JPH1087344A - Phase separated transparent electrically conductive film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phase separated transparent electrically conductive film having high electric conductivity. SOLUTION: A homogeneous liq. mixture contg. at least one kind of inorg. alkoxide and/or a polymer formed by hydrolyzing and polycondensing the alkoxide is prepd. and a heterogeneous liq. mixture contg. an inorg. salt of at least one kind of element selected among In, Sn, Zn, Ga, Mg, Cd and Sb, a compd. forming an electrically conductive metal oxide to be doped into the inorg. salt, a binder and an org. solvent is prepd. The mixtures are mixed to prepare a multicomponent liq. mixture and at least one side of a substrate is coated with the multicomponent liq. mixture. The resultant coating film is subjected to primary heat treatment at 80-150 deg.C and then secondary heat treatment is carried out at a temp. above the glass transition temp. of a sol-gel glass component. An electrically conductive metal oxide phase is separated from a glass phase by spinodal, decomposition mechanism and the objective phase separated transparent electrically conductive film is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phase-separated transparent conductive film and a method for producing the same, and more particularly, to a display device for precision equipment and optical equipment used in the information and electronics industries, a photocell, an electrode for an image pickup tube, and the like. Glass for antistatic and electrostatic shielding of various devices,
The present invention relates to a phase-separated transparent conductive film suitable for glass for waterproofing and anti-fog of automobiles, buildings, aircrafts, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art A transparent conductive film is generally made of In ₂ O, as represented by an ITO film.
₃ , made of an oxide semiconductor such as SnO ₂ , Cd ₂ SnO ₄ , ZnO, and TiO ₂ . It is known that these oxides exhibit high conductivity due to a high density of conduction electrons involved in electron conduction. By doping these oxides with appropriate impurities, more practical conductivity can be obtained.

[0003] As a conventional method for producing a transparent conductive film, there is the following method. (1) Gas phase method (A) Evaporation method, (B) Sputtering method, (C) CVD method. (2) Non-gas phase method (D) Electroless plating method, (E) Spray method, pyrosol method. (3) Coating method (F) Sol-gel method, (G) Pyrolysis method, (H) Fine particle coating method.

However, these methods have various problems. For example, in the gas phase method, a large-sized apparatus is required for supplying a raw material and heating a substrate under vacuum, and the raw material efficiency is low.
In the non-gas phase electroless plating, the adhesion to the substrate is insufficient, and it is difficult to control pH and the like. The spray method close to the liquid phase method is suitable for small-scale production and research, but has a problem that the raw material efficiency is extremely poor because the raw material evaporates before reaching the substrate.

[0005] The coating method can operate not only under normal pressure, but also
This has the advantage that the apparatus is simple and a large area film can be formed. However, the fine particle coating method is a method in which solid fine particles are applied to a substrate in the form of a paste, followed by baking, and has the disadvantages that the film quality and performance are not sufficient and that the adhesion to the substrate is weak. In addition, since the thermal decomposition method forms an oxide thin film only by thermal decomposition of the precursor, there are advantages such as easy application process and excellent controllability, but as a pretreatment to prevent deterioration of conductivity due to alkali ions. It is necessary to pre-coat the substrate with a silica film, which has a disadvantage that the manufacturing process is complicated.

Japanese Patent Application No. 58-242534 (JP-A-60-137818)
No. 61-113772, etc. disclose a sodium silicate-containing aqueous solution obtained by neutralizing an aqueous solution containing sodium silicate and extracting the same with an organic solvent and a salting-out agent.
A gel method is disclosed. However, the purification purity of the non-aqueous silica sol is insufficient, which is impractical.

Accordingly, an object of the present invention is to solve these drawbacks and to provide a phase-separated transparent conductive film which is easy to manufacture and has high conductivity, and a method for manufacturing the same.

