JP2009199733A - Manufacturing method of electrically conductive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a conductive material capable of improving conductivity, while suppressing deposition of a metal plated in a non-image portion which is not preferred in a substance. <P>SOLUTION: In the manufacturing method of the conductive material, a conductive material precursor, having at least a single layer of silver halide emulsion layer on a support body, is exposed in image-like and then a curing development treatment is carried out, and thereafter, is applied a non-electrolytic plating treatment, a fixing treatment is applied by a treatment agent, containing a silver halide solvent between the curing treatment and the non-electrolytic plating treatment. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to 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, and more particularly to a method for producing a transparent conductive material having a metal part and a light transmission part.

  In recent years, with the rapid development of the information-oriented society, technologies related to information-related devices have rapidly advanced and become popular. Of these, display devices are used for televisions, personal computers, information 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, JP-A-9-53030, JP-A-11-122024, JP-A 2000-294980, JP-A 2000-357414, JP-A 2000-329934, JP-A 2001-38843, JP-A-2001-47549, JP-A-2001-51610, JP-A-2001-57110, JP-A-2001-60416, and the like.

  As a method for producing these transparent conductive materials, a conductive metal such as silver, copper, nickel, or indium is formed on a transparent resin film by sputtering, ion plating, ion beam assist, vacuum deposition, or wet coating. In general, a method of forming a metal thin film is generally used. However, since these conventional methods are extremely complicated, there has been a problem of high cost and poor productivity.

  Another performance required for the transparent conductive material is conductivity and light transmittance. In order to increase the conductivity, it is necessary to make a metal thin film fine pattern with a certain width and thickness, but at the same time, increasing the line width of the metal pattern that blocks light reduces the transmittance. In order to satisfy the above, it is necessary to manufacture a fine metal pattern having sufficient conductivity, particularly a uniform pattern with a minimum necessary width, but this cannot be satisfied by the conventional method.

  From the viewpoint of forming a uniform pattern, a method of using a silver salt photographic light-sensitive material having a silver halide emulsion layer as a transparent conductive material precursor has been proposed in recent years. For example, in WO 01/51276 pamphlet (Patent Document 1) and Japanese Patent Application Laid-Open No. 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 obtain a transparent conductive material. Proposals have been made for methods for producing functional materials. When these silver salt photographic light-sensitive materials are used, the silver halide contained in the unexposed portion at the time of image exposure serving as the light transmitting portion is removed, but the binder remains without being removed. The remaining binder is contaminated and colored by the processing solution during the manufacturing process of the conductive material, or the fog developed silver that has been developed and developed while remaining unexposed remains with the binder. For example, there is a problem that the transparency of the light transmission part is still insufficient.

  Similarly, a method using a silver salt diffusion transfer method has been proposed as a method using a silver salt photosensitive material, for example, International Publication WO 2004-007810 (Patent Document 3). In this method, since the binder at the light transmitting portion is removed by washing with water after development, there is basically no problem with the aforementioned dyeing of the binder or remaining fogged silver. However, since a thick and heavy silver halide emulsion layer is coated on a very thin physical development nucleus layer, simultaneous multi-layer coating is difficult and there is a problem that productivity is deteriorated.

  On the other hand, as a method of using a silver salt photosensitive material, for example, a relief image is formed on a support by the principle of a curing development method, and the relief image is used as a conductive material, for example, Japanese Patent Application Laid-Open No. 2007-059270 (Patent Document). 4), and disclosed in JP 2007-095408 A (Patent Document 5). The curing development method is described in J.I. Photo. Sci. Magazine No. 11 p1, A. G. Tull (1963) or “The Theory of the Photographic Process (4th edition, p326-327)”, T. H. As described in James et al., An unhardened silver halide emulsion layer substantially free of a hardener prepared on a substrate is developed with a developer containing a developing agent such as polyhydroxybenzene. By processing, when the exposed silver halide is reduced by the developing agent, the oxidized compound produced from the developing agent itself crosslinks the water-soluble polymer such as gelatin and hardens it into an image. is there. The method of forming a relief image on a support based on the principle of such a curing and developing method does not have the problem of binder dyeing or fogging silver remaining as described above, and also uses a silver salt diffusion transfer method. Thus, since it is not necessary to provide a physical development nucleus layer, it is a preferable method from the viewpoint of productivity.

