃ / Sb ₂ O _5.
A range of 1 is preferred. If it is less than 0.1, the refractive index cannot be sufficiently increased. On the other hand, if the weight ratio of WO ₃ / Sb ₂ O ₅ exceeds 1, the content of alkali increases and tungstate remains unpreferably.

Tungsten oxide-antimony pentoxide composite aqueous sol obtained by mixing acidic aqueous antimony pentoxide sol and tungstate is stable as it is, but improves the dispersion stability by adding amine and further carboxylic acid. As a result, a stable tungsten oxide-antimony pentoxide composite aqueous sol is obtained.

As the amine used in the present invention, methylamine, ethylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, isopropylamine,
Examples thereof include alkylamines such as n-propylamine and n-butylamine, aralkylamines such as benzylamine and phenethylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. Of these, alkylamines are particularly preferred. The amount of amine added was WO ₃ and Sb ₂
30 wt% or less based on the total amount of O _5, and preferably 1 to 30 wt%. Although 30% by weight or more may be added, even if it is added more, the dispersing effect is not improved.

Examples of the carboxylic acid used in the present invention include water-soluble carboxylic acids, for example, monocarboxylic acids such as formic acid, acetic acid, and propionic acid, and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and maleic acid. , Also lactic acid,
Oxycarboxylic acids such as tartaric acid, citric acid, gluconic acid, malic acid, hydroacrylic acid, glycolic acid, tartonic acid, salicylic acid, and mandelic acid. Of these, oxycarboxylic acids are particularly preferred. Further, in the present invention, in addition to the water-soluble carboxylic acid, acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and sulfamic acid can be added. The addition amount of the carboxylic acid is 30 wt% or less based on the total amount of WO ₃ and Sb ₂ O _5, preferably from 0.1 to 30 wt%. The addition of 30% by weight or more does not improve the dispersing effect. Further, it is possible to add only carboxylic acid to the tungsten oxide-antimony pentoxide composite aqueous sol, but it is not preferable because the dispersibility is not improved, and viscosity and gelation are often caused.

Tungsten oxide of the present invention - antimony pentoxide composite aqueous sol with WO ₃ and the sum of the concentrations of Sb ₂ O ₅ is from 2 to 60 wt%, the preferred concentration is 10 to 50 wt%. If it is less than 2% by weight, it is too thin to be economical. If necessary, the tungsten oxide-antimony pentoxide composite aqueous sol of the present invention can be concentrated by a membrane filtration method such as an evaporation method or an ultrafiltration method.

The pH of the tungsten oxide-antimony pentoxide composite aqueous sol of the present invention can be adjusted to pH 1 depending on the amount of amine and acid added.
~ 9 can be prepared.

In the above-mentioned tungsten oxide-antimony pentoxide composite aqueous sol, the dispersion medium can be replaced with a hydrophilic organic solvent rather than water. As the hydrophilic organic solvent, methyl alcohol, ethyl alcohol, lower alcohols such as isopropyl alcohol, dimethylformamide, linear amides such as N, N'- dimethylacetamide, cyclic amides such as N-methyl-2-pyrrolidone, Glycols such as ethyl cellosolve, butyl cellosolve, and ethylene glycol are exemplified.

The composite aqueous sol of the present invention used when obtaining an organic solvent sol using this hydrophilic organic solvent as a dispersion medium contains oxycarboxylic acid as a carboxylic acid in a range of 0.1 to 30% by weight, and further contains an alkylamine as an amine. It contains 1 to 30% by weight. A stable organic solvent sol cannot be obtained with other amines or carboxylic acids.

The replacement of the dispersion medium with water by a hydrophilic organic solvent can be performed by a method such as an evaporation method by heating under reduced pressure or normal pressure, or a membrane filtration method.

In the first production method of the present invention, by using molybdate, vanadate, niobate, tantalate, and stannate instead of tungstate, oxides of these metals and antimony pentoxide are used. Aqueous sol or hydrophilic organic solvent sol can be produced. In these composite sols, other than the vanadium oxide-antimony pentoxide composite aqueous sol to be colored, it can be used as a refractive index control of a hard coat agent and an abrasion resistance improver.

The dried product of the composite sol of the present invention has the property of dissolving in water and returning to the sol.

In a second production method, an aqueous solution of tungstate is treated with a cation exchange resin to form a tungstic acid solution, and the solution is mixed with an acidic aqueous antimony pentoxide sol and / or an alkali metal antimonate in WO ₃ / Sb _2. in a weight ratio of O ₅ 0.1~100
And aged at room temperature to 100 ° C. to obtain a tungsten oxide-antimony pentoxide composite aqueous sol. Furthermore, a stable tungsten oxide-antimony pentoxide composite aqueous sol can be obtained by a method of adding an alkali metal hydroxide or ammonia and adding an amine and a carboxylic acid. Since the tungstic acid solution treated with the cation exchange resin is unstable, it is better to continue the next step after the treatment.

The tungstate used in the present invention includes salts of lithium, potassium, rubidium, cesium, ammonia, amine, quaternary ammonium, guanidine and the like. Particularly, sodium tungstate is preferable.

The concentration of tungstate 0.1-15 wt% as WO _3,
0.1 to 10% by weight is preferred. If it is less than 0.1% by weight, it is too thin to be economical, and if it exceeds 15% by weight, the produced tungstic acid solution gels immediately and is difficult to handle.

The alkali metal antimonate used in the present invention may be a hydrate or an anhydride, and examples of the alkali metal include lithium, sodium, and potassium.

In the present invention, aging is possible in the range of room temperature to 100 ° C,
Preferably it is in the range of 30 to 80 ° C. The aging time varies depending on the concentration and temperature, but is preferably 0.5 to 48 hours.