[0008]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned objects, the present inventors have found that a homogeneous mixture of inorganic alkoxide and / or a hydrolyzed / polycondensed product thereof is added to a precursor of a conductive metal oxide. By applying a multi-component mixed solution obtained by adding a binder to the body and mixing a heterogeneous mixed solution dispersed in an organic solvent on the surface of the base material, and performing heat treatment at a predetermined temperature, good conductivity is obtained. It has been found that a transparent conductive film having the same can be obtained, and reached the present invention.

That is, the phase-separated transparent conductive film of the present invention comprises:
(a) a homogeneous mixture containing at least one inorganic alkoxide and / or a polymer formed by hydrolysis / polycondensation thereof; and (b) In, Sn, Zn, Ga, Mg, C
a heterogeneous mixed solution containing an inorganic salt of at least one element selected from the group consisting of d and Sb, a conductive metal oxide-forming compound doped into the inorganic salt, a binder, and an organic solvent. Is applied and heat-treated at a temperature equal to or higher than the glass transition point of the sol-gel glass component, and is separated into a glass phase and a conductive metal oxide phase by a spinodal decomposition mechanism. It is characterized by the following.

The method for producing a phase-separated transparent conductive film according to the present invention comprises the steps of (1) preparing a homogeneous mixed solution containing at least one inorganic alkoxide and / or a polymer formed by hydrolysis and polycondensation thereof. (2) In, Sn, Zn, G
a, an inorganic salt of at least one element selected from the group consisting of Mg, Cd, and Sb, a conductive metal oxide-forming compound doped into the inorganic salt, a binder, and an organic solvent. Prepare a homogeneous mixture, (3) mix the homogeneous mixture and the heterogeneous mixture to prepare a multi-component mixture, (4) apply the multi-component mixture to at least one surface of a substrate (5) The obtained coating film is subjected to a primary heat treatment at a temperature of 80 to 150 ° C., and (6) a secondary heat treatment is carried out at a temperature equal to or higher than the glass transition point of the sol-gel glass component. The phase is separated into a phase and a conductive metal oxide phase.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [1] Components of phase-separated transparent conductive film The phase-separated transparent conductive film of the present invention comprises: (a) a homogeneous mixed solution containing an inorganic alkoxide and / or a polymer formed by hydrolysis and polycondensation thereof; b) In, Sn, Zn, G
a, an inorganic salt of at least one element selected from the group consisting of Mg, Cd, and Sb, a conductive metal oxide-forming compound doped into the inorganic salt, a binder, and an organic solvent. A multi-component mixed solution is prepared by mixing with a homogeneous mixed solution, applied to a substrate, and then heat-treated at a temperature equal to or higher than the glass transition point to cause phase separation of the multi-component gel-sol. ,can get.

(A) Homogeneous mixture A homogeneous mixture is a solution of an inorganic alkoxide in an organic solvent,
It is a solution of a low molecular weight polymer formed by hydrolysis and polycondensation of an inorganic alkoxide in an organic solvent, or a mixture thereof.

(1) Inorganic alkoxide A preferable example of the inorganic alkoxide used in the present invention is represented by the following formula: M (OR) _n (where M is Si, Al, Ti, Zr, Ca, Fe,
At least one element selected from the group consisting of V, Sn, Li, Be, Y, B and P, R is an alkyl group, and n is an integer corresponding to the valence of M. ). The alkyl group R preferably has 1 to 4 carbon atoms. Specific examples of such an inorganic alkoxide are listed below.

(A) Alkoxysilane When M is Si (valence: 4), the inorganic alkoxide is represented by Si (OR ¹ ) ₄ . Such alkoxysilanes include Si (OCH ₃ ) ₄ , Si (OC ₂ H)
₅ ) _{4 and the} like.

(B) Aluminum alkoxide When M is Al (valence: 3), the inorganic alkoxide is represented by Al (OR ² ) ₃ . Such aluminum alkoxides include Al (OCH ₃ ) ₃ , Al
(OC ₂ H ₅ ) ₃ , Al (On-C ₃ H ₇ ) ₃ , Al
_{(O-i- C 3 H 7} ) 3, Al (OC 4 H 9) 3 and the like.

