JP2009188360A - Electronic circuit and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electronic circuit which is prevented from migration and is free of the reduction in insulation resistance even when being driven for a long time, and to provide a method of forming a conductive film having high conductivity at low cost. <P>SOLUTION: A method of manufacturing the electronic circuit 10 includes: a metal wiring part forming step of forming a metal wiring part 14 containing a metal on a supporting member 12; and a mercapto compound adsorption step of bringing a metal ion trapping agent (mercapto compound-containing solution) into contact with the metal wiring part to cause the metal wiring part to adsorb a mercapto compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electronic circuit and a manufacturing method thereof.

In recent years, with the increasing use of various electric facilities and electronic application facilities, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly, and various types of electromagnetic shielding films have been developed. ) And translucency have been proposed so far.
(1) Mesh printed with silver paste For example, Patent Document 1 discloses a method of obtaining a silver mesh by printing a paste made of silver powder in a mesh shape.
(2) Irregular mesh silver mesh For example, Patent Document 2 discloses an irregular fine mesh silver mesh and a method for producing the same.
(3) Etching processed copper mesh using photolithography method For example, Patent Document 3 proposes a method of forming a copper mesh on a transparent substrate by etching a copper foil using a photolithography method.

(4) Method for forming conductive silver using silver salt For example, Patent Document 4 discloses a method of forming a metallic silver thin film pattern having conductivity by a silver salt diffusion transfer method in which silver is deposited on a physical development nucleus in the 1960s. It is disclosed.

  The electromagnetic shielding film described above has also been proposed for use in electronic circuits in addition to its application. However, the silver mesh obtained by the method (1) has problems such as a large line width and a high surface resistance because it depends on the printing method. Further, the production method (2) has a problem that only a large mesh having a surface resistance value of 10Ω / sq can be obtained. In the method (3), the manufacturing process always includes many steps, and there is a problem that must be manufactured through these steps. Further, according to the method (4), a silver mesh can be formed by exposing and developing a photosensitive material having an emulsion layer containing a silver salt, and a silver thin film of 10Ω / sq to 100 kΩ / sq is obtained. However, a material having excellent conductivity could not be obtained.

By the way, metal silver is most susceptible to ion migration. For this reason, when metallic silver is used as it is as an electronic circuit, migration occurs due to the movement of metal ions between metal wiring portions when driven for a long time, resulting in dielectric breakdown between the electrodes. In this regard, Patent Document 5 discloses a technique for preventing migration by bringing HZr ₂ (PO ₄ ) ₃ into contact with an electronic circuit having a metallic silver portion. However, the technique disclosed in Patent Document 5 has an insufficient effect of preventing migration.
JP 2000-13088 A Japanese Patent Laid-Open No. 10-340629 Japanese Patent Laid-Open No. 10-41682 Japanese Patent Publication No.42-23746 JP-A-1-319202

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide an electronic circuit that prevents migration of the electronic circuit and does not decrease the insulation resistance even when driven for a long time, and a method for manufacturing the same. .

  As a result of intensive studies to solve the above problems, the present inventors have adsorbed a metal ion trapping agent (mercapto compound) that forms a hardly soluble metal salt on the surface of the metal wiring portion, so that the compound becomes a metal ion. It was found that the occurrence of migration can be suppressed. The present invention has been made based on such findings.

The problems of the present invention have been solved by the following means.
[1] An electronic circuit comprising a metal wiring part containing metal, wherein a metal ion trap agent that forms a hardly soluble metal salt is adsorbed on the metal wiring part.
[2] The electronic circuit according to the item [1], wherein the metal ion trapping agent has a pKsp of 9 or more.
[3] The electronic circuit according to [1] or [2], wherein the metal ion trapping agent is at least one selected from benzotriazole, a benzotriazole derivative, and a mercapto compound.
[4] The electronic circuit according to any one of [1] to [3], wherein the metal ion trapping agent is a mercapto compound represented by the following general formula (1).
General formula (1) RR'-SH
(In the formula, R ′ is a 5- or 6-membered heterocycle and may be condensed. R is a substituent having 6 or more carbon atoms.)
[5] The electronic circuit according to any one of [1] to [4], wherein the metal is silver.
[6] The electronic circuit according to any one of [1] to [5], wherein the metal wiring portion has a volume resistance of 10 ⁻⁴ or less.
[7] the metal ion trapping agent is 1mg / m ² ~500mg / m ² adsorbed on the metal wiring portion, [1] an electronic circuit according to any one of to [6].

[8] A method for producing an electronic circuit comprising a metal wiring part containing a metal on a support,
A metal wiring part forming step of forming a metal wiring part containing metal on the support;
A metal ion trap agent (mercapto compound-containing solution) is contacted with the metal wiring part, and a mercapto compound adsorption step of adsorbing the mercapto compound on the metal wiring part;
A method for manufacturing an electronic circuit, comprising:
[9] The electronic circuit according to item [8], wherein the metal wiring part forming step is performed by exposing and developing a photosensitive layer containing silver salt to form a metal wiring part containing metal silver. Manufacturing method.
[10] The method for manufacturing an electronic circuit according to the item [8] or [9], wherein the metal wiring part forming step is performed by applying a metal paste.

[11] The method for manufacturing an electronic circuit according to any one of [8] to [10], further including a consolidation step of performing consolidation treatment on the metal wiring portion.
[12] The method for manufacturing an electronic circuit according to the item [11], wherein the consolidation treatment is performed at a linear pressure of 1960 N / cm (200 kgf / cm) or more.
[13] The method for manufacturing an electronic circuit according to [11] or [12], wherein the consolidation treatment is performed at a linear pressure of 2940 N / cm (300 kgf / cm) or more.
[14] The method for manufacturing an electronic circuit according to any one of [11] to [13], wherein the consolidation treatment is performed at a linear pressure of 6860 N / cm (700 kgf / cm) or more.

[15] After the metal wiring portion forming step, there is a wet heat treatment step in which the formed metal wiring portion is left in an atmosphere of humidity control conditions of a temperature of 40 ° C. or higher and a relative humidity of 5% or higher. ] The manufacturing method of the electronic circuit of any one of [14].
[16] The method for manufacturing an electronic circuit according to the item [15], wherein the temperature of the humidity control condition is 60 ° C. or higher.
[17] The method for manufacturing an electronic circuit according to the item [15] or [16], wherein the temperature of the humidity control condition is 80 ° C. or higher.
[18] The method for manufacturing an electronic circuit according to any one of [15] to [17], wherein the relative humidity under the humidity control condition is 60% or more.
[19] The method for manufacturing an electronic circuit according to any one of [15] to [18], wherein the relative humidity under the humidity control condition is 80% or more.

[20] The electronic circuit manufacturing according to any one of [8] to [14], further including a vapor contact step of bringing the formed metal wiring portion into contact with vapor after the metal wiring portion forming step. Method.
[21] The method for manufacturing an electronic circuit according to the item [20], wherein the temperature of the vapor is 80 ° C. or higher.
[22] The method for manufacturing an electronic circuit according to the item [20] or [21], wherein the vapor is water vapor.
[23] The method according to any one of [8] to [14], further including a hot water treatment step of immersing the formed metal wiring portion in hot water having a temperature of 60 ° C. or higher after the metal wiring portion forming step. Electronic circuit manufacturing method.
[24] The method for manufacturing an electronic circuit according to the item [23], wherein the temperature of the hot water is 80 ° C. or higher.

[25] The method for manufacturing an electronic circuit according to any one of [8] to [24], wherein the mercapto compound adsorption step immerses the formed metal wiring part in a mercapto compound-containing liquid.
[26] The method for manufacturing an electronic circuit according to the item [25], wherein the mercapto compound-containing solution contains 1 to 100 g / L of a mercapto compound.
[27] The method for manufacturing an electronic circuit according to any one of [8] to [26], further including an alcohol cleaning treatment step of immersing and cleaning the metal wiring part in alcohol after the mercapto compound adsorption step.
[28] The method for manufacturing an electronic circuit according to the item [27], wherein the alcohol is methanol.
[29] The method for manufacturing an electronic circuit according to the item [27], wherein the alcohol is ethanol.

  In this specification, “warm water” refers to water of 40 ° C. or higher. “Steam” means saturated steam or heated steam at 80 ° C. or higher. Examples of the substance that becomes a vapor include water and organic solvents (specifically, alcohol, ether, and the like). Any organic solvent may be used as long as it does not dissolve the support. Among these, water vapor is preferable. In this specification, steam includes steam. “Humidity” refers to relative humidity.

ADVANTAGE OF THE INVENTION According to this invention, even when it drives for a long time, the electronic circuit with which the migration which generate | occur | produces by the movement of a metal ion between metal wiring parts was suppressed can be manufactured.
Since the electronic circuit of the present invention is excellent in flexibility, it can be applied to electrodes such as solar cells and touch panels, and can be widely applied to printed wiring boards as a conductive patterning material.

