JP5144092B2 - Manufacturing method of conductive material - Google Patents

Description

  The present invention relates to a method for producing a conductive material that can be used for applications such as an electronic circuit, an antenna circuit, an electromagnetic wave shielding material, and a touch panel.

  In recent years, with the rapid development of the information-oriented society, technologies related to information-related devices have rapidly advanced and become popular. Among them, the display device is used for televisions, personal computers, guidance displays for stations, airports, and other information. In particular, plasma displays have attracted attention in recent years.

  In such an information society, there is a concern about the influence of electromagnetic waves radiated from these display devices. For example, the influence on surrounding electronic devices and the influence on the human body are considered. In particular, the impact on the health of the human body is not negligible, and it is required to reduce the intensity of the electromagnetic field applied to the human body, and various conductive materials have been developed in response to such a demand. ing. For example, it is disclosed in JP-A Nos. 11-125024, 2000-329934, 2001-38843, 2001-47549, 2001-57110, 2001-60416, and the like. .

  An electromagnetic shielding material is well known as a conductive material for reducing the intensity of the electromagnetic field irradiated to the human body. Known electromagnetic shielding materials can be broadly classified into two types: an electromagnetic shielding material using a conductive film using ITO or the like, and an electromagnetic shielding material using a conductive metal mesh. Among these, the electromagnetic shielding material made of a conductive film is superior in transparency to the electromagnetic shielding material made of metal mesh, but has a large surface resistivity and inferior electromagnetic wave shielding performance. For this reason, the electromagnetic shielding material by a metal mesh is preferable in the use which shields the electromagnetic waves from the apparatus which generate | occur | produces strong electromagnetic waves, such as PDP (plasma display panel), for example.

  In recent years, a method using a silver salt photographic light-sensitive material containing a silver halide emulsion layer as a conductive material precursor has been proposed as an electromagnetic wave shielding material using a metal mesh. For example, in WO 01/51276 pamphlet (Patent Document 1) and JP-A-2004-221564 (Patent Document 2), a silver salt photographic light-sensitive material is subjected to image exposure and development treatment, and then subjected to metal plating treatment to conduct electricity. Proposals have been made for methods for producing functional materials. Similarly, a method using a silver salt diffusion transfer method has been proposed as a method of using a silver salt photographic light-sensitive material, for example, JP-A-2003-77350 (Patent Document 3).

  In the conductive material using these various silver salt photographic light-sensitive materials as the conductive material precursor, metal plating is performed when higher conductivity is required. However, particularly when trying to perform electrolytic metal plating on a fine metal pattern, the resistance of the pattern is too high for electrolytic plating in the fine pattern, and only the power feeding portion may be plated. Therefore, there has been a demand for a conductive material using a silver salt photographic light-sensitive material capable of obtaining high conductivity even with a fine metal pattern and a method for producing the same so that the electrolytic metal plating process is made uniform.

Furthermore, conductive materials that use various silver halide photographic materials as the conductive material precursor may change in conductivity due to fatigue of the developer or washing solution during development, or change in conductivity during storage. was there. As an example in which this is a problem, there is a 1 / 4λ type electromagnetic wave absorber. The 1 / 4λ type wave absorber has a structure in which a transparent resistive film equal to 377Ω which is a characteristic impedance of free space is installed at a position separated by ¼ of the wavelength λ of the radio wave absorbed from the radio wave reflector. . A conductive material using silver salt photographic light-sensitive material as a conductive material precursor can make a highly transparent resistor, but the resistance shifts due to the problem of the conductivity variation, and the performance of the radio wave absorber varies. Resulting in. As can be seen from this example, there has been a demand for a conductive material that not only has sufficiently high conductivity but also has high production stability and storage stability and a method for manufacturing the same.
WO 01/51276 pamphlet (1 page) JP 2004-221564 A (pages 1 to 5) JP 2003-77350 A (pages 1 to 5)

  Accordingly, an object of the present invention is to provide a method for producing a conductive material which is excellent in conductivity and has high production stability and storage stability.

After forming a silver image on at least one surface of the support by a photographic method, the silver image is subjected to an ultraviolet irradiation treatment as a treatment for decomposing the water-soluble polymer binder contained in the constituent layer of the photosensitive material. It was achieved by a method for producing a conductive material, which is treated with a treatment liquid containing at least one compound according to any one of (I) to (III).
(I) Reducing substances (II) Water-soluble phosphorus oxoacid compounds (III) Water-soluble halides

  According to the method for producing a conductive material of the present invention, it is possible to provide a method for producing a conductive material having excellent conductivity and high production stability and storage stability.

As a result of various studies focusing on the above problems, the present inventors have formed a silver image on at least one surface of the support by a photographic method, and then formed the silver image on the constituent layer of the photosensitive material. By performing a treatment for decomposing the water-soluble polymer binder contained, and then treating with a treatment liquid containing at least one compound described in any of the following (I) to (III), excellent conductivity, In addition, the inventors have found a method capable of producing a conductive material having high production stability and storage stability.
(I) Reducing substances (II) Water-soluble phosphorus oxoacid compounds (III) Water-soluble halides

In the silver image used in the present invention, the treatment for decomposing the water-soluble polymer binder contained in the constituent layer of the photosensitive material is an ultraviolet irradiation treatment, and the light source used in the ultraviolet irradiation treatment is a short wavelength end (400 nm) of visible light. What is necessary is just to be able to irradiate light of a shorter wavelength. Generally, mercury lamps such as low-pressure mercury lamps and high-pressure mercury lamps, ultraviolet lasers such as helium-cadmium lasers and excimer lasers, barrier discharge lamps, microwave electrodeless discharge lamps and the like. Are known. In the present invention, any of the above-mentioned light sources may be used. In particular, a high-pressure mercury lamp and an ultraviolet laser are preferable because the light intensity is high and an effect can be obtained with a short irradiation.

The irradiation amount of ultraviolet rays used in the present invention is preferably at least 50 mJ / cm ² or more, and if it is less than 50 mJ / cm ² , sufficient effects may not be obtained. If the amount of irradiation is too large, heat will be generated depending on the type of light source, the support will be deformed, the power cost will be high, the irradiation time will be too long, and the productivity will decrease, so the upper limit will be 10,000 mJ / cm ^{About 2} is preferable. The irradiation amount of ultraviolet rays can be measured with a commercially available integrated illuminometer, and can be easily measured using, for example, an eye ultraviolet integrated illuminometer UVPF-A1 (trade name of an integrated illuminometer manufactured by Iwasaki Electric Co., Ltd.). .

  Moreover, after irradiating with ultraviolet rays, when performing the treatment with a treatment liquid containing at least one compound described in any of (I) to (III) above, treatment such as degreasing treatment and washing treatment prior to the treatment May be applied. In this case, since the decomposed product of the decomposed water-soluble polymer is not mixed in the treatment liquid containing at least one compound described in any of (I) to (III) above, there is an adverse effect on the life of the treatment liquid. This is preferable because it can be reduced.

  Next, a processing method subsequently applied after the processing for decomposing the water-soluble polymer binder contained in the constituent layer of the light-sensitive material of the present invention will be described. The treatment liquid used here contains at least one compound described in any of (I) a reducing substance, (II) a water-soluble phosphorus oxoacid compound, and (III) a water-soluble halide. As the reducing substance described in the above (I) of the present invention, a developing agent known in the field of photographic development can be used. These are described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) or described in cited documents. Specifically, hydroquinone, potassium hydroquinone monosulfonate, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone and other polyhydroxybenzenes, ascorbic acid and its derivatives, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1 -3-Pyrazolidones such as phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, aminophenols such as paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylene Examples include polyaminobenzenes such as diamine, hydroxylamines, and the like. Among these, ascorbic acid having high water solubility and low toxicity is preferable. These reducing substances are preferably used as an aqueous solution of at least 1% by mass or more, preferably 5 to 30% by mass. Further, when the photosensitive material is processed using a processing solution containing a reducing substance, fogging may occur when the photosensitive material is processed with a reducible silver salt remaining. Therefore, in the case of using a processing solution containing a reducing substance, among the following three photographic methods for forming a silver image using a photosensitive material, (1) development processing according to the silver salt diffusion transfer method, or (3) When a development process according to the curable development method is used, it is preferably performed after the water washing removal process, and when the development process method (2) a development process method for fixing after direct development is used, it is particularly preferably performed after fixing. .

  In the present invention, the water-soluble phosphorus oxoacid compound includes phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid and the like, and salts thereof. is there. Any water-soluble phosphorus oxo acid compound can be used as long as the solubility in water at 25 ° C. is at least 0.1% by mass or more. Specific examples of these water-soluble phosphorus oxoacid compounds include phosphates such as monosodium phosphate, monopotassium phosphate and disodium phosphate, hypophosphites such as sodium hypophosphite, and disodium dihydrogen pyrophosphate. Various known water-soluble phosphorus oxoacid compounds such as pyrophosphates, tripolyphosphates, hexametaphosphates, etc., and water-soluble phosphorus oxoacid compounds such as various phosphate esters such as polyoxyethylene alkyl ether phosphates, alkyl phosphates, etc. These esters can be used. Of these, inorganic water-soluble phosphorus oxoacid compounds and phosphates are preferred. These water-soluble phosphorus oxoacid compounds are preferably used as an aqueous solution of at least 5% by mass, preferably 10 to 30% by mass.

