JPH11158427A - Preparation of ink for forming transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation method of an ink for forming a transparent conductive film which ink can be used for forming a dense and uniform transparent conductive film and is excellent in continuous printability. SOLUTION: A solution for forming a transparent conductive film comprises at least one kind of partially hydrolyzed organic metal compound, an alcohol having a boiling point of 30-below 150 deg.C, at least one kind of low boiling-point solvent selected from alcoholes, ketones, esters and ethers, at least one kind of stabilizer selected from amines, organic acids, inorganic acids, β-diketones and β-ketoesters. This solution is concentrated at normal temperature to 60 deg.C to form a viscous solution. Then at least one kind of high boiling-point solvent selected from glycols, carbitols and cellosolves having a boiling point of 150-280 deg.C is added into the viscous solution to control the ink such that the high boiling-point solvent be to occupy 40-95 wt.% of the solvents and the ink viscosity be 5-200 mPa.s.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display device,
For forming a transparent conductive film used for various electronic components such as flat displays and touch panels such as electroluminescent elements, plasma display elements, fluorescent display tubes, and field emission displays. The present invention relates to a method for producing an ink.

[0002]

2. Description of the Related Art As a method of forming a wet transparent conductive film, an organic metal compound such as an organic acid salt containing a chelate compound such as indium or tin, or a metal alkoxide such as an alcoholate, a solvent for dissolving the organic metal compound, and an acid. , Using an ink for forming a transparent conductive film composed of an additive such as a base or a thickener, by a coating method such as a spin coating method, a dipping method, and a printing method such as a screen printing method, an offset printing method, and a gravure printing method. There is a method of forming a film. In the coating method, since a film can be formed only by a coating step and a baking step, the steps are simple and advantageous in cost. The printing method is more advantageous because the amount of ink used is smaller than that of the coating method.

For example, there is a printing method using a thin film forming apparatus as disclosed in Japanese Patent Publication No. 3-11630 (see FIG. 1). The thin film forming apparatus includes an intaglio roll 3 rotatably supported by a support frame 2 of a base 1 and having a large number of ink cells having a depth of 1.0 to several tens μm on a surface thereof, and an intaglio roll 3 having a surface of 1.0 to 30,000 mPa · and an ink supply device 5 for supplying the s ink, and provided at a predetermined location around the intaglio roll 3 supported by the support frame 2, and the ink supplied to the intaglio roll 3 is spread over the surface of the intaglio roll 3 and kept in the ink cell. A doctor 6 for holding an amount of ink and an intaglio roll 3 for the support frame 2
A printing roll 4 rotatably supported below and having a convex portion 7 in contact with the intaglio roll 3 to transfer the ink in the ink cells to the convex portion 7 on the surface of the intaglio roll 3; A driving device 8 for synchronously driving the roll 4 and the intaglio roll 3, a printing position A on which the printing medium is placed and in contact with the printing roll 4 on the base 1, and a retracting position B separated from the printing roll 4; Surface plate 9 movably with C
A printing medium driving device 10 for moving the platen 9 between the two positions; a rotation of the printing roll 4 and a retreat position B of the platen 9;
The control device (not shown) controls the movement from C to the printing position A and prints the ink transferred to the convex portion 7 of the printing roll 4 on the printing medium.

When a thin film forming apparatus having such a configuration is used, a thin film having a constant film thickness can be easily formed.

[0005]

However, the transparent conductive film forming ink used in the above thin film forming apparatus has the following problems.

[0006] As disclosed in Japanese Patent Application Laid-Open No. 60-1703, there is an ink for forming a transparent conductive film in which the solvent is only a low boiling point solvent such as alcohol. However, when the above-described thin film forming apparatus is used, the transparent conductive film forming ink is dried when the transparent conductive film forming ink is supplied to the intaglio roll 3 of the thin film forming apparatus, and the transparent conductive film formation ink is formed on the printing medium. Since the ink for transfer cannot be transferred, a transparent conductive film cannot be formed.