(C) Titanium alkoxide When M is Ti (valence: 4), the inorganic alkoxide is represented by Ti (OR ³ ) ₄ . Such titanium alkoxides include Ti (OCH ₃ ) ₄ and Ti (O
C ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (OC ₄ H
₉ ) ₄ , Ti (Oi-C ₃ H ₇ ) _{4 and the} like.

(D) Zirconium alkoxide When M is Zr (valence: 4), the inorganic alkoxide is represented by Zr (OR ⁴ ) ₄ . Such zirconium alkoxides include Zr (OCH ₃ ) ₄ , Zr
(OC ₂ H ₅ ) ₄ , Zr (O-i-C ₃ H ₇ ) ₄ , Zr
_{(O-t- C 4 H 9} ) 4, Zr (O-n- C 4 H 9) 4 , and the like.

(E) Other alkoxides Other alkoxides include, for example, Ca (OC _{2
H 5) 2, Fe (OC} 2 H 5) 3, V (O-i- C
₄ H ₉ ) ₃ , Sn (OiC ₄ H ₉ ) ₄ , Li (OC _{2
H 5), Be (OC 2} H 5) 2, B (OC 2 H 5) 3,
Y (OCH ₃ ) ₃ , Y (OC ₂ H ₅ ) ₃ , P (OC
_{H 3) 3, P (OC} 2 H 5) 3 and the like.

(2) Hydrolysis / Polycondensate In the present invention, it is preferable to use a solution of a low molecular weight polymer obtained by hydrolyzing / polycondensing an inorganic alkoxide in an organic solvent. The hydrolysis and polycondensation are preferably performed in the presence of an acid catalyst and water.

Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, mineral acids such as hydrogen chloride gas, tartaric acid, phthalic acid, maleic acid, dodecylsuccinic acid, hexahydrophthalic acid, methylnadic acid, and pyromellitic acid. Acid, benzophenonetetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, phthalic anhydride, maleic anhydride, dodecylsuccinic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride And organic acids such as dichlorosuccinic anhydride and chlorendic anhydride or anhydrides thereof.

The amount of the acid catalyst used varies extremely depending on the type of the metal or inorganic substance of the inorganic alkoxide, and is not limited here, but can be set as appropriate.

The amount of water added for the hydrolysis of the inorganic alkoxide is not more than the amount theoretically necessary for completing the hydrolysis / polycondensation reaction. For example, in the case of tetraethoxysilane,
Since the molar amount of water theoretically required for hydrolysis and polycondensation is twice the molar amount of tetraethoxysilane, the ratio of the molar amount of water to be added to the molar amount of tetraethoxysilane is 2.
The following is assumed. By making the amount of added water insufficient, 2
A dimensional polymer can be obtained. If the amount of water to be added exceeds the theoretical amount, the resulting polymer will have a three-dimensional network, and it will be difficult to separate the phases later. In addition, it is preferable that the lower limit of the amount of added water is the above-mentioned theoretical amount. For example, in the case of tetraethoxysilane, a preferable addition amount of water is 1 to 2 mol, and particularly preferably 1.75 to 2 mol, per 1 mol of tetraethoxysilane.

The hydrolysis and polycondensation reaction of the inorganic alkoxide varies depending on the type of the inorganic alkoxide.
It is preferable to carry out at a temperature of 25 to 50 ° C for 0.5 to 3 hours. The resulting polymer has a low molecular weight and is uniformly soluble in organic solvents.

(3) Organic solvent  As the organic solvent used in the present invention, methyl alcohol,
Lower alcohols such as chill alcohol and isopropyl alcohol
Coals, ketones such as acetone, benzene, toluene
Aromatic hydrocarbons, such as methylene chloride, etc.
Japanese aliphatic hydrocarbons. Among them, ethyl alcohol
Are preferred. Organic solvent and inorganic alkoxide or its
The weight ratio with the hydrolysis / polycondensate is not particularly limited,
Generally, it is preferable to set the ratio to 1:10 to 10: 1.

