JP5192711B2 - Method for manufacturing conductive film and conductive film - Google Patents

Description

The present invention relates to a conductive film and a method for manufacturing the same. For example, the front surface of a display such as a CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), FED (field emission display), microwave oven, electronic The present invention relates to a conductive film that is used in devices, printed wiring boards, and the like and is effective in shielding electromagnetic waves, and a method for manufacturing the same.

  2. Description of the Related Art In recent years, with the increase in use of various electric facilities and electronic application facilities, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly. EMI has been pointed out to cause malfunctions and failures of electronic and electrical equipment, as well as health problems for operators of these devices. For this reason, in the electronic and electrical equipment, it is required to suppress the intensity of electromagnetic wave emission within the standard or regulation.

  Although it is necessary to shield electromagnetic waves as a countermeasure against the EMI, the property of not allowing metal electromagnetic waves to penetrate may be used. For example, there are a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, a method of covering the cable with a metal foil, and the like. However, in CRT and PDP, the operator needs to recognize characters and the like displayed on the screen, so that transparency in the display is required. As such a material, translucent electromagnetic wave shielding films disclosed in Patent Documents 1 and 2 below are known.

JP 2004-221564 A JP 2004-221565 A

  In Patent Documents 1 and 2, a photosensitive film having a silver salt-containing layer is exposed and developed to produce a translucent electromagnetic wave shielding film in which a metallic silver portion is formed.

However, at present, there is a demand for further reducing the surface resistance of the film after development. Therefore, an attempt to manufacture with less gelatin is the binder, can not be the line width uniform, it was found that it is pepper-like Animal Crossing outside metallic silver portion than.

The present invention has been made in consideration of such problems, can reduce the surface resistance of the film after development, has a uniform line width, and generates a pot-shaped bump other than the metallic silver portion. There is suppressed, a conductive film having high conductivity, and an object thereof is to provide a method of manufacturing a conductive film that can be manufactured at low cost.

  Another object of the present invention is to provide a conductive film having a low surface resistance and suitable for use in an electromagnetic shielding film or a printed wiring board.

As a result of intensive studies, the inventor has found that the present invention can be effectively achieved by the following method for producing a conductive film and the conductive film , and has completed the present invention.

[1] That is, in the method for producing a conductive film according to the first invention, a silver halide photosensitive material for obtaining a conductive metal film by subjecting a silver salt emulsion layer provided on a support to exposure and development. The silver salt emulsion layer contains a natural polymer polysaccharide derived from red algae, and a protective layer further contains gelatin or a natural polymer polysaccharide derived from red algae on the silver salt emulsion layer. A conductive film having a metal silver forming step of forming a conductive metal silver portion on the support by exposing and developing a silver halide photosensitive material having a thickness of the protective layer of 0.5 μm or less. In the manufacturing method, the method has a smoothing process for smoothing the metallic silver part, and the smoothing process is performed at a linear pressure of 2940 N / cm (300 kgf / cm) or more .

As a result, the surface resistance of the film after development can be reduced, and the conductive film having high conductivity, with a uniform line width, suppressed generation of pot-like bumps in addition to the metallic silver portion, It can be manufactured at low cost. Further, the surface resistance of the photosensitive material after development can be reduced, and a conductive film suitable for use in an electromagnetic wave shielding film or a printed wiring board can be obtained. Furthermore, in the present invention, the surface resistance of the conductive film can be sufficiently reduced by performing the smoothing process at a high linear pressure of 2940 N / cm (300 kgf / cm) or higher. 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.

[ 2 ] In the first aspect of the present invention, the natural high molecular weight polysaccharide derived from red algae is at least one selected from kappa carrageenan, iota carrageenan, lambda carrageenan, and far selerain.

[ 3 ] In the first aspect of the present invention, a conductive metal silver portion and a light transmissive portion are formed by the development process. In this case, the conductive film is suitable as a translucent electromagnetic wave shielding film.

[ 4 ] In the first aspect of the present invention, the smoothing treatment is performed at a linear pressure of 6860 N / cm (700 kgf / cm) or less.

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.

[ 5 ] Next, the conductive film according to the second aspect of the present invention is manufactured by the above-described method for manufacturing a conductive film according to the first aspect of the present invention.

As described above, according to the present invention, the line width is uniform, the generation of pepper-like Animal Crossing outside metallic silver portion than is suppressed, a conductive film having a high conductivity, can be manufactured at low cost it can. In the present invention, it is possible to suppress the formation of pepper-like Animal Crossing capable besides the conductive metal silver portion. Therefore, plating on the bumped portion is not generated, which contributes to improving the transparency of the translucent conductive film. Further, according to the present invention, the protective layer exhibits the effect of preventing scratches and improving mechanical properties. Further, by adding a natural polymer polysaccharide such as carrageenan to the protective layer and the emulsion, the line width of the conductive metal silver portion when the light-transmitting conductive film is formed can be made uniform.