  In the present invention, the halogen used as the water-soluble halogen compound may be any of fluorine, chlorine, bromine and iodine, and is a compound having a solubility in water at 25 ° C. of at least 0.1% by mass or more in the aqueous solution. Any compound can be used as long as it can release. Examples of such water-soluble halogen compounds include hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid and other hydrochloric acids, sodium chloride, ammonium chloride, chlorides such as rubidium chloride, sodium bromide, potassium bromide, Various inorganic halides such as bromides such as lithium bromide, iodides such as sodium iodide, fluorides such as sodium fluoride and potassium fluoride, amine salts such as dimethylamine hydrochloride and trimethylamine bromide, and benzil chloride Examples thereof include luconium, alkylpyridinium hydrochloride, imidazolinium hydrochloride, polyallylamine hydrochloride and diallyldimethylammonium chloride polymer. Among these, compounds capable of releasing chloride ions in an aqueous solution are preferable, and water-soluble inorganic chlorides such as sodium chloride and potassium chloride are particularly preferable. These water-soluble halogen compounds are preferably used as an aqueous solution of at least 1% by mass or more, preferably 5 to 30% by mass.

  A reducing substance, a water-soluble phosphorus oxoacid compound, and a water-soluble halogen compound as a component of a treatment solution containing at least one compound according to any one of (I) to (III) used in the present invention are used alone. Alternatively, for example, a reducing substance and another reducing substance may be used in combination with a plurality of components of the same type, or different kinds of ingredients such as a reducing substance and a water-soluble halogen compound may be mixed. You may use it. Of these, it is most preferable to use a water-soluble halogen compound having high processing efficiency and high storage stability and processing stability of the processing solution. Although it is preferable that the temperature of the treatment using the treatment liquid containing at least one compound described in any one of (I) to (III) is higher than Tg of the substance used as the support for the conductive material, If it is not used, the conductive material will be stretched or cut during the treatment, so the treatment is performed at a temperature of Tg or less. The treatment temperature is preferably 30 ° C. or higher when using a water-soluble halogen compound, 40 ° C. or higher when using other materials, more preferably 50 to 80 ° C., and even more preferably 60 to 80 ° C. To do. The treatment time depends on the components of the treatment liquid, but is 10 seconds or longer, preferably 30 seconds to 3 minutes. As a treatment method, a method of dipping treatment, a method of applying a treatment liquid in a shower, a method of applying, etc. are possible, but a method of dipping treatment in which temperature stability and crystallization of the components of the treatment liquid hardly occur is used. Is preferred. Moreover, it is preferable to take a treatment to prevent crystallization of components of the treatment liquid on the surface of the conductive material after the treatment.

  The treatment solution containing at least one compound according to any one of (I) to (III) of the present invention has a pH of 10 or less, preferably 4 to 9. In particular, when a reducing substance is used as a component of the treatment liquid, if the pH is high, the reducing substance in the treatment liquid is likely to be oxidized, and the storage stability of the treatment liquid is deteriorated. The pH is preferably 8 or less. In order to adjust to a preferred pH, a known pH buffering agent can be used for the treatment liquid. The processing liquid containing at least one compound according to any one of (I) to (III) used in the present invention contains a known surfactant, antifoaming agent, preservative, etc. in addition to them. You can also.

Next, a method for forming a silver image using the photographic method according to the present invention will be described. As such a method, there is a method shown in the following (a), (b) or (c).
(A) A method in which a light-sensitive material having at least a silver halide emulsion layer on a support is exposed, developed, and then fixed.
(B) A photosensitive material having at least a physical development nucleus layer and a silver halide emulsion layer on the support is exposed and subjected to development processing according to a silver salt diffusion transfer method, and then at least a silver halide emulsion layer which is no longer necessary is provided. How to wash with water.
(C) A light-sensitive material having at least a silver halide emulsion layer on the support is exposed to light and subjected to a development treatment according to a hardening development method, and then at least the uncured silver halide emulsion layer which has become unnecessary is washed away with water. Method.

  In the present invention, the light-sensitive material is image-formed by any one of the photographic methods (a) to (c) after exposure. The method (a) is, for example, the method described in JP-A-2004-221564, the method (b) is, for example, the method described in JP-B-42-23745, and the method (c). For example, J. et al. Photo. Sci. Magazine No. 11 p 1, A. G. By Tull (1963) or “The Theory of the Photographic Process (4th edition, p326-327)”, T. H. As described in James et al., A relief image is formed on a support according to a curing development method. The curing development method is to treat an uncured silver halide emulsion layer substantially free of a hardener prepared on a substrate with a developer containing a developing agent such as a polyhydroxybenzene, This is a method in which when the exposed silver halide is reduced by the developing agent, water-soluble polymers such as gelatin are cross-linked by an oxidized compound produced from the developing agent itself to form an image.

  A method for producing a silver image forming material used in the photographic production methods (a) to (c) of the present invention will be described. A method for producing a silver image forming material using the photographic process (a) is type A, a method for producing a silver image forming material using the photographic process (b) is type B, and a silver image forming material using the photographic process (c). These manufacturing methods are abbreviated as type C and will be described in order.

<Type A>
The type A silver image forming material of the present invention can be obtained by exposing a light-sensitive material having at least a silver halide emulsion layer on a support, subjecting it to development processing, and then fixing processing. Therefore, the photosensitive material is a support in which at least a silver halide emulsion layer is coated, and the support is preferably plastic, glass, rubber, ceramics or the like. In the case of producing a transparent conductive substrate, a material such as plastic or glass that has transparency in the visible region and has a total light transmittance of 60% or more is preferable. Among plastics, a resin film having flexibility is preferably used because it is easy to handle. Specific examples of the resin film used for the support of the present invention include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, Examples thereof include resin films having a thickness of 50 to 300 μm made of acetate resin, triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin and the like. Examples of the glass include conductive glass such as NESA glass and ITO glass, soda lime glass, non-alkali glass (Corning 7059 glass) and the like. When plastic is used as the support, an adhesive layer such as vinylidene chloride or polyurethane is preferably provided on the support. When glass is used as the support, a metal oxide layer such as colloidal silica or titanium oxide is used. It is preferable to heat-treat at 150-500 degreeC after that.

  The silver halide emulsion layer of the light-sensitive material used in the type A of the present invention is a silver halide photographic film, photographic paper, printing plate making film, emulsion mask for photomask, etc. relating to silver halide. It can also be used as it is.

  The halide contained in the silver halide may be any of chloride, bromide, iodide and fluoride, or a combination thereof. For the formation of silver halide emulsion grains, methods well known in the art such as forward mixing, reverse mixing, and simultaneous mixing are used. In particular, it is preferable to use a so-called controlled double jet method in which a pAg in a liquid phase in which grains are formed is kept constant, which is one of the simultaneous mixing methods, from the viewpoint of obtaining silver halide emulsion grains having a uniform grain size. In the present invention, the average grain size of preferable silver halide emulsion grains is 0.25 μm or less, particularly preferably 0.05 to 0.2 μm.

  The shape of the silver halide grains is not particularly limited. For example, the shape can be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagon flat plate shape, a triangular flat plate shape, a quadrangular flat plate shape, etc.), an octahedron shape, and a tetrahedron shape. Can be.

  In the production of silver halide emulsions, group VIII such as sulfite, lead salt, thallium salt, rhodium salt or complex thereof, iridium salt or complex thereof, in the process of silver halide grain formation or physical ripening, if necessary A metal element salt or a complex salt thereof may coexist. Further, it can be sensitized by various chemical sensitizers, and methods commonly used in the art such as sulfur sensitization method, selenium sensitization method and noble metal sensitization method can be used alone or in combination.

  The silver halide emulsion can be spectrally sensitized as necessary. Further, the silver halide emulsion does not necessarily have to be negative photosensitive, and may be a direct reversal emulsion having positive sensitivity if necessary. Thereby, a negative type can be converted into a positive type, and a positive type can be converted into a negative type. Direct inversion emulsions can be prepared by the methods described in JP-A-8-17120 and JP-A-8-202041.

The amount of coated silver in the silver halide emulsion layer of the light-sensitive material used in Type A of the present invention is at least 0.01 g (in terms of silver nitrate) / m ² in order to form a silver image. Moreover, when using a silver image for the fine wiring part excellent in electroconductivity, 2.0-4.0 g (silver nitrate conversion) / m < ² > is preferable. If the amount of coated silver is too large, there is a problem that a long development time is required or the photosensitivity of the silver halide emulsion grains on the side close to the support is lowered, so 5.0 g (in terms of silver nitrate) / M ² should be the upper limit.

  The silver halide emulsion layer of the light-sensitive material used in Type A of the present invention contains a water-soluble polymer as a binder. Preferred binders include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, poly Examples include hyaluronic acid and carboxycellulose. Moreover, it is preferable to use a water-soluble polymer crosslinking agent as required.

  Examples of water-soluble polymer crosslinking agents include inorganic compounds such as chromium alum, aldehydes such as formalin, glyoxal, malealdehyde and glutaraldehyde, N-methylol compounds such as urea and ethyleneurea, mucochloric acid, 2 Aldehyde equivalents such as 1,3-dihydroxy-1,4-dioxane, active halogens such as 2,4-dichloro-6-hydroxy-s-triazine salts and 2,4-dihydroxy-6-chloro-triazine salts Compounds, divinyl sulfones, divinyl ketones, N, N, N-triacroyl hexahydrotriazines, compounds having two or more active three-membered ethyleneimino groups or epoxy groups in the molecule, polymer hardeners One or more of various compounds such as dialdehyde starch can be used. The amount of the crosslinking agent is preferably 0.1 to 30% by mass, particularly preferably 1 to 20% by mass, based on the water-soluble polymer contained in the silver halide emulsion layer.

