JPH02312106A - Conductive inorganic oxide composite and manufacture thereof - Google Patents

Abstract

PURPOSE:To improve conductivity of heteropolyacid and salt thereof useful for a conductive filler and other materials by heating respective materials near the decomposition temperature thereof under a reducing atmosphere while reducing and decomposing a part thereof in order to make the reduced and decomposed products to be contained. CONSTITUTION:Deminerallized water 700wt.% is added to molybdenum oxide 72wt.%, while 85wt.% phosphoric acid 4.79wt.% is added to be held at 95 deg.C for 3 hours while mixing up the liquid. Being later cooled, a phosphor molybdenic acid (H3PMo12O40) water solution removed of insoluble substances by suction filtration is concentrated, dried and solidified, powder obtained is reduced at 450 deg.C for 5 hours under a nitrogen atmosphere containing hydrogen 10% to obtain a composite sample. As a result, of X-ray diffraction, this sample is a composite containing phosphor molybedenum acid and a reduced and decomposed product thereof, while the reduced product is specified as H0.30MoO3 whose content in the composite is 60% having some crystallization water. In spite of a small composition amount, a conductive inorganic oxide composite obtained thereby can give uniform conductivity to a compact or a coating obtained therefrom.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an inorganic oxide composition having electrical conductivity and a method for producing the same. More specifically, the present invention relates to an S-electroconductive inorganic oxide composition containing a heteropolyacid and/or a salt thereof, and a decomposition and reduction product thereof as main components. Furthermore, the present invention relates to a method for producing a conductive R oxide composition by heating a heteropolyacid and/or a salt thereof in a reducing atmosphere.

The conductive MS compound composition provided by the present invention exhibits stable S conductivity and is compatible with resins, solvents, etc.

Due to its excellent compatibility, it can be used as a conductive filler and other materials in electronics, electrical equipment, paints,! 1. It is useful in various fields such as navy blue and plastics.

(Prior art) Conventionally used conductive fillers include, for example, carbon-based fillers such as carbon black and carbon fiber, metal-based fillers such as metal powder and metal powder, and carbides such as silicon carbide and tungsten carbide. filler,
Or gold such as tin oxide or indium oxide! l! There are iQ compound fillers, etc., which are used for various purposes depending on their characteristics.

However, these conductive fillers may have non-uniform conductivity due to variations in shape or composition, or even if there is no variation in shape or composition, they may be obtained due to poor dispersibility in resin or paint. There have been problems such as non-uniform conductivity in the resin dispersion or coating, and poor stability over time in the resin dispersion or coating. Moreover, there are problems in that it is necessary to add a large amount of conductive filler in order to obtain the desired conductivity, and the color tone of the resin dispersion or coating film is also limited.

Also, conductive resins and conductive paints containing surfactants such as quaternary ammonium salts are known, but these do not have the effect of imparting conductivity unless they are blended in large quantities, and the surface of the resulting resin and coating film is There were problems in that it became sticky and its effectiveness decreased when washed with water.

On the other hand, it has been known that heteropolyacids having a Keggin structure and their salts are good ionic conductors [Kagaku to Kogyo, Vol. 11, No. 4, pp. 332-328 (1958), etc.゜When the present inventors investigated the conductivity of these compounds, the volume resistivity value was 104 to 10
It was 6Ω・cry.

Their conductivity is relatively low, so they are used in electronics, electrical equipment, paints, etc.
It has the disadvantage that it cannot fully meet the wide range of demands in various fields such as textiles and plastics.

(Problems to be Solved by the Invention) The present inventors have conducted extensive studies with the aim of improving the conductivity of heteropolyacids and their salts, and have found that the conductivity is superior to the original heteropolyacids and their salts. The present inventors have discovered a conductive inorganic oxide composition that does not impair other physical properties of heteropolyacids and their salts, and an industrially advantageous method for producing the same, and have completed the present invention.

(Means and effects for solving the problem) That is, the first invention of the present invention provides a heteropolyacid and/or a salt thereof and the general formula % formula % () (However, in the general formula (I), X is 0< any number of X<1,
y is any number satisfying O≦y<3, and 2 represents at least one element selected from the group consisting of molybdenum, tungsten, and vanadium. I will provide a.

Further, a second aspect of the present invention provides a method for producing the above-mentioned conductive inorganic oxide composition by heating a heteropolyacid and/or its salt in a reducing atmosphere to decompose and reduce a part of the heteropolyacid and/or its salt.

