JP3305629B2 - UV curable transparent conductive film forming coating liquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transparent conductive metal oxide which is finely patterned by coating and drying on glass, ceramic, etc., irradiating with ultraviolet rays while leaving a photomask, and developing and firing. In addition, the present invention provides a coating liquid for forming an ultraviolet-curable transparent conductive film which can be developed with water, which does not pollute the environment during development and has excellent work safety, and a method for producing the same.

[0002]

2. Description of the Related Art A transparent conductive film is used as a display tube such as a liquid crystal display, a fluorescent display tube and a plasma display, and a transparent electrode such as a solar cell and a touch panel. Indium oxide and tin oxide films are known as such transparent conductive films.

[0003] As a method of forming a pattern of these films,
The transparent conductive paste obtained by printing by screen printing or the like using a transparent conductive paste, baking the printed film to obtain a patterned transparent conductive film, and evaporating, sputtering, applying and baking the resulting transparent conductive film. A method of forming a pattern of a transparent conductive film by masking in a pattern with a resist or the like and etching with a strong acid such as aqua regia has been used. However, in each of these methods, the former is difficult to form a fine pattern of 100 μm or less due to paste leveling or bleeding, and the latter lacks safety due to the use of strong acids for etching. There is a drawback such as that processing of is difficult.

[0004] Separately from this method, a photosensitive resin is added to a solution containing an indium compound and a tin compound, and the solution is applied to a substrate, dried, exposed, developed, and fired to form a patterned transparent film. A method for obtaining a conductive film has been considered. An example using this method is disclosed in JP-A-2-109.
27. A transparent conductive film having a pattern formed from a coating liquid for forming a transparent conductive film comprising an indium compound, a tin compound, a radiation curable resin, and an organic solvent according to 27.
However, when this coating solution is used, since the components of the coating solution are dissolved in the water-insoluble organic solvent, a non-water-soluble organic solvent such as xylene must be used as a developing solution during development. However, work safety is lacking, and there is a problem that exhaust equipment and the like need to be installed and the air is polluted.

[0005]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, a method for easily and inexpensively manufacturing a transparent conductive film patterned on a substrate such as glass, and a material suitable therefor are developed. As a result of diligent research, we used a water-soluble organic polymer that can be developed with water without using a water-insoluble organic solvent in the developer, and added an additive to dissolve the indium compound and tin compound. The inventors have found that the above problem can be solved by preparing a coating liquid for forming an ultraviolet-curable transparent conductive film which is stable for a long time.

More specifically, using fatty acid indium as an indium compound and fatty acid tin as a tin compound,
By adding ethanolamine as an additive,
Fatty acid indium is made soluble in water, and hydrolysis of fatty acid tin is suppressed for long-term stabilization.Furthermore, carboxylic acid is added to clear aqueous solution of fatty acid tin dissolved in water, or ethanolamine is added. By making the fatty acid indium soluble in alcohol, the hydrolysis of fatty acid tin is suppressed, and the long-term stabilized transparent alcohol solution is added to the water-soluble organic polymer and photocrosslinking agent, A coating liquid for forming an ultraviolet-curable transparent conductive film can be prepared. This coating liquid is applied to a substrate such as glass and dried to form a dried coating film for forming a transparent conductive film, and a predetermined film is formed on the dried film. The patterned photomask is left standing, irradiated with ultraviolet rays, and developed with water to obtain a patterned dry film, which is baked at a temperature of 300 ° C. or more. Finely to form a transparent conductive film which is patterned in a easily found that to achieve its objectives, the present invention has been attained.

That is, the present invention can not only form a finely patterned oxide film having excellent transparency and conductivity, which was impossible with the prior art, but also contaminate the environment during pattern formation. In addition, the present invention provides a coating liquid which can be developed with water, which has excellent work safety, and a method for producing the same.

The coating solution of the present invention uses water as a developing solution as compared with the coating solution of the prior art, that is, a coating solution comprising an indium compound, a tin compound, a radiation curable resin and an organic solvent. And is advantageous in that the work safety is excellent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION There are two types of coating solutions of the present invention, a transparent aqueous solution and a transparent alcohol solution. First, a method for producing a transparent aqueous solution will be described. Ethanolamine is added to a mixture of fatty acid indium and water to produce a transparent aqueous solution of fatty acid indium.