The aging may be performed after the addition of alkali hydroxide or ammonia, or after the addition of an amine or oxycarboxylic acid, or the composite aqueous sol obtained by the second method may be dispersed in the same manner as the composite aqueous sol obtained by the first method. Can be replaced with a hydrophilic organic solvent rather than water. In this case, aging may be performed after the replacement with the hydrophilic organic solvent, but it is most preferable before adding alkali hydroxide or ammonia.

The amount of the alkali metal hydroxide or ammonia added is M ₂ O / (Sb ₂ O ₅ + WO ₃ ) [M indicates an alkali metal or ammonium in the composite sol. ] It is possible that the molar ratio is in the range of 0.02 to 0.7. If it exceeds 0.7, the refractive index will decrease,
It is not preferable because the stability of a hydrophilic organic solvent sol is lowered.

When the acidic aqueous antimony pentoxide sol contains alkali, alkali hydroxide or ammonia may not be added.

The feature of the second production method is that a composite sol which is stable even at a high concentration can be produced in a range where the weight ratio of WO ₃ / Sb ₂ O ₅ exceeds 1 which could not be obtained by the first production method. There is something. The weight ratio of WO ₃ / Sb ₂ O ₅ can be in the range of 0.1 to 100. If the weight ratio of WO ₃ / Sb ₂ O ₅ exceeds 100, the effect of stabilizing tungstic acid is lost, which is not preferable. When the content of antimony pentoxide is small, it can be referred to as a tungsten oxide sol stabilized with antimonic acid rather than a tungsten oxide-antimony pentoxide composite sol.

The amine and carboxylic acid used in the second production method are
Are the same as the amines and carboxylic acids used in the production method, and the addition amounts are the same.

That is, the addition amount of the amine relative to the total amount of WO ₃ and Sb ₂ O ₅
30% by weight or less, and the amount of carboxylic acid added is WO ₃
And Sb ₂ O _{5 in} an amount of 30% by weight or less based on the total amount.

The total concentration of Sb ₂ O ₅ and WO _{3 in} the tungsten oxide-antimony pentoxide composite aqueous sol obtained by the second production method is 2
6060% by weight, and can be concentrated by an evaporation method or a membrane filtration method such as an ultrafiltration membrane if necessary.

The dispersion aqueous medium of the composite aqueous sol obtained by the second method can be replaced with a hydrophilic organic solvent from water by the same operation as the composite aqueous sol obtained by the first method. At this time, the composite aqueous sol to be used contains the oxycarboxylic acid as the carboxylic acid in the range of 0.1 to 30% by weight and further contains the alkylamine in the range of 1 to 30% by weight as in the case of the first method. Is what it is.

In the present invention, when aging is performed by adding sodium antimonate to a tungstic acid solution obtained by cation exchange of an aqueous solution of a tungstate, an oxidizing agent such as hydrogen peroxide or a reducing agent such as L-ascorbic acid is used. It is possible to add. When hydrogen peroxide is added, the obtained tungsten oxide-antimony pentoxide composite sol becomes yellowish,
L- For Asukorobin acid deep blue of _{W 2 O 5 Sb 2 O 5} -W
₂ O ₅ composite sol is obtained. This composite sol is also included in the tungsten oxide-antimony pentoxide composite sol of the present invention.
Although sodium arsenate can be used in place of antimonate, it is not preferable in terms of safety.

〔The invention's effect〕

Tungsten oxide of the present invention - antimony pentoxide composite sol freely be controlled between 0.1 in a weight ratio of WO ₃ / Sb ₂ O _5, thereby tungsten oxide - 1.65～ the refractive index of the antimony pentoxide composite sol It can be widely changed to 2.0. And, the tungsten oxide of the present invention
The antimony pentoxide composite sol is stable at a high concentration and does not cause precipitation of tungstic acid (H ₂ WO ₄ ) during storage or gelation by thickening.

Further, the tungsten oxide-antimony pentoxide composite sol of the present invention has a negative charge, and particularly when an alkylamine is used, a hydrophilic organic solvent or a partially hydrolyzed solution of a silane compound, a resin emulsion, an anionic It is well compatible with surfactants and the like.

Further, the tungsten oxide-antimony pentoxide composite sol has good coating properties and is well adsorbed and adheres to fibers, paper, plastics, metals and the like.

Furthermore, the tungsten oxide-antimony pentoxide composite sol of the present invention has a high binding property between tungsten oxide and antimony pentoxide, and the dried product is hard.

From the above, the tungsten oxide-antimony pentoxide composite sol of the present invention does not impair the transparency of the hard cord layer by using it as a hard coating agent such as plastic, and has a refractive index, abrasion resistance, dyeability, and antistatic property. , Adhesion,
Various physical properties such as heat resistance can be improved.

Further, the tungsten oxide-antimony pentoxide composite sol of the present invention can be used as a fiber or paper treating agent, a metal surface treating agent, a nonflammable paint material, a flame retardant auxiliary for fibers or plastics, a binder for ceramic fibers or ceramics. It can also be used in many applications such as antistatic agents for paper and plastics.

Hereinafter, the present invention will be described in more detail by way of examples.
However, the present invention is not limited by these examples. In addition,% shows weight%, and a refractive index is a refractive index of a dry gel.

Example 1 JP aqueous diantimony pentoxide sol obtained by the method described in Japanese 61-227918 (specific gravity 1.130, pH 3.0, viscosity 4.5cp, Sb ₂ O _{5
12.3%, Na 2 O, 0.94} %, Na 2 O / Sb 2 O 5 molar ratio 0.40, the particle diameter 15~25mμ) 750g the first glass container with an electron microscope, with stirring tungstate sodium (Na
₂ WO ₄ · 2H ₂ O) of 30 wt% aqueous solution of _{(WO 3 21.1%, Na 2} O5.64
%) And stirring was continued for 2 hours. Then, while stirring, 4.5 g of tartaric acid and 4.0 g of n-propylamine were added to obtain a tungsten oxide-antimony pentoxide composite aqueous sol.

