JP2899891B2 - Transparent conductive film laminate and method for forming transparent conductive pattern - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for forming an electrode pattern on a transparent conductive film, and more particularly, to a method for etching a transparent conductive layer containing a compound semiconductor on a polymer film by etching. The present invention relates to a novel method for forming a pattern on a substrate.

Transparent conductive films are considered to be used for transparent electrodes for flat panel displays such as liquid crystal and EL, electrodes for touch panels, etc.For such applications, the transparent conductive layer is partially removed to remove the pattern. Need to be formed.

(Prior Art) Japanese Patent Application Laid-Open No. 62-75632 proposes the use of a water-soluble treatment type photosensitive film resist for such a purpose. Japanese Patent Application Laid-Open No. 61-208047 discloses that a conductive layer can be patterned with high precision by a method of contacting an acid aqueous solution after alkali development and then etching. Although it is possible to pattern the transparent conductive layer with high resolution by these methods, there are various problems when applied to the patterning of the transparent conductive layer containing the compound semiconductor of the present invention. That is, etching was difficult with the disclosed acidic aqueous solution. When an aqueous solution of dichloroethane or sodium hydroxide was used for stripping the resist, the transparent conductive layer was easily damaged.
Further, in the first place, the method for producing a transparent conductive film described in these specifications is expensive because it involves a large-scale production facility because it involves vapor deposition and other processing steps.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to form a substrate, an undercoat layer thereon, and a solution containing a compound semiconductor and a resin precursor on the undercoat layer. An object of the present invention is to realize highly accurate patterning of a transparent conductive layer.

Another object of the present invention is to provide a transparent conductive film laminate in which a photosensitive resist layer useful for realizing the patterning of the transparent conductive layer is previously laminated.

Another object of the present invention is to provide a method for quickly forming a transparent conductive electrode with low cost and high precision.

Another object of the present invention is to provide a good etching solution for a conductive layer containing a compound semiconductor.

Another object of the present invention is to expose, develop, and peel off the alkali-developable photosensitive resist layer after etching without deteriorating the conductivity, transparency, film strength, etc. of the conductive layer. It is to provide a stripping solution.

Further objects of the present invention will become clear from the description hereinafter.

(Means for Solving the Problems) An object of the present invention is to provide a support, an undercoat layer, and a transparent conductive layer formed by applying a solution containing a compound semiconductor and a resin precursor on the undercoat layer. A transparent conductive film laminate comprising a photosensitive laminate having a photosensitive resist layer capable of alkali development and a transparent and peelable temporary support laminated on a conductive film laminate comprising: This was achieved by a pattern forming method using

 Hereinafter, the present invention will be described in detail.

As the support used in the present invention, conventionally known, for example, polyesters such as polyethylene terephthalate, polyethylene, polyolefins such as polypropylene, celluloses such as cellulose acetate, acrylic esters such as polymethyl methacrylate, 6,6
-Polyamides such as nylon; polyimides, polycarbonates, polyvinyl alcohols, and vinyl chloride-vinyl acetate copolymers.

As the transparent conductive layer used in the present invention, Japanese Patent Application No.
Those described in Japanese Patent Application No. 8377 and Japanese Patent Application No. 63-88378 can be used.

Examples of the undercoat layer include polyesters, polyvinyl acetal, vinyl chloride resin, vinylidene chloride resin, and resins forming a multidimensional network structure. Of these, vinylidene chloride resins are preferred, for example, vinylidene chloride / methyl acrylate, vinylidene chloride /
Acrylic acid, vinylidene chloride / acrylonitrile, vinylidene chloride / itaconic acid, vinylidene chloride / methyl acrylate / acrylic acid, vinylidene chloride / methyl methacrylate / itaconic acid, vinylidene chloride / methyl acrylate / itaconic acid, vinylidene chloride / acrylonitrile / acrylic acid, chloride Vinylidene / acrylonitrile /
Examples include multicomponent copolymers such as itaconic acid, vinylidene chloride / methyl acrylate / methyl methacrylate / acrylic acid, and vinylidene chloride / acrylonitrile / itaconic acid / acrylic acid. Among them, a particularly preferred resin is a copolymer of a vinylidene chloride compound represented by the general formula (I).