In this case, when the fatty acid indium is mixed with water only, the fatty acid indium is not dissolved but exists as a solid dispersed or precipitated, and cannot be used as a coating solution as it is. By adding an appropriate amount of ethanolamine to this, all of the fatty acid indium is dissolved, and a homogeneous stable transparent aqueous solution is obtained. Therefore, ethanolamine completely dissolves indium fatty acid in water, and makes it possible to prepare a long-term stable transparent aqueous solution of indium fatty acid.

The indium fatty acid used as the indium source includes, for example, indium acetate and indium propionate. Fatty acid salts having a large number of carbon atoms have a large weight loss during thermal decomposition. preferable. The amount of water as the solvent is preferably such that the indium concentration becomes 0.05 to 2 mol / l. This amount keeps the indium concentration in the solution at an appropriate value,
In addition, this is an amount for obtaining a viscosity suitable for coating. If the solvent is too large, the indium concentration becomes low, and a thin film with insufficient conductivity may be formed, which is not preferable. On the other hand, if the amount of the solvent is too small, the viscosity may increase, or the composition may become unsuitable as a coating solution, cracking may occur in the coating film, or a film having low visible light transmittance may be formed.

Next, apart from the transparent aqueous solution of indium fatty acid described above, a fatty acid tin and ethanolamine are mixed to prepare a transparent solution of fatty acid tin. If necessary, a small amount of alcohol may be added.

The tin fatty acid is easily hydrolyzed and is hydrolyzed by water. Therefore, by adding ethanolamine to the fatty acid tin and coordinating the fatty acid tin with the ethanolamine, hydrolysis of the fatty acid tin is suppressed, and the fatty acid tin is stabilized with respect to water. Therefore, ethanolamine suppresses hydrolysis of the fatty acid tin, and enables the production of a stable transparent solution of the fatty acid tin. When the transparent solution of fatty acid tin and ethanolamine becomes very viscous and lacks workability, a small amount of alcohol may be added to the transparent solution to reduce the viscosity.

Examples of the tin fatty acid used include tin acetate, tin propionate, tin caproate, and tin 2-ethylhexanoate. When alcohol is added, the alcohol to be added is, for example, methanol,
Ethanol, n-propanol, i-propanol and the like can be mentioned. When the alcohol is added, the amount is preferably such that the concentration of the fatty acid tin becomes 0.5 mol / l or more. This amount is to lower the proportion of alcohol in the solution after adding the tin solution to the indium aqueous solution.

Next, after the carboxylic acid is added to the above-mentioned transparent aqueous solution of fatty acid indium, the above-mentioned transparent solution of fatty acid tin is added to obtain a transparent aqueous solution in which fatty acid indium and fatty acid tin are dissolved.

When a transparent solution of fatty acid tin is added to a transparent aqueous solution of indium fatty acid to which no carboxylic acid is added, the fatty acid tin to which ethanolamine is coordinated does not dissolve in water as it is, so that the fatty acid tin solution is separated. Therefore, by adding carboxylic acid to a transparent aqueous solution of fatty acid indium in advance to make the aqueous solution acidic, it becomes possible to dissolve the fatty acid tin in the transparent aqueous solution of fatty acid indium. The amount of the carboxylic acid to be added is preferably such that the pH of the transparent aqueous solution of indium fatty acid becomes 5 or less. This amount is for preparing a stable transparent aqueous solution. If the pH of the indium aqueous solution is higher than 5, the solubility of the fatty acid tin in the indium aqueous solution may be insufficient, resulting in a separated coating solution.

The amount of the transparent solution of fatty acid tin added to the transparent aqueous solution of indium fatty acid is such that the concentration of fatty acid tin in the aqueous solution is 1 to 25 (mol%) with respect to the concentration of indium fatty acid. preferable. Considering the conductivity of the transparent conductive film to be produced, the ratio of the indium concentration to the tin concentration is preferably the above-mentioned mol%.

