JPH02149424A - White color conductive material and its production - Google Patents

Abstract

PURPOSE:To obtain the title white conductive material having high whiteness, excellent weatherability, and stabilized conductivity and heat resistance by coating the surface of a white or quasiwhite base material with the film of a tin-antimony-cobalt multicomponent oxide. CONSTITUTION:The surface of a white or quasi-white base material is coated with the film of a multicomponent oxide consisting of the oxides of tin, antimony, and cobalt. The multicomponent film contains about 90-85wt.% tin oxide and the balance antimony oxide and cobalt oxide. The content of the antimony oxide in the film is preferably controlled to about 10-15wt.%, and that of the cobalt oxide to about 0.05-1wt.% based on the total oxide. The white conductive material is obtained by the following method. Namely, the base material, stannous chloride, an antimony compd., and a cobalt compd. are allowed to react with one another in an alkaline soln. to form a multicomponent hydroxide film on the base material surface, and the obtained material is then aged in an acidic soln., filtered off, dried, further heated to a high temp. to convert the multicomponent hydroxide film to a multicomponent oxide film.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a conductive material with high whiteness and excellent weather resistance, and a method for producing the same.

Conventional technologies and their problems With the development of science and technology and the diversification of needs, the development of high-performance, multifunctional materials is actively being carried out, and even in the electronics industry etc., the development of conductive polymer materials. Various studies have been conducted regarding this, and for example, polymeric materials using carbon particles or fibers or metal powders such as copper, silver, and gold as conductive fillers have been proposed. however,
Carbon particles, carbon fibers, metal powders such as copper, silver, and gold are all black or have a color unique to the metal, and are conductive polymers that can be used as conductive fillers in plastics, etc. is colored, and a white conductive polymer cannot be obtained, so its uses are limited.

The present inventors have previously made the invention described in JP-A-59-6235, and have developed a white conductive material whose main component is fibrous potassium titanate whose surface is covered with stannic oxide. The invention described in JP-A No. 59-102820 is made by adding (a) one or more metal compounds selected from the metal group consisting of tin, indium, antimony, copper, and nickel to an aqueous dispersion of alkali metal titanate; and (b) an aqueous solution of alkali hydroxide or alkali halide are added simultaneously, and the water-insoluble metal oxide produced by the reaction between both solutions is deposited on the surface of the alkali metal titanate. We have disclosed a manufacturing technology for conductive alkali metal titanate.

However, although the conductive substances according to any of the inventions have stable conductivity and heat resistance, they are not particularly satisfactory in terms of whiteness and weather resistance.

The object of the present invention is to provide a white conductive material that has high whiteness, excellent weather resistance, and stable conductivity and heat resistance.

Means for Solving the Problems As a result of intensive research to improve the shortcomings of the above-mentioned known techniques, the present inventor has discovered that the surface of a white or pseudo-white base material is a composite consisting of oxides of tin and antimony elements. Covered with an oxide film, and the ratio of tin oxide in the composite oxide film is about 90 to about 85% by weight, and the remaining components are antimony oxide and cobalt oxide.It has high whiteness and is weather resistant. We have developed a white conductive material with excellent conductivity and stable heat resistance, as well as a method for producing the same.

In the present invention, the materials used as raw materials include:
A white or pseudo-white color is desirable.

The shape of the base material may be any shape such as scale, plate, needle, powder, granule, sphere, or fiber.

The scale-like or plate-like base material is also called a flake-like base material, and mica is commonly used. Taking natural mica as an example, mica is an aluminum silicate mineral with interstices, and there are many types depending on the components contained, but among these, muscovite (muscovite) is preferable. Further, sericite, talc, etc. can also be mentioned. Examples of artificial materials include mica coated with titanium oxide, glass flakes, and alumina flakes.

Acicular base materials include natural and artificial materials, with aspect and wollastonite being representative natural materials. Asbestos has a long history as a needle-shaped base material and has excellent reinforcing properties, but its use has been banned in many countries as it is a causative agent of asbestosis and cancer. Wollastonite is an anhydrous calcium silicate that is widely used. Artifacts include potassium titanate whiskers, gypsum fibers, xonotrite, MO8 fibers (M g S Oa ・5 Mg
0・8H20), PMF (Processed
MineralF 1bcr) and the like.