[0007] Not only low-boiling solvents, but also
As disclosed in Japanese Patent Publication No. 018, a mixed solvent of 97 to 80% by weight of a low boiling point solvent having a boiling point of 30 to 100 ° C. and 3 to 20% by weight of a high boiling point solvent having a boiling point of 130 to 250 ° C. was used. In this case, too, the ink is dried when the ink for forming the transparent conductive film is supplied to the intaglio roll 3, and printing is difficult. Even if printing is possible, if printing is performed continuously, the viscosity of the transparent conductive film forming ink gradually increases on the intaglio roll 3, causing unevenness in the film thickness of the transparent conductive film forming ink. Eventually, the viscosity of the ink for forming a transparent conductive film increases over the entire surface of the intaglio roll 3 and loses fluidity, making continuous printing impossible.

Therefore, as disclosed in JP-A-58-89666, it is conceivable to add a thickening agent such as nitrocellulose to increase the viscosity of the ink and improve the printability. However, even though it is possible to print the transparent conductive film forming ink, the thickener component causes decomposition gas generation in the subsequent baking step, and the formed transparent conductive film tends to be porous and dense. It is hard to be a structure. In addition, carbon in the thickener component remains in the transparent conductive film on which it is formed, and the conductivity of the transparent conductive film tends to be low, and the color of the transparent conductive film tends to be dark.

Accordingly, an object of the present invention is to provide a method for producing an ink for forming a transparent conductive film, which is capable of forming a dense and uniform transparent conductive film and having excellent continuous printability.

[0010]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides an ink for forming a transparent conductive film, comprising a partially hydrolyzed product of at least one organometallic compound and a boiling point of 30%.
Alcohols, ketones, esters below ~ 150 ° C,
A transparent conductive film forming solution comprising at least one low-boiling solvent of ethers and at least one stabilizer of amines, organic acids, inorganic acids, β-diketones, and β-ketoesters Is concentrated under the condition of normal temperature to 60 ° C. or lower to form a viscous solution. Then, the viscous solution contains at least one of glycols, carbitols, and cellosolves having a boiling point of 150 to 280 ° C. The boiling point solvent is added so that the high boiling point solvent in the solvent component is adjusted to 40 to 95% by weight and the ink viscosity is adjusted to 5 to 200 mPa · s.

The ink for forming a transparent conductive film has a basic structural unit represented by the following general formula: M (OH) _x (R—CO—CH ₂ —CO—R ′) _Y m = X + Y (where M is In, Sn , Sb, B, P, Al, B
i, Si, Ti, Se, Te, Hf, an element which is one of the group consisting of Zn, R and R 'are substituted allyl groups or substituted alkyl groups, m is the valence of M, and X and Y are natural numbers Is shown. ) A partial hydrolyzate of at least one organometallic compound represented by formula (I), at least one low-boiling solvent selected from alcohols, ketones, esters, and ethers having a boiling point of less than 30 to 150 ° C, and amines A transparent conductive film forming solution comprising at least one stabilizer selected from the group consisting of organic acids, inorganic acids, β-diketones, and β-ketoesters is concentrated at room temperature to 60 ° C. or lower to form a viscous solution. age,
Next, at least one high-boiling solvent of glycols, carbitols, and cellosolves having a boiling point of 150 to 280 ° C is added to the viscous solution, and the high-boiling solvent in the solvent component is added.
40-95% by weight and ink viscosity 5-200mPa · s
It is configured to adjust so that

Further, in the above invention, the basic structural unit represented by the following general formula _{M 1 (OH) X1 (R} 1 -CO-CH 2 -CO-R 1 ') Y1 m 1 = X1 + Y1 M 2 (OH) X2 ( R ₂ —CO—CH ₂ —CO—R ₂ ′) _{Y 2} m ₂ = X 2 + Y 2 (where M ₁ and M ₂ are In, Sn, Sb, B, P, A
1, one element of Bi, Si, Ti, Se, Te, Hf, and Zn, R ₁ , R ₁ ′, R ₂ , and R ₂ ′ are a substituted allyl group or a substituted alkyl group, m ₁ , m ₂ is M ₁ ,
M valence of _2, X1, Y1, Y2 is a natural number, X2 represents 0 or a natural number. ), Each having a partial hydrolyzate of at least one organometallic compound and a boiling point of 30 to
At least one low-boiling solvent selected from alcohols, ketones, esters and ethers having a temperature of less than 150 ° C. and at least one selected from amines, organic acids, inorganic acids, β-diketones and β-ketoesters; The solution for forming a transparent conductive film comprising various kinds of stabilizers is concentrated under a condition of room temperature to 60 ° C. or lower to form a viscous solution. Then, glycols having a boiling point of 150 to 280 ° C. At least one high-boiling solvent of talls and cellosolves is added so that the high-boiling solvent in the solvent component is adjusted to 40 to 95% by weight and the ink viscosity is adjusted to 5 to 200 mPa · s. You may comprise.

