JP2002274848A - Electrically conductive oxide grain and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide electrically conductive oxide grains having a composition consisting of indium atoms, antimony atoms and oxygen atoms, or to which zinc atoms are added, and electrically conductive oxide grains having a structure consisting of indium atoms, niobium atoms and oxygen atoms, or to which antimony atoms are added thereto, and a production method therefor. SOLUTION: The electrically conductive oxide grains consist of indium atoms, antimony atoms and oxygen atoms so that the molar ratios of Sb/In is controlled to 0.03 to 0.08, and also have the primary grain sizes of 2 to 300 nm. Then, the electrically conductive oxide grains have a crystal structure of indium oxide. Alternatively, the electrically conductive oxide grains consist of indium atoms, niobium atoms and oxygen atoms so that the molar ratio of Sb/In is controlled to 0.03 to 0.08%, and have the primary grain sizes of 2 to 300 nm. Then, the electrically conductive oxide grains have a crystal structure of indium oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a conductive oxide particle composed of an indium atom, an antimony atom and an oxygen atom, or a zinc atom added thereto, furthermore, an indium atom, a niobium atom, and an oxygen atom, or The present invention relates to a conductive oxide particle having a configuration in which antimony atoms are added to a conductive oxide particle. Since the conductive oxide particles of the present invention have electronic conductivity, they are used for conductive agents such as plastic, fiber, paper, glass, and ceramics, antistatic agents, electromagnetic wave blocking agents, electric resistors, and the like.

[0002]

2. Description of the Related Art A transparent conductive thin film is an essential component of a liquid crystal display (LCD) used for a display element of an electronic device. As a conductive oxide particle which is a main material for forming such a thin film, tin-doped indium oxide (ITO) has been conventionally cited as a lead.

Japanese Patent Application Laid-Open No. 9-142922 describes a method for producing an ITO sintered body by hot pressing a powder mixture containing indium oxide and tin oxide as main components in a graphite mold.

[0004] Along with various thin film forming techniques, more excellent I
Development of TO particles has been undertaken. Recently, a method of applying a coating material in which ITO particles are dispersed has been studied, and various studies have been made on ITO particles suitable for this coating method.

In Japanese Patent Application Laid-Open No. 8-131815, S
one or two selected from i, Ge, Sn, Zr and Ti
An indium oxide sol in which crystalline indium oxide fine particles containing at least one kind of different elements are dispersed in water and / or an organic solvent is disclosed.

In Japanese Patent Application Laid-Open No. Hei 7-144917, the molar ratio of In: Sb: O is 1: 0.02-1.
A conductive oxide particle comprising an indium atom, an antimony atom and an oxygen atom in a ratio of 25: 1.55 to 4.63 is disclosed. Then, conductive oxide particles having a crystal structure of indium antimonate contained in a molar ratio of In: Sb: O of 1: 0.83 to 1.25: 3.58 to 4.63, and further, In: A conductive oxide particle having a crystal structure of indium oxide in a molar ratio of Sb: O of 1: 0.02 to 0.10: 1.55 to 1.75 is disclosed.

[0007]

[SUMMARY OF THE INVENTION] Although antimonate, indium described above shows a press-molded ones resistivity 10Ωcm and good conductivity at 300 kg / cm ^2, it is possible to further improve the conductivity found.

The present invention provides conductive oxide particles exhibiting extremely good conductivity by examining the molar ratio of antimony and indium, the production method, and the like, and suitable for a coating method.

It has been found that niobium can be used instead of antimony. By controlling the molar ratio of niobium, antimony and indium, the production method, and the like, the present invention provides conductive oxide particles exhibiting extremely good conductivity and suitable for a coating method.

[0010]

According to a first aspect of the present invention, an indium atom, an antimony atom and an oxygen atom are contained in a molar ratio of Sb / In of 0.03 to 0.08, and 2%. A conductive oxide particle having a primary particle diameter of about 300 to 300 nm and having a crystal structure of indium oxide, as a second aspect, composed of indium atoms, antimony atoms and oxygen atoms, and having a molar ratio of Sb / In of 0.1. 04 to 0.06, and 2 to 300
A conductive oxide particle having a primary particle diameter of nm and a crystal structure of indium oxide, as a third aspect, composed of indium atom, antimony atom, zinc atom and oxygen atom, and having a molar ratio of Sb / In 0.03-0.0
8, containing Zn / Sb in a molar ratio of 0.02 to 2.50 and having a primary particle diameter of 2 to 300 nm;
A conductive oxide particle having a crystal structure of indium oxide, as a fourth aspect, composed of indium atoms, niobium atoms, and oxygen atoms, and having a molar ratio of Nb / In of 0.0
1 to 0.10, and 1 to 2 to 300 nm
A conductive oxide particle having a secondary particle diameter and a crystal structure of indium oxide. As a fifth aspect, the conductive oxide particle is composed of an indium atom, a niobium atom, and an oxygen atom, and has a molar ratio of Nb / In of 0.03-0. 08 and 2
A conductive oxide particle having a primary particle diameter of ~ 300 nm and having a crystal structure of indium oxide. As a sixth aspect, the conductive oxide particle is composed of an indium atom, a niobium atom, an antimony atom, and an oxygen atom, and has a (Nb + Sb) / In It is contained in a molar ratio of 0.01 to 0.10 as a molar ratio, 0.01 to 0.99 as a molar ratio of Sb / (Nb + Sb), and 2 to 3
A conductive oxide particle having a primary particle diameter of 00 nm and having a crystal structure of indium oxide, as a seventh aspect,
The conductive oxide particles having a crystal structure of indium oxide according to any one of the first to sixth aspects, wherein the particles are rod-shaped particles having an aspect ratio of 2 to 10, and an eighth aspect, an In compound and A composition selected from the group consisting of a mixture of an Sb compound, a mixture of an In compound, an Sb compound, and a Zn compound, a mixture of an In compound and an Nb compound, and a mixture of an In compound, an Nb compound, and a Sb compound. The method for producing conductive oxide particles according to any one of the first to sixth aspects, wherein the method is performed at a temperature of 500 to 900 ° C.
A mixture of a compound and an Sb compound, a mixture of an In compound and an Sb compound and a Zn compound, a mixture of an In compound and an Nb compound, and a composition selected from the group consisting of a mixture of an In compound, an Nb compound and an Sb compound. 5 in the atmosphere
After firing at a temperature of 00 to 900 ° C, 80 to 4 in an atmosphere composed of 2 to 100: 98 to 0% by volume of hydrogen: nitrogen.
The method for producing conductive oxide particles according to any one of the first to sixth aspects, wherein reduction firing is performed at a temperature of 50 ° C.,
As a zero viewpoint, a mixture of an In compound and an Sb compound, I
a mixture of an n compound, a Sb compound and a Zn compound, a mixture of an In compound and a Nb compound, and a composition selected from the group consisting of a mixture of an In compound, an Nb compound and a Sb compound, and an alkali compound in an aqueous medium. To form a slurry of indium hydroxide doped with a metal element. The slurry is washed, dried, and dried in air at 500 to 9%.
The method for producing conductive oxide particles according to any one of the first to sixth aspects, characterized in that the method is performed at a temperature of 00 ° C., as an eleventh aspect, a mixture of an In compound and an Sb compound, A mixture of an In compound, a Sb compound and a Zn compound, a mixture of an In compound and an Nb compound, and a composition selected from the group consisting of a mixture of an In compound, an Nb compound and a Sb compound, and an alkali compound in an aqueous medium. To form a slurry of indium hydroxide doped with a metal element. The slurry is washed, dried and calcined at a temperature of 500 to 900 ° C. in the atmosphere. : 80 in an atmosphere composed of 98-0
The method for producing conductive oxide particles according to any one of the first to sixth aspects, wherein reduction firing is performed at a temperature of from about 450 ° C. to about 450 ° C.
As a twelfth aspect, a mixture of an In compound and an Sb compound, a mixture of an In compound, an Sb compound, and a Zn compound,
A composition selected from the group consisting of a mixture of an In compound and an Nb compound, and a mixture of an In compound, an Nb compound and an Sb compound, and an alkali compound are mixed with an alkali compound in an aqueous medium at 0 to 1%.
The method according to the seventh aspect, wherein the slurry is contacted at a temperature of 0 ° C. to form a slurry of indium hydroxide doped with a metal element, and the slurry is washed, dried, and fired at a temperature of 500 to 900 ° C. in the atmosphere. Production method of conductive oxide particles, thirteenth method
From a viewpoint, a mixture of an In compound and an Sb compound, In
A mixture of a compound, a Sb compound and a Zn compound, a mixture of an In compound and a Nb compound, and a composition selected from the group consisting of a mixture of an In compound, a Nb compound and a Sb compound, and an alkali compound in an aqueous medium. The slurry is contacted at a temperature of 0 to 10 ° C. to form a slurry of indium hydroxide doped with a metal element, and the slurry is washed, dried, and fired at a temperature of 500 to 900 ° C. in the atmosphere. The method for producing conductive oxide particles according to the seventh aspect, wherein the composition is reduced and fired at a temperature of 80 to 450 ° C. in an atmosphere having a volume percentage of 2 to 100: 98 to 0.
A composition selected from the group consisting of a mixture of an n compound and a Sb compound, a mixture of an In compound, a Sb compound, and a Zn compound, a mixture of an In compound and a Nb compound, and a mixture of an In compound, a Nb compound, and a Sb compound. Contact with an aqueous medium containing
The conductive material according to the seventh aspect, wherein the slurry is heated at a temperature of 0 to 100 ° C. to produce a slurry of indium hydroxide doped with a metal element, and the slurry is dried and fired at a temperature of 500 to 900 ° C. in the air. A method for producing oxide particles, and as a fifteenth aspect, a mixture of an In compound and a Sb compound, a mixture of an In compound, a Sb compound, and a Zn compound,
An aqueous medium containing a mixture of an In compound and an Nb compound, and a composition selected from the group consisting of a mixture of an In compound, an Nb compound and an Sb compound, and a heat-resistant strong basic ion exchange resin, The slurry is heated at a temperature of 100 ° C. to form a slurry of indium hydroxide doped with a metal element, and the slurry is dried and dried in air at 500 ° C.
After firing at a temperature of ~ 900 ° C, hydrogen: nitrogen volume% is 2 ~
80: 450 in an atmosphere composed of 100: 98-0
The method according to the seventh aspect, wherein the conductive oxide particles are reduced and fired at a temperature of ° C.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises an indium atom, an antimony atom and an oxygen atom, and contains Sb atom / In atom in a molar ratio of 0.03 to 0.08,
The conductive oxide particles (1) have a primary particle diameter of 2 to 300 nm and a crystal structure of indium oxide.

Here, the primary particle diameter is determined not as the diameter of the conductive oxide particles in the aggregated form but as the diameter of one conductive oxide particle when separated into individual particles.

In the present invention, it is composed of indium atom, antimony atom and oxygen atom, contained in a molar ratio of Sb / In of 0.04 to 0.06 and 2 to 300 n
The conductive oxide particles (2) having a primary particle diameter of m and a crystal structure of indium oxide are preferably obtained.

Further, conductive oxide particles containing zinc as a constituent metal element in addition to indium and antimony can be obtained. That is, it is composed of an indium atom, an antimony atom, a zinc atom, and an oxygen atom, and is contained in a molar ratio of Sb / In of 0.03 to 0.08 and a molar ratio of Zn / Sb in a ratio of 0.02 to 2.50. , And 2 to 300
Conductive oxide particles (3) having a primary particle diameter of nm and a crystal structure of indium oxide.