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

The electronic circuit of the present invention is an electronic circuit provided with a metal wiring portion containing metal, and a metal ion trap agent that forms a hardly soluble metal salt is adsorbed on the metal wiring portion.
Such an electronic circuit according to the present invention is a method of manufacturing an electronic circuit including a metal wiring portion containing a metal on a support, and forms a metal wiring portion containing a metal on the support. It is obtained by a method for producing an electronic circuit comprising: a forming step; and a mercapto compound adsorption step in which a metal ion trap agent (mercapto compound-containing solution) is brought into contact with the metal wiring portion and a mercapto compound is adsorbed on the metal wiring portion.

  A method for manufacturing the electronic circuit (conductive film) of the present invention will be described. In the present invention, first, a metal wiring portion containing a metal is formed on a support. The method for forming the metal wiring portion is not particularly limited, but on the support on which the conductive metal portion formed of a conductive substance and a water-soluble binder is formed on the support, and then the conductive metal portion is formed, A method of forming the metal wiring part by performing any one of wet heat treatment, steam contact treatment, or hot water treatment described later is preferable. The electronic circuit manufactured in the present invention is preferably light transmissive, but is not limited thereto.

  As the support, those similar to the support for photosensitive material described later can be used, but a plastic film (thermoplastic resin film), a plastic plate, a glass plate and the like can be used. Among these, a transparent material, for example, a transparent flexible support is preferable. In addition, it is preferable that it is 200 micrometers or less from a flexible viewpoint, and, as for the film thickness of a support body, it is more preferable that it is 100 micrometers or less.

  As the conductive material, copper, silver, aluminum, indium tin oxide (ITO), or the like can be used, and silver is particularly preferable. Moreover, the particle diameter should just be 500 micrometers or less, and 300 micrometers or less are more preferable. In addition, when nano-sized conductive metal fine particles are used, the effect of improving conductivity in the steam treatment process is particularly excellent. Specific examples of the conductive substance include silver paste (silver nano paste when nano-sized conductive metal fine particles are used). Silver paste is a conductive paste-like substance (paste) obtained by dispersing silver particles having a predetermined particle diameter in a suitable solvent such as a resin binder, and is used for attaching a sample or conducting a conductive treatment. Examples of commercially available products include Pertron K-3424LB (trade name, manufactured by Pernox Co., Ltd.). Moreover, when using silver nanopaste, the shape of electroconductive substance particle is granular, acicular, etc. are mentioned. In addition, the average particle size represented by a sphere equivalent diameter is preferably 25 μm or less, and more preferably 1000 nm or less. The lower limit is 10 nm or more.

  As the binder, those described below can be used. The binder is preferably a water-soluble polymer. The amount of binder used is preferably such that the conductive material / binder volume ratio is 1/4 or more, and more preferably 1/1 or more.

The volume resistance of the metal wiring portion satisfies the following formula (1), where A is the density of the conductive material in the metal wiring portion, B is the density of the binder in the metal wiring portion, and C is the volume resistance of the metal wiring portion. It is preferable. Here, the density of the conductive material and the density of the binder can be determined from the amount of silver, gelatin, and carrageenan added during coating. Further, the volume resistance of the metal wiring part can be obtained from (surface resistance) × (film thickness) from the surface resistance and film thickness. The surface resistance can be measured by a resistance measuring instrument, and the film thickness can be measured by a cross-sectional SEM (scanning electron microscope). An electronic circuit having this characteristic is obtained by the manufacturing method of the present invention. For example, the conductive metal that has been in the form of particles after development is converted into a conductive metal by any one of wet heat treatment, steam contact treatment, or hot water treatment. Is obtained by fusing.

  As a method for forming the metal wiring portion, there is a method of bonding, in addition to a method using a photosensitive material described later. Here, the term “bonding” means forming a transparent conductive film by separately forming and overlapping a fine-line structure portion of a network metal and / or alloy and a transparent film on which a transparent conductive film is formed. That is, the fine wire structure portion of metal and / or alloy and the transparent conductive film may be bonded together. The metal wiring part may be formed by a printing method. Printing methods include screen printing and gravure printing. Specifically, the methods described in JP-A-11-170420, JP-A-2003-109435, JP-A-2007-281290, International Publication No. WO2007 / 119707A1, etc. can be used.

  Hereinafter, a method using a photosensitive material will be described as a preferred method for forming the metal wiring portion. In this method, a conductive metal silver portion and a light transmissive portion are formed on the support by exposing and developing a photosensitive material having a photosensitive layer containing a photosensitive silver salt and a water-soluble binder on the support. Form.

<Sensitive material for making conductive film>
[Support]
As the support of the photosensitive material used in the production method of the present invention, a plastic film, a plastic plate, a glass plate, or the like can be used.
Examples of the raw material for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene and EVA; Vinyl resins such as vinyl chloride and polyvinylidene chloride; others, polyetheretherketone (PEEK), polysulfone (PSF), polyethersulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetylcellulose (TAC) or the like can be used.
The plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined. A metal foil base such as aluminum can also be used.
As the support, PET (258 ° C.), PEN (269 ° C.), PE (135 ° C.), PP (163 ° C.), polystyrene (230 ° C.), polyvinyl chloride (180 ° C.), polyvinylidene chloride (212 ° C.) A plastic film or a plastic plate having a melting point of about 290 ° C. or less such as TAC (290 ° C.) is preferable, and PET is particularly preferable for a light-transmitting electromagnetic wave shielding film from the viewpoint of light transmittance and workability.

Since the transparent conductive film is required to be transparent, the support is preferably highly transparent. In this case, the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. Moreover, in this invention, what was colored to such an extent that the objective of this invention is not disturbed can also be used as the said plastic film and a plastic board.
The plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.

  When a glass plate is used as the support in the present invention, the type thereof is not particularly limited, but when used as a conductive film for display, it is preferable to use tempered glass having a tempered layer on the surface. There is a high possibility that tempered glass can prevent breakage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.

[Emulsion layer (photosensitive layer containing silver salt)]
The photosensitive material used in the production method of the present invention has an emulsion layer (silver salt-containing photosensitive layer) containing a silver salt emulsion as a photosensor on a support. The silver salt-containing photosensitive layer can contain additives such as a solvent and a dye in addition to the silver salt and the binder.
Preferably, the emulsion layer is substantially disposed on the uppermost layer. Here, “the emulsion layer is substantially the uppermost layer” not only means that the emulsion layer is actually disposed on the uppermost layer, but also the total thickness of the layers provided on the emulsion layer is 0. .5 μm or less. The total thickness of the layers provided on the emulsion layer is preferably 0.2 μm or less.

Hereinafter, each component contained in the emulsion layer will be described.
<Dye>
The light-sensitive material may contain a dye at least in the emulsion layer. The dye is contained in the emulsion layer as a filter dye or for various purposes such as prevention of irradiation. The dye may contain a solid disperse dye. Examples of the dye preferably used in the present invention include dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication are preferable. Further, (II-2) to (II-24) described in JP-A-7-152112, (III-5) to (III-18) described in JP-A-7-152112, and JP-A-7-152112. (IV-2) to (IV-7) described in the publication are also preferably used.

  In addition, as dyes that can be used in the present invention, solid fine particle dispersed dyes to be decolored during development or fixing processing include cyanine dyes, pyrylium dyes, and aminium dyes described in JP-A-3-138640. Can be mentioned. Further, as dyes that do not decolorize during processing, cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes not containing an acidic group described in JP-A-8-245902, and those described in JP-A-8-333519 Lake type cyanine dyes, cyanine dyes described in JP-A-1-266536, holopolar cyanine dyes described in JP-A-3-136638, pyrylium dyes described in JP-A-62-299959, JP-A-7-253039 Polymer type cyanine dyes described in JP-A No. 2-282244, solid fine particle dispersions described in JP-A No. 2-282244, light scattering particles described in JP-A No. 63-131135, Yb3 + compounds described in JP-A No. 9-5913 And ITO powder described in JP-A-7-113072. . In addition, dyes represented by general formula (F1) and general formula (F2) described in JP-A-9-179243, specifically, compounds F35 to F112 described in the same publication can also be used.

  Moreover, as said dye, a water-soluble dye can be contained. Such water-soluble dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and benzylidene dyes are particularly useful in the present invention. Specific examples of water-soluble dyes that can be used in the present invention include British Patent Nos. 584,609, 1,177,429, JP-A-48-85130, 49-99620, No. 49-114420, No. 52-20822, No. 59-154439, No. 59-208548, US Pat. No. 2,274,782, No. 2,533,472, No. 2 No. 3,956,879, No. 3,148,187, No. 3,177,078, No. 3,247,127, No. 3,540,887, No. 3 , 575,704 specification, 3,653,905 specification, and 3,718,427 specification.

  The content of the dye in the emulsion layer is preferably 0.01 to 10% by mass with respect to the total solid content, from the viewpoint of preventing irradiation and the like, and from the viewpoint of lowering sensitivity due to an increase in the amount added. More preferred is mass%.