  In the silver halide emulsion layer, a hydrophobic polymer may be used in combination with the water-soluble polymer as a binder. Generally, these hydrophobic polymers are used as aqueous dispersions, and known ones such as homopolymers and copolymers of various monomers can be used. Homopolymers include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene. Copolymers include ethylene / butadiene copolymers, styrene / butadiene copolymers, Styrene / p-methoxystyrene copolymer, styrene / vinyl acetate copolymer, vinyl acetate / vinyl chloride copolymer, vinyl acetate / diethyl maleate copolymer, methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene copolymer Polymer, methyl methacrylate / styrene copolymer, methyl methacrylate / vinyl acetate copolymer, methyl methacrylate / vinylidene chloride copolymer, methyl acrylate / acrylonitrile copolymer, methyl acrylate / butadiene copolymer Methyl acrylate-styrene copolymer, methyl acrylate-vinyl acetate copolymer, an acrylic acid-butyl acrylate copolymer, methyl acrylate-vinyl chloride copolymer, and butyl acrylate-styrene copolymer.

  With regard to the total amount of water-soluble polymer and hydrophobic polymer contained in the silver halide emulsion layer, that is, the total amount of binder, if the amount of the binder is small, the coating property is adversely affected, and stable silver halide grains can also be obtained. Disappear. On the other hand, if the amount is too large, a decrease in conductivity is observed. A preferred binder amount is such that the mass ratio of silver halide (in terms of silver nitrate) and binder (silver nitrate / total binder) is 2.0 or more, more preferably 2.4 to 5.5.

  In the silver halide emulsion layer, known photographic additives can be used for various purposes. These are described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) or cited.

  The photosensitive material used in the type A of the present invention can be provided with a non-photosensitive layer such as a backing layer, an over layer, and an adhesive layer as necessary. The backing layer is provided on the opposite side of the support from the silver halide emulsion layer, and is provided for the purpose of adjusting curl. The over layer is provided on the silver halide emulsion layer for the purpose of preventing scratches. The adhesive layer is provided for the purpose of improving the adhesiveness between the support and the silver image. Therefore, it is preferably provided between the support and the silver halide emulsion layer.

These non-photosensitive layers are layers having a water-soluble polymer as a main binder. Here, “mainly” means that 50% by mass or more of the total solid content of the non-photosensitive layer is a water-soluble polymer. Further, the water-soluble polymer referred to here can be selected as long as it easily swells with a developer and easily penetrates the developer. Specifically, gelatin, albumin, casein, polyvinyl alcohol, or the like can be used. Particularly preferred water-soluble polymers are proteins such as gelatin, albumin and casein. The amount of binder in the non-photosensitive layer, varies by each application, a range of 0.001 to 10 g / m ² is preferred. However, when an overlayer is provided on the photosensitive material used in Type A of the present invention, silver is difficult to be exposed on the surface, so it is preferable that the layer be as thin as possible. The preferred amount is 0.1 g / m ² or less, and more preferably 0. 0.05 g / m ² or less.

  These non-photosensitive layers may be added to known photographic additives as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989), if necessary. An agent can be contained, and the film can be hardened with the aforementioned water-soluble polymer crosslinking agent.

  In addition, each layer constituting the photosensitive material can be applied by a coating method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, etc. Various coating aids such as surfactants and thickeners can be used in accordance with the method.

In the light-sensitive material used in the type A of the present invention, a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion in the above-described constituent layer is added to the halation or irradiation prevention agent for improving the image quality. It is preferable to use as. The antihalation agent is preferably used in a backing layer or a layer provided between a silver halide emulsion layer such as an adhesive layer and a support, and may be used separately in these two or more layers. The irradiation inhibitor is preferably used in a silver halide emulsion layer. The addition amount of these non-sensitizing dyes or pigments can vary over a wide range as long as the desired effect can be obtained, but a range of 0.01 to 1 g / m ² is preferable.

  The photosensitive material used in Type A of the present invention may contain a developing agent in the constituent layers. Specific examples of the developing agent include hydroquinone, ascorbic acid, p-aminophenol, p-phenylenediamine, phenidone and the like.

  Next, a method for forming a silver image of type A will be described. In order to form a silver image, the photosensitive material needs to be exposed and developed. As an exposure method, scanning exposure is performed using a method in which a transparent original and a silver halide emulsion layer are in close contact with each other, or various laser beams, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm. There are ways to do this.

  In the development processing of type A of the present invention, when the negative type silver halide emulsion is used as the photosensitive material, a development processing step of reducing the silver halide in the portion irradiated with light by exposure, and light irradiation There is a fixing processing step for dissolving and removing the unexposed portion of the silver halide. On the other hand, when a positive-type silver halide emulsion is used as the photosensitive material, a development process that reduces the portion of the silver halide that has not been irradiated with light by light exposure and the portion of the silver halide that has been irradiated with light are dissolved. There is a fixing process for removal. In addition, regardless of whether negative or positive silver halide emulsions are used, development is stopped using an acidic aqueous solution containing, for example, acetic acid, citric acid, etc. between the development processing step and the fixing processing step. You may perform the water-washing process for removing the unnecessary salt produced | generated by the process, the image development process, or the fixing process.

  In the type A development processing of the present invention, the developer used in the development processing comprises a developing agent, a preservative, an alkali agent, an antifoggant and the like as a basic composition. Specific examples of the developing agent include hydroquinone, ascorbic acid, p-aminophenol, p-phenylenediamine, phenidone and the like. Some of these may be contained in the photosensitive material. Examples of preservatives include sulfite ions. The alkaline agent is necessary for exhibiting the reducing ability of the developing agent, and is added so that the pH of the developer is 9 or more, preferably 10 or more. In addition, a buffering agent such as carbonate or phosphate is also used in order to keep the basicity stably. Furthermore, examples of the antifoggant added so that silver halide grains having no development nucleus are not reduced include bromide ions, benzimidazole, benzotriazole, 1-phenyl-5-mercaptotetrazole and the like.

  Further, the type A developer of the present invention preferably contains a soluble silver complex salt forming agent. Specific examples of soluble silver complex forming agents include thiosulfates such as ammonium thiosulfate and sodium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and sulfites such as sodium sulfite and potassium hydrogen sulfite. Thioethers such as 1,10-dithia-18-crown-6,2,2'-thiodiethanol, oxazolidones, 2-mercaptobenzoic acid and its derivatives, cyclic imides such as uracil, alkanolamines, diamines, JP-A-9-171257 discloses mesoionic compounds, 5,5-dialkylhydantoins, alkylsulfones, and other “The Theory of the Photographic Process (4th edition, p474-475”, T.H. Compounds that are described in James al.

  Of these soluble silver complex salt forming agents, alkanolamines are particularly preferred. Examples of the alkanolamine include N- (2-aminoethyl) ethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N- Examples include dimethylethanolamine, 3-aminopropanol, and 2-amino-2-methyl-1-propanol.

  These soluble silver complex salt forming agents can be used alone or in combination. The amount of the soluble silver complex salt forming agent is 0.1 to 40 g / L, preferably 1 to 20 g / L. The development processing temperature is usually selected between 15 ° C and 45 ° C, more preferably 25 ° C to 40 ° C. The development time is preferably 120 seconds or less in consideration of production efficiency.

The developing solution supply system for developing may be an immersion system or a coating system. In the dipping method, for example, the exposed photosensitive material is conveyed while being immersed in a large amount of developer stored in a tank, and in the coating method, for example, the developer is applied on the silver halide emulsion layer. About 40 to 120 ml is applied per 1 m ² .

  The fixing process is performed for the purpose of removing and stabilizing the silver salt in the undeveloped part. The fixing process can be performed by using a fixing process technique used in known silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, etc. And a fixing solution described in p321.

  Among them, a fixing solution containing a desilvering agent other than thiosulfate is preferable. In this case, as a desilvering agent, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sulfites such as sodium sulfite and potassium bisulfite, 1,10-dithia-18-crown-6, 2,2 ′ -Thioethers such as thiodiethanol, oxazolidones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, 5,5 -Dialkylhydantoins, alkylsulfones, and other compounds described in "The Theory of the Photographic Process (4th edition, p474-475)", TH James.

  Among these desilvering agents, alkanolamine is particularly preferable. As the alkanolamine, the same compounds as those used as the soluble silver complex forming agent described in the developer can be used. Further, thiocyanate has a high desilvering ability, but it is not preferable to use it from the viewpoint of safety to the human body.

  These desilvering agents can be used alone or in combination. Further, the amount of desilvering agent is preferably 1 to 500 g / L, more preferably 10 to 300 g / L in total of the desilvering agent.

  In addition to the desilvering agent, the fixing solution may contain sulfite or bisulfite as a preservative, and acetic acid, borate amine, phosphate, or the like as a pH buffer. In addition, water-soluble aluminum (eg, aluminum sulfate, aluminum chloride, potassium alum) as a hardener, dibasic acid (eg, tartaric acid, potassium tartrate, sodium tartrate, etc.) or tribasic acid (cien Acid sodium, lithium citrate, potassium citrate and the like). The preferred pH of the fixing solution varies depending on the type of desilvering agent, and is 8 or more, preferably 9 or more, particularly when an amine is used. The fixing processing temperature is usually selected between 10 ° C. and 45 ° C., more preferably 18 ° C. to 30 ° C.