(B) Heterogeneous mixture The heterogeneous mixture contains at least two kinds of inorganic salts, a binder and an organic solvent. One of the inorganic salts is for a matrix and the other is for doping.

(1) Inorganic Salt The inorganic salt used in the present invention becomes a conductive oxide by heat treatment. Specifically, In, Sn, Zn, Ga,
It is a compound of at least one element selected from the group consisting of Mg, Cd and Sb. Such inorganic salts include inorganic indium salts, inorganic tin salts, inorganic zinc salts,
Inorganic gallium salts, inorganic magnesium salts, inorganic cadmium salts and inorganic antimony salts.

As the inorganic indium salts, indium chloride or indium nitrate is preferred. As the inorganic tin salts, stannic chloride is preferred. As the inorganic gallium salts, gallium (III) chloride, gallium (III) nitrate or gallium (IV) sulfate is preferred. As the inorganic magnesium salts, magnesium chloride, magnesium sulfate or magnesium nitrate is preferable. As the inorganic cadmium salts, cadmium chloride, cadmium sulfate or cadmium nitrate are preferable. As the inorganic antimony salts, antimony chloride, antimony sulfate or antimony bromide is preferable.

(2) Doping Agent The doping agent is a conductive metal oxide-forming compound which is doped into the inorganic salt, and may be the same as the inorganic salt. In addition, aluminum compounds can be used,
Aluminum alkoxide is used as the aluminum compound. When a doping agent composed of an inorganic salt is used, it is necessary that the inorganic salt for matrix and the inorganic salt for doping, which are main components, are different.

It is preferable that the amount of the doping agent is 3 to 10 parts by weight (in terms of a metal element) based on 100 parts by weight of the inorganic salt. If the addition amount of the doping agent is less than 3 parts by weight, the conductivity is lowered and poor, and if it exceeds 10 parts by weight, the light transmission and the conductivity are poor.

Examples of combinations of elements of the inorganic salt for the matrix and the doping agent are shown in the following table, but are not limited to the combinations of these elements.

[0031]

(3) Binder The binder is composed of soluble cellulose or monosaccharide,
Particularly, a modified cellulose soluble in a lower alcohol is preferable. Specific examples of the modified cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose,
Examples include nitrocellulose and cellulose acetate. Among them, hydroxypropyl cellulose is preferred. Sorbitol and the like can be used as the monosaccharide.

Inorganic salt for matrix + doping agent is 10
The amount of the binder is preferably 10 to 35 parts by weight as 0 parts by weight (in terms of metal element). If the amount of the binder is less than 10 parts by weight, the film formability is poor, and if it exceeds 35 parts by weight, the conductivity of the transparent conductive film is reduced. A particularly preferred addition amount of the binder is 20 to 30 parts by weight.

(4) Coating liquid A homogeneous liquid mixture and a heterogeneous liquid mixture are mixed to prepare a multi-component sol-gel glass coating liquid (multi-component liquid mixture). The mixing ratio between the homogeneous mixture and the heterogeneous mixture is such that the weight ratio of the oxide obtained from the inorganic alkoxide to the oxide obtained from the inorganic metal salt by heat treatment is 10:90 to 40:60, preferably 30:40. Set so that 70-35: 65.

[2] Substrate The substrate used in the present invention includes glass, plastic,
Examples include metals, ceramics, and semiconductors.

[3] Method of Producing Transparent Conductive Film (a) Application of Multi-Component Mixture A multi-component mixture is applied to at least one surface of a substrate. The application method is not particularly limited, and a known method such as a spray method, an immersion method, a brush application method, and a roll coater method can be used.

