JP2011138628A - Conductive element and method of manufacturing the same, and photosensitive material for forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive element having little induction loss and high conductivity, along with a method of manufacturing the same, and to provide a photosensitive material for forming the conductive element, suitable for obtaining the conductive element. <P>SOLUTION: The conductive element includes support, a metal mesh layer containing a mesh made of a conductive metal, and a conductive particle-containing layer having a binder content of ≤0.2 g/m<SP>2</SP>. The conductive element is manufactured by the manufacturing method comprising subjecting the photosensitive material for forming the conductive element to pattern exposure and a developing process, the photosensitive material having support, a silver-salt-containing layer, and a conductive particle-containing layer with a binder content of ≤0.2 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a conductive element, a method for producing the same, and a photosensitive material for forming a conductive element.

In recent years, conductive elements by various manufacturing methods have been studied. Among these, there is a conductive element produced using a photosensitive material for forming a conductive element, which has a silver salt-containing layer such as a silver halide emulsion layer on a support. The photosensitive material is pattern-exposed in a mesh shape and developed to produce a conductive element having a mesh conductive portion composed of developed silver and an opening for ensuring transparency (for example, a patent) References 1-3).
However, when this conductive element is used as various electrodes such as an electromagnetic shielding film, an organic EL or inorganic EL electrode, and an electrode of an electrochromic element, the dielectric loss is still large and the conductivity is unsatisfactory. .

JP 2004-221564 A JP 2004-221565 A JP 2007-95408 A

  An object of the present invention is to provide a conductive element having a small dielectric loss and high conductivity, a method for producing the same, and a photosensitive material for forming a conductive element suitable for obtaining the conductive element.

Means for solving the problems are as follows.
<1> A conductive element having a support, a metal mesh layer composed of a conductive metal, and a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less.
<2> The conductive element according to <1>, including the support, the metal mesh layer, and the conductive fine particle-containing layer in this order.
<3> The conductive element according to <1> or <2>, wherein the conductive metal is silver.
<4> The conductive fine particles contained in the conductive fine particle-containing layer are conductive metal oxide fine particles having a particle diameter of 0.005 μm to 0.12 μm, according to any one of <1> to <3>. Conductive elements.
<5> The metal oxide is at least one metal oxide selected from the group consisting of SnO ₂ , ZnO, TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO ₃ , and a composite thereof <4> The conductive element according to <4>, which is a metal oxide or a metal oxide containing a heteroatom in these metal oxides.
<6> The conductive element according to <4>, wherein the metal oxide is SnO ₂ doped with antimony.
<7> The content of the conductive particles contained in the conductive fine particle-containing layer is ^conductive according to any one of <6> from a ^{0.05g / m 2 ~0.99g / m 2} <1> element.
<8> The conductive element according to any one of <1> to <7>, wherein the conductive fine particle-containing layer does not contain a binder.
<9> A photosensitive element-forming photosensitive material comprising a support, a silver salt-containing layer, and a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less.
<10> A method for producing a conductive element, comprising subjecting the photosensitive material for forming a conductive element according to <9> to pattern exposure and development processing in a mesh shape.
<11> Conductive element forming photosensitive material having a support and a silver salt-containing layer is subjected to pattern exposure and development treatment in a mesh shape to produce a conductive element precursor having a developed silver mesh layer, A method for producing a conductive element, comprising forming a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less on a developed silver mesh layer.
<12> The method for producing a conductive element according to <11>, wherein the conductive element precursor is smoothed after the development treatment and before the formation of the conductive fine particle-containing layer.
<13> A metal mesh layer including a mesh composed of a conductive metal, a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less, and an energized layer adjacent to the conductive fine particle-containing layer. Having electrode structure.

  According to the present invention, there are provided a conductive element having a small dielectric loss and high conductivity, a method for producing the same, and a photosensitive material for forming a conductive element suitable for obtaining the conductive element.

The electroconductive element of this invention has a support body, the metal mesh layer comprised with the electroconductive metal, and the electroconductive fine particle content layer whose binder amount is 0.2 g / m < ² > or less.
In the conductive element of the present invention, a conductive element having a low dielectric loss and high conductivity can be obtained by setting the binder amount of the conductive fine particle-containing layer to 0.2 g / m ² or less.

Hereinafter, each material used for the conductive element of the present invention will be described.
[Support]
Examples of the support used in the conductive element of the present invention include a plastic film, a plastic plate, and a glass plate.
As the support, polyethylene terephthalate (PET) (melting point: 258 ° C.), polyethylene naphthalate (PEN) (melting point: 269 ° C.), polyethylene (PE) (melting point: 135 ° C.), polypropylene (PP) (melting point: 163 ° C.) ), Polystyrene (melting point: 230 ° C.), polyvinyl chloride (melting point: 180 ° C.), polyvinylidene chloride (melting point: 212 ° C.), triacetyl cellulose (TAC) (melting point: 290 ° C.), etc. A plastic film or a plastic plate is preferred. PET is particularly preferable from the viewpoints of light transmittance and processability.
The thickness of the support is selected from the range of 10 μm to 200 μm, more preferably from the range of 70 μm to 180 μm.
The transparency of the support is preferably high. The total visible light transmittance of the support is preferably 70% or more, more preferably 85% or more, and particularly preferably 90% or more. Of course, a colored support can be used as long as it does not interfere with the object of the present invention.

[Metal mesh layer]
The metal mesh layer used for the conductive element of the present invention is composed of a conductive metal. As the conductive metal, any metal exhibiting conductivity can be used. As the conductive metal, copper, aluminum, silver or the like is preferable because of its excellent conductivity.
The conductive metal may be composed of a single metal or an alloy. Moreover, the metal which comprises a metal mesh may be a laminated structure of 2 or more types of metals, when it sees in the cross section of a surface perpendicular | vertical to the plane of an electroconductive element.
The thickness of the metal mesh layer is generally selected from the range of 0.1 μm to 5 μm, more preferably from the range of 1 μm to 3 μm. From the viewpoint of improving the conductivity, it is preferable that the thickness of the metal mesh layer is large.
A metal mesh layer is formed by the method as described in the following (1)-(4), for example.
(1) By exposing a photosensitive material having an emulsion layer containing photosensitive silver halide on a support and performing development processing, a metallic silver portion and a light-transmitting portion are formed in an exposed portion and an unexposed portion, respectively. Thus, a metal mesh layer can be formed. Further, a conductive metal may be supported on the metal silver portion by further subjecting the metal silver portion to physical development and / or plating treatment.
(2) The photoresist film on the copper foil formed on the support is exposed and developed to form a resist pattern, and the copper foil exposed from the resist pattern is etched to form a metal mesh layer. Also good.
(3) A metal mesh layer may be formed by printing a paste containing metal fine particles (containing a catalyst) on a support and performing metal plating on the paste.
(4) The metal mesh layer may be printed on the support by a screen printing plate or a gravure printing plate. When forming by printing, a catalyst layer (containing a catalyst) corresponding to the metal mesh layer is formed first, and then the metal mesh layer is formed by performing metal plating on the catalyst layer. Can be improved.