  Moreover, the translucent electromagnetic wave shielding film which has a mesh-shaped metallic silver part and a translucent part can be provided by making the metallic silver part of an electrically conductive film into a thin line pattern.

  In addition, according to the present invention, the formation of a fine line pattern is possible in a short process, and it has high electromagnetic shielding properties and high transparency, and the mesh portion has a black transparent electromagnetic shielding film. The manufacturing method of the translucent electromagnetic wave shielding film which can be manufactured in large quantities can be provided.

  Further, according to the present invention, a printed circuit board having high conductivity and few pinholes can be provided.

  Further, according to the present invention, it is possible to provide a method for manufacturing a printed circuit board that can be formed into a thin line pattern, has a low environmental load, and can be mass-produced at low cost.

The light-sensitive material used in the production method of the present invention is a silver halide light-sensitive material for obtaining a conductive metal film by subjecting a silver salt emulsion layer provided on a support to exposure and development, and a silver salt emulsion The layer contains natural polymeric polysaccharides derived from red algae. The method for producing a conductive film according to the present invention is characterized in that a conductive metal part comprising a conductive substance and a water-soluble binder such as a natural polymer polysaccharide such as carrageenan is formed on a support. is there. In addition, a protective layer is provided on the support.

  The use of natural polymer polysaccharides such as carrageenan and the use of a protective layer for improving setability during film formation is well known in photographic materials (for example, JP-A-6-67330, 6-75318 and JP-A-6-95297). Both relate to photography, not to conductive films.

  Hereinafter, the manufacturing method of the electrically conductive film of this invention is demonstrated. In addition, the electrically conductive film of this invention can be used also as a translucent electromagnetic wave shielding film and a printed circuit board.

  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.

<Photosensitive material for conductive film production>
[Support]
As the support for 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 the plastic plate include, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and EVA; polyvinyl chloride, Vinyl-based resins such as polyvinylidene chloride; polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC) Etc. 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 support such as aluminum can also be used.

[Silver salt-containing layer]
The light-sensitive material used in the production method of the present invention has an emulsion layer (silver salt-containing layer) containing a silver salt as an optical sensor on a support. A silver salt content layer can contain a binder, a solvent, etc. besides silver salt. When there is no doubt, an emulsion layer containing silver salt (or a silver salt-containing layer) may be simply referred to as “emulsion layer”.

  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.

  In addition to the silver salt, the emulsion layer can contain a dye, a binder, a solvent, and the like, if necessary. 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 acid 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, horopora-type 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. Examples of 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 Patents 584,609, 1,177,429, JP-A-48-85130, 49-99620, and 49-. No. 114420, No. 52-20822, No. 59-154439, No. 59-208548, US Pat. No. 2,274,782, No. 2,533,472, No. 2,956,879. No. 3,148,187, No. 3,177,078, No. 3,247,127, No. 3,540,887, No. 3,575,704, Examples are described in Japanese Patent Nos. 3,653,905 and 3,718,427.

  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 effects such as prevention of irradiation and a decrease in sensitivity due to an increase in the amount of addition, 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 having excellent characteristics as an optical sensor, and the technique used in a silver salt photographic film, photographic paper, printing plate-making film, 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 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.

  Here, “silver halide mainly composed of AgBr (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 AgBr may contain iodide ions and chloride ions in addition to bromide ions.

  The silver iodide content in the silver halide emulsion is preferably 1.5 mol% per mole of silver halide emulsion. By setting the silver iodide content to 1.5 mol%, fogging can be prevented and pressure characteristics 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.

  The sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and having a spherical shape.

  The shape of the silver halide grains is not particularly limited. For example, 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.), octahedral shape, tetrahedral shape, etc. A cube and a tetrahedron are preferable.

  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 the inside or the surface of a particle | grain.

  The silver halide emulsion which is a coating solution for an emulsion layer used in the present invention is described in P.I. By Grafkides Chimieet Physique Photographic (published by Paul Montel, 1967), G.K. F. Dufin, Photographic Emission Chemistry (published by The Focal Press, 1966), V. L. It can be prepared using the method described in Zelikman et al., Making and Coating Photographic Emulsion (published by The Formal Press, 1964).

  That is, as a method for preparing the silver halide emulsion, either an acidic method, a neutral method, or the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, a one-side mixing method, a simultaneous mixing method, Any combination thereof may be used.

  As a method for forming silver particles, a method of forming particles in the presence of excess silver ions (so-called back mixing method) can also be used. Furthermore, as one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is generated, that is, a so-called controlled double jet method can be used.

It is also preferable to form grains using a so-called silver halide solvent such as ammonia, thioether or tetrasubstituted thiourea. As these methods, tetra-substituted thiourea compounds are more preferable, which are described in JP-A Nos. 53-82408 and 55-77737. Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

  In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal type and a narrow grain size distribution, and is preferably used in the present invention. it can.