  For applications that require high-definition wiring patterns and high electrical conductivity, such as wiring boards used in small devices such as mobile phones and digital cameras, and electromagnetic shielding films used in plasma displays As described in Patent Documents 1 to 5, it is useful to further increase the conductivity by subjecting the obtained silver image to metal plating (electroless plating and / or electrolytic plating). . Further, in the case of an image in which the wiring is isolated, since electroplating cannot be performed, electroless plating is useful as a plating method. However, when an electroless plating process is performed on a silver image obtained by the curing and developing method, the plated metal may be deposited not only on the image portion but also on the non-image portion.

Since the amount of metal deposited on the non-image area is extremely small, in applications such as printed circuit boards and address electrodes, there is no problem of further electrical conductivity between adjacent wirings causing malfunction or short circuit. However, there was a problem that the consumer value was given to consumers and the commercial value was lost. Further, in the display application such as an electromagnetic wave shielding film, there is a problem that the light transmittance is impaired, and the consumer value is also given to the consumer and the commercial value is impaired.
International Publication WO01 / 51276 pamphlet (1 page) JP 2004-221564 A (pages 1 to 5) International Publication WO 2004-007810 Pamphlet (1 page) JP 2007-059270 A (1 page) JP 2007-095408 A (1 page)

  Accordingly, an object of the present invention is to provide a conductive material which is imagewise exposed to a conductive material precursor containing at least one silver halide emulsion layer on a support, then subjected to curing and development, and then subjected to electroless plating. It is an object of the present invention to provide a method for producing a conductive material capable of suppressing the deposition of a metal plated on a non-image portion which is originally undesirable, and improving the conductivity.

  The above object of the present invention is to provide a conductive material that is imagewise exposed to a conductive material precursor containing at least one silver halide emulsion layer on a support, then subjected to curing and development, and then subjected to electroless plating. This is basically achieved by a method for producing a conductive material, characterized in that a fixing treatment is performed with a processing agent containing a silver halide solvent between the curing development treatment and the electroless plating treatment. The

  By the method for producing a conductive material according to the present invention, it is possible to provide a conductive material capable of suppressing the deposition of the metal plated on the non-image area and improving the conductivity.

  As the support for the conductive material precursor used in the present invention, plastics, glass, rubber, ceramics and the like are preferably used. In the case of producing a transparent conductive substrate, it is preferable to have transparency in the visible region, such as plastics and glass, and a total light transmittance of 60% or more. 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 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluorine resins, silicone resins, polycarbonate resins, diacetate resins, Examples thereof include resin films having a thickness of 50 to 300 μm made of 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 plastics is used as the transparent support, it is preferable to provide an undercoat layer such as vinylidene chloride or polyurethane on the support. When glass is used as the support, metal oxides such as colloidal silica and titanium dioxide are used. It is preferable to provide an undercoat layer such as a physical layer and then heat-treat at 150 to 500 ° C.

  In the conductive material precursor used in the present invention, a silver halide emulsion layer is provided on a support as an optical sensor. Techniques used in silver halide photographic films, photographic papers, printing plate-making films, emulsion masks for photomasks, etc. relating to silver halide can also be used as they are in the present invention.

  The halogen element contained in the silver halide in the present invention may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For the formation of silver halide emulsion grains, methods well known in the art such as forward mixing, back mixing and simultaneous mixing are used. Of these, the so-called controlled double jet method, which is one of the simultaneous mixing methods and keeps pAg in the liquid phase in which the grains are formed, is preferable from the viewpoint of obtaining silver halide emulsion grains having a uniform particle diameter. 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 in the present invention is not particularly limited. For example, 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, a tetrahedron shape, etc. Can be.

  In the production of the silver halide emulsion in the present invention, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof is formed in the process of forming silver halide grains or physical ripening as necessary. A group VIII 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 industry such as sulfur sensitization method, selenium sensitization method, noble metal sensitization method and the like can be used alone or in combination. In the present invention, the silver halide emulsion can be dye-sensitized as necessary.

