JP6204284B2 - Conductive material - Google Patents

Description

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

  In recent years, the demand for conductive materials has been rapidly increasing in applications such as electric circuits, electromagnetic shielding materials, and touch panels.

  In such a conductive material, for example, a method for forming an electric circuit pattern or the like is as follows: 1) On a support coated with a conductive material such as silver, copper, gold, ITO, or tin oxide; A photoresist agent such as a resin is provided, 3) a mask having a desired pattern is irradiated and irradiated with ultraviolet rays, 4) the photoresist agent is cured, 5) an uncured portion is removed, and 6) chemical etching, etc. A method of forming an electric circuit by removing an unnecessary conductive material portion (subtractive method) by 1), applying an electroless plating catalyst on a support, 2) applying a photoresist agent, exposing and developing. 3) Electroless plating is performed to form a conductive pattern, 4) A method of removing the plating resist (full additive method), or 1) An electroless plating catalyst is provided on the support, and electroless plating is performed. 2) Application of a photoresist agent, exposure and development, 3) electroplating, formation of a conductive pattern, and 4) a method of removing a plating resist or the like (semi-additive method). .

  In addition, as a simple manufacturing method, a metal paste is printed on a support by a screen printing method or an ink jet printing method, and a method of forming an electric circuit pattern by sintering or supporting a paste having an electroless plating catalyst. A method is known in which an electric circuit pattern is formed by printing on a body by a screen printing method, an ink jet printing method, or the like, and performing electroless plating.

  Light transmittance is required as the performance of conductive materials used in electromagnetic shielding materials and touch panels. In this case, a thin metal wire is formed in a mesh pattern, for example, on the light transmissive support, and a high light transmittance is maintained by adjusting the line width and pitch of the fine metal wire, and further the pattern shape, etc. It is known to impart electrical conductivity. Normally, the fine line width and film thickness of these metal mesh patterns are generally about 1 to 50 μm and the fine line width is 1 to 50 μm in consideration of the difficult visibility, light transmission, and conductivity of the fine metal lines. A thin metal wire that is as uniform as possible is used with a film thickness of the order. The pitch is set to about 100 to 1000 μm. The fine line width and pitch of the metal mesh pattern are appropriately adjusted according to each application.

  Among metals forming an electric circuit or a mesh pattern, silver has the highest conductivity. Therefore, compared to other metals, high conductivity can be obtained with a thin wire having a narrower line width and a thinner film thickness. If the line width is narrow, it is possible to reduce the size of the electric circuit, and it is advantageous in terms of light transmittance and difficult pattern visibility. Further, if the thin wire is thin, various functional layers such as an adhesive layer and a hard coat layer can be easily provided on the pattern. For example, when a pressure-sensitive adhesive layer is provided on the surface of the metal pattern, such as a touch sensor that bonds two electrodes together or an electromagnetic wave shielding film that is bonded to a window glass, etc., the thinner the metal pattern, the more mixed air Since there are few and it is easy to bond uniformly, it is a big advantage that the thickness of a pattern is thin. Therefore, the expectation for the electrically conductive material which has the silver patterning layer formed of the thin wire containing silver has increased.

  As a method for forming a silver patterning layer on a support, in addition to the subtractive method, the full additive method and the screen printing method as described above, for example, silver as disclosed in International Publication No. 04/007810 pamphlet. Methods using photosensitive silver halide are also known, such as a method using a salt diffusion transfer method and a method using chemically developed silver as disclosed in JP-A-2004-221564.

  As described above, the use of a silver patterning layer has many advantages, but it has also been found that there are various problems. For example, since ion migration is likely to occur in silver, when the electronic circuit is driven for a long time, the dielectric breakdown between the electrodes may occur due to the movement of silver ions. As countermeasures, for example, JP-A-1-319202 (Patent Document 1) uses an example of using a zirconium phosphate compound, JP-A-2009-188360 (Patent Document 2), and JP-A-2013-12597. An example using a mercapto compound is proposed as a solution in Japanese Patent Publication (Patent Document 3). In addition, there is a problem that fluctuation of resistance value or disconnection occurs due to the manufacturing process of the pattern or its storage, and for this, a mercaptotriazine compound is used in JP2013-19679A (Patent Document 4). A solution that had been proposed.

  In recent years, especially when a conductive material is used for a touch panel, examples of mobile use and the like have been dramatically increased. For these applications, the stability of the resistance value is more severe than before, that is, for example, at higher temperatures and higher humidity. In addition, in order to impart high light transmittance to the conductive pattern, it is necessary to narrow the fine line width. However, since the resistance value increases when the narrow line width is narrowed, the minimum necessary thin line width is selected in order to ensure the necessary conductivity. There is a case where the quality required for the product is not satisfied even if it rises to about twice, and improvement has been demanded.