  In order to make the grain size uniform, as described in British Patent No. 1,535,016, Japanese Patent Publication No. 48-36890, and Japanese Patent Publication No. 52-16364, silver nitrate or alkali halide is used. Using a method of changing the concentration of the aqueous solution as described in British Patent No. 4,242,445 and JP-A-55-158124 Thus, it is preferable to grow silver quickly in a range not exceeding the critical saturation. 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 more preferably 20% or less. Is preferably 15% or less, 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 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 such as methylamine and ethylenediamine, heterocyclic compounds such as imidazole, thiazole, 5-methylthiazole and mercaptoimidazole, urea and thiourea can be mentioned.

In order to increase the sensitivity, doping of a metal hexacyanide complex such as K ₄ [FeCN] ₆ ], K ₄ [RuCN] ₆ ] or K ₃ [CrCN] ₆ ] is advantageously performed.

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.

Examples of the iridium compound include hexachloroiridium complex salts such as K ₂ IrCl ₆ and K ₃ IrCl ₆ , hexabromoiridium complex salts, hexaammineiridium complex salts, and pentachloronitrosyliridium complex salts.

Examples of the ruthenium compound include hexachlororuthenium, pentachloronitrosylruthenium, K ₄ [RuCN) ₆ ] and the like.

  Examples of the iron compound include potassium hexacyanoferrate (II) and ferrous thiocyanate.

The ruthenium and osmium are added in the form of water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855, etc. Preferable examples include hexacoordination complexes represented by the following formula.
[ML ₆ ] ^-n

  Here, M represents Ru and Os, and n represents 0, 1, 2, 3, and 4.

  In this case, the counter ion is not important, and for example, ammonium or alkali metal ions are used. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.

[RuCl ₆ ] ⁻³ , [RuCl ₄ H ₂ O) ₂ ] ⁻¹ , [RuCl ₅ NO)] ⁻² , [RuBr ₅ NS)] ⁻² , [RuCO) ₃ Cl ₃ ] ⁻² , [RuCO) Cl _5] ^-2, [Ruco) Br _5] ^-2, [OsCl _6] ^-3, [OsCl ₅ NO)] ^-2, [OsNO) CN) _5] ^-2, [OSNs) Br _5] ^-2, [OsCN) _6] ^-4, [OsO) ₂ CN) _5] ^-4.

The amount of these compounds added is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, more preferably 10 ⁻⁹ to 10 ⁻³ mol / mol Ag.

  In addition, in the present invention, 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 in the surface layer 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 No. 2000-275770 is halogenated. By adding to the silver emulsion. As the silver salt used in the light-sensitive material of the present invention, an emulsion not subjected to 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.

  In the present invention, in order to further improve the sensitivity as an optical sensor, chemical sensitization performed with a photographic emulsion can be performed. As the chemical sensitization method, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination. When the above chemical sensitization methods are used in combination, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization. A combination of a method and a gold sensitization method is preferable.

The sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the sulfur sensitizer, known compounds can be used. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. Can be used. Preferred sulfur compounds are thiosulfate and thiourea compounds. The amount of sulfur sensitizer added varies under various conditions such as pH, temperature, and size of silver halide grains during chemical ripening, and is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. It is preferably 10 ⁻⁵ to 10 ⁻³ mol.

  A known selenium compound can be used as the selenium sensitizer used for the selenium sensitization. That is, the selenium sensitization is usually carried out by adding unstable and / or non-labile selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used. In particular, it is preferable to use compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855.

  The tellurium sensitizer used in the tellurium sensitizer is a compound that generates silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide grain. The silver telluride formation rate in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640, No. 4-271341, 4-3333043, 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), 1102 (1979), 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. P). rkin.Trans.1, 2191 (1980), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Compounds, The Selenium and Tellunium Compound, 1 The compounds described in Volumes (1986) and 2 (1987) can be used, in particular, the compounds represented by the general formulas (II), (III), and (IV) in JP-A-5-313284. preferable.

The amount of selenium sensitizer and tellurium sensitizer that can be used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, etc., but is generally 10 ⁻⁸ to 10 ⁻² per mole of silver halide. A mole, preferably about 10 ⁻⁷ to 10 ⁻³ mole is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used for gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, thioglucose gold (I), and thiomannose gold (I). About 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt or the like may coexist in the process of silver halide grain formation or physical ripening.

  In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion by the method disclosed in the public method of European Published Patent (EP) 293917. The silver halide emulsion used in the preparation of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Combinations of different chemical sensitization conditions and different sensitivities) may be used. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.

<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, as the binder, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but a water-soluble polymer is preferably used.

  Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacrylic acid, poly Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. 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, enzymatic degradation product of gelatin, etc. (gelatin phthalated gelatin modified with amino group or carboxyl group, acetylated gelatin) Can be 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. The content of the binder in the emulsion layer is preferably such that the Ag / binder volume ratio is 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, acetone, ketones, amides such as formamide, dimethyl sulfoxide, etc. Sulfoxides, 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 used in the production method of 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 material-containing layer having a surface resistivity of 10 ¹² (ohm / sq) 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 US Pat. No. 5,575,957, JP-A-10-142738, paragraph numbers 0045 to 0043 and JP-A-11-223901, paragraphs 0013 to 0019, 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. As an example containing a small amount of different atoms, 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 addition 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 for the conductive metal oxide particles is preferably a material 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 equivalent diameter is 0.5-25 micrometers.

  In order to obtain conductivity, for example, a soluble salt (for example, chloride, nitrate, etc.), a deposited metal layer, an ionic polymer as described in US Pat. Nos. 2,861,056 and 3,206,312 or a US patent Insoluble inorganic salts as described in Japanese Patent No. 3428451 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 volume resistivity of the photosensitive material is preferably 1.0 × 10 ⁷ to 1.0 to 10 ¹² (ohm · cm) 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, page 13 of the same publication, even better antistatic properties can be obtained.

<Other additives>
With respect to various additives used in the sensitive light material is not particularly limited, and may be for example preferably those described in the following publications and the like.

(1) Nucleation Accelerator As the nucleation accelerator, general formulas (I), (II), (III), (IV), (V), (VI) described in JP-A-6-82934 And compounds of general formulas (II-m) to (II-p) and compound examples II-1 on page 9, upper right column, line 13 to page 16, upper left column, line 10 of JP-A-2-103536. Examples thereof include II-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 lower right column, line 4 and JP-A-2-103536, page 16, lower right column. Spectral sensitizing dyes described in JP-A Nos. 1-112235, 2-124560, 3-7928, and 5-11389 are also provided from the third line to the left lower column on page 17, 20th line. Can be mentioned.

(3) Surfactant As the surfactant, JP-A-2-12236, page 9, upper right column, line 7 to right-bottom 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 The antifoggant is disclosed in 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. Furthermore, 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) Hardener Examples of the hardener include the compounds described in JP-A-2-103536, page 18, upper right column, lines 5 to 17.

(8) Black spot preventive agent The black spot preventive agent is a compound that suppresses generation of spot-like developed silver in an unexposed portion. For example, US Pat. No. 4,956,257 and Japanese Patent Application Laid-Open No. 1-118832. And the compounds described in the publication No ..

(9) Redox compounds As redox compounds, compounds represented by the general formula (I) of JP-A-2-301743 (especially Compound Examples 1 to 50), and pages 3 to 20 of JP-A-3-174143. And general formulas (R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in JP-A-5-257239 and 4-278939. It is done.

(10) 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).

(11) 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 for producing conductive film>
A method for producing a conductive film using the above photosensitive material will be described.

  In the method for producing a conductive film of the present invention, first, a photosensitive material having an emulsion layer containing at least one silver salt on a support is applied and dried. Then, the produced photosensitive material is exposed and developed. Thereafter, the metal silver portion formed by the development processing is smoothed (for example, calendar processing). When forming the metallic silver portion, the metallic silver portion and the light transmitting portion or the metallic silver portion and the insulating portion may be formed, and the entire surface of the film is formed by exposing the entire surface. You can also. In addition, although the electrically conductive film obtained by this invention has the metal formed on the support body by pattern exposure, pattern exposure may be a scanning exposure system or a surface exposure system. Further, the metallic silver part may be formed in the exposed part and may be formed in the unexposed part.

  Examples of the pattern include a mesh pattern for the production of an electromagnetic shielding film, and a wiring pattern for the production of a printed circuit board. Further details of the pattern shape can be appropriately adjusted according to the purpose. it can.

  The method for producing a conductive film of 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 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 or a conductive film having a printed wiring is formed on a 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. Or the like, or a conductive film having a printed wiring is formed. This is also an integrated black-and-white development type. Although the developing action is precipitation on 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 light-transmitting conductive film such as a film or a conductive film having a printed wiring is formed. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.

  In either case, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer method, a mode in which negative development processing is performed by using an auto-positive type photosensitive material as a photosensitive material is also possible. Is).

  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 edition” etc. edited by Mees.

[Coating / Drying]
For the coating used in the present invention, a pre-meta ring type slide bead coater or a die coater is preferably used in order to improve the coating accuracy. The wind speed of the drying air is preferably 10 m / s or more from the viewpoint of the drying speed.

[exposure]
In the production method of the present invention, the silver salt-containing 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. The pattern of irradiation light is a mesh pattern for manufacturing an electromagnetic wave shielding film, and a wiring pattern for manufacturing a printed circuit board.

  Examples of the light source include scanning exposure using a cathode ray (CRT). The cathode ray tube exposure apparatus is simple, compact, and low in cost as compared with 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 phosphors that emit light in the yellow, orange, purple, or infrared region are 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 performed by using a monochromatic high 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 a pumping light source and a nonlinear optical crystal. A scanning exposure method using density light can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F2 laser, or the like can also be 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 may be performed using a normal 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. 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.