(B) Heating and drying (1) Primary heat treatment The coated substrate is heated and dried at a temperature in the range of 80 to 150 ° C. to cause a dehydration reaction between the substrate and the polymer. In addition, the polymer and the substrate are strongly adhered to each other, and the crosslinking is advanced as a gel. If necessary, the heating and drying treatment may be performed after the coating liquid is applied several times. The time for the first heat treatment is preferably about 0.1 to 0.5 hours.

(2) Secondary heat treatment Next, heat treatment is performed at a temperature equal to or higher than the glass transition temperature of the multi-component sol-gel glass component. The upper limit of the secondary heat treatment temperature is preferably lower than the melting point of the multi-component sol-gel glass component. Specifically, the secondary heat treatment temperature is 400 to 55
Preferably, the temperature is 0 ° C. The secondary heat treatment time is about 1
Preferably, it is 2 hours.

[4] Characteristics of Transparent Conductive Film The thickness of the transparent conductive film is preferably 0.05 to 1.0 μm, more preferably 0.08 to 1.0 μm.
0.5 μm is particularly preferred. The film thickness of the transparent conductive film can be appropriately adjusted by thickly applying or repeatedly applying the above-mentioned coating solution.

In the obtained transparent conductive film, a multi-component sol
The gel is separated into a glass phase and a conductive metal oxide phase. The specific resistance of the phase-separated transparent conductive film is 1 × 10 ⁻¹ Ω · cm
Or less, preferably 1 × 10 ⁻³ Ω · cm or less. Also,
The formed transparent conductive film is insoluble in water and organic solvents,
And it has high surface hardness, abrasion resistance and weather resistance.

[5] Principle Originally, the phase separation of a molten glass is a phenomenon generated from a multi-component glass component obtained by mixing a homogeneous mixed system and a heterogeneous mixed system. When a melt of a multi-component glass component that shows a single phase during melting (a mixture of a homogeneous mixture and a heterogeneous mixture) is cooled and kept above the glass transition point, the single phase becomes two phases Separation into the above-mentioned glass phases, followed by rapid cooling results in a phase-separated glass having a two-phase structure.

The phenomenon of phase separation by the spinodal decomposition mechanism in a temperature range below the melt phase temperature and above the glass transition point is called stable or metastable immiscibility. This is the important phase separation in glass engineering. For example, Pyrex glass, Pycor glass, and the like are examples of application of phase-separated glass.

The glass obtained by the sol-gel method is very similar to the molten glass in terms of glass transition temperature, density and expansion coefficient. It is common to both that about 1/2 to 1/3 (absolute temperature) of the melting point of glass is the glass transition point. These have a similar structure because the basic structure has already been formed at a relatively low temperature and in a dry gel stage.

The present invention focuses on the fact that the multi-component gel separates into a silica phase and a conductive metal oxide phase (indium oxide / tin oxide component) at a temperature higher than the glass transition point to form an amorphous phase. Things. In addition, by treating various conductive metal oxides and doping oxides in the same manner, a phase-separated transparent conductive film can be formed on the silica film.

The coating solution for the phase-separated transparent conductive film of the present invention comprises:
According to a sol-gel method, an inorganic alkoxide (tetraethoxysilane or the like) was used as a starting material, water was added to a stoichiometric amount or less of a hydrolysis / polycondensation reaction, and the mixture was heated and stirred. A conductive oxide-forming compound (indium salt and stannic salt) is mixed, and both liquids are mixed with a heterogeneous mixed liquid in which modified cellulose is added as a binder. And subjected to low-temperature heat treatment, the hydroxyl groups on the substrate surface and the SiOH in the mixed solution cause a dehydration reaction, and the substrate surface has Si-O
-Si bonds are formed, and the coating film adheres strongly to the substrate and is crosslinked.

Next, the coating film becomes a metastable unmixed state by high-temperature heat treatment at a temperature higher than the glass transition point, crosslinks and thermally shrinks the Si component, and separates the indium salt and the stannic salt component. Is deposited on the upper layer of the silica film. The heat treatment oxidizes indium and stannic ions together with the burnout of the binder, and the silica component is almost phase-separated thermodynamically, and a conductive oxide glass film is formed on the SiO ₂ film.