The conductive oxide particles (1) comprising indium atoms, antimony atoms and oxygen atoms are prepared by mixing an indium compound and an antimony compound in a molar ratio of Sb / In of 0.03 to 0.08, 500 ~ 900
It is obtained by a production method of firing at a temperature of ° C. Preferably,
The method for producing the conductive oxide particles (2) comprising an indium atom, an antimony atom, and an oxygen atom comprises mixing an indium compound and an antimony compound in a molar ratio of Sb / In of 0.04 to 0.06, 500 ~ 900
It is obtained by a production method of firing at a temperature of ° C.

The conductive oxide particles comprising indium atoms, antimony atoms, zinc atoms and oxygen atoms (3)
Is an indium compound, an antimony compound, and a zinc compound in a molar ratio of Sb / In of 0.03 to 0.08;
It is obtained by a method of mixing at a molar ratio of n / Sb of 0.02 to 2.50 and firing at a temperature of 500 to 900 ° C. in the atmosphere.

In the present invention, as a method for producing particles having higher conductivity, the above method can be further combined with reduction firing.

That is, the conductive oxide particles (1) comprising indium atoms, antimony atoms and oxygen atoms are obtained by mixing an indium compound and an antimony compound in a molar ratio of Sb / In of 0.03 to 0.08, 500 ~ in air
After firing at a temperature of 900 ° C., the volume percentage of hydrogen: nitrogen is 2-1.
00: 80 to 450 ° C in an atmosphere composed of 98 to 0
At the temperature described above. Preferably, the conductive oxide particles (2) composed of indium atoms, antimony atoms and oxygen atoms are obtained by mixing an indium compound and an antimony compound at a Sb / In molar ratio of 0.04 to 0.06, After calcination at a temperature of 500 to 900 ° C., it is obtained by reduction and calcination at a temperature of 80 to 450 ° C. in an atmosphere composed of 2 to 100: 98 to 0% by volume of hydrogen: nitrogen.

The conductive oxide particles comprising indium atoms, antimony atoms, zinc atoms and oxygen atoms (3)
Is an indium compound, an antimony compound, and a zinc compound in a molar ratio of Sb / In of 0.03 to 0.08;
After mixing at a molar ratio of n / Sb of 0.02 to 2.50 and calcination in air at a temperature of 500 to 900 ° C., the volume percentage of hydrogen: nitrogen is 2 to 100: 98 to 0. At a temperature of 80 to 450 ° C. in a reducing atmosphere.

The indium compound used in the present invention may be a monovalent to trivalent indium compound, and may be selected from indium hydroxide, indium oxide, inorganic acid salts of indium, organic acid salts of indium and organic compounds of indium. At least one indium compound selected from the following group can be used.

Examples of the inorganic acid salt of indium include indium nitrate, indium chloride, indium sulfate, and indium sulfamate. Examples of the organic acid salt of indium include indium oxalate. The organic compound of indium is, for example, an alkoxide of indium, such as triethoxyindium. As these indium compounds, those commercially available as industrial chemicals can be used. In the case of using indium salts, salts having an acid which is easily volatilized by firing, that is, nitrates, hydrochlorides, and organic acid salts are desirable. Among these, indium chloride is particularly preferred, and these can be used alone or in combination. These indium compounds can be used in the form of an aqueous solution, a solution dispersed or dissolved in an organic solvent, or a powder.

As the antimony compound used in the present invention, trivalent to pentavalent antimony compounds can be used, and antimony oxide, antimony inorganic acid salt, antimonate, antimony organic acid salt, and antimony organic compound can be used. At least one antimony compound selected from the group consisting of:

Examples of the inorganic acid salts of antimony include antimony nitrate, basic antimony nitrate, antimony chloride, antimony oxychloride and antimony sulfate. Examples of the antimonate include potassium antimonate. Examples of the organic acid salt of antimony include potassium antimony oxalate.
The organic compound of antimony is, for example, an alkoxide of antimony, such as triethoxyantimony. As these antimony compounds, those commercially available as industrial chemicals can be used. When using antimony salts, salts having an acid which is easily volatilized by firing, that is, nitrates, hydrochlorides, and organic acid salts are desirable. Among these, antimony chloride and potassium antimonate are particularly preferred, and these can be used alone or as a mixture. These antimony compounds can be used in the form of an aqueous solution, a solution dispersed or dissolved in an organic solvent, or a powder.

The zinc compound used in the present invention is at least one selected from the group consisting of zinc hydroxide, zinc oxide, an inorganic acid salt of zinc, a zincate, an organic acid salt of zinc and an organic compound of zinc. A zinc compound can be used.

Examples of the inorganic acid salt of zinc include zinc nitrate, basic zinc carbonate, zinc chloride and zinc sulfate. Examples of the zincate include potassium zincate. Examples of the zinc organic acid salt include zinc acetate. The organic compound of zinc is, for example, an alkoxide of zinc, such as methoxyethoxy zinc. As these zinc compounds, those commercially available as industrial chemicals can be used. In the case of using zinc salts, salts having an acid which is easily volatilized by firing, that is, nitrates, hydrochlorides, and organic acid salts are desirable. Among these, zinc chloride and zinc oxide are particularly preferred, and these can be used alone or as a mixture. These zinc compounds
It can be used in the form of an aqueous solution, a solution dispersed or dissolved in an organic solvent, or a powder.

When any of the above-mentioned indium compound and antimony compound, or those obtained by adding a zinc compound thereto, is a solution, the mixing is carried out using a device such as a Satake stirrer, a Faudler stirrer, or a disper. The mixing can be performed at 0 to 100 ° C. for 0.1 to 30 hours.

When any of the above-mentioned indium compound and antimony compound, or those obtained by adding a zinc compound thereto, is in the form of a powder, mixing can be carried out using a mortar, V-type mixer, Henschel mixer, ball mill or the like.

It is particularly preferred to mix a water-soluble indium compound with a water-soluble antimony compound. At this time, the mixing temperature can be from 0 to 100 ° C., however, the higher the mixing temperature, the larger the particle size of the conductive oxide particles to be generated and the lower the transparency at the time of dispersion. The lower the better, the better.

At the time of mixing, if necessary, the pH of the mixture is adjusted with an organic base such as ammonia, an alkali metal hydroxide or guanidine hydroxide, or an inorganic acid such as hydrochloric acid or nitric acid or an organic acid such as acetic acid. Can be controlled. Of these, it is preferable to use an alkali metal hydroxide, and particularly preferable is an aqueous potassium hydroxide solution.

In the above invention, the mixture (slurry) of the indium compound and the antimony compound is separated by suction filtration, centrifugal filtration, filter press, or the like, and soluble impurities derived from the raw materials can be removed by washing with water. In the washing, the electric conductivity of the filtrate was 1000 μS / c.
m, preferably 100 μS / cm or less. Cake or slurry obtained after washing, spray dryer, drum dryer, box-shaped hot air dryer,
It can be dried by a vacuum dryer, freeze dryer or the like. The drying temperature is not particularly limited, but is preferably 300 ° C. or lower in view of the apparatus or operation.

In the above invention, the dried product of the mixture of the indium compound and the antimony compound, or the dried product of the mixture of the indium compound and the antimony compound, having a calcination temperature of 50
0-900 ° C, preferably 600-750 ° C, 0.5
The reaction is carried out for up to 50 hours, preferably 1 to 20 hours. At this time, air can be used as the firing atmosphere, but the ratio of oxygen to nitrogen or another inert gas can also be changed. By baking in this manner, indium oxide and antimony oxide, or indium oxide, antimony oxide and zinc oxide react with each other by a solid phase reaction to obtain conductive oxide particles having a crystal structure of indium oxide.

When the calcined powder requires higher conductivity, hydrogen is 2 to 100% by volume, preferably 2 to 100% by volume.
50% by volume, 80% in an atmosphere composed of nitrogen
~ 450 ° C, preferably 100 ~ 300 ° C, 0.1 ~
The reduction firing is performed for 30 hours, preferably 0.5 to 10 hours. By performing the reduction firing in this manner, oxygen defects are generated in the crystal structure, so that conductive oxide particles having extremely good conductivity can be obtained.

The conductive oxide particles of the present invention exhibit yellowish green to bluish gray. The X-ray diffraction peak of the conductive oxide particles having a crystal structure of indium oxide obtained by the method of the present invention slightly shifted from the diffraction peak of pure indium oxide.

The conductive oxide particles of the present invention had primary particles of 2 to 300 nm as observed by transmission electron microscopy.
It is preferably 5 to 50 nm, and it was confirmed that the particles were colloidal.

Further, the conductive oxide particles of the present invention may have a particle size of 300
0.1 to 50Ωcm when pressed at kg / cm ²
And confirmed to have good electron conductivity. The conductive oxide particles obtained by the above invention,
An aqueous sol or an organic solvent sol can be easily obtained by wet pulverization in water or an organic solvent using a sand grinder, a ball mill, a homogenizer, a disper, a colloid mill, an ultrasonic homogenizer, a high-pressure homogenizer, or the like. In the present invention, the obtained aqueous sol of the conductive oxide particles may be, if desired, removed by contacting with an ion exchange resin to remove the impurity ions to obtain a high-purity aqueous sol of the conductive oxide particles. it can.

In the above invention, by using an indium compound and an antimony compound, an oxide having excellent conductivity can be formed since the reactivity is remarkably high even at 1000 ° C. or less and a uniform phase can be formed. . Further, in the above invention, since firing at a high temperature exceeding 900 ° C. is not performed, there is no particle growth due to sintering, and 2
Since it is obtained as particles having a size of about 300 nm, it is possible to easily obtain a sol in which those particles are dispersed in water and / or an organic solvent.

In the above invention, the molar ratio of Sb / In is 0.1.
If it exceeds 1, impurities are mixed in the product, and the conductivity is undesirably reduced. On the other hand, when the Sb / In molar ratio is less than 0.02, distortion of the crystal structure of indium oxide is reduced, and the conductivity is undesirably reduced. In the above invention, the mixing time of the indium compound and the antimony compound, or those obtained by adding the zinc compound thereto, is 0.1 to 30 hours, and may be less than 0.1 hour, but the mixing may be insufficient. Not preferred. In addition, the treatment may be performed for more than 30 hours, but the production time becomes longer than necessary, which is not efficient. In the above invention, the baking temperature of the dried product of the mixture of the indium compound and the antimony compound or the dried product of the mixture of the indium compound, the antimony compound and the zinc compound is 500 to 900 ° C.
If the temperature is lower than 500 ° C., the solid phase reaction does not sufficiently occur, and conductive oxide particles cannot be obtained. Also, 9
When the temperature is higher than 00 ° C., the solid phase reaction between indium oxide and antimony oxide proceeds, but it is not preferable because particle growth occurs due to sintering.

In the above invention, after drying a dried product of a mixture of an indium compound and an antimony compound or a dried product of a mixture of an indium compound, an antimony compound and a zinc compound at 500 to 900 ° C., it is necessary to obtain higher conductive particles. The reduction firing temperature performed in an atmosphere composed of 2 to 100% by volume of hydrogen and the balance of nitrogen is 80 to 45%.
Although the temperature is 0 ° C., if the temperature is lower than 80 ° C., the reduction reaction is not sufficiently performed and a sufficient oxygen defect cannot be generated, which is not preferable. If the temperature exceeds 450 ° C., the reduction reaction proceeds more than necessary, and a mixture of indium metal and antimony metal is generated, which is not preferable.