General formula (I) Where A is Represents at least one structural unit selected from

B is Represents at least one structural unit selected from

R ₁ represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group.

R ₂ represents a methyl group, an ethyl group, or a propyl group.

x, y, z are mol%, x is 65 to 90, y is 0 to 35, z
Is in the range of 0 to 35 and has a relation of x + y + z = 100.

The content of the vinylidene chloride component of the general formula (I) has a significant effect on conductivity and light resistance. When the content is 65 mol% or more, a highly conductive film having a surface resistance of 10 ⁵ Ω / □ or less can be formed, and when it is less than that, only a low conductive film can be obtained. On the other hand, when the content of the vinylidene chloride component exceeds 90 mol%, light resistance is poor.

A in the general formula (I) is a structural unit derived from acrylonitrile, α-alkylacrylonitrile, alkyl acrylate, alkyl α-alkyl acrylate, dialkyl maleate, and dialkyl itaconate. Good. As the amount of this component increases, the light fastness improves, and although the reason is not clear, when A is acrylonitrile, particularly good light fastness is exhibited. The preferred content of A is 0 to 35 mol%, and a particularly preferred range is 10 to 30 mol%.

B in the general formula (I) is a unit derived from acrylic acid, α-alkylacrylic acid, maleic acid, monoalkyl maleate, itaconic acid, monoalkyl itaconate, and may be used alone or in combination of two or more. good. By containing the component B, the adhesion to the support is improved. B
Is preferably from 0 to 35 mol%, and particularly preferably from 1 to 25 mol%.

Preferred specific examples of the vinylidene chloride copolymer represented by the general formula (I) include vinylidene chloride / methyl acrylate / itaconic acid (molar ratio = 84: 11: 5) copolymer, vinylidene chloride / methyl acrylate (mol Ratio = 84:16)
Copolymer, vinylidene chloride / acrylonitrile (molar ratio = 75: 25) copolymer, vinylidene chloride / acrylic acid (molar ratio = 84: 16) copolymer, vinylidene chloride / methyl acrylate / acrylic acid (molar ratio = 84) : 11: 5) copolymer,
Vinylidene chloride / acrylonitrile / acrylic acid (molar ratio = 75: 21: 4) copolymer, vinylidene chloride / methyl acrylate / maleic acid (molar ratio = 84: 11: 5) copolymer,
Vinylidene chloride / acrylonitrile / itaconic acid (molar ratio = 75: 21: 4) copolymer, vinylidene chloride / methacrylate / itaconic acid (molar ratio = 75: 23: 2) copolymer, vinylidene chloride / acrylonitrile / itaconic acid ( Molar ratio =
70: 25: 5) copolymer, vinylidene chloride / diethyl itaconate / itaconic acid (molar ratio = 82: 13: 5) copolymer, vinylidene chloride / diethyl maleate / maleic acid (molar ratio = 82: 13: 5) Copolymer, vinylidene chloride / methyl acrylate / acrylic acid (molar ratio = 81: 8: 7: 6) copolymer, vinylidene chloride / acrylonitrile / acrylic acid / itaconic acid (molar ratio = 75: 20: 5: 5) Copolymers, such as vinylidene chloride / methyl acrylate / acrylic acid / maleic acid (molar ratio = 80: 10: 5: 6).

The thickness of the undercoat layer is not particularly limited, but is 0.01 to 100 μm
It is particularly preferable that the thickness be in the range of 0.05 to 10 μm.

Preferred as compound semiconductors are cuprous iodide and silver iodide, but other metal-containing compound semiconductors, such as other cuprous halides; silver halides; bismuth, gold, indium, iridium, Halides of lead, nickel, palladium, rhenium, tin, tellurium and tungsten; cuprous thiocyanate, cupric thiocyanate;
Silver thiocyanate; or mercury iodide may also be used. Of these, cuprous iodide is particularly preferred. As a solvent for cuprous iodide, acetonitrile or a volatile mixed solvent containing acetonitrile is preferable.

The compound semiconductor layer used in the present invention can be formed by dissolving the above-mentioned compound semiconductor at a concentration of 0.1 to 50% by weight together with the resin precursor and coating the solution on a support. The content of the compound semiconductor in the applied layer is 40 to 2000.
It is preferably mg / m ^2, and particularly preferably 100-1000 mg / m ^2.