Further, in the above invention, an intaglio roll rotatably supported by a support frame of a base and having a large number of ink cells having a depth of 1.0 to several tens μm on the surface, and an intaglio roll having a surface of 1.0 to 30,000 mPa · The ink supply device that supplies the s ink, and the ink supplied to the intaglio roll are provided at predetermined locations around the intaglio roll supported by the support frame, and the ink supplied to the intaglio roll is spread over the intaglio roll surface to maintain a certain amount of ink in the ink cells. A doctor roll, a printing roll that is rotatably supported below the intaglio roll of the support frame and has a convex portion that comes into contact with the intaglio roll, and transfers the ink in the ink cell to the convex portion on the intaglio roll surface; A driving device which is supported and synchronously drives the printing roll 4 and the intaglio roll to rotate; a printing position A on which the printing medium is placed and which comes into contact with the printing roll on the base; B, a plate having movable between C, a printing substrate drive device for moving the surface plate between the two positions, retracted position of the rotating surface plate of the printing roll B, C
And a controller for controlling the movement of the ink to the printing position A and printing the ink transferred to the convex portion of the print roll on the printing medium, thereby producing an ink for forming a transparent conductive film usable in a thin film forming apparatus. May be configured like the method according to any one of claims 1 to 3.

[0014]

Embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a perspective view showing a thin film forming apparatus which can be applied to the method for producing an ink for forming a transparent conductive film of the present invention. In the figure, 1 is a base, 2 is a support frame, 3 is an intaglio roll, 4 is a printing roll, 5 is an ink supply device, 6 is a doctor, 7 is a convex portion, 8 is a driving device, 9 is a surface plate, and 10 is a platen. The printing medium driving device 11 is a glass plate as a printing medium.

The method for producing an ink for forming a transparent conductive film according to the present invention is characterized in that a partial hydrolyzate of at least one kind of organometallic compound and an alcohol, ketone, ester or ether having a boiling point of less than 30 to 150 ° C. A transparent conductive film forming solution comprising at least one of the above-mentioned low-boiling solvents and at least one stabilizer selected from amines, organic acids, inorganic acids, β-diketones, and β-ketoesters; 60 ℃
Concentrate to a viscous solution under the following conditions, and then add at least one high-boiling solvent of glycols, carbitols, and cellsolves having a boiling point of 150 to 280 ° C to the viscous solution. It is adjusted so that the high boiling point solvent in the solvent component becomes 40 to 95% by weight and the ink viscosity becomes 5 to 200 mPa · s.

Examples of the organometallic compound include organic acid salts and metal alkoxides, and partially hydrolyzed products thereof. The organometallic compound is not limited to one kind, and two or more different kinds can be used in combination. The partial hydrolyzate of the organic metal compounds, in particular, of the general formula _{M (OH) X (R-} CO-CH 2 -CO-R ') at least one organometallic compound represented by _Y m = X + _Y below It is preferable to use a partial hydrolyzate. Here, M is an element which becomes an oxide in a subsequent firing step, is transparent in that state, and shows electrical conductivity, and In, Sn, Sb, B, P, Al,
One of Bi, Si, Ti, Se, Te, Hf and Zn
Indicates a seed element. R and R 'each represent a substituted allyl group or a substituted alkyl group, and R and R' may be the same or different. m represents the valence of M. X and Y indicate natural numbers. These partial hydrolysates of organometallic compounds are not limited to one kind, and two or more different kinds can be used in combination.