Various types of powder or powder base material can be used as the base material of the present invention, and specific examples include titanium dioxide, silica powder, zinc white, lithopone, calcium sulfate, barium sulfate, and calcium carbonate. , magnesium hydroxide, calcium silicate, kaolinite, montmorionite and the like. - Powder or powdery substances exhibiting a white or pseudo-white hue can also be used as the substrate of the present invention, but substrates that decompose, melt, or change in quality in the temperature range of 200 to 800°C are not preferred.

Spherical substrates can be divided into beads with a filled interior and balloons with a hollow interior. Many balloon-shaped materials can be used as the white or pseudo-white base material in the present invention. Specific examples of the balloon-shaped substrate include silica balloons, glass balloons, fly ash balloons, and the like. Among artificially controlled beads, silicon beads, glass beads, etc. can be used as the base material of the present invention.

Examples of the fibrous base material include white or pseudo-white fibrous base materials such as glass fiber, alumina fiber, ceramic fiber, and rock wool fiber.

The white conductive material with high whiteness and high weather resistance of the present invention has a structure in which a composite oxide film made of oxides of tin and antimony elements is provided on the surface of the various white or pseudo-white base materials described above. However, the ratio of tin oxide in the composite oxide film is about 90 to about 85% by weight, and the remaining components are antimony oxide and cobalt oxide.

Conventionally, white conductive materials are known in which a coating layer of tin oxide or silver oxide doped with ammothine oxide is provided on the surface of the various white or pseudo-white substrates described above. however,
Although conductivity was imparted, the whiteness of the white conductive material was low, less than 80 in so-called value, and its hue was grayish-white, so it could hardly be called white. Weather resistance is also not sufficient, and white conductive materials are generally used in areas that are visible to the human eye, and hue change due to light is a major problem, so known white conductive materials Color difference (hereinafter referred to as “
ΔE'') is 4 or more, numerically 5 to 12, which poses a big problem in practice.

The present inventor has discovered that the composition of the conductive composite oxide film applied to the surface of a white or pseudo-white base material is approximately 90% to 90% as tin oxide.
By making the remaining components antimony oxide and cobalt oxide, the white color has an L value of 80 or more and a ΔE value of 4 or less, which has a wide range of practical uses. It has been discovered that a conductive material can be obtained.

In the composition of the composite oxide film, the ratio of tin oxide is 9
If it exceeds 0% by weight, the whiteness will be higher, but it will not be possible to develop conductivity. Conversely, the ratio of tin oxide is 85
If it is less than % by weight, the composite oxide film will turn from gray to black, making it impossible to obtain the object of the present invention. In the present invention, a small amount of cobalt oxide is newly added to the composition of the tin oxide/antimony oxide composite oxide film, which has traditionally been a conductive material with a large ΔE, thereby improving whiteness and reducing ΔE. I was able to do that. Addition of cobalt oxide can exhibit its effect even in extremely small amounts. That is, in the composition of the composite oxide of the present invention, antimony oxide is about 10 to about 1
5% by weight, and cobalt oxide may be added in a proportion of about 0.05 to about 1% by weight based on the total weight of tin oxide/antimony oxide constituting the composite oxide film.

The significant difference in performance between the white conductive material of the present invention and conventionally known white conductive materials is made more stable by the manufacturing method.

The object of the present invention is to have high whiteness and excellent weather resistance,
The method for producing a white conductive substance with stable conductivity and heat resistance is as follows.

The manufacturing method of the present invention involves reacting a white or pseudo-white base material, stannous chloride, an ammothine-based compound, and a cobalt-based compound in an alkaline aqueous solution, and forming a tin-ammothine-cobalt composite hydroxide on the surface of the base material. This is a method in which a film is formed, then aged in an acidic aqueous solution, dehydrated and dried, and further heated to a high temperature to form the composite hydroxide film into a composite oxide film.

The raw material for tin oxide used in the present invention is specified as stannous chloride. In the method of manufacturing a white conductive substance with high whiteness and high weather resistance, which is the object of the present invention, it is not appropriate to use other tin compounds as raw materials.

The antimony compounds and cobalt compounds used in the present invention may be those that are soluble in water or water-soluble organic solvents, such as halogenated salts, oxides, etc. that are alkaline and water-soluble, and metal alcoholides. Examples include those soluble in water-soluble organic solvents such as metal acetylacetonate. Specifically, 5bC13, 5bC15, CoC! ! ,
Examples include water-soluble compounds such as Co CZ 5 , antimony oxide, cobalt oxide, and compounds soluble in water-soluble organic solvents such as methylate, ethylate, propionate, butyrate, and acetylacetonate of antimony and cobalt. It is desirable to use these stannous chloride, antimony compounds, and cobalt compounds as an aqueous solution from the viewpoint of labor safety and resource conservation, but water-soluble organic solvents,
For example, one or more of alcohols having 4 or less carbon atoms, acetone, ethylene glycol, propylene glycol, dioxane, glycerin, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diacetone alcohol, acetylacetate, etc. Examples include mixed solvents and aqueous solutions thereof.