[Conductive fine particles]
The conductive fine particles used in the conductive fine particle-containing layer included in the conductive element of the present invention include SnO ₂ , ZnO, TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, and MoO _3. Examples thereof include metal oxides such as these, composite oxides thereof, and metal oxide particles further containing different atoms in these metal oxides. An example of the heteroatom is antimony.
As the metal _{oxide, SnO 2, ZnO, TiO 2} , Al 2 O 3, In 2 O 3, MgO is preferred, SnO ₂ is particularly preferable. The SnO _2, SnO ₂ are preferred doped with antimony, SnO ₂ is preferred which is particularly doped antimony 0.2-2.0 mol%.

There is no restriction | limiting in particular about the shape of the electroconductive fine particles used for this invention, A granular form, needle shape, etc. are mentioned. The particle diameter of the conductive fine particles is preferably 0.005 to 0.12 μm.
The lower limit of the particle diameter is more preferably 0.008 μm and even more preferably 0.01 μm. The upper limit of the particle diameter is more preferably 0.08 μm and even more preferably 0.05 μm. By satisfy | filling the said particle diameter conditions, it is excellent in transparency and can form a uniform conductive layer in the electroconductive in-plane direction.
The lower limit value of the powder resistance (9.8 MPa green compact) of the conductive fine particles is preferably 0.8 Ωcm, more preferably 1 Ωcm, and even more preferably 4 Ωcm. The upper limit value of the powder resistance (9.8 MPa compact) of the conductive fine particles is preferably 35 Ωcm, more preferably 20 Ωcm, and even more preferably 10 Ωcm. By satisfying the above powder resistance condition, it is possible to form a conductive layer that is uniform in the conductive in-plane direction.
The specific surface area (Simple BET method) is preferably from ^{60m 2 / g~120m 2 / g,} 70m 2 / g~100m 2 / g is more preferable. Among these, those satisfying all of the above preferred conditions are particularly preferable.
When the conductive fine particles are spherical particles, the average primary particle size is preferably 0.005 to 0.12 μm, more preferably 0.008 to 0.05 μm, and 0.01 to 0.03 μm. Further preferred. The powder resistance is preferably 0.8-7 Ωcm, more preferably 1-5 Ωcm.
In the case of needles, the average axial length is preferably 0.2-20 μm in the long axis and 0.01-0.02 μm in the short axis. The powder resistance is preferably 3 to 35 Ωcm, and more preferably 5 to 30 Ωcm.
As the conductive fine particles having the above-described characteristics, SN series, FS series manufactured by Ishihara Sangyo Co., Ltd., and conductive materials manufactured by Mitsubishi Materials Electronic Chemicals, Inc. can be used.

[Binder of conductive fine particle-containing layer]
In the conductive element according to the present invention, the binder amount of the conductive fine particle-containing layer is set to 0.2 g / m ² or less. Binder amount of the conductive fine particle-containing layer is preferably from 0.20 g / ^{m 2} or less, 0.1 g / ^{m 2} or less is more preferable. Thereby, the dielectric loss of an electroconductive element becomes small, and the electroconductive element which has high electroconductivity is obtained. The reason is that by setting the binder amount to 0.2 g / m ² or less, the influence of the binder interposed between two adjacent conductive fine particles is reduced, and the flow of electrons between the conductive fine particles is improved. It is estimated that the increase in dielectric loss is suppressed. Therefore, it is most preferable that the conductive fine particle-containing layer does not contain a binder. The “binder amount is 0.2 g / m ² or less” in the present invention includes the case where the binder amount is 0 g / m ² , that is, the case where no binder is included.

  When the conductive fine particle-containing layer contains a binder, the binder is selected from those having a function of uniformly dispersing the conductive fine particles in the conductive fine particle-containing layer and fixing the conductive layer to the support surface. It is preferable. As such a binder, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but it is preferable to use a water-soluble polymer.

  Specific examples of the water-soluble polymer include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polysaccharides such as starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, Examples include polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxycellulose, and the like. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group. Gelatin may be chemically modified gelatin such as acetylation, deamination, benzoylation, dinitrophenylation, trinitrophenylation, carbamylation, phenylcarbamylation, succinylation, succination, phthalation. There are gelatin and the like. Among these, the case where phthalated gelatin is used is preferable. When phthalated gelatin is used, it is possible to achieve both improved conductivity and improved coated surface. In the present invention, gelatin is particularly preferable as the binder.

Conductive fine particle-containing layer, preferably the amount of conductive fine particles provided to be in the range of ^{0.05g / m 2 ~0.99g / m 2} . The lower limit is more preferably ^{0.1g / m 2, 0.2g / m} 2 is more preferred. The above upper limit is more preferably ^{0.5g / m 2, 0.45g / m} 2 is particularly preferred.

  The metal mesh layer and the conductive fine particle-containing layer are preferably disposed so as to be adjacent to each other so that electrons flow between the conductive metal and the conductive fine particles constituting the mesh. Although there is no restriction | limiting in the order, Preferably it is set as the order of a metal mesh layer and an electroconductive fine particle content layer from the side near a support body.

An undercoat layer may be provided between the support and the metal mesh layer or the conductive fine particle-containing layer for the purpose of ensuring sufficient adhesion between them. Further, the surface of the conductive element on the side having the metal mesh layer and the conductive fine particle-containing layer may have a protective layer for the purpose of preventing damage to the conductive fine particle-containing layer.
Furthermore, you may have a back layer in the surface on the opposite side to the side in which the metal mesh layer of the support body was formed. The back layer prevents the conductive element from curving or curling, and provides a conductive element with excellent planarity. Further, the back layer may have a function as an adhesive layer when the conductive element according to the present invention is incorporated as an electrode such as inorganic EL or organic EL.
When an undercoat layer is provided between the support and a layer adjacent thereto, the undercoat layer is a layer containing a polymer binder as a constituent component.
Moreover, when it has a protective layer as a layer most distant from a support body, it is set as a layer which uses a polymer binder as a protective layer as a protective layer.
Examples of the polymer binder used for the undercoat layer or the protective layer include the binders used for the conductive fine particle-containing layer described above.