A dopant such as stannic oxide doped into indium oxide provides a transparent conductive film,
For SnO ₂ , the light absorption wavelength is in the range of 300 to 400 nm, the long wavelength absorption by conduction electrons remains in the infrared region,
The transmissivity of visible light is good. Further, an infrared protection film is formed by absorption in the infrared region.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Embodiment 1 1. Preparation and Application of Multi-Component Mixture A isopropyl alcohol solution of tetraethoxysilane was prepared with the composition shown in Table 1, and heated at 50 ° C. for 90 minutes.
A hydrolysis / polycondensation reaction was caused to prepare a homogeneous solution. However, hydrochloric acid per mole of tetraethoxysilane is
0.01 mole and distilled water 1.75 mole.

[0050]

Next, indium chloride (InCl ₃ ) and stannic chloride (SnC) having the composition (% by weight) shown in Table 2 were used.
The l ₄₎ was dissolved in isopropyl alcohol was added hydroxypropylcellulose was stirred to prepare a heterogeneous mixture.

[0052]

13.02 for 86.98% by weight of the heterogeneous mixture
% By weight of a homogeneous mixture (Table 1) was added, bringing the total amount to 100% by weight. The weight ratio of SiO ₂ to In ₂ O ₃ is 40: 100
Met. The obtained mixture was stirred at room temperature (25 ° C.) for 1 hour to obtain a transparent multi-component mixture.

One side of a transparent soda glass substrate was coated by dipping at a speed of 10 mm / min.
A low-temperature heat treatment was performed for 15 minutes. Next, high-temperature heat treatment was performed for 1 hour at 500 ° C., which is a temperature higher than the glass transition point of the glass component. As a result, the SiO ₂ component becomes a layer in close contact with the substrate surface, and the conductive oxides In ₂ O ₃ and SnO 2
₂ was phase-separated into its upper layer, and a phase-separated transparent conductive film was obtained.
In addition, hydroxypropyl cellulose was completely burned off.

The thickness of the obtained transparent conductive film was 150 nm, the sheet resistance was 200 Ω, and the specific resistance was 3 × 10 ⁻³ Ω · cm. As a result of measurement with a spectrophotometer, the transmittance of visible light (550 nm) was 86%.

Example 2 A homogeneous mixture having the same composition as in Table 1 of Example 1 was prepared. Next, a heterogeneous mixture was prepared having the same composition as in Table 2 except that the same amount of sorbitol was added instead of hydroxypropylcellulose. A homogeneous mixture and a heterogeneous mixture were mixed in the same ratio as in Example 1 to prepare a multi-component mixture.

The multi-component mixture was applied to one surface of the same soda glass as in Example 1 by dipping, and heat-treated in the same manner as in Example 1. The thickness of the obtained transparent conductive film is 30.
0nm, sheet resistance is 1200Ω, specific resistance is 3.6 × 1
It was 0 ^-2 Ω · cm.

[0058] Since this embodiment, in which a high temperature heat treatment remain captured structure ions of indium and tin on the three-dimensional structure of the SiO ₂ which had been grown by low-temperature heat treatment, SiO ₂
According to the drying shrinkage of the three-dimensional structure, the binodal region (homogeneous system) increases, the spinodal region shrinks, and the phase-separated portion shrinks. Therefore, it is considered that the function of the conductive film of the transparent conductive film of Example 2 is lower by one digit than that of Example 1.