In the present invention, both a solution in which stannous chloride, an ammothine compound, and a cobalt compound are dissolved separately, and a solution in which stannous chloride, an antimony compound, and a cobalt compound are dissolved simultaneously can be used.

When preparing an aqueous dispersion of a white or pseudo-white base material, the apparent concentration is about 0.01 to 50% by weight, preferably about 0.
．． It is preferable to adjust the amount to 1 to 3% by weight.

The concentration of the stannous base, antimony compound, and cobalt compound solution added to the aqueous dispersion of the white or pseudo-white base material can be selected freely, but if the concentration is too low, the liquid level will be too high (
This is not preferable because it is inconvenient to handle and reduces productivity. On the other hand, when using a solution containing stannous chloride, antimony compounds, and cobalt compounds in a higher solubility, the hydrolyzate of these compounds will be deposited unevenly on the white or pseudo-white substrate, resulting in This is not preferable because there is a risk of variations in the conductivity, whiteness, and weather resistance of the white conductive material.

In the present invention, the component of the composite oxide coating on the surface of the white or pseudo-white base material contains about 10 to 15% by weight of a mixture of metal oxides consisting of antimony and cobalt, and the remainder consists essentially of tin oxide. be done. If the amount of antimony oxide contained in the composite oxide film is less than 10% by weight, the doping effect will be poor and high conductivity will tend to become undesirable. In addition, there was no particular upper limit in the past, but if it exceeds 15%, the color becomes gray or bluish, and the whiteness tends to decrease, reducing its utility value as a white conductive material. However, they generally tend to be expensive (industrial applicability decreases).

Regarding the coating amount of the composite oxide coating on the surface of the white or pseudo-white base material, if the coating amount is too small, the coating will not be uniform and the conductivity will not be developed or the conductivity will be low, and conversely if it is too large. However, the conductivity of the -layer cannot be expected, and the whiteness will be reduced, which will not meet the purpose of the present invention. The composite oxide film of the present invention has a total composition of about 20 to 40% by weight.
A range of is preferred.

A white or pseudo-white aqueous dispersion of stannous chloride,
The method of adding the antimony compound and cobalt compound solutions requires adjusting the conditions to cause hydrolysis.

The first method of hydrolysis uses organometallic compounds such as tin chloride and antimony and cobalt alcoholade and aticel alcoholate, and dissolves these in a water-soluble organic solvent to form a white or pseudo-white group. When added to an aqueous dispersion of the material, tin chloride, antimony compounds, and cobalt compounds are hydrolyzed and deposited in the form of composite hydroxides on the surface of the white or pseudo-white substrate.

Since these hydrolysis reactions are accelerated in the presence of an alkaline substance under heating, it is preferable to carry out the reaction by heating a white or pseudo-white aqueous dispersion of the base material to a temperature of 50° C. or above and below the boiling point. At this time, as the alkaline substance, alkali metal hydroxides, carbonates, nitrates, ammonia, etc. can be used.

The second method of hydrolysis is to use stannous chloride and a halide as an antimony compound or a cobalt compound, and add an alcohol solution of these to an aqueous dispersion of a white or pseudo-white base material. Similar to the first method, the hydrolysis reaction is promoted by heating and in the presence of an alkaline substance.

The third method of hydrolysis is to add an aqueous solution of stannous chloride, an antimony compound, and a cobalt compound to an aqueous dispersion of a white or pseudo-white base material, which is labor-safe because it does not use an organic solvent. This method has high industrial applicability from the viewpoints of safety, disaster prevention, and economic efficiency. However, many stannous chloride, antimony compounds, and cobalt compounds are immediately hydrolyzed or altered when they come into contact with water, and it is often difficult to obtain a stable aqueous solution. However, by making an acidic aqueous solution, a stable aqueous solution can be obtained can get. It should be noted that, as in the first and second methods, the hydrolysis of those which are stable in such an acidic aqueous solution is carried out under heating and in the presence of an alkaline substance.