The sol had Sb ₂ O ₅ 10.66%, WO ₃ 2.6%, pH 5.86.

This sol was concentrated under reduced pressure at 50 ° C. using a rotary evaporator to obtain 375 g of a high-concentration tungsten oxide-antimony pentoxide composite aqueous sol.

This sol has a specific gravity of 1.432, pH 5.60, viscosity of 2.2 cp, and Sb ₂ O ₅ 2
_{4.6%, WO 3 6.0%,} Na 2 O3.47%, n- propylamine 1.0
7% (3.5% based on Sb ₂ O ₅ + WO ₃ ), 1.20% tartaric acid (Sb ₂ O 5
₅ 3.92% against _{+ WO 3), WO 3 /} Sb 2 O 5 weight ratio 0.244, Na ₂
O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.55, transmittance 20%, refractive index 1.7
2, the particle diameter 15~25mμ in electron microscopic observation, the particle diameter 89mμ of a dynamic light scattering method (Coulter N _4), was a transparent milky.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 2 750 g of the same aqueous antimony pentoxide sol as in Example 1 was added to 1
Then, 32 g of sodium tungstate (Na ₂ WO ₄ .2H ₂ O) was added thereto while stirring in the same manner as in Example 1 to obtain a tungsten oxide-antimony pentoxide composite aqueous sol.

This sol had a specific gravity of 1.168, pH 5.49, viscosity of 2.0 cp, and Sb ₂ O ₅ 1
1.8%, was WO ₃ 2.86%. This sol was concentrated under reduced pressure at 40 ° C. using a rotary evaporator to obtain a high-concentration tungsten oxide-antimony pentoxide composite aqueous sol.

This sol has a specific gravity of 1.36, pH 5.38, viscosity of 3.2 cp, Sb ₂ O ₅ 2
_{2.5%, WO 3 5.46%,} Na 2 O3.2%, WO 3 / Sb 2 O 5 weight ratio 0.24
2, Na ₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.55, transmittance 16%, refractive index 1.73, particle diameter 102mμ by dynamic light scattering method, yellowish transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 3 0.5 g of n-propylamine and 0.75 g of tartaric acid were added to 375 g of the high-concentration tungsten oxide-antimony pentoxide composite aqueous sol obtained in Example 1 while stirring, and then 3 l of methanol was added at 60 ° C. using a rotary evaporator. The solvent was replaced while adding, to obtain 370 g of a tungsten oxide-antimony pentoxide composite methanol sol.

This sol has a specific gravity of 1.192, pH 6.02 (when mixed with water at 1: 1), viscosity of 4.7 cp, Sb ₂ O ₅ 24.9%, WO ₃ 6.1%, Na ₂ O 3.2
_{%, WO 3 / Sb 2 O} 5 weight ratio _{0.24 4, Na 2 O / (} Sb 2 O 5 + WO 3) molar ratio 0.55, (3.93% relative to the _{Sb 2 O 5 + WO 3)} n- propylamine 1.22%, 1.42% tartaric acid (4.58 relative to Sb ₂ O ₅ + WO ₃₎
%), Water content 6.5%, transmittance 22%, refractive index 1.72, particle diameter 90mμ by dynamic light scattering in methanol, and transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 4 Aqueous antimony pentoxide sol (specific gravity: 1.443, pH 6.61, viscosity: 4.3 cp, Sb ₂ O
₅ 32.6%, Na ₂ O, 2.06%, Na ₂ O / Sb ₂ O ₅ molar ratio 0.33, particle size 5-15 μm observed by electron microscope) antimony pentoxide (Sb ₂ O ₅ ) concentration 13% with water After dilution, the solution is passed through a column filled with a cation exchange resin and passed through an acidic aqueous antimony pentoxide sol (specific gravity 1.134, pH 1.92, viscosity 3.8 cp, Sb ₂ O ₅ 12.8
% To obtain Na ₂ O, 0.64%, a Na ₂ O / Sb ₂ O ₅ molar ratio 0.26).

Acidic aqueous antimony pentoxide sol thus obtained
Take 1500 g in a 2 liter container, add 90 g of sodium tungstate (Na ₂ WO ₄ .2H ₂ O) with stirring, stir for 2 hours, add 10 g of tartaric acid and 11.7 g of n-propylamine and add tungsten oxide -5 g. An antimony oxide composite sol was obtained.

This sol had Sb ₂ O ₅ 11.9%, WO ₃ 3.9%, and pH 5.60. This sol was concentrated under reduced pressure at 40 ° C. using a rotary evaporator to obtain 805 g of a high-concentration tungsten oxide-antimony pentoxide composite aqueous sol.