<Silver salt>
Examples of the silver salt used in the present invention include inorganic silver salts such as silver halide and organic silver salts such as silver acetate. In the present invention, it is preferable to use silver halide having excellent characteristics as an optical sensor.
The silver halide preferably used in the present invention will be described.
In the present invention, it is preferable to use a silver halide excellent in characteristics as an optical sensor, and the technique used in a silver salt photographic film or photographic paper, a printing plate-making film, a photomask emulsion mask, etc. relating to silver halide, It can also be used in the present invention.
The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halides mainly composed of silver chloride, silver bromide and silver iodide are preferably used, and silver halides mainly composed of silver bromide and silver chloride are preferably used. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred are silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.

  Here, “silver halide mainly composed of silver bromide” refers to silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of silver bromide may contain iodide ions and chloride ions in addition to bromide ions.

  The silver iodide content in the silver halide emulsion is preferably in a range not exceeding 1.5 mol% per mole of silver halide emulsion. By setting the silver iodide content in a range not exceeding 1.5 mol%, fogging can be prevented and the pressure property can be improved. A more preferred silver iodide content is 1 mol% or less per mole of silver halide emulsion.

Silver halide is in the form of solid grains. From the viewpoint of image quality of the patterned metallic silver layer formed after exposure and development, the average grain size of silver halide is 0.1 to 1000 nm in terms of sphere equivalent diameter ( 1 μm) is preferred, 0.1 to 100 nm is more preferred, and 1 to 50 nm is even more preferred.
Incidentally, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.

The shape of the silver halide grains is not particularly limited, and may be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, tetragonal flat plate shape, etc.), octahedron shape, and tetrahedron shape. There can be a cube and a tetrahedron.
The silver halide grains may be composed of a uniform phase or a different surface layer. Moreover, you may have the localized layer from which a halogen composition differs in a particle | grain inside or the surface.
The silver halide emulsion used for forming the emulsion layer in the present invention is preferably a monodispersed emulsion, and the coefficient of variation represented by {(standard deviation of grain size) / (average grain size)} × 100 is 20% or less, and more. It is preferably 15% or less, and most preferably 10% or less.

  The silver halide emulsion used in the present invention may be a mixture of a plurality of types of silver halide emulsions having different grain sizes.

The silver halide emulsion used in the present invention may contain a metal belonging to Group VIII or Group VIIB. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound, or the like. These compounds may be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and such pseudohalogens. In addition to ammonia, organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, etc.), urea, thiourea and the like can be mentioned.
For high sensitivity, doping with a metal hexacyanide complex such as K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ], K ₃ [Cr (CN) ₆ ] is advantageous. Done.

A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium halide (III) compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt, a hexabromorhodium (III) complex salt, and a hexaamine rhodium (III). ) Complex salt, trizalatodium (III) complex salt, K ₃ Rh ₂ Br _{9 and the} like.
These rhodium compounds are used by dissolving in water or a suitable solvent, and are generally used in order to stabilize the rhodium compound solution, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, hydrofluoric acid). Or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add another silver halide grain previously doped with rhodium and dissolve it at the time of silver halide preparation.

In addition, in the present invention, a silver halide containing Pd (II) ions and / or Pd metal can also be preferably used. Pd may be uniformly distributed in the silver halide grains, but is preferably contained in the vicinity of the surface layer of the silver halide grains. Here, Pd “contains in the vicinity of the surface layer of the silver halide grains” means that the Pd content is higher than the other layers within 50 nm in the depth direction from the surface of the silver halide grains. means.
Such silver halide grains can be prepared by adding Pd in the course of forming silver halide grains. After adding silver ions and halogen ions to 50% or more of the total addition amount, Pd Is preferably added. It is also preferred that Pd (II) ions be present on the surface of the silver halide by a method such as addition at the time of post-ripening.
The Pd-containing silver halide grains increase the speed of physical development and electroless plating, increase the production efficiency of a desired electromagnetic shielding material, and contribute to the reduction of production costs. Pd is well known and used as an electroless plating catalyst. However, in the present invention, Pd can be unevenly distributed on the surface layer of silver halide grains, so that extremely expensive Pd can be saved. is there.

In the present invention, the content of Pd ions and / or Pd metals contained in the silver halide is preferably 10 ^{−4 to} 0.5 mol / mol Ag with respect to the number of moles of silver in the silver halide. More preferably, it is 0.01 to 0.3 mol / mol Ag.
Examples of the Pd compound to be used include PdCl ₄ and Na ₂ PdCl ₄ .

In the present invention, chemical sensitization may or may not be performed in the same manner as in general silver halide photographic light-sensitive materials. As a method of chemical sensitization, for example, a chemical sensitizer composed of a chalcogenite compound or a noble metal compound having a sensitivity sensitizing action for a photographic light-sensitive material cited in paragraph No. 0078 of JP-A-2000-275770 is halogenated. By adding to the silver emulsion. As the silver salt emulsion used in the light-sensitive material of the present invention, an emulsion that does not undergo such chemical sensitization, that is, an unchemically sensitized emulsion can be preferably used. In the present invention, a preferable method for preparing a non-chemically sensitized emulsion is to add an amount of a chemical sensitizer composed of chalcogenite or a noble metal compound, such that the increase in sensitivity due to the addition of these is less than 0.1. It is preferable to keep it at. The specific amount of chalcogenite or noble metal compound added is not limited, but as a preferred method for preparing the unchemically sensitized emulsion in the present invention, the total amount of these chemically sensitized compounds is 5 × per mol of silver halide. It is preferable to make it 10 ⁻⁷ mol or less.

<Water-soluble binder>
In the emulsion layer, a binder is used for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. In the present invention, as the binder, a water-soluble binder that is removed by wet heat treatment described later is used. As such a water-soluble binder, it is preferable to use a water-soluble polymer.
Examples of the binder include polysaccharides such as gelatin, carrageenan, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, and polyacrylic acid. , Polyalginic acid, polyhyaluronic acid, carboxycellulose, gum arabic, sodium alginate and the like. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.
In addition to lime-processed gelatin, acid-processed gelatin may be used as gelatin. Hydrolyzate of gelatin, enzyme-decomposed gelatin, and other gelatins modified with amino and carboxyl groups (phthalated gelatin, acetylated gelatin) Can be used.
Latex can also be used as a binder. Here, as the latex, the polymer latex described in JP-A-2-103536, page 18, lower left column, lines 12 to 20 can be preferably used.

  The content of the binder contained in the emulsion layer is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited. As for the content of the binder in the emulsion layer, the Ag / binder volume ratio is preferably 1/2 or more, and more preferably 1/1 or more.

<Solvent>
The solvent used for forming the emulsion layer is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, etc. , Esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.
The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of silver salt, binder and the like contained in the emulsion layer. Preferably there is.

<Antistatic agent>
The light-sensitive material according to the present invention preferably contains an antistatic agent, and is desirably coated on the support surface opposite to the emulsion layer.
As the antistatic layer, a conductive substance-containing layer having a surface resistivity of 10 ¹² Ω or less in an atmosphere of 25 ° C. and 25% RH can be preferably used. As the antistatic agent preferable in the present invention, the following conductive substances can be preferably used.
A conductive substance described in JP-A-2-18542, page 2, lower left line 13 to page 3, upper right line 7th line. Specifically, the metal oxides described in the second lower right line on page 2 to the lower right tenth line of the same publication, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication . Needle-like metal oxides described in U.S. Pat. No. 5,575,957, paragraphs 0045 to 0043 of JP-A-10-142738, paragraphs 0013 to 0019 of JP-A-11-223901, and the like can be used.

The conductive metal oxide particles used in the present invention include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO _3, and composite oxides thereof, and metal oxides thereof. Further, metal oxide particles containing different atoms can be mentioned. As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ , and MgO are preferable, SnO ₂ , ZnO, In ₂ O ₃ and TiO ₂ are preferable, and SnO ₂ is particularly preferable. preferable. Examples of containing a small amount of different atoms include Al or In for ZnO, Nb or Ta for TiO ₂ , Sn for In ₂ O ₃ , and Sb, Nb or halogen elements for SnO ₂ . An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. When the added amount of the different element is less than 0.01 mol%, it becomes difficult to impart sufficient conductivity to the oxide or composite oxide, and when it exceeds 30 mol%, the degree of blackening of the particles increases, Not suitable because the antistatic layer is dark. Therefore, in the present invention, the material of the conductive metal oxide particles is preferably one containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

As the conductive metal oxide particles containing a small amount of the dissimilar atom, SnO ₂ particles are preferred antimony-doped, SnO ₂ particles are preferred which are particularly doped antimony 0.2-2.0 mol%.

  There is no restriction | limiting in particular about the shape of the electroconductive metal oxide used for this invention, A granular form, needle shape, etc. are mentioned. Moreover, the average particle diameter represented by the spherical conversion diameter becomes like this size, Preferably it is 0.5 nm-25 micrometers.

  In order to obtain conductivity, for example, soluble salts (for example, chloride, nitrate, etc.), vapor deposited metal layers, ionic polymers as described in US Pat. Nos. 2,861,056 and 3,206,312 or Insoluble inorganic salts such as those described in US Pat. No. 3,428,451 can also be used.