Example 3 Hydrochloric acid and distilled water were added to an ethanol solution of aluminum isopropoxide at the ratios shown in Table 3, and the mixture was heated at 80 ° C. for 20 minutes to carry out a hydrolysis reaction.
A homogeneous mixture was prepared. The obtained homogeneous mixed solution containing the hydrolyzed / polycondensed product of aluminum isopropoxide was mixed with zinc chloride, hydroxypropylcellulose and isopropyl alcohol at the ratios shown in Table 4 to prepare a heterogeneous mixed solution. To 88.32 parts by weight of the heterogeneous mixed solution in Table 4, the hydrolysis and hydrolysis of tetraethoxysilane shown in Table 1
11.68 parts by weight of the homogeneous mixture containing the polycondensate was mixed to prepare a multi-component mixture.

[0060]

[0061]

In the same manner as in Example 1, the multi-component mixture was applied to soda glass by dipping. Al ₂ O ₃ was 2.0 parts by weight and SiO ₂ was 40.0 parts by weight based on 100 parts by weight of ZnO in the obtained conductive film. The obtained coating film was heat-treated in the same manner as in Example 1, and the obtained transparent conductive film was evaluated. As a result, the thickness of the transparent conductive film is 150 nm, the sheet resistance is 60Ω, and the specific resistance is 9.0 × 10 ⁻⁴ Ωcm.
Met. As a result of measurement with a spectrophotometer, visible light (550 nm
) Was 87%.

[0063]

As described in detail above, in the phase-separated transparent conductive film of the present invention, since the conductive metal oxide phase is formed on the glass phase by phase separation, the adhesion to the substrate is increased. And has excellent conductivity. The phase-separated transparent conductive film of the present invention having such a configuration is suitable for use in precision equipment and optical equipment in the information and electronics industries.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeo Yoshida 6 Oosinohara, Yasu-cho, Yasu-gun, Shiga Prefecture Inside Nakato Research Laboratories Co., Ltd. Inside Nakato Research Center Co., Ltd.

Claims (16)