The amount of silver halide contained in the conductive material precursor used in the present invention is 0.1 g / m ² or more in terms of silver, preferably from 0.3 to 3 g / m ^2.

  In the present invention, the silver halide emulsion layer contains a binder. In the present invention, both the water-insoluble polymer and the water-soluble polymer can be used as a binder, but it is preferable to use a water-soluble polymer. Preferred binders in the present invention include, for example, proteins such as gelatin and casein, 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. Of these water-soluble polymers, proteins such as gelatin are preferred.

  In the present invention, a water-insoluble polymer may be used in combination with the silver halide emulsion layer as a binder in addition to the water-soluble polymer. In general, these water-insoluble 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. The average particle size of the water-insoluble polymer used in the present invention is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.8 μm.

Regarding the total amount of water-soluble polymer and water-insoluble polymer contained in the silver halide emulsion layer in the present invention, 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 are also obtained. On the other hand, if the amount is too large, it is difficult to obtain conductivity, and the productivity is greatly affected. The mass ratio (silver / total binder) between the preferred silver halide (in terms of silver) and the total binder is 0.3 or more, more preferably 0.5 to 3.5. Moreover, a preferable total binder amount is 0.05-3 g / m < ² >, More preferably, it is 0.1-2.5 g / m < ² >.

  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) and 308119 (December 1989) or cited.

  If necessary, the conductive material precursor used in the present invention is an overlayer on the backing layer or the silver halide emulsion layer on the opposite side of the silver halide emulsion layer of the support, and under the silver halide emulsion layer. An undercoat layer or the like can be provided.

For the overlayer and undercoat layer of the conductive material precursor used in the present invention, the same binder as that for the silver halide emulsion layer can be used. The preferred binder amount varies depending on the purpose of use of each layer. In particular, when the layers are cured in an image form using a curing development process and it is desired to leave only necessary portions, for example, an electroless plating is applied to the over layer. In the case of containing catalyst nuclei, etc., since the curing reaction occurring in the silver halide emulsion layer is used, it is preferable that the layer be as thin as possible. The preferable total binder usage of the over layer is 0.1 g / m ² or less, more preferably 0. 0.05 to 0.001 g / m ² . Further, the over layer and the undercoat layer may contain known surfactants, development inhibitors, irradiation prevention dyes, pigments, matting agents, lubricants and the like.

  The conductive material precursor used in the present invention may contain a hardened developer. Specific examples of the hardened developing agent include polyhydroxybenzenes such as hydroquinone, catechol, chlorohydroquinone, pyrogallol, bromohydroquinone, isopropylhydroquinone, 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- Examples include diethylhydroquinone and 2,5-benzoylaminohydroquinone. Also, aminophenol compounds such as N-methyl-p-aminophenol, p-aminophenol, 2,4-diaminophenol, p-benzylaminophenol, 2-methyl-p-aminophenol, 2-hydroxymethyl-p- In addition, aminophenols 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 layer of the conductive material precursor, but are preferably contained in the silver halide emulsion layer or the undercoat layer, and particularly in the silver halide emulsion layer. preferable. The preferable amount of the hardened developer to be contained is an amount sufficient to make the water-soluble binder of the silver halide emulsion layer water-resistant, and therefore varies depending on the amount of the water-soluble binder used. A preferable amount of the hardened developer is 0.1 to 2.0 mmol per 1 g of the water-soluble binder, and more preferably 0.3 to 1.5 mmol per 1 g of the water-soluble binder. These hardened developers may be dissolved in the coating solution or contained in each layer, or may be dissolved in the oil dispersion and contained in each layer.

The conductive material precursor used in the present invention can contain a swelling inhibitor. The swelling inhibitor in the present invention is to prevent the water-soluble binder from swelling when the conductive material precursor is processed with a hardened developer, to prevent blurring of the image, to increase transparency, and to increase conductivity. Use. Whether or not it acts as a swelling inhibitor is determined by whether or not gelatin precipitation occurs by adding 0.35 mol / L of swelling inhibitor to a 5% by weight gelatin aqueous solution at pH 3.5. All the chemicals that cause the occurrence of swelling 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, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, 1-hydroxy- Sulfonic acids such as 3,6-naphthalenedisulfonic acid and dinaphthylmethanesulfonic acid, for example, polyvinylbenzenesulfonic acid, a copolymer of maleic anhydride and vinylsulfonic acid, and a polymer precipitant such as polyvinylacrylamide It includes compounds that are needed. 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 layer of the conductive material precursor, 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.