When the conductive element according to the present invention has a protective layer, the protective layer preferably contains silica. The content of silica is, 0.16 g / ^{m 2} or more preferably, 0.24 g / ^{m 2} or more is more preferable. The content of silica is more preferably not more than ^{0.5g / m 2, 0.4g / m} 2 or less is more preferred.
As silica, colloidal silica (colloidal silica) is preferably used.

Colloidal silica refers to a colloid of silicic acid fine particles having an average particle diameter of 1 nm or more and 1 μm or less, and is described in JP-A-53-112732, JP-B-57-009051, and 57-51653. You can refer to what is being done. These colloidal silicas can be prepared and used by a sol-gel method, or commercially available products can be used.
For preparing colloidal silica by the sol-gel method, see Werner Stober et al., J. MoI. Colloid and Interface Sci., 26, 62-69 (1968), Ricky D. It can be synthesized with reference to the description of Badley et al., Langmuir 6, 792-801 (1990), Journal of Color Material Association, 61 [9] 488-493 (1988).
In addition, when using commercially available products, SNOWTEX-XL (average particle size 40-60 nm), SNOWTEX-YL (average particle size 50-80 nm), SNOWTEX-ZL (average particle) manufactured by Nissan Chemical Co., Ltd. 70-100 nm in diameter), PST-2 (average particle diameter 210 nm), MP-3020 (average particle diameter 328 nm), Snowtex 20 (average particle diameter 10-20 nm, SiO ₂ / Na ₂ O> 57), Snowtex 30 (Average particle size 10 to 20 nm, SiO ₂ / Na ₂ O> 50), SNOWTEX C (average particle size 10 to 20 nm, SiO ₂ / Na ₂ O> 100), SNOWTEX O (average particle size 10 to 20 nm, _{SiO 2 / Na 2 O> 500} ) preferably can be used (trade names and the like. the _{SiO 2} / Na 2 O, where hydroxide with silicon dioxide The content mass ratio of thorium, sodium hydroxide is a representation in terms of Na 2 _O, are described in the catalog.). When using a commercial item, SNOWTEX-YL, SNOWTEX-ZL, PST-2, MP-3020, and SNOWTEX C are particularly preferable.
The main component of colloidal silica is silicon dioxide, but it may contain alumina or sodium aluminate as a minor component, and as a stabilizer, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia. Or an organic base such as tetramethylammonium.
Examples of colloidal silica include colloidal silica having an elongated shape with a thickness of 1 to 50 nm and a length of 10 to 1000 nm described in JP-A-10-268464, JP-A-9-218488, or JP-A-10-111544. Also, composite particles of colloidal silica and organic polymer described in the above publication can be preferably used.

When the metal mesh layer has a square opening, when the width of the opening (one side of the square) is X (unit: μm) and the surface resistance of the opening is Y (unit: Ω / □) In addition, it is preferable to be formed so as to satisfy the following formulas (a) and (b).
Formula (a) 50 ≦ X ≦ 7000
Formula (b) 10 ⁵ ≦ Y ≦ (5 × 10 ²³ ) × X ^−4.02
The Y is more preferably formed to satisfy the following (b1), more preferably the following (b2).
Formula (b1) 10 ⁵ ≦ Y ≦ 1 × 10 ²³ × (X) ^−4.02
Formula (b2) 10 ⁵ ≦ Y ≦ 3 × 10 ²² × (X) ^−4.25
When the conductive element is used as a transparent electrode, the mesh line width D is preferably as narrow as possible because high transparency is secured. Generally, it is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. The line width is preferably 1 μm or more, and more preferably 3 μm or more. For example, in the linear lattice pattern, the ratio of the line width D / the width X of the opening, that is, the line / space is preferably 5/995 to 10/595.
In the present invention, the width X of the opening of the metal mesh is 50 μm to 7,000 μm, more preferably 100 μm to 5,000 μm, and further preferably 200 to 2,000 μm.

The conductive element according to the present invention is a pattern exposure of a photosensitive material for forming a conductive element having a support, a silver salt-containing layer, and a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less. And a development method (a), or a conductive element-forming photosensitive material having a support and a silver salt-containing layer is subjected to pattern exposure and development processing in a mesh form, and is composed of a support and developed silver. Production method (b) of producing a conductive element precursor having a developed silver mesh layer containing a fine mesh and forming a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less on the developed silver mesh layer ). In addition, as a conductive element precursor of a manufacturing method (b), the metal mesh layer formed by the method as described in said (2)-(4) can also be used.
Hereinafter, these manufacturing methods will be described.

As described above, in the production method (a), the photosensitive element-forming photosensitive material having a support, a silver salt-containing layer, and a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less ( a) (hereinafter also referred to as “photosensitive material (a)”) is used, and in the above production method (b), the photosensitive element-forming photosensitive material (b) having a support and a silver salt-containing layer is used. (Hereinafter also referred to as “photosensitive material (b)”).
In both the photosensitive material (a) and the photosensitive material (b), the support described above for the conductive element support is used as the support.

<Silver salt-containing layer>
Examples of the silver salt contained in the silver salt-containing layer used in the photosensitive material (a) and the photosensitive material (b) 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 having excellent characteristics as an optical sensor, and the silver halide is used as a silver halide emulsion dispersed and contained as particles in a binder as a protective colloid. Techniques used in silver halide photographic films, photographic papers, printing plate making films, photomask emulsion masks, etc. relating to silver halide emulsions 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 halide mainly composed of AgCl, AgBr, and AgI is preferably used, and silver halide mainly composed of AgBr or AgCl is 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.
Silver halide is in the form of solid grains. From the viewpoint of image quality of the patterned metallic silver portion formed after exposure and development processing, the average grain size of silver halide is 0.1 nm to 1000 nm in terms of sphere equivalent diameter ( 1 μm), preferably 0.1 nm to 100 nm, more preferably 1 nm to 50 nm. The sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and having a spherical shape.
A silver halide emulsion (hereinafter also simply referred to as “emulsion layer”), which is a coating solution for an emulsion layer used in a preferred embodiment of the silver salt-containing layer used in the present invention, is described in P.I. By Glafkides Chimie et Physique Photographic (published by Paul Montel, 1967), G. F. Dufin, Photographic Emulsion Chemistry (published by The Focal Press, 1966), V.C. L. It can be prepared using the method described in Zelikman et al., Making and Coating Photographic Emulsion (published by The Focal Press, 1964).

<Binder>
In the emulsion layer, a binder can be 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, both the water-insoluble polymer and the water-soluble polymer can be used as the binder. However, the ratio of the water-soluble binder to be removed by the immersion in hot water described below or the contact with steam is large. Is preferred.
Examples of the binder include gelatin, carrageenan, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, and polyacrylic acid. , Polyalginic acid, polyhyaluronic acid, carboxycellulose and the like. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.
Preferably gelatin is used. As gelatin, lime-processed gelatin or acid-processed gelatin may be used, and gelatin hydrolyzate, gelatin enzyme decomposition product, and others (phthalated gelatin modified with amino group and carboxyl group, acetylated gelatin) are used. However, the gelatin used in the silver salt preparation step is preferably gelatin in which the positive charge of the amino group is changed to uncharged or negative charge, and more preferably phthalated gelatin.

