JPH0365503A - Stabilizer for peroxy poly-acid, composition containing the same, radiation-sensitive composition and electrochromic display element - Google Patents

Abstract

PURPOSE:To improve the stability of a peroxy poly-acid containing W and/or V by adding one or more water-soluble nitrogen-containing organic compounds selected from nitriles, amines and amides as a stabilizer to the peroxy poly-acid. CONSTITUTION:A water-soluble nitrogen-containing organic compound including one or more organic compounds selected from nitriles, amines and amines such as N,N-dimethyl formamide is added in a concentration of >=1wt.% to and mixed with the aqueous solution of a peroxy poly-acid containing one or more elements selected from W, Nb, Ta and Ti and represented by formula I (0<=x+y+z<1, 0<l<=1, 0.16<m<4, 0<=n<=0.025) to provide a radiation-sensitive composition. ON the other hand a water-soluble nitrogen-containing organic compound including one or more organic compounds selected from nitriles, amines and amides such as acetoamide is added to concentration of >=1wt.% and mixed with the aqueous solution of a peroxy poly-acid containing V, W and Mo and represented by formula II (0<=l+m<1, 0.05<=x<=1, 1.5<=y<=3) to obtain a color-generating composition for electrochromic display elements.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a stabilizer for peroxycondensed acid, a composition containing peroxycondensation acid, a method for producing the same, a radiation-sensitive composition, a pattern forming method, an electrolytic The present invention relates to a composition for a coloring film of a chromic display element and an electrochromic display element.

[Conventional technology]

Conventionally, several types of peroxide condensed acids have been used in radiation-sensitive materials and electrochromic display devices (hereinafter abbreviated as ECD).

For example, JP-A-63-100448 and JP-A-63-2
↓No. 6042 describes inorganic resist materials containing peroxide condensed acids such as peroxide condensed tungstic acid and peroxide condensed niobium tungstic acid. This material is a peroxide of peroxoborotungstic acid obtained by dissolving metallic tungsten (or tungsten carbide) in an aqueous hydrogen peroxide solution, and is an amorphous material expressed by the following empirical formula (general formula).

(1, x y z)WOi'x/2Nb20. ;'
y/2Ta20. ．． 'zTj○2・αH2O2・mH2
O-nC02(1-O≦z + y + z (1,0
≦1.0, 16 <m and n are each 0.025
) In general, inorganic resists, such as materials such as amorphous chalcogenide, require vacuum techniques such as evaporation or sputtering to form thin films, but this material can be formed by applying an aqueous solution. A homogeneous thin film can be formed. This coating film is coated with patterned deep ultraviolet light, excimer laser 1 electron beam, and X! By irradiating iA, the solubility of the irradiated area in the developer decreases, and the
The following fine patterns can be formed.

In addition, conventional ECDs have used a transition metal oxide such as tungsten oxide or vanadium oxide as a coloring film, and an electrolyte such as a solution of lithium perchlorate in diluted pyrene carbonate, or a solid ionic quaternary material. Alternatively, a structure in which a coloring film and a dielectric material such as tantalum oxide are combined is known. However, since these methods rely on vacuum techniques such as vapor deposition and sputtering to form thin films such as color-forming films, there is a problem in that the product price is high. Therefore, a method of forming a color-forming film of ECD by an inexpensive wet coating method using vanadium oxide was disclosed in the proceedings of the 56th Annual Conference of the Electrochemical Society, 2DO4 (1989). This method uses condensed vanadate containing peroxo or peroxide ions synthesized by the reaction of vanadium and hydrogen peroxide as a coloring film.

[Problem to be solved by the invention]

The peroxycondensed acid-based inorganic resists have the problem of low reproducibility in the pattern formation process because the solubility of the coating film in the developer tends to change over time due to changes in temperature and humidity during the process. .

In addition, in the conventional technology described in the Proceedings of the 56th Electrochemical Society of Japan, peroxo or peroxide ions contained in peroxide-condensed vanadate are easily decomposed, and dehydration condensation easily progresses to form a gel and solid. Therefore, there was a problem that the coating solution for forming the coloring film became unusable within a short time after its preparation.

A first object of the present invention is to provide the radiation-sensitive composition, EC
Our objective is to provide a stabilizer for peroxycondensed acids used in D-former compositions and other applications.

A second object of the present invention is to provide a stable composition containing a peroxycondensed acid and a method for producing the same.

A third object of the present invention is to provide a stable radiation-sensitive composition and a pattern forming method using the same.

A fourth object of the present invention is to provide a stable coating composition for producing ECD and ECD produced using the same.