In the present invention, it is also one of preferable modes to produce an electroconductive material by adding an electroless plating catalyst to the electroconductive material precursor and subjecting it to electroless plating after curing and development. A well-known thing can be used as an electroless-plating catalyst in this invention. For example, noble metal sols such as palladium, silver, gold, and platinum can be used. Even base metals such as zinc and aluminum can be activated with a palladium solution before electroless plating to make the surface palladium. These base metal sols can also be used because they can be substituted and act as a catalyst for electroless plating, but it is preferable to use a noble metal, particularly palladium sol, which requires little activation treatment. These metal sols can be added to the silver halide emulsion layer, overlayer, subbing layer, etc., but in particular when they are contained in the overlayer, the fog does not increase with respect to the silver halide emulsion, and the binder By reducing the amount, it is preferable because it facilitates plating and high conductivity can be easily obtained. As a method for producing the metal sol, a known method such as the method described in JP-A No. 1-100545 can be used. A preferable metal sol content is 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol / m ² .

As the conductive material precursor, it is preferable to use a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer as a halation for improving image quality or an irradiation prevention agent. The antihalation agent can be contained in the undercoat layer or the backcoat layer between the silver halide emulsion layer and the support. The irradiation inhibitor is preferably contained in the silver halide emulsion layer. The amount added may vary widely as long as the desired effect can be obtained. For example, when it is contained in the backing layer as an antihalation agent, the range of ²⁰ mg to 1 g / m ² is desirable, preferably the maximum absorption wavelength. The optical density is 0.5 or more.

  In the present invention, after the conductive material precursor is imagewise exposed, the curing and developing treatment is performed. Here, for example, an image pattern means an arbitrary image pattern such as a mesh pattern in the use of an electromagnetic shielding film, and an arbitrary image provided according to the purpose in an application such as a printed circuit board or an address electrode. Means a pattern. Examples of the exposure method include a method in which a transparent original having an arbitrary image pattern and a silver halide emulsion layer are in close contact with each other and a method in which scanning exposure is performed using various laser beams. In the above-described method of exposing with laser light, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm can be used.

  In the present invention, the curing and developing treatment is an unnecessary portion after the development step of curing the water-soluble polymer at the same time as reducing the silver halide in the portion where the image is formed, using a curing developer described below. The process up to the water washing process for washing away the non-cured portion is collectively referred to as a curing development process. Moreover, you may perform a development stop process using the acidic aqueous solution containing an acetic acid, a citric acid etc., for example between a hardening development process and a water-washing process process.

  Cured developers include alkaline substances such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, lithium hydroxide, tribasic sodium phosphate, or amine compounds, and thickeners such as carboxymethyl cellulose and auxiliary developing agents. As, for example, 3-pyrazolidinones, as antifoggants, for example, potassium bromide, as development regulators, for example, polyoxyalkylene compounds, as silver halide solvents, for example, thiosulfate, thiocyanate, cyclic imide, thiosalicylic acid, Additives such as mesoionic compounds can be included. The pH of the developer is usually 9-14. In addition, a preservative is added to a general black-and-white developer for the purpose of enhancing the stability of the developing agent. Such a preservative, such as sodium sulfite, acts to suppress the curing reaction caused by curing development. Therefore, in the hardened developer in the present invention, the preservative is used in an amount of 20 g / L or less, preferably 10 g / L or less.

  The cured developer in the present invention contains a cured developer when the conductive material precursor does not contain a cured developer. As the hardened developer, the same hardened developer as that contained in the conductive material precursor can be used. A preferable content of the hardened developer is 1 to 30 g / L.

  In the present invention, the cured developer preferably contains the aforementioned swelling inhibitor. As the swelling inhibitor, the same swelling inhibitor as that contained in the conductive material precursor can be used. The content of a preferred swelling inhibitor is 20 to 300 g / L, preferably 30 to 250 g / L.