  In the manufacturing method of the present invention, by performing the above exposure and development processing, a metal silver portion is formed in the exposed portion, and a light transmissive portion described later is formed in the unexposed portion.

  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 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 Ag / nonconductive polymer is preferably 2/1 or more, and 3/1 or more. More preferably.

  The gradation after development processing in the present invention 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. 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 metallic 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.

  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 the support by exposure / development treatment. Therefore, it is not necessary to provide the metal silver part with a physical phenomenon and / or a plating treatment to provide conductivity again. For this reason, a translucent electromagnetic wave shielding film can be manufactured by a simple process.

  As above-mentioned, the translucent electromagnetic wave shield of this invention can be used suitably as a translucent electromagnetic wave shielding film for plasma display panels. For this reason, the plasma display panel formed using the light-transmitting electromagnetic wave shielding film for plasma display panel comprising the light-transmitting electromagnetic wave shielding film of the present invention has high electromagnetic wave shielding ability, high contrast and high brightness, Moreover, it can be manufactured at low cost.

[Reduction treatment]
By immersing in a reducing aqueous solution after the development treatment, a film having a preferable high conductivity can be obtained.

  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 aqueous solution PH is more preferably 10 or more.

[Smoothing process]
In the production method of the present invention, a smoothing process is performed on a developed metal silver part (entire metal silver part, metal mesh pattern part or metal wiring pattern part). 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.

  The smoothing process can be performed by, for example, a calendar roll. 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 upper limit of the linear pressure is preferably 1960 N / cm (200 kgf / cm). More preferably, it is 2940 N / cm (300 kgf / cm) or more. The upper limit of the linear pressure is 6880 N / cm (700 kgf / cm) or less.

  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 varies depending on the line density and shape of the metal mesh pattern or metal wiring pattern, and the binder type. Is in the range of approximately 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.

[Plating treatment]
In the present invention, the smoothing process may be performed, but the metal silver part may be plated. By plating, the surface resistance can be further reduced and the conductivity can be increased. The smoothing process may be performed either before or after the plating process. However, when the smoothing process is performed before the plating process, the plating process becomes 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.

  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, 2006-228478, Special JP 2006-228480, JP 2006-228836, JP 2006-267627, JP 2006-269975, JP 2006-267635, JP 2006-286410, JP 2006-283133, JP 2006-283137.

  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.

[Examples 1-14 and Comparative Examples 1-8]
(Preparation of emulsion A)
・ 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 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 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 under the same conditions except that the amount of gelatin in one solution was changed to 8 g.

(Preparation of coated sample)
The emulsions A and B were 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 , 100 mg / m ^{2 of} polyethyl acrylate latex, 100 mg of latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (weight ratio 88: 5: 7) / m ^2, the core-shell latex core: styrene / butadiene copolymer weight ratio 37/63), shell: styrene 2-acetoxyethyl acrylate (weight ratio 84/16, core / shell ratio = 50/50) was added 100 mg / m ^2, 4 wt% of the compound to gelatin (Cpd-7), a coating solution with citric acid The pH was adjusted to 5.6.

With emulsion A, Ag10.5g / m ² on a polyethylene terephthalate (PET) the emulsion layer coating liquid prepared as above, was coated so as to gelatin 0.94 g / m ^2, then dried This was designated as coated sample A.

Further, by using the emulsion B, and emulsion layer coating liquid prepared as described above Ag10.5g / m ² on a polyethylene terephthalate (PET), was applied so as to gelatin 0.33 g / m ^2, then dried The obtained sample was designated as coated sample B.

  PET that had been subjected to surface hydrophilization in advance was used.

  The obtained coated sample A has an Ag / binder volume ratio (silver / GEL ratio (vol)) of the emulsion layer of 1 / 0.7, and is preferably used for the photosensitive material for forming a conductive film of the present invention. This corresponds to a ratio of 1/1 or more (see Examples 1 and 2 and Comparative Examples 1 and 2).

  In the coated sample B, the Ag / binder volume ratio (silver / GEL ratio (vol)) of the emulsion layer is 4/1, and the Ag / binder ratio 2/1 that is more preferably used in the photosensitive material for forming a conductive film of the present invention. The above applies (see Examples 3 and 4 and Comparative Example 3). Further, samples with different amounts of gelatin were prepared, and Examples 5 to 11 were prepared.

(Exposure and development processing)
Next, through a photomask having a grid-like photomask line / space = 195 μm / 5 μm (pitch 200 μm), which can give a developed silver image of line / space = 5 μm / 195 μm to the dried coating film. Then, it is exposed using parallel light using a high-pressure mercury lamp as a light source, developed with the following developer, and further developed with a fixer (trade name: N3X-R for CN16X: manufactured by Fuji Photo Film Co., Ltd.). After that, rinsing was performed with pure water to obtain samples a and b having different line widths and aperture ratios.