JP-A-1-319202 JP 2009-188360 A JP2013-125797A JP 2013-196679 A

  An object of the present invention is to provide a conductive material having improved resistance variation due to storage over time.

The aforementioned problems of the present invention are achieved by the following invention.
(1) An undercoat layer containing a polymer compound having an amino group on a support, and silver patterning treated on the undercoat layer with at least one compound represented by the following general formula (1) A conductive material having a layer.

  In the formula, Z represents an atomic group necessary for forming an oxazole ring or an oxadiazole ring together with the carbon atom, oxygen atom and nitrogen atom of the compound of the general formula (1).

  According to the present invention, it is possible to provide a conductive material in which a variation in resistance value due to storage over time is improved.

Electrode patterns used in the examples

  As an example of the form of the conductive material obtained by the present invention, a light-transmitting conductive material having a silver patterning layer in which metallic silver is drawn in a mesh pattern, or an electric circuit having a silver patterning layer in which wiring portions are drawn with metallic silver Etc.

  As the support of the conductive material of the present invention, plastic, glass, rubber, ceramics and the like are preferably used. In the present invention, the support is preferably a light-transmitting support having a total light transmittance of 60% or more. Among plastics, a resin film having flexibility is preferably used in terms of excellent handleability. Specific examples of the resin film used as the light transmissive support include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, Examples of the resin film include acetate resin, triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, and cyclic polyolefin resin. It is preferable that it is 300 micrometers. The support may have a known layer such as an easy adhesion layer.

  The undercoat layer provided on the support in the conductive material of the present invention contains a polymer compound having an amino group. Examples of the polymer compound having an amino group include aminated cellulose, polyethyleneimine, polyallylamine, polydiallylamine, and allylamine described in Chapter 2.6.4 of “Polymer chemical reaction” (Nobuo Okawara, 1972, Chemical Dojinsha). Copolymer of diallylamine and diallylamine, copolymer of diallylamine and maleic anhydride, copolymer of diallylamine and sulfur dioxide, aminoalkyl esters of acrylic acid and methacrylic acid dimethylaminoethyl ester and aminoethyl ester Polymer compounds such as coalescence, proteins such as gelatin, albumin, casein, and polyzine, and mucopolysaccharides typified by hyaluronic acid can be mentioned, and any compound can be used in the present invention. Among these, polyethyleneimine capable of obtaining a high amino group content and aminoalkyl esters of acrylic acid and methacrylic acid are preferably used.

  The undercoat layer of the conductive material of the present invention can contain a polymer compound having no amino group in addition to the polymer compound having an amino group described above. Examples of the polymer compound having no amino group include polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid. The polymer compound may be a polymer latex, and various known latexes such as a homopolymer and a copolymer can be used. Examples of the homopolymer include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene polymer. Examples of the copolymer include ethylene / butadiene copolymer and styrene / butadiene copolymer. Polymer, 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, methyl methacrylate / styrene copolymer, methyl methacrylate / vinyl acetate copolymer, methyl methacrylate / vinylidene chloride copolymer, methyl acrylate / acrylonitrile copolymer, methyl acrylate / Tadiene copolymer, methyl acrylate / styrene copolymer, methyl acrylate / vinyl acetate copolymer, acrylic acid / butyl acrylate copolymer, methyl acrylate / vinyl chloride copolymer, butyl acrylate / styrene copolymer, polyether Urethane, polyester urethane, polycarbonate urethane and the like.

The content of the polymer compound having an amino group in the present invention is preferably 10 to 500 mg / ^{m 2,} more preferably from 20 to 100 mg / ^{m 2.} The proportion of the polymer compound having an amino group in the undercoat layer is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total solid content of the undercoat layer.

  The undercoat layer used in the present invention preferably further contains a crosslinking agent in addition to the components described above. Examples of the crosslinking agent contained in the undercoat layer include inorganic compounds such as chromium alum, aldehydes such as formaldehyde, glyoxal, malealdehyde, and glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, Aldehyde equivalents such as 2,3-dihydroxy-1,4-dioxane, activities such as 2,4-dichloro-6-hydroxy-s-triazine salts and 2,4-dihydroxy-6-chloro-triazine salts Halogen-containing compounds, divinyl sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups, and having two or more epoxy groups in the molecule Compounds such as sorbitol polyglycidyl ether and polyglycerol Liglycidyl ether, Diglycerol polyglycidyl ether, Glycerol polyglycidyl ether, Polyethylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, etc. Other than these, "Polymer chemical reaction" (Nobuyoshi Okawara 1972, Chemical Dojinsha) Known polymer cross-linking agents such as the cross-linking agents described in 2.6.7, 5.2, 9.3 and the like can also be contained. Of these, compounds having two or more epoxy groups in the molecule are preferred.