This sol has a specific gravity of 1.454, pH 5.42, viscosity 6.5 cp, Sb ₂ O ₅ 2
_{3.8, WO 3 7.8%, Na} 2 O3.29%, n- propylamine 1.45
% (4.6% based on Sb ₂ O ₅ + WO ₃ ), tartaric acid 1.24% (Sb ₂ O ₅
+ 3.92% with respect to _{WO 3), WO 3 / Sb} 2 O 5 weight ratio 0.33, Na ₂ O
/ (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.50, transmittance 56%, refractive index 1.7
4.Electron microscope observation particle size 5-15mμ, particle size 56mμ by dynamic light scattering method, transparent milky white, X-ray diffraction analysis of the dried product of this sol, tungsten oxide and sodium tungstate Was not observed.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 5 805 g of a tungsten oxide-antimony pentoxide composite methanol sol was subjected to solvent replacement by adding 805 g of the high-concentration tungsten oxide-antimony pentoxide composite aqueous sol obtained in Example 4 while adding 5.5 l of methanol at 60 ° C. using a rotary evaporator. I got

The obtained sol had a specific gravity of 1.182, a pH of 6.75 (when mixed with water at a ratio of 1: 1), a viscosity of 7.5 cp, Sb ₂ O ₅ 22.9%, WO ₃ 7.5%, and Na ₂ O 3.
_{15%, WO 3 / Sb 2} O 5 weight ratio _{0.33, Na 2 O / (Sb} 2 O 5 + WO 3) molar ratio 0.50, (4.57% relative to the _{Sb 2 O 5 + WO 3)} n- propylamine 1.39%, 1.42% tartaric acid (3.92% for Sb ₂ O ₅ + WO ₃₎
%), Moisture 6.5%, transmittance 60%, refractive index 1.74, particle diameter 65mμ by dynamic light scattering in methanol, and transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 6 770 g of the acidic aqueous antimony pentoxide sol obtained in Example 4
In a single container while stirring
After adding 74 g of (Na ₂ WO ₄ .2H ₂ O) and stirring for 2 hours, 8.0 g of tartaric acid and 7.5 g of n-propylamine were added to obtain a tungsten oxide-antimony pentoxide composite aqueous sol.

This sol had a specific gravity of 1.205, pH 7.16, viscosity of 2.7 cp, and Sb ₂ O ₅ 1
_{1.5%, WO 3 6.0%,} Na 2 O2.19%, n- propylamine 0.8
7% (Sb ₂ O ₅ + 5.0% based on WO ₃ ), tartaric acid 0.93% (Sb ₂ O 5
₅ + 5.3% with respect to _{WO 3), WO 3 / Sb} 2 O 5 weight ratio 0.52, Na ₂ O
/ (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.575, transmittance 22%, refractive index 1.7
8. The particle diameter was 65 mμ by a dynamic light scattering method, and the material was transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 7 860 g of the high-concentration tungsten oxide-antimony pentoxide composite aqueous sol obtained in Example 6 was subjected to solvent replacement while adding 4 l of methanol at 50 ° C. using a rotary evaporator.
The mixture was further heated at 60 ° C. for 5 hours to obtain 740 g of a tungsten oxide-antimony pentoxide composite methanol sol.

The obtained sol had a specific gravity of 1.060, pH8.70 (water and 1: when mixed with 1), the viscosity _{20c.p., Sb 2 O 5 13.3%} , WO 3 7.0%, Na 2 O2.5
_{4%, WO 3 / Sb 2} O 5 weight ratio _{0.52, Na 2 O / (Sb} 2 O 5 + WO 3) molar ratio 0.575, n-propylamine 1.01% (5.0% of the _{Sb 2 O 5 + WO 3)} , 1.08% tartaric acid (5.3% for Sb ₂ O ₅ + WO ₃₎
%), Water 14%, transmittance 23%, refractive index 1.78, particle diameter 72mμ by dynamic light scattering in methanol, and transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 8 90 g of sodium tungstate (Na ₂ WO ₄ .2H ₂ O) was added to water 790.
g of sodium tungstate in aqueous solution (WO ₃ 7.16
%), And passed through a column filled with a cation exchange resin (Amberlite 120B, manufactured by Organo) to prepare a tungstic acid solution.

The tungstic acid solution, specific gravity 1.068, PH1.60, viscosity _{2.0cp, WO 3 6.8%, Na} 2 O0.04%, Na 2 O / WO 3 molar ratio of 0.
022 was a yellowish clear liquid. This solution gelled after one hour by standing.

Immediately after passing, 820 g of the tungstic acid solution was placed in a 2 liter container, and added to 830 g of the acidic aqueous antimony pentoxide sol (Sb ₂ O ₅ 12.8%) obtained in Example 4 with stirring.
Aged for hours. Next, after cooling, 47 g of a 20% aqueous sodium hydroxide solution was added with stirring, and 6.2 g of n-propylamine was further added to obtain a tungsten oxide-antimony pentoxide composite aqueous sol.

The sol had Sb ₂ O ₅ 6.2%, WO ₃ 3.27%, pH 5.62. This sol was concentrated under reduced pressure by a rotary evaporator to obtain 780 g of a high-concentration tungsten oxide-antimony pentoxide composite sol.

This sol had a specific gravity of 1.216, pH 5.48, viscosity of 4.0 cp, and Sb ₂ O ₅ 1
_{3.6%, WO 3 7.1%,} Na 2 O1.66%, n- propylamine 0.7
9% (3.8% based on Sb ₂ O ₅ + WO ₃ ), WO ₃ / Sb ₂ O ₅ weight ratio of 0.
52, Na ₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.364, transmittance 24%,
Refractive index 1.78, particle size observed by electron microscope 5 to 15 mμ (larger than raw material antimony pentoxide colloid, no particles of tungsten oxide colloid are recognized), particle size by dynamic light scattering method 58 mμ, transparency It was milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 9 After aging at 50 ° C. for 2 hours in the same manner as in Example 8,
Composite aqueous sol 1697 obtained by adding 20% aqueous solution of caustic soda
3.6 g of tartaric acid and 7.8 g of n-propylamine with stirring
Was added to obtain a tungsten oxide-antimony pentoxide composite aqueous sol.

This sol had 6.22% Sb ₂ O ₅ , 3.26% WO ₃ and pH 5.40.

This sol was concentrated under reduced pressure by a rotary evaporator to obtain a high-concentration tungsten oxide-antimony pentoxide composite sol.
710 g was obtained.

