JP3113851B2 - Method for producing ink for forming transparent conductive film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display device,
For forming transparent conductive films used for various electronic components such as flat displays and touch panels such as electroluminescent devices, plasma display devices, fluorescent display tubes, and field emission displays, for forming transparent conductive films that can be printed by a printing method. 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. Hei 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 the surface thereof. An ink supply device 5 for supplying an ink of up to 30,000 mPa · s, and an ink supply device 5 provided at a predetermined location around the intaglio roll 3 supported by the support frame 2 and spreading the ink supplied to the intaglio roll 3 on the surface of the intaglio roll 3 6 to hold a certain amount of ink in the ink cell
A printing roll 4 having a convex portion 7 rotatably supported below the intaglio roll 3 of the support frame 2 and in contact with the intaglio roll 3, and transferring the ink in the ink cells to the convex portion 7 on the surface of the intaglio roll 3. A driving device 8 supported by the support frame 2 for synchronously driving the printing roll 4 and the intaglio roll 3; a printing position A on which the printing medium is placed and which comes into contact with the printing roll 4 on the base 1; A platen 9 movably provided between the retracted positions B and C distant from the roll 4, a printing medium driving device 10 for moving the platen 9 between the two positions, and rotation and rotation of the print roll 4. A control device (not shown) for controlling the movement of the board 9 from the retracted positions B and C to the printing position A and printing the ink transferred to the convex portion 7 of the printing roll 4 on the printing medium. Is configured.

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.

As disclosed in Japanese Patent Application Laid-Open No. Sho 60-1703, there is an ink for forming a transparent conductive film in which the solvent is only a low-boiling solvent such as alcohol. However, when the above-mentioned 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 forming 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 JP-A-9018, the boiling point is 30.
97 to 80% by weight of a low boiling point solvent having a boiling point of
Even when a mixed solvent with a high boiling point solvent having a temperature of 30 to 250 ° C. and 3 to 20% by weight is used, the ink is dried when the ink for forming a 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]

In order to achieve the above objects, the present invention provides an ink for forming a transparent conductive film, which 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, Se, Te, Hf, an element that 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 . ) A partial hydrolyzate of at least one organometallic compound represented by the formula (I), and alcohols having a boiling point of less than 30 to 150 ° C;
Ketones, esters, at least one low-boiling solvent of ethers, amines, organic acids, inorganic acids,
A solution for forming a transparent conductive film comprising at least one stabilizer selected from β-diketones and β-ketoesters is concentrated at room temperature to 60 ° C. or lower to form a viscous solution. A high-boiling solvent of at least one of glycols, carbitols and cellosolves having a boiling point of 150 to 280 ° C. is added to a simple solution, so that the high-boiling solvent in the solvent component becomes 40 to 95% by weight and the ink viscosity increases. Is 5
It is configured to adjust to 200 mPa · s.

In the above invention, the following general formula: M ₁ (OH) _{X 1} (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 ′) _Y2 m ₂ = X2 + Y2 (where M ₁ and M ₂ are In, Sn, Sb, B, P, A
l, Bi, Si, Se, Te, Hf, an element which is one kind of Zn, R ₁ , R ₁ ′, R ₂ , R ₂ ′ are a substituted allyl group or a substituted alkyl group, and m ₁ , m ₂ are M ₁ ,
The valence of _{M 2, X1, X2, Y1} , Y2 represents a natural number. ) A partial hydrolyzate of at least two kinds of organometallic compounds represented by the formula (1), a low-boiling solvent of at least one of alcohols, ketones, esters and ethers having a boiling point of less than 30 to 150 ° C., and amines A solution for forming a transparent conductive film 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. And then into the viscous solution a boiling point of 150-280
At least one high-boiling solvent selected from glycols, carbitols and cellosolves at 40 ° C. is added so that the high-boiling solvent in the solvent component becomes 40 to 95% by weight and the ink viscosity becomes 5 to 200 mPa · s. It may be configured to adjust as follows.

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, An ink supply device for supplying an ink of up to 30,000 mPa · s, and an ink supply device which is provided at a predetermined position around an intaglio roll supported by a support frame, spreads the ink supplied to the intaglio roll on the surface of the intaglio roll, and keeps the ink in an ink cell. A doctor roll that holds an amount of ink, and a printing roll that has a convex portion rotatably supported below the intaglio roll of the support frame and that comes into contact with the intaglio roll, and transfers the ink in the ink cells to the convex portion on the surface of the intaglio roll. A driving device supported by the support frame and synchronously driving the printing roll 4 and the intaglio roll, and a printing position A on which the printing medium is placed and which contacts the printing roll on the base. A platen movably provided between retreat positions B and C separated from the roll, a printing medium driving device for moving the platen between the two positions, a rotation of the printing roll and a retreat position B of the platen. A control device for controlling the movement from C to the printing position A to print the ink transferred to the convex portion of the printing roll on the printing medium. You may comprise like the method in any one of Claims 1-3 for manufacturing.

