JPS6230619A - Production of aqueous vanadium oxide - Google Patents

Abstract

PURPOSE:To obtain aqueous vanadium oxide having a low surface resistance value as well as to drop the melting temperature by blending V2O5 with a vanadium lower oxide having a smaller amount of oxygen than V2O5, melting them under heating at a specific temperature and running the molten material into pure water rapidly and quenching it. CONSTITUTION:V2O5 is blended with >20wt% based on the weight of V2O5 of one or more vanadium lower oxides such as V6O13, VO2, V2O3, etc., having a small amount of oxygen than V2O5, heated to the melting point of V2O5-=1,200 deg.C and they are melted. Then, the molten material is rapidly run into pure water and quenched. Preferably the amount of the pure water is an amount to make the temperature of water after the cooling sufficiently lower than 100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to a method for producing V2O, aqueous antistatic compositions, compositions for catalytic electrochromic display elements, and the like.

[Prior art and problems]

Conventionally, V2O5 alone or containing 80% or more of V2O, and also containing MOOI and Na5PaOxo, is called V2O1.
1+7) A method for obtaining an aqueous antistatic composition consisting of amorphous V2O5 by heating it to a temperature above 10 (11) melting point and pouring it into an underwater trap is known from Japanese Patent Publication No. 57-29502. There is.

However, in this known method, as described in the same publication, dilution of 5 to 25 y/lK is performed, and this is diluted to 20 y/lK per 1 d of support.
When applied to a support made of polyethylene 7-talate at a ratio of 40%, the lowest value of surface resistance (GΩ) is V2O.
Even when using an oxide obtained by melting 3 at 1100"C, the surface resistance is 0.I when V2O5 is 10y/l.
It's just GΩ.

In other words, it is thought that the main element that exerts the antistatic effect is ■4+ contained in the aqueous oxide, but when the applicant company retested the known product described in Japanese Patent Publication No. 57-29502, ■4+ was 1 Only .3%,
The others were vl+, which had little to do with conductivity.

Furthermore, in the known method, the most effective bath melting temperature is high, making handling difficult and requiring a lot of energy.

[Problem to be solved]

The purpose of this invention is to improve the drawback that conventional methods have only been able to obtain products with high surface resistance, and the purpose of this invention is to obtain products with a low melting temperature and a low surface resistance value.゛ [Means to solve the problem] This invention Hv, o, K V, 0. , ,VO2,v
2o4natoV2O5J: ') is also made by adding at least one type of vanadium lower oxide with low oxygen in a range exceeding 20% by weight, and melting them by heating to a temperature above the melting point of V2O5 and below 1200''C. We solved the construction problem by adopting a manufacturing method for aqueous vanadium oxide, which is characterized by rapidly pouring the molten material into pure water and rapidly cooling it.

〔Production method〕

The method of this invention will now be specifically explained.

First, VxOs is heated to a temperature higher than the melting point of VxOs in a porcelain crucible under air, nitrogen gas, or an inert gas atmosphere to melt it.

Next, one or two of vanadium oxides lower than V and Os, such as VOz, V2O4, VaOxa, etc.
Jtfk exceeding 20% of the weight of V2O6 above the seed
For example, it is added in an amount of 25% to 45%, and these are also melted together.

When these are sufficiently melted and homogeneously mixed, they are poured into distilled water (pure water) and rapidly cooled to produce aqueous vanadium oxide containing v4+.

It is desirable that the amount of distilled water is sufficient for the melt, and the temperature of the water after cooling is preferably lower than 100% by light. A method using distilled water containing 1/10 to 1/3 acetone also falls within the scope of the present invention.

When the product produced by the method of the present invention was diluted to a V concentration of 1% and coated and dried on a ceramic plate to a thickness of 100 μm, it was found that 21 The surface resistance value of 74 kQ/d is one order of magnitude lower than that of the conventional method using a material containing 80% or more of V2O5 as a raw material, and it can exhibit excellent effects as an antistatic agent and as a catalyst for chemical reactions. The effects can be fully expected.