[Claims] 1. A homogeneous mixture containing (a) at least one inorganic alkoxide and / or a polymer formed by hydrolysis and polycondensation thereof, and (b) In, Sn, Zn,
An inorganic salt of at least one element selected from the group consisting of Ga, Mg, Cd and Sb, a conductive metal oxide-forming compound doped into the inorganic salt, and a binder;
A transparent conductive film obtained by applying a multi-component mixed solution obtained by mixing a heterogeneous mixed solution containing an organic solvent with a sol-gel glass component and applying a heat treatment at a temperature equal to or higher than the glass transition point of the sol-gel glass component. A transparent conductive film, which is separated into a glass phase and a conductive metal oxide phase. 2. The phase-separated transparent conductive film according to claim 1, wherein the inorganic alkoxide has a chemical formula: M (OR) _n.
(However, M is Si, Al, Ti, Zr, Ca, Fe,
At least one element selected from the group consisting of V, Sn, Li, Be, Y, B and P, R is an alkyl group, and n is an integer corresponding to the valence of M. ). A phase-separated transparent conductive film characterized by the following: 3. The phase-separated transparent conductive film according to claim 2, wherein the inorganic alkoxide is Si (OC
_{2 H 5) 4, Si (} OC 3 H 7) 4, Al (O-i- C 3
H ₇ ) ₃ , Ti (O-i-C ₃ H ₇ ) ₄ , Zr (O-i-C
_{3 H 7) 4, Zr (} O-n- C 4 H 9) 4, Ca (OC 2
_{H 5) 2, Fe (OC} 2 H 5) 3, V (O-i- C
₄ H ₉ ) ₄ , Sn (OC ₂ H ₅ ) ₄ , Sn (O-i-C ₄
H ₉ ) ₄ , Li (OC ₂ H ₅ ), Be (OC
_{2 H 5) 2, B (} OC 2 H 5) 3, Y (OCH 3) 3,
Y (OC ₂ H ₅ ) ₃ , P (OCH ₃ ) ₃ and P (OC ₂
H ₅₎ phase separation of the transparent conductive film, characterized in that at least one selected from the group consisting of _3. 4. The phase-separated transparent conductive film according to claim 1, wherein the inorganic salt of In is indium chloride or indium nitrate. 5. The phase-separated transparent conductive film according to claim 1, wherein the inorganic salt of Sn is stannic chloride. 6. The phase-separated transparent conductive film according to claim 1, wherein the inorganic salt of Zn is zinc chloride, zinc bromide, zinc iodide, zinc chlorate, or zinc nitrate. A phase-separated transparent conductive film, characterized in that: 7. The phase-separated transparent conductive film according to claim 1, wherein the inorganic salt of Ga is gallium chloride.
(III) A phase-separated transparent conductive film, which is gallium nitrate (III) or gallium (IV) sulfate. 8. The phase-separated transparent conductive film according to claim 1, wherein the inorganic salt of Mg is magnesium chloride, magnesium nitrate or magnesium sulfate. film. 9. The phase-separated transparent conductive film according to claim 1, wherein the Cd inorganic salt is cadmium chloride, cadmium nitrate, or cadmium sulfate. film. 10. The phase-separated transparent conductive film according to claim 1, wherein the inorganic salt of Sb is antimony chloride, antimony sulfate or antimony bromide. Conductive film. 11. The phase-separated transparent conductive film according to claim 1, wherein the binder is hydroxypropylcellulose, ethylhydroxyethylcellulose, cellulose acetate, nitrocellulose, which is soluble in lower alcohol or water. A phase-separated transparent conductive film, which is a methylcellulose or a monosaccharide. 12. The phase-separated transparent conductive film according to claim 1, wherein the polymer formed by hydrolysis / polycondensation of the inorganic alkoxide is Si (OC ₂
H _{5) 4} and 1 of water: min phasing transparent conductive film, characterized in that is obtained from a mixture of 2 following molar ratios. 13. A homogeneous mixture obtained by dissolving a polymer formed by hydrolysis and polycondensation of an inorganic alkoxide mainly consisting of Si (OC ₂ H ₅ ) ₄ in an organic solvent, and (b) an inorganic indium. At least one inorganic salt selected from the group consisting of salts, inorganic tin salts, inorganic zinc salts, inorganic gallium salts, inorganic magnesium salts, inorganic cadmium salts and inorganic antimony salts, and a conductive metal doped into the inorganic salts An oxide-forming compound, a binder, and a heterogeneous mixed solution obtained by dissolving an organic solvent in an organic solvent as a raw material, and a multi-component mixed solution obtained by mixing the homogeneous mixed solution and the heterogeneous mixed solution. A transparent conductive film obtained by heat-treating the coating film obtained from the above at a temperature not lower than the glass transition point of the sol-gel glass component. Transparent conductive film, characterized by being products phase and two-minute-phased. 14. A method for producing a phase-separated transparent conductive film, comprising: (1) preparing a homogeneous mixed solution containing at least one kind of inorganic alkoxide and / or a polymer formed by hydrolysis / polycondensation thereof; 2) In, Sn, Zn, G
a, an inorganic salt of at least one element selected from the group consisting of Mg, Cd, and Sb, a conductive metal oxide-forming compound doped into the inorganic salt, a binder, and an organic solvent. Prepare a homogeneous mixture, (3) mix the homogeneous mixture and the heterogeneous mixture to prepare a multi-component mixture, (4) apply the multi-component mixture to at least one surface of a substrate (5) The obtained coating film is subjected to a primary heat treatment at a temperature of 80 to 150 ° C., and (6) a secondary heat treatment is carried out at a temperature equal to or higher than the glass transition point of the sol-gel glass component. A method comprising separating into a phase and a conductive metal oxide phase. 15. The method for producing a phase-separated transparent conductive film according to claim 14, wherein the organic solvent is a lower alcohol,
A method characterized by being ketones, aromatic hydrocarbons or halogenated saturated aliphatic hydrocarbons. 16. The method for producing a phase-separated transparent conductive film according to claim 14, wherein the temperature of the secondary heat treatment is 400.
550 ° C.