The resin precursor used in the present invention is a precursor that is soluble in a solvent that dissolves the compound semiconductor and can form a film by a treatment (heating, light irradiation, chemical reaction, or the like) during or after coating. A wide range of known monomers, prepolymers, cross-linking agents and the like can be used. A preferred resin precursor in the present invention is a composition containing a crosslinking agent and capable of forming a network structure by treatment during or after coating. Typical examples include natural or synthetic rubbers, unsaturated polyesters, alkyd resins and the like, which have an unsaturated bond and are crosslinked by oxidation, or in the presence or absence of an initiator in the presence of an unsaturated monomer, and in the presence of an actinic ray. Crosslinked by radiation such as an electron beam or heat, crosslinked by a polyamine, polyamide, polycarboxylic anhydride or the like like an epoxy resin or an epoxy group-containing acrylic resin, or a polyisocyanate crosslinking agent and a hydroxyl group, a carboxyl group Examples include a combination of resins containing a group or an amino group, a self-crosslinkable polyisocyanate which is crosslinked by reacting as moisture in the air, and a combination of a polyamine with an organic acid or an acid anhydride.

Particularly preferable examples of the resin precursor include a resin precursor having an isocyanate group or an epoxy group as a crosslinking component. The compound having an isocyanate group as a cross-linking component contains two or more isocyanate groups in one molecule, and can form a multi-element network alone or in combination with an active hydrogen compound. Particularly preferred specific examples of the isocyanate compound include triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-tolylene diisocyanate, and polyisocyanate. Polyisocyanate types such as polyisocyanate types such as methylene polyphenyl isocyanate and hexamethylene diisocyanate, adducts of tolylene diisocyanate and trimethylolpropane, adducts of hexamethylene diisocyanate and water, and adducts of xylylene diisocyanate and trimethylolpropane Body type and the like can be mentioned.

Along with these resin precursors, it is also possible to use various known resins within a range that does not substantially affect the conductivity, the resist stripping liquid resistance, the etching treatment characteristics, and the like.

As the active hydrogen compound used in the present invention, for example, a compound containing a hydroxyl group, a carboxyl group, an amino group, or an amide group can be used, and for example, 1,4-butanediol, ethylene glycol, glycerin, polyether type Polyols, polyester-type polyols, acrylic-type polyols, epoxy-resin-type polyols, 4,4-methylenebis (2-chloroaniline), hydroxypropylated ethylenediamine, and the like can be given, but are not particularly limited thereto.

The isocyanate compound is used at 1 to 100% by weight, preferably 3 to 50% by weight of the compound semiconductor. If the amount is small, it is not preferable because the effect of preventing crystallization of the compound semiconductor is small, and if it is too large, the conductivity tends to decrease.

The epoxy resin used in the present invention includes, for example, an ordinary epoxy resin and an epoxy group-containing acrylic resin. Epoxy resins are generally made by the reaction of a diol with epichlorohydrin. Specific commercially available epoxy resins include EPON-812, EPON-8
15, EPON-820, EPON-828, EPON-834, EPON-836, EP
ON-1001, EPON-1002, EPON-1004, EPON-1007, EPON-1
009, EPON-1031 (these brand names are Shell products), Araldite-
252, Araldite-260, Araldite-280, Araldite-502,
Araldite-6005, Araldite-6071, Araldite-6700, Ar
aldite-6084, Araldite-6097, Araldite-6099 (trade name, manufactured by Ciba-Geigy), Dow-331, Dow-332, Dow-6
61, Dow-664, Dow-667, (trade name of Dow Chemical Company), Bakelite-2774, Bakelite-2975, Bakelite-20
02, Bakelite-2053, Bakelite-2003, Bakelite-3794
(Trade name, manufactured by Bakelite Co., Ltd.), Epoxide-201 (trade name, manufactured by Union Carbide Chemical Co., Ltd.), Epicoat 828, Epicoat 1001, (trade name, manufactured by Asahi Denka Co., Ltd.) and the like.