  In the present invention, the curing and developing treatment may be performed by an immersion method or a coating method. In the immersion method, for example, the conductive material precursor is transported while being immersed in a treatment liquid stored in a large amount in a tank. In the coating method, for example, the treatment liquid is 1 square meter on the conductive material precursor. About 40 to 120 ml is applied. In particular, when a curable developer containing a curable developer is used, it is preferable to use a coating method so that curable development is used only once.

  Preferred curing and developing conditions in the present invention are as follows. The development temperature is 2 to 30 ° C, and 10 to 25 ° C is more preferable. The development time is 5 to 90 seconds, preferably 10 to 30 seconds.

  The main purpose of the water-washing process is to remove the silver halide emulsion in the non-image area that is no longer needed, so that the processing liquid used in this step is mainly composed of water. The treatment liquid may contain a buffer component. Moreover, a preservative can be contained in order to prevent the removed gelatin from being spoiled. As a method of removing the silver halide emulsion, there are a method of rubbing with a sponge or the like, a method of peeling off by applying a roller to the film surface and slipping, a method of winding the roller by contacting the roller with the film surface, and the like. As a method of applying the treatment liquid stream to the silver halide emulsion surface, a shower method, a slit method, or the like can be used alone or in combination. Also, a plurality of showers and slits can be provided to increase the removal efficiency.

  The method for producing a conductive material of the present invention is characterized in that a fixing treatment is performed with a treatment agent containing a silver halide solvent between the curing development treatment and the electroless plating treatment. As a result, the conductivity of the image area is improved, and further, it is possible to suppress the deposition of the metal plated on the non-image area which is originally undesirable. The reason for this is not clear, but undeveloped silver halide grains that are considered to still exist in the hardened image area, or silver ions that are still considered to exist in image silver obtained by development, are subjected to the fixing process. It is considered that the efficiency of electroless plating is improved by the removal. On the other hand, undeveloped silver halide grains and silver ions that are considered to remain slightly in the non-cured portion due to insufficient washing treatment are removed by performing the fixing treatment according to the present invention, so that the non-image portion It is presumed that it is based on the fact that the deposition of plating metal which is inherently undesirable due to these contaminations is suppressed.

  That is, it is generally known that the electroless plating solution contains a reducing agent such as formalin and glyoxylic acid as described later. However, when the above silver ions or undeveloped silver halide grains remain, it may be precipitated as metallic silver particles due to the influence of these reducing agents present in the electroless plating solution. It is presumed that it causes the deposition of a plating metal which is essentially undesirable in the electrolytic plating solution. Therefore, the fixing process according to the present invention is considered to be extremely effective. In the present invention, the fixing process refers to a process for dissolving and removing undeveloped silver halide and silver ions.

  Further, as described above, in the present invention, it is preferable that the conductive material precursor or the cured developer contains a swelling inhibitor. In the curing development method, it is generally known that a swelling inhibitor is generally used to improve the image quality of a cured part obtained. However, when the swelling inhibitor is used, the metal plated on the non-image part is There is a tendency to more easily precipitate (it is considered that the silver ions and undeveloped silver halide grains tend to remain more easily), and the present invention is particularly effective in a curing development method using a swelling inhibitor. It works effectively.

  As the fixing solution used in the fixing process of the present invention, a fixing process technique used for a known silver salt photographic film or photographic paper, a film for printing plate making, an emulsion mask for a photomask, or the like can be used for the fixing process. Examples include fixing solutions described in “Photochemistry” (written by Sakurai, Photo Kogyo Publishing Co., Ltd.) p321.

  The fixing solution contains a silver halide solvent. Examples of the silver halide solvent include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sodium sulfite, Sulphites such as potassium hydrogen sulfite, thioethers such as 1,10-dithia-18-crown-6, 2,2'-thiodiethanol, oxazolidones, 2-mercaptobenzoic acid and its derivatives, cyclic such as uracil Imides, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, 5,5-dialkylhydantoins, alkylsulfones, and other “The Theory of the Photographic Process (4th edition, 474-475) ", T. H. Examples include compounds described in James.