<Type B>
The silver image-forming material in Type B of the present invention is unnecessary after exposing a photosensitive material having at least a physical development nucleus layer and a silver halide emulsion layer on a support and performing development processing according to a silver salt diffusion transfer method. The obtained silver halide emulsion layer can be obtained by washing at least with water. Therefore, as the light-sensitive material, a material in which at least a physical development nucleus layer and a silver halide emulsion layer are coated in this order on a support is used. As the support of the photosensitive material used in the type B of the present invention, materials and performance materials used in the type A photosensitive material described above can be used.

The physical development nucleus layer of the photosensitive material used in Type B of the present invention contains at least a physical development nucleus. As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include colloids such as gold and silver, metal fluids obtained by mixing water-soluble salts such as palladium and zinc, and sulfides. The fine particle layer of these physical development nuclei can be provided on the support by a coating method or an immersion treatment method. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg / m ² in terms of solid content.

  The physical development nucleus layer of the photosensitive material used for Type B of the present invention preferably contains a water-soluble polymer. The addition amount of the water-soluble polymer is preferably about 10 to 500% by mass with respect to the physical development nucleus. As the water-soluble polymer, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like can be used. Preferred water-soluble polymers are proteins such as gelatin, albumin and casein.

  Furthermore, it is preferable that the physical development nucleus layer of the light-sensitive material used in Type B of the present invention contains a water-soluble polymer crosslinking agent (hardener). The cross-linking agent for the water-soluble polymer has the same meaning as the cross-linking agent used in the above-described type A photosensitive material, but preferably glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, adipaldehyde, etc. Dialdehydes and a more preferred crosslinking agent is glutaraldehyde. The crosslinking agent preferably contains 0.1 to 30% by mass of the water-soluble polymer contained in the physical development nucleus layer, and more preferably 1 to 20% by mass.

  The physical development nucleus layer can be applied by an application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating and the like.

As the silver halide emulsion used for the type B photosensitive material of the present invention, the same silver halide emulsion as that of the type A photosensitive material described above is used. The silver halide emulsion of the photosensitive material used for the type B of the present invention is used. There is a preferable range for the halide composition, and it is preferable that 80 mol% or more of chloride is contained, and it is particularly preferable that 90 mol% or more is chloride. Further, the silver halide emulsion can be spectrally sensitized as necessary, as in the case of Type A described above. Further, the silver halide emulsion does not necessarily have to be negative photosensitive, and may be a direct reversal emulsion having positive sensitivity if necessary. As the silver coating amount of the silver halide emulsion layer, at least 0.01 g (in terms of silver nitrate) / m ² is necessary to form a silver image, as in the photosensitive material used for Type A described above. When used for a fine wiring portion having excellent conductivity, 2.0 to 4.0 g (in terms of silver nitrate) / m ² is preferable.

  The silver halide emulsion layer contains a water-soluble polymer as a binder in the same manner as the silver halide emulsion layer of the light-sensitive material used for type A described above. Preferred binders include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, poly Examples include hyaluronic acid and carboxycellulose. Further, as in the case of the silver halide emulsion layer of the light-sensitive material used for type A, a water-soluble polymer crosslinking agent may be used if necessary, but the light-sensitive material used for type B of the present invention is used in the development processing. In order to remove at least the silver halide emulsion layer which has become unnecessary after development by washing with water, when a water-soluble polymer crosslinking agent is used, it can be used within a range that does not hinder the removal by washing with water. As for the photographic additives, known photographic additives can be used for various purposes as in the case of the silver halide emulsion layer of the light-sensitive material used in Type A described above. Further, in the silver halide emulsion layer of the light-sensitive material used for type B of the present invention, various coating aids such as surfactants and thickeners are used in accordance with the coating method in the same manner as the light-sensitive material used for type A described above. The same method can be used for the coating method.

The photosensitive material used for type B of the present invention can be provided with a non-photosensitive layer such as a backing layer, an over layer, an adhesive layer, etc., if necessary, as in the photosensitive material used for type A described above. Since the adhesive layer is provided for the purpose of improving the adhesion between the support and the silver image, it is preferably provided between the support and the physical development nucleus layer. In the photosensitive material used for Type B of the present invention, the over layer has the effect of suppressing the silver in the photosensitive material from diffusing out of the system during the development process and increasing the efficiency of silver deposition on the physical development nuclei. Accordingly, the over layer is preferably provided on the silver halide emulsion layer. These non-photosensitive layers are layers mainly composed of a water-soluble polymer, and water-soluble polymers used for the non-photosensitive layer similar to the photosensitive material used for type A described above can be used. Although the water-soluble high molecular weight of a non-photosensitive layer changes with each use, the range of 0.001-10 g / m < ² > is preferable. In addition, a water-soluble polymer crosslinking agent can be used for these non-photosensitive layers. However, in the development processing of type B of the present invention, a non-photosensitive silver halide emulsion layer is removed at least by washing with water. When a water-soluble polymer crosslinking agent is used in the photosensitive layer, it can be used within a range that does not hinder the washing and removal of the silver halide emulsion layer after development.

In the case of the photosensitive material used for Type B of the present invention, it is preferable to further provide a water washing removal promoting layer as the non-photosensitive layer. In this case, the water washing removal promoting layer is provided for the purpose of facilitating removal of unnecessary silver halide emulsion layers, and therefore it is preferably provided between the physical development nucleus layer and the silver halide emulsion layer. The water washing removal promoting layer uses a water-soluble polymer as a binder. Preferred binders include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polysaccharides such as starch, cellulose and its derivatives, polyethylene oxide, Polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxycellulose and the like can be mentioned. Further, it is not preferable to use a water-soluble polymer crosslinking agent for the water washing removal promoting layer. The coating amount of the water-soluble polymer is preferably 1.0 g / m ² or less. If the amount of water-soluble polymer applied is too large, the distance between the physical development nucleus layer and the silver halide emulsion layer will increase, so the amount of silver deposited during image formation will decrease and the image quality will deteriorate. About 0.3 g / m ² is preferable.

In the photosensitive material used for type B of the present invention, as in the photosensitive material used for type A described above, a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion in the constituent layer is improved in image quality. It is preferable to use it as a halation or irradiation prevention agent. The antihalation agent is preferably used in the above-mentioned backing layer or a layer provided between a silver halide emulsion layer such as an adhesive layer, a physical development nucleus layer, and a water washing removal promoting layer and a support. You may divide and use for the above layer. The irradiation inhibitor is preferably used in a silver halide emulsion layer. The addition amount of these non-sensitizing dyes or pigments can vary over a wide range as long as the desired effect is obtained, but a range of about 0.01 to about 1 g / m ² is preferable. The photosensitive material used for Type B of the present invention can contain known photographic additives, surfactants, matting agents, lubricants and the like, if necessary, as in Type A described above.

  Also in the photosensitive material used for Type B of the present invention, a developing agent may be contained in the constituent layers as in the photosensitive material used for Type A described above. As the developing agent, a developing agent known in the field of photographic development can be used. For example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, 1-phenyl-4,4-dimethyl- 3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone , 3-pyrazolidones such as 1-p-chlorophenyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine and the like, and two or more of these can be used in combination. .

  Next, a method for forming a silver image in Type B of the present invention will be described. In order to form a silver image of type B of the present invention, the photosensitive material must be exposed and developed. As an exposure method, a method similar to the above-described type A can be used.

  In the development processing of type B of the present invention, the silver halide in the image forming portion is dissolved, diffused, reduced on the physical development nuclei, and deposited, and the silver halide that has become unnecessary There is a water removal step for removing the layer with water. In this case, when a negative type silver halide emulsion is used as the light-sensitive material, the portion not exposed to light by exposure becomes a portion for forming an image, and when a positive type silver halide emulsion is used, the exposure is performed. Thus, the portion irradiated with light becomes a portion for forming an image. In addition, regardless of whether negative or positive silver halide emulsions are used, development is stopped using an acidic aqueous solution containing, for example, acetic acid, citric acid, etc. between the development processing step and the water washing removal step. Processing may be performed.

  The developer used in the type B development processing of the present invention is an alkaline solution containing a soluble silver complex salt forming agent and a reducing agent. The soluble silver complex forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a developing agent for reducing the soluble silver complex salt to deposit metallic silver on the physical development nucleus. is there.

  As the developing agent, a developing agent known in the field of photographic development can be used. For example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, 1-phenyl-4,4-dimethyl- 3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone , 3-pyrazolidones such as 1-p-chlorophenyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine and the like, and two or more of these can be used in combination. .

  In the type B developer of the present invention, as in the above type A, the developing agent may be contained in the constituent layer of the photosensitive material, in the developer, or in both. However, it is preferably contained in the developer. The content of the developing agent in the developer is suitably used in the range of 1 to 100 g / L. When contained in the constituent layer of the light-sensitive material, the developing agent may be contained in any layer of the light-sensitive material, and is particularly preferably contained in the silver halide emulsion layer. A preferable amount in this case is in the range of 0.005 to 0.5 g per 1 g of the water-soluble polymer. These developing agents may be dissolved in the coating solution or contained in each layer, or may be dissolved in an oil dispersion and contained in each layer.