Examples of the epoxy resin curing agent used simultaneously with the epoxy resin include organic polyamines, boron halide complexes, ketene imines, acid anhydrides, isocyanate compounds, and phenol resins.

A resin precursor used with a compound semiconductor in the present invention,
And in some cases, the mixture of the resin precursor and the resin is used at 1 to 100% by weight, preferably 3 to 50% by weight of the compound semiconductor. If the amount is small, the effect of preventing crystallization of the compound semiconductor is small, and if too large, the conductivity tends to decrease, which is not preferable.

The alkali-developable photosensitive resist layer used in the present invention may be a flexible resin composition that can be developed with a weakly alkaline aqueous solution and that can be insolubilized in a weakly alkaline aqueous solution by irradiation with actinic rays. Examples thereof include those described in the following specifications. JP-B-55-38961, JP-B-54-34327, JP-B-58-12577, JP-B-55-6210, JP-B-5
4-25957 specification, JP-A-57-20732, JP-A-60-
No. 159743, JP-A-60-258539, JP-A-62-28539
24246, JP-A-61-169829, JP-A-61-1
No. 72139, JP-A-61-213213, JP-A-63-1
No. 47159. 0.1μ for the thickness of the photosensitive resist layer
m to 100 μm, more preferably 1 μm to 60 μm
m.

As the temporary support used in the present invention, any conventionally known support may be used as long as it is transparent and smooth to actinic rays and can be peeled off from the photosensitive photoresist layer after exposure. For example, polyesters such as polyethylene terephthalate, polyethylene, polyolefins such as polypropylene, celluloses such as cellulose acetate, acrylic esters such as polymethyl methacrylate, polyamides such as 6,6-nylon, polyimides, polycarbonates, Polyvinyl alcohols,
Examples thereof include vinyl chloride-vinyl acetate copolymers.

A preferred method for forming the conductive layer in the present invention is to dissolve a compound semiconductor dissolved in a volatile solvent and a resin precursor soluble in the volatile solvent, and in some cases, a mixture of the resin precursor and the resin. After coating on an undercoat layer formed on a suitable support, the solvent is evaporated.

To laminate the photosensitive resist layer and the temporary support on the conductive layer, a photosensitive solution is coated on the temporary support film to form a photosensitive resist layer, and then the photosensitive resist is formed on the conductive layer. It can be advantageously implemented by laminating so that the resist layer side is in contact.

Alternatively, it can be prepared by directly applying a solution of a volatile solvent containing various components of the photosensitive resist layer onto the conductive layer, and then laminating a transparent film similar to the temporary support. It is.

The coating of the conductive layer or the photosensitive resist layer of the present invention includes, for example, spin coating, immersion liquid coating, spray coating, bead coating with a continuous coating machine, a continuously moving wick method, a coating method using a hopper, and the like. There is, but is not limited to these.

The method of laminating the photosensitive resist layer and the temporary support in the present invention, while heating or at room temperature,
It can be carried out by a known method by laminating under an atmosphere of reduced pressure or normal pressure while applying pressure.

The method for forming a transparent conductive pattern using the transparent conductive film laminate of the present invention comprises the following steps.

(A) exposing the temporary support from the support side or from the support side with actinic light through a photomask having a desired pattern; and (b) removing the temporary support from the unexposed portion of the resist layer after removing the temporary support. (C) etching a portion of the compound semiconductor layer that is not covered with the resist layer with an aqueous solution containing an alkali metal and / or ammonium iodide, and (d) miscibility with water Removing the remaining resist using an organic solvent or an aqueous solution of an organic solvent miscible with water.

In the present invention, the exposure is carried out by irradiating an actinic ray that causes insolubilization of the photosensitive resist layer.As the actinic ray, ultraviolet rays having a wavelength of 200 nm to 700 nm, stationary light or laser light of visible light are usually used. .

The weak alkaline aqueous solution used in the present invention dissolves the unexposed photosensitive resist layer, and is preferably a 0.01 to 10% by weight aqueous solution of an alkali metal hydroxide or an alkali metal weak acid salt. Specific examples include lithium hydroxide, sodium hydroxide, an aqueous solution of 0.1 to 1% by weight of potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate,
Examples thereof include a 0.2 to 10% by weight aqueous solution of sodium hydrogen carbonate and potassium hydrogen carbonate. These may be used alone or as a mixture of two or more. Particularly preferred is a 0.5 to 2% by weight aqueous solution of sodium carbonate. During development, 10 to 50 ° C., more preferably room temperature to 40 ° C.
It is carried out by dipping in a vat at 0 ° C or spraying from a nozzle.