The antistatic layer containing such conductive metal oxide particles is preferably provided as an undercoat layer on the back surface, an undercoat layer of the emulsion layer, or the like. The addition amount is preferably 0.01 to 1.0 g / m ² in total on both sides.
The internal resistivity of the photosensitive material is preferably 1.0 × 10 ⁷ to 1.0 to 10 ¹² Ω in an atmosphere of 25 ° C. and 25% RH.

  In the present invention, in addition to the conductive material, JP-A-2-18542, page 4, upper right 2nd line, page 4 lower-right lower 3rd line, JP-A-3-39948, page 12, lower left 6 By using together the fluorine-containing surfactant described in the lower right line on page 13 of the same publication from the line, even better antistatic properties can be obtained.

<Other additives>
There are no particular restrictions on the various additives used in the light-sensitive material in the present invention, and for example, those described in the following publications can be preferably used. However, in the present invention, it is preferable not to use a hardener. This is because, when a hardener is used, resistance increases and conductivity decreases when wet heat treatment described below is performed.
1) Nucleation promoter The nucleation promoter is represented by the general formulas (I), (II), (III), (IV), (V), (VI) described in JP-A-6-82934. Compounds, general formulas (II-m) to (II-p) and compound examples II-1 to II in page 9, upper right column, line 13 to page 16, upper left column, line 10 of JP-A-2-103536. -22, and compounds described in JP-A-1-179939.
2) Spectral sensitizing dye As the above spectral sensitizing dye, JP-A-2-12236, page 8, lower left column, line 13 to the lower right column, line 4 and JP-A-2-103536, page 16, lower right column 3 Spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and JP-A-5-11389 are listed from the first line to the lower left column, line 20, from page 17. It is done.
3) Surfactant As the surfactant, JP-A-2-12236, page 9, upper right column, line 7 to lower-right column, line 7 and JP-A-2-18542, page 2, lower-left column, line 13 From the eyes, the surfactants described on page 18, lower right column, line 18 can be mentioned.
4) Antifoggant As the antifoggant, JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, Further, thiosulfinic acid compounds described in JP-A-1-237538 can be mentioned.
5) Polymer Latex Examples of the polymer latex include those described in JP-A-2-103536, page 18, lower left column, lines 12 to 20.
6) Compound having an acid group Examples of the compound having an acid group include compounds described in JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1.
7) Black spot preventive agent The black spot preventive agent is a compound that suppresses the occurrence of spot-like developed silver in unexposed areas. For example, U.S. Pat. No. 4,956,257 and JP-A No. 1-181832. Examples include compounds described in the publication.
8) Redox compounds As redox compounds, compounds represented by the general formula (I) of JP-A-2-301743 (particularly Compound Examples 1 to 50), pages 3 to 20 of JP-A-3-174143 are disclosed. Examples include general formulas (R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in JP-A-5-257239 and 4-278939. .
9) Monomethine Compound Examples of the monomethine compound include compounds of the general formula (II) of JP-A-2-287532 (particularly compound examples II-1 to II-26).
10) Dihydroxybenzenes The compounds described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and European Patent Publication EP452772A can be mentioned.

[Other layer structure]
A protective layer may be provided on the emulsion layer. In the present invention, the “protective layer” means a layer composed of a binder such as gelatin or a high molecular polymer, and is formed on an emulsion layer having photosensitivity in order to exhibit an effect of preventing scratches and improving mechanical properties. The thickness is preferably 0.2 μm or less. The coating method and forming method of the protective layer are not particularly limited, and a known coating method can be appropriately selected.

<Method of forming metal wiring part>
A method for forming a metal wiring portion using the above photosensitive material will be described.
The electronic circuit (conductive film) obtained by the present invention is not limited to a metal formed on the support by pattern exposure, but may be a metal formed by surface exposure. Moreover, when using an electroconductive film as a printed circuit board, you may form a metal silver part and an insulating part.

The method for forming a metal wiring portion in the present invention includes the following three forms depending on the photosensitive material and the form of development processing.
(1) An embodiment in which a photosensitive silver halide black-and-white photosensitive material not containing physical development nuclei is chemically developed or thermally developed to form a metallic silver portion on the photosensitive material.
(2) An embodiment in which a photosensitive silver halide black-and-white photosensitive material containing physical development nuclei in a silver halide emulsion layer is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
(3) A photosensitive silver halide black-and-white photosensitive material that does not contain physical development nuclei and an image-receiving sheet having a non-photosensitive layer that contains physical development nuclei are overlaid and diffused and transferred to develop a metallic silver portion on the non-photosensitive image-receiving sheet. Form formed on top.

The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive film such as a light-transmitting electromagnetic wave shielding film is formed on the photosensitive material. The resulting developed silver is chemically developed silver or heat developed and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.
In the above aspect (2), in the exposed portion, the silver halide grains close to the physical development nucleus are dissolved and deposited on the development nucleus, whereby a light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film is formed on the photosensitive material. A translucent conductive film such as is formed. This is also an integrated black-and-white development type. Although the development action is precipitation on the physical development nuclei, it is highly active, but developed silver has a spherical shape with a small specific surface.
In the above aspect (3), the silver halide grains are dissolved and diffused in the unexposed area and deposited on the development nuclei on the image receiving sheet, whereby a light transmitting electromagnetic wave shielding film or a light transmitting conductive film is formed on the image receiving sheet. A translucent conductive film such as a film is formed. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.
In any embodiment, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer system, negative development processing is possible by using an auto-positive type photosensitive material as the photosensitive material). .

  The chemical development, thermal development, dissolution physical development, and diffusion transfer development referred to here have the same meanings as are commonly used in the art, and a general textbook of photographic chemistry such as Shinichi Kikuchi, “Photochemistry” (Kyoritsu) Published by publisher), C.I. E. K. It is described in “The Theory of Photographic Process, 4th ed.” Edited by Mees (Mcmillan, published in 1977). Further, for example, refer to the techniques described in Japanese Patent Application Laid-Open Nos. 2004-184893, 2004-334077, 2005-010752, Japanese Patent Application Nos. 2004-244080, 2004-085655, and the like. You can also

[exposure]
In the production method of the present invention, the silver salt-containing photosensitive layer provided on the support is exposed. The exposure can be performed using electromagnetic waves. Examples of the electromagnetic wave include light such as visible light and ultraviolet light, and radiation such as X-rays. Furthermore, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.
Examples of the light source include scanning exposure using a cathode ray (CRT). The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. As the illuminant, for example, one or more of a red illuminant, a green illuminant, and a blue illuminant are mixed and used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used. An ultraviolet lamp is also preferable, and g-line of a mercury lamp, i-line of a mercury lamp, etc. are also used.
In the manufacturing method of the present invention, exposure can be performed using various laser beams. For example, the exposure in the present invention is a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using high-density light can be preferably used, and a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be used. In order to make the system compact and inexpensive, exposure is preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal. In order to design an apparatus that is particularly compact, inexpensive, long-life, and highly stable, it is preferable to perform exposure using a semiconductor laser.

Specifically, as a laser light source, a blue semiconductor laser with a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001) and a semiconductor laser (with an oscillation wavelength of about 1060 nm) are introduced. About 530 nm green laser, wavelength about 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (Hitachi), extracted by wavelength conversion with LiNbO ₃ SHG crystal having a waveguide inversion domain structure Type No. HL6501MG) is preferably used.
The method for exposing the silver salt-containing layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.

[Development processing]
In the production method of the present invention, after the silver salt-containing layer is exposed, development processing is further performed. The development processing can be performed by a general development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like. The developer is not particularly limited, but a PQ developer, MQ developer, MAA developer and the like can also be used. Commercially available products include, for example, CN-16, CR-56, CP45X, FD-3, Papitol manufactured by Fuji Film, C-41, E-6, RA-4, Dsd-19, D manufactured by KODAK. A developer such as -72 or a developer included in the kit can be used (both are trade names). A lith developer can also be used. As the lith developer, D85 (trade name) manufactured by KODAK Co., Ltd. can be used.
In the method for producing a translucent conductive film of the present invention, a patterned metal silver portion is formed in the exposed portion by performing the above exposure and development treatment, and a light transmissive portion described later is formed in the unexposed portion. Is done. In the present invention, the development temperature, fixing temperature and washing temperature are preferably 35 ° C. or less.
The development processing in the production method of the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. In the production method of the present invention, the fixing process may be performed using a fixing process technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like.
The developer used in the development process can contain an image quality improver for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as benzotriazole. Further, when a lith developer is used, it is particularly preferable to use polyethylene glycol.
The mass of the metallic silver contained in the exposed portion after the development treatment is preferably a content of 50% by mass or more, and 80% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. More preferably. If the mass of silver contained in the exposed portion is 50% by mass or more based on the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity is easily obtained.
The gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0. When the gradation after development processing exceeds 4.0, the conductivity of the metal wiring portion can be increased while keeping the transparency of the light transmitting portion high. Examples of means for setting the gradation to 4.0 or higher include the aforementioned doping of rhodium ions and iridium ions.