  The alkaline agent contained in the developer used for Type B of the present invention can also be the same as that of Type A described above. The pH of the developer is preferably 10 or more, more preferably 11-14. Further, the developer used for Type B may contain a compound known in the field of photographic development, such as a development inhibitor for controlling the development rate, a preservative for a developing agent, etc., as in Type A described above. it can.

  The developer used for Type B of the present invention contains a soluble silver complex salt forming agent. As a soluble silver complex salt forming agent, it is synonymous with the soluble silver complex salt forming agent utilized for the above-mentioned type A developing solution. The amount of the soluble silver complex salt forming agent used is 0.1 to 40 g / L, preferably 1 to 20 g / L.

  The development processing temperature of type B of the present invention is preferably 15 ° C. to 30 ° C., and 20 ° C. to 25 ° C. in order to prevent the silver halide emulsion layer from eluting into the developer. A range is preferred. The development time is preferably 120 seconds or less in consideration of production efficiency. The developer supply method for performing type B development may be an immersion method or a coating method, as in the above-described type A.

  In the development processing of type B of the present invention, the developer is supplied by a method other than the so-called mono-sheet type method in which a silver halide emulsion layer is provided on a support provided with a physical development nucleus layer. There is a two-sheet type method in which a silver halide emulsion layer is provided on a support such as, and the other material is supplied. From the viewpoint of cost and production efficiency, the former method using a mono sheet type is preferable.

  Next, the water washing removal process in the type B development processing of the present invention will be described. In the type B development processing of the present invention, the water washing removal removes a layer provided on a physical development nucleus layer such as a silver halide emulsion layer which becomes unnecessary after the development processing. Therefore, water is the main component of the water removal treatment liquid. In addition, this treatment liquid may contain a buffer component, and may contain a preservative for the purpose of preventing the removed gelatin from being spoiled.

  As a water washing removal method, a treatment method can be used alone or in combination with a shower method, a slit method, or the like using a scrubbing roller or the like. Also, a plurality of showers and slits can be provided to increase the removal efficiency. Moreover, you may use the method of carrying out transfer peeling to a release paper etc. instead of water washing removal. As a method of transferring and peeling with release paper, etc., excess developer on the silver halide emulsion layer is squeezed out beforehand with a roller, etc., and the silver halide emulsion layer etc. This is a method of transferring from a plastic resin film to release paper and peeling. As the release paper, water-absorbing paper or non-woven fabric, or paper having a water-absorbing void layer formed of fine pigment such as silica and binder such as polyvinyl alcohol on the paper is used.

<Type C>
In the silver image forming material of type C of the present invention, a photosensitive material having at least a silver halide emulsion layer is exposed on a support, and after development processing according to a curing development processing method, an unnecessary portion of the silver halide emulsion. It can be obtained by at least removing the layer by washing with water. Accordingly, the light-sensitive material used is one in which at least a silver halide emulsion layer is coated on a support. In this method, photosensitive silver halide grains are exposed imagewise to form a latent image, and when this is used as a catalyst to reduce silver halide, a reducing agent whose oxidized form such as hydroquinone has a hardening action on gelatin. The metal silver is formed at the same time as the gelatin around the metal silver is hardened to form an image, and then washed away with water to wash away non-hardened parts which are unnecessary parts. As a result, the silver particles are held by the binder, but only the support remains in the non-image area. As the support of the photosensitive material used in the type C of the present invention, materials and performance materials used in the above-described type A and type B photosensitive materials can be used.

As the silver halide emulsion of the light-sensitive material used in Type C of the present invention, the same silver halide emulsion as that of the light-sensitive material used in Type A described above is used. Further, the silver halide emulsion can be spectrally sensitized as necessary, as in the above-mentioned types A and B. Further, the silver halide emulsion does not necessarily have to be negative photosensitive, and may be a direct reversal emulsion having positive sensitivity if necessary. As the silver coating amount of the silver halide emulsion layer, at least 0.01 g (in terms of silver nitrate) / m ² is necessary in order to form a silver image, as in the photosensitive materials used in the above-mentioned types A and B. When using a silver image for the fine wiring part excellent in conductivity, 2.0 to 4.0 g (in terms of silver nitrate) / m ² is preferable.

  The silver halide emulsion layer contains a water-soluble polymer as a binder in the same manner as the silver halide emulsion layer of the light-sensitive material used in the above-described types A and B. Preferred binders include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, poly Examples include hyaluronic acid and carboxycellulose. Further, as in the case of the silver halide emulsion layer of the light-sensitive material used for Type A, a water-soluble polymer crosslinking agent may be used as necessary. However, the light-sensitive material used for Type C of the present invention is used in development processing. In order to remove at least the unnecessary silver halide emulsion layer after development by washing with water, as in the case of the silver halide emulsion layer of the light-sensitive material used for type B described above, when a water-soluble polymer crosslinking agent is used, It is possible to use in the range which does not prevent removal. As for the photographic additives, known photographic additives can be used for various purposes as in the case of the silver halide emulsion layers of the light-sensitive materials used in the above-mentioned types A and B. Further, in the silver halide emulsion layer of the type C photosensitive material of the present invention, various coating aids such as a surfactant and a thickener are used in accordance with the coating method, as in the type A and type B photosensitive materials described above. The same method can be used for the coating method.

The photosensitive material used for Type C of the present invention can be provided with a non-photosensitive layer such as a backing layer, an over layer, and an adhesive layer, if necessary, as in the photosensitive materials used for Type A and B described above. However, since the adhesive layer is provided for the purpose of improving the adhesion between the support and the silver image, it is provided between the support and the silver halide emulsion layer in the same manner as the light-sensitive material used for type A described above. . Further, since the over layer is provided for the purpose of preventing scratches, it is provided on the silver halide emulsion layer. These non-photosensitive layers are layers having a water-soluble polymer as a main binder in the same manner as the photosensitive material used for type A, and are the same non-photosensitive layers as the photosensitive materials used for type A and type B described above. Water-soluble polymers used in the above can be used. Although the water-soluble high molecular weight of a non-photosensitive layer changes with each use, the range of 0.001-10 g / m < ² > is preferable. In addition, a water-soluble polymer crosslinking agent can be used for these non-photosensitive layers, but in the development processing of type C of the present invention, at least the unnecessary portion of the silver halide emulsion layer is removed by washing with water. When a water-soluble polymer crosslinking agent is used for the non-photosensitive layer, it can be used in a range that does not hinder the removal of the silver halide emulsion layer after development with water.

The photosensitive material used for Type C of the present invention preferably contains a swelling inhibitor. The swelling inhibitor in the present invention has the effect of suppressing the swelling of the water-soluble polymer during the development processing of the photosensitive material and increasing the silver density by suppressing the diffusion of silver in the image area. When the density of silver becomes high, the metal precipitation in the plating process is improved. Whether or not it acts as a swelling inhibitor is determined by whether or not gelatin precipitation occurs by adding a swelling inhibitor of 0.35 mol / L to a 5% gelatin aqueous solution at pH 3.5. Any chemicals that occur will act as swelling inhibitors. Specific examples of the swelling inhibitor include inorganic salts such as sodium sulfate, lithium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, magnesium chloride, sodium chloride, manganese chloride, and magnesium phosphate. Or, for example, benzenesulfonic acid, diphenylsulfonic acid, 5-sulfosalicylic acid, p-toluenesulfonic acid, phenol disulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, 1-hydroxy- Sulfonic acids such as 3,6-naphthalenedisulfonic acid and dinaphthylmethanesulfonic acid, for example, polyvinyl benzene sulfonic acid, a copolymer of maleic anhydride and vinyl sulfonic acid, and a polymer precipitant such as polyvinyl acrylamide. And the compounds used. These swelling inhibitors may be used alone or in combination, but it is preferable to use inorganic salts, particularly sulfates. These swelling inhibitors may be contained in any constituent layer of the light-sensitive material used in Type C of the present invention, but are particularly preferably contained in the silver halide emulsion layer. The preferred content of these swelling inhibitors 0.01 to 10 g / m ^2, still more preferably 0.1-2 g / m ^2.

  The photosensitive material used for Type C of the present invention can further contain an electroless plating catalyst, a conductive substance, and the like.

  The photosensitive material used for Type C of the present invention may be provided with a water washing removal promoting layer as a non-photosensitive layer, similarly to the photosensitive material used for Type B described above. In this case, it is preferably provided between the support and the silver halide emulsion layer. The water washing removal accelerating layer can use, as a binder, a water-soluble polymer similar to the photosensitive material used for Type B described above.

  In the photosensitive material used for type C of the present invention, similarly to the photosensitive material used for type A and type B described above, a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion in the constituent layers is used. Further, it is preferably used as a halation for improving image quality or as an irradiation inhibitor. Further, the photosensitive material used for Type C of the present invention contains known photographic additives, surfactants, matting agents, lubricants, etc., if necessary, as in the photosensitive materials used for Type A and Type B described above. can do.