The amount of ethanolamine added to prepare a transparent aqueous solution of fatty acid indium is such that the amount of ethanolamine is 1 to the mole of fatty acid indium.
When the molar ratio is less than (molar ratio), the dissolution of the fatty acid indium is insufficient, and the coating may result in a rough coated film on which undissolved fatty acid indium particles are deposited. Therefore, the addition amount of ethanolamine is preferably 1 (molar ratio) or more with respect to the mole of fatty acid indium. When the amount of ethanolamine added to the fatty acid tin is less than 1 (molar ratio) to the mole of fatty acid tin, the hydrolysis of fatty acid tin is not sufficiently controlled, and Precipitation and white turbidity of the coating solution may occur. Therefore, the amount of ethanolamine added is preferably 1 (molar ratio) or more based on the mole of fatty acid tin. Further, when the amount of ethanolamine to be added is more than 8 (molar ratio) with respect to the total mole of fatty acid indium and fatty acid tin, unevenness may occur in the coating film. Therefore, the amount of ethanolamine added to the transparent aqueous solution in which indium fatty acid and fatty acid tin are dissolved is preferably 8 (molar ratio) or less with respect to the total mole of fatty acid indium and fatty acid tin.

The ethanolamine to be added includes monoethanolamine, diethanolamine and triethanolamine. Ethanolamine may be used alone or in combination of two or more. As the carboxylic acid to be added, for example, acetic acid, propionic acid,
Tartaric acid, citric acid, gluconic acid and the like can be mentioned. One type of carboxylic acid may be used, or two or more types may be used. A transparent aqueous solution from which a transparent conductive film can be formed by the above manufacturing method is obtained.

By adding a water-soluble organic polymer and a photocrosslinking agent to the above-mentioned transparent aqueous solution, a coating liquid for forming an ultraviolet-curable transparent conductive film is produced. Examples of the water-soluble organic high-molecular polymer include polyvinylpyrrolidone and a copolymer of vinylpyrrolidone and vinyl acetate. The water-soluble organic polymer may be used alone or in combination of two or more. If the weight average molecular weight of polyvinylpyrrolidone is less than 100,000, the molecular chain is short,
After the ultraviolet irradiation, curing of the film at the ultraviolet irradiation portion becomes insufficient, and the film at the ultraviolet irradiation portion may be removed during development. On the other hand, when the weight average molecular weight is larger than 2900000, the effect of stringiness of the coating liquid is increased, and it may be difficult to obtain a uniform coating film. Therefore, when polyvinylpyrrolidone is used, it is preferable to select one having a weight average molecular weight of 100,000 to 29,000,000.

When the amount of the water-soluble organic high molecular polymer to be added is less than 0.05 (weight ratio) with respect to the above-mentioned coating solution, the resin component in the dried coating solution for forming the transparent conductive film is small. Insufficient curing of UV-irradiated parts after UV irradiation,
At the time of development, the film at the portion irradiated with ultraviolet rays may be removed. When the amount of the water-soluble organic high molecular polymer to be added is more than 0.3 (weight ratio) with respect to the above-mentioned coating liquid, the amount of the resin component in the dried coating liquid for forming the transparent conductive film is large. There are many components that burn and decompose in the film, which may cause cracks in the fired film or increase the resistance value of the fired film. Therefore, the amount of the water-soluble organic high molecular polymer to be added is preferably 0.05 to 0.3 (weight ratio) with respect to the above coating solution.

Examples of the photocrosslinking agent include bisazide compounds. The bisazide compound can be exemplified by sodium 4,4′-diazidostilbene-2,2′-disulfonate (ultraviolet functional type, water-soluble), and can be selected in accordance with the wavelength of the irradiated ultraviolet light. The amount of the photocrosslinking agent to be added is 0.05 to 0.
It is preferably within the range of 2 (weight ratio). The transparent aqueous solution obtained by the above-described manufacturing method is optimal as a coating liquid for forming a transparent conductive film finely patterned by ultraviolet curing.

A method for producing a transparent alcohol solution, which is another type of coating solution, will be described. The fatty acid indium and the fatty acid tin are mixed in the alcohol so that the tin concentration in the alcohol solution is preferably 1 to 25 (mol%) with respect to the indium concentration. In consideration of conductivity, the ratio between the indium concentration and the tin concentration is preferably the above-mentioned mol%.