  Examples of such alkanolamines include, for example, N-aminoethylethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N-dimethyl. Examples include ethanolamine, 3-aminopropanol, N-ethyl-2,2′-iminodiethanol, 2-amino-2-methyl-1-propanol, and the like. Further, thiocyanate has a high ability to dissolve silver halide, but it is not preferable to use it from the viewpoint of safety to the human body.

  These silver halide solvents can be used alone or in combination. The total amount of the silver halide solvent is preferably 0.1 to 400 g / L, and more preferably 10 to 350 g / L.

  It is desirable that the fixing solution according to the present invention does not substantially contain a reducing agent capable of reducing silver halide or silver ions, such as the above-mentioned developing agent and / or auxiliary developing agent. In addition, it does not contain substantially here means that content of a reducing agent is less than 0.1 g / L.

  In addition, the fixing solution according to the present invention may contain sulfite and bisulfite as preservatives, and acetic acid, amine borate, phosphate and the like as pH buffering agents. In addition, water-soluble aluminum (for example, aluminum sulfate, aluminum chloride, potassium alum) as a hardener, dibasic acid (for example, tartaric acid, potassium tartrate, sodium tartrate, etc.) or tribasic acid ( Acid sodium, lithium citrate, potassium citrate and the like). The preferred pH of the fixing solution varies depending on the type of silver halide solvent, and is 8 or more, preferably 9 or more, particularly when amines are used. The fixing processing temperature is usually selected between 10 ° C. and 45 ° C., more preferably 18-30 ° C.

  Further, in order to efficiently perform the electroless plating treatment, a water washing treatment step may be provided between the fixing treatment and the electroless plating treatment.

  Prior to the electroless plating treatment, a solution containing palladium in the image portion obtained by curing development for the purpose of accelerating the electroless plating following the fixing treatment or the water washing treatment step performed after the fixing treatment. It can also be activated by. Palladium may be 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 from the viewpoint of the stability of the liquid and the stability of the treatment.

  Next, the electroless plating process will be described. There are an electrolytic method and an electroless method for the plating treatment. In the present invention, an electroless plating method is used for the plating treatment performed after the fixing treatment. The electroless plating technique is described in “Electroless plating” (Electric plating research group, Nikkan Kogyo Shimbun, 1994). The electroless plating of the present invention is so-called autocatalytic chemical reduction plating in which metal ions such as nickel and copper are reduced and precipitated by a reducing agent, and this precipitation reaction proceeds continuously to form a plating film. Electroless plating using nickel-phosphorus or copper is widely used industrially today, and the present invention is effective for any of them.

  Electroless copper plating includes thin plating baths used for through-hole plating of printed circuit boards and thick plating baths for full additive methods. The former has a thin plating film thickness of 0.1 to 0.3 μm, but is suitable for a case where the bath temperature is low and stable, and electroplating is subsequently performed with an electrically connected pattern. On the other hand, the latter is a high-temperature bath, and the plating film thickness is 10 μm or more, which is suitable for plating an isolated pattern. Any method is possible in the present invention.

  The electroless copper plating solution in the present invention includes a copper source such as copper sulfate and copper chloride, a reducing agent such as formalin, glyoxylic acid, potassium tetrahydroborate, and dimethylamine borane, EDTA, diethylenetriaminepentaacetic acid, Rochelle salt, and glycerol. , Meso-erythritol, adonitol, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 1,3-diaminopropan-2-ol, glycol ether diamine, triisopropanolamine And copper complexing agents such as triethanolamine, and 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 stabilization and plating film smoothness.

  As described above, various complexing agents can be used in electroless copper plating. However, copper oxide is co-deposited depending on the type of complexing agent, 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, and plating solutions using such a preferable complexing agent are, for example, high-temperature types used for 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” (edited by Electroplating Research Group) p105 and the like. In high-temperature type plating, the treatment is usually performed at 50 to 70 ° C., and the treatment time varies depending on whether or not the electrolytic plating treatment is performed after the electroless plating treatment, but usually 1 to 30 minutes, preferably 3 to 20 minutes. By performing the processing, the object of the present invention can be achieved.