The invention of the present application also comprises an indium atom, a niobium atom and an oxygen atom, which are contained in a molar ratio of Nb atom / In atom of 0.01 to 0.10.
It is a conductive oxide particle (4) having a primary particle diameter of 300 nm and having a crystal structure of indium oxide.

Here, the primary particle diameter is determined not as the diameter of the conductive oxide particles in the aggregated form but as the diameter of one conductive oxide particle when separated into individual particles.

In the present invention, it is composed of an indium atom, a niobium atom and an oxygen atom, and has a Nb / In molar ratio of 0.1.
The conductive oxide particles (5), which are contained in a ratio of 03 to 0.08, have a primary particle diameter of 2 to 300 nm, and have a crystal structure of indium oxide, are preferably obtained.

In addition, conductive oxide particles containing antimony in addition to indium and niobium as constituent metal elements are obtained. That is, indium atom, niobium atom,
(Nb + Sb) consisting of antimony atoms and oxygen atoms
/ In molar ratio of 0.01 to 0.10, Sb / (N
The conductive oxide particles (6) are contained in a molar ratio of b + Sb) of 0.01 to 0.99, have a primary particle diameter of 2 to 300 nm, and have a crystal structure of indium oxide. .

The conductive oxide particles (4) comprising an indium atom, a niobium atom and an oxygen atom contain an indium compound and a niobium compound in a molar ratio of Nb / In of 0.01%.
At least a step of mixing at a temperature of 500 to 900 ° C. Preferably, the conductive oxide particles (5) comprising an indium atom, a niobium atom, and an oxygen atom form the indium compound and the niobium compound with Nb /
Indium was mixed to a molar ratio of 0.03 to 0.08, and 50
At least a step of firing at a temperature of 0 to 900 ° C is included.

The conductive oxide particles (6) composed of indium atoms, niobium atoms, antimony atoms, and oxygen atoms contain an indium compound, a niobium compound, and an antimony compound in a molar ratio of (Nb + Sb) / In of 0.1.
01 to 0.10, mixed at a molar ratio of Sb / (Nb + Sb) of 0.01 to 0.99, and mixed at 500 to 900 ° C.
Baking at a temperature of at least.

In the method for producing conductive particles according to the present invention, the above steps are further combined with reduction firing.

That is, the conductive oxide particles (4) composed of indium atoms, niobium atoms and oxygen atoms are obtained by mixing an indium compound and a niobium compound in a molar ratio of Nb / In of 0.01 to 0.10, After firing at a temperature of 500-900 ° C., the volume percentage of hydrogen: nitrogen is 2-100: 98-0.
And reduced and fired at a temperature of 80 to 450 ° C. in an atmosphere composed of Preferably, the conductive oxide particles (5) composed of indium atoms, niobium atoms and oxygen atoms are:
The indium compound and the niobium compound are mixed at a molar ratio of Nb / In of 0.03 to 0.08, and are mixed at 500 to 900.
After calcination at a temperature of ° C., the volume percentage of hydrogen: nitrogen is 2-100:
It is obtained by reducing and firing at a temperature of 80 to 450 ° C. in an atmosphere composed of 98 to 0.

The conductive oxide particles (6) composed of indium atoms, niobium atoms, antimony atoms, and oxygen atoms contain an indium compound, a niobium compound, and an antimony compound in a molar ratio of (Nb + Sb) / In of 0.1.
01 to 0.10, mixed at a molar ratio of Sb / (Nb + Sb) of 0.01 to 0.99, and mixed at 500 to 900 ° C.
After firing at a temperature of 2 to 100: 9 by volume
It is obtained by a method of performing reduction firing at a temperature of 80 to 450 ° C. in an atmosphere composed of 8 to 0 °.

As the indium compound used in the present invention, a monovalent to trivalent indium compound can be used, and indium hydroxide, indium oxide, an inorganic acid salt of indium, an organic acid salt of indium and an organic compound of indium can be used. At least one indium compound selected from the following group can be used.

Examples of the inorganic acid salt of indium include indium nitrate, indium chloride, indium sulfate, indium sulfamate and the like. Examples of the organic acid salt of indium include indium oxalate. The organic compound of indium is, for example, an alkoxide of indium, such as triethoxyindium. As these indium compounds, those commercially available as industrial chemicals can be used. In the case of using indium salts, salts having an acid which is easily volatilized by firing, that is, nitrates, hydrochlorides, and organic acid salts are desirable. Among these, indium chloride is particularly preferred, and these can be used alone or in combination. These indium compounds can be used in the form of an aqueous solution, a solution dispersed or dissolved in an organic solvent, or a powder.

As the niobium compound used in the present invention, a trivalent to pentavalent niobium compound can be used, and niobium oxide, an inorganic acid salt of niobium, a niobate, an organic acid salt of niobium and an organic compound of niobium can be used. At least one niobium compound selected from the following group can be used.

Examples of the niobium inorganic acid salt include niobium pentachloride and niobium oxychloride. Examples of the niobate include potassium niobate, rubidium niobate, and cesium niobate.
Examples of the organic acid salt of niobium include niobium hydrogen oxalate. The organic compound of niobium is, for example, an alkoxide of niobium, such as pentaethoxyniobium. As these niobium compounds, those commercially available as industrial chemicals can be used. When a niobium salt is used, a salt having an acid which is easily volatilized by firing, that is, a hydrochloride or an organic acid salt is desirable. Of these, niobium pentachloride and hexapotassium octo niobate are particularly preferred, and these can be used alone or as a mixture. These niobium compounds can be used in the form of an aqueous solution, a solution dispersed or dissolved in an organic solvent, or a powder. In addition, the water-soluble hexapotassium octniobate can be obtained by eutecticizing niobium pentoxide with excess potassium carbonate.

As the antimony compound used in the present invention, trivalent to pentavalent antimony compounds can be used, and antimony oxide, inorganic salts of antimony, antimonates, organic salts of antimony and organic compounds of antimony can be used. At least one antimony compound selected from the group consisting of:

Examples of the inorganic acid salts of antimony include antimony nitrate, basic antimony nitrate, antimony chloride, antimony oxychloride, and antimony sulfate. Examples of the antimonate include potassium antimonate. Examples of the organic acid salt of antimony include potassium antimony oxalate.
The organic compound of antimony is, for example, an alkoxide of antimony, such as triethoxyantimony. As these antimony compounds, those commercially available as industrial chemicals can be used. When using antimony salts, salts having an acid which is easily volatilized by firing, that is, nitrates, hydrochlorides, and organic acid salts are desirable. Among these, antimony chloride and potassium antimonate are particularly preferred, and these can be used alone or as a mixture. These antimony compounds can be used in the form of an aqueous solution, a solution dispersed or dissolved in an organic solvent, or a powder.

When any of the above-mentioned indium compound and niobium compound, or those obtained by adding an antimony compound thereto, is a solution, mixing is performed using a device such as a Satake-type stirrer, a Faudler-type stirrer, or a disper. The mixing can be performed at 0 to 100 ° C. for 0.1 to 30 hours.

When any of the above-mentioned indium compound and niobium compound, or those obtained by adding an antimony compound thereto, is in the form of a powder, the mixing can be carried out by using an apparatus such as a mortar, a V-type mixer, a Henschel mixer or a ball mill.

In particular, it is preferable to mix a water-soluble indium compound, a water-soluble niobium compound, and a water-soluble antimony compound. At this time, the mixing temperature is 0 to 100.
° C, but the higher the temperature at the time of mixing, the larger the particle size of the conductive oxide particles to be generated and the lower the transparency at the time of dispersion, so that the lower the mixing temperature, the better. ° C
It is preferable to carry out in.

When mixing these, if necessary, the pH of the mixture is adjusted with an organic base such as ammonia, an alkali metal hydroxide or guanidine hydroxide, or an inorganic acid such as hydrochloric acid or nitric acid, or an organic acid such as acetic acid. Can be controlled. Of these, it is preferable to use an alkali metal hydroxide, and particularly preferable is an aqueous potassium hydroxide solution.

In the above invention, a mixture (slurry) of the above indium compound, niobium compound and antimony compound
Is separated by suction filtration, centrifugal filtration, filter press, etc.
Water-soluble washing can remove soluble impurities derived from the raw material. In the washing, the electric conductivity of the filtrate was 10%.
The process is performed until the pressure becomes 100 μS / cm or less, preferably 100 μS / cm or less.

The cake or slurry obtained after washing can be dried by a spray drier, a drum drier, a box-type hot-air drier, a vacuum drier, a freeze drier or the like. The drying temperature is not particularly limited, but is preferably 300 ° C. or lower in view of the apparatus or operation.

In the above invention, the dried product of the mixture of the indium compound and the niobium compound, or the dried product of the mixture of the indium compound and the antimony compound, has a firing temperature of 50%.
0-900 ° C, preferably 600-750 ° C, 0.5
The reaction is performed for up to 50 hours, preferably 1 to 20 hours. At this time, air can be used as the firing atmosphere, but the ratio of oxygen to nitrogen or another inert gas can also be changed. By firing in this manner, indium oxide and niobium oxide, or indium oxide, niobium oxide and antimony oxide react with each other by a solid-phase reaction to obtain conductive oxide particles having a crystal structure of indium oxide.

The calcined powder is 2 to 100% by volume of hydrogen, preferably 2 to 100% by volume, in order to make the conductive oxide higher.
50% by volume, 80% in an atmosphere composed of nitrogen
~ 450 ° C, preferably 100 ~ 300 ° C, 0.1 ~
The reduction firing is performed for 30 hours, preferably 0.5 to 10 hours. By performing the reduction firing in this manner, oxygen defects are generated in the crystal structure, so that conductive oxide particles having extremely good conductivity can be obtained.

The conductive oxide particles of the present invention have a yellow to bluish gray color. The X-ray diffraction peak of the conductive oxide particles having a crystal structure of indium oxide obtained by the method of the present invention slightly shifted from the diffraction peak of pure indium oxide.

The conductive oxide particles of the present invention were observed by transmission electron microscopy to have primary particles of 2 to 300 nm,
It is preferably 5 to 50 nm, and it was confirmed that the particles were colloidal.

Further, the conductive oxide particles of the present invention have a particle size of 300
0.1 to 50Ωc when pressed at kg / cm ²
m, and confirmed to have good electron conductivity.

In the above invention, by using an indium compound and a niobium compound or an antimony compound added thereto, the reactivity is remarkably high even at 1000 ° C. or less, and a uniform phase can be formed. Oxide. In the above invention, since firing at a high temperature exceeding 900 ° C. is not performed,
Since there is no particle growth due to sintering and particles are obtained with a size of 2 to 300 nm, it is possible to easily obtain a sol in which those particles are dispersed in water and / or an organic solvent.

In the above invention, if the (Nb + Sb) / In molar ratio exceeds 0.10, impurities are mixed in the product, and the conductivity is undesirably reduced. Also, (N
When the molar ratio b + Sb) / In is less than 0.01, the distortion of the crystal structure of indium oxide is reduced, and the conductivity is undesirably reduced.