In the present invention, all types and amounts of the stannous chloride solution and the ammothine compound and cobalt compound solutions may be mixed and added at the same time, but in order to adjust the composition of the composite hydroxide coating layer to be produced, The method of addition is not particularly limited, such as adding each solution separately or partially mixed. However, it is effective to add the cobalt compound at the final stage of the reaction.

In the above hydrolysis reaction, the pH of the solution is 10 to 1.
A range of 4 is preferred.

After forming a composite hydroxide film on the surface of a white or pseudo-white base material in an alkaline solution with a pH of 10 to 14,
An acidic solution is added to bring the pH of the system to 6 or lower, and the mixture is aged for a sufficient amount of time. This aging reaction is important in order to obtain the white conductive material aimed at in the present invention.

The solid content in the slurry liquid after the aging reaction is separated using means such as filtration, decantation, or centrifugation, and this is washed with water and dried.

Next, in order to obtain a white conductive material, which is the object of the present invention, the temperature is 400 to 800°C, preferably 500 to 700°C.
The composite hydroxide film is converted into a composite oxide film by firing at a temperature of . The time required for this heat treatment depends on the thickness of the composite hydroxide film, but is usually in the range of 30 minutes to 3 hours, preferably 1 to 2 hours.

During this heat treatment, a reducing atmosphere can be used to improve the conductivity, if necessary. In this reducing heat treatment, gases such as hydrogen gas, ammonia gas, -carbon oxide, and nitrogen gas may be used alone or in combination.

In the present invention, a composite hydroxide film is formed on the surface of a white or pseudo-white base material, and after being filtered and dried, it is classified and defibrated before heating and firing, thereby minimizing the variation in quality during the heat treatment process. (Also, after heating and baking to obtain the white conductive material which is the object of the present invention,
If a classification and defibration step is included as a subsequent step, a white conductive material with extremely good dispersibility during use can be obtained.

Examples are given below to further clarify the present invention.

In the examples, "%" means "% by weight" and "parts" means "parts by weight."

Example 1 Potassium titanate whiskers (manufactured by Otsuka Chemical Co., Ltd., T I
Take 250g of 5M0-N) and disperse it in 3000cm of ionized water. Then, 15% caustic soda aqueous solution 2
55 g was added and the pH was adjusted to 12. The alkaline aqueous solution is charged into a three-ring flask (51). The three-lough flask was heated to raise the liquid temperature to 70°C, and 127 g of a 45% HCJ solution of stannous chloride (manufactured by Nihon Kagaku Sangyo Co., Ltd., industrial grade) and antimony trichloride (manufactured by Nippon Kagaku Sangyo Co., Ltd., 99.9%) were added. H of
Pour a mixture of 222g of CI solution into one mouth and add another 15%
200g of caustic soda solution from the other mouth at the same time
Drip over time. Then, 45% of the above stannous chloride
A mixture of 127 g of HCl solution and 75 g of 12.3% HC2 solution was added dropwise from one port, and 160 g of 15% caustic soda solution was simultaneously added from the other port over about 1 hour. Cobalt chloride (manufactured by Wako Pure Chemical Industries, Ltd., CoC/26H
Add 2 g of a 20% aqueous solution of 20). After the completion of the above two-step reaction, while maintaining the liquid temperature at 70°C, add 30% HC.
1 solution was gradually added dropwise to adjust the pH of the entire reaction system to 4, and stirring was continued for 30 minutes. Thereafter, the product is filtered, dehydrated, washed with ionized water, and then dried. The dried product is
After coarsely crushing, it is heated in an oxidizing atmosphere in an electric furnace (Matsufuru furnace) for 50 minutes.
It was baked at 0°C for 1 hour.

The 8E of the white conductive material thus obtained is 2.8
, the L value is 85, and the conductivity value is 100Ω/cm
Met. Here, ΔE is a numerical value representing weather resistance, and is numerically described and defined in JIS2 8730 dye display method. Similarly, the L value is a numerical value representing lightness, and is described and defined in JIS Z 8728 color display method. Further, the conductivity value was measured in accordance with the JIS K 6911 method (hereinafter, the same measurement method was adopted in Example 2 and subsequent examples).

Example 2 Anatase type titanium dioxide (manufactured by Teikoku Kako Co., Ltd., JA-1)
Take 100g and disperse it in ionized water of 1000cnf. Then, 76 g of 15% aqueous caustic soda solution was added to adjust the pH to 12. The alkaline aqueous solution is charged into a three-loaf flask (21).