The partial hydrolyzate of the organometallic compound has the following general formula: M ₁ (OH) _X1 (R ₁ —CO—CH ₂ —CO—R ₁ ′) _{Y 1} m ₁ = X ₁ + Y 1 M ₂ (OH) _{X 2} (R ₂ —CO—CH ₂ —CO—R ₂ ′) It is preferable to use a partial hydrolyzate of at least one organometallic compound represented by Y ₂ m ₂ = X 2 + Y 2. Where M ₁ ,
M ₂ is In, Sn, Sb, B, P, Al, Bi, Si,
The element is one of Ti, Se, Te, Hf, and Zn. R ₁ , R ₁ ′, R ₂ and R ₂ ′ represent a substituted allyl group or a substituted alkyl group, and R ₁ , R ₁ ′, R ₂ and R ₂ ′ may be the same or different. m ₁ and m ₂ represent the valences of M ₁ and M ₂ , respectively. X1, Y1, and Y2 are natural numbers, and X2 is 0 or a natural number. These partial hydrolysates of organometallic compounds are not limited to one kind, and two or more different kinds can be used in combination.

By using a partial hydrolyzate of an organometallic compound having such a composition, an ink for forming a transparent conductive film which has little change with time and is excellent in continuous printability can be obtained. In addition, since the slightly remaining ligand is uniformly dispersed in the ink for forming a transparent conductive film, when the oxide film is formed in the subsequent baking step, there is no elemental skew and a transparent material having excellent conductivity. It becomes an ink for forming a conductive film. Furthermore, since the ligand, which is a main organic component, is small, the decomposition temperature of the organometallic compound does not increase in the subsequent firing step, and no carbon residue is generated.
A transparent conductive film having good transparency can be obtained.

The partial hydrolyzate of the organometallic compound represented by the above general formula is a kind of metal chelate compound.
However, when completely chelated, the decomposition point temperature of the transparent conductive film forming ink rises, and the generation of carbon residues in the transparent conductive film is promoted, so that the resistance value of the transparent conductive film increases and the transmittance decreases. For example, the physical properties of the transparent conductive film deteriorate. Therefore, the partial hydrolyzate of the organometallic compound must not be completely chelated.

When a partially hydrolyzed product of an organometallic compound containing a partially unreacted metal alkoxide is used, the substitution reaction easily proceeds at the site of the alkoxide, and the viscosity changes with time. It is difficult to obtain a film having a film thickness and quality.

As the solvent, 5 to 60% by weight of at least one high-boiling solvent selected from alcohols, ketones, esters and ethers having a boiling point of less than 30 to 150 ° C .;
40 to 95% by weight of at least one low-boiling solvent selected from glycols, carbitols and cellosolves having a temperature of less than 280 ° C.
Use a mixture with If the ratio of the low boiling point solvent is less than 5% by weight, the quality of the finally obtained film deteriorates, so that the desired conductivity cannot be obtained. On the other hand, when the ratio of the low boiling solvent exceeds 60% by weight, the ratio of the high boiling solvent becomes less than 40%,
When printing is performed using the above-described thin film forming apparatus, the ink for forming a transparent conductive film is remarkably dried, and it is difficult to continuously form a transparent conductive film.

Examples of the low boiling solvent include methanol, ethanol, n-propanol, isopropanol, 2-propanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, secondary amyl alcohol,
Alcohols such as pentanol, tertiary amyl alcohol, fusel oil, acetone, methyl acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n
-Butyl ketone, methyl isobutyl ketone, methyl-n
-Amyl ketone, diethyl ketone, ketones such as ethyl-n-butyl ketone, methyl formate, ethyl formate, propyl formate, n-butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, -n-propyl acetate,
Esters such as isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate;
Di-n-propyl ether, diisopropyl ether,
1,2-butylene oxide, dioxane, trioxane, 2-methylfuran, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,1-dimethoxymethane, 1,1-diethoxyethane It is preferable to use ethers such as.
The low-boiling solvent may be a combination of two or more low-boiling solvents in consideration of the evaporation rate, the saturated vapor pressure, the viscosity, the compatibility with the compound, and the like.

Examples of the high boiling solvent include ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monophenyl ether acetate, and ethylene glycol benzyl ether. , Ethylene glycol monohexyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Tylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triglycol dichloride, propylene glycol, propylene glycol monobutyl ether, 1 -Butoxyethoxypropanol, propylene glycol derivatives, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, butanediol, 1,5-pentanedioate , Hexylene glycol, octylene glycol, glyceryl monoacetate, glyceryl diacetate, glyceryl triacetate, glyceryl butyrate, glycerol ethers, glycerol-.alpha., .gamma. dichlorohydrin, 1, 2,
In addition to glycols such as 6-hexanetriol, carbitols and cellosolves may be used. Among high-boiling solvents, glycols, in particular, serve as a dispersant for the organometallic compound, helping to uniformly disperse the organometallic compound. The high-boiling solvent may be a combination of two or more high-boiling solvents in consideration of the evaporation rate, the saturated vapor pressure, the viscosity, the compatibility with the compound, and the like.