The alkali metal and / or ammonium iodides used in the present invention are lithium iodide, sodium iodide, potassium iodide, and ammonium iodide, and particularly preferably include sodium iodide and potassium iodide. These may be used alone or as a mixture of two or more. These aqueous solutions are used as an etchant, but the preferred concentration is 1 to 60.
%, Particularly preferably 10 to 40% by weight. When etching, 10 to 50 ° C., more preferably room temperature to 40 ° C.
It is carried out by dipping in a vat at 0 ° C or spraying from a nozzle.

As a water-miscible organic solvent used for stripping the resist in the present invention, alcohol, alkylene glycol, triol, alkylene glycol monoether,
Alkylene glycol diether, alkylene glycol monoether monoester, cyclic ether, cyclic ether alcohol, ketone, cyclic ketone, formate, fatty acid ester, lactic acid ester, cyclic lactone, formamide, fatty acid amide, phosphoric amide, sulfonamide, cyclic It is selected from lactam, aliphatic nitrile, aromatic nitrile, lower fatty acid and the like. Preferred specific examples include methanol, ethanol, n-propanol, isopropanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate,
Propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, tetrahydrofuran,
Dioxane, furan, furfuryl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl formate, ethyl acetate, methyl acetate, propyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, formamide, acetamide, hexamethylphosphoramide, Examples thereof include benzenesulfonic acid amide, toluenesulfonic acid amide, pyrrolidone, acetonitrile, benzonitrile, formic acid, acetic acid, and propionic acid. These may be used alone or as a mixture of two or more. When these organic solvents are mixed with water, it is preferable to use them in a range compatible with each other at a weight ratio of 1:99 to 99: 1. Particularly preferred organic solvents are methanol, ethanol and acetone, which are used alone or in a weight ratio of 99: 1 to 90:10 with water.

(Examples) Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Example 1 On a polyethylene terephthalate film having a thickness of 100 μm, 4 g of vinylidene chloride resin (Saran R202: trade name, manufactured by Asahi Kasei Corporation) was added with 696 g of dichloromethane and cyclohexanone 30.
A solution dissolved in 0 g of the mixed solvent was extruded, applied using a hopper, and dried at 100 ° C. The thickness of this undercoat layer is 0.4 μm
Met. After that, a solution containing 3 g of cuprous iodide and 0.3 g of an isocyanate compound (Coronate L: trade name of Nippon Polyurethane Co., Ltd.) in 97 g of acetonitrile was dried on this layer to a weight of 0.3 g / was applied so that the m ² 100
Dried at ° C. This solution was absorbed by the undercoat layer, and a layer of cuprous iodide fine particles was formed mainly on the upper layer of the undercoat layer. The surface resistance of this conductive layer is determined by Loresta MCP-TESTER
9.3 × 10 ³ Ω / □
Met. The light transmittance at a wavelength of 550 nm was 78%.

On the other hand, a solution having the following composition was applied on a 25 μm-thick polyethylene terephthalate film (temporary support) to a dry film thickness of 25 μm.
To form a photosensitive resist layer.

