JPH0623043B2 - Manufacturing method of aqueous vanadium oxide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an aqueous antistatic composition, a composition for a catalytic electrochromic display element, or the like from V ₂ O ₅ .

[Prior art and problems]

Conventional V ₂ O ₅ alone or containing 80% or more of V ₂ O ₅ and additionally containing M ₀ O ₃ and Na ₅ P ₃ O ₁₀ is heated to a temperature above the melting point of V ₂ O ₅ by 100 ° C. , A method of pouring this into water to obtain an aqueous antistatic composition comprising amorphous V ₂ O ₅ is disclosed in Japanese Examined Patent Publication No. 57-295.
No. 02 patent publication.

However, in this known method, it was diluted to 25 g / m as described in the same note, and this was diluted to 20 g / m ² of the support.
when applied to a support made of polyethylene terephthalate at a ratio of mg, even smallest value surface resistance (G [Omega]) is an alien in the case of using the oxide is melted V ₂ O ₅ at 1100 ℃, V ₂ O _{When 5} is 10 g /, the surface resistance is only 0.1 GΩ.

In other words, it is considered that the main element having the antistatic effect is due to V ⁴⁺ contained in the aqueous oxide, but when the applicant company additionally tested the one described in the above-mentioned Japanese Patent Publication No. 57-29502, V ⁴⁺ Was only 1.3%, and the others were V ⁵⁺ having almost no relation to conductivity.

Further, in the known method, the most effective melting temperature is high, the handling is difficult, and much energy is required.

[Problems to be solved]

It is an object of the present invention to improve the drawback that only a high surface resistance can be obtained in the conventional method, to obtain a low melting temperature and a low surface resistance value.

[Means for solving problems]

The present invention, V ₆ O ₁₃ to _{V 2 O 5, VO 2,} V 2 O 3 , etc. V ₂
One or more vanadium lower oxides containing less oxygen than O ₅ are added in a range of more than 20% by weight, and these are melted by heating them to a temperature not lower than the melting point of V ₂ O ₅ and not higher than 1200 ° C. A method for producing an aqueous vanadium oxide is characterized in that the product is rapidly poured into distilled water or one kind of distilled water containing 10% to 33% of acetone to be rapidly cooled.

〔Production method〕

 Now, the method of the present invention will be specifically described.

First, the porcelain crucible is heated as an atmospheric gas under air, nitrogen gas or an inert gas to a temperature not lower than the melting point of V ₂ O ₅ to melt it.

Next, vanadium oxide lower than V ₂ O ₅ such as V
_{O 2, V 2 O 3,} V 6 O 13 V one or two or more previous among such
20% by weight of ₂ O ₅ such as 25% to 45%
So that they also melt together.

Then, when these are sufficiently melted and are in a homogeneously mixed state, they are poured into distilled water and rapidly cooled to V ^4+.
An aqueous vanadium oxide containing is produced.

The distilled water is preferably in a sufficient amount with respect to the melt, and the water temperature after cooling is preferably sufficiently lower than 100 ° C. Acetone is added to distilled water at 1/10 to 1/3 (1
A method using water containing 0% to 33%) also belongs to the scope of the present invention.

The product produced by the method of the present invention was diluted to a V concentration of 1%, and was applied and dried on a ceramic plate to a thickness of 100 μm. It depends on the kind of the vanadium lower oxide mentioned above. The surface resistance value of 74 to 74 kΩ / cm ² is 1 order less than that of the conventional method containing 80% or more of V ₂ O ₅ as a raw material, which is effective as an antistatic agent. The effect can be expected sufficiently as a reaction catalyst.

In addition, the V ⁴⁺ produced was contained in a high ratio of about 5.6 to 27%, and the V ⁴⁺ content in the conventional method was at most 1.3%. Therefore, it has an excellent effect as an antistatic agent.

In the method of the present invention, the temperature of the molten vanadium is 690 to 1200 ° C, preferably around 800 ° C (750 to 110 ° C).
(0 ° C.) is sufficient, and the amount of V ₂ O ₅ that evaporates as vapor is small, and the raw materials are effectively used.

The aqueous vanadium oxide produced by this method exhibits the following appearance depending on its concentration.

Experimental Example 1 40 g of V ₂ O ₅ was placed in a porcelain crucible, kept at 800 ° C. for 30 minutes in an electric furnace, and V ₂ O ₅ was completely melted, and then V ₆ O ₁₃ 15
g was added, and when these were melted to a completely mixed state, quickly 1 while maintaining about 800 ° C.
When it was poured into the distilled water of Example 1 and V ⁴⁺ in the aqueous vanadium oxide was measured by the following test method, it contained 5.6% of V ⁴⁺ .

An example of the method for measuring the content of V ⁴⁺ is shown below.

An aliquot of aqueous vanadium oxide was collected, and (1 + 1) H ₂ SO ₄
Add 20 ml and slowly heat decomposition. 1/10 it
Titrate with NKMnO ₄ solution to determine the amount of V ⁴⁺ . Then, this solution is titrated with a 1 / 10N ferrous ammonium sulfate solution to determine the total amount of V. This V ⁴⁺ is divided by the total amount of V to obtain the V ⁴⁺ content (%).

The product manufactured by the method of this experimental example configured as described above was diluted to a V concentration of 1%, applied on a ceramic plate with a thickness of 100 μm, and dried to obtain a surface resistance of 74 k.
Ω / cm ² was shown.

Experimental Examples 2 to 5 The same experiment was conducted by changing the kind and amount of vanadium lower oxide to be added later and the heating temperature, and those produced are shown in Table 2. In the examples, 2 was melted in nitrogen gas, and the rest was performed in air. As a control experiment, V ₂ O ₅
The results of these experiments are shown in Table 2 below.

As is clear from the above results, the content of V ⁴⁺ is about 4 to 20 times higher than that produced by the known method, and the surface resistance is 21 to 71 kΩ / cm ² and the control experiment. As is clear from comparison with, the value is 1 / 8.5 to 1/3
It is extremely small as 0 and has a remarkable effect.

In each of the above-mentioned experiments, the surface resistance was measured by a width of 10 on the coating surface formed on the ceramic plate in each experiment.
mm copper plates were paired and pressure-bonded at an interval of 1 cm, and the resistance therebetween was measured.

Claims (1)

[Claims] 1. A V ₆ O ₁₃ to _{V 2 O 5, VO 2,} V 2 O 3 , etc. V ₂
One or more vanadium lower oxides containing less oxygen than O ₅ are added in a range of more than 20% by weight, and these are melted by heating them to a temperature not lower than the melting point of V ₂ O ₅ and not higher than 1200 ° C. A process for producing an aqueous vanadium oxide, which comprises rapidly pouring a substance into distilled water or one of distilled water containing 10% to 33% of acetone and quenching.