In the above invention, the mixing time of the indium compound and the niobium compound, or the mixture thereof with the antimony compound is 0.1 to 30 hours, and may be less than 0.1 hour, but the mixing may be insufficient. It is not preferable because there is.

Although it may be performed for more than 30 hours,
The manufacturing time becomes longer than necessary and is not efficient. In the above invention, the firing temperature of the dried product of the mixture of the indium compound and the niobium compound or the dried product of the mixture of the indium compound, the niobium compound and the antimony compound is 500 to 9;
If the temperature is lower than 500 ° C. at 00 ° C., the solid phase reaction does not sufficiently occur, and conductive oxide particles cannot be obtained.
At 900 ° C. or higher, indium oxide and niobium oxide,
Although the solid phase reaction of antimony oxide proceeds, it is not preferable because particle growth occurs due to sintering.

In the above invention, a dried product of a mixture of an indium compound and a niobium compound or a dried product of a mixture of an indium compound, a niobium compound and an antimony compound is used.
After firing at 00 to 900 ° C., the reduction firing temperature in an atmosphere composed of 2 to 100% by volume of hydrogen and the balance of nitrogen to obtain higher conductive particles is 80 to 450.
However, if the temperature is lower than 80 ° C., the reduction reaction is not sufficiently performed and a sufficient oxygen defect cannot be generated, which is not preferable. If the temperature exceeds 450 ° C., the reduction reaction proceeds more than necessary, and a mixture of indium metal, niobium metal, and antimony metal is generated, which is not preferable.

In the conductive oxide particles having a crystal structure of indium oxide according to the present invention, indium, antimony, indium, antimony and zinc, indium and niobium, and indium and niobium are used as raw materials. It has a combination of metal compounds consisting of antimony atoms. In the production process of the conductive oxide particles (1) to (6) of the present invention, the mixing step of the metal compound and the alkali compound is performed by bringing the mixture into contact with an aqueous medium at a liquid temperature of more than 10 ° C and less than 40 ° C. In addition, a slurry of indium hydroxide doped with a metal element can be generated. After drying through this mixing step, 500-90
Conductive oxide particles (1) to (6) obtained by the production method (1) in which calcination at 0 ° C. and further reduction calcination are additionally performed.
Has a spherical or elliptical particle shape.

In the step of producing the conductive oxide particles (1) to (6), the metal compound and the alkali compound are brought into contact in an aqueous medium at a liquid temperature of 0 to 10 ° C. A production method in which a slurry of indium hydroxide is produced and dried, and calcined in the air at a temperature of 500 to 900 ° C., and thereafter, the volume% of hydrogen: nitrogen is 2 to 1
00: 80 to 450 ° C in an atmosphere composed of 98 to 0
The conductive oxide particles (1) to (6) obtained by the production method (2) in which reduction firing is additionally performed at a temperature of 2 to 10
Rod-shaped particles having an aspect ratio of

The conductive oxide particles (1) to (6)
In the production process, the aqueous medium containing the metal compound is contacted with a heat-resistant ion-exchange resin,
At a temperature of preferably 60 to 90 ° C. to produce and dry a slurry of indium hydroxide doped with a metal element, followed by baking at a temperature of 500 to 900 ° C. in the air, and further, Thereafter, 80 to 4 in an atmosphere in which the volume percentage of hydrogen: nitrogen is 2 to 100: 98 to 0.
Manufacturing method with additional reduction firing at a temperature of 50 ° C (3)
The conductive oxide particles (1) to (6) obtained by
These are rod-shaped particles having an aspect ratio of 10 to 10.

In the production method (3), the above-mentioned ion exchange resin is a strongly basic ion exchange resin, and for example, DIAION XSA-1200 (trade name) manufactured by Mitsubishi Chemical Corporation can be used. The amount of the ion exchange resin added to the aqueous medium containing the metal compound is determined by the pH of the mixed aqueous medium, and the amount of the ion exchange resin at which the initial pH of mixing becomes 2 to 4 can be thrown into the aqueous medium. preferable. The aqueous medium containing the metal compound into which the ion exchange resin has been cast is heated with stirring at the above temperature for 0.1 to 10 hours to obtain an aqueous medium having a pH of 2 to 4. After separating the ion exchange resin from the thus obtained aqueous medium using a mesh, filter paper, or the like, an alkali substance such as potassium hydroxide is added to obtain a slurry of indium hydroxide doped with a metal element.

The above manufacturing method (2) and manufacturing method (3)
The rod-shaped particles of the conductive oxide having the crystal structure of indium oxide obtained by the method described above can be used for producing a ceramic fiber or the like having conductivity due to its shape characteristics.

The conductive oxide particles (1) to (6) obtained according to the present invention are wet-processed in a water or organic solvent by a sand grinder, a ball mill, a homogenizer, a disper, a colloid mill, an ultrasonic homogenizer, a high-pressure homogenizer, or the like. An aqueous sol or an organic solvent sol can be easily obtained by pulverization.

In the present invention, the obtained aqueous sol of the conductive oxide particles (1) to (6) is optionally brought into contact with an ion exchange resin to remove impurity ions.
An aqueous sol of high-purity conductive oxide particles can be obtained.

The conductive oxide particles (1) to (6) of the present invention
If wet crushed to obtain a sol of water or an organic solvent, if necessary, ammonia, a hydroxide of an alkali metal, acetone, methyl ethyl ketone, ketones such as diacetone alcohol, acetylacetone, β-diketone such as acetonylacetone , Acetoacetate, lactate,
Esters such as 2-methoxyethyl acetate and 2-ethoxyethyl acetate; ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; and heterocyclic compounds such as furfuryl alcohol and tetrahydrofurfuryl alcohol N-methylpyrrolidone. In addition, it can be stabilized by adding an inorganic acid such as hydrochloric acid and nitric acid, and an oxycarboxylic acid such as lactic acid, tartaric acid, malic acid and citric acid. Also,
As the organic solvent, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol, glycols such as ethylene glycol, diethylene glycol and hexylene glycol, and ethers such as methyl cellosolve and ethyl cellosolve can be used.

In the present invention, the conductive oxide particles (1) to
After obtaining the aqueous sol of (6), substitution with the organic solvent described above may be performed to obtain an organic solvent sol.
The particle diameter of the aqueous sol or organic solvent sol of the conductive oxide particles (1) to (6) was 300 nm or less as a result of observation with a transmission electron microscope.

The conductive oxide particles (1) to (6) of the present invention
Is a transparent antistatic agent, a coating agent having an antistatic ability by being mixed with a silicon compound, an active energy ray polymerizable methacrylate, a resin emulsion, a water-soluble polymer liquid, a silicone oil, a paint, and the like, It can be used as a transparent electromagnetic wave shielding agent, an electrorheological fluid or the like.

The silicon compound includes, for example, the following A component and / or B component. A component: General formula (I) (R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} (I) (where R ¹ and R ³ are an alkyl group, an alkenyl group, an aryl group, respectively) Group, an acyl group, a halogen group, a glycidoxy group, an epoxy group, an amino group, a phenyl group, a mercapto group, a methacryloxy group, and an organic group selected from the group consisting of a cyano group, and R ² has 1 to 8 carbon atoms. An organic group selected from the group consisting of an alkyl group, an alkoxy group, an acyl group and a phenyl group, wherein a and b are 0 or 1
Is an integer. ) Or a hydrolyzate thereof. B component: General formula (II) {(OX) _3-a Si (R ⁴ )} ₂ Y (II) (where R ⁴ represents an organic group having 1 to 5 carbon atoms, and X represents 1 to 4 carbon atoms) An alkyl group or an acyl group having 1 to 4 carbon atoms, Y represents an organic group having 2 to 20 carbon atoms, and a is an integer of 0 or 1.) or a hydrolyzate thereof. .

The component A is represented by the above general formula (I), and specific examples of the organosilicon compound or its hydrolyzate include methyl silicate, ethyl silicate, n-propyl silicate, and iso-propyl silicate. , N-butylsilicate, tetraacetoxysilane, methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyl Oxysilane, methyltriphenethyloxysilane, glucidoxymethyltrimethoxysilane,
Glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxytriethoxysilane, β-glycidoxytrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-
Glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane,
γ-glycidoxypropyltriphenoxysilane, α-
Glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ- Glycidoxybutyltrimethoxysilane, δ
-Glycidoxybutyltriethoxysilane, (3,4-
Epoxycyclohexyl) methyltrimethoxysilane,
(3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyl Trimethoxysilane,
γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyl Dimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyl Dimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypro Methyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ -Glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinylmethoxysilane,
γ-glycidoxypropylvinylethoxysilane, γ-
Glycidoxypropylvinylphenylmethoxysilane,
γ-glycidoxypropylvinylphenylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,
3,3-trifluoropropyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β
-Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropyltriethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyl Diethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ
-Chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and the like, and hydrolysates thereof are exemplified.

Next, the B component will be described. The B component is
Examples of the specific organosilicon compound or its hydrolyzate represented by the general formula (II) described above include methylenebismethyldimethoxysilane, ethylenebisethyldimethoxysilane, propylenebisethyldiethoxysilane, butylenebismethyl Examples include diethoxysilane and the like and hydrolysates thereof.

The organosilicon compounds of component A and component B
The component or the component B alone can be used alone, or the components A and B can be mixed and used. Of course, it is also possible to use two or more types of the A component and two or more types of the B component.

The hydrolysis of the organic silicon of the component A and the component B is carried out by adding an acidic aqueous solution such as an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, or an aqueous solution of acetic acid to the organic silicon compound of the component A or the component B and stirring.

The active energy ray-polymerizable methacrylate can be arbitrarily selected from ultraviolet or electron beam-curable methacrylates having one or more methacryloyl groups in the molecule, and can be used alone or as a mixture. . Specific examples of this methacrylate include:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl acrylate, 2-ethylhexyl carbitol acrylate, ω-carboxypolycaprolactone mono Acrylate, acryloyloxyethyl acid, acrylic acid dimer, lauryl methacrylate, 2-methoxyethyl acrylate, butoxyethyl acrylate,
Ethoxyethoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, N-vinyl-2-pyrrolidone, isobonyl methacrylate, dicyclopentenyl acrylate, benzyl acrylate , Phenylglycidyl ether epoxy acrylate, phenoxyethyl methacrylate, phenoxy polyethylene glycol acrylate, nonylphenol ethoxylated acrylate, acryloyloxyethyl phthalic acid, tribromophenyl acrylate, tribromophenol ethoxylated methacrylate, methyl methacrylate, tribromophenyl methacrylate G, methacryloyloxyethyl acid, methacryloyloxyethyl maleic acid, methacryloyloxyethyl phthalic acid, polyethylene glycol methacrylate, polypropylene glycol methacrylate, β-carboxyethyl acrylate, N-methylolacrylamide, N-methoxymethylacrylamide, N- Ethoxymethylacrylamide, N
-N-butoxymethylacrylamide, t-butylacrylamide sulfonic acid, vinyl stearylate, N-methylacrylamide, N-dimethylacrylamide, N
-Dimethylaminoethyl methacrylate, N-dimethylaminopropylacrylamide, acryloyl morpholine, glycidyl methacrylate, n-butyl methacrylate, ethyl methacrylate, allyl methacrylate, cetyl methacrylate, pentadecyl methacrylate, methoxypolyethylene glycol methacrylate, diethylamino Ethyl methacrylate, methacryloyloxyethyl succinic acid, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, hydroxypivalate neopentyl, pentaerythritol diacrylate mono Stearate, glycol Acrylate, 2-hydroxyethyl methacrylate acryloyl phosphate, bisphenol A
Ethylene glycol adduct acrylate, bisphenol F ethylene glycol adduct acrylate, tricyclodecane methanol diacrylate, trishydroxyethyl isocyanurate diacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane,
Trimethylolpropane triacrylate, trimethylolpropane ethylene glycol adduct triacrylate, trimethylolpropane propylene glycol adduct triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, trishydroxyethyl isocyanurate triacrylate, modified ε-caprolactone Triacrylate,
Trimethylolpropaneethoxy triacrylate, glycerin propylene glycol adduct trisacrylate, pentaerythritol tetraacrylate, pentaerythritol ethylene glycol adduct tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexapentaacrylate, dipentaerythritol monohydroxypentaacrylate, Examples include, but are not limited to, urethane acrylates, epoxide acrylates, polyester acrylates, unsaturated polyesters, and the like.
These can be used singly or arbitrarily as a mixture. Preferably, a methacryloyl group is used in the molecule.
The film after polymerization of the polyfunctional methacrylate monomer or oligomer containing at least one is hard and has good scratch resistance, which is preferable.