Also, manufactured items ~ ■4+ is approximately 5.6 to 27%
The v4+ content in the conventional method was 7.3% at most. Therefore, an outstanding effect as an antistatic agent is exhibited. Also, in the method of this invention, the temperature of molten vanadium may be 690 to 1200 t', preferably around 800°C (750 to 1100'C), and v2o
The amount of water that evaporates into steam is small, so raw materials can be used effectively.

Aqueous vanadium oxide produced by this method has the following appearance depending on its concentration.

Table 1 Experimental Example 1 V2O340y was placed in a porcelain crucible and heated for 30 minutes in an electric furnace.
After maintaining CK for 800 minutes and V2O5 completely melting, add V2O3 and 15 min. II! was poured into pure water to obtain aqueous vanadium oxide.

When the v4+ in this aqueous vanadium oxide was measured by the following test method, it contained 56% v4+.

An example of a method for measuring the content of v4+ is shown below.

A certain amount of aqueous vanadium oxide is collected and (1+1)H2
Add 1 t of SO42Q and gently heat to decompose.

Titrate it with 1/10 NKM HOa bath solution, and
Find the amount of +. Thereafter, this solution is titrated with a 1/iON ferrous ammonium sulfate solution to determine the total amount of ■. Divide this ■ 4+ by the total amount of ■ to determine ■ the content (%) of 4+.

When the material manufactured by the method of this experimental example configured as above was diluted to 1% VA and coated on a ceramic plate to a thickness of 100 μm and dried, the surface resistance was 74M.
It showed 1/d.

Experimental Examples 2 to 5 Similar experiments were conducted using vanadium melted in lower oxynitrogen gas added later, and the rest were conducted in air. As a control experiment, only v2o was heated at 800'C,
Pure water 1/cP [The results of these experiments showing what was injected are shown in Table 2.

Table 2 However, the pace was set at VzOs 40/.

As is clear from the above results, the content of v4+ is approximately 4 to 20 times higher than that produced by a known method, and the surface resistance is 21 to 74 Ω, compared to the control experiment. It is clear that the value is 145~1/3o
Although it is extremely small, it has a remarkable effect.

In each of the above experiments, the surface resistance was measured by applying a width of 10 mm to the surface of the coating formed on the ceramic plate in each experiment.
1 pair of g copper plates, 1c! They were crimped at intervals of 11, and the resistance between them was measured.

that's all Patent applicant: Shinko Kagaku Kogyo Co., Ltd. Self P'Hir' Procedural amendment (, wa.

9810, 1985 fl + Director General Uga Michibu Tono 1'11 I'1 Indication It/l fn 60 XH Patent Application No. 1707389
2 Title of the invention Process for producing aqueous vanadium oxide 3, 7
Relationship with city commissioner Nagisa 11411 Patent applicant 1r″l(;j, 1-3-1 Nishihonmachi, Nishi-ku, Osaka
No. 0 U'''' also (wa 1, 11, Shinko Kagaku Kogyo Co., Ltd. representative 2nd person Hiroya Takeuchi 4th generation Jllj person method i - mock → gin → call ・1.. (-ri 6, amendment content declaration attached) In the description of , the following matters are amended.

(1) The "Scope of Claims" shall be amended as follows.

r VzOaK V6O13, VO2, V2O3 NatoVzOsyo') is also V2e by adding one or more types of vanadium lower oxides with less oxygen in a range exceeding 20% by weight.
Melt these by heating to a temperature above the melting point of g and below 1200'C, then quickly pour this melt into pure water and quench it.
! A method for producing aqueous dispersion of vanadicum, which is characterized by ” (2), page 1-1, line 13, replace “,catalyst” with “r,catalyst,”.

(3) On page 3, line 5, 3rd line from the bottom, it says “...
・V2O4..." should be replaced with "...V2O3...
-l.

(4) In the 3rd line from the bottom of the 4th page, you can expect F... term. If it says j, then r...you can expect it. ”.

Claims (1)

[Claims] V_2O_5 to V_6O_1_3, VO_2, V_2O
At least one type of vanadium lower oxide containing less oxygen than V_2O_5, such as _4, is added in an amount exceeding 20% by weight, and these are melted by heating to a temperature above the melting point of V_2O_5 and below 1200°C, and this melt is purified. A manufacturing method for aqueous vanadium oxide, which is characterized by quickly pouring it into water and rapidly cooling it.