[Oxidation treatment]
In the production method of the present invention, the metal silver portion after the development treatment is preferably subjected to an oxidation treatment. By performing the oxidation treatment, for example, when a metal is slightly deposited on the light transmissive portion, the metal can be removed and the light transmissive portion can be made almost 100% transparent.
Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment. The oxidation treatment can be performed after exposure and development processing of the silver salt-containing layer.
In the present invention, the metal silver portion after the exposure and development treatment can be further treated with a solution containing Pd. Pd may be a divalent palladium ion or metallic palladium. By this treatment, it is possible to suppress the black color of the metallic silver portion from changing with time.

[Reduction treatment]
A film having a preferable conductivity can be obtained by immersing in a reducing aqueous solution after the development treatment.
As the reducing aqueous solution, sodium sulfite aqueous solution, hydroquinone aqueous solution, paraphenylenediamine aqueous solution, oxalic acid aqueous solution and the like can be used, and the pH of the aqueous solution is more preferably 10 or more.

<Smoothing treatment for metal wiring>
[Smoothing (Calendar)]
In the production method of the present invention, it is preferable to perform a smoothing treatment on the developed metal silver portion (entire metal silver portion, metal mesh pattern portion or metal wiring pattern portion). This significantly increases the conductivity of the metallic silver part. Furthermore, by suitably designing the areas of the metallic silver part and the light transmissive part, it has high electromagnetic shielding properties and high light transmissive properties at the same time, and the mesh part has a black transparent electromagnetic shielding film and high A printed circuit board without pinholes having both conductivity and high insulation can be obtained.
After forming the metal wiring part, it is preferable to perform a smoothing process (consolidation process) in order to increase the number of joints between the metal particles in the metal wiring part. In particular, it is preferable to perform a smoothing treatment before a hot water immersion treatment, a steam contact treatment or a wet heat treatment, which will be described later. By conducting warm water immersion treatment, steam contact treatment or wet heat treatment after smoothing, the conductive particles can be bonded and then fused, and the conductivity can be improved more effectively.

The smoothing process can be performed by a calendar roll, for example. The calendar roll usually consists of a pair of rolls. Hereinafter, the smoothing process using the calendar roll is referred to as a calendar process.
As a roll used for the calendar treatment, a plastic roll or a metal roll such as epoxy, polyimide, polyamide, polyimide amide or the like is used. In particular, when emulsion layers are provided on both sides, it is preferable to treat with metal rolls. When an emulsion layer is provided on one side, a combination of a metal roll and a plastic roll can be used from the viewpoint of preventing wrinkles. The lower limit of the linear pressure is preferably 1960 N / cm (200 kg / cm) or more, and more preferably 2940 N / cm (300 kg / cm) or more. The upper limit of the linear pressure is preferably 6860 N / cm (700 kgf / cm) or less. Here, the line pressure (load) is a force applied per 1 cm of the film sample to be consolidated.

  The application temperature of the smoothing treatment represented by the calendar roll is preferably 10 ° C. (no temperature control) to 100 ° C., and the more preferable temperature depends on the line density and shape of the metal mesh pattern or metal wiring pattern, and the binder type. Although it is different, it is approximately in the range of 10 ° C. (no temperature control) to 50 ° C.

As described above, a conductive film having high conductivity can be manufactured easily and at low cost by the manufacturing method of the present invention. In the present invention, in the method for producing a conductive film using a silver salt (especially silver halide) photosensitive material, the smoothing treatment is preferably performed at a high linear pressure of 1960 N / cm (200 kgf / cm) or more, The surface resistance of the conductive film can be sufficiently reduced. When smoothing is performed at such a high line pressure, if the metal silver part is formed in a thin line shape (particularly, the line width is 25 μm or less), the line width of the metal silver part is increased to form a desired pattern. It will be difficult to do. However, when the object of the smoothing process is a silver salt (especially silver halide) photosensitive material, the line width is small and a metal silver portion having a desired pattern can be formed. That is, since the metal silver portion having a uniform shape can be formed with a desired pattern, the occurrence of defective products can be suppressed, and the productivity of the conductive film can be further improved. When performing the smoothing treatment with the linear pressure, the smoothing treatment is preferably performed with a calender roll, and is performed with a pair of metal rolls or a combination of a metal roll and a resin roll. In this case, it is preferable that the surface pressure between the rolls is set to 600 kgf / cm ² or more, it is more preferable to set the 800 kgf / cm ² or more, further preferably set to 900 kgf / cm ² or more. Moreover, it is preferable to set the upper limit at this time to 2000 kgf / cm ² or less.

  In the method of the present invention, it is preferable to perform a steam contact treatment, a hot water treatment, or a wet heat treatment after forming the metal wiring portion on the support. Each process will be described below.

<Steam contact treatment>
The vapor contact treatment is performed by bringing the conductive metal portion into contact with the vapor after forming the conductive metal portion on the support. Thereby, electroconductivity and transparency can be improved simply in a short time. The reason why the conductivity of the conductive film is improved is not yet clear, but it is considered that at least a part of the binder is removed and the bonding sites between the metals (conductive substances) are increased.
The temperature of the steam brought into contact with the support is preferably 80 ° C. or higher. The temperature of the steam is more preferably 100 ° C. or higher and 140 ° C. or lower at 1 atmosphere. The contact time with steam varies depending on the type of binder used, but when the support is 60 cm × 1 m, it is preferably about 10 seconds to 5 minutes, more preferably 1 minute to 5 minutes.

<Washing treatment>
It is preferable to wash the conductive metal part after bringing it into contact with steam. By washing with water after the steam contact treatment, it is considered that the binder dissolved or brittle with steam can be washed away, thereby further reducing the resistance.

  Here, in a further preferred embodiment of the present invention, a water washing treatment is performed after the steam contact step. In another more preferred embodiment of the present invention, the vapor contact treatment is performed after the smoothing treatment. Furthermore, in another more preferable embodiment of the present invention, the smoothing treatment, the steam contact step, and the water washing treatment are performed in this order.

<Warm water immersion treatment>
The hot water immersion treatment is performed by immersing the conductive metal portion in warm water of 40 ° C. or higher after forming the conductive metal portion on the support. Thereby, electroconductivity and transparency can be improved simply in a short time. As described above, the reason why the conductivity of the conductive film is improved is not yet clear, but it is considered that at least a part of the water-soluble binder is removed and the bonding sites between the metals (conductive substances) are increased. It is done.
The temperature of the hot water in which the support is immersed is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 60 ° C. to 100 ° C. Particularly preferably, the temperature is about 80 ° C. to 100 ° C., and the higher the temperature is, the more remarkable the improvement in conductivity is. 2-13 are preferable, as for pH of warm water, 2-9 are more preferable, and 2-5 are still more preferable. The immersion time in warm water of 40 ° C. or higher or heated water of a temperature higher than that varies depending on the type of water-soluble binder used, but when the size of the support is 60 cm × 1 m, it is preferably about 10 seconds to 5 minutes, 1 minute to 5 minutes is more preferable.
Here, in a further preferred embodiment of the present invention, the warm water immersion treatment is performed after the smoothing treatment.

<Humid heat treatment>
In the wet heat treatment, after the conductive metal part is formed on the support, the support on which the conductive metal part is formed is placed in an atmosphere of humidity control conditions at a temperature of 40 ° C. or higher and a relative humidity of 5% or higher. This is done by leaving it alone. Thereby, electroconductivity and transparency can be improved simply in a short time. As described above, the reason why the conductivity of the conductive film is improved is not yet clear, but at least a part of the water-soluble binder becomes easy to move minutely with an increase in humidity, and the bonding site between the metals (conductive substances) It is thought that it is increasing.
The temperature of the humidity control condition is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 60 ° C. to 100 ° C. Particularly preferably, the temperature is about 80 ° C. to 100 ° C., and the higher the temperature is, the more remarkable the improvement in conductivity is. The relative humidity of the humidity control condition is preferably 5% to 100%, more preferably 40% to 100%, still more preferably 60% to 100%, and particularly preferably 80% to 100%. It is. The wet heat treatment time varies depending on the type of the water-soluble binder used, but when the size of the support is 60 cm × 1 m, it is preferably about 5 minutes to about 60 minutes, more preferably about 5 minutes to about 30 minutes, Particularly preferred is 5 minutes to about 10 minutes.
Here, in a further preferred embodiment of the present invention, the wet heat treatment is performed after the smoothing treatment.

  The binder is removed by performing any one of the steam contact treatment, the hot water treatment, and the wet heat treatment, but the binder may remain between the metal wiring portions.

  In the production method of the present invention, a mesh-shaped metallic silver portion having a specified line width, aperture ratio, and Ag content is directly formed on a support by exposure / development treatment, so that the surface resistance value is sufficient. Furthermore, it is not necessary to give the metal silver part a physical development and / or a plating treatment to give conductivity again. For this reason, a translucent electronic circuit can be manufactured by a simple process.