Methyl methacrylate / meta 15 g Crylic acid / benzyl methacrylate / 2-ethylhexyl acrylate copolymer (molar ratio: 50/23/7/25) Polypropylene glycol 5.5 g (molecular weight ≒ 700) diaacrylate polyethylene glycol 2.5 g (molecular weight ≒ 200 ) Dimethacrylate bis- (4-diethylamino) 0.04 g benzophenone benzophenone 0.5 g phenyltribromomethyls 0.15 g rufone p-toluenesulfonamide 1.5 g leuco crystal violet 0.2 g malachite green 0.001 g 1-phenyl-3-morpholy 0.001 g Nomethyl-1,3,4-triazole-2-thione methyl cellosolve 15 g Methyl ethyl ketone 10 g Using a hot roll laminator, heat-pressing and applying pressure to the photosensitive resist layer and the transparent conductive layer. Laminated. The photosensitive resist layer showed good adhesion to the transparent conductive layer, and no air was trapped between both layers. A photomask carrying an electrode pattern was placed on the 25 μm-thick polyethylene terephthalate film side of the temporary support and baked under an ultra-high pressure mercury lamp. 20
After minutes, the temporary support is peeled off, the unexposed resist portion is dissolved by immersion in a 1% by weight aqueous sodium carbonate solution, washed with water, and then immersed in a 30% by weight aqueous solution of potassium iodide to be covered with the resist. The unreacted portion of cuprous iodide was dissolved.
Finally, the film was immersed in ethanol to remove the remaining resist. The electrode pattern of the conductive layer thus obtained had a resolution of 30 μm, and it was found that the light transmittance and conductivity of the conductive layer did not change before and after these patterning treatments.

Example 2 A film having a patterned conductive layer was obtained in the same manner as in Example 1 except that 30% by weight of sodium iodide was used instead of 30% by weight of potassium iodide as an etching solution. The resolution, light transmittance and conductivity of this pattern were also good.

Example 3 A film having a patterned conductive layer was obtained in the same manner as in Example 1 except that 30% by weight of ammonium iodide was used instead of 30% by weight of potassium iodide as an etching solution. The resolution, light transmittance and conductivity of this pattern were also good.

Example 4 A film having a patterned conductive layer was obtained in the same manner as in Example 1 except that methanol was used instead of ethanol as a stripping solution. The resolution of this pattern,
Light transmittance and conductivity were also good.

Example 5 A film having a patterned conductive layer was obtained in the same manner as in Example 1 except that acetone was used instead of ethanol as a stripping solution. The resolution, light transmittance and conductivity of this pattern were also good.

Example 6 A mixed solvent of 4 g of a resin obtained by copolymerizing vinylidene chloride / methyl acrylate / itaconic acid at a molar ratio of 84: 11: 5 on a polyethylene terephthalate film having a thickness of 100 μm, 700 g of methylene chloride and 300 g of cyclohexanone Was applied to form a 0.4 μm undercoat layer. On this layer, 100 ° C. by applying a solution of acetonitrile 97g containing cuprous iodide 3g as dry weight is 0.3 g / m ²
And dried. Loreste MCP
As a result of measurement with −TESTER, it was 7.8 × 10 ³ Ω / □. The light transmittance at 550 nm was 78%. On this conductive layer, a photosensitive resist layer and a polyethylene terephthalate film were provided in the same manner as in Example 1. By treating this laminate in the same manner as in Example 1, a transparent conductive electrode pattern could be obtained.

Comparative Example 1 When 3% sodium hydroxide was used in place of ethanol of Example 1 as the stripping solution, the resist could be stripped, but the portion of the conductive layer covered with the resist turned yellow and showed conductivity. Did not. This indicates that the conductive layer was separated by the 3% aqueous solution of sodium hydroxide.

Comparative Example 2 When methylene chloride was used in place of ethanol of Example 1 as the stripping solution, the resist could be stripped, but the conductivity of the portion of the conductive layer covered by the resist was not observed. This indicates that the conductive layer was separated by the 3% aqueous solution of sodium hydroxide.

Comparative Example 3 On a polyethylene terephthalate film having a thickness of 100 μm, 4 g of vinylidene chloride resin (Saran R202: trade name, manufactured by Asahi Kasei Corporation) 696 g of dichloromethane and 30 parts of cyclohexanone 30
A solution dissolved in 0 g of the mixed solvent was extruded, applied using a hopper, and dried at 100 ° C. The thickness of this undercoat layer is 0.4 μm
Met. After that, a solution containing 3 g of cuprous iodide and 0.3 g of an isocyanate compound (Coronate L: trade name of Nippon Polyurethane Co., Ltd.) in 97 g of acetonitrile was dried on this layer to a weight of 0.3 g / was applied so that the m ² 100
Dried at ° C. This solution was absorbed by the undercoat layer, and a layer of cuprous iodide fine particles was formed mainly on the upper layer of the undercoat layer. The surface resistance of this conductive layer is determined by Loresta MCP-TESTER
9.3 × 10 ³ Ω / □
Met. The light transmittance at a wavelength of 550 nm was 78%.