[0086]

EXAMPLES Production Example 1 Production of Indium / Antimony Chloride Aqueous Solution as Raw Material 350.0 g of 35% hydrochloric acid was diluted with 50.0 g of water, and then 29.3 g of antimony trioxide (manufactured by Sangoku Refining Co., Ltd.) was added. Add, warm to 90-100 ° C, react for 30 minutes,
An antimony trichloride aqueous solution was obtained. To this, 68.0 g of 10% aqueous hydrogen peroxide was added at room temperature with stirring, and 90 to 10% of hydrogen peroxide solution was added.
The mixture was heated to 0 ° C. and reacted for 30 minutes. Then, 91.9 g of a 48% aqueous solution of indium trichloride (manufactured by Indium Corp.) was added, and the mixture was further reacted for 1 hour. An aqueous solution of antimony chloride in hydrochloric acid) was obtained. The resulting aqueous solution was In ₂ O ₃ .Sb ₂ O ₅
Was 11.0% by weight.

Production Example 2 / Production of a Potassium Antimonate Aqueous Solution as a Raw Material 45.3 g of antimony trioxide (manufactured by Sangoku Refinery Co., Ltd.) was dispersed in 258.0 g of a 6.7% aqueous potassium hydroxide solution, and then 35% 30.0 g of hydrogen oxide water was added, and 9
The mixture was heated to 0 to 100 ° C. and reacted for 30 minutes to obtain an aqueous solution of potassium antimonate. The resulting aqueous solution is KSbO ₃
Was 16.4% by weight.

Production Example 3 Zinc, Indium, and Raw Materials
Preparation of Antimony Chloride Aqueous Solution 350.0 g of 35% hydrochloric acid was diluted with 50.0 g of water, and 29.3 g of antimony trioxide (manufactured by Mikuni Smelting Co., Ltd.) was added, followed by heating to 90 to 100 ° C. React for minutes,
An antimony trichloride aqueous solution was obtained. To this, 68.0 g of 10% aqueous hydrogen peroxide was added at room temperature with stirring, and 90 to 10% of hydrogen peroxide solution was added.
The mixture was heated to 0 ° C. and reacted for 30 minutes. Then, 4.1 g of zinc oxide (manufactured by Sakai Chemical) and a 48% aqueous solution of indium trichloride (Indium) were added.
(available from Indium Corp.) was added, and the mixture was further reacted for 1 hour to obtain an aqueous solution of zinc / indium / antimony chloride (aqueous hydrochloric acid of zinc chloride, indium trichloride and antimony pentachloride). The resulting aqueous solution was ｛(ZnO) _1/2 (I
n ₂ O ₃₎ was 10.7 wt% concentration as a _1/2} · Sb ₂ O _5.

Production Example 4 Production of Mixed Aqueous Solution of Potassium Niobate Salt and Potassium Carbonate as Raw Materials 52.0 g of niobium pentoxide (manufactured by Junsei Chemical Co., Ltd.) and 128.0 g of potassium carbonate were weighed into an alumina crucible. This was heated to 800 ° C. and reacted for 15 hours, then 900 ° C.
And reacted for 5 hours. After cooling, 156.7 g of the obtained solid was dissolved in water, stirred for 3 hours while heating to 90 to 100 ° C., and the obtained aqueous solution was filtered to obtain a potassium salt of niobic acid (eight niobium). A mixed aqueous solution of potassium carbonate and potassium carbonate was obtained. The resulting aqueous solution had a concentration of 4.88% by weight as Nb ₂ O _{5 and a} concentration of 12.05% by weight as K ₂ CO ₃ .

Example 1 A 48% aqueous solution of indium trichloride (manufactured by Indium Corp.) 36
After adding and diluting 630.8 g of water to 1.1 g, 116.2 g of the indium antimony chloride aqueous solution prepared in Production Example 1 was added at room temperature with stirring. Next, 1812.8 g of a 10% aqueous potassium hydroxide solution was added and reacted for 1 hour to obtain an antimony-doped indium hydroxide slurry. The slurry had an In ₂ O ₃ concentration of 3.9% by weight, a Sb ₂ O ₅ concentration of 0.2% by weight,
_The molar ratio calculated as ₂ O ₅ / In ₂ O ₃ was 0.05.

The slurry was filtered and washed with water until the electric conductivity of the filtrate became 100 μS / cm or less, to obtain 242.9 g of a wet cake.

569.1 g of water was added to the wet cake, and the mixture was stirred for 5 hours, and the obtained slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain 146.0 g of a dried product. The dried product was pulverized in a mortar to obtain a powder, put into an alumina crucible, and fired in an electric furnace at 650 ° C. for 2 hours in the air to obtain 121.8 g of a powder. This powder exhibited a yellowish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 51.
4m ² / g, the particle diameter calculated from the specific surface area is 16.7 n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance value of 1.5 Ωcm.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 140 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance of nitrogen. This powder exhibited a bluish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 51.
4m ² / g, the particle diameter calculated from the specific surface area is 16.7 n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance of 0.5 Ωcm.

The powder was analyzed by X-ray fluorescence. The analysis results showed that the Sb ₂ O ₅ content was 4.9% and the In ₂ O ₃ content was 95.
The molar ratio in terms of 1%, Sb ₂ O ₅ / In ₂ O ₃ was 0.05
Met.

5.0 g of this powder was dispersed in 20 g of water,
By irradiation with ultrasonic waves, 21.5 g of a sol in which antimony-doped indium oxide particles were dispersed in an aqueous medium was obtained. This aqueous sol is transparent blue-green with a specific gravity of 1.
246, pH 3.59, viscosity 2.1 mPa · s, electric conductivity 475 μS / cm, concentration of antimony-doped indium oxide particles 23.2% by weight, average particle diameter 139 nm by dynamic light scattering, particle diameter 16 by BET method 0.7 nm,
The primary particle diameter was 10 to 30 nm by a transmission electron microscope, and the average particle diameter was 0.09 μm by a centrifugal sedimentation method.

This sol was stable even after standing at 50 ° C. for one month without any abnormalities such as formation of a sediment and gelation. This sol was applied on a glass plate with an applicator and dried at 200 ° C. to form a conductive film of about 2 μm. The transmittance of this coating film was 99%, indicating good transparency. When the sheet resistance was measured, it was 3 × 10 ⁴
Ω / □.

124.8 g of the above aqueous sol was collected in an eggplant-shaped flask, and the solvent was replaced while charging 2.5 liters of methanol under reduced pressure using a rotary evaporator, and a methanol sol in which antimony-doped indium oxide particles were dispersed in methanol. 172.5 g were obtained. This methanol sol had a specific gravity of 0.894, a pH of 4.75 (measured by diluting with an equal weight of water), a viscosity of 1.6 mPa · s, and an electric conductivity of 23 μS / cm (measured by diluting with an equal weight of water).
Antimony-doped indium oxide concentration 13.3% by weight,
Average particle size by dynamic light scattering method: 147 nm, BET method particle size: 16.7 nm, primary particle size by transmission electron microscope: 1
0-30 nm, average particle size 0.11μ by centrifugation
m, the transmittance of the liquid at a concentration of 0.2% was 20%.

0.4 g of acetylacetone (2,4-pentadione) was added to 88.7 g of the above methanol sol.
After stirring for 10 minutes, ultrasonic waves were further applied for 20 minutes to obtain 89.0 g of stabilized methanol sol. The stabilized methanol sol had a specific gravity of 0.897, a pH (measured by diluting with an equal weight of water) 4.66, a viscosity of 1.4 mPa · s,
Electrical conductivity (measured after dilution with an equal weight of water) 31 μS / c
m, antimony-doped indium oxide concentration: 13.4% by weight, average particle diameter by dynamic light scattering: 131 nm, BET particle diameter: 16.7 nm, primary particle diameter by transmission electron microscope: 10 to 30 nm, average by centrifugal sedimentation Particle size 0.1
The transmittance of the liquid at 1 μm and 0.2% was 37%.

Example 2 48% aqueous solution of indium trichloride (manufactured by Indium Corp.) 38
After adding and diluting 665.3 g of water to 0.2 g, 41.7 g of the aqueous solution of potassium antimonate prepared in Production Example 2 was added at room temperature with stirring. Next, 1446.4 g of a 10% aqueous solution of potassium hydroxide was added and reacted for 1 hour to obtain a slurry of antimony-doped indium hydroxide. This slurry had an In ₂ O ₃ concentration of 4.5% by weight, an Sb ₂ O ₅ concentration of 0.3% by weight, and Sb ₂ O ₅ / I
The molar ratio converted to n ₂ O ₃ was 0.05.

The slurry was filtered, and washed with water until the electric conductivity of the filtrate became 100 μS / cm or less, to obtain 272.6 g of a wet cake.

539.8 g of water was added to this wet cake, and the mixture was stirred for 5 hours. The obtained slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain 146.0 g of a dried product. The dried product was pulverized in a mortar to obtain a powder, put into an alumina crucible, and fired in an electric furnace at 650 ° C. for 2 hours in the air to obtain 121.8 g of a powder. This powder exhibited a yellowish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 44.
4m ² / g, particle size calculated from specific surface area is 19.3n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance of 2.5 Ωcm.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 140 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance of nitrogen. This powder exhibited a bluish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 44.
4m ² / g, particle size calculated from specific surface area is 19.3n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed a conductivity of a specific resistance value of 0.9 Ωcm.

The powder was analyzed by X-ray fluorescence. The analysis results showed that the Sb ₂ O ₅ content was 4.9% and the In ₂ O ₃ content was 95.
The molar ratio in terms of 1%, Sb ₂ O ₅ / In ₂ O ₃ was 0.05
Met.