[Metal ion trapping agent adsorption treatment]
After forming the metal wiring part, a metal ion trapping agent that forms a hardly soluble metal salt is brought into contact with the metal wiring part, and the metal ion trapping agent is adsorbed on the metal wiring part. By adsorbing a metal ion trapping agent that forms a sparingly soluble metal salt to the metal wiring part, the electronic circuit of the present invention suppresses migration caused by the movement of metal ions between the metal wiring parts even when driven for a long time. can do.

  The metal ion trapping agent preferably has a pKsp of 9 or more, more preferably 10-20. Here, pKsp is defined as follows.

The compound HA is dissociated in an aqueous solution, and the anion A ⁻ reacts with silver ions to form a hardly soluble silver salt Ag · A.
The solubility product Ksp of silver is a measure of the strength of interaction of these compounds with silver ions. The measurement method of Ksp is “Kiken Sakaguchi and Shinichi Kikuchi, Journal of the Japan Photography Society, 13, 126, (1951)” and “A.Pailliofet and J.Pouradier, Bull.Soc.chim.France, 1982, I-445 ( 1982) ".

The metal ion trapping agent used in the present invention is preferably a nitrogen-containing heterocyclic compound or an organic mercapto compound, and among them, a nitrogen-containing heterocyclic compound is preferably used.
Moreover, it is preferable that the metal ion trap agent used for this invention is a mercapto compound represented by following General formula (1).
General formula (1) RR'-SH
(In the formula, R ′ is a 5- or 6-membered heterocycle and may be condensed. R is a substituent having 6 or more carbon atoms.)

  Preferable examples of the nitrogen-containing organic heterocyclic compound are preferably 5- or 6-membered ring azoles, and more preferably 5-membered ring azoles. The metal ion trapping agent used in the present invention is preferably a nitrogen-containing organic heterocyclic compound or an organic mercapto compound.

  A preferred nitrogen-containing 5-membered or 6-membered ring structure is a non-necessity necessary to form a 5- or 6-membered heterocyclic ring composed of at least one atom selected from the group consisting of carbon, nitrogen, oxygen, sulfur and selenium. Represents a metal atom group. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring.

Examples of the hetero ring include a tetrazole ring, a triazole ring, an imidazole ring, a thiadiazole ring, an oxadiazole ring, a selenodiazole ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a benzthiazole ring, a benzimidazole ring, a pyrimidine ring, and a triazaine. Examples thereof include a den ring, a tetraazaindene ring, and a pentaazaindene ring. R _a1 is a carboxylic acid or a salt thereof (for example, sodium salt, potassium salt, ammonium salt, calcium salt), a sulfonic acid or a salt thereof (for example, sodium salt, potassium salt, ammonium salt, magnesium salt, calcium salt), phosphonic acid or a salt thereof Salt (for example, sodium salt, potassium salt, ammonium salt), substituted or unsubstituted amino group (for example, unsubstituted amino, dimethylamino, diethylamino, methylamino, bismethoxyethylamino), substituted or unsubstituted ammonium group (for example, trimethyl) Ammonium, triethylammonium, dimethylbenzylammonium).

  These rings may have a substituent, and the substituent is a nitro group, a halogen atom (for example, chlorine atom or bromine atom), a mercapto group, a cyano group, or a substituted or unsubstituted alkyl group (for example, methyl group). , Ethyl, propyl, t-butyl, cyanoethyl groups), aryl groups (for example, phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl groups), alkenyl groups ( For example, allyl group), aralkyl group (for example, benzyl, 4-methylbenzyl, phenethyl groups), sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl groups), carbamoyl group (for example, unsubstituted carbamoyl, methyl) Carbamoyl, phenylcarbamoyl groups), sulfamoyl groups (eg Sulfamoyl, methylsulfamoyl, phenylsulfamoyl groups), carbonamido groups (eg acetamido, benzamide groups), sulfonamido groups (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide groups) ), Acyloxy groups (for example, acetyloxy and benzoyloxy groups), sulfonyloxy groups (for example, methanesulfonyloxy), ureido groups (for example, unsubstituted ureido, methylureido, ethylureido, and phenylureido groups), acyl groups ( For example, acetyl, benzoyl groups), oxycarbonyl groups (for example, methoxycarbonyl, phenoxycarbonyl groups), oxycarbonylamino groups (for example, methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyl) Each group sill butyloxycarbonylamino), optionally substituted with hydroxyl group and the like. Multiple substituents may be substituted on one ring.

  Specific examples of preferable nitrogen-containing organic heterocyclic compounds include the following. That is, imidazole, benzimidazole, benzoindazole, benzotriazole, benzoxazole, benzothiazole, pyridine, quinoline, pyrimidine, piperidine, piperazine, quinoxaline, morpholine, etc., these include alkyl groups, carboxyl groups, sulfo groups, etc. May have the following substituents.

  Preferred nitrogen-containing 6-membered ring compounds are compounds having a triazine ring, a pyrimidine ring, a pyridine ring, a pyrroline ring, a piperidine ring, a pyridazine ring or a pyrazine ring, and among them, a compound having a triazine ring or a pyrimidine ring is preferable. These nitrogen-containing 6-membered ring compounds may have a substituent, and the substituent in that case is 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, more preferably 1 to 6 carbon atoms. Preferably 1-3 lower alkoxy groups, hydroxyl groups, carboxyl groups, mercapto groups, 1-6 carbon atoms, more preferably 1-3 alkoxyalkyl groups, 1-6 carbon atoms, more preferably 1-3 hydroxyalkyls. Groups.

  Specific examples of preferable nitrogen-containing 6-membered ring compounds include triazine, methyltriazine, dimethyltriazine, hydroxyethyltriazine ring, pyrimidine, 4-methylpyrimidine, pyridine and pyrroline.

Examples of organic mercapto compounds include alkyl mercapto compounds, aryl mercapto compounds, and heterocyclic mercapto compounds.
Examples of the alkyl mercapto compound include cysteine and thiomalic acid, examples of the aryl mercapto compound include thiosalicylic acid, and examples of the heterocyclic mercapto compound include 2-phenyl-1-mercaptotetrazole, 2-mercaptobenzimidazole, Examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptopyrimidine, 2,4-dimercaptopyrimidine, 2-mercaptopyridine, and the like. These include substituents such as an alkyl group, a carboxyl group, and a sulfo group. May be included.

  As the metal ion trapping agent of the present invention, benzotriazole, 5-methylbenzotriazole, 5-aminobenzotriazole, 5-chlorobenzotriazole, tetrazole, 5-aminotetrazole, 5-methyltetrazole, and 5-phenyltetrazole are particularly preferable. Benzotriazole is most preferred.

These metal ion trapping agents can be used alone or in combination.
The metal ion trapping agent solution preferably contains the metal ion trapping agent compound in a concentration of 0.0001 to 0.1 mol, preferably 0.001 to 0.05 mol, in 1 liter. As a preferable metal ion trapping agent, it is desirable to be more hydrophobic, and as a solubilizing agent, alcohols such as methanol, ethanol and isopropanol or glycols such as diethylene glycol can be added, and methanol and ethanol are particularly preferable. preferable. Further, the pH of the aqueous solution is preferably adjusted to 2 to 12 and particularly preferably 4 to 8 from the viewpoint of dissolving the metal ion trapping agent. The pH can be adjusted by using phosphoric acid or a salt thereof, carbonate, acetic acid or a salt thereof, boric acid or a salt thereof, or the like, in addition to a normal alkali or acid such as sodium hydroxide or sulfuric acid.

Specific examples of the mercapto compound preferably used as the metal ion trapping agent in the present invention are shown below, but the present invention is not limited thereto.

The mercapto compound-containing solution used in the present invention is a solution in which a mercapto compound is dissolved in a solvent. As the solvent, alcohol is preferable, and methanol or ethanol is particularly preferable. The mercapto compound-containing solution preferably contains a mercapto compound in an amount of 0.1 to 100 g / L, and more preferably 1 to 50 g / L.
In the electronic circuit obtained by the present invention, it is preferred that the mercapto compound is 1mg / m ² ~500mg / m ² adsorbed on the metal wiring portion, it is more preferable that 1mg~300mg adsorbed.

[Alcohol cleaning]
After the mercapto compound adsorption treatment, it is preferable to remove the mercapto compound remaining on the electronic circuit by immersing and washing the metal wiring part in alcohol. The alcohol used is preferably methanol or ethanol.

[Plating treatment]
In the present invention, the conductive metal portion may be further plated. By plating, the surface resistance can be further reduced and the conductivity can be increased. The plating treatment may be electrolytic plating or electroless plating. Further, the constituent material of the plating layer is preferably a metal having sufficient conductivity, and copper is preferable.
It should be noted that the present invention and the technology disclosed in the following publication can be used in combination without departing from the spirit of the present invention. JP, 2004-221564, JP, 2004-221565, JP, 2006-012935, JP, 2006-0110795, JP, 2006-228469, JP, 2006-228473, JP, JP JP 2006-228478 A, JP 2006-228480 A, JP 2006-228836 A, JP 2006-267627 A, JP 2006-269597 A, JP 2006-267635 A, JP 2006-2006 A. No. 286410, JP-A 2006-283133, and JP-A 2006-283137.