[0013]

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 organometallic compound and an alcohol, ketone, ester or ether having a boiling point of less than 30 to 150 ° C. At least one of the low-boiling solvents, amines, organic acids, inorganic acids, β-
At least one of diketones and β-ketoesters
A solution for forming a transparent conductive film composed of various kinds of stabilizers
The solution is concentrated under a condition of 0 ° C. or less to form a viscous solution, and 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 solvent in the solvent component becomes 40 to 95% by weight and the ink viscosity becomes 5 to 2%.
It was adjusted to be 00 mPa · s.

Examples of the organometallic compound include organic acid salts, metal alkoxides, and partial hydrolysates 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,
An element that is one of Bi, Si, Se, Te, Hf, and Zn is shown. 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 is represented by the following general formula: M ₁ (OH) _{X 1} (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 two kinds of organometallic compounds represented by Y ₂ m ₂ = X 2 + Y 2. Here, M ₁ and M ₂ are I
n, Sn, Sb, B, P, Al, Bi, Si, Se, T
e, an element that is one of Hf and Zn. R ₁ ,
R ₁ ′, R ₂ , R ₂ ′ represent a substituted allyl group or a substituted alkyl group, and R ₁ , R ₁ ′, R ₂ , R ₂ ′ may be the same or different. m ₁ and m ₂ represent the valences of M ₁ and M ₂ , respectively. X1, X2, Y1, and Y2 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.

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 over 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, in the case of complete chelation, 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 significantly with time. It is difficult to obtain a film having a film thickness and quality.

Examples of the solvent include 5 to 60% by weight of at least one high-boiling solvent selected from alcohols, ketones, esters and ethers having a boiling point of from 30 to 150 ° C. and glycol having a boiling point of from 150 to 280 ° C. , Carbitols and cellosolves are used in a mixture with 40 to 95% by weight of a low-boiling solvent. 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%, and when the printing is performed by the thin film forming apparatus described above, the drying of the transparent conductive film forming ink is remarkable, It becomes 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
-Ketones such as amyl ketone, diethyl ketone, 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, saturated vapor pressure, viscosity, compatibility with the compound, and the like.

Examples of the high boiling point 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 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 evaporating 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.

As the stabilizer, 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 above-mentioned organometallic compound, a low-boiling solvent and a stabilizer is concentrated at room temperature to 60 ° C. or lower.
After forming a viscous solution, a high boiling solvent is added as a diluting solvent. When the temperature is lower than room temperature, the condensation polymerization reaction hardly proceeds, while 6
When the temperature exceeds 0 ° C., the polycondensate does not dissolve in the high boiling point solvent. In addition, when concentrating, by performing under vacuum conditions,
Work time can be reduced.

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, by appropriately selecting the concentration of the organic metal compound or the solvent. When the viscosity is less than 5 mPa · s, dripping and unevenness in film thickness on the coated surface are remarkable, and it is difficult to obtain a uniform resistance value or film thickness. On the other hand, when the viscosity exceeds 200 mPa · s, although the desired film thickness can be obtained by adjusting the depth of the intaglio roll, 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 not by adding a thickener but by using a low-boiling solvent and a high-boiling solvent. 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-based rubber, and the like are mainly used as a material of the convex portion of the printing roll of the thin film forming apparatus. Therefore, the low-boiling solvent is preferably composed mainly 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 projections are degraded, causing various problems such as pinholes, lack of smoothness, and poor conductivity.

[0030]

Example 1 88 parts by weight of indium nitrate trihydrate was completely dissolved in 1200 parts by weight of ethanol (low boiling point solvent), and 25 parts by weight of 2,4-pentanedione (chelating agent) and lactic acid ( (Stabilizer) 20 parts by weight was added to obtain a uniform transparent transparent conductive film forming solution.

30 parts by weight of acetic acid (stabilizing agent) and tin acetylacetone (chelating agent) are added to this transparent conductive film forming solution.
17 parts by weight of a 2-propanol (low-boiling solvent) 60% solution were added, and the mixture was concentrated by removing the solvent at 20 mmHg and 50 ° C., and 20 parts by weight of acetic acid (stabilizer) and 340 parts by weight of hexylene glycol (high-boiling point solvent) were added. Was added and stirred uniformly to obtain an ink for forming a transparent conductive film. The ink for forming a transparent conductive film has a high boiling point solvent in the solvent component of 94%.
% By weight, and the viscosity was 50 mPa · s.