The mixed solution of the fatty acid indium and the alcohol also exists as a solid dispersed or precipitated without dissolving the fatty acid indium, and cannot be used as a coating solution as it is. By adding an appropriate amount of ethanolamine to this, all of the fatty acid indium is dissolved, and a homogeneous and stable transparent solution is obtained. In addition, the fatty acid tin is easily hydrolyzed, and if used as a coating solution as it is, the coating film is hydrolyzed by moisture in the air when dried, or hydrolyzed and whitened during development with water. I will. Thus, by adding ethanolamine to coordinate the fatty acid tin with the ethanolamine, hydrolysis of the fatty acid tin is suppressed, and a transparent alcohol solution stable to water is obtained. Therefore, ethanolamine completely dissolves fatty acid indium in alcohol and suppresses hydrolysis of fatty acid tin, thereby making it possible to produce a long-term stable transparent alcoholic solution of fatty acid indium and fatty acid tin, and applying this solution. Plays a role in keeping the transparent and homogeneous film.

The fatty acid indium used as the indium source includes, for example, indium acetate, indium propionate and the like. Fatty acid salts having a large number of carbon atoms have a large weight loss during thermal decomposition. preferable. Examples of the alcohol to be used include methanol, ethanol, n-propanol, i-propanol and the like. The amount of the alcohol is preferably such that the indium concentration becomes 0.05 to 2 mol / l. This amount is an amount for keeping the indium concentration in the liquid at an appropriate value, and for making the viscosity suitable for coating.If the solvent is too much, the indium concentration becomes low, and the coating film thickness is insufficient and the conductivity is not sufficient. A film may be formed, which is not preferable. On the other hand, if the amount of the solvent is too small, the viscosity may increase, or the composition may become unsuitable as a coating solution, cracking may occur in the coating film, or a film having low visible light transmittance may be formed.

If the amount of ethanolamine to be added is less than 1 (molar ratio) to the total moles of fatty acid indium and fatty acid tin, the dissolution of fatty acid indium is insufficient.
During coating, undissolved fatty acid indium particles are deposited on the surface to form a rough coated film, hydrolysis of fatty acid tin is not sufficiently controlled, and it is hydrolyzed by atmospheric moisture, or when developed with water. May be hydrolyzed and whitened. Further, the amount of ethanolamine to be added is 8 (molar ratio) with respect to the total mole of fatty acid indium and fatty acid tin.
If the number is larger, unevenness may occur in the coating film. Therefore, the amount of ethanolamine to be added is 1 to 8 with respect to the total mole of fatty acid indium and fatty acid tin.
(Molar ratio) is preferred.

The ethanolamine to be added includes monoethanolamine, diethanolamine and triethanolamine. Ethanolamine may be used alone or in combination of two or more.

The fatty acid tin used includes, for example, tin acetate, tin propionate, tin caproate, tin 2-ethylhexanoate and the like. A transparent alcohol solution from which a transparent conductive film can be formed by the above manufacturing method is obtained.

By adding a water-soluble organic polymer and a photocrosslinking agent to the above-mentioned transparent alcohol solution, a coating liquid for forming an ultraviolet-curable transparent conductive film is produced. Examples of the water-soluble organic high-molecular polymer include polyvinylpyrrolidone and a copolymer of vinylpyrrolidone and vinyl acetate.
As the water-soluble organic high-molecular polymer, only one type may be used, or two or more types may be used. If the weight average molecular weight of polyvinylpyrrolidone is less than 100,000, the molecular chain is short, so that the curing of the film irradiated with the ultraviolet rays becomes insufficient after the irradiation of the ultraviolet rays, and the film irradiated with the ultraviolet rays may be removed during the development. The weight average molecular weight is 29000
If it is larger than 00, the influence of the stringing property of the coating liquid becomes large, so that it may be difficult to obtain a uniform coating film. Therefore, when polyvinylpyrrolidone is used, it is preferable to select one having a weight average molecular weight of 100,000 to 29,000,000.

When the amount of the water-soluble organic high molecular polymer to be added is less than 0.05 (weight ratio) with respect to the above-mentioned coating solution, the resin component in the dried coating solution for forming a transparent conductive film is small. Insufficient curing of UV-irradiated parts after UV irradiation,
At the time of development, the film at the portion irradiated with ultraviolet rays may be removed. When the amount of the water-soluble organic high molecular polymer to be added is more than 0.3 (overlap ratio) with respect to the above-mentioned coating liquid, the resin component in the dried coating liquid for forming the transparent conductive film is large. There are many components that burn and decompose in the film, which may cause cracks in the fired film or increase the resistance value of the fired film. Therefore, the amount of the water-soluble organic high molecular polymer to be added is preferably 0.05 to 0.3 (weight ratio) with respect to the above coating solution.