Example 3 A 48% aqueous solution of indium trichloride (manufactured by Indium Corp.) 40
After adding and diluting 705.8 g of water to 3.3 g, 127.2 g of the aqueous solution of zinc / indium / antimony chloride prepared in Production Example 3 was added at room temperature with stirring. Then 1
2002.1 g of a 0% aqueous potassium hydroxide solution was added, and 1
By reacting for a time, a slurry of zinc and antimony-doped indium hydroxide was obtained. This slurry is Z
4. nO concentration of 0.1% by weight; In ₂ O ₃ concentration of 5.
1% by weight, 0.3% by weight as Sb ₂ O ₅ concentration, ZnO /
The molar ratio in terms of Sb ₂ O ₅ / In ₂ O ₃ was 0.02 / 0.
05/1.

The slurry was filtered, and washed with water until the electric conductivity of the filtrate became 100 μS / cm or less, to obtain 303.8 g of a wet cake.

600.2 g of water was added to the wet cake, and the mixture was stirred for 5 hours. The resulting slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain 164.0 g of a dried product. The dried product was pulverized in a mortar to obtain powder, put into an alumina crucible, and fired in an electric furnace at 650 ° C. for 2 hours in the air to obtain 135.6 g of powder. This powder exhibited a yellowish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder by the BET method was 42.
6m ² / g, the particle diameter calculated from the specific surface area is 20.1n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance value of 1.5 Ωcm.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 140 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance of nitrogen. This powder exhibited a bluish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder measured by the BET method was 42.
6m ² / g, the particle diameter calculated from the specific surface area is 20.1n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance of 1.0 Ωcm.

This powder was analyzed by X-ray fluorescence. The analysis results showed that the content was 0.7% as ZnO, the content was 5.6% as Sb ₂ O ₅ , the content was 93.7% as In ₂ O ₃ ,
The molar ratio converted to nO / Sb ₂ O ₅ / In ₂ O ₃ is 0.02
/0.05/1.

Example 4 The same procedure as in Example 1 was carried out except that the molar ratio in terms of Sb ₂ O ₅ / In ₂ O ₃ was changed to 0.03.

Example 5 The same procedure as in Example 1 was carried out except that the molar ratio in terms of Sb ₂ O ₅ / In ₂ O ₃ was changed to 0.06.

Example 6 Example 6 was carried out in the same manner as in Example 1 except that the molar ratio in terms of Sb ₂ O ₅ / In ₂ O ₃ was 0.08.

Example 7 The molar ratio in terms of ZnO / Sb ₂ O ₅ / In ₂ O ₃ was 0.0
The same operation as in Example 3 was performed except that the ratio was set to 5 / 0.05 / 1.

Example 8 A 48% aqueous solution of indium trichloride (manufactured by Indium Corp.) 21
After adding and diluting 3790 g of water to 66.3 g, the indium prepared in Production Example 1 was stirred at a liquid temperature of 0 to 5 ° C.
750.1 g of an antimony chloride aqueous solution was added. Next, 11.3 kg of a 10% aqueous potassium hydroxide solution was added,
By reacting at a liquid temperature of 0 to 5 ° C. for 1 hour, an antimony-doped indium hydroxide slurry was obtained. This slurry had an In ₂ O ₃ concentration of 3.9% by weight, an Sb ₂ O ₅ concentration of 0.2% by weight, and a molar ratio converted to Sb ₂ O ₅ / In ₂ O ₃ of 0.05.

The slurry was filtered, and washed with water until the filtrate had an electric conductivity of 100 μS / cm or less to obtain a wet cake.

Water was added to the wet cake to bring the total amount to 8.74 kg, and the mixture was stirred for 5 hours, and the obtained slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain a dried product 8.
76.0 g were obtained. This dried product was pulverized in a mortar to obtain a powder, put into an alumina crucible, and placed in an electric furnace in the air.
It was calcined at a temperature of 50 ° C. for 2 hours to obtain 742.3 g of powder. This powder has a yellow-green color, and as a result of X-ray diffraction, A
A diffraction peak slightly shifted from the diffraction peak of indium oxide (In ₂ O ₃ ) of STM was obtained.

The specific surface area of this powder by the BET method was 42.
8m ² / g, the particle diameter calculated from the specific surface area is 20.0n
m. Observation with a transmission electron microscope revealed that the particles were rod-shaped particles having an average minor axis of 5 to 10 nm, an average major axis of 20 to 30 nm, and an aspect ratio of 2 to 6. 30 of this powder
A sheet pressed at 0 kg / cm ² has a specific resistance of 14.
It showed a conductivity of 7 Ωcm.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 160 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance being nitrogen. This powder exhibited a bluish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder by the BET method was 42.
8m ² / g, the particle diameter calculated from the specific surface area is 20.0n
m. Observation with a transmission electron microscope revealed that the particles were rod-shaped particles having an average minor axis of 5 to 10 nm, an average major axis of 20 to 30 nm, and an aspect ratio of 2 to 6. 30 of this powder
A sheet pressed at 0 kg / cm ² has a specific resistance of 1.0
It showed conductivity of Ωcm.

The powder was analyzed by X-ray fluorescence. Analysis 5.6% by weight content as Sb ₂ O _5, the content as In ₂ O ₃ is 94.4 wt%, with Sb ₂ O ₅ / In molar ratio is 0.05 in terms of ₂ O ₃ there were.

Example 9 48% indium trichloride aqueous solution (manufactured by Indium Corp.) 12
After adding and diluting 209.7 g of water to 0.0 g, 41.2 g of the indium antimony chloride aqueous solution prepared in Production Example 1 was added at room temperature with stirring. Next, a heat-resistant ion exchange resin (trade name: DIAION XSA-120)
90, manufactured by Mitsubishi Chemical Corporation) at 90 ° C.
The reaction was carried out at a liquid temperature of 5 hours. The heat-resistant ion-exchange resin was removed from the obtained slurry, 277.9 g of a 10% aqueous potassium hydroxide solution was further added, and the mixture was reacted for 1 hour to obtain an antimony-doped indium hydroxide slurry. This slurry had an In ₂ O ₃ concentration of 3.9% by weight, an Sb ₂ O ₅ concentration of 0.2% by weight, and Sb ₂ O ₅ / In
_The molar ratio converted to ₂ O ₃ was 0.05.

The slurry was washed with water by ultrafiltration until the electric conductivity became 100 μS / cm or less to obtain 621.8 g of a washed slurry. The obtained slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain 20.5 g of a dried product. The dried product was pulverized in a mortar to obtain a powder, placed in an alumina crucible, and fired in an electric furnace at 650 ° C. for 2 hours in the air to obtain 17.2 g of a powder. This powder exhibited a yellowish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 41.
3m ² / g, the particle diameter calculated from the specific surface area is 20.7 n
m. Further, by observation with a transmission electron microscope, a mixture of elliptical colloidal particles having a primary particle diameter of 10 to 30 nm and rod-like particles having an average minor axis of 5 to 10 nm, an average major axis of 20 to 50 nm, and an aspect ratio of 2 to 10 is shown. Met. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance value of 900 Ωcm.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 160 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance being nitrogen. This powder exhibited a bluish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder by the BET method was 41.
3m ² / g, the particle diameter calculated from the specific surface area is 20.7 n
m. Further, by observation with a transmission electron microscope, a mixture of elliptical colloidal particles having a primary particle diameter of 10 to 30 nm and rod-like particles having an average minor axis of 5 to 10 nm, an average major axis of 20 to 50 nm, and an aspect ratio of 2 to 10 is shown. Met. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance of 2.2 Ωcm.

This powder was analyzed by X-ray fluorescence. The analysis results show that the Sb ₂ O ₅ content is 4.4% by weight and the In ₂ O ₃ content is 9%.
The molar ratio in terms of 5.6% by weight and Sb ₂ O ₅ / In ₂ O ₃ was 0.04.

Example 10 A 48% aqueous solution of indium trichloride (Indium Corp.) 20
After adding and diluting 352.7 g of water to 1.9 g, the mixture was stirred.
At room temperature, the zinc-indium-anneal prepared in Production Example 3
57.9 g of an aqueous solution of thymon chloride was added. Then heat resistant
Ionic exchange resin (DIAION XSA-1200:
625.0 g of Mitsubishi Chemical Co., Ltd. was added, and a
The reaction was carried out at a temperature for 5 hours. Heat resistance from the obtained slurry
Remove the ion exchange resin and add 10% potassium hydroxide
To add 497.5 g of aqueous solution and react for 1 hour
More zinc and antimony doped indium hydroxide
A slurry was obtained. This slurry had a ZnO concentration of 0.1.
1% by weight, In_TwoO_ThreeThe concentration is 5.1% by weight, Sb_TwoO_Five
0.3% by weight as concentration, ZnO / Sb_TwoO_Five/ In _TwoO_Three
The molar ratio converted to was 0.02 / 0.05 / 1.

The slurry was washed with water by ultrafiltration until the electric conductivity became 100 μS / cm or less, to obtain 422.8 g of a washed slurry. The obtained slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain 47.5 g of a dried product. The dried product was pulverized in a mortar into powder, put into an alumina crucible, and fired in an electric furnace at 650 ° C. for 2 hours in the air to obtain 31.8 g of powder. This powder exhibited a yellowish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 32.2.
1 m ² / g, the particle diameter calculated from the specific surface area is 26.7 n
m. Further, by observation with a transmission electron microscope, a mixture of elliptical colloidal particles having a primary particle diameter of 10 to 30 nm and rod-like particles having an average minor axis of 5 to 10 nm, an average major axis of 20 to 50 nm, and an aspect ratio of 2 to 10 is shown. Met. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance value of 25.3 Ωcm.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 160 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance being nitrogen. This powder exhibited a bluish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 32.
1 m ² / g, the particle diameter calculated from the specific surface area is 26.7 n
m. Further, by observation with a transmission electron microscope, a mixture of colloidal particles having a primary particle diameter of 10 to 30 nm and rod-shaped particles having an average minor axis of 5 to 10 nm, an average major axis of 20 to 50 nm, and an aspect ratio of 2 to 10 is shown. Met. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance of 2.7 Ωcm.

The powder was analyzed by X-ray fluorescence. The analysis results showed that the content as ZnO was 0.30% by weight, the content as Sb ₂ O ₅ was 5.44% by weight, and the content as In ₂ O ₃ was 9
The molar ratio in terms of 4.26% by weight and ZnO / Sb ₂ O ₅ / In ₂ O ₃ was 0.01 / 0.05 / 1.

Example 11 A 47.6% aqueous solution of indium trichloride (manufactured by Indium Corp.)
To 384.6 g, 74.8 g of 10% hydrochloric acid and 586.0 g of water.
Was added and diluted, and 115.6 g of the aqueous potassium niobate solution prepared in Production Example 4 was added at room temperature with stirring.
Next, 1400 g of a 10% aqueous potassium hydroxide solution was added and reacted for 1 hour to obtain a niobium-doped indium hydroxide slurry. This slurry had an In ₂ O ₃ concentration of 4.5% by weight, an Nb ₂ O ₅ concentration of 0.2% by weight, and a molar ratio converted to Nb ₂ O ₅ / In ₂ O ₃ , ie, Nb /
The molar ratio of In was 0.051.

The slurry was filtered, and washed with water until the electric conductivity of the filtrate became 100 μS / cm or less, to obtain 254.4 g of a wet cake.