The ink for forming a transparent conductive film was coated with SiO ₂ using the above-described 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 00 mm × 300 mm × 1.1 mm.

After preliminarily drying the glass substrate on a hot plate, the glass substrate is fired 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. Also,
The transparent conductive film is (9.4 ± 0.1) × 10 ⁻⁴ Ω · cm
With excellent volume conductivity and excellent 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.

The 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.
/ □, transmittance at 550 nm (air reference)
It was in a range of 92 ± 1% (including a glass substrate having a thickness of 1.1 mm), and was excellent in uniformity of the film thickness and the resistance value distribution.

Comparative Example To a solution for forming a transparent conductive film prepared in the same manner as in Example 1, 300 parts by weight of ethanol (a low-boiling solvent) and acetic acid (a stabilizer)
20 parts by weight, hexylene glycol (high boiling point solvent) 40
The weight part was added and stirred uniformly to obtain an ink for forming a transparent conductive film.

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 out and could not be continuously printed.

[0041]

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 of the present invention comprises a mixture of a specific ratio of a low-boiling solvent and a high-boiling solvent, and the solvent evaporates sequentially during the subsequent baking, so that the film quality is dense and uniform. 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 thickener for adjusting the viscosity, the transparent conductive film does not easily become porous, and an ink for forming a transparent conductive film having excellent transparency can be easily prepared. Obtainable.

Also, it has an appropriate drying property, does not immediately dry at the time of printing, 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 Continuation of the front page (56) References JP-A-5-28834 (JP, A) JP-A-62-180740 (JP, A) JP-A-62-202736 (JP, A) JP-A-11-118 148038 (JP, A) JP-A-11-158426 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 C09D 5/24 C03C 17/28 H01B 1/20

Claims (3)

(57) [Claims] 1. 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, Se, Te, Hf, an element that 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 . ) A partial hydrolyzate of at least one organometallic compound represented by the formula (I), and alcohols having a boiling point of less than 30 to 150 ° C;
Ketones, esters, at least one low-boiling solvent of ethers, amines, organic acids, inorganic acids,
A solution for forming a transparent conductive film comprising at least one stabilizer selected from β-diketones and β-ketoesters is concentrated at room temperature to 60 ° C. or lower to form a viscous solution. A high-boiling solvent of at least one of glycols, carbitols and cellosolves having a boiling point of 150 to 280 ° C. is added to a simple solution, so that the high-boiling solvent in the solvent component becomes 40 to 95% by weight and the ink viscosity increases. Is 5
A method for producing an ink for forming a transparent conductive film, wherein the method is adjusted to be 200 mPa · s. 2. A 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 ′) _Y2 m ₂ = X2 + Y2 (where M ₁ and M ₂ are In, Sn, Sb, B, P, A
l, Bi, Si, Se, Te, Hf, an element which is one kind of Zn, R ₁ , R ₁ ′, R ₂ , R ₂ ′ are a substituted allyl group or a substituted alkyl group, and m ₁ , m ₂ are M ₁ ,
The valence of _{M 2, X1, X2, Y1} , Y2 represents a natural number. ) A partial hydrolyzate of at least two kinds of organometallic compounds represented by the formula (1), a low-boiling solvent of at least one of alcohols, ketones, esters and ethers having a boiling point of less than 30 to 150 ° C., and amines A solution for forming a transparent conductive film 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. And then into the viscous solution a boiling point of 150-280
At least one of high-boiling solvents selected from glycols, carbitols, and cellosolves at 40 ° C. is added to make the high-boiling solvent in the solvent component 40 to 95% by weight, and the ink viscosity becomes 5-200 mPa · s. A method for producing an ink for forming a transparent conductive film, characterized in that the method is adjusted as follows. 3. 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 its surface, and an intaglio roll having a surface of 1.0 to 30,
An ink supply device for supplying 000 mPa · s of ink, and an ink supply device provided at a predetermined location around an intaglio roll supported by a support frame, the ink supplied to the intaglio roll is spread on the surface of the intaglio roll, and a certain amount of ink is placed in an ink cell. And 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 cells to the convex portion on the intaglio roll surface, and a support. A drive device supported by the frame and synchronously driving the printing roll 4 and the intaglio roll, and a printing position A on which the printing medium is placed and in contact with the printing roll on the base, and a retracting position B separated from the printing roll, C, a printing plate driving device for moving the platen between the two positions, a rotation of the printing roll and a retreat position B, C of the platen to the printing position A. Move And a control device for printing the ink transferred to the convex portion of the printing roll by printing on the printing medium by controlling the printing method. The method for producing an ink for forming a transparent conductive film according to any one of the above.