Examples of the photocrosslinking agent include a mixed form of a bisazide compound and an organic carboxylic acid or an organic carboxylic anhydride. The bisazide compound is exemplified by 4,4'-diazidobenzalcyclohexanone (ultraviolet functional type, alcohol-soluble), and can be selected according to the wavelength of the irradiation ultraviolet light. Examples of the organic carboxylic acid include benzoic acid and cinnamic acid. Examples of the organic carboxylic anhydride include phthalic anhydride and maleic anhydride. The effect of the mixed form of the bisazide compound and the organic carboxylic acid or organic carboxylic acid anhydride is that, when the bisazide compound is used alone, the water resistance of the film irradiated with ultraviolet light after the irradiation of ultraviolet light is insufficient, The film of the irradiated part may be removed. On the other hand, by using the mixed form of the bisazide compound and the organic carboxylic acid or the organic carboxylic acid anhydride, the water resistance of the film irradiated with the ultraviolet light is improved after the irradiation of the ultraviolet light, and the film irradiated with the ultraviolet light is removed during the development. Disappears.

The amount of the photocrosslinking agent to be added is such that the addition amount of the bisazide compound is 0.05 to 0.1 (weight ratio) based on the weight of the water-soluble organic polymer, and the amount of the organic carboxylic acid or organic carboxylic anhydride is Is preferably 0.1 to 1.0 (weight ratio) with respect to the water-soluble organic polymer. The transparent alcohol solution obtained by the above manufacturing method is optimal as a coating liquid for forming a transparent conductive film finely patterned by ultraviolet curing.

As a method of applying the two kinds of coating liquids produced as described above, screen printing, roll coating, bar coating, spin coating, immersion, etc. are excellent methods for easily producing a uniform film. After a coating solution is formed on the surface of a substrate such as glass by the above method, the coating solution is dried at, for example, 90 to 120 ° C. for 30 minutes to 2 hours to remove the solvent, thereby forming a dried coating film for forming a transparent conductive film. . Next, a photomask having a predetermined pattern is left on the dried film of the coating liquid for forming a transparent conductive film, irradiated with ultraviolet rays, and developed by dipping or spraying water. Developing and dissolving and removing the transparent conductive film-forming coating liquid dried film in the unirradiated portion of the ultraviolet ray, and holding the substrate holding the patterned transparent conductive film-forming coating liquid dried film at, for example, a temperature of 300 ° C. or more for 10 minutes to
Perform baking for 2 hours. Regarding the firing atmosphere, the firing may be performed in the air or oxygen, and in some cases, the firing may be performed subsequently in an inert atmosphere (nitrogen, argon, or the like) or a reducing atmosphere. By this method, a finely patterned transparent conductive film is obtained.

As described above, the coating liquid of the present invention is inexpensive, easily and highly productive, and can form a finely patterned transparent conductive film. Can be developed with water having excellent properties.

[0035]

【Example】

Example 1 0.5 mol of indium acetate and 650 ml of water were mixed and stirred, and the mixture was mixed with 0.25 mol of monoethanolamine.
and 0.75 mol of diethanolamine,
The mixture was mixed for 1 hour to obtain an indium acetate aqueous solution. Next, 2
-0.038 mol of tin ethylhexanoate, 0.13 mol of monoethanolamine and 0.3 of diethanolamine
8 mol was mixed for 1 hour to obtain a tin 2-ethylhexanoate solution. 6 mol of acetic acid was added to the aqueous solution of indium acetate, followed by addition of the solution of tin 2-ethylhexanoate, and mixing for 1 hour to obtain a transparent aqueous solution in which indium acetate and tin 2-ethylhexanoate were dissolved. Indium acetate was completely dissolved by the reaction with monoethanolamine and diethanolamine. Further, the hydrolysis of tin 2-ethylhexanoate was suppressed by the reaction with monoethanolamine and diethanolamine, and dissolved in water by addition of acetic acid to obtain a transparent aqueous solution. This solution 1
Polyvinylpyrrolidone (ISP J
K-90 manufactured by APAN, weight average molecular weight 1270000)
10 parts by weight and 4,4'-diazidostilbene-2,
0.5% by weight of sodium 2'-disulfonate was added and mixed for 1 hour to obtain a coating liquid for forming an ultraviolet-curable transparent conductive film. This coating solution was very stable, and remained transparent without any precipitation or cloudiness of the solution even after standing at room temperature for one year.