Example 1 of JP-A-61-208047 was used for this film.
Was laminated (liston 3410, manufactured by DuPont) and exposed through a photomask. After dissolving and removing the unexposed portion with a dilute alkaline aqueous solution, an acid treatment was performed using a 0.5% by weight aqueous solution of sulfuric acid (25 ° C.). Thereafter, etching was performed with a 25% by volume aqueous hydrochloric acid solution (25 ° C.). After drying, the resist was stripped off with dichloroethane. The conductive film dissolved and no conductivity was observed.

Comparative Example 4 On a polyethylene terephthalate film having a thickness of 100 μm, 4 g of vinylidene chloride resin (Saran R202: trade name, manufactured by Asahi Kasei Corporation) 696 g of dichloromethane and cyclohexanone 30
A solution dissolved in 0 g of the mixed solvent was extruded, applied using a hopper, and dried at 100 ° C. The thickness of this undercoat layer is 0.4 μm
Met. After that, a solution containing 3 g of cuprous iodide and 0.3 g of an isocyanate compound (Coronate L: trade name of Nippon Polyurethane Co., Ltd.) in 97 g of acetonitrile was dried on this layer to a weight of 0.3 g / was applied so that the m ² 100
Dried at ° C. This solution was absorbed by the undercoat layer, and a layer of cuprous iodide fine particles was formed mainly on the upper layer of the undercoat layer. The surface resistance of this conductive layer is determined by Loresta MCP-TESTER
9.3 × 10 ³ Ω / □
Met. The light transmittance at a wavelength of 550 nm was 78%.

The film was coated with the following resist layer coating solution described in JP-A-62-75632 using an applicator and dried to form a 15 μm-thick resist layer.

Poly (methyl methacrylate / 50 g acrylic acid) (75/25 wt%) Trimethylolpropane tri 30 g Acrylate Benzophenone 0.5 g Michler's ketone 0.05 g Victoria blue 0.03 g Methyl ethyl ketone 20 g Tetrahydrofuran 30 g Further, a 25 μm thick polyethylene glycol terephthalate film Lamination was performed to obtain a photosensitive resist laminate.

After this, the laminate film was removed after UV exposure through a photomask, and developed with a 1% aqueous sodium carbonate solution at 40 ° C. When the resist was removed with an aqueous solution of sodium hydroxide after the treatment with a hydrochloric acid etching solution, the conductive portion was also peeled off.

(Effect of the Invention) The conductive film obtained by using the transparent conductive film laminate of the present invention suppresses undesired crystallization of the compound semiconductor over time, and the transparency and the conductivity are stable for a long time. Naturally, it is a highly stable conductive film having excellent organic solvent resistance and adhesion to an upper layer when applied in a multilayer structure such as electrophotography.

Further, the method of the present invention makes it possible to pattern an inexpensive and highly accurate transparent conductive film.

The method of the present invention comprises a transparent electrode for a thin liquid crystal display,
It can be widely used for the transparent electrode of the dispersion type EL, the transparent electrode of the touch panel, the transparent heater, the heat ray shield and the like.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) H01B 5/14 H01B 13/00 503

Claims (2)

(57) [Claims] 1. A conductive film laminate comprising a support, an undercoat layer, and a transparent conductive layer formed by applying a solution containing a compound semiconductor and a resin precursor on the undercoat layer, A transparent conductive film laminate comprising a photosensitive laminate having an alkali-developable photosensitive resist layer and a transparent and peelable temporary support laminated. 2. A method for forming a transparent conductive pattern using the transparent conductive film laminate according to claim 1, comprising the following steps. (A) exposing the temporary support or the support with active light through a photomask having a desired pattern; and (b) removing the unexposed portion of the resist layer after removing the temporary support. (C) removing the transparent conductive layer that is not covered by the resist layer in the exposed portion with a processing solution that does not substantially affect the resist layer; (d) forming the transparent conductive layer by the transparent conductive layer Removing the remaining resist layer by using a processing liquid that does not substantially affect the formed pattern.