This sol has a specific gravity of 1.264, pH 5.25, viscosity of 4.8 cp, and Sb ₂ O ₅ 1
_{5.0%, WO 3 7.9%,} Na 2 O1.82%, n- propylamine 1.1
% (4.8% based on Sb ₂ O ₅ + WO ₃ ) and tartaric acid 0.51% (Sb ₂ O ₅
+ 2.23% with respect to _{WO 3), WO 3 / Sb} 2 O 5 weight ratio 0.527, Na ₂ O
/ (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.364, transmittance 30%, refractive index 1.7
8. The particle diameter was 56 mμ by a dynamic light scattering method, and the emulsion was transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 10 Using 710 g of the aqueous sol of tungsten oxide and antimony pentoxide obtained in Example 9, the solvent was replaced by adding 4 l of methanol at 60 ° C. using a rotary evaporator in the same manner as in Example 3 to obtain a tungsten oxide. 820 g of antimony pentoxide methanol sol was obtained.

This sol has a specific gravity of 1.070, a pH of 5.85 (when mixed with water at a ratio of 1: 1), a viscosity of 4.0 cp, Sb ₂ O ₅ 13.0%, WO ₃ 6.8%, and Na ₂ O 1.57
%, (4.8% relative to the _{Sb 2 O 5 + WO 3)} WO 3 / Sb 2 O 5 weight ratio _{0.52, Na 2 O / (Sb} 2 O 5 + WO 3) molar ratio 0.364, 0.95% n-propylamine, tartaric acid 0.44% (2.23% for Sb ₂ O ₅ + WO ₃₎
%), Moisture 20.5%, transmittance 28%, refractive index 1.78, particle diameter 64mμ by dynamic light scattering, and transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 11 A tungstic acid solution obtained by the same method as in Example 8 (WO
₃ 6.8%) stirred taken up in 1 of container 820g while sodium antimonate _{(Na 2 O · Sb 2 O} 5 · 6H 2 O: Sb 2 O 5 65%, Na 2 O12.5
%, Was added H ₂ O22.5%) 6.0g, it was carried out for 3 hours aging at 60 ° C.. The tungstic acid solution turned into a pale yellow sol without gelling. After cooling, 8.3 g of 20% caustic soda was added thereto, and 3.4 g of n-propylamine was added thereto to obtain a tungsten oxide-antimony pentoxide composite sol.

This sol is almost colorless and slightly colloidal,
₃ 6.65%, Sb ₂ O ₅ 0.465%, pH 4.37. This sol was concentrated under reduced pressure using a rotary evaporator to obtain 210 g of a high-concentration tungsten oxide-antimony pentoxide composite sol.

This sol has a specific gravity of 1.295, pH 4.27, viscosity of 2.0 cp, and Sb ₂ O
₅ 1.86%, WO ₃ 26.55%, Na ₂ O 0.77%, n-propylamine 1.62% (5.7% based on Sb ₂ O ₅ + WO ₃ ), WO ₃ / Sb ₂ O ₅ weight ratio 1.42, Na ₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.10, transmittance 68
%, Refractive index 1.95, primary particle diameter 2-8m by electron microscope observation
μ, the particle diameter was 140 mμ by dynamic light scattering, colorless, transparent, and slightly colloidal.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Although the primary particle diameter is remarkably small, the particle diameter in the dynamic light scattering method is large irrespective of transparency because the primary particles are micro-aggregated.

Example 12 A tungstic acid solution obtained by the same method as in Example 8 (WO
₃ 6.8%) with stirring taking 750g to 1 vessel was added sodium antimonate _{(Na 2 O · Sb 2 O} 5 · 6H 2 O) 8.0g, 65 ℃
For 2.5 hours. After cooling, 9.0 g of 20% caustic soda was added thereto, followed by stirring for 1 hour, and further 10.2 g of tartaric acid,
8.0 g of isopropylamine was added to obtain a tungsten oxide-antimony pentoxide composite sol.

This sol is almost colorless and slightly colloidal,
₃ 6.5%, pH 4.52. This sol was concentrated under reduced pressure at 40 ° C. using a rotary evaporator to obtain 280 g of a high-concentration tungsten oxide-antimony pentoxide composite sol.

This sol has a specific gravity of 1.236, pH 4.26, viscosity of 3.2 cp, and Sb ₂ O
_{5 1.86%, WO 3 18.2%} , Na 2 O0.96%, tartaric acid 3.64% (Sb ₂ O
₅ + 18.1% based on WO ₃ ), 2.86% isopropylamine
(14.3% based on Sb ₂ O ₅ + WO ₃ ), WO ₃ / Sb ₂ O ₅ weight ratio 9.7
8, Na ₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.184, transmittance 62%, refractive index 1.91, primary particle diameter 2-8 μm by electron microscope observation, particle diameter 160 mμ by dynamic light scattering method, Transparent and slightly opalescent colloidal.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 13 280 g of the high-concentration tungsten oxide-antimony pentoxide sol obtained in Example 12 was subjected to solvent replacement while adding 240 g of dimethylformamide at 80 ° C. with a rotary evaporator, and 360 g of a tungsten oxide-antimony pentoxide composite dimethylformamide sol was obtained. Obtained.

The obtained sol had a specific gravity of 1.160, pH 4.85 (when mixed with water at a ratio of 1: 1), a viscosity of 30 c.p., Sb ₂ O _{5 of} 1.45%, WO ₃ 14.16%, and Na ₂ O.
0.75%, WO ₃ / Sb ₂ O ₅ weight ratio 9.78, Na ₂ O / (Sb ₂ O ₅ + WO ₃ )
Molar ratio 0.184, isopropylamine 2.22% (Sb ₂ O ₅ + WO ₃
18.1% for tartaric acid, 2.83% for tartaric acid (based on Sb ₂ O ₅ + WO ₃₎
14.3%), moisture 20.3%, transmittance 38%, refractive index 1.91, particle diameter 220mμ by dynamic light scattering method, transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 14 820 g of a tungstic acid solution (WO ₃ 6.9%, Na ₂ O 0.03%, pH 1.54) prepared in the same manner as in Example 8 was placed in a vessel, and sodium antimonate (Na ₂ O・ Sb ₂ O ₅
6H ₂ O) was added, and the mixture was aged at 65 ° C. for 1.5 hours to obtain a transparent milky white sol.