The coating solution for forming the ultraviolet-curable transparent conductive film thus prepared was coated with a bar coat (No. 14, wire diameter of about 360 μm).
m) to form a coating film on the glass substrate. The coated film was dried at 100 ° C. for 1 hour to remove the solvent and cure the film. A photomask (line width 250
μm, 80 μm between lines) and set to ultraviolet light (80 mW / cm
After irradiation of ² ), the dried film irradiated with ultraviolet rays was developed by spraying water. Developing was performed to remove the unexposed portion of the dried film, and the patterned dried film was fired in an electric furnace at 550 ° C. for 30 minutes in the air to obtain a finely patterned transparent conductive film. The finely patterned transparent conductive film of this embodiment can reproduce the pattern of the photomask, has a thickness of 0.5 μm, and has a sheet resistance of 7 kΩ /
It was □. Further, it was found that the visible light transmittance was as high as 91%.

Example 2 The composition of the tin 2-ethylhexanoate solution was 0.038 mol of tin 2-ethylhexanoate and 0.1% of ethanolamine.
A UV-curable transparent conductive film forming coating solution was prepared using 3 mol, diethanolamine 0.38 mol, and n-propanol 20 ml, and using the same aqueous coating solution for forming a transparent conductive film as in Example 1 except for the above. The coating liquid for forming the ultraviolet-curable transparent conductive film thus prepared was coated with a bar coat (No. 14,
A coating film was formed on a glass substrate with a wire diameter of about 360 μm. The coated film was dried at 100 ° C. for 1 hour to remove the solvent and cure the film. A photomask (line width: 250 μm, line interval: 80 μm) was allowed to stand on the dried film, irradiated with ultraviolet rays (80 mW / cm ² ), and developed by immersing the glass substrate in water. Developing was performed to remove the unexposed portion of the dried film, and the patterned dried film was fired in an electric furnace at 550 ° C. for 30 minutes in the air to obtain a finely patterned transparent conductive film. The finely patterned transparent conductive film of this embodiment can reproduce the pattern of the photomask, and has a thickness of 0.5 μm and a sheet resistance of 7 k.
Ω / □. Further, it was found that the visible light transmittance was as high as 91%.

Example 3 0.5 mol of indium acetate and 0.038 mol of tin 2-ethylhexanoate were mixed and stirred in 1000 ml of n-propanol, and the mixture was mixed with 0.25 mol of monoethanolamine and 0.75 mol of diethanolamine.
1 and mix for 1 hour. Indium acetate was completely dissolved by the reaction with monoethanolamine and diethanolamine, and hydrolysis of tin 2-ethylhexanoate was suppressed by the reaction with monoethanolamine and diethanolamine, whereby a clear solution was obtained. To 100 parts by weight of this solution, polyvinylpyrrolidone (I
6.7 parts by weight of SPVP, PVP K-90, weight average molecular weight 1270000) and a copolymer of vinylpyrrolidone and vinyl acetate (ISP Japan, PVP /
VA E-735, vinylpyrrolidone: vinyl acetate =
7: 3) 13.4 parts by weight, 2,4 parts by weight of 4,4'-diazidobenzalcyclohexanone and 2.5 parts by weight of benzoic acid are added, mixed for 1 hour, and coated for forming an ultraviolet-curable transparent conductive film. A liquid was obtained. The coating solution was very stable, and remained transparent without any precipitation or cloudiness of the solution even after standing at room temperature for one year.