  The content of the binder contained in the emulsion layer is not particularly limited, and can be appropriately determined as long as the dispersibility of silver halide and the adhesion of the photosensitive layer can be exhibited. From the viewpoint of the conductive element, it is preferable that the content of the binder in the emulsion layer is small. From these viewpoints, the volume ratio of the silver halide converted to silver / the volume of the binder (hereinafter referred to as “silver / binder volume ratio”) is preferably 1/2 or more, and is 1/1 or more. It is more preferable. The upper limit of the silver / binder volume ratio is preferably 4/1 and more preferably 3/1.

<Solvent>
The solvent used for the formation of 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, dimethyl sulfoxide, etc. Sulphoxides, esters such as ethyl acetate, ionic liquids, and mixed solvents thereof The content of the solvent used in the emulsion layer of the present invention includes the silver salt and binder contained in the emulsion layer. It is the range of 30 mass%-90 mass% with respect to the total mass of etc., and it is preferable that it is the range of 50 mass%-80 mass%.

The emulsion layer preferably contains a fog inhibitor. The fogging inhibitor is preferably selected from nitrogen atom-containing heterocyclic compounds, among which indazoles, imidazoles, benzimidazoles, triazoles, benzotriazoles, tetrazoles, and triazaindolizines. These compounds suppress the occurrence of black spots (also referred to as black spots) in the opening of the conductive element, and do not lower the conductivity as the conductive element due to the addition of the fog inhibitor. This is preferable. A preferred range of the amount of fog-inhibiting agent has low generation of Kuropotsu, yet was 3mg / m ² ~15mg / m ² from the viewpoint of an increase in the surface resistance of the conductive element can be suppressed, still more preferably in the range of 6 mg / m ^{2 to} 13 mg / m ² . The content in terms of mole of the fog inhibitor is 0.02 mmol / m ^{2 to} 0.13 mmol / m ² , and a more preferable range is 0.06 mmol / m ^{2 to} 0.11 mmol / m ² .

  In addition to the silver salt-containing layer, various additives conventionally added to photographic silver halide emulsions, such as dyes, polymer latex, hardeners, contrast enhancers, toning agents, conductive agents, etc. Can be contained.

The photosensitive layer of the electrically conductive element for forming the light-sensitive material of the present invention is preferably provided so that the amount of silver salt is 5g / m ² ~30g / m ² in terms of silver on a support, further range of 7g ^{/ m 2} ~15g ^/ m 2 is more preferable.
The thickness of the photosensitive layer is preferably in the range of 1 μm to 20 μm, and more preferably in the range of 1 μm to 10 μm.

When the conductive element according to the present invention is produced by the production method (b), a photosensitive material (b) including a support and a silver salt-containing layer is used. In the production method (a), a photosensitive material (a) in which a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less is further provided on the silver salt-containing layer is used. Is done. Regarding the composition and thickness of the conductive fine particle-containing layer, the contents described for the conductive element are applied as they are. In the photosensitive material (a) and the photosensitive material (b), an undercoat layer may be provided between the support and the photosensitive layer. In the case of the photosensitive material (a), a protective layer may be further provided on the conductive fine particle-containing layer. In the case of the photosensitive material (b), a protective layer may be provided on the silver salt-containing layer.

<Method for manufacturing conductive element>
The production method (a) for producing a conductive element according to the present invention using the above-described photosensitive element forming photosensitive material (a) and the conductive element according to the present invention using the above photosensitive element forming photosensitive material (b). The production method (b) for producing the sex element will be described.

<Method for Manufacturing Conductive Element (a)>
In the conductive element manufacturing method (a), first, a photosensitive material (a) containing a support, a silver salt-containing layer, and a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less is meshed. The pattern is exposed to a shape and developed. Here, the development processing includes a development step of reducing silver halide grains having latent image nuclei formed by exposure to silver and a fixing step of dissolving and removing silver halide grains in which the latent image nuclei have not been formed. It is a waste.

<exposure>
The exposure is performed in a pattern according to the shape of the mesh. The shape of the mesh is a desired shape such as a square, a rectangle, a triangular system, or a hexagon.
The pattern exposure method may be performed by surface exposure using a photomask, or may be performed 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>
The photosensitive material (a) subjected to pattern exposure in a mesh shape is developed. For the development processing, a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like is used. The developer is not particularly limited, but a PQ developer, MQ developer, MAA developer and the like can also be used. Examples of commercially available products include CN-16, CR-56, CP45X, FD-3, and papillol prescribed by Fuji Film, and C-41, E-6, RA-4, Dsd-19, D prescribed by KODAK. A developer such as -72 or a developer included in the kit can be used. A lith developer can also be used. As the lith developer, D85 or the like prescribed by KODAK can be used.

  The development processing in the production method (a) of the present invention can include a fixing step performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. In the production method of the present invention, a fixing process technique used for a silver salt photographic film, photographic paper, a printing plate making film, a photomask emulsion mask, or the like is used in the fixing step.

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 metallic silver part contained in the exposed part after the development treatment is composed of silver and a nonconductive polymer, and the volume ratio of silver / nonconductive polymer is preferably 2/1 or more, and 3/1 or more. More preferably.
The gradation after the development processing is not particularly limited, but is preferably more than 4.0. When the gradation after the development processing exceeds 4.0, the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high. As a means for setting the gradation to 4.0 or more, for example, there is a high contrast means for doping silver halide grains with rhodium ions or iridium ions at the time of preparing a silver halide emulsion.

  A film having higher conductivity can be obtained by performing a smoothing process and a binder removal process as necessary following the development process. In the present invention, the developing temperature, fixing temperature and washing temperature are preferably 25 ° C. or less.

In the present invention, by performing the above pattern exposure and development processing, a mesh composed of developed silver is formed in the exposed portion, and an opening is formed in the unexposed portion. And on the metal silver mesh layer formed in this way, a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less is provided, and thus the conductive element according to the present invention is obtained. .

<Method for Manufacturing Conductive Element (b)>
In the production method (b), first, a photosensitive material (b) including a support and a silver salt-containing layer is subjected to pattern exposure in a mesh shape, developed, and then a support and a mesh composed of developed silver. A conductive element precursor having a developed silver mesh layer containing is prepared. For pattern exposure, the same pattern exposure as in the case of the production method (a) can be applied as it is. In the development process, the same development process as in the production method (a) is applied as it is, including the fixing process and washing with water.
The conductive element precursor thus obtained has a mesh layer composed of developed silver on one surface of the transparent support.