  The amount of the crosslinking agent contained in the undercoat layer used in the present invention is preferably an amount that does not bind and react with all the amino groups of the polymer compound having an amino group. In the case of binding reaction with all, the desired effect of the present invention may not be obtained. The amino group that has not undergone a binding reaction is preferably 20 mol% or more, more preferably 50 mol% or more, based on the number of amino groups before addition of the crosslinking agent.

  In the undercoat layer used in the present invention, as necessary, as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) Known additives can also be included.

  The undercoat 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.

  Next, a method for forming a silver patterning layer on the undercoat layer will be described. Various methods can be used as a method for forming the silver patterning layer. For example, a printing method, a photolithography method, a silver salt method using photosensitive silver halide, or the like can be used.

  The printing method includes, for example, a method in which metallic silver ink or paste is printed by means such as screen printing, as disclosed in Japanese Patent Application Laid-Open No. 55-91199, and then fired to impart conductivity. For example, a method of printing a resin paint containing an electroless plating catalyst or the like, and applying electroless silver plating to give a conductive pattern, as disclosed in Japanese Patent Publication No. 04/39138, can be used.

  The photolithographic method is a subtractive method in which a photoresist is coated on a support having a uniform metal silver layer, and after exposure and development, the metal silver layer from which the resist has been peeled is removed by etching to obtain a conductive pattern. A resist containing an electroless plating catalyst as disclosed in JP-A-11-170421 is coated on a substrate, exposed and developed to remove unexposed portions of the resist, and then electroless silver-plated. It is possible to use an additive method for obtaining a conductive pattern.

  The silver salt system using photosensitive silver halide is disclosed in International Publication No. 04/007810 pamphlet, Japanese Patent Application Laid-Open No. 2003-77350, Japanese Patent Application Laid-Open No. 2005-250169, and Japanese Patent Application Laid-Open No. 2007-188655. And those using chemically developed silver as disclosed in International Publication No. 01/51276 pamphlet and Japanese Patent Application Laid-Open No. 2004-221564 can be used. The method using chemically developed silver is to make conductive by applying electroless plating with chemically developed silver, which is formed by reducing the silver halide at the exposed site by the developing agent present in the developer, as the catalyst core. It is.

  The method using the silver salt diffusion transfer method is called a physical development nucleus layer on a support, a catalyst nucleus layer for the silver complex to be reduced by a developing agent to become metallic silver, and a silver halide emulsion layer thereon. The provided material is used (the silver halide photographic emulsion layer may be coated on another support). In the development process, a compound (silver halide solvent) that dissolves silver halide is allowed to act in addition to the developing agent. When this material is exposed and developed, when a negative-type silver halide emulsion is used, the silver halide in the exposed portion is converted into chemically developed silver and remains in the silver halide emulsion layer. On the other hand, the silver halide in the unexposed area is dissolved by the silver halide solvent added in the developer and becomes a silver complex that moves and diffuses to the physical development nucleus layer on the support, where it is reduced by the developing agent. As a result, conductive metallic silver is deposited. Thereafter, the emulsion layer containing the chemically developed silver at the exposed portion is removed by washing and removing, which will be described later, or a method of transferring and peeling to a release paper.

  Among the methods of forming a silver pattern on the undercoat layer, it is possible to easily and stably produce a uniform silver patterning layer having a fine wire thickness of preferably 1.0 μm or less, more preferably 0.3 μm or less. A method using a silver salt diffusion transfer method is particularly preferred. Moreover, most of the silver patterning layer produced by the method using the silver salt diffusion transfer method is formed only of metallic silver and is not reinforced with a binder or the like. This is very preferable from the viewpoint of conductivity, and extremely high conductivity can be obtained even if the metal silver is thin. Furthermore, a thin line width of 15 μm or less may be required to achieve the high transmittance required for sensor electrodes for touch panels and the low visibility of a silver pattern, but it is obtained by a method using a silver salt diffusion transfer method. The silver pattern is suitable because a uniform and high-definition image can be obtained.

  In the conductive material of the present invention, the silver salt diffusion transfer method, which is the most preferable method for forming a silver patterning layer on the undercoat layer, will be described in detail below.

  The conductive material precursor used in the silver salt diffusion transfer system is at least an undercoat layer containing a polymer compound having at least an amino group and a physical development nucleus on a support, and a silver halide emulsion layer from the side closer to the support. Have in this order. The conductive material precursor further has an intermediate layer between the silver halide emulsion layer and the subbing layer containing the non-photosensitive layer, the outermost layer farthest from the support and / or the physical development nucleus. May be. When such a conductive material precursor is exposed according to a required pattern