The sol _{WO 3 6.66%, Sb 2 O} 5 2.29%, a specific gravity of 1.087, pH
The viscosity was 2.26 and the viscosity was 2.0 cp.

After adding 10.2 g of tartaric acid and 4.5 g of isopropylamine to this sol with stirring, use a rotary evaporator.
The mixture was concentrated under reduced pressure at 40 ° C. to obtain 250 g of a high-concentration tungsten oxide-antimony pentoxide composite aqueous sol.

This sol has a specific gravity of 1.356, pH 4.05, viscosity of 3.2 cp, and Sb ₂ O
_{5 7.8%, WO 3 22.7%} , Na 2 O1.60%, 4.08% tartaric acid (Sb ₂ O ₅
+ WO ₃ 13.4%), isopropylamine 1.80% (S
b ₂ O ₅ + 5.9% with respect to WO ₃ ), WO ₃ / Sb ₂ O ₅ weight ratio 2.91, Na
₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.212, primary particle diameter 5-20 mμ observed by electron microscope, particle diameter 180 m by dynamic light scattering method
μ, refractive index 1.88, transmittance 18%, transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 15 Using 250 g of the high-concentration tungsten oxide-antimony pentoxide composite aqueous sol obtained in Example 14 and methanol at 60 ° C. with a rotary evaporator in the same manner as in Example 3.
The solvent was replaced while adding 1.7 l of tungsten oxide.
340 g of antimony pentoxide composite methanol sol was obtained.

This sol has a specific gravity of 1.050, pH 5.02 (when mixed with water at 1: 1), viscosity of 2.5 cp, Sb ₂ O ₅ 5.4%, WO ₃ 15.7%, Na ₂ O 1.11
%, WO ₃ / Sb ₂ O ₅ weight ratio 2.91, Na ₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.212, isopropylamine 1.25% (4.60% based on Sb ₂ O ₅ + WO ₃ ), tartaric acid 2.83% (13.4 for Sb ₂ O ₅ + WO ₃
%), Moisture 16.9%, transmittance 16%, refractive index 1.88, particle diameter 210 mμ by dynamic light scattering, and transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 16 840 g of a tungstic acid solution (WO ₃ 6.9%, Na ₂ O 0.03%, pH 1.56) prepared in the same manner as in Example 8 was placed in a container, and sodium antimonate (Na ₂ O・ Sb ₂ O ₅
• 16 g of 6H ₂ O) was added and the mixture was aged at 65 ° C for 4 hours to obtain a pale yellow tungsten oxide-antimony pentoxide composite sol.

This sol had a pH of 1.58. After cooling, 15.0 g of tartaric acid and 13.4 g of isopropylamine were added with stirring, and the mixture was concentrated under reduced pressure at 40 ° C. with a rotary evaporator.
290 g of a high-concentration tungsten oxide-antimony pentoxide composite aqueous sol was obtained.

This sol has a specific gravity of 1.300, pH 3.72, viscosity of 3.2 cp, Sb ₂ O
_{5 3.6%, WO 3 20.0%} , Na 2 O0.69%, 5.17% tartaric acid (Sb ₂ O ₅
+ WO ₃ 21.9%), isopropylamine 4.62% (S
b 19.6% against _{2 O 5 + WO 3),} WO 3 / Sb 2 O 5 weight ratio 5.56, N
a ₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.13, particle diameter 2-15 mμ by electron microscope observation, particle diameter 180 mμ by dynamic light scattering method, refractive index 1.90, transmittance 24%, transparent milky white Met.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 17 Using a high-concentration tungsten oxide-antimony pentoxide aqueous sol (290 g) obtained in Example 16 in the same manner as in Example 3 using a rotary evaporator at 60 ° C and methanol 1.
The solvent was replaced while adding 2 l, to obtain 370 g of a tungsten oxide-antimony pentoxide composite methanol sol.

This sol has a specific gravity of 1.088, pH 4.65 (when mixed with water at a ratio of 1: 1), viscosity of 4.2 cp, Sb ₂ O ₅ 2.8%, WO ₃ 15.7%, Na ₂ O 0.54
_{%, WO 3 / Sb 2 O} 5 weight ratio _{5.56, Na 2 O / (Sb} 2 O 5 + WO 3) molar ratio 0.13, 3.62% isopropyl amine (19.6% relative to the _{Sb 2 O 5 + WO 3)} , tartaric acid 4.05% (21.9 for Sb ₂ O ₅ + WO ₃
%), Moisture 16.9%, transmittance 22%, refractive index 1.90, particle diameter 210mμ by dynamic light scattering, and transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 18 820 g of a tungstic acid solution (WO ₃ 6.9%, Na ₂ O 0.03%, pH 1.56) prepared in the same manner as in Example 8 was placed in a 2 liter container, and sodium antimonate (Na ₂ O ・ Sb
₂ O ₅ · 6H ₂ O) was added 8.0 g, further acidic aqueous diantimony pentoxide sol obtained in Example _{4 (Sb 2 O 5 12.8%} , WO 3 15.7%,
Was added Na ₂ O0.54%) 410g, it was 60 ° C. 2 hours aging.
After cooling, add 23 g of a 20% aqueous solution of caustic soda while stirring,
Further, 7.2 g of isopropylamine and 6.8 g of tartaric acid were added to obtain a tungsten oxide-antimony pentoxide composite aqueous sol.