As described above, by using the low-boiling solvent and the high-boiling solvent, a leveling effect can be obtained by performing the evaporation of the solvent step by step, and the drying of the transparent conductive film forming ink can be prevented. . In high boiling solvents,
In particular, glycols play a role of a dispersant for the organometallic compound and help uniform dispersion of the organometallic compound.

Examples of the stabilizer include amines, organic acids,
It is preferable to use at least one of inorganic acids, β-diketones, and β-ketoesters. Also, N, N'-
Drying regulators such as dimethylformamide and dimethylacetamide can also be added. One of these
It is advisable to use a mixture of species or species.

In order to obtain an ink for forming a transparent conductive film, a solution for forming a transparent conductive film comprising the organometallic compound, a low-boiling solvent and a stabilizer is concentrated at a temperature of from room temperature to 60 ° C. After forming the solution, a high boiling solvent is added as a diluting solvent. If the temperature is lower than room temperature, the condensation polymerization reaction is difficult to proceed, while 60
When the temperature exceeds ℃, the polycondensate does not dissolve in the high boiling solvent.
The work time can be reduced by performing the concentration under vacuum conditions.

Further, the viscosity of the ink for forming a transparent conductive film is adjusted to 5 to 200 mPa · s by adjusting the partial hydrolysis, the concentration of the organic metal compound, or the appropriate selection of the solvent. 5mP viscosity
If the value is less than a · s, dripping and unevenness in film thickness on the applied surface are remarkable, and it is difficult to obtain uniformity of the resistance value or the film thickness. On the other hand, if the viscosity exceeds 200 mPas, the desired film thickness can be obtained by adjusting the depth of the intaglio roll, but the amount of ink transferred at one time increases, and it is difficult to control the film thickness of the obtained film. Become. Further, the leveling property of the printed transparent conductive film is deteriorated, and it is difficult to obtain a smooth film.

In the present invention, the viscosity of the ink is adjusted by using a low-boiling solvent and a high-boiling solvent instead of adjusting the ink viscosity by adding a thickener. No gas is generated, and the formed transparent conductive film has a dense structure.

When the ink for forming a transparent conductive film of the present invention is applied to the above-described thin film forming apparatus, a transparent conductive film can be effectively formed (see FIG. 1). Styrene-butadiene-styrene (SBR), isobutylene-styrene-isobutylene (ISI), urethane rubber, and the like are mainly used as the material of the convex portion of the printing roll of the thin film forming apparatus. Therefore, it is desirable that the low-boiling solvent is mainly composed of alcohol, and the proportion of the esters or ketones in the low-boiling solvent is preferably 15% by weight or less. If the content exceeds 15% by weight, the convex portions are deteriorated, which causes various problems such as pinholes, lack of smoothness, and poor conductivity.

[0031]

Example 1 88 parts by weight of indium nitrate trihydrate was completely dissolved in 1200 parts by weight of ethanol (a low-boiling solvent).
25 parts by weight of pentanedione (chelating agent) and 20 parts by weight of lactic acid (stabilizer) were added to obtain a uniform transparent transparent conductive film forming solution.

To this solution for forming a transparent conductive film, 30 parts by weight of acetic acid (stabilizer) and 17 parts by weight of a 60% solution of tin acetylacetone (chelating agent) in 2-propanol (low boiling point solvent) were added, and the solvent was added at 20 mmHg and 50 ° C. Concentrated by removal, acetic acid (stabilizer) 20 parts by weight, hexylene glycol (high boiling point solvent)
By adding 340 parts by weight and stirring uniformly, an ink for forming a transparent conductive film was obtained. In the ink for forming a transparent conductive film, the high boiling point solvent in the solvent component was 94% by weight, and the viscosity was
It was 50 mPa · s.