  The electronic circuit manufactured by the method of the present invention has low resistance and can be widely applied to electrodes such as solar cells and touch panels, printed circuit boards, and the like.

Hereinafter, a preferred embodiment of the electronic circuit of the present invention will be described. FIG. 1 is a cross-sectional view of a preferred embodiment of the electronic circuit of the present invention.
The electronic circuit 10 includes a transparent support 12, a fine wire structure portion 14 made of a conductive metal, and a translucent conductive film 16 provided on the support 12. Here, the thin wire structure portion 14 corresponds to the metal wiring portion described above. As shown in FIG. 1, the thickness (height) of the fine line structure portion 14 may be substantially the same as the thickness (height) of the translucent conductive film 16, and the upper surface of the fine line structure portion 14 may be exposed. . In order to improve the adhesion between the translucent conductive film 16 and the conductive film of the present invention, it is preferable to use an intermediate layer made of an organic polymer material or to perform a surface treatment. it can.

[Translucent conductive film 16]
The translucent conductive film 16 is made of a transparent conductive organic polymer such as PEDOT (polyethylenedioxythiophene) / PSS, polyaniline, polypyrrole, polythiophene, polyisothianaphthene on a transparent film such as polyethylene terephthalate or polyethylene naphthalate base. Metal oxide, metal fine particles, conductive metals such as metal nanorods and nanowires, conductive inorganic fine particles such as carbon nanotubes, or organic water-soluble salts are uniformly attached and formed by a method such as coating or printing. Obtained by filming. These coating liquids may be blended with other non-conductive polymers or latexes for improving coating suitability and adjusting film physical properties. A multilayer structure in which a silver thin film is sandwiched between high refractive index layers may be used. These transparent conductive materials are described in “Current Status and Future of Electromagnetic Shielding Materials” published by Toray Research Center, Japanese Patent Laid-Open No. 9-147639, and the like. As a coating and printing method, a coating coater such as a slide coater, a slot die coater, a curtain coater, a roll coater, a bar coater, or a gravure coater, screen printing, or the like is used.

  The volume resistance of the conductive film 16 is preferably 0.05 Ω · cm or more. The surface resistance of the conductive film 16 is preferably 1000 Ω / sq or more. The surface resistance of the conductive film 16 can be measured according to the measurement method described in JIS K6911.

  The conductive film 16 is preferably cross-linked because water resistance, solvent resistance, and the like are improved. In that case, the conductive film 16 may be cross-linked by a cross-linking agent, or by using a photochemical reaction induced by light irradiation without adding a cross-linking agent by means that does not affect the photosensitivity. It may be. Examples of the crosslinking agent include vinyl sulfones (for example, 1,3-bisvinylsulfonylpropane), aldehydes (for example, glyoxal), pyrimidine chlorides (for example, 2,4,6-trichloropyrimidine), triazine chlorides (for example, cyanuric chloride). , Epoxy compounds, carbodiimide compounds, and the like.

  Examples of the epoxy compound include 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ-acetoxy-β-oxy Propyl) isosinurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether, 1,3,5-triglycidyl (2-hydroxyethyl) isocyanurate, glycerol poly Epoxy compounds such as glycerol ethers and trimethylolpropane polyglycidyl ethers are preferred, and specific commercial products thereof include, for example, Denacol EX-521 and EX-614B (both trade names, manufactured by Nagase Chemical Industries, Ltd.) However, it is not limited to these.

  As the carbodiimide compound, it is preferable to use a compound having a plurality of carbodiimide structures in the molecule. Polycarbodiimide is usually synthesized by a condensation reaction of organic diisocyanate. Here, the organic group of the organic diisocyanate used for the synthesis of the compound having a plurality of carbodiimide structures in the molecule is not particularly limited, and either aromatic or aliphatic, or a mixed system thereof can be used. An aliphatic system is particularly preferred from the viewpoint of reactivity. As the synthetic raw material, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used. As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used. Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used. Moreover, as a concrete commercial item of a carbodiimide type compound, carbodilite V-02-L2 (brand name: Nisshinbo Co., Ltd. product) etc. can be obtained, for example.

  As a method for forming the conductive film 16, various physical methods such as sputtering, generally well-known coating methods such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, and an extrusion method are used. Various coating methods such as a coating method can be used.

  When the conductive film 16 is formed by these methods, (A) the conductive film 16 is filled such that the concave portion of the fine line pattern is filled and the surface of the fine line structure portion 14 and the surface of the conductive film 16 form a smooth surface, for example. (B) A method of adjusting the surface of the fine wire structure 14 and the surface of the conductive film 16 to form a smooth surface by polishing, (C) On the surface of the fine wire structure 14, A method of forming the conductive film 16 after performing a surface treatment for preventing the material of the conductive film 16 from attaching is preferably used.

  In the method (C), since the coating solution of the material of the conductive film 16 is generally highly polar or hydrophilic, it is desirable that the surface of the fine wire structure portion 14 be low polarity or hydrophobic. Specifically, it is preferable that the surface of the fine wire structure portion 14 is subjected to a surface treatment using a hydrophobic metal surface treatment agent represented by alkylthiols. More preferably, this treatment agent is removed by post-treatment.

  In addition, the conductive film 16 may be provided with a functional layer having functionality separately as necessary. This functional layer can have various specifications for each application. For example, an antireflection layer with an antireflection function with an adjusted refractive index or film thickness, a non-glare layer or an antiglare layer (having a glare prevention function), a near infrared absorbing layer made of a compound or metal that absorbs near infrared rays, A layer with a color tone adjustment function that absorbs visible light in a specific wavelength range, an antifouling layer with a function that easily removes dirt such as fingerprints, a hard-coat layer that is difficult to scratch, a layer with an impact absorption function, and glass A layer having a function of preventing glass scattering at breakage or the like can be provided.

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1
(Preparation of emulsion A)
To the following 1 liquid maintained at 38 ° C. and pH 4.5, an amount corresponding to 90% of each of the following 2 and 3 liquids was added simultaneously over 20 minutes with stirring to form 0.16 μm core particles. Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and the remaining 10% of the following 2 liquid and 3 liquid were further added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.

・ 1 liquid:
750 ml of water
Gelatin (phthalated gelatin) 20g
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids:
300 ml of water
150 g silver nitrate
・ Three liquids:
300 ml of water
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium salt
(0.005% KCl 20% aqueous solution) 5 ml
Ammonium hexachlororhodate
(0.001% NaCl 20% aqueous solution) 7 ml
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids are respectively KCl 20% aqueous solution and NaCl 20% aqueous solution. And heated at 40 ° C. for 120 minutes.

・ 4 liquids:
100ml water
Silver nitrate 50g
・ 5 liquids:
100ml water
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., and the pH was lowered using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed (first water washing). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. The emulsion after washing and desalting is adjusted to pH 6.4 and pAg 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid are added. And 1,3,3a, 7-tetraazaindene (100 mg) as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain diameter of 0.22 μm and a coefficient of variation of 9% was obtained. The final emulsion was pH = 6.4, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg / m ³ , and viscosity = 60 mPa · s.

(Preparation of emulsion B)
Emulsion B was prepared in the same manner as in the preparation of Emulsion A, except that the amount of gelatin in the first solution was 8 g.

(Preparation of coated sample)
<< Preparation of Emulsion Layer Coating Solution-1 >>
The emulsion A was subjected to spectral sensitization by adding sensitizing dye (SD-1) 5.7 × 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag and compound (Cpd-3) 8.0 × 10 ⁻⁴ mol / mol Ag were added and mixed well.
Then, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 90 mg / m ² , colloidal silica having a particle size of 10 μm of 15% by mass with respect to gelatin, aqueous latex (aqL-6) 50 mg / m ² , 100 mg / m ^{2 of} polyethyl acrylate latex, latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (mass ratio 88: 5: 7) 100 mg / m ^2, core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63), shell: styrene / - acetoxyethyl acrylate (weight ratio 84/16) was added a core / shell ratio = 50/50) 100mg / m 2, and with respect to gelatin 4% by weight of the hardener (Cpd-7), using citric acid Thus, the coating solution pH was adjusted to 5.6 to prepare emulsion layer coating solution-1.

<< Emulsion layer coating solution-2 >>
Emulsion layer coating solution-2 was prepared in the same manner as emulsion layer coating solution-1, except that the above hardener (Cpd-7) was not added.

Carrageenan, which is a water-soluble binder, was added to the emulsion layer coating solution-1 or 2 thus prepared in an amount of 0.19 g / m ² with respect to Ag. And this was apply | coated so that it might become Ag10.5g / m < ² > and binder 0.525g / m < ² > on a polyethylene terephthalate (PET) support body, and it was made to dry after that. PET that had been previously hydrophilized was used.
In all of the obtained coated samples, the Ag / binder volume ratio of the emulsion layer was 4/1. This sample corresponds to an Ag / binder ratio of 1/1 or more preferably used for the photosensitive material for forming a conductive film of the present invention.