This sol had 4.52% of Sb ₂ O ₅ , 4.44% of WO ₃ and pH 4.62.

This sol was concentrated under reduced pressure at 40 ° C. using a rotary evaporator to obtain 380 g of a high-concentration tungsten oxide-antimony pentoxide composite sol.

This sol has a specific gravity of 1.348, pH 4.48, viscosity of 5.6 cp, and Sb ₂ O ₅ 1
_{4.9%, WO 3 15.2%,} Na 2 O1.96%, 1.79% tartaric acid (Sb ₂ O ₅
+ WO ₃ with respect to 5.95%), 1.89% isopropyl amine (Sb
6.28% based on ₂ O ₅ + WO ₃ ), WO ₃ / Sb ₂ O ₅ weight ratio 1.02, Na
_{2 O / (Sb 2 O 5} + WO 3) molar ratio 0.286, the particle size 10~20mμ in electron microscopic observation, the particle diameter of a dynamic light scattering method 110Emumyu, refractive index 1.81, transmittance 24%, with transparency opalescent there were.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 19 Using 380 g of the high-concentration tungsten oxide-antimony pentoxide aqueous sol obtained in Example 18, in the same manner as in Example 3, solvent replacement was performed while adding 2 L of methanol at 50 to 60 ° C. using a rotary evaporator. Performed tungsten oxide
560 g of antimony pentoxide methanol sol was obtained.

The resulting sol had a specific gravity of 1.068, a pH of 5.02 (when mixed with water at a ratio of 1: 1), a viscosity of 4.6 cp, Sb ₂ O ₅ 10.1%, WO ₃ 10.3%, and Na ₂ O
1.33%, WO ₃ / Sb ₂ O ₅ weight ratio 0.1.02, Na ₂ O / (Sb ₂ O ₅ + W
O ₃ ) molar ratio 0.286, isopropylamine 1.28% (Sb ₂ O ₅ +
WO ₃ with respect to 6.28%), tartaric acid _{1.21% (Sb 2 O 5 +} WO 3 with respect to 5.95 %%), 18.2% water, transmittance 22%, refractive index 1.8
1. The particle diameter was 128 mμ according to the dynamic light scattering method, and the material was transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Example 20 750 g of a tungstic acid solution (WO ₃ 6.8%, Na ₂ O 0.04%, pH 1.60) prepared in the same manner as in Example 8 was placed in a vessel, and sodium antimonate (Na ₂ O · Sb ₂ O ₅ · 6
8.0 g of H ₂ O) was added, and the mixture was aged at 60 ° C. for 3 hours. After cooling, 9.0 g of a 20% aqueous sodium hydroxide solution was added thereto while stirring,
After stirring for 1 hour, 8.0 g of tartaric acid and 13.8 g of triethanolamine were further added to obtain a tungsten oxide-antimony pentoxide composite aqueous sol.

The sol _{WO 3 6.47%, Sb 2 O} 5 0.66%, was PH4.62. This sol was concentrated under reduced pressure at 40 ° C. using a rotary evaporator to obtain 280 g of a high-concentration tungsten oxide-antimony pentoxide composite aqueous sol.

This sol has a specific gravity of 1.240, pH 4.32, viscosity of 4.0 cp, Sb ₂ O
_{5 1.86%, WO 3 18.2%} , Na 2 O0.96%, tartaric acid 2.86% (Sb ₂ O
₅ + 14.2% with respect to WO _3), triethanolamine 4.93%
(24.6% based on Sb ₂ O ₅ + WO ₃ ), WO ₃ / Sb ₂ O ₅ weight ratio 9.7
8, Na ₂ O / (Sb ₂ O ₅ + WO ₃ ) molar ratio 0.184, transmittance 60%, refractive index 1.91, transparent milky white.

This sol was stable even when left at 60 ° C. for one month or longer, without showing any increase in viscosity, gelation, or formation of sediment.

Comparative Example 1 The high-concentration tungsten oxide-antimony pentoxide composite aqueous sol obtained in Example 2 (specific gravity 1.36, pH 5.38, viscosity 3.2c.
p., Sb ₂ O ₅ 22.5%, WO ₃ 5.46%, Na ₂ O 3.2%) 205 g of oxalic acid
When 4.5 g was added, the sol turned cloudy and gelled.

Comparative Example 2 840 g of a tungstic acid solution (WO ₃ 6.9%, Na ₂ O 0.03%, pH 1.56) prepared in the same manner as in Example 8 was placed in one container, and aged at 60 ° C. for 4 hours while stirring. However, the tungstic acid solution gelled, and even after aging, the gel was not peptized and no sol was obtained.

Comparative Example 3 A high-concentration tungsten oxide-antimony pentoxide composite aqueous sol (specific gravity 1.216, pH 5.48, viscosity 4.0) prepared in Example 6
780 g of cp, Sb ₂ O ₅ 13.6, WO ₃ 7.1%, Na ₂ O 1.66%, n-propylamine 0.79%) was placed in a 3 l eggplant-shaped flask, and the solvent was added thereto at 40 ° C. with a rotary evaporator at 40 ° C. After the substitution, 830 g of a tungsten oxide-antimony pentoxide composite methanol sol was obtained.

This sol has a specific gravity of 1.078, pH 5.83 (mixed 1: 1 with water), viscosity 52 c.p., Sb ₂ O ₅ 12.8%, WO ₃ 6.67%, n-propylamine 0.74%, moisture 23.2%, dynamic 72m particle system by light scattering method
μ, a refractive index of 1.79, and a transparent white color.