In the present invention, the disclosed conductive inorganic oxide composition and method for producing the same have the following characteristics.

(1) Particles made of a conductive tlIM compound composition having an average particle size in the range of 0.01 μTrL to 10 μL can be easily produced.

(2) Conductivity expressed as volume resistivity: 10 to 106Ω・
It can be freely controlled within the scope of employment.

(3) It has excellent affinity with polar solvents such as water and alcohols, and in the case of particles, it is well dispersed therein.

(4) Conductivity is stable even in various atmospheric environments.

(5) Stable and chemical resistant to resins and solvents.

(6) Heat resistant up to about 500°C.

Therefore, when the particulate composition is dispersed in paint or resin, etc. and then formed into various molded bodies or coatings, the particles do not easily peel off, and a stable and reliable conductor with low environmental dependence is obtained. can get.

Furthermore, it also possesses various specific chemical, electrical, and other physical properties derived from its heteropolyacid structure, and is of industrial significance.

The heteropolyacids constituting the heteropolyacids and their salts that can be used in the present invention include elements that can be central in the crystal structure (hereinafter referred to as Δ group elements), oxyacids of group A elements, and complex oxyacids. elements (hereinafter referred to as group 2 elements), such as the following elements 1 to 3.
Table 1 (When the Z group element is molybdenum) Table 3 (When the 2 group elements are multiple) , Ia group such as sodium, potassium, rubidium, cesium; Ib group such as copper, silver; Ira group such as beryllium, magnesium, calcium, strontium, barium; Ub group such as zinc, cadmium, mercury; Scandium, yttrium, etc. ■Group B Coniboron Il such as aluminum, gallium, indium, and thallium [Group A; Group II such as iron, cobalt, and nickel; Metal ions of lanthanides such as lanthanum and cerium, or ammonium ions or quaternary ammonium ions, pyridinium ions, Salts with organic bases such as organic amines are used, and particularly preferably, ammonium ions or quaternary ammonium ions of the above-mentioned heteropolyacids and alkyl amines or alkyl groups in which the alkyl group has 1 to 20 carbon atoms are used. Salts with organic amines such as alkanolamines having 1 to 20 carbon atoms are used.

In addition, heteropolyacids and their salts generally have unique crystals depending on the type and ratio of group A elements and group Z elements constituting the heteropolyacid salt, the type and ratio of cations forming the salt with the heteropolyacid, or the manufacturing method of the heteropolyacid salt. Although it contains water, it can also be used in the present invention after being dried to have any water of crystallization below the characteristic value, or anhydrous heteropolyacids and salts thereof.

The method for producing the above-mentioned heteropolyacid and its salt is described, for example, in the Journal of the Japanese Crystallographic Society Vol. 1.17. P127 (1975), l
nd.

Eng, ChetProd, Res, Develop,
, Vol. 13. m4. P267-274 (197
4), Catalyst, Vol. 18. k6. P2S5~179
(1976) etc. can be used. In addition, spherical heteropolyacid acid fine particles obtained by the methods of JP-A-61-83609 and JP-A-61-101407 previously disclosed by the present inventors can also be suitably used.

The above general formula % formula % () (However, in the general formula (I), X is any number satisfying Q<x<1,
y is any number in the range 0≦y<1 determined by the constituent elements, 2
(represents at least one element selected from the group consisting of molybdenum, tungsten, and vanadium) is a type of non-stoichiometric compound called "bronze", and has a bronze luster similar to metal in appearance.
Although it exhibits unique properties such as electrical conductivity, it is a chemically stable compound.

The electrocardiographic inorganic oxide composition disclosed in the present invention contains the above-mentioned compound as a main component, and contains other substances such as a part or all of H in the above general formula HxZO3-V(I). Compounds in which atoms of alkali metals such as Na and Ni or transition metals such as AQ and Cu are replaced, P2O5, S i 0
2, inorganic oxides such as WO3, MOO3, ■205, etc.
Alternatively, organic substances such as polymers may be mixed.

The present inventors heated the above heteropolyacid and/or its salt in a reducing atmosphere near the decomposition temperature of each substance,
By reductively decomposing a part of it, reductive decomposition products (I
) was found to improve the conductivity compared to the heteropolyacid and its salt before treatment.

The reducing atmosphere refers to an atmosphere of nitrogen, helium, or other inert gas, or an atmosphere in which at least hydrogen, ammonia gas, or other reducing gas is present.