  The plating bath may be prepared by itself, but those commercially available from Meltex Co., Ltd., Okuno Pharmaceutical Co., Ltd., etc. are used stably. The plating solution is preferably aerated in order to increase stability.

  In the present invention, prior to the electroless plating treatment, known degreasing treatment and catalyst application treatment as shown below may be performed.

  The degreasing process is a process for washing and removing oil and the like adhering to the substrate, and known processing conditions can be used. In general, an alkaline degreasing agent, a surfactant, an organic solvent, or the like is used, and immersion treatment is performed at 10 to 60 ° C. for 1 to 10 minutes.

  A catalyst provision process is a process which provides catalyst metals, such as palladium, iron, cobalt, nickel, platinum, and palladium is preferable as a specific catalyst metal. An aqueous solution containing these catalytic metal ions is used as the catalyst application treatment liquid. The counter anion is not particularly limited as long as the metal compound is an aqueous solution, and examples thereof include sulfate ions, halogen ions, phosphate ions, and nitrate ions. The catalyst metal is preferably 10 to 5000 mg / L in the aqueous solution, more preferably in the range of 50 to 1000 mg / L. In addition, as a stabilizer in the catalyst application treatment solution, acetic acid, citric acid, lactic acid, tartaric acid, succinic acid, butyric acid, propionic acid, formic acid, succinic acid, glutaric acid, malonic acid, malic acid, fumaric acid, adipic acid, malein An acid or the like may be used. 1-9 are preferable and, as for the pH of a catalyst provision process liquid, More preferably, it is the range of 1-4. The temperature and time for the catalyst application treatment are not particularly limited, but the treatment temperature is preferably 20 to 90 ° C., and the treatment time is preferably 30 to 120 seconds in consideration of production efficiency.

  In the present invention, an electrolytic plating treatment can be performed, but it is preferably performed after the electroless plating treatment in combination with the electroless plating treatment. As the electroplating method, it is preferable to use, for example, a copper plating bath or a copper pyrophosphate bath described in “Plating Technology Guidebook” (Tokyo Sheet Metal Cooperative Technical Committee, edited by 1987) p.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but it is needless to say that the present invention is not limited by this description.

  In order to produce the precursor used in the present invention, a 100 μm-thick polyethylene terephthalate film having an undercoat layer containing vinylidene chloride was used as a transparent support. A backing layer having the following composition was coated on this support.

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

  Subsequently, a silver halide emulsion layer was coated on the side of the support opposite to the backing layer. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared such that silver chloride was 40 mol% and silver bromide 60 mol%, and the average particle size was 0.15 μm. Further, low molecular gelatin having a molecular weight of 10,000 or less was used as a part of the protective binder of the silver halide emulsion so that the low molecular gelatin was removed at the time of water washing removal in the desalting treatment step after mixing. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 1.0 g of gelatin per 1 g of silver (in terms of silver nitrate).

<Silver halide emulsion layer composition (1) per 1 m ² >
Gelatin 1.0g
Silver halide emulsion 1.0g Equivalent to silver 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg
4-Phenylcatechol 500mg

  The conductive material precursor (1) thus obtained was passed through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source, and a transparent original having a mesh pattern with a fine line width of 20 μm and a lattice spacing of 250 μm was prepared. It was exposed in close contact. Subsequently, a curing and developing treatment is performed by immersing in the following cured developer (A) at 20 ° C. for 30 seconds, followed by washing with warm water at 35 ° C., and further at 20 ° C. for 180 seconds with the following fixing solution (A). Treated and then washed with water. When sodium sulfate used for the hardened developer (A) was added to a 5% by weight gelatin aqueous solution having a pH of 3.5 so as to be 0.35 mol / L, gelatin precipitation was observed in all cases.

<Curing developer (A)>
Sodium hydroxide 20g
Sodium sulfate 200g
Potassium bromide 1g
Add water to bring the total volume to 1L.

<Fixing solution (I)>
300g monoethanolamine
Adjust the pH to 10.5 with 5N aqueous sodium hydroxide solution and add water to make the total volume 1L.