Using the emulsion layer coating solution-2, gelatin was added, and the mixture was coated on a polyethylene terephthalate (PET) support and dried. PET that had been previously hydrophilized was used. The obtained coated sample had an Ag amount of 10.5 g / m ² and an Ag / binder volume ratio (silver / Gel ratio (vol ratio)) of the emulsion layer of 1/1. This corresponds to an Ag / binder ratio of 1/1 or more preferably used in the photosensitive material for forming a conductive film of the present invention.
Further, a protective layer was provided on the emulsion layer. The structure of the protective layer is as follows.
Gelatin 0.135 g / m ²
Water 8.21 g / m ²
Surfactant 0.015 g / m ²
Preservative 0.003g / m ²
The protective layer was formed by a well-known coating method on the upper layer of the emulsion layer. The film thickness of the protective layer after drying was 0.15 μm.

(Exposure and development processing)
Next, the sample coated and dried using the emulsion layer coating solution-2 was subjected to parallel light using a high-pressure mercury lamp as a light source through a photomask capable of giving a developed silver image having the test pattern shown in FIG. Exposed. The test pattern is a pattern based on IPC-TM650orSM840. The line width is 50 μm, the space width is 50 μm, and the number of lines is 17/18. After exposure, the film was developed with the following developer, developed with a fixer (trade name: N3X-R for CN16X: manufactured by Fuji Photo Film Co., Ltd.), and rinsed with pure water to obtain a sample. .

[Developer composition]
The following compounds are contained in 1 liter of developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

  The sample developed and fixed as described above was calendered. The calender roll was a metal roll, and a sample was passed between the rollers under a calender load (linear pressure) of 3920 N / cm (400 kg / cm). Thereafter, the sample was immersed in warm water at a temperature of 90 ° C. for 5 minutes.

  Next, the mercapto compound adsorption process which makes a metal ion trap agent (mercapto compound containing solution) contact the sample in which the metal wiring part was formed was performed. The sample was conveyed in a methanol solution containing 2% by mass of Compound A, and then the sample was washed with methanol. Thus, an electronic circuit was produced.

Example 2
An electronic circuit was produced in the same manner as in Example 1 except that Compound A was changed to Compound B.

Comparative Example 1
An electronic circuit was produced in the same manner as in Example 1 except that the mercapto compound adsorption treatment and the alcohol washing treatment were not performed.

Comparative Example 2
Cu wiring was formed on the polyimide support by sputtering and patterning by etching to form an electronic circuit having the same test pattern as in Example 1.

<Evaluation>
The following evaluation was performed about the produced electronic circuit.
As shown in FIG. 2, the lines in the electronic circuit are insulated. A test was conducted to determine whether or not migration occurred over time with voltage applied to the electronic circuit. When migration occurs, the metal grows in a tree shape and shorts between the lines, causing dielectric breakdown.
Wiring was connected to the electrodes (black portions in the figure) at both ends of the manufactured electronic circuit, and a DC 10 V current was continuously applied from one side in a wet heat atmosphere at 60 ° C. and 90%. For the insulation, the test was temporarily interrupted, taken out from the atmosphere at 60 ° C. and 90%, an R8340A manufactured by Advantest Corporation was used, an applied voltage of DC 10 V was applied, and the insulation resistance value was measured.
An insulation resistance value of 10 ¹⁰ Ω or more was evaluated as ◯, an insulation resistance value of 10 ⁶ Ω or more and less than 10 ¹⁰ Ω was evaluated as Δ, and an insulation resistance value of less than 10 ⁶ Ω was evaluated as ×. The results are shown in Table 1.
Moreover, the time-dependent change of the insulation resistance in each electronic circuit was measured. The results are shown in FIG.

As is apparent from the results of Table 1 and FIG. 3, in Comparative Examples 1 and 2 in which the mercapto compound adsorption treatment was not performed, migration occurred over time in a state where a voltage was applied, and energization (dielectric breakdown) occurred. Insulation resistance decreased. In particular, in Comparative Example 1 in which the metal wiring portion is formed using a photosensitive material, the electrode is metallic silver that is most likely to generate ion migration, and the insulating portion between the electrodes contains a binder that is likely to absorb moisture. It is considered that ion migration occurred in a short time.
On the other hand, in Examples 1 and 2 in which the mercapto compound adsorption treatment was performed, it was found that the insulation resistance did not decrease even when driven for a long time, and the occurrence of migration could be suppressed.

FIG. 1 is a cross-sectional view of a preferred embodiment of the electronic circuit of the present invention. FIG. 2 shows test patterns of electronic circuits produced in the examples and comparative examples. FIG. 3 is a graph showing the change over time in the insulation resistance in Examples and Comparative Examples.

Claims (29)

  An electronic circuit comprising a metal wiring part containing metal, wherein a metal ion trapping agent that forms a hardly soluble metal salt is adsorbed on the metal wiring part.   The electronic circuit according to claim 1, wherein the metal ion trapping agent has a pKsp of 9 or more.   The electronic circuit according to claim 1, wherein the metal ion trapping agent is at least one selected from benzotriazole, a benzotriazole derivative, and a mercapto compound. The electronic circuit according to any one of claims 1 to 3, wherein the metal ion trapping agent is a mercapto compound represented by the following general formula (1).
General formula (1) RR'-SH
(In the formula, R ′ is a 5- or 6-membered heterocycle and may be condensed. R is a substituent having 6 or more carbon atoms.)   The electronic circuit according to claim 1, wherein the metal is silver. The electronic circuit according to claim 1, wherein a volume resistance of the metal wiring portion is 10 ⁻⁴ Ω · cm or less. The metal ion trapping agent is 1mg / m ² ~500mg / m ² adsorbed on the metal wiring portion, the electronic circuit according to any one of claims 1-6. A method for producing an electronic circuit comprising a metal wiring part containing a metal on a support,
A metal wiring part forming step of forming a metal wiring part containing metal on the support;
A metal ion trap agent (mercapto compound-containing solution) is contacted with the metal wiring part, and a mercapto compound adsorption step of adsorbing the mercapto compound on the metal wiring part;
A method for manufacturing an electronic circuit, comprising:   9. The method of manufacturing an electronic circuit according to claim 8, wherein the metal wiring part forming step is performed by exposing and developing a photosensitive layer containing silver salt to form a metal wiring part containing metal silver.   The method for manufacturing an electronic circuit according to claim 8, wherein the metal wiring part forming step is performed by applying a metal paste.   The manufacturing method of the electronic circuit of any one of Claims 8-10 which has a consolidation process which consolidates the said metal wiring part.   The method of manufacturing an electronic circuit according to claim 11, wherein the consolidation treatment is performed at a linear pressure of 1960 N / cm (200 kgf / cm) or more.   The method for manufacturing an electronic circuit according to claim 11, wherein the consolidation treatment is performed at a linear pressure of 2940 N / cm (300 kgf / cm) or more.   The method of manufacturing an electronic circuit according to claim 11, wherein the consolidation treatment is performed at a linear pressure of 6860 N / cm (700 kgf / cm) or more.   15. A wet heat treatment step of leaving the formed metal wiring portion in an atmosphere under humidity control conditions of a temperature of 40 ° C. or higher and a relative humidity of 5% or higher after the metal wiring portion forming step. The manufacturing method of the electronic circuit of any one of these.   The method of manufacturing an electronic circuit according to claim 15, wherein the temperature of the humidity control condition is 60 ° C. or higher.   The manufacturing method of the electronic circuit of Claim 15 or 16 whose temperature of the said humidity control conditions is 80 degreeC or more.   The manufacturing method of the electronic circuit of any one of Claims 15-17 whose relative humidity of the said humidity control conditions is 60% or more.   The manufacturing method of the electronic circuit of any one of Claims 15-18 whose relative humidity of the said humidity control conditions is 80% or more.   The method for manufacturing an electronic circuit according to claim 8, further comprising a vapor contact step of bringing the formed metal wiring portion into contact with vapor after the metal wiring portion forming step.   21. The method of manufacturing an electronic circuit according to claim 20, wherein the temperature of the vapor is 80 ° C. or higher.   The method for manufacturing an electronic circuit according to claim 20 or 21, wherein the steam is steam.   The method of manufacturing an electronic circuit according to claim 8, further comprising a hot water treatment step of immersing the formed metal wiring portion in hot water having a temperature of 60 ° C. or higher after the metal wiring portion forming step. .   The method for manufacturing an electronic circuit according to claim 23, wherein the temperature of the hot water is 80 ° C or higher.   The method of manufacturing an electronic circuit according to any one of claims 8 to 24, wherein the mercapto compound adsorption step immerses the formed metal wiring part in a mercapto compound-containing liquid.   26. The method of manufacturing an electronic circuit according to claim 25, wherein the mercapto compound-containing solution contains 1 to 100 g / L of a mercapto compound.   27. The method of manufacturing an electronic circuit according to any one of claims 8 to 26, further comprising an alcohol cleaning treatment step of immersing and cleaning the metal wiring portion in alcohol after the mercapto compound adsorption step.   28. The method of manufacturing an electronic circuit according to claim 27, wherein the alcohol is methanol.   28. The method of manufacturing an electronic circuit according to claim 27, wherein the alcohol is ethanol.

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