  Moreover, in the photosensitive material used for Type C of the present invention, it is preferable to contain a hardened developing agent in the constituent layers. Cured developing agents include polyhydroxybenzenes such as hydroquinone, catechol, chlorohydroquinone, pyrogallol, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dimethylhydroquinone, 2,3- Dibromohydroquinone, 1,4-dihydroxy-2-acetophenone, 2,5-dimethylhydroquinone, 4-phenylcatechol, 4-t-butylcatechol, 4-s-butylpyrogalol, 4,5-dibromocatechol, 2,5- Diethylhydroquinone, 2,5-dibenzoylaminohydroquinone, and the like. Also, aminophenol compounds such as N-methyl-p-aminophenol, p-aminophenol, 2,4-diaminophenol, p-benzylaminophenol, 2-methyl-p-aminophenol, 2-hydroxymethyl-p- Aminophenol and the like, and other known hardened developing agents described in, for example, Japanese Patent Application Laid-Open Nos. 2001-215711, 2001-215732, 2001-312031, and 2002-62664 are used. In particular, benzene having a hydroxyl group substituted at least in the 1,2-position or 1,4-position of the benzene nucleus is preferred. Moreover, it is also possible to use these hardened developing agents in combination. Further, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3- It is also possible to use reducing agents used in known photographic developers such as pyrazolidone and 1-p-chlorophenyl-3-pyrazolidone in combination with the above hardened developing agent.

  These hardened developing agents may be contained in any of the constituent layers of the light-sensitive material, but are preferably contained in the silver halide emulsion layer or the undercoat layer, particularly in the silver halide emulsion layer. Is preferred. A preferable amount to be contained is an amount sufficient to make the water-soluble binder of the silver halide emulsion layer water-resistant, and thus varies depending on the amount of the water-soluble binder used. A preferable amount of the hardened developer is 0.005 to 0.5 g, more preferably 0.01 to 0.4 g, per 1 g of the water-soluble polymer. These hardened developers may be dissolved in the coating solution or contained in each layer, or may be dissolved in an oil dispersion and contained in each layer.

  Next, a method for forming a silver image in Type C of the present invention will be described. In order to form a silver image of type C of the present invention, the photosensitive material must be exposed and developed. As the exposure method, the same method as the above-described Type A and Type B can be used.

  The development processing of type C of the present invention includes a development processing step for curing the water-soluble polymer at the same time when silver halide reduction is performed on the image forming portion, and a water washing removal step for washing away the uncured portion which is an unnecessary portion. . In this case, when a negative type silver halide emulsion is used as the light-sensitive material, a portion irradiated with light by exposure becomes a portion for forming an image, and when a positive type silver halide emulsion is used, by exposure, The portion not irradiated with light is a portion that forms an image. In addition, regardless of whether negative or positive silver halide emulsions are used, development is stopped using an acidic aqueous solution containing, for example, acetic acid, citric acid, etc. between the development processing step and the water washing removal step. Processing may be performed.

  The developer used in the type C development processing of the present invention includes alkaline substances such as potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, amine compounds, and thickeners such as carboxymethyl. Sesulose, development aids such as 3-pyrazolidinones, antifoggants such as potassium bromide, development modifiers such as polyoxyalkylene compounds, silver halide solvents such as thiosulfate, thiocyanate, Additives such as cyclic imide, thiosalicylic acid and mesoionic compounds can be included. The pH of the developer is usually 10-14. Since a preservative such as sodium sulfite used in the above-mentioned type B developer has an action of stopping the curing reaction by the curing development, the preservative is used at least 20 g / L or less in the cured developer in the present invention. An amount, preferably a use amount of 10 g / L or less is preferred.

  The type C developer of the present invention contains a hardened developer when the photosensitive material does not contain a hardened developer. As the hardened developer, the same hardened developer as that contained in the photosensitive material can be used. A preferable content of the hardened developer is 1 to 50 g / L. When the hardened developer is contained in the developer, the preservability is poor and the air is immediately oxidized. Therefore, it is preferable to dissolve in an alkaline aqueous solution immediately before use.

  Further, the type C developer of the present invention preferably contains a swelling inhibitor. As the swelling inhibitor, the same swelling inhibitor as that contained in the photosensitive material can be used. The content of a preferred swelling inhibitor is 50 to 300 g / L, preferably 100 to 250 g / L.

  The development temperature of Type C of the present invention is 2 ° C to 30 ° C, and more preferably 10 ° C to 25 ° C. The development time is 5 seconds to 30 seconds, preferably 5 seconds to 10 seconds. The development time is preferably 120 seconds or less in consideration of production efficiency. The developer supply method for performing type C development may be an immersion method or a coating method, as in the above-described types A and B. In particular, when a curable developer containing a curable developer is used, it is preferable to use a coating method and avoid repeated use of curable development.

  Next, the water washing removal process in the type C development processing of the present invention will be described. The removal by washing with water in the type C development processing of the present invention removes a layer provided on a support such as a silver halide emulsion layer in an unnecessary portion after the development processing. Therefore, the same water removal treatment solution and method as in the above-described Type B can be used.

  In the type C of the present invention, a non-image area silver halide emulsion layer is removed to prepare a relief image, and then a stronger relief image is prepared by processing with a solution containing a hardener well known to those skilled in the art. I can do it. Various hardeners such as aldehydes such as chrome alum and formalin, ketones such as diacetyl, mucochloric acid, and the like can be used.

  In the type C of the present invention, there can be used a method of developing a photosensitive material using a second developer containing a silver halide solvent after the development with the developer. By this method, the silver in the relief image cured by the first development process can be increased by the second development process. The second development step may be before or after the washing removal step of the silver halide emulsion layer, but since the silver halide in the non-image area can also be used as a silver supply source, before the washing removal. It is preferable to carry out. Further, silver can be further increased in the second developing step by further supplying silver ions such as adding a silver salt to the second developing solution.

  In the present invention, a silver image forming material produced by any type A, Type B, or Type C photographic process is used for various purposes such as obtaining higher conductivity or changing the color tone of the silver image. Is possible. As a possible plating treatment, electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating can be used. The degree of conductivity imparted by the plating process varies depending on the application to be used. For example, for use as an electromagnetic shielding material for PDP, the surface resistance value is 2.5Ω / □ or less, preferably 1.5Ω / □. The following are required:

  In the case of performing electroless plating treatment, activation treatment can also be performed with a solution containing palladium for the purpose of promoting electroless plating. Palladium may be in the form of a divalent palladium salt or a complex salt thereof, or may be metallic palladium. However, it is preferable to use a palladium salt or a complex salt thereof in view of the stability of the liquid and the stability of the treatment.

  In the case of performing electroless plating, known electroless plating techniques such as electroless nickel plating, electroless cobalt plating, electroless gold plating, and silver plating can be used, but in order to obtain the necessary conductivity described above. It is preferable to perform electroless copper plating.

  Electroless copper plating solutions include copper sources such as copper sulfate and copper chloride, reducing agents such as formalin, glyoxylic acid, potassium tetrahydroborate, dimethylamine borane, EDTA, diethylenetriaminepentaacetic acid, Rochelle salt, glycerol, meso-erythritol, Adenyl, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 1,3-diaminopropan-2-ol, glycol etherdiaminetetraacetic acid, triisopropanolamine, triethanol It contains copper complexing agents such as amines, pH adjusting agents such as sodium hydroxide, potassium hydroxide and lithium hydroxide. In addition, polyethylene glycol, yellow blood salt, bipyridyl, o-phenanthroline, neocuproine, thiourea, cyanide, and the like can also be added as additives for improving bath stability and plating film smoothness. The plating solution is preferably aerated to increase stability.

  As described above, various complexing agents can be used in electroless copper plating. However, depending on the type of complexing agent, copper oxide co-deposits, greatly affecting conductivity, or with copper ions such as triethanolamine. It is known that a complexing agent having a low complex stability constant tends to precipitate copper, making it difficult to produce a stable plating solution or plating replenisher. Therefore, the complexing agents usually used industrially are limited, and in the present invention, the selection of the complexing agent is particularly important as the composition of the plating solution for the same reason. Particularly preferable complexing agents include EDTA and diethylenetriaminepentaacetic acid, which have a large stability constant of copper complex. Examples of plating solutions using such a complexing agent include high-temperature types used in the production of printed circuit boards. There is electroless copper plating. The method of high-temperature type electroless copper plating is described in detail in “Electroless plating basics and applications” (ed. In high-temperature type plating, the treatment is usually performed at 60 to 70 ° C., and the treatment time varies depending on whether or not the electrolytic plating is performed after the electroless plating. Usually, the electroless plating treatment is performed for 1 to 30 minutes, preferably 3 to 20 minutes. By doing so, the object of the present invention can be achieved.

  In the case of performing electroless plating treatment other than copper, for example, the method described in “Plating Technology Guidebook” (Tokyo Sheet Metal Cooperative Technical Committee, 1987) p406 to 432 can be used.

  In the case of performing electrolytic plating, a known plating method such as copper plating, nickel plating, zinc plating, tin plating or the like can be used. For example, “Plating Technology Guidebook” (Tokyo Sheet Metal Cooperative Technology) Committee, 1987) can be used. Which plating method is used varies depending on the use of the conductive material to be manufactured, but when plating is performed in order to further increase the conductivity, copper plating or nickel plating is preferable. Preferred examples of the copper plating method include a copper sulfate bath plating method and a copper pyrophosphate bath plating method, and preferred nickel plating methods include a Watt bath plating method and a black plating method.

  Hereinafter, the present invention will be described in more detail with reference to examples.

A photosensitive material used in the photographic production method (b) was prepared as follows. After applying an adhesive layer of 50 mg / m ² of gelatin to a polyethylene terephthalate film having a subbing layer containing vinylidene chloride having a thickness of 100 μm, the physical development nucleus layer containing the following palladium sulfide sol was added to the solid content of palladium sulfide. Was applied to 0.4 mg / m ² and dried.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40ml
1000ml distilled water
B liquid sodium sulfide 8.6g
1000ml distilled water
Liquid A and liquid B were mixed with stirring, and 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.