  Subsequent to the above treatment, after the degreasing treatment, a catalyst application treatment was conducted, followed by an electroless copper plating treatment. The degreasing treatment was carried out at 60 ° C. for 1 minute by using a cleaner 160 manufactured by Meltex Co., Ltd. so as to be 50 g / L. In addition, the catalyst application treatment was carried out at 25 ° C. for 2 minutes after activating an activator 350 manufactured by the same company so that the concentration of palladium was 100 ppm. For the electroless copper plating, an electroless copper plating manufactured by the same company, Melplate CU-5100 was constructed with a standard dilution and performed at 60 ° C. for 15 minutes to obtain a conductive material (1).

  The total light transmittance of the conductive material (1) thus obtained was measured with a double beam type haze computer manufactured by Suga Test Instruments Co., Ltd. at the portion of the mesh-patterned silver thin film. The surface resistivity was measured using a Lorester GP / ESP probe manufactured by Dia Instruments Co., Ltd. according to JIS-K7194. The results are shown in Table 1. Table 1 shows the result of visual observation of the state of the non-image area. In Table 1, ○ indicates that no copper deposition is observed in the non-image area, Δ indicates slight deposition but no discomfort, and × indicates a level where precipitation is observed and discomfort. .

  The polyethylene terephthalate film having the undercoat layer and the backing layer described in Example 1 was used, and the cured developing agent (4-phenylcatechol) used in Example 1 was removed on the surface opposite to the backing layer. The conductive material precursor (2) was prepared by coating with the following silver halide emulsion layer composition (2).

<Silver halide emulsion layer composition (2) per 1 m ² >
Gelatin 1.0g
Silver halide emulsion 1.0g Equivalent to silver 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg

  Then, the electroconductive material (2) was obtained like Example 1 except having changed the hardening developer (A) used in Example 1 into the following hardening developer (B). The obtained conductive material (2) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Curing developer (B)>
Sodium carbonate 30g
Sodium sulfite 1g
Sodium sulfate 100g
Catechol 2g
Add water to bring the total volume to 1L.

  A conductive material (3) was obtained in the same manner as in Example 2 except that the following fixing solution (b) was used instead of the fixing solution (a) used in Example 2. The obtained conductive material (3) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Fixing solution (b)>
240g sodium thiosulfate
28% acetic acid 48ml
Boric acid 7.5g
Powdered potash alum 15g
Bring the total volume to 1 L with deionized water.

  The conductive material precursor (1) used in Example 1 was exposed and cured and developed with a cured developer (A) in the same manner as in Example 1, and then replaced with the fixer (A). A conductive material (4) was obtained in the same manner as in Example 1 except that the liquid (b) was used. The obtained conductive material (4) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, a conductive material (5) was obtained in the same manner as in Example 1 except that the fixing treatment with the fixing solution (a) was not performed. The obtained conductive material (5) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In Example 3, a conductive material (6) was obtained in the same manner as in Example 3 except that the fixing treatment with the fixing solution (b) was not performed. The obtained conductive material (6) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
In Example 1, a conductive material (7) was obtained in the same manner as in Example 1 except that the following oxidation treatment solution was used instead of the fixation solution (a). The obtained conductive material (7) was evaluated in the same manner as in Example 1. The results are shown in Table 1. The surface resistivity was not measurable because there were many places where the mesh-patterned silver thin film obtained with the treatment with the oxidation treatment solution was partially disconnected or missing.

<Oxidation treatment liquid>
PDTA ferric iron 72g
Potassium bromide 8g
Boric acid 5g
1g of borax
Water was added to make 1L. The pH was adjusted to 6.0.

  From the results in Table 1, by performing a fixing process with a processing agent containing a silver halide solvent between the curing development process and the electroless plating process, the deposition of the metal plated on the non-image area is suppressed, It can also be seen that the conductivity can be improved.

Claims (1)

  In the method for producing a conductive material, a conductive material precursor having at least one silver halide emulsion layer on a support is imagewise exposed and then cured and developed, followed by electroless plating. A method for producing a conductive material, wherein a fixing treatment is performed with a treatment agent containing a silver halide solvent between the treatment and the electroless plating treatment.