The ink for forming a transparent conductive film was coated with SiO ₂ by using the above-mentioned thin film forming apparatus (Angstroma® (registered trademark) in-line type manufactured by Nissha Printing Co., Ltd.).
Printing was performed on a soda glass substrate of mm × 300 mm × 1.1 mm.

After the glass substrate is preliminarily dried on a hot plate, it is baked at 500 ° C. in a conveyor-type atmosphere separation furnace, and subsequently heated from 500 ° C. in a nitrogen atmosphere containing a small amount of hydrogen gas in the conveyor-type atmosphere separation furnace. By cooling to room temperature, a transparent conductive film was obtained.

This transparent conductive film was excellent in uniformity with a surface resistance of 150 ± 20 Ω / □ in a region inside 1 cm from the edge portion. The transparent conductive film had a volume resistance of (9.4 ± 0.1) × 10 ⁻⁴ Ω · cm and was excellent in conductivity.

Example 2 As in Example 1, 72 parts by weight of indium chloride, 1200 parts by weight of 2-propanol (low-boiling solvent), 32 parts by weight of ethyl acetoacetate (chelating agent) and 20 parts by weight of acetic acid (stabilizing agent) To obtain an ink for forming a transparent conductive film. In the ink for forming a transparent conductive film, the high boiling point solvent in the solvent component was 80% by weight, and the viscosity was 40 mPa · s.

The ink for forming a transparent conductive film was printed on a glass substrate in the same manner as in Example 1.

A glass substrate was treated in the same manner as in Example 1 to obtain a transparent conductive film.

The transparent conductive film has a surface resistance of 500 ± 100Ω / □ in a region inner than 1 cm from the edge.
The transmittance (air reference) at 550 nm was in the range of 92 ± 1% (including a glass substrate having a thickness of 1.1 mm), and the film thickness and the resistance value distribution were excellent in uniformity.

Comparative Example A solution for forming a transparent conductive film prepared in the same manner as in Example 1 was mixed with 300 parts by weight of ethanol (a solvent having a low boiling point) and 20 parts of acetic acid (a stabilizer).
Parts by weight and 40 parts by weight of hexylene glycol (high boiling point solvent) were added and uniformly stirred to obtain a transparent conductive film forming ink.

When an attempt was made to print the ink for forming a transparent conductive film in the same manner as in Example 1, after printing several sheets, the ink for forming a transparent conductive film on the intaglio roll dried and could not be continuously printed.

[0042]

Since the present invention has the above-described structure, it has the following effects.

The method for producing an ink for forming a transparent conductive film according to the present invention comprises a mixture of a specific proportion of a low-boiling solvent and a high-boiling solvent, and the solvent evaporates sequentially during the subsequent baking to provide a dense and uniform film. An ink for forming a transparent conductive film that can form a transparent conductive film can be easily obtained.

Further, since the transparent conductive film has an appropriate viscosity and does not contain a thickening agent for adjusting the viscosity, the transparent conductive film does not easily become porous, and the ink for forming a transparent conductive film having excellent transparency can be easily prepared. Obtainable.

Also, it has an appropriate drying property, does not dry immediately during printing, and has high film thickness accuracy on the same printing medium, and has high film thickness accuracy even when printing is repeated. In addition, an ink for forming a transparent conductive film having excellent continuous printability can be easily obtained.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a thin film forming apparatus which can be applied to a method for producing an ink for forming a transparent conductive film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base 2 Support frame 3 Intaglio roll 4 Printing roll 5 Ink supply device 6 Doctor 7 Convex part 8 Drive device 9 Surface plate 10 Printed object drive device 11 Printed object

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazumitsu Tsuji 3 Mibuhanaicho, Nakagyo-ku, Kyoto, Kyoto Japan Photographic Printing Co., Ltd.