Samples prepared for the coated sample A were Aa (see Comparative Example 1 and Example 1), Ab (see Comparative Example 2 and Example 2), and those prepared for the coated sample B were Ba (comparative example). 3, Examples 3 and 4) and B-b (Example 5). In addition, a sample for overall exposure was also prepared (see Comparative Example 8, Reference Examples 1 and 2 ).

[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

(Calendar processing)
The sample developed as described above was calendered. The calender roll consists of a metal roll (iron core + hard chrome plating, roll diameter 250 mm), and linear pressure 1960 N / cm (200 kg / cm) (700 kgf / cm ² in terms of surface pressure ⁾ to 7840 N / cm (800 kg / cm) (In terms of surface pressure, 1850 kgf / cm ² was applied to pass the sample between the rollers, and the surface resistivity (Ω / sq) before and after the treatment was measured.

  Before the calendar process of sample Aa, Aa-1 (Comparative Example 1), after the process, Aa-2 (Example 1), before the calendar process of Sample Ab, A-b-1 (Comparative) Example 2) and after the treatment were referred to as Ab-2 (Example 2).

  Sample B before the calendar treatment was designated as Ba-1 (Comparative Example 3), and after treatment as Ba-2 (Example 3).

In the obtained sample Ba-2 (Example 3), the Ag / non-conductive polymer volume ratio of the metal silver part was 3.1 / 1, the density was 8.5 g / cm ³ , and the thickness was 1. The volume ratio of Ag / non-conductive polymer of the metal silver part preferably used in the conductive film of the present invention is 3/1 or more, and the thickness is 0.5 to 5 μm.

(Blackening treatment)
Next, the transparent film on which the mesh-like silver image was formed was electroplated using carbon as an anode electrode in a blackening plating solution bath having the following composition.

The plating solution in the blackening plating process is as follows. [Blackening solution composition]
Nickel sulfate hexahydrate 120g
17g ammonium thiocyanate
Zinc sulfate heptahydrate 28g
Sodium sulfate 16g
Add pure water 1L
pH 5.0 with sulfuric acid and sodium hydroxide (pH adjustment)

[Plating conditions]
Bath temperature: about 30 ° C
Time: 20 seconds Cathode current density: 0.1-0.2 A / dm ²
Current of 0.03A for the whole cathode (35mm x 12cm)
The blackening-treated sample of sample Ba-2 (Example 3) was designated Ba-3 (Example 4).

(Comparative Examples 4-7)
As a representative of the “etched copper mesh using photographic method” in the above-mentioned prior art column, in order to compare it with the most highly conductive and light transmissive technology known in the art, A metal mesh described in Japanese Patent No. 10-41682 was produced and used as a sample of Comparative Example 4.

  This sample (Comparative Example 4) was produced by performing the same experiment as that of the example of Japanese Patent Laid-Open No. 10-41682.

  In order to match the sample of the present invention with the mesh shape line width and pitch, a photomask having the same pitch of 200 μm as described above was used.

  In addition, a metal mesh described in Japanese Patent Publication No. 42-23746 as a representative of the silver salt diffusion transfer method in which silver is deposited on physical development nuclei, which is the “conducting silver formation method using silver salt” in the above-mentioned prior art column. The sample of Comparative Example 5 was prepared. The sample (Comparative Example 5) was prepared by applying a physical development nucleus layer on a transparent TAC (triacetyl cellulose) support hydrophilized in the same manner as described in Example 3 of JP-B-42-23746. And a photosensitive layer were applied, exposed through a mesh photomask with a pitch of 200 μm, and developed by DTR method.

  Further, as a representative of “mesh on which silver paste is printed” in the above-mentioned prior art column, a metal mesh described in JP-A-2000-13088 was prepared, and samples of Comparative Examples 6 and 7 having different aperture ratios were prepared.

[Evaluation]
The aperture ratio was obtained by measuring the line width of the conductive metal portion of the sample of the present invention having the conductive metal portion and the light transmissive portion thus obtained and the sample of the comparative example, and the surface resistivity. (Ohm / sq) was measured. For each measurement, an optical microscope, a scanning electron microscope, and a low resistivity meter were used.

  Further, the color of the metal part of the mesh was visually evaluated, and a black one was “◯”, and a brown or gray one was “x”. Furthermore, regarding the number of steps in the production method, those having 5 or less steps were evaluated as “◯”, and those requiring more than 5 steps were evaluated as “x”.

  The film strength was evaluated as follows.

  The surface side on which the mesh metal part is formed is scratched at a speed of 1 cm / second using a 0.1 mmφ sapphire needle. The load of the sapphire needle was changed from 0 to 100 g, and the film strength was measured with the load when the scratch reached the base.