Heat the three-lough flask and raise the liquid temperature to 70℃, and 45% HC of stannous chloride! ! 38 g of solution (manufactured by Nihon Kagaku Sangyo Co., Ltd., industrial grade) and antimony trichloride (manufactured by Nippon Kagaku Sangyo Co., Ltd.)
A mixed solution of 67 g of a 99.9% (99.9%) HCl solution was added dropwise from one port, and 60 g of a 15% caustic soda solution was simultaneously added dropwise from the other port over a period of about 1 hour. Then, 12,396 g of the above 45% HCf solution of stannous chloride was added.
22.5 g of HCl solution was added thereto from one port, and 48 g of 15% caustic soda solution was simultaneously added dropwise from the other port over a period of about 1 hour. Then cobalt chloride (
Manufactured by Wako Tsumugi Co., Ltd., CoC/! Add 1.2 g of a 10% aqueous solution of 2.6H20). After the above reaction is completed, lower the liquid temperature to 7
While maintaining the temperature at 0°C, 30% HCJ solution V1k was gradually added dropwise to adjust the pH of the entire reaction system to 4, and stirring was continued for 60 minutes. The product is filtered, dehydrated, washed with ionized water, and then dried. The dried product is coarsely ground and then heated in an electric furnace (
It was fired in an oxidizing atmosphere at 600°C for 11 hours in a Matsufuru furnace.

The 8E of the white conductive material thus obtained is 2.6
The L value was 84, and the conductivity value was 80Ω/cm.

Example 3 Muscovite powder (muscovite, passing 60-200 mesh,
80%) was taken and dispersed in 3000 cm of ionized water. Then, a 15% aqueous solution of caustic soda 25%
0g was added and the pH was adjusted to 12. The alkaline aqueous dispersion thus prepared was heated to 80° C. and charged into a three-ring flask. Next, the three-lough flask was heated to 80°C, and 120 g of a 45% hydrochloric acid acidic aqueous solution of stannous chloride (manufactured by Nippon Kagaku Sangyo Co., Ltd.) and antimony trichloride (manufactured by Nippon Kagaku Sangyo Co., Ltd., purity 99.9%) were added to the hydrochloric acid solution. 220g of aqueous solution
At the same time, add 15% of the mixture of
200 g of caustic soda solution was dripped from the other opening over about 1.5 hours. Thereafter, 45% of the above stannous chloride
% Hydrochloric acid acidic aqueous solution 120g, 12.5% Hydrochloric acid aqueous solution 7
5 g of the solution was added through one port, and 160 g of 1596 caustic soda aqueous solution was simultaneously added dropwise from the other port over a period of about 1 hour. Furthermore, cobalt chloride (manufactured by Wako Tsumugi Co., Ltd., C
30% aqueous solution of oCl2.6H20, reagent 1st class)
After adding g, a 30% aqueous hydrochloric acid solution was gradually added dropwise while maintaining the liquid temperature at 80°C, and after adjusting the pH of the entire reaction system to 4, stirring was continued for 30 minutes. Then the product (slurry)? Each house is dehydrated, washed with ionized water, and dried at 105°C.

The dried product was crushed and classified, and then calcined in an electric furnace (Matsufuru furnace) at 600° C. for about 2 hours in an oxidizing atmosphere to obtain a white conductive material.

The ΔE of the white conductive material thus obtained is 2.3
The L value was 80, and the conductivity value was 15Ω/cm.

Example 4 Silicon balloon (Toshiba Silicone Co., Ltd., Tospearl)
150g of silica balloon baked at 400℃ for 1 hour, 2000cn? Disperse in ionized water. then 1
125 g of 5% aqueous caustic soda solution was added to adjust the pH to 12. The alkaline dispersion was poured into a three-ring flask (31).
Prepare it. This container was heated, the liquid temperature was raised to 70°C, and 45% HC of stannous chloride was added. Solution (manufactured by Nihon Kagaku Sangyo Co., Ltd.) 62
g and antimony trichloride (manufactured by Nihon Kagaku Sangyo Co., Ltd., 99.9
%) of HCl solution from one port, and 100 g of 15% caustic soda solution from the other port.
At the same time, drip for about 1 hour. Then, 3 g of the 12.3% HCl solution was added to 62 g of the 45% HCJ solution of the stannous chloride.
Add 5 g of the solution and dropwise add 80 g of 15% caustic soda solution from the other port at the same time over about 1 hour. After that, cobalt chloride (manufactured by Wako Tsumugi Co., Ltd., Co
Add 0.7 g of a 30% aqueous solution of C12.6H20'). After the completion of the above reaction, while maintaining the liquid temperature at 70°C,
%HCf solution was gradually added dropwise to adjust the pH of the entire reaction system to 4, and stirring was continued for 60 minutes. The product is then filtered off, dehydrated, washed with ionized water and dried. The dried product was coarsely pulverized and then calcined in an oxidizing atmosphere at 500° C. for 11 hours in an electric furnace (Matsufuru furnace).