[Means to solve the problem]

The first object is to provide (1) a stabilizer for peroxycondensed condensed acid made of a water-soluble nitrogen-containing organic substance; (2) the water-soluble nitrogen-containing organic substance to be at least one selected from the group consisting of nitriles, amines, and amides; (3) the stabilizer for peroxylated condensed acids as described in 1 above, characterized in that the peroxidized condensed acid contains at least tungsten; Stabilizer (4) The above-mentioned peroxide condensed acid is achieved by the stabilizer for peroxide condensed acid described in 1 above, which is characterized in that it contains at least vanadium.

The second object is to provide a composition comprising (5) a water-soluble nitrogen-containing organic substance and an aqueous solution of a peroxycondensed acid; (6) the water-soluble nitrogen-containing organic substance is selected from the group consisting of nitriles, amines, and amides; The composition according to 5 above, characterized in that it contains at least one organic substance, (7) the peroxide condensed acid is
5 above, characterized in that it contains at least tungsten.
(8) The composition as described in (9) above, wherein the peroxide condensed acid contains at least vanadium; This is achieved by a method for producing a composition containing a characteristic peroxide condensed acid.

The third object is to provide a radiation-sensitive composition comprising (10) an aqueous solution of a peroxycondensed acid containing tungsten and a water-soluble nitrogen-containing organic substance; (11) the peroxycondensate contains niobium, tantalum and The radiation-sensitive composition according to 1o above, characterized in that it contains at least one element selected from the group consisting of titanium; (12) the water-soluble nitrogen-containing organic substance is selected from the group consisting of nitriles, amines and amides; The radiation-sensitive composition as described in 10 above, characterized in that it contains at least one organic substance.
The water-soluble nitrogen-containing organic substance is 1% relative to the peroxidized condensed acid.
The radiation-sensitive composition according to 10 above, characterized in that the radiation-sensitive composition is contained in a concentration of % by weight or more, (14) general formula (1
-x-y-z) WO, x/2Nb, 0s-y/2Ta
20. -ZTiO2-QH,02・mH2O・nC02
(1-x, y, z, 1, m, n are each O≦x+y
+z<1.0<Q≦l, 0.16<m, n is 0 respectively
．． 025) and a water-soluble nitrogen-containing organic substance.

(15) The radiation-sensitive composition as described in 14 above, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitriles, amines, and amides; (16) from 10 above↓ Applying the radiation-sensitive composition according to any one of items 5 to 5 on a substrate, applying a coating film onto the substrate, and irradiating the coating film with radiation in a desired pattern,
This is achieved by a pattern forming method characterized by development.

The third object is to provide (17) a composition for a coloring film of an electrochromic display element comprising an aqueous solution of a peroxycondensed acid containing vanadium and a water-soluble nitrogen-containing organic substance; (18) the water-soluble nitrogen-containing organic substance is a nitrile , the composition for a coloring film of an electrochromic display element as described in 17 above, which is characterized by containing at least one organic substance selected from the group consisting of amines and amides, (19) general formula 2QWO,
2mMoo, ・(1-Q-m)V20sj xH,0,
・yH20 (however, sad, m, x, y are each O≦Q
1.0.05≦X≦1.1.5≦y≦3) and a water-soluble nitrogen-containing organic substance. Composition for a coloring film of a chromic display element, (20) the electrochromic as described in 19 above, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitrile, amine, and amide. Composition for a coloring film of an electrochromic display element (21) Applying the composition for a coloring film of an electrochromic display element described in 1721 above on a substrate on which a conductive film is formed, This is achieved by an electrochromic display element having at least a color-forming film formed by heating, a counter electrode, and an electrolyte held between the two.

Substances such as nitriles, amines, and amides are generally known as nitrogen-containing organic substances, but in order to be used in the present invention, it is necessary that this organic substance can be dissolved in an aqueous solution of peroxidized condensed acid. Examples of such substances are acetonitrile, pentylamine, cyclohexylamine,
Ethylenediamine, piperidine, pyridine, picoline,
Examples include lutidine and various amide-based organic substances, and two or more of these may be used as a mixture. Among such organic substances, amide-based organic substances are particularly preferable. Examples of amide-based organic substances include formamide, N-methylformamide, N-methylformamide, and N-methylformamide.
, N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-
Examples include methylpropionamide, 1,1,3,3-tetramethylurea, pyrrolidinone, caprolactam, and hexamethylphosphortriamide, and two or more of these can also be used as a mixture. Even in small amounts, these organic substances have the effect of suppressing changes in the solubility of the peroxide-condensed acid over time, but it is preferable to add them at a concentration of 1% by weight or more, and preferably at a concentration of 3% by weight or more relative to the peroxide-condensed acid in an aqueous solution. It is more preferable to add it, and it is most preferable to add it in a concentration of 10% by weight or more.