A: The load at which scratching begins to occur is 80 g or more. O: The load at which scratching begins to occur is 50 g or more and less than 80 g. X: The load at which scratching begins to occur is 20 g or more but less than 50 g. .

  As can be seen from Table 1, in the etched copper mesh of Comparative Example 4, the color of the mesh was brown and the number of steps was also multi-step. Moreover, the mesh using the silver salt of Comparative Example 5 had a large surface resistivity and insufficient electromagnetic wave shielding ability. Furthermore, the mesh on which the silver paste of Comparative Example 6 was printed had a low aperture ratio because of the large line width. In this case, as shown in Comparative Example 7, it is possible to increase the aperture ratio by widening the pitch, but a new problem of increasing the surface resistivity has occurred.

  In contrast, Examples 1 and 2 do not have the problems seen in the above comparative examples, have a narrow line width, almost no expansion from the original line width, a large aperture ratio, and a surface resistivity. Low electromagnetic shielding ability.

  Furthermore, since the metal part of a mesh is black, Example 4 which is a preferable form can avoid the bad contrast fall to the image of a display. Moreover, the number of processes at the time of manufacture was a short process.

  In addition, it was found that Examples 1 to 4 had high film strength, and the mesh portion was not easily chipped or peeled off during handling, and the quality was highly reliable.

  In Examples 5 to 8 in which the amount of gelatin was changed, the line width was slightly thicker than those in Examples 1 to 4. However, since the surface resistivity was low even when the pitch was increased to increase the aperture ratio, the aperture ratio could be made larger than in Examples 1 to 4. In addition, the film strength is high and the reliability is high.

Although the surface exposure comparative example 8 had good low surface resistivity, the film strength was small and there was a problem in reliability. On the other hand, Reference Examples 1 and 2 for overall exposure had lower surface resistivity than Comparative Example 8, and also had high film strength, which was sufficient in terms of reliability.

  In Examples 9 to 11, the surface resistivity was higher than 2.5 (ohm / sq), which was insufficient in terms of conductivity, but the film strength was large and sufficient in terms of reliability. there were.

Among Examples 1 to 11 and Reference Examples 1 and 2 shown in Table 1, the surface resistivity of Reference Example 2 in which calendaring was performed after development and further calendaring was performed after fixing was 0.08 (Ohm) / Sq) shows the lowest value.

  Therefore, the relationship between the linear pressure and the surface resistivity in the calendering after development and the calendering after fixing was examined. The result is shown in FIG.

  The sample is the same as the above-described sample Ba-2 (see Example 3), and after exposure and development as described above, the sample is washed with pure water for 1 minute, and further dried at 40 ° C. Processed. Next, a calendar process after development is performed, and then a fixing process is performed using a fixing solution (trade name: N3X-R for CN16X: manufactured by Fuji Photo Film Co., Ltd.), followed by washing with pure water for 2 minutes, Furthermore, the drying process was performed and the calendar process after fixing was performed.

  There are two types of calendar rolls used for calendering. One is a first calendar roll that is a combination of a metal roll with an embossed surface and a metal roll with a mirror finish. The other is a mirror surface with a mirror finish. It is the 2nd calendar roll by the combination of the processed metal roll and resin rolls.

  The change in surface resistivity during calendar processing (after development and after fixing) with a different linear pressure on the first calendar roll is shown by a rhombus plot, and the calendar processing (after development and after changing the linear pressure on the second calendar roll) The change in surface resistivity when fixing) is shown as a square plot.

  From FIG. 1, when calendering is performed after development and after fixing, it hardly depends on the type of calender roll, and if the linear pressure is 200 (kgf / cm) or more, it is 1.8 (ohm / sq) or less. It was found that the surface resistivity can be obtained. Further, since the surface resistivity slightly increases after the linear pressure is 700 (kgf / cm), it is understood that the upper limit is preferably 700 (kgf / cm) or less.

  Next, the effect of suppressing the occurrence of black spots was observed depending on the presence or absence of carrageenan in the coated sample and the presence or absence of a protective layer.

  First, a coated sample C was prepared in the same manner except that the compound (Cpd-7) was not added to the coated sample B.

To the coated sample B or C, 0.09 g / m ^{2 of} carrageenan, which is a water-soluble binder, was added to Ag. And this polyethylene terephthalate (PET) Ag4.0g / m ² is applied onto a substrate so as to gelatin 0.14 g / m ^2, then dried. PET that had been previously hydrophilized was used.
Further, the Ag amount difference, 0.19 g / m ² is added to Ag carrageenan and applying this Ag10.5g / m ² on a PET support, so as to gelatin 0.33 g / m ^2, Then it was dried. All of the obtained coated samples had an Ag / gelatin volume ratio of the emulsion layer of 4/1.

(Protective layer)
A part of the sample was provided with a protective layer 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 film thickness after drying was 0.15 μm.