<Formation of conductive fine particle-containing layer>
Next, a conductive fine particle-containing layer is formed on the silver mesh layer of the conductive element precursor.
As the conductive fine particles and binder used in the conductive fine particle-containing layer, the same conductive fine particles and binder as those used in the conductive fine particle-containing layer of the conductive element according to the present invention described above are used.

The conductive fine particle-containing layer has a binder amount of 0.2 g / m ² or less. In order to form the conductive fine particle-containing layer having such a binder amount, the following method is preferably employed.

(1) A dispersion containing the conductive fine particles and the binder in the solvent at a mass ratio of 4.5 / 1 or more, more preferably 10/1 or more, and even more preferably 30/1 or more is provided in the silver mesh layer, and the solvent To remove (i.e., dry).
The upper limit of the mass ratio of the conductive fine particles and the binder is as small as possible as long as the conductive fine particles are fixed on the silver mesh layer after drying, and is preferably 1000/1, more preferably 500/1, more preferably 100/1.

  As a coating method, a bar coating method in which the above dispersion liquid is applied with a wire bar, and the above dispersion liquid is made into fine droplets with a spray gun such as a rotary atomizer, and the droplets adhere to the surface of the silver mesh layer. For example, a spray coating method in which coating is performed is preferable.

(2) A method in which conductive fine particles are dispersed to form a layer of conductive fine particles on the surface of the silver mesh layer before the silver mesh layer obtained by the development treatment is touch-dried.
An existing rotary feeder method, table feeder method, screw feeder method, or the like is used as a powder supply device for spraying conductive fine particles. In the case of this method, the binder amount of the conductive fine particle-containing layer can be made zero.

Also, in the spray coating method described in (1) above, the time from the formation of fine droplets with a spray gun to the adhesion to the surface of the silver mesh layer is adjusted to be long, and the solvent in the droplets is adjusted. A method of evaporating and adhering to the surface of the silver mesh layer may also be used. In the case of this method, before the conductive fine particles adhere to the surface of the silver mesh layer, the binder can also be configured to cover the surface of the conductive fine particles, and the coated binder serves as a paste, Conductive fine particles can be fixed to the surface of the silver mesh layer.
By the above, the electroconductive element by this invention which has the electroconductive layer comprised by the silver mesh layer and the electroconductive fine particle content layer on the transparent support body is manufactured.

<Other optional steps>
In the method (b) for producing a conductive element, after the conductive element precursor is produced, before the conductive fine particle-containing layer is formed, the conductive element precursor is subjected to oxidation treatment and reduction treatment described below. Smoothing treatment, hot water treatment or steam treatment, plating treatment, etc. may be performed.

<Oxidation treatment>
The developed silver after the development treatment is preferably subjected to an oxidation treatment. By performing the oxidation treatment, for example, when silver is slightly deposited on the light-transmitting portion, the silver can be removed, and the light-transmitting 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 process is performed after the development process.

  Furthermore, the developed silver after pattern exposure and development processing can be processed 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 developed silver from changing with time.

  In the production method of the present invention, a mesh composed of developed silver having a specified line width, aperture ratio, and silver content is directly formed on the support by exposure / development treatment, so that the surface resistivity is sufficient. Therefore, it is not necessary to apply a physical phenomenon and / or a plating treatment to the developed silver constituting the mesh to newly impart conductivity. For this reason, a translucent conductive element can be manufactured by a simple process.

<Reduction treatment>
In order to remove silver oxide and silver sulfide which are impurities generated by the development treatment, it is preferable to perform a water washing treatment after the development treatment and immerse in a reducing aqueous solution. Thereby, the electroconductive element which has much higher electroconductivity is obtained.
As the reducing aqueous solution, a sodium sulfite aqueous solution, a hydroquinone aqueous solution, a paraphenylenediamine aqueous solution, an oxalic acid aqueous solution, or the like can be used, and the aqueous solution pH is more preferably 10 or more.

<Smoothing process>
The conductive element precursor is preferably subjected to a smoothing treatment. This significantly increases the conductivity of the mesh composed of developed silver. In the smoothing treatment, the gap between the nips of at least a pair of rolls constituted by a combination in which the first calendar roll and the second calendar roll are arranged to face each other so that their respective rotation axes are parallel is 2940 N / cm or more. It is preferable to carry out by passing the conductive element precursor under linear pressure. Hereinafter, the smoothing process using the calendar roll is referred to as “calendar process”.
As a roll used for the first calender roll and the second calender roll, at least the material forming the surface is made of resin such as epoxy, polyimide, polyamide, polyimide amide, and the surface is metal. A configured metal roll is included. In particular, in the case of a conductive element precursor made of a photosensitive material for forming a conductive element having a photosensitive layer only on one surface of a support, a calendar is formed under the following conditions in order to suppress the generation of wrinkles. It is preferable to process.

(1) The thickness of the support of the conductive element precursor after the development processing is 95 μm or more.
(2) In the calendering process, the conductive element precursor is pressed using a first calender roll and a second calender roll arranged to face each other.
(3) The first calendar roll contacting the support is a resin roll.

More preferable conditions are as follows. It suffices to satisfy at least one of them.
(A) The second calender roll that contacts the mesh of the conductive element precursor is a metal roll.
(B) The surface of the metal roll is mirror-finished.
(C) The surface of the metal roll is embossed.
(D) The surface roughness of the embossed metal roll is 0.05 s to 0.8 s at the maximum height Rmax.
(E) The mesh has a silver / binder volume ratio of 1/1 or more.
(F) The calendar treatment is performed at a linear pressure between the nips of 2940 N / cm to 5880 N / cm with respect to the conductive element precursor.
(G) The calendar process is performed at a conveyance speed of the conductive element precursor of 10 m / min to 50 m / min.
(H) When the surface resistance of the conductive element precursor is R1, and the surface resistance of the conductive element is R2,
0.58 ≦ R2 / R1 ≦ 0.77
Be.

  The application temperature of the calendar treatment is preferably 10 ° C. (no temperature control) to 100 ° C. The more preferable temperature varies depending on the shape of the mesh pattern, the area ratio and shape of the mesh and opening, and the binder type, but is approximately 10 ° C. (temperature No adjustment) is in the range of 50 ° C.