549.9 g of water was added to the wet cake, and the mixture was stirred for 5 hours. The obtained slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain 145.0 g of a dried product. The dried product was pulverized in a mortar into powder, put into an alumina crucible, and fired in an electric furnace at 650 ° C. for 2 hours in the air to obtain 120.6 g of powder. This powder was yellow, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder measured by the BET method was 20.
9m ² / g, the particle diameter calculated from the specific surface area is 41.0 n
m. Observation by a transmission electron microscope revealed that the particles were elliptical colloidal particles having a primary particle diameter of 10 to 50 nm. What pressed this powder at 300 kg / cm ²
It showed little conductivity.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 350 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance of nitrogen. This powder was blue-gray, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 20.
9m ² / g, the particle diameter calculated from the specific surface area is 41.0 n
m. Observation by a transmission electron microscope revealed that the particles were elliptical colloidal particles having a primary particle diameter of 10 to 50 nm. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance value of 0.17 Ωcm.

The powder was analyzed by X-ray fluorescence. The analysis results showed that the Nb ₂ O ₅ content was 4.5% and the In ₂ O ₃ content was 95.
5%, molar ratio converted to Nb ₂ O ₅ / In ₂ O ₃ , that is, Nb
The molar ratio of / In was 0.051.

Example 12 57.8 g of the aqueous potassium niobate solution prepared in Production Example 4
And aqueous potassium antimonate solution 2 prepared in Production Example 2
0.9 g was stirred and Sb_TwoO_Five/ (Nb_TwoO_Five+ Sb _TwoO_Five)
As the molar ratio of Sb / (Nb + Sb)
78.7 g of a mixed solution of 0.50 was obtained. Then 48%
Indium trichloride aqueous solution (manufactured by Indium Corp.) 384.6
72.9 g of 10% hydrochloric acid and 587.9 g of water were added to
After dilution, the resulting potassium niobate was stirred at room temperature.
-Add 78.7 g of potassium antimonate mixed aqueous solution
Was. Then, 1400 g of a 10% aqueous solution of potassium hydroxide was added.
And reacting for 1 hour to obtain niobium and anti
A slurry of mon-doped indium hydroxide was obtained. This
Rally In_TwoO_Three5.49% by weight in concentration, Nb_TwoO_Five
0.11% by weight as concentration, Sb_TwoO_Five0.1 as concentration
3% by weight, Nb_TwoO_Five/ Sb_TwoO_Five/ In_TwoO_ThreeModel converted to
The fuel ratio was 0.026 / 0.026 / 1. this is
(Nb + Sb) / In molar ratio of 0.052, Sb
The molar ratio of / (Nb + Sb) was 0.50.

This slurry was filtered, and washed with water until the electric conductivity of the filtrate became 100 μS / cm or less, to obtain 264.0 g of a wet cake.

544.4 g of water was added to this wet cake, and the mixture was stirred for 5 hours, and the obtained slurry was evaporated to dryness at 110 ° C. using a hot-air drier to obtain 145.8 g of a dried product. The dried product was pulverized in a mortar to obtain a powder, placed in an alumina crucible, and fired in an electric furnace at 670 ° C. for 2 hours in the air to obtain 121.3 g of powder. This powder exhibited a yellowish green color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder determined by the BET method was 48.
6m ² / g, the particle diameter calculated from the specific surface area is 17.6n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity of a specific resistance value of 13.8 Ωcm.

The fired powder thus obtained was placed in a glass fired tube.
Reduction firing was performed at 170 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance of nitrogen. The powder exhibited a blue color, and as a result of X-ray diffraction, a diffraction peak slightly shifted from that of indium oxide (In ₂ O ₃ ) of ASTM was obtained.

The specific surface area of this powder measured by the BET method was 48.
6m ² / g, the particle diameter calculated from the specific surface area is 17.6n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance value of 0.85 Ωcm.

This powder was analyzed by X-ray fluorescence. As a result of analysis, the content was 2.26% as Nb ₂ O ₅ , the content was 2.59% as Sb ₂ O ₅ , and the content was 95.4 as In ₂ O _3.
The molar ratio converted to 5%, Nb ₂ O ₅ / Sb ₂ O ₅ / In ₂ O ₃ , was 0.025 / 0.023 / 1. That is, (Nb
+ Sb) / In molar ratio of 0.048, Sb / (N
The molar ratio of (b + Sb) was 0.479.

50 g of this powder and 200 g of water were mixed and dispersed using a high-pressure homogenizer to obtain 224 g of a sol in which niobium and antimony-doped indium oxide particles were dispersed in an aqueous medium. This aqueous sol is a transparent blue color, specific gravity 1.233, pH 3.74, viscosity 2.1 mPa · s, electric conductivity 1400 μS / cm, concentration of niobium and antimony-doped indium oxide particles 2
2.3% by weight, average particle size 94n by dynamic light scattering method
m, particle diameter 17.6nm by BET method, color difference meter ((Yes)
Tokyo Denshoku TOPSCAN MODEL TC-180
0MK), the total light transmittance of a 0.2% solution of niobium and antimony-doped indium oxide particles is 38.1.
9. The color difference was a = 4.17, b = 19.23, the primary particle diameter was 10 to 30 nm by a transmission electron microscope, and the average particle diameter was 0.09 μm by centrifugal sedimentation.

This sol was stable even after standing at 50 ° C. for one month without any abnormality such as formation of a sediment or gelation. This sol was applied on a glass plate with an applicator and dried at 200 ° C. to form a conductive film of about 2 μm. The transmittance of this coating film was 99%, indicating good transparency. The sheet resistance was measured to be 1.7 × 1
0 ⁵ Ω / □.

Example 13 The molar ratio converted to Nb ₂ O ₅ / In ₂ O ₃ , that is, Nb / In
Was carried out in the same manner as in Example 11 except that the molar ratio was 0.032.

Example 14 The molar ratio converted to Nb ₂ O ₅ / In ₂ O ₃ , that is, Nb / In
Was carried out in the same manner as in Example 11 except that the molar ratio was 0.079.

Example 15 The molar ratio in terms of Nb ₂ O ₅ / Sb ₂ O ₅ / In ₂ O ₃ was 0.1.
049 / 0.002 / 1, that is, the same as Example 12 except that the molar ratio of (Nb + Sb) / In was 0.051, the molar ratio of Sb / (Nb + Sb) was 0.039, and the reduction firing temperature was 300 ° C. I went to.

Example 16 The molar ratio in terms of Nb ₂ O ₅ / Sb ₂ O ₅ / In ₂ O ₃ was 0.1.
038 / 0.013 / 1, that is, the same as Example 12 except that the molar ratio of (Nb + Sb) / In was 0.051, the molar ratio of Sb / (Nb + Sb) was 0.255, and the reduction firing temperature was 250 ° C. I went to.

Example 17 The molar ratio in terms of Nb ₂ O ₅ / Sb ₂ O ₅ / In ₂ O ₃ was 0.1.
013 / 0.038 / 1, that is, the same as Example 12 except that the molar ratio of (Nb + Sb) / In was 0.051, the molar ratio of Sb / (Nb + Sb) was 0.745, and the reduction firing temperature was 170 ° C. I went to.

Example 18 The molar ratio converted to Nb ₂ O ₅ / Sb ₂ O ₅ / In ₂ O ₃ was 0.1.
013 / 0.013 / 1, the molar ratio of (Nb + Sb) / In is 0.026, and the molar ratio of Sb / (Nb + Sb) is 0.1.
The procedure was performed in the same manner as in Example 12 except that 500 was set.

Example 19 The molar ratio in terms of Nb ₂ O ₅ / Sb ₂ O ₅ / In ₂ O ₃ was 0.1.
038 / 0.038 / 1, that is, the same operation as in Example 12 except that the molar ratio of (Nb + Sb) / In was 0.076 and the molar ratio of Sb / (Nb + Sb) was 0.500.

Reference Example 1 The procedure of Example 1 was repeated, except that the molar ratio in terms of Sb ₂ O ₅ / In ₂ O ₃ was changed to 0.10.

Comparative Example 1 48% aqueous solution of indium trichloride (manufactured by Indium Corp.) 39
After adding and diluting 694.2 g of water to 6.7 g, a 10% aqueous sodium hydroxide solution 1078.9 at room temperature was stirred.
g was added and reacted for 1 hour to obtain an indium hydroxide slurry. This slurry had an In ₂ O ₃ concentration of 5.6% by weight.

This slurry was filtered and further washed with water until the electric conductivity of the filtrate became 100 μS / cm or less, to obtain 268.8 g of a wet cake.

531.2 g of water was added to the wet cake, and the mixture was stirred for 5 hours, and the obtained slurry was evaporated to dryness at 110 ° C. using a hot air drier to obtain 143.2 g of a dried product. The dried product is pulverized in a mortar, powdered, placed in an alumina crucible, and heated at 650 ° C. in an electric furnace in the atmosphere.
It was baked for 2 hours to obtain 120.0 g of powder. This powder was yellow, and as a result of X-ray diffraction, it coincided with the diffraction peak of indium oxide (In ₂ O ₃ ) of ASTM.

The specific surface area of this powder measured by the BET method was 28.
6 m ² / g, the particle diameter calculated from the specific surface area is 29.5 n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed almost no conductivity.

The obtained fired powder was placed in a glass fired tube,
Reduction firing was performed at 140 ° C. for 2 hours in an atmosphere composed of 20% by volume of hydrogen and the balance of nitrogen. This powder was yellow, and as a result of X-ray diffraction, it coincided with the diffraction peak of indium oxide (In ₂ O ₃ ) of ASTM.

The specific surface area of this powder determined by the BET method was 28.
6 m ² / g, the particle diameter calculated from the specific surface area is 29.5 n
m. Further, it was found to be elliptical colloid particles having a primary particle diameter of 10 to 30 nm by observation with a transmission electron microscope. A product obtained by press-molding this powder at 300 kg / cm ² showed conductivity with a specific resistance value of 250 Ωcm.

The specific resistance value is a product of Mitsubishi Chemical Corporation, trade name L
The measurement was performed by a four-probe method using oresta IP MCP-T250.

Table 1 shows the measurement results of the specific resistance values of Examples 1 to 10, Comparative Example 1 and Reference Example 1.

[0170]

[Table 1] Table 1 ――――――――――――――――――――――――――――――――― Example ZnO / Sb ₂ O ₅ / In ₂ O ₃ Specific resistance after firing Specific resistance after reduction firing (Molar ratio) (Ωcm) (Ωcm) ―――――――――――――――――――――――― ――――――――――― Example 1 0 / 0.05 / 1 1.5 0.5 Example 2 0 / 0.05 / 1 2.5 0.9 Example 3 0.02 / 0.05 / 1 1.5 1.0 Example 4 0 / 0.03 / 1 3.6 1.5 Example 5 0 / 0.06 / 1 5.6 0.7 Example 6 0 / 0.08 / 1 2.1 0.8 Example 7 0.05 / 0.05 / 1 1.6 1.3 Example 8 0 / 0.05 / 1 14.7 1.0 Example 9 0 / 0.04 / 1 900 2.2 Example 10 0.01 / 0.05 / 1 25.3 2.7 Reference Example 1 0 / 0.10 / 1 8.1 2.0 Comparative Example 1 0/0/1 5000000 250 ――――――――――――――――――― ―――――――――――――――― Table 2 shows the measurement results of the specific resistance values of Examples 11 to 19.