The radiation-sensitive composition of the present invention has strong resistance to oxygen plasma when formed into a coating film. Therefore, for example, when forming a fine pattern on an element having a structure with steps on the surface, first a coating film of organic polymer resin is formed to make the surface almost flat, and then the radiation-sensitive composition of the present invention is used to form an upper layer. A coating film of the organic polymer resin is formed, this upper coating film is formed into a desired pattern, and the coating area of the organic polymer resin is processed using this pattern as a mask to form the desired pattern.

The composition for a colored film of ECD of the present invention can be synthesized by adding a water-soluble nitrogen-containing organic substance to an aqueous solution obtained by, for example, a reaction between vanadium and hydrogen peroxide, or a reaction between vanadium pentoxide and hydrogen peroxide. A uniform thin film can be formed using a coating method, which is an extremely simple and inexpensive method. This peroxidized condensed vanadate has the empirical formula % formula % (where x and y are respectively 0.05≦X≦1, (,5≦
(a value in the range of y≦3).

This coating film becomes difficult to dissolve in a solvent by heat treatment. This property is an important property as an ECD coloring material. In particular, this property is essential for devices that use an electrolytic solution such as a propylene carbonate solution of lithium perchlorate. Furthermore, this coated film has a lower water content and is denser than a film made from a colloidal solution, so it does not peel off even after heat treatment.

Furthermore, it is possible to synthesize peroxide condensed vanadate containing tungsten and molybdenum by mixing vanadium with tungsten and molybdenum and dissolving the mixture in hydrogen peroxide. This substance has the empirical formula % (1-Q, m, x, y are each O<lack+m<1.0.
05 ≦
can be easily created.

This method is useful as a method for creating an ECD that can display various colors, such as yellow and green other than blue.

[Effect]

The ten peroxide condensed acid contains protons (H or dimensions H, O) as cations, but by adding the above-mentioned organic substance, some of the protons are replaced with organic functional groups having nitrogen atoms. This stabilizes the polyanion structure of the peroxidized condensed acid, making it possible to suppress changes in solubility over time due to changes in temperature and humidity during the process.

Examples of such substituted structures include (1) For example, in the case of peroxide-condensed tungsten, at least a portion has the structure R-N-0-W- (R represents an organic group), and in the case of peroxide-condensed vanadate, , it is thought that a structure R-N-0-V- (R represents an organic group) is formed at least in part.

〔Example〕

Hereinafter, the details of the present invention will be specifically illustrated by examples.

Example 1 Peroxide condensed niobium-tungstic acid was synthesized by the following method. 10.1 g of metal tungsten powder and 0.50 g of niobium carbide powder were weighed and mixed, then transferred to a reaction vessel, and 50 mQ of 15% hydrogen peroxide aqueous solution was added thereto. When the dissolution reaction accompanied by intense bubbling had almost come to an end, 20 mQ of a 30% aqueous hydrogen peroxide solution was added, and the mixture was allowed to stand at room temperature. Almost all the contents were dissolved in 1 to 2 days, and a pale yellow acidic solution was obtained. Insoluble or undissolved components were filtered and unreacted hydrogen peroxide was decomposed using a platinum catalyst, followed by drying at room temperature to obtain an amorphous powder of peroxide condensed niobium-tungstic acid. As a result of elemental analysis and thermogravimetric analysis, this substance was found to be 0.92WO3・0.04Nb205・QH202・m
H2O-nC02 (1-O<Q≦1.0.16<m<4
, O≦n≦0.025). Here, a, m
, n is shown as a range rather than a fixed value because of conditions that are difficult to control, such as the holding time of each synthesis process, drying conditions, temperature and humidity in the storage atmosphere, etc. This is because the values of m and n change easily. 1 g of peroxide-condensed niobium-tungstic acid thus obtained was dissolved in pure water ig to prepare a peroxide-condensed niobium-tungstic acid aqueous solution. In this aqueous solution, N,
5 g of N-dimethylformamide was added. This solution was spin-coated onto a silicon wafer to form a coating film (hereinafter referred to as coating film A) having a thickness of about 0.1 μm.

After heat treatment at 80℃ for 30 minutes, 25℃, relative humidity 50
% air for 10 hours. During this period, the required development time for an aqueous sulfuric acid solution adjusted to pH 2 was measured at regular intervals to examine changes in solubility over time. On the other hand, for comparison, the film thickness of peroxide condensed niobium tungstic acid without adding N,N-dimethylformamide was about 0.1 μm.
A coating film (hereinafter referred to as coating film B) was prepared and the change in solubility over time was investigated. The results of comparing changes in the required development time for coating films A and B are shown in Table 1.