<Hot water treatment or steam treatment>
After forming a silver mesh layer composed of developed silver on a transparent support, and before forming a conductive fine particle-containing layer, a hot water treatment in which the conductive element precursor is immersed in warm water or heated water at a temperature higher than that. Alternatively, it is preferable to perform a steam treatment in contact with water vapor. Thereby, electroconductivity and transparency can be improved simply in a short time. It is considered that a part of the water-soluble binder is removed and the bonding sites between developed silver (conductive substances) are increased.
Although this process can be performed after the development process, it is desirable to perform the process after the smoothing process.
The temperature of the hot water used in the hot water treatment is preferably 60 ° C. or higher and 100 ° C. or lower, more preferably 80 ° C. to 100 ° C. Further, the temperature of the water vapor used in the steam treatment is preferably 100 ° C. or more and 140 ° C. or less at 1 atmosphere. The treatment time of the hot water treatment or the steam treatment varies depending on the type of the water-soluble binder to be used, but when the size of the support is 60 cm × 1 m, it is preferably about 10 seconds to about 5 minutes, and about 1 minute to about 5 minutes. Is more preferable.

<Plating treatment>
You may perform a metal-plating process with respect to a mesh in the front | former stage or the back | latter stage of the said smoothing process. By plating, the surface resistance can be further reduced and the conductivity can be increased. By performing the plating process after the smoothing process, the plating process is made efficient and a uniform plating layer is formed. 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.

ADVANTAGE OF THE INVENTION According to this invention, the electroconductive element which has high electroconductivity, the photosensitive material for electroconductive element formation which can manufacture the electroconductive element which has high electroconductivity, and the manufacturing method from which a high electroconductive element is obtained are provided. Using such a conductive element, a metal mesh layer composed of a conductive metal, a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less, and a coating adjacent to the conductive fine particle-containing layer. It is preferable to produce an electrode structure having an energization layer. Since the conductive element according to the present invention has high conductivity, even if it is used as an electrode structure for a touch panel, an inorganic EL element, an organic EL element, or a solar cell, the visibility or light transmittance of the screen is lowered. I will not let you. Moreover, since the electroconductive element by this invention functions also as a heat_generation | fever sheet | seat which heat | fever-generates by sending an electric current, it can be used as electrode structures, such as a vehicle defroster (defrosting apparatus) and a window glass. Furthermore, since the photosensitive material for forming a conductive element according to the present invention can be easily manufactured in a large area, it can be used in an application field where a conductive element of a large area is required, for example, reducing the illuminance of incident light. Alternatively, the present invention can be applied to an electrode of an electrochromic device used for obtaining a window having a dimming function for blocking incident light.

<EL element>
Hereinafter, an example in which the electrode structure of the present invention is applied to an EL element will be described in detail.
The EL element of the present invention has a configuration in which a phosphor layer is sandwiched between a pair of opposing electrodes, and the conductive element is included in at least one of the electrodes. The EL element may be an organic EL element or an inorganic EL element.
An inorganic EL element according to a preferred embodiment of the present invention has a transparent electrode (the conductive element), a phosphor layer, a reflective insulating layer, and a back electrode in this order, and the phosphor layer on the conductive layer side of the conductive film. Have The transparent electrode and the back electrode are electrically connected via the electrode. A silver paste is applied as an auxiliary electrode to the electrode in contact with the transparent electrode, and an insulating paste is applied to the phosphor layer side.

The phosphor layer, the reflective insulating layer, and the back electrode can be printed on the transparent electrode, or can be bonded to form an element. Here, “provided by printing” means that the phosphor layer, the reflective insulating layer, and the back electrode are directly printed on the transparent electrode. “Bonding” refers to a material formed by thermocompression bonding of a transparent electrode and a phosphor layer, a reflective insulating layer, and a back electrode integrated together.
By applying a voltage to the transparent electrode and the back electrode, a potential difference is applied to the phosphor in the phosphor layer. The potential difference becomes light emission energy, and the light emission state is maintained by continuously applying the potential difference using an AC power source. In this example, the phosphor layer is the energized layer.

[Transparent electrode]
As the transparent electrode in the present invention, the conductive fine particle-containing layer of the conductive element is used in contact with the phosphor layer.

[Phosphor layer]
The phosphor layer (phosphor particle layer) is formed by dispersing phosphor particles in a binder. As the binder, a polymer having a relatively high dielectric constant such as a cyanoethyl cellulose resin, or a resin such as polyethylene, polypropylene, polystyrene resin, silicone resin, epoxy resin, or vinylidene fluoride can be used. The thickness of the phosphor layer is preferably 1 μm or more and 50 μm or less.
The phosphor particles contained in the phosphor layer are, as the base material, specifically at least one element selected from the group consisting of Group II elements and Group VI elements, Group III elements and Group III elements. It is a semiconductor fine particle composed of at least one element selected from the group consisting of group V elements, and is arbitrarily selected depending on the necessary emission wavelength region. For example, ZnS, CdS, CaS, etc. can be preferably used.
The phosphor particles have an average sphere equivalent diameter of preferably 0.1 μm to 15 μm. The variation coefficient of the equivalent sphere diameter is preferably 35% or less, more preferably 5% or more and 25% or less. These average sphere equivalent diameters can be measured with LA-500 (trade name) manufactured by Horiba, Ltd. using a laser light scattering method, a Coulter counter manufactured by Beckman Coulter, or the like.

[Reflective insulating layer]
In the inorganic EL element of the present invention, it is preferable to provide a reflective insulating layer (hereinafter also referred to as a dielectric layer in some cases) between the phosphor layer and the back electrode.
As the dielectric layer, any material can be used as long as it has a high dielectric constant and insulation and has a high dielectric breakdown voltage. These are selected from metal oxides and nitrides, and for example, BaTiO ₃ , BaTa ₂ O _{6 and the} like are used. The dielectric layer containing a dielectric substance may be provided on one side of the phosphor particle layer, and is preferably provided on both sides of the phosphor particle layer.
The phosphor layer and the dielectric layer are preferably formed by coating or screen printing using a spin coating method, a dip coating method, a bar coating method, a spray coating method, or the like.

[Back electrode]
For the back electrode on the side from which light is not extracted, any material having conductivity can be used. As long as it is conductive, for example, a transparent electrode such as ITO or an aluminum / carbon electrode may be used, and the above-described conductive film may be used as a back electrode.
[Sealing / Water absorption]
The EL element of the present invention preferably has an appropriate sealing material on the opposite side of the transparent conductive film, and is preferably processed so as to eliminate the influence of humidity and oxygen from the external environment. In the case where the substrate of the element itself has sufficient shielding properties, a moisture or oxygen shielding sheet is overlaid on the fabricated element, and the periphery can be sealed with a curable material such as epoxy. In order not to curl the planar element, a shielding sheet (moisture-proof film) may be provided on both sides. When the substrate of the element has moisture permeability, it is necessary to provide a shielding sheet on both sides.
[Voltage and frequency]
Usually, the dispersion type EL element is driven by alternating current. Typically, it is driven using an AC power source of 50 Hz to 400 Hz at 100V.