Tungsten oxide in Comparative Example 4 Example 20 - diantimony pentoxide aqueous sol 280g at 40 ° C. on a rotary evaporator is taken up in 1 eggplant type flask was added methanol was attempted solvent substitution immediately tungstic acid (H ₂ WO ₄ ), And a stable methanol sol could not be obtained.

Claims (15)

(57) [Claims] The weight ratio of tungsten oxide to antimony pentoxide is 0.1 to 100 in terms of WO ₃ / Sb ₂ O ₅ , and alkali metal or ammonium is converted to M ₂ O / (WO ₃ + Sb ₂ O ₅ ) [M Indicates alkali metal or ammonium. ] In a molar ratio of 0.02 to
A tungsten oxide-antimony pentoxide composite aqueous sol containing 0.7. 2. A tungsten oxide-antimony pentoxide composite aqueous sol according to claim 1, further comprising an amine or an amine and a carboxylic acid. 3. The content of amine and carboxylic acid is 30 to the total amount of tungsten oxide and antimony pentoxide, respectively.
The tungsten oxide-antimony pentoxide composite aqueous sol according to claim 2, which is not more than weight%. 4. The method according to claim 1, wherein the weight ratio of tungsten oxide to antimony pentoxide is 0.1 to 100 in terms of WO ₃ / Sb ₂ O ₅ weight ratio, and alkali metal or ammonium is converted to M ₂ O / (WO ₃ + Sb ₂ O ₅ ) [M Indicates alkali metal or ammonium. ] In a molar ratio of 0.02 to
A tungsten oxide-antimony pentoxide composite hydrophilic, characterized by containing 1 to 30% by weight of alkylamine and 0.1 to 30% by weight of oxycarboxylic acid based on the total amount of tungsten oxide and antimony pentoxide. Organic solvent sol. 5. A tungsten oxide-antimony pentoxide composite aqueous sol comprising an acidic aqueous antimony pentoxide sol and a tungstate in a weight ratio of WO ₃ / Sb ₂ O ₅ of 1 or less. Production method. 6. The method for producing a tungsten oxide-antimony pentoxide composite aqueous sol according to claim 5, wherein an amine or an amine and a carboxylic acid are further added. 7. An amine and a carboxylic acid are added in an amount of 30 to the total amount of tungsten oxide and antimony pentoxide, respectively.
The method for producing a tungsten oxide-antimony pentoxide composite aqueous sol according to claim 6, which is not more than 10% by weight. 8. An aqueous solution of a tungstate is treated with a cation exchange resin to form a tungstic acid solution. The solution is mixed with an acidic aqueous antimony pentoxide sol and / or an alkali metal antimonate in a weight ratio of WO ₃ / Sb. method for producing antimony pentoxide composite aqueous sol - ₂ O ₅ were mixed with 0.1 to 100 range, tungsten oxide, characterized in that the aging at room temperature to 100 ° C.. 9. The method according to claim 1, further comprising adding an alkali hydroxide or ammonia.
M ₂ O / (WO ₃ + Sb ₂ O ₅ ) [M represents an alkali metal or ammonium. The method for producing a tungsten oxide-antimony pentoxide composite aqueous sol according to claim 8, wherein the amine or the amine and the carboxylic acid are added in a molar ratio of 0.02 to 0.7. 10. The amounts of the amine and carboxylic acid added to the total amount of tungsten oxide and antimony pentoxide, respectively.
The tungsten oxide according to claim 9, which is not more than 30% by weight.
A method for producing an antimony pentoxide composite aqueous sol. 11. The tungstate is lithium, potassium, rubidium, cesium, ammonia, amine, quaternary
9. The method for producing a tungsten oxide-antimony pentoxide composite aqueous sol according to claim 8, which is at least one tungstate selected from quaternary ammonium and guanidine. 12. An acidic aqueous antimony pentoxide sol and tungstate are mixed in a weight ratio of WO ₃ / Sb ₂ O ₅ of 1 or less, and then alkyl is added to the total amount of tungsten oxide and antimony pentoxide. Amine oxide is added in an amount of 1 to 30% by weight, and oxycarboxylic acid is added in an amount of 0.1 to 30% by weight.
A method for producing a tungsten oxide-antimony pentoxide composite hydrophilic organic solvent sol, comprising obtaining an antimony pentoxide composite aqueous sol and replacing the dispersion medium of the aqueous sol with a hydrophilic organic solvent rather than water. 13. An aqueous solution of tungstate is treated with a cation exchange resin to form a tungstic acid solution. The solution is mixed with an acidic aqueous antimony pentoxide sol and / or an alkali metal antimonate in a weight ratio of WO ₃ / Sb. ₂ O ₅ Mix in the range of 0.1 to 100, aged at room temperature to 100 ° C, and then 1 to 30% by weight of alkylamine and 0.1 to 30% by weight of oxycarboxylic acid based on the total amount of tungsten oxide and antimony pentoxide. % Of a tungsten oxide-antimony pentoxide composite aqueous sol, wherein the dispersion medium of the aqueous sol is replaced with a hydrophilic organic solvent rather than water. Production method. 14. After aging, the alkali hydroxide or ammonia is further converted into M ₂ O / (WO ₃ + Sb ₂ O ₅ ) [M represents an alkali metal or ammonium. 14. The method for producing a tungsten oxide-antimony pentoxide composite hydrophilic organic solvent sol according to claim 13, wherein the sol is added in a molar ratio of 0.02 to 0.7. 15. Tungstates are lithium, potassium, rubidium, cesium, ammonia, amine, quaternary
14. The method for producing a tungsten oxide-antimony pentoxide composite hydrophilic organic solvent sol according to claim 13, wherein the sol is at least one tungstate selected from quaternary ammonium and guanidine.