The heating temperature varies depending on the type of reducing atmosphere, but 1
00°C or higher, preferably the heating temperature (1) is to -200 relative to the decomposition temperature (to) of each substance in air.
The temperature range is ℃≦(≦to+100℃, more preferably to -, 100℃≦t≦to 450℃. , 1981゜(3) P3
3B-342, etc.

The heating time varies depending on the atmosphere and temperature, but may be 30 minutes to 20 hours.

The content of the reductive decomposition product (I) in the composition can be arbitrarily controlled by changing the heating conditions, and the conductivity can also be controlled depending on the content. That is, the higher the content of compound (I), the higher the conductivity, and the lower the content, the lower the conductivity, but it is higher than the 11 character of the heteropolyacid and/or its salt used as a raw material.

That is, the conductivity of the ii* compound-free composition according to the present invention can be expressed as a volume resistivity in the range of 10 to 10<6 >[Omega].alpha. as desired.

(Effect of the invention) The conductive inorganic oxide composition of the present invention synthesized from a heteropolyacid or its salt can be easily mixed and dispersed in, for example, resins and paint base materials, and even if the amount of compounding is small, it can be easily mixed and dispersed. Homogeneous conductivity can be imparted to the obtained molded body or coating film.

When applied as a resin dispersion to molded bodies or coating films, it is suitable as a material for batteries, electrode materials, solid electrolytes, etc., as well as charging rollers, developing rolls, cleaning rollers, etc. of electrophotography and copying machines. It is also suitable as a paint for creating control elements for current, voltage, resistance, etc., such as electric field relaxing paint, antistatic paint, secondary electron emitting paint, etc.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples. There are no restrictions on the area.

In addition, powder X-ray diffraction method was used to analyze the product.
Ds, Powder Diffraction, F
Created with reference to ile J (commonly known as ASTH card)
The product was identified.

Example 1 700 parts by weight of deionized water were added to 72 parts by weight of molybdenum oxide, 4.79 parts by weight of 85% by weight phosphoric acid was added, and the solution was held at 95° C. for 3 hours while stirring. After that, it is cooled and the insoluble matter is removed by suction filtration. Phosphormolybdenum M (83PMO
1204o) An aqueous solution was obtained.

The obtained phosphomolybdic acid aqueous solution was concentrated to dryness, and the obtained powder was reduced at 450° C. for 5 hours in a nitrogen atmosphere containing 10% hydrogen to produce a composition sample (a).

As a result of X-ray diffraction, the composition sample (a) is a composition containing phosphomolybdic acid and its reduction decomposition products, and the reduction products are identified as Ho, so Mo Os, and the content in the composition is The percentage was 60%, and thermal bond analysis revealed that it contained some crystal water.

Table 4 shows the results of measuring the physical properties of the composition.

Example 2 Keimolybdenum i! (H4S iMo1204o・2
A composition sample (b) was prepared by reducing the powder of 9H20) at 350° C. for 3 hours in a nitrogen atmosphere containing 10% hydrogen.

As a result of X-ray diffraction, the composition sample (b) is a composition containing silicon molybdic acid and its reduction product, and the reduction product is identified as 80.30 M OO3, and the content in the composition is 40%, and thermogravimetric a analysis revealed that it contained some crystal water.

Table 4 shows the results of measuring the physical properties of the composition.

Examples 3 and 4 The silicon molybdic acid of Example 2 was converted to phosphotungstic acid (H
Composition samples (C) and ( D) was manufactured.

Table 4 shows the results of measuring the physical properties of the composition.

Example 5 Phosphortungstic acid (H3P) was added to 800 layers of deionized water.
W1204o.29)-120>15 Nm parts were added and dissolved. Further, 10% by weight of sodium hydroxide was added under stirring while stirring to adjust the pH to 10, and then 1.7 parts by weight of ammonium chloride was added to obtain a homogeneous solution. Next, concentrated hydrochloric acid was added to the solution to finally adjust the DH of the solution to 2, and the reaction was continued with stirring (1000 rpm) at room temperature for an additional 2 hours to obtain a suspension of ammonium phosphotungstate salt. Thereafter, it was filtered to separate fine particles.

After repeating water washing and furnace separation for these fine particles twice,
It was flushed with acetone and air-dried to produce ammonium phosphotungstate salt fine particles.

The fine particles were reduced at 550° C. for 5 hours under a nitrogen stream to produce a composition sample (e).

As a result of X-ray diffraction, the composition sample (E) is a composition containing ammonium phosphotungstate and its reduction decomposition product, and the reduction product is identified as Ho, 5sWO3, and the content in the composition is was 75%, and thermogravimetric analysis revealed that it contained some water of crystallization.