As described above, in the above-described conductive element of the present invention, known documents listed below can be used in appropriate combination.
JP 2004-221564, JP 2004-221565, JP 2007-200922, JP 2006-352073, WO 2006 / 001461A1, pamphlet 2007-129205, JP 2007- JP 235115, JP 2007-207987, JP 2006-012935, 2006-010795, 2006-228469, 2006-332459, 2007-207987 JP, JP 2007-226215, WO 2006 / 088059A1, pamphlet, JP 2006-261315, JP 2007-072171, JP 2007-102200, JP 2006-228473, JP 2006-269795, JP-2006-267635, JP-2006-267627, WO2006 / 098333 pamphlet, JP-2006-324203, JP-2006-228478, JP-2006-228836 JP, JP 2006-228480, WO 2006 / 098336A1, pamphlet, WO 2006 / 098338A1, pamphlet, JP 2007-009326, JP 2006-336057, JP 2006-339287, JP 2006-339 No. 336090 JP, 2006-336099, JP, 2007-039738, JP, 2007-039739, JP, 2007-039740, JP, 2007-002296, JP, 2007-084886, JP 2007-092146, JP 2007-162118, JP 2007-200872, JP 2007-197809, JP 2007-270353, JP 2007-308761, JP 2006 -286410, JP-2006-283133, JP-2006-283137, JP-2006-348351, JP-2007-270321, JP-2007-270322, WO2006 / 098335A1 , JP2007-088218, JP2007-201378, JP2007-335729, WO2006 / 098334A1, pamphlet 2007-134439, JP2007-149760, JP2007 JP-A-208133, JP-A-2007-178915, JP-A-2007-334325, JP-A-2007-310091, JP-A-2007-311646, JP-A-2007-013130, JP-A-2006-339526 JP, JP 2007-116137, JP 2007-088219 JP, 2007-207883, JP 2007-207893, JP 2007-207910, JP 2007-013130, WO 2007/001008, JP 2005-302508, JP JP 2005-197234, JP 2008-218784, JP 2008-227350, JP 2008-227351, JP 2008-244067, JP 2008-267814, JP 2008- 270405, 2008-277675, 2008-277676, 2008-282840, 2008-283029, 2008-288305, 2008-288419 JP, 2008-300720, 2008-300721, 2009-4213, 2009-10001, 2009-16526, 2009-21334, JP2009-26933, 2008-147507, 2008-159770, 2008-159771, 2008-171568, 2008-198388, JP JP 2008-218096, JP 2008-218264, JP 2008-224916, JP 2008-235224, JP 2008-235467, JP 2008-241987, JP 2008-251274, JP 2008-251275, JP 2008-252046, JP 2008 -277428, JP 2009-21153.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto. “%” Means “% by mass”.
[Example 1]
<< Preparation of Emulsion A (Silver / Binder Volume Ratio: 1/1) >>
・ 1 liquid:
750 ml of water
20g phthalated gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
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 were mixed with their respective complex powders, KCl 20% aqueous solution and NaCl 20%, respectively. It was dissolved in an aqueous solution and prepared by heating at 40 ° C. for 120 minutes.

  To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes with stirring to form 0.16 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were 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.

・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
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 with water and desalting was adjusted to pH 6.4 and pAg 7.5, 100 mg of 1,3,3a, 7-tetraazaindene as a stabilizer, and Proxel (trade name, manufactured by ICI Co., Ltd. as a preservative). ) 100 mg was 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 = 4000 μS / cm, density = 1.4 × 10 ³ kg / m ³ , and viscosity = 20 mPa · s.

<< Preparation of coating liquid A >>
The following compound (Cpd-1) 8.0 × 10 ⁻⁴ mol / mol Ag, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag was added to the emulsion A and mixed well. did. Next, the following compound (Cpd-2) was added as necessary for adjusting the swelling ratio, and the coating solution pH was adjusted to 5.6 using citric acid.

<< Preparation of Emulsion B (Silver / Binder Volume Ratio: 4/1) >>
・ 1 liquid:
750 ml of water
Gelatin (phthalated gelatin) 8g
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
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 were mixed with their respective complex powders, KCl 20% aqueous solution, NaCl. It was dissolved in a 20% aqueous solution and prepared by heating at 40 ° C. for 120 minutes.
To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes with stirring to form 0.16 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were 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.

・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
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 was adjusted to pH 6.4, pAg 7.5, and 10 mg sodium benzenethiosulfonate, 3 mg sodium benzenethiosulfinate, 15 mg sodium thiosulfate and 10 mg chloroauric acid were added, and the optimum sensitivity was obtained at 55 ° C. Was added, and 100 mg of 1,3,3a, 7-tetraazaindene 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 coating liquid B >>
The emulsion B was spectrally sensitized 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 at 90 mg / m ² , colloidal silica having a particle size of 10 μm of 15 wt% based on gelatin, and aqueous latex (aqL-6) at 50 mg / m ² m ² , polyethyl acrylate latex 100 mg / m ² , methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt, and 2-acetoxyethyl methacrylate latex copolymer (mass ratio 88: 5: 7) 100 mg / M ² , core-shell type latex core: styrene / butadiene copolymer mass ratio 37/63), shell 100 mg / m ^{2 of} styrene / 2-acetoxyethyl acrylate (mass ratio 84/16, core / shell ratio = 50/50), 4% of the following compound (Cpd-7) based on gelatin was added, and citric acid Was used to adjust the coating solution pH to 5.6.

(Silver halide emulsion layer)
Using emulsion A, emulsion layer coating solution A prepared as described above has a silver / binder volume ratio (silver / GEL ratio (vol)) of 1.03 / 1, Ag 8.0 g / m ² , and gelatin 0.99 g. provided with a layer such that / m ^2.
With emulsion B, the silver / binder volume ratio of (silver / GEL ratio (vol)) is ^{4.0 / 1, Ag10.0g / m 2} , provided with a layer such that the gelatin 0.32 g / ^{m 2} .
(Polyethylene terephthalate (PET) (thickness: 100 μm) was used as the support. The surface was hydrophilized in advance.)

(Conductive fine particle content layer)
As described below, a conductive fine particle-containing layer was provided by coating 5 cc / m ^{2 of} the following conductive fine particle solution on the silver halide emulsion layer.
・ 1 liquid:
943 ml of water
10g gelatin
Sb-doped tin oxide (trade name: SN100P, manufactured by Ishihara Sangyo Co., Ltd.) 48.4g
In addition, a surfactant, preservative, and pH adjuster were added as appropriate.