As is clear from this result, by adding N,N-dimethylformamide, the insolubilization rate (increase rate of development time) of peroxycondensed niobium tungstic acid was reduced to 1710, and N,N-dimethylformamide was It was shown that it has the effect of reducing the change in solubility of niobium tungstic acid over time.

Furthermore, coating films A and B are patterned with light from a 600W xenon-mercury lamp or through a ROM mask.
Irradiation was performed for 1 second at a distance of 35 cm from the lamp. after that,
As a result of developing with a pH 2 sulfuric acid aqueous solution and dissolving and removing the unexposed areas, both samples had a 0.5 μm line and a 0.5 μm line.
A repeating pattern of m wide spaces was formed.

As shown above, by adding N,N-dimethylformamide to peroxidized condensed niobium-tungstic acid, it is possible to reduce the change in solubility over time, but at the same time, it has the advantage of improving the coating properties of the coating liquid. In other words, since the surface tension of water is as large as 70 dyn/c+++ at room temperature,
A peroxidized condensed niobium/tungstic acid solution using only water as a solvent has poor paintability because it is difficult to spread it uniformly on a substrate during coating. However, since the surface tension of N,N-dimethylformamide at room temperature is 32 dyn/Cm, which is lower than that of water, a peroxide-condensed niobium-tungstic acid solution containing it has good coating properties, and can be coated homogeneously using the normal spin coating method. A coating film can be easily created.

Example 2 A peroxide condensed niobium-tungstic acid solution was prepared in the same manner as in Example 1, with various concentrations of N,N-dimethylformamide added in the coating solution. These solutions were applied onto the substrate to the same thickness, and the films were kept at 25° C. and 50% relative humidity for 10 hours.

The results of measuring the solubility (necessary development time) after holding are
Shown in the table. The concentration of N,N-dimethylformamide added is
Weight percent based on peroxide condensed niobium-tungstic acid.

Table 2 Examples 3 to 2O Coating films were formed using peroxidized condensed niobium-tungstic acid to which 50% of various water-soluble nitrogen-containing organic substances containing nitrogen atoms other than N,N-dimethylformamide were added. As in Example 2, these membranes were kept at 25° C. and 50% relative humidity for IO hours.

Solubility of coating film for each additive organic substance (required development time)
The results of the measurements are shown in Table 3.

The results in Table 3 show that even when 1 tyt% of N,N-dimethylformamide is added to peroxide condensed niobium-tungstic acid, the change in development time over time is significantly reduced, but 10 wt%
It can be seen that it is more preferable to add the above amount.

These results indicate that the change in development time over time can be significantly reduced by adding a water-soluble nitrogen-containing organic substance to an aqueous peroxide condensed acid solution. Further, although the development time varies depending on the type of organic material, it is found that organic materials having an amide group are particularly effective in reducing changes in development time over time.

Example 21 Peroxidized condensed tungstic acid containing tantalum was synthesized by the method shown below. 50 mQ of 15% hydrogen peroxide aqueous solution was added to 1 g of metallic tungsten powder L 2 O. When the intense dissolution reaction accompanied by foaming had almost ceased, 30 mQ of a 30% aqueous hydrogen peroxide solution was added and the mixture was allowed to stand at room temperature. 1-2
In time, all the contents dissolved and a pale yellow acidic solution was obtained. A solution prepared by dissolving 2 g of pentaethoxy tantalum in ethanol was added dropwise to this solution. After removing ethanol from the liquid, it was shaken with diethyl ether to remove impurities such as esters. After decomposing unreacted hydrogen peroxide with a platinum catalyst, it was dried at room temperature to obtain an amorphous powder of peroxidized condensed tungstic acid containing tantalum. As a result of elemental analysis and thermogravimetric analysis, this substance has the following properties: 0.92W03・0.04Ta20.・QH202・m
H2O・nC○2(1-0<sad≦1.0.16<m<4
, O≦n≦0.025). here.

The reason why m, n and m are not fixed values but are shown as ranges is due to the holding time of each synthesis process, drying conditions, temperature and humidity in the storage atmosphere, etc.
This is because the values of α, m, and n are likely to change due to conditions that are difficult to control. 1 g of peroxidized condensed tungstic acid containing tantalum thus obtained was dissolved in 1 g of pure water. 5 g of N,N-dimethylformamide was added to this aqueous solution. This solution was spin-coated onto a silicon wafer to form a coating film (hereinafter referred to as coating film C) having a thickness of about 0.1 μm.

After heat treatment at 80℃ for 5 minutes, 25℃, relative humidity 50%
It was kept in the air for 10 hours. During this period, the required development time for an aqueous sulfuric acid solution adjusted to pH 2 was measured at regular intervals to examine changes in solubility over time. On the other hand, for comparison, a film thickness of about 0.1
A coating film (hereinafter referred to as coating film) with a thickness of μm was prepared and the change in solubility over time was investigated. Table 4 shows the results of comparing changes in required development time for coatings C and D.

Table 4 As is clear from the results, the insolubilization rate (rate of increase in development time) of peroxidized condensed tungstic acid containing tantalum increased by 1710 by adding N,N-dimethylformamide.
It was shown that N,N-dimethylformamide has the effect of reducing the change in solubility over time of peroxidized condensed tungstic acid containing tantalum.

Furthermore, coating films C and D are coated with a narrow-band KrF excimer laser using a patterned chrome mask with an NA value of 0.3.
The light was irradiated through a No. 5 quartz lens. Thereafter, as a result of developing with an aqueous sulfuric acid solution of pH 2 and dissolving and removing the unexposed areas, a folded pattern of 0.4 μm wide lines and 0.4 μm wide spaces was formed in both samples.

Example 22 Peroxide condensed tungstic acid containing titanium was synthesized by the method shown below. Weighed 10.1 g of metallic tungsten powder and 0.29 K of titanium carbide powder, mixed them, and then transferred them to a reaction vessel, and added 5% of a 15% hydrogen peroxide aqueous solution to this.
0mA was applied. When the violent dissolution reaction had almost finished, 20 mQ of a 30% aqueous hydrogen peroxide solution was added, and the mixture was left at room temperature. Almost all the contents dissolve in 1 to 2 days,
A red acidic solution was obtained. After filtering out insoluble or undissolved components and decomposing unreacted hydrogen peroxide with a platinum catalyst, drying at room temperature yielded an amorphous powder of peroxidized condensed tungstic acid in which part of the tungsten was replaced with titanium. . This substance is the result of elemental analysis and thermogravimetric analysis.

0.92WO,' 0.08TiO2”D H,02
” mH2O・nCO□(1-0kuα≦K, 0, 16
< m < 4, O≦n≦0.025). Here, sad, m
, n are shown as ranges rather than fixed values because the values of Q, m, and n are likely to change depending on conditions that are difficult to control, such as the holding time of each synthesis process, drying conditions, temperature and humidity in the storage atmosphere, etc. It is.

1 g of peroxide condensed tungstic acid containing titanium thus obtained was dissolved in 1 g of pure water to prepare a peroxide condensed titanium/tungstic acid aqueous solution. 5 g of N,N-dimethylformamide was added to this aqueous solution. This solution was spin-coated onto a silicon wafer to form a coating film (hereinafter referred to as chamber 11IE) having a thickness of about 0.1 μm. After heat treatment at 80°C for 3 minutes, it was kept in air at 25°C and 50% relative humidity for 10 hours.

During this period, the completion time of development in an aqueous sulfuric acid solution adjusted to pH 2 was measured at regular intervals to examine changes in solubility over time. On the other hand, for comparison, a coating film having a thickness of about 0.1 μm (hereinafter referred to as coating film F) was prepared using peroxide condensed titanium/tungstic acid without the addition of N,N-dimethylformamide, and the change in solubility over time was investigated. Table 5 shows the results of comparing changes in the required development time for coatings E and F.

Table 5 As is clear from the results, by adding N,N-dimethylformamide, the insolubilization rate (rate of increase in development time) of peroxidized condensed tungstic acid containing titanium was reduced to 171O, and N,N-dimethyl It has been shown that formamide has the effect of reducing the change in solubility of peroxidized condensed titanium/tungstic acid over time.

Coatings E and F were irradiated with a focused gallium ion beam at an acceleration voltage of 50 kV and a dose of μC/c1. After that, as a result of developing with a pH 2 sulfuric acid aqueous solution and dissolving the unexposed areas, both samples showed a line with a width of 0.3 μm and a 0.3 μm wide line.
A repeating pattern of m wide spaces was formed.

Example 23 As shown in FIG. 1(a), an aluminum film 2, which is a film to be processed, was formed on a silicon substrate l having a step on its surface. On top of that, a polyimide-based heat-resistant polymer resin (manufactured by Hitachi Chemical Co., Ltd., trade name: P) is applied so that the step is flattened.
IQ) was spin-coated and heated at 200° C. for 30 minutes and at 350° C. in nitrogen for 60 minutes to form the lower layer 3 of the organic polymer film.

Furthermore, on the lower WI3, a peroxide condensed niobium-tungstic acid aqueous solution prepared in the same manner as in Example 1 and added with N,N-dimethylformamide was spin-coated to a thickness of 0. tμ
An upper layer 4 of a condensed tungstic acid coating of m was formed. Thereafter, the upper layer 4 was irradiated with an electron beam (acceleration voltage 30 kV) at an irradiation dose of 40 μC/am'' according to a predetermined pattern. After irradiation, a sulfuric acid aqueous solution of pH 2, 12 g of acetic acid and 15 g of sodium acetate were added to the upper layer 4 at a dose of 40 μC/am". An aqueous solution containing 9:
Developing was performed using a solution mixed at a ratio of 1:1. The unirradiated area was dissolved, and an upper layer pattern 4' with a width of 0.3 μm was formed (
Figure 1(b)〉. Subsequently, oxygen ion etching was performed for 1 hour at an oxygen pressure of 2.5 mTorr, and the upper layer pattern 4' was transferred to the lower layer 3, resulting in a lower layer pattern 3' with a width of 0.3 μm (see Figure (C)). ).

Example 24 While cooling 1.2 g of vanadium pentoxide with ice water,
% hydrogen peroxide solution (5 mQ). Insoluble and undissolved components were removed by filtration to obtain a brown peroxide condensed vanadate aqueous solution (hereinafter referred to as aqueous solution A). This aqueous solution gelled at 25° C. for 30 minutes after preparation, making it impossible to apply. Gelation here means that a liquid becomes solid. on the other hand,
Immediately after preparing aqueous solution A, 0.05 g of N,N-dimethylformamide was added. In this aqueous solution (hereinafter referred to as aqueous solution B), gelation began at 25° C. for 5 hours.

As is clear from these results, the addition of N,N-dimethylformamide lowers the gelation rate of peroxide-condensed vanadate to 1/10, and N,N-dimethylformamide reduces the gelation rate of peroxide-condensed vanadate. It was shown to have a suppressive effect.

Aqueous solution B before gelation was spin-coated onto glass coated with a conductive film. Rotation speed during coating is 2000 per minute
The thickness of the coating film was 0.4 μm based on the rotation speed. The peroxidized condensed vanadate in this film was found to have an empirical formula of % by compositional analysis, redox titration, and thermogravimetric analysis. The reason why there is a wide range in the values of x and y is that the composition tends to change depending on how hydrogen peroxide is added when creating the brown solution, changes in atmospheric humidity, etc. This coating film was heated in air at 60° C. for 1 hour. This heat treatment does not change the value of X in the above empirical formula, but y
It was determined by thermogravimetric analysis that the value of is approximately 2. The solubility of the coating film after this heat treatment was lower than that before heating. This coating film was used as a coloring film, and part of it was dissolved in alkaline water to form a current collecting part of a coloring electrode. Using propylene carbonate containing lithium perchlorate as the electrolyte, current 0.2 mA/Cm", electricity amount 10 m C
/cn+". As a result, the yellow film changed to dark green and then to gray-black. Also, when the opposite voltage was applied and oxidized, it was confirmed that it changed to its original yellow color. Even after repeating the above redox treatment, no dissolution of the colored film into the electrolytic solution was observed, indicating good reversibility.

Example 25 Peroxidized condensed vanadate solutions were prepared in the same manner as in Example 24, with various concentrations of N,N-dimethylformamide added. Table 6 shows the results of measuring the gelation initiation time of these solutions at 25°C. The concentration of N,N-dimethylformamide added is weight % relative to peroxidized condensed vanadate.

Table 6 The results are shown in Table 7.

Table 7 The results show that gelation is suppressed even when the concentration of N,N-dimethylformamide added is 1wt%, but it is more preferably 3vt% or more.

Examples 26 to 43 Various water-soluble organic substances having a nitrogen atom other than N,N-dimethylformamide were reacted with peroxidized condensed vanadate to 3
Example 2 A peroxidized condensed vanadate aqueous solution containing wt%
It was prepared in the same manner as 4. The gelation initiation times of these solutions at 25° C. were measured, and the results showed that gelation was suppressed by adding the water-soluble nitrogen-containing organic substance. Further, although the gelation start time varies depending on the type of organic substance, organic substances having an amide group are particularly effective in suppressing gelation.

Example 44 Peroxide condensed vanadate was synthesized by dissolving 1.2 g of metal vanadium in 15% hydrogen peroxide solution. The details of the synthesis are the same as in Example 24.

Add 0.0 of N,N-dimethylformamide to the resulting solution.
5 gti was added. This aqueous solution started to gel in 5 hours at 25°C. The aqueous solution before gelation was spin-coated onto glass coated with a conductive film in the same manner as in Example 24, and
Heat treatment was performed at ℃ for 1 hour.

When coloring and fading due to electrolytic reduction and oxidation was investigated, it was found that the same characteristics as in Example 24 were exhibited.

Example 45 Peroxide condensed vanadium-tungstic acid was synthesized by the following method. 0.3 g of metal vanadium was dissolved in 4 mfl of 15% hydrogen peroxide while cooling with ice water. Insoluble and undissolved components were removed by filtration to obtain a brown solution (aqueous solution C). Next, 11 g of metallic tungsten powder was dissolved in 50 mQ of a 15% hydrogen peroxide aqueous solution. When the dissolution reaction accompanied by intense bubbling had almost come to an end, 20 mQ of a 30% aqueous hydrogen peroxide solution was added, and the mixture was allowed to stand at room temperature. Almost all the contents were dissolved in 1-2 hours and a pale yellow acidic solution was obtained. After filtering out insoluble or undissolved components and decomposing unreacted hydrogen peroxide with a platinum catalyst.

It was dried at room temperature to obtain an amorphous powder of peroxidized condensed tungstic acid. 4.8 g of this peroxidized condensed tungstic acid was dissolved in 2.5 g of pure water (aqueous solution D). The obtained aqueous solution C and the aqueous solution were mixed. 0.05 g of N,N-dimethylformamide was added to this mixed solution. This solution was spin-coated onto glass coated with a conductive film. The rotation speed during coating was 2000 revolutions per minute, and the thickness of the coating film was 0.4μ.
It was m. The peroxide condensed acid in this film is determined by compositional analysis, redox titration, and thermogravimetric analysis. This is because the composition tends to change depending on how it is added, changes in atmospheric humidity, etc.

This coating film was heated in air at 100° C. for 1 hour.

It was determined by thermogravimetric analysis that this heat treatment did not change the value of X in the above experimental formula, but the value of y increased to about 2. The solubility of the colored film after this heat treatment was lower than that before heating. A part of the coloring film was dissolved in an alkaline aqueous solution to form a current collecting part of the coloring electrode. Propylene carbonate containing lithium perchlorate was used as the electrolyte, and the current was 0.
, 2 mA/cm2, electricity ↓Om C/cm2
The coloring film was reduced with

As a result, the colorless film turned black-blue. It was also confirmed that oxidation by applying a reverse voltage causes decolorization.

Example 46 A transparent conductive film containing indium oxide (■n20.) as the main component and having a sheet resistance of 10 Ω/cm2 was coated on a glass substrate to a film thickness of 0.4 μ by the same coating method as in Example 24.
A colored film of m was formed. Next, a coloring film was patterned by ordinary photoresist processing, and the EC shown in Fig. 2 was formed.
I created a D cell.

In the figure, 21 is a glass substrate on the display electrode side, 22 is a transparent conductive film, 23 is a coloring film, 24 is a protective film, 25 is an electrolytic solution,
26 is a counter electrode, and 28 is a spacer 29 which is a background material.

A 1M/Q propylene carbonate solution of lithium perchlorate is used as the cell electrolyte, silicon dioxide is used as the protective film 24 of the transparent conductive film 22, and a porous material containing titanium dioxide, which is a white pigment, is used as the background material 29. A Teflon sheet was used. Further, the counter electrode 26 used was one in which fibrous carbon 26# was bonded onto a transparent conductive film 26' having a sheet resistance of 10 Ω/can2.

The voltage applied to this cell during color development is 1. OV (negative on the coloring film side, positive on the counter electrode side), applied voltage when decoloring is 1.5V
(The coloring film side was positive and the counter electrode side was negative), a square wave was continuously applied, and the characteristics of Elec 1 to Rochromink were investigated. As a result, color changes of yellow, green, and gray were observed. Also, the optical density change (Δ○, D,) 0 at a wavelength of 800 nm
．． The amount of injected charge required to obtain 5 is approximately 30 mC/
cm". These characteristics are comparable in performance to conventional elements using vanadium oxide as a coloring film.

〔Effect of the invention〕

As described in detail above, according to the present invention, a peroxidized condensed acid can be stably retained by the water-soluble nitrogen-containing organic substance.

Furthermore, a composition containing a water-soluble nitrogen-containing organic substance and an aqueous peroxide condensed acid solution can be stably maintained.

Furthermore, by including a water-soluble nitrogen-containing organic substance, it is possible to reduce changes in solubility over time due to changes in temperature, humidity, etc. of the inorganic radiation-sensitive composition, making it possible to establish a reproducible lithography process. .

Furthermore, by using a coating composition containing a water-soluble nitrogen-containing organic substance, EC can be applied using a simple and stable wet coating method.
D can be stably produced.

[Brief explanation of drawings]

FIG. 1 is a process diagram for explaining the process of an embodiment of the pattern forming method of the present invention, and FIG. 2 is a sectional view showing a schematic structure of an embodiment of the ECD of the present invention. 1... Silicon substrate 2... Aluminum intestine 3
...lower layer 3'...lower layer pattern 4.
... Upper layer 4'... Upper layer pattern 21.
...Substrate 22...Transparent conductive film 23...
Coloring film 24...Protective film 25...Electrolyte solution
26... Counter electrode 26'... Transparent conductive film
26″...Fibrous carbon 27...Substrate
28... Spacer 29... Background material

Claims (1)

[Claims] 1. A stabilizer for peroxidized condensed acid comprising a water-soluble nitrogen-containing organic substance. 2. The stabilizer for peroxycondensed acid according to claim 1, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitriles, amines, and amides. 3. The peroxide condensed acid stabilizer according to claim 1, wherein the peroxide condensed acid contains at least tungsten. 4. The peroxide condensed acid stabilizer according to claim 1, wherein the peroxide condensed acid contains at least vanadium. 5. A composition comprising a water-soluble nitrogen-containing organic substance and an aqueous solution of peroxycondensed acid. 6. The composition according to claim 5, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitriles, amines, and amides. 7. The composition according to claim 5, wherein the peroxide condensed acid contains at least tungsten. 8. The composition according to claim 5, wherein the peroxide condensed acid contains at least vanadium. 9. A method for producing a composition containing peroxycondensed acid, which comprises adding a water-soluble nitrogen-containing organic substance to an aqueous solution of peroxycondensed acid. 10. A radiation-sensitive composition comprising an aqueous solution of peroxycondensed acid containing tungsten and a water-soluble nitrogen-containing organic substance. 11. The radiation-sensitive composition according to claim 10, wherein the peroxide condensed acid contains tungsten and at least one element selected from the group consisting of niobium, tantalum, and titanium. 12. The radiation-sensitive composition according to claim 10, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitriles, amines, and amides. 13. The radiation-sensitive composition according to claim 10, wherein the water-soluble nitrogen-containing organic substance is contained in a concentration of 1% by weight or more based on the peroxide condensed acid. 14, General formula (1-x-y-z)WO_3・x/2Nb_2O_5・
y/2Ta_2O_5・zTiO_2・lH_2O_2
・mH_2O・nCO_2 (However, x, y, z, l,
m and n are 0≦x+y+z<1, 0<l≦1, 0, respectively
．． 16<m<4, 0≦n≦0.025) A radiation-sensitive composition comprising an aqueous solution of peroxycondensed acid and a water-soluble nitrogen-containing organic substance. 15. The radiation-sensitive composition according to claim 14, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitriles, amines, and amides. 16. The radiation-sensitive composition according to any one of claims 10 to 15 is applied onto a substrate to form a coating film, and the coating film is irradiated with radiation in a desired pattern and developed. A pattern forming method. 17. A composition for a coloring film of an electrochromic display element, comprising an aqueous solution of a peroxide condensed acid containing vanadium and a water-soluble nitrogen-containing organic substance. 18. The composition for a coloring film of an electrochromic display element according to claim 17, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitriles, amines, and amides. 19, General formula 2lWO_3・2mMoO_3・(1-l-m)V_2
O_5・xH_2O_2・yH_2O (however, l, m,
x and y are respectively 0≦l+m<1, 0.05≦x≦1,
1. A composition for a coloring film of an electrochromic display element, comprising an aqueous solution of a peroxycondensed acid represented by the following formula (1.5≦y≦3) and a water-soluble nitrogen-containing organic substance. 20. The composition for a coloring film of an electrochromic display element according to claim 19, wherein the water-soluble nitrogen-containing organic substance contains at least one organic substance selected from the group consisting of nitriles, amines, and amides. 21. Claims 17 to 2 on the substrate on which the conductive film is formed.
An electrochromic display element comprising at least a coloring film formed by coating and heating the composition for a coloring film of an electrochromic display element according to any one of items 1 to 0 above, a counter electrode, and an electrolyte held between the two.