Table 4 shows the results of measuring the physical properties of the composition.

Incidentally, an X-ray diffraction chart of the composition is shown in FIG.

Examples 6 to 8 Except that phosphotungstic acid in Example 5 was replaced with phosphomolybdic acid, silicomolybdic acid, or silicotungstic acid, and the decomposition and reduction conditions were changed as shown in Table 4,
Composition samples (f), (t), and (h) were produced in the same manner as in Example 5.

Table 4 shows the results of measuring the reduction conditions and physical properties in the production of each sample.

Note that an X-ray diffraction chart of the composition obtained in Example 6 is shown in FIG.

Example 9 A composition sample was produced in the same manner as in Example 5, except that triethanolamine was used instead of ammonium chloride.

Table 4 shows the reduction conditions in the production of the sample and the results of measuring the physical properties of the sample.

Examples 10-13 Composition samples (nu) were prepared in the same manner as in Example 5, except that the decomposition and reduction conditions in Large Dust Example 5 were changed as shown in Table 5.
, (L), (O), and (W) were manufactured.

Table 5 shows the results of measuring the physical properties of the composition.

(Leaving space below) Table 5 Example 14 30 parts by weight of the composition sample (e) obtained in Example 5 was added to Aloron 50 (trade name: medium oil-based alkyd resin, resin solid content 50%, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.) ) was added to 1 part of 200 weight ff and mixed for 30 minutes using a paint shaker to obtain a conductive paint. This conductive coating material was applied to a polyethylene terephthalate film by a doctor blade method so that the thickness of the coating film after drying was 5 μm.

When the surface resistance value of the obtained coating film was measured at 20° C. and 50% RH, it was 3.0×10 10 Ω/mouth.

Comparative Example 1 The volume resistivity value of ammonium phosphotungstate [(NH4)3 PW1204o・4H20] which was not subjected to decomposition and reduction treatment was measured under the conditions shown in Table 4.
．． It was 4×104Ω・CIM.

[Brief explanation of drawings]

FIG. 1 is an X-ray diffraction chart of the composition sample (E) obtained in Example 5, and FIG. 2 is an X-ray diffraction chart of the composition sample (E) obtained in Example 6. Procedural amendment (voluntary) February 23, 1989

Claims (6)

[Claims] (1) Heteropolyacid and/or its salt and the general formula HxZO_3-y...(I) (However, in the general formula (I), x is any number satisfying 0<x<1,
A conductive inorganic oxide composition containing as a main component a compound represented by: y is an arbitrary number of 0≦y<3, and Z represents at least one element selected from the group consisting of molybdenum, tungsten, and vanadium. thing. (2) Complex oxygen in which the heteropolyacid and/or its salt is composed of at least one element (a) selected from Group A below and at least one element (b) selected from the group consisting of molybdenum, tungsten, and vanadium. The conductive inorganic oxide composition according to claim 1, which is an acid and/or a salt thereof. (Note) Group A: boron, aluminum, gallium, silicon, germanium, cerium, titanium, zirconium, antimony, bismuth, rhodium, copper, platinum, phosphorus, iron, cobalt and nickel (3) The conductive inorganic oxide composition according to claim (1) or (2), wherein the compound (I) is obtained by decomposing and reducing a heteropolyacid and/or a salt thereof. (4) The conductive inorganic oxide composition according to claim (1), (2) or (3), wherein the heteropolyacid salt is an ammonium salt or an organic amine salt. (5) A heteropolyacid and/or a salt thereof characterized by heating the heteropolyacid and/or its salt in a reducing atmosphere to decompose and reduce a portion thereof and the general formula HxZO_3-y...( I) (However, in general formula (I), x is any number satisfying 0<x<1, y is any number satisfying 0≦y<3, and Z is at least one selected from the group consisting of molybdenum, tungsten, and vanadium. A method for producing a conductive inorganic oxide composition containing as a main component a compound represented by (each representing a type of element). (6) Complex oxygen in which the heteropolyacid and/or its salt is composed of at least one element (a) selected from Group A below and at least one element (b) selected from the group consisting of molybdenum, tungsten, and vanadium. The method for producing a conductive inorganic oxide composition according to claim (5), which is an acid and/or a salt thereof. (Note) Group A: boron, aluminum, gallium, silicon, germanium, cerium, titanium, zirconium, antimony, bismuth, rhodium, copper, platinum, phosphorus, iron, cobalt and nickel