[0171]

[Table 2] Table 2 ――――――――――――――――――――――――――――――――― Example Nb ₂ O ₅ / Sb ₂ O ₅ / In ₂ O ₃ specific resistance after firing Specific resistance after reduction firing (molar ratio) (Ωcm) (Ωcm) ――――――――――――――――――――― ―――――――――――――― Example 11 0.051 / 0/1 17200 0.17 Example 22 0.026 / 0.026 / 1 13.8 0.85 Example 13 0.032 / 0/1 20000 0.22 Example 14 0.079 / 0 / 1 21000 0.55 Example 15 0.049 / 0.002 / 1 1250 0.71 Example 16 0.038 / 0.013 / 1 63.7 0.89 Example 17 0.013 / 0.038 / 1 3.1 0.99 Example 18 0.013 / 0.013 / 1 26.2 0.54 Example 19 0.038 / 0.038 / 1 12.3 1.88 ――――――――――――――――――――――――――――――――――

[0172]

The conductive oxide particles of the present invention are composed of indium atoms, antimony atoms and oxygen atoms, and are composed of Sb / I
n has a primary particle diameter of from 2 to 300 nm in a molar ratio of 0.03 to 0.08, preferably in a molar ratio of Sb / In of 0.04 to 0.06. ,
The conductive oxide particles have a crystal structure of indium oxide. Furthermore, it is composed of an indium atom, an antimony atom, a zinc atom and an oxygen atom, and has a molar ratio of Sb / In of 0.03 to 0.08 and a molar ratio of Zn / Sb of 0.02 to 2.50. Contains and 2-3
It is a conductive oxide particle having a primary particle diameter of 00 nm and a crystal structure of indium oxide.

Further, the conductive oxide particles of the present invention are composed of indium atoms, niobium atoms and oxygen atoms, and Nb / I
n is contained in a molar ratio of 0.01 to 0.10 as a molar ratio of n, preferably in a ratio of 0.03 to 0.08 as a molar ratio of Nb / In, and has a primary particle diameter of 2 to 300 nm. ,
The conductive oxide particles have a crystal structure of indium oxide. Furthermore, it is composed of an indium atom, a niobium atom, an antimony atom and an oxygen atom, and (Nb + S
b) / In molar ratio of 0.01 to 0.10, Sb /
Containing (Nb + Sb) in a molar ratio of 0.01 to 0.99 and having a primary particle diameter of 2 to 300 nm;
The conductive oxide particles have a crystal structure of indium oxide.

The conductive oxide particles have a primary particle of 2-3.
It is a fine particle of 00 nm, and a sol with high transparency can be obtained by dispersing in a solvent. The oxide has electronic conductivity and a specific resistance of 0.1 to 50 Ωcm. This oxide is stable in an aqueous solution or an organic solvent, and is stable even at a high temperature.

As described above, the conductive oxide particles of the present invention can be used as an antistatic agent or an electromagnetic wave shielding agent by adding or coating on a plastic molded product, plastic film, plastic fiber, glass, paper, or the like. it can. For those fired by reduction,
It can be used as an infrared absorber. Further, it can be used as a high refractive index coating agent or an antireflection agent. It is particularly effective as a transparent antistatic agent. Also,
It can be used as a resistor by applying it to the surface of glass or ceramics and baking it.

The conductive oxide particles of the present invention can be used as a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane. By mixing with a partial hydrolysis solution, a hydrolysis solution of ethyl silicate or methyl silicate, a resin emulsion, a water-soluble polymer solution, a solution of an organic solvent such as methyl methacrylate, a silicone oil, a paint, etc. It can be used as a transparent antistatic agent, a coating agent having antistatic ability, a transparent electromagnetic wave shielding agent, an electrorheological fluid, and the like.

The conductive oxide particles of the present invention can be used as a metal surface treating agent by mixing with water glass, an aqueous solution of aluminum phosphate, an aqueous solution of chromic acid, a plating solution, or the like.

This oxide can also be used as a microfiller for composite materials such as metals, plastics, and ceramics.

[Brief description of the drawings]

FIG. 1 is a transmission electron micrograph showing a particle structure of an aqueous sol of conductive oxide particles having a crystal structure of indium oxide prepared in Example 1, with a magnification of 200,000.

FIG. 2 is an X-ray diffraction diagram of a conductive oxide particle having a crystal structure of indium oxide prepared in Example 1.

FIG. 3 is a transmission electron micrograph showing the particle structure of an aqueous sol of conductive oxide particles having a crystal structure of indium oxide prepared in Example 8, and the magnification is 200,000.

FIG. 4 is a transmission electron micrograph showing the particle structure of an aqueous sol of conductive oxide particles having a crystal structure of indium oxide prepared in Example 12, and the magnification is 200,000.

FIG. 5 is an X-ray diffraction diagram of a conductive oxide particle having a crystal structure of indium oxide prepared in Example 12.

FIG. 6 is an X-ray diffraction diagram of indium oxide prepared in Comparative Example 1.

Claims (15)

[Claims] 1. An indium atom, an antimony atom and an oxygen atom, having a Sb / In molar ratio of 0.03 to
Conductive oxide particles which are contained in a ratio of 0.08, have a primary particle diameter of 2 to 300 nm, and have a crystal structure of indium oxide. 2. An indium atom, an antimony atom and an oxygen atom, having a molar ratio of Sb / In of 0.04 to 0.04.
Conductive oxide particles containing at a ratio of 0.06, having a primary particle diameter of 2 to 300 nm, and having a crystal structure of indium oxide. 3. It comprises an indium atom, an antimony atom, a zinc atom and an oxygen atom, and has a Sb / In molar ratio of 0.03 to 0.08 and a Zn / Sb molar ratio of 0.03.
2 to 2.50 and 1 to 2 to 300 nm
Conductive oxide particles having a secondary particle size and a crystal structure of indium oxide. 4. It is composed of an indium atom, a niobium atom and an oxygen atom, and has a molar ratio of Nb / In of 0.01 to 0.1.
Conductive oxide particles containing at a ratio of 10 and having a primary particle size of 2 to 300 nm and having a crystal structure of indium oxide. 5. It is composed of an indium atom, a niobium atom and an oxygen atom, and has a molar ratio of Nb / In of 0.03-0.
08: a conductive oxide particle having a primary particle diameter of 2 to 300 nm and having a crystal structure of indium oxide. 6. An indium atom, a niobium atom, an antimony atom and an oxygen atom, wherein the molar ratio of (Nb + Sb) / In is 0.01 to 0.10, and Sb / (Nb + S
Conductive oxide particles containing b) in a molar ratio of 0.01 to 0.99, having a primary particle diameter of 2 to 300 nm, and having a crystal structure of indium oxide. 7. The conductive oxide particles having a crystal structure of indium oxide according to claim 1, wherein the particles are rod-shaped particles having an aspect ratio of 2 to 10. 8. A mixture of an In compound and an Sb compound,
A mixture selected from the group consisting of a mixture of an n compound, a Sb compound and a Zn compound, a mixture of an In compound and a Nb compound, and a mixture of a mixture of an In compound, a Nb compound and a Sb compound, at 500 to 900 ° C. The method for producing conductive oxide particles according to any one of claims 1 to 6, wherein the method is performed at a temperature of: 9. A mixture of an In compound and an Sb compound,
A composition selected from the group consisting of a mixture of an n compound, a Sb compound and a Zn compound, a mixture of an In compound and a Nb compound, and a mixture of a mixture of an In compound, a Nb compound and a Sb compound, at 500 to 900 ° C. in air. The reduction firing at a temperature of 80 to 450 ° C. in an atmosphere in which the volume percentage of hydrogen: nitrogen is 2 to 100: 98 to 0 after firing at a temperature of 7 to 7. A method for producing the conductive oxide particles according to the above. 10. A mixture of an In compound and an Sb compound,
A mixture of an In compound, an Sb compound, and a Zn compound;
Mixture of compound and Nb compound, and In compound and Nb
Contacting a composition selected from the group consisting of a mixture of a compound and an Sb compound with an alkali compound in an aqueous medium,
A slurry of indium hydroxide doped with a metal element is generated, and the slurry is washed, dried, and dried in air at 500 to 500 μm.
The method for producing conductive oxide particles according to any one of claims 1 to 6, wherein the firing is performed at a temperature of 900 ° C. 11. A mixture of an In compound and an Sb compound,
A mixture of an In compound, an Sb compound, and a Zn compound;
Mixture of compound and Nb compound, and In compound and Nb
Contacting a composition selected from the group consisting of a mixture of a compound and an Sb compound with an alkali compound in an aqueous medium,
A slurry of indium hydroxide doped with a metal element is generated, and the slurry is washed, dried, and dried in air at 500 to 500 μm.
After firing at a temperature of 900 ° C., the volume percentage of hydrogen: nitrogen is 2-1.
00: 80 to 450 ° C in an atmosphere composed of 98 to 0
The method for producing conductive oxide particles according to any one of claims 1 to 6, wherein reduction firing is performed at the following temperature. 12. A mixture of an In compound and an Sb compound,
A mixture of an In compound, an Sb compound, and a Zn compound;
Mixture of compound and Nb compound, and In compound and Nb
A composition selected from the group consisting of a mixture of a compound and an Sb compound, and an alkali compound in an aqueous medium at 0 to 10 ° C.
The conductive material according to claim 7, wherein a slurry of indium hydroxide doped with a metal element is produced by contacting at a temperature of, and the slurry is washed, dried, and fired in air at a temperature of 500 to 900C. A method for producing oxide particles. 13. A mixture of an In compound and an Sb compound,
A mixture of an In compound, an Sb compound, and a Zn compound;
Mixture of compound and Nb compound, and In compound and Nb
A composition selected from the group consisting of a mixture of a compound and an Sb compound, and an alkali compound in an aqueous medium at 0 to 10 ° C.
To produce a slurry of indium hydroxide doped with a metal element, washing the slurry, drying and firing in air at a temperature of 500 to 900 ° C., followed by hydrogen:
The method for producing conductive oxide particles according to claim 7, wherein reduction firing is performed at a temperature of 80 to 450 ° C in an atmosphere in which the volume percentage of nitrogen is 2 to 100: 98 to 0. 14. A mixture of an In compound and an Sb compound,
A mixture of an In compound, an Sb compound, and a Zn compound;
Mixture of compound and Nb compound, and In compound and Nb
An aqueous medium containing a composition selected from the group consisting of a mixture of a compound and an Sb compound is brought into contact with a heat-resistant strong basic ion-exchange resin, and heated at a temperature of 40 to 100 ° C. to dope the metal element. A slurry of indium hydroxide is formed, and the slurry is dried and dried in air at 500 to 9%.
The method for producing conductive oxide particles according to claim 7, wherein the firing is performed at a temperature of 00 ° C. 15. A mixture of an In compound and an Sb compound,
A mixture of an In compound, an Sb compound, and a Zn compound;
Mixture of compound and Nb compound, and In compound and Nb
An aqueous medium containing a composition selected from the group consisting of a mixture of a compound and an Sb compound is brought into contact with a heat-resistant strong basic ion-exchange resin, and heated at a temperature of 40 to 100 ° C. to dope the metal element. A slurry of indium hydroxide is formed, and the slurry is dried and dried in air at 500 to 9%.
After firing at a temperature of 00 ° C., the volume percentage of hydrogen: nitrogen is 2-10
The method for producing conductive oxide particles according to claim 7, wherein reduction firing is performed at a temperature of 80 to 450 ° C. in an atmosphere composed of 0: 98 to 0. 9.