<Preparation of physical development nucleus layer coating solution>
50 ml of palladium sulfide sol
20% 1% gelatin solution
Surfactant (1 below) 0.2g
Add water to make a total volume of 2000 ml.

  Subsequently, a backing layer having the following composition was applied on the side opposite to the side on which the physical development nucleus layer was applied.

<Backcoat layer composition / per 1 m ² >
2g of gelatin
Amorphous silica matting agent (average particle size 5μm) 20mg
Dye 1 200mg
Surfactant (S-1) 400mg
Surfactant (S-2) 5mg

  Subsequently, a silver halide emulsion layer and a non-photosensitive overlayer coating solution having the following composition were prepared. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. A silver halide emulsion layer was coated on the physical development nucleus layer. This silver halide emulsion was prepared with 95 mol% of silver chloride and 5 mol% of silver bromide so that the average grain size was 0.1 μm. To this silver halide emulsion, sodium thiosulfate and chloroauric acid were added and chemically sensitized at 50 ° C. The silver halide emulsion has a silver (silver nitrate) / gelatin mass ratio of 2.0.

Using the silver halide emulsion thus prepared, the following silver halide emulsion layer coating solution was prepared. Further, the following non-photosensitive overlayer coating solution was prepared, and both were applied on the physical development nucleus layer by simultaneous slide coating. The obtained photographic light-sensitive material had a total amount of 3.0 g including 3.0 g of silver per 1 m ² (silver nitrate) and 1.0 g of gelatin including the over layer.

<Silver halide emulsion layer coating solution>
50g gelatin
Silver halide emulsion 300 g Silver nitrate equivalent 1-phenyl-5-mercaptotetrazole 0.3 g
Surfactant (S-1) 3g

<Non-photosensitive overlayer coating solution>
Gelatin 100g
Amorphous silica matting agent (average particle size 3.5μm) 1g
Surfactant (S-1) 1g
Surfactant (S-2) 10mg

The light-sensitive material thus obtained is exposed at an energy amount of 0.6 mJ / cm ² with a close contact printer using a mercury lamp as a light source, and a transparent original having a fine line width of 20 μm and a lattice pattern of 250 μm is closely attached. Subsequently, after dipping in the following developer 1 (developer for photographic production method (b)) at 25 ° C. for 40 seconds, a silver halide emulsion layer, a backing layer, an intermediate layer, and a silver halide emulsion layer The non-photosensitive over layer was removed by washing with warm water, and a silver image forming material in which a silver image was formed in a mesh pattern was obtained by the photographic method (b).

<Developer 1>
Sodium hydroxide 20g
Hydroquinone 20g
1-phenyl-3-pyrazolidone 2g
Sodium sulfite 30g
N-methylethanolamine 10g
Potassium bromide 2g
Adjust the total volume to 1000 ml with water. Adjust to pH13.

This silver image forming material was cut into a size of 10 cm × 15 cm, and the entire surface was irradiated with light from a surface on which the silver image was formed using a high pressure mercury lamp. The ultraviolet energy of the high-pressure mercury lamp at this time was 200 mJ / cm ² when measured using an eye ultraviolet ray integrating illuminometer UVPF-A1 (trade name of an integrating illuminometer manufactured by Iwasaki Electric Co., Ltd.). As the light receiver, PD-365 (trade name of a light receiver for integrated illuminometer manufactured by Iwasaki Electric Co., Ltd.) was used in order to receive light in the vicinity of 365 nm. Then, using each of the following treatment liquids 1 to 3 (treatment liquid containing at least one compound described in any of (I) to (III) above), an immersion treatment is performed at 60 ° C. for 90 seconds, and further Washed with pure water at 20 ° C. and dried with warm air at 60 ° C. using a film dryer (2 minutes) to prepare conductive materials A1 to A3.

<Processing liquid 1>
Ascorbic acid 50g
950ml of pure water

<Processing liquid 2>
Monosodium phosphate 250g
750 ml of pure water

<Processing liquid 3>
150g of potassium chloride
850ml of pure water

  For comparison, in the method for producing the conductive material A1, a comparative conductive material A4 and further a conductive material A1 are produced in the same manner as in the case where pure water is used as the treatment liquid instead of using the treatment liquid 1. In this way, a comparative conductive material A5 was produced in the same manner except that the treatment using the treatment liquid 1 was not performed. Further, as a comparison, in the method of manufacturing the conductive materials A1 to A3, comparative conductive materials A6 to A8 are manufactured in the same manner except that the silver image forming material is not irradiated with light using a high-pressure mercury lamp. did.

  The surface resistivity of the conductive material on which the mesh pattern silver image obtained as described above was formed was measured according to JIS K 7194 using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. The results obtained are summarized in Table 1.

  Furthermore, the conductive material on which the mesh pattern silver image was formed was placed in a constant temperature and humidity chamber at 60 ° C. and 80% RH for one week and heated. The surface resistance value after heating is measured, and the value obtained by subtracting the surface resistance value before heating from the surface resistance value after heating is calculated to correspond to what percentage of the surface resistance value before heating. Thus, the rate of change before and after heating was determined and is also shown in Table 1.

  From the results of Table 1, after using a silver image forming material on which a silver image is formed by the photographic manufacturing method (b) and irradiating ultraviolet rays using a high-pressure mercury lamp, it is described in any one of (I) to (III) above. By performing the treatment using a treatment liquid containing at least one compound, a conductive material having excellent conductivity and high storage stability can be obtained.

In the light-sensitive material of Example 1 described above, the physical development nucleus layer was not provided, the non-light-sensitive overlayer was not provided, and the silver halide emulsion silver (silver nitrate) / gelatin mass ratio was 3 in the silver halide emulsion layer. A photosensitive material used in the photographic manufacturing method (a) was prepared in the same manner as in Example 1 except that the thickness was 0.0. After that, with a contact printer using the same mercury lamp as the light source as in Example 1, a transparent original having a mesh pattern with a fine line width of 20 μm and a lattice spacing of 250 μm used in Example 1 was brought into close contact, and the energy amount was 0.6 mJ / cm ^2. Followed by dipping for 90 seconds at 20 ° C. in Geckol developer (developer for photographic process (a)) manufactured by Mitsubishi Paper Industries Co., Ltd. Used and soaked at 20 ° C. for 30 seconds. Further, it was immersed in the fixing solution 1 described below at 20 ° C. for 3 minutes, then washed with running water for 5 minutes, and a silver image forming material on which a mesh pattern was formed was obtained by the photographic method (a). Then, using the following enzyme-containing treatment solution 1 or 2, immersion treatment is performed at 17 ° C. for 10 minutes, followed by washing with pure water at 20 ° C., and then using the following treatment solutions 4 to 7 (combinations are shown in the table). according to 2), for 3 minutes immersion at 60 ° C., and further washed with pure water 20 ° C., using a film dryer was dried at 60 ° C. hot air (2 minutes), the conductivity of reference example materials B1 ~ 4 were made.

<Fixing solution 1>
200 g of N- (2-aminoethyl) ethanolamine
Sodium thiosulfate pentahydrate 5g
Anhydrous sodium sulfite 15g
Adjust the total volume to 1000 ml with water. Adjust to pH 10.5.

<Enzyme treatment solution 1>
20g triethanolamine
Potassium bisulfite 6g
1 g of Bioplase AL-15
(Bacterial proteinase: Proteolytic enzyme, manufactured by Nagase Sangyo Co., Ltd.)
Add water to adjust the total volume to 1000 ml. The pH was adjusted to 7.4.

<Enzyme treatment liquid 2>
Lactic acid 20g
Sodium hydroxide 2g
Denapsin 1g
(Bacterial proteinase: Proteolytic enzyme, manufactured by Nagase Sangyo Co., Ltd.)
Add water to adjust the total volume to 1000 ml. The pH was adjusted to 3.0.

<Treatment liquid 4>
150 g of hydroquinone monosulfonate potassium
850ml of pure water

<Treatment liquid 5>
Sodium hexametaphosphate 150g
850ml of pure water

<Treatment liquid 6>
DDP8 150g
(Nippon Surfactant dipolyoxyethylene alkyl phosphate ester)
850ml of pure water

<Treatment liquid 7>
150g sodium chloride
850ml of pure water

  For comparison, in the treatment using the enzyme-containing treatment liquid of the conductive material B4, pure water is used in place of the enzyme-containing treatment liquid, and the treatment is performed at 17 ° C. for 10 minutes in the same manner as in the comparative conductive material B5. Furthermore, in the method for producing the conductive material B4, a comparative conductive material B6 was produced in the same manner except that the treatment using the treatment liquid 7 was not performed. Further, as a comparison, in the method for producing the conductive materials B1 and B2, instead of using the treatment liquid 4 and the treatment liquid 5, pure water is used as the treatment liquid, and the treatment is performed at 60 ° C. for 3 minutes in the same manner. Comparative conductive materials B7 and B8 were produced.

  The surface resistivity of the conductive material on which the mesh pattern silver image obtained as described above was formed was measured according to JIS K 7194 using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. The results obtained are summarized in Table 2.