Claims (4)

[Claims] 1. A partial hydrolyzate of at least one organometallic compound and at least one of alcohols, ketones, esters and ethers having a boiling point of less than 30 to 150 ° C.
Species of low boiling solvents, amines, organic acids, inorganic acids, β
-A solution for forming a transparent conductive film comprising at least one stabilizer selected from diketones and β-ketoesters;
The solution is concentrated under a condition of 60 ° C. or lower to form a viscous solution. Then, at least one high-boiling solvent of glycols, carbitols, and cellsolves having a boiling point of 150 to 280 ° C. is added to the viscous solution. In addition, the high boiling point solvent in the solvent component is 40
A method for producing an ink for forming a transparent conductive film, wherein the ink is adjusted to have a viscosity of 5 to 200 mPa · s and a viscosity of 5 to 200 mPa · s. 2. The basic structural unit is represented by the following general formula: M (OH) _X (R—CO—CH ₂ —CO—R ′) _Y m = X + Y (where M is In, Sn, Sb, B, P, Al , B
i, Si, Ti, Se, Te, Hf, an element which is one of the group consisting of Zn, R and R 'are substituted allyl groups or substituted alkyl groups, m is the valence of M, and X and Y are natural numbers Is shown. ) A partial hydrolyzate of at least one organometallic compound represented by formula (I), at least one low-boiling solvent selected from alcohols, ketones, esters, and ethers having a boiling point of less than 30 to 150 ° C, and amines A transparent conductive film forming solution comprising at least one stabilizer selected from the group consisting of organic acids, inorganic acids, β-diketones, and β-ketoesters is concentrated at room temperature to 60 ° C. or lower to obtain a viscous solution. age,
Next, at least one high-boiling solvent of glycols, carbitols, and cellosolves having a boiling point of 150 to 280 ° C is added to the viscous solution, and the high-boiling solvent in the solvent component is added.
40-95% by weight and ink viscosity 5-200mPa · s
A method for producing an ink for forming a transparent conductive film, characterized in that the method is adjusted to be as follows. 3. A basic unit is represented by the following general formula _{M 1 (OH) X1 (R} 1 -CO-CH 2 -CO-R 1 ') Y1 m 1 = X1 + Y1 M 2 (OH) X2 (R 2 -CO- _{CH2-CO-R 2 ')} Y2 m 2 = X2 + Y2 ( However, M _1, M ₂ is in, Sn, Sb, B, P, A
1, one element of Bi, Si, Ti, Se, Te, Hf, and Zn, R ₁ , R ₁ ′, R ₂ , and R ₂ ′ are a substituted allyl group or a substituted alkyl group, m ₁ , m ₂ is M ₁ ,
M valence of _2, X1, Y1, Y2 is a natural number, X2 represents 0 or a natural number. ), Each having a partial hydrolyzate of at least one organometallic compound and a boiling point of 30 to
At least one low-boiling solvent selected from alcohols, ketones, esters and ethers having a temperature of less than 150 ° C. and at least one selected from amines, organic acids, inorganic acids, β-diketones and β-ketoesters; The solution for forming a transparent conductive film comprising various kinds of stabilizers is concentrated under a condition of room temperature to 60 ° C. or lower to form a viscous solution. Then, glycols having a boiling point of 150 to 280 ° C. At least one high-boiling solvent of tolls and cellosolves is added so that the high-boiling solvent in the solvent component is adjusted to 40 to 95% by weight and the ink viscosity is adjusted to 5 to 200 mPa · s. A method for producing an ink for forming a transparent conductive film. 4. An intaglio roll rotatably supported by a support frame of a base and having a large number of ink cells having a depth of 1.0 to several tens of μm on its surface, and supplying ink of 1.0 to 30,000 mPa · s to the surface of the intaglio roll. A doctor which is provided at a predetermined location around the intaglio roll supported by the support frame and spreads the ink supplied to the intaglio roll on the surface of the intaglio roll to hold a certain amount of ink in the ink cell; A printing roll that is rotatably supported below the intaglio roll of the frame and has a projection that comes into contact with the intaglio roll to transfer the ink in the ink cells to the projection on the surface of the intaglio roll; And a drive device for synchronously driving the intaglio roll and the printing roll, and movable between a printing position A on which the printing medium is placed and in contact with the printing roll on the base and a retracted position B, C away from the printing roll. To The platen obtained above, a printing medium driving device for moving the platen between the two positions, and the rotation of the printing roll and the movement of the platen from the retracted positions B and C to the printing position A to control the printing roll. The transparent conductive material according to any one of claims 1 to 3, for producing a transparent conductive film forming ink that can be used in a thin film forming device including a control device that prints the ink transferred to the convex portions on a printing medium. A method for producing a film-forming ink.