A sample having an Ag amount of 10.5 g / m ² was prepared using the coated sample C. A calender load of 3920 N / cm (400 kg / cm) was applied to the sample.
As shown in Table 2 below, Sample A1 was a sample containing only an emulsion, and Sample B1 was obtained by adding 0.19 g / m ² of kappa carrageenan to Ag relative to Ag. Samples C1 to E1 are samples in which a protective layer is provided on the emulsion layer. Among them, Sample C1 uses a protective layer gelatin having an average molecular weight of about 190 × 10 ³ . Sample D1 has an average molecular weight of about 133 × 10 ³ , and sample E1 uses gelatin with an average molecular weight of about 21 × 10 ³ . Samples F1 to G1 are samples in which 0.19 g / m ² of kappa carrageenan is added to Ag in the emulsions of samples C1 to E1.

  As an evaluation, the samples A1 to H1 were observed with a microscope, and the number of black spots with a size of 1 μm or more in the opening of 300 μm square was measured. The smaller the black pot shape, the more effective the suppression.

  From samples A1 and B1, it can be seen that the number of black pots decreases when kappa carrageenan is added. In addition, it can be seen from Sample A1 and Samples C1 to E1 that a protective layer is also effectively suppressed. Moreover, it turned out that it is the best to add a kappa carrageenan and to provide a protective layer from the sample A1 and the samples F1-G1. It was also found that the increased molecular weight of the gelatin with increased protection is more effective.

  Next, the change in surface resistivity before and after the calendar treatment was observed. The results are shown in Table 3 below.

First, a sample having an Ag amount of 10.5 g / m ² was prepared using the coated sample C. For the protective layer, gelatin having an average molecular weight of about 21 × 10 ³ is used. In the emulsion layer, kappa carrageenan was added at 0.19 g / m ² to Ag.
Sample A2 is a sample that is not subjected to calendar processing, and sample B2 is a sample that is subjected to calendar processing at 1960 N / cm (200 kg / cm). Sample C2 was subjected to 2940 N / cm (300 kg / cm). Sample D2 was subjected to 3920 N / cm (400 kg / cm). Sample E2 was subjected to 5880 N / cm (600 kg / cm).

  From Table 3, it was found that when kappa carrageenan was added and a protective layer was provided, as in Example 1, the conductivity was effective when the calendar load was 200 kg / cm or more.

Next, the change in the surface resistivity before and after the calendar treatment was observed by changing the Ag / binder volume ratio. The results are shown in Table 4 below.
First, gelatin was added to the coated sample C, and samples A3 to G3 having an Ag amount of 10.0 g / m ² with an emulsion in which the Ag / binder volume ratio was changed from 4.0 / 1 to 1.0 / 1 were prepared. Each sample A3 to G3 was calendered with a calendar load of 3920 N / cm (400 kg / cm). As the protective layer, gelatin having an average molecular weight of about 21 × 10 ³ is used. In the emulsion layer, kappa carrageenan was added at 0.19 g / m ² to Ag.

  From Table 4, it can be seen that even when the Ag / binder volume ratio is changed from 4/1 to 1.0 / 1, the resistance decreases even when a protective layer is provided or carrageenan is added in the same manner as in Example 1. .

Incidentally, engagement Ru conductive film and its manufacturing method of the present invention is not limited to the above embodiments without departing from the gist of the present invention, it is should be understood that various configurations.

It is a characteristic view which shows the change of the surface resistivity with respect to the linear pressure of a calendar process.

Claims (5)

A silver halide photosensitive material for obtaining a conductive metal film by subjecting a silver salt emulsion layer provided on a support to exposure and development, wherein the silver salt emulsion layer is a natural polymer derived from red algae. A silver halide containing a saccharide, further having a protective layer containing a natural polymeric polysaccharide derived from gelatin or red algae on the silver salt emulsion layer, wherein the protective layer has a thickness of 0.5 μm or less. In the method for producing a conductive film having a metallic silver forming step of exposing and developing a photosensitive material to form a conductive metallic silver portion on the support,
Having a smoothing process for smoothing the metallic silver part,
The method for producing a conductive film, wherein the smoothing treatment is performed at a linear pressure of 2940 N / cm (300 kgf / cm) or more. In the manufacturing method of the electrically conductive film of Claim 1,
The method for producing a conductive film, wherein the natural polymer polysaccharide derived from red algae is at least one selected from kappa carrageenan, iota carrageenan, lambda carrageenan, and far celerane. In the manufacturing method of the electrically conductive film of Claim 1 ,
An electroconductive metal silver portion and a light transmissive portion are formed by the development treatment, and a method for producing a conductive film. In the manufacturing method of the electrically conductive film of any one of Claims 1-3 ,
The method for producing a conductive film, wherein the smoothing treatment is performed at a linear pressure of 6860 N / cm (700 kgf / cm) or less. The electrically conductive film manufactured by the manufacturing method of the electrically conductive film of any one of Claims 1-4 .

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