  Furthermore, the conductive material on which the mesh pattern silver image was formed was placed in a constant temperature and humidity chamber at 60 ° C. and 80% RH for one week and heated. The surface resistance value after heating is measured, and the value obtained by subtracting the surface resistance value before heating from the surface resistance value after heating is calculated to correspond to what percentage of the surface resistance value before heating. Thus, the rate of change before and after heating was determined and is also shown in Table 2.

  From the results in Table 2, the silver image-forming material on which a silver image was formed by the photographic manufacturing method (a) was used, and after treatment with an enzyme-containing treatment solution, the compound according to any one of (I) to (III) above By performing the treatment using a treatment liquid containing at least one kind, a conductive material having excellent conductivity and high storage stability can be obtained.

A photosensitive material used for the photographic process (c) was prepared in the same manner as in Example 2 except that the silver halide emulsion layer of the photosensitive material of Example 2 contained 20 mg of 4-phenyl-catechol per 1 m ² . . After that, with the contact printer using the same mercury lamp as the light source as in Example 1, the transparent original having the mesh pattern used in Example 1 was brought into close contact and exposed at an energy amount of 0.6 mJ / cm ² , followed by the following development. After immersing the film in solution 2 (developer for photographic process (c)) at 23 ° C. for 30 seconds to cure and developing, the unnecessary silver halide emulsion layer was removed by washing with warm water, followed by photographic process (c). A silver image forming material in which a silver image was formed in a mesh pattern was obtained.

<Developer 2>
Sodium hydroxide 20g
Sodium sulfate 200g
Potassium bromide 1g
Adjust the total volume to 1000 ml with water. Adjust to pH13.

Thereafter, in the same manner as in Example 1, the whole surface was irradiated with light using a high-pressure mercury lamp from the surface on which the silver image was formed. The ultraviolet energy of the high-pressure mercury lamp at this time was measured using an eye ultraviolet ray integrating illuminometer UVPF-A1 and a light receiver PD-365 (trade name of an integrating illuminometer manufactured by Iwasaki Electric Co., Ltd.). cm ² . Then, using each of the following treatment liquids 8 to 11, immersion treatment is performed at 60 ° C. for 3 minutes, further washed with pure water at 20 ° C., and dried with warm air at 60 ° C. using a film dryer (2 minutes). The conductive materials C1 to C4 of the present invention were produced.

<Treatment liquid 8>
Pyrogallol 150g
850ml of pure water

<Treatment liquid 9>
150g of disodium dihydrogen pyrophosphate
850ml of pure water

<Treatment liquid 10>
150g ammonium chloride
850ml of pure water

<Treatment solution 11>
Unisense FPA100L 150g
(Dialyldimethylammonium chloride polymer produced by Senka Co., Ltd.)
850ml of pure water

  For comparison, in the method for producing the conductive material C1, a comparative conductive material C5 and further a conductive material C1 were produced in the same manner except that pure water was used as the treatment liquid instead of using the treatment liquid 8. A comparative conductive material C6 was produced in the same manner as described above except that the treatment using the treatment liquid 8 was not performed. For comparison, in the method for producing the conductive materials C1 to 4, comparative conductive materials C7 to C10 are produced in the same manner except that the silver image forming material is not irradiated with light using a high-pressure mercury lamp. did.

  The surface resistivity of the conductive material on which the mesh pattern silver image obtained as described above was formed was measured according to JIS K 7194 using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. The results obtained are summarized in Table 3.

  Furthermore, the conductive material on which the mesh pattern silver image was formed was placed in a constant temperature and humidity chamber at 60 ° C. and 80% RH for one week and heated. The surface resistance value after heating is measured, and the value obtained by subtracting the surface resistance value before heating from the surface resistance value after heating is calculated to correspond to what percentage of the surface resistance value before heating. Thus, the rate of change before and after heating was determined and is also shown in Table 3.

  From the result of Table 3, after irradiating ultraviolet rays using a high-pressure mercury lamp using a silver image forming material on which a silver image is formed by the photographic manufacturing method (c), the material according to any one of the above (I) to (III) By performing the treatment using a treatment liquid containing at least one compound, a conductive material having excellent conductivity and high storage stability can be obtained.

In the method for producing the conductive material A1 of Example 1, silver image formation was performed using an ultraviolet laser (helium-cadmium laser) having a wavelength of 325 nm instead of irradiating the silver image forming material with a high-pressure mercury lamp. From the surface on the side where the silver image of the material is formed, the entire surface was irradiated with light so that the energy amount was 200 mJ / cm ² . Then, using the following treatment liquids 12 to 13, respectively, the immersion treatment is performed at 60 ° C. for 90 seconds, further washed with pure water at 20 ° C., and dried with hot air at 60 ° C. using a film dryer (2 minutes). The conductive materials D1 to 3 of the present invention were produced.

<Treatment liquid 12>
200g of hydroxylamine
800ml of pure water

<Treatment liquid 13>
Sodium bromide 150g
850ml of pure water

<Treatment liquid 14>
150g potassium iodide
850ml of pure water

For comparison, in the method for producing the conductive materials D1 to 3, a silver image forming material was used by using an argon laser having a wavelength of 488 nm instead of irradiating the silver image forming material with an ultraviolet laser having a wavelength of 325 nm. The conductive material D4 for comparison is the same as in Example 1 except that the entire surface is irradiated with light so that the energy amount is 200 mJ / cm ² from the surface on which the silver image is formed. ~ 6 were made.

  The surface resistivity of the conductive material on which the mesh pattern silver image obtained as described above was formed was measured according to JIS K 7194 using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. The results obtained are summarized in Table 4.

  Furthermore, the conductive material on which the mesh pattern silver image was formed was placed in a constant temperature and humidity chamber at 60 ° C. and 80% RH for one week and heated. The surface resistance value after heating is measured, and the value obtained by subtracting the surface resistance value before heating from the surface resistance value after heating is calculated to correspond to what percentage of the surface resistance value before heating. Thus, the rate of change before and after heating was determined and is also shown in Table 4.

  From the results of Table 4, after using a silver image forming material on which a silver image is formed by the photographic manufacturing method (b) and irradiating a laser beam having a wavelength of 400 nm or less, the return is described in any one of (I) to (III) above. By using a treatment liquid containing at least one compound of the above, a conductive material having excellent conductivity and high storage stability can be obtained. It can also be seen that the effect of the present invention cannot be obtained even when light having a wavelength longer than that of ultraviolet rays is irradiated.

In Example 1, the developer is the same as that of Example 1 except that the fatigue developer of Developer-1 (developer after 5 m ² treatment per liter) is used as the developer. A silver image forming material in which a silver image was formed in a pattern was obtained.

This silver image forming material was cut into a size of 10 cm × 15 cm, and the entire surface was irradiated with light from a surface on which the silver image was formed using a high pressure mercury lamp. The ultraviolet energy of the high-pressure mercury lamp at this time was 200 mJ / cm ² when measured using an eye ultraviolet ray integrating illuminometer UVPF-A1 (trade name of an integrating illuminometer manufactured by Iwasaki Electric Co., Ltd.). As the light receiver, PD-365 (trade name of a light receiver for integrated illuminometer manufactured by Iwasaki Electric Co., Ltd.) was used in order to receive light in the vicinity of 365 nm. Then, each of the treatment solutions 1 to 3 is used for immersion treatment at 60 ° C. for 90 seconds, further washed with pure water at 20 ° C., and dried with warm air at 60 ° C. using a film dryer (2 minutes). The conductive materials E1 to E3 of the present invention were produced.

  For comparison, in the method for producing the conductive materials E1 to E3, comparative conductive materials E4 to E6 are produced in the same manner except that the silver image forming material is not irradiated with light using a high-pressure mercury lamp. did.

  The surface resistivity of the conductive material on which the mesh pattern silver image obtained as described above was formed was measured according to JIS K 7194 using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. The results obtained are summarized in Table 5.

  Furthermore, the conductive material on which the mesh pattern silver image was formed was placed in a constant temperature and humidity chamber at 60 ° C. and 80% RH for one week and heated. The surface resistance value after heating is measured, and the value obtained by subtracting the surface resistance value before heating from the surface resistance value after heating is calculated to correspond to what percentage of the surface resistance value before heating. Thus, the rate of change before and after heating was determined and is also shown in Table 5.

  From the results of Table 5, after using a silver image forming material on which a silver image is formed by a photographic manufacturing method (b) and irradiating ultraviolet rays using a high-pressure mercury lamp, it is described in any of (I) to (III) above. By performing the treatment using a treatment liquid containing at least one compound, a conductive material having excellent conductivity and high storage stability can be obtained. Further, after using a silver image forming material on which a silver image is formed by the photographic production method (b) and irradiating ultraviolet rays using a high-pressure mercury lamp, at least one compound described in any of (I) to (III) above is used. By processing using the processing solution contained, even when development processing is performed using a fatigue developer, development processing is performed using a developer that is not fatigued (results of surface resistance values in Table 1). It can be seen that there is no difference and stable conductivity is obtained.

Claims (1)

After a silver image is formed on at least one surface of the support by a photographic method, the silver image is subjected to an ultraviolet irradiation treatment as a treatment for decomposing the water-soluble polymer binder contained in the constituent layer of the photosensitive material, The manufacturing method of the electroconductive material characterized by processing with the process liquid containing at least 1 sort (s) of compounds in any one of following (I)-(III).
(I) Reducing substances (II) Water-soluble phosphorus oxoacid compounds (III) Water-soluble halides