The emulsion layer coating solution A is used for the silver halide emulsion layer, and the conductive fine particle solution 1 solution is used for the conductive fine particle-containing layer.
In the photosensitive material A, the conductive fine particles are applied to the protective layer so that the conductive fine particles are 0.23 g / m ² and the conductive fine particle / binder ratio is 4.84 / 1 (mass ratio). In order to examine the resistance (conductive film resistance) of the conductive fine particles alone, the photosensitive material A was not exposed and developed, and only the fixing process was performed. The surface resistance was measured by removing the silver halide and found to be 10 ⁷ Ω. / □. The surface resistance (Ω / □) was measured with a digital ultrahigh resistance / microammeter 8340A (trade name, manufactured by ADC Corporation).

Photosensitive material A was coated in the same manner as photosensitive material A except that the coating amount of the conductive fine particle-containing layer was changed to 10 cc / m ² , 20 cc / m ² , 30 cc / m ² , and 40 cc / m ^2. Materials B, C, D and E were obtained. These light-sensitive materials B~E, the conductive fine particles / binder ratio is not changed, the amount of conductive fine particles, respectively ^{0.46g / m 2, 0.93g / m} 2, 1.3g / m 2 and 1. It was 63 g / m ² .

<Exposure and development processing>
Next, the photomask lines / spaces = 595 μm / 5 μm (pitch 600 μm), which can give a developed silver image of line / space = 5 μm / 595 μm, to the photosensitive materials A to E prepared above, have a grid-like space. Exposure using parallel light using a high-pressure mercury lamp as a light source through a photomask, development with the following developer, and further development with a fixer (trade name: N3X-R for CN16X: manufactured by Fujifilm) After processing, it rinsed with the pure water and obtained sample AE.

[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

(Production of electroluminescence element)
Samples A to E produced as described above were incorporated into a dispersion-type inorganic EL (electroluminescence) element, and a light emission test was performed.
A reflective insulating layer containing a pigment having an average particle size of 0.03 μm and a light emitting layer having phosphor particles of 50 to 60 μm are coated on an aluminum sheet serving as a back electrode and dried at 110 ° C. for 1 hour using a hot air dryer. did.
Thereafter, Samples A to E were stacked on the phosphor layer and the dielectric layer surface of the back electrode and thermocompression bonded to form an EL element. The element was thermocompression bonded between two sheets of nylon 6 and two moisture-proof films. The size of the EL element was 3 cm × 5 cm.

(Evaluation)
A constant frequency constant voltage power source CVFT-D series (manufactured by Tokyo Seiden Co., Ltd., trade name) was used as the power source used for measuring the emission luminance. Further, a luminance meter BM-9 (trade name, manufactured by Topcon Technohouse Co., Ltd.) was used for measurement of luminance (cd / m ² ).
(result)
The brightness was measured by driving the inorganic EL element at a peak voltage of 100 V and a frequency of 400 Hz. The results are shown in Table 1.

Samples A to C in which the binder amount of the conductive fine particle-containing layer is in the range of 0.2 g / m ² or less have higher luminance than Samples D and E, where the binder amount is more than 0.2 g / m ^2. I understand that.

[Example 2]
In the same manner as in the preparation of the photosensitive material A, except that the emulsion layer coating solution B is used for forming the silver halide emulsion layer and the conductive fine particle solution 1 solution is used for forming the conductive fine particle-containing layer. Produced. Further, in the same manner as in the production method of the photosensitive material F, except that the coating amount of one conductive fine particle liquid is changed to 10 cc / m ² , 20 cc / m ² , 30 cc / m ² or 40 cc / m ² , Photosensitive materials G, H, I and J were obtained, respectively. Conductive fine particles / binder ratio is not changed, the amount of conductive fine particles, respectively ^{0.46g / m 2, 0.93g / m} 2, was 1.3 g / ^{m 2} and 1.63 g / ^{m 2.}
In the same manner as in Example 1, the photosensitive materials F to J were exposed and developed. Thereafter, calendering was performed on the sample at a linear pressure between nips of 3500 N / cm and a conveyance speed of 10 m / min. Thereafter, steam treatment was performed at 100 ° C. under a pressure of 1 at a treatment time of about 30 seconds to prepare Samples F to J.

(Evaluation results)
An inorganic EL element was produced in the same manner as described above, and the luminance (cd / m ² ) was measured by driving at a peak voltage of 100 V and a frequency of 400 Hz. The results are shown in Table 2.

Samples F to H in which the binder amount of the conductive fine particle-containing layer is in the range of 0.2 g / m ² or less have higher luminance than Samples I and J, where the binder amount is more than 0.2 g / m ^2. I understand that.

Claims (13)

A conductive element comprising a support, a metal mesh layer composed of a conductive metal, and a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less.   The electroconductive element of Claim 1 which has the said support body, the said metal mesh layer, and the said electroconductive fine particle content layer in this order.   The conductive element according to claim 1, wherein the conductive metal is silver.   4. The conductive fine particles contained in the conductive fine particle-containing layer are conductive metal oxide fine particles having a particle diameter of 0.005 μm to 0.12 μm. 5. Conductive elements. The metal oxide is at least one metal oxide selected from the group consisting of SnO ₂ , ZnO, TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO ₃ , and a composite metal oxide thereof The conductive element according to claim 4, wherein the metal oxide is a metal oxide containing a heteroatom in these metal oxides. The conductive element according to claim 4, wherein the metal oxide is SnO ₂ doped with antimony. The content of the conductive particles contained in the conductive fine particle-containing layer is, conductive element as claimed in any one of claims 6 a 0.05g ^/ m ² ~0.99g / m 2 .   The conductive element according to any one of claims 1 to 7, wherein the conductive fine particle-containing layer does not contain a binder. A photosensitive material for forming a conductive element, comprising a support, a silver salt-containing layer, and a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less.   A method for producing a conductive element, comprising subjecting the photosensitive material for forming a conductive element according to claim 9 to pattern exposure and development processing in a mesh shape. Conductive element forming photosensitive material having a support and a silver salt-containing layer is subjected to pattern exposure and development processing in a mesh form to produce a conductive element precursor having a developed silver mesh layer, and the developed silver mesh The manufacturing method of the electroconductive element including forming the electroconductive fine particle content layer whose binder amount is 0.2 g / m < ² > or less on a layer.   The method for producing a conductive element according to claim 11, wherein the conductive element precursor is smoothed after the development process and before the conductive fine particle-containing layer is formed. An electrode structure having a metal mesh layer including a mesh made of a conductive metal, a conductive fine particle-containing layer having a binder amount of 0.2 g / m ² or less, and a conductive layer adjacent to the conductive fine particle-containing layer .