The ΔE of the white conductive material thus obtained is 1.7
The L value was 86, and the conductivity value was 95Ω/cm.

Example 5 Alumina fiber (Safil RF, manufactured by ICI, UK) was made with a length of 1
D&E(K) cut to ~3mm (specific surface area 3~4m
Take 100g of 3/g) and give 2000cn? Disperse in ionized water. Then, 15% caustic soda aqueous solution 10
0 g was added and the pH was adjusted to 12.

The alkaline dispersion was heated to 70°C and 45% of stannous chloride was added.
% HCl solution and 87 g of an antimony trichloride HCf solution was simultaneously added dropwise from one port and 80 g of a 15% caustic soda solution from the other port over a period of about 1 hour. Then, 30 g of 12.3% HCl solution was added to 50 g of the 45% HCl solution of stannous chloride mentioned above from one mouth, and then 60 g of 15% caustic soda solution was added from the other mouth at the same time for about 1 hour. Drip.

Then 1 g of a 20% aqueous solution of cobalt chloride is added. After the completion of the above reaction, 30% IC was added while maintaining the liquid temperature at 70°C.
1 solution was gradually added dropwise to adjust the pH of the entire reaction system to 4, and stirring was continued for 60 minutes.

Thereafter, according to Example 4, a white conductive material was obtained.

The ΔE of the white conductive material thus obtained is 1°9
The L value was 87, and the conductivity value was 20Ω/cm.

Effects of the Invention According to the present invention, a white conductive substance with high whiteness and excellent weather resistance that can be applied to conductive paints, inks, composite materials, etc. can be obtained.

(that's all)

Claims (1)

[Claims] (1) The surface of a white or pseudo-white base material is covered with a composite oxide film made of oxides of tin and antimony elements,
and the ratio of tin oxide in the composite oxide film is about 90 to about 8.
5% by weight, the remaining components being antimony oxide and cobalt oxide.A white conductive material with excellent whiteness and light resistance. (2) The ratio of antimony oxide in the composite oxide film is approximately 1
The white conductive material according to claim 1, wherein the proportion of cobalt oxide is about 0.05 to about 1% by weight based on the total oxides constituting the composite oxide film. (3) The white conductive material according to claim (1), which has a light resistance (ΔE) of 4 or less. (4) The white conductive material according to claim 1, which has a whiteness (L value) of 80 to 90. (5) The white conductive material according to claim 1, wherein the white or pseudo-white base material is a scale-like or plate-like material. (6) The white conductive material according to claim (1), wherein the white or pseudo-white base material is a needle-like material. (7) The white conductive material according to claim (1), wherein the white or pseudo-white base material is a powdery or granular material. (8) The white conductive material according to claim (1), wherein the white or pseudo-white base material is a balloon-like material. (9) The white conductive material according to claim 1, wherein the white or pseudo-white base material is a fibrous material. (10) reacting a white or pseudo-white base material, stannous chloride, an antimony compound, and a cobalt compound in an alkaline solution to form a tin-antimony-cobalt composite hydroxide film on the surface of the base material; A method for producing a white conductive substance, which comprises aging the composite hydroxide film in an acidic solution, filtering it, drying it, and heating the composite hydroxide film to a high temperature to form a composite oxide film. (11) The method according to claim (10), wherein the antimony compound is antimony trichloride. (12) The method according to claim (10), wherein the alkaline solution has a pH of 10 to 14, and the acidic solution has a pH of 6 or less. (13) Claim (1) wherein the heating temperature is 400 to 800°C.
0) Manufacturing method described. (14) The method according to claim (10), wherein the white or pseudo-white base material is a scale-like or plate-like substance. (15) The method according to claim (10), wherein the white or pseudo-white base material is a needle-like substance. (16) The method according to claim (10), wherein the white or pseudo-white base material is a needle-like substance. (17) The method according to claim (10), wherein the white or pseudo-white base material is a balloon-like substance. (18) The method according to claim (10), wherein the white or pseudo-white base material is a fibrous material.