The coating solution for forming the ultraviolet-curable transparent conductive film thus prepared was coated with a bar coat (No. 14, a wire diameter of about 360 μm).
m) to form a coating film on the glass substrate. The coated film was dried at 100 ° C. for 1 hour to remove the solvent and cure the film. A photomask (line width 250
μm, 80 μm between lines) and set to ultraviolet light (80 mW / cm
After irradiation of ² ), the glass substrate was developed by immersing it in water. Develop to remove the dried film in the unexposed portion of the ultraviolet light.
Firing was performed in the air for 0 minutes to obtain a finely patterned transparent conductive film. The finely patterned transparent conductive film of this example was able to reproduce the pattern of the photomask, and had a thickness of 0.5 μm and a sheet resistance of 10 kΩ / □. Further, it was found that the visible light transmittance was as high as 91%.

From the results of the above examples, it can be seen that the coating liquid of the present invention is stable for a long period of time, does not pollute the environment, can be developed with water having excellent work safety, and can be easily formed into a finely patterned transparent liquid. A conductive film was obtained, and the film was found to be excellent in transparency and conductivity.

[0041]

The coating liquid for forming an ultraviolet-curable transparent conductive film of the present invention is applied to a substrate such as glass, dried, irradiated with ultraviolet light, developed and baked while a photomask is allowed to stand, to form a fine pattern. The formed dense film exhibits high transmission characteristics with respect to light in the visible light region and has excellent conductivity. The coating solution of the present invention is inexpensive and easily productive, and can form a finely patterned transparent conductive film, and can be developed with water that does not pollute the environment and is excellent in work safety during pattern formation. It is possible to do.

Continued on the front page (72) Inventor Tomoyo Shimura 2-9-19-1 Kamimaezu, Naka-ku, Nagoya-shi, Aichi Tsuchi Indoor Co., Ltd. Tsuchi indoor (72) Inventor Yasuyuki Ohara 2-9-1-9 Kamimaezu, Naka-ku, Nagoya-shi, Aichi Tsuchi indoor Co., Ltd. (56) References JP-A-6-325637 (JP, A) JP-A-6-136162 (JP) JP-A-1-287278 (JP, A) JP-A-63-19713 (JP, A) JP-A-62-29016 (JP, A) JP-B-56-25723 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 5/24 H01B 13/00 503 H01B 1/00-1/24 H01B 5/14

Claims (4)

(57) [Claims] 1. A fatty acid indium of the formula In (OCOR) ₃ (where R represents a linear or branched alkyl group having 1 to 8 carbon atoms) and a formula Sn (OCOR ′) _{2 wherein} R '
Represents a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms.) An ultraviolet-curable transparent conductive material containing a fatty acid tin, ethanolamine, carboxylic acid, water, a water-soluble organic polymer, and a photocrosslinking agent. Coating solution for film formation. 2. A fatty acid indium of the formula In (OCOR) ₃ , wherein R represents a linear or branched alkyl group having 1 to 8 carbon atoms, and a formula Sn (OCOR ′) ₂ , wherein R '
Represents a linear or branched alkyl group having 1 to 8 carbon atoms) for forming an ultraviolet-curable transparent conductive film containing a fatty acid tin, ethanolamine, an alcohol, a water-soluble organic polymer, and a photocrosslinking agent. Coating liquid. 3. A transparent aqueous solution obtained by adding ethanolamine to indium fatty acid of the formula In (OCOR) ₃ (wherein R represents a linear or branched alkyl group having 1 to 8 carbon atoms) and water. After that, a solution obtained by adding a carboxylic acid to this solution was mixed with a solution of the formula Sn (OCOR ') ₂ (wherein R' has 1 to 8 carbon atoms).
2. A transparent solution obtained by adding ethanolamine to a fatty acid tin having a linear or branched alkyl group), a water-soluble organic polymer and a photo-crosslinking agent are mixed. A method for producing a coating liquid for forming an ultraviolet-curable transparent conductive film. 4. A fatty acid indium of the formula In (OCOR) ₃ , wherein R represents a linear or branched alkyl group having 1 to 8 carbon atoms, and a formula Sn (OCOR ′) ₂ , wherein R '
Represents a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms). Ethanolamine is added to a mixed solution of a fatty acid tin and alcohol to form a transparent alcohol solution, and further photocrosslinked with a water-soluble organic polymer. The method for producing a coating liquid for forming an ultraviolet-curable transparent conductive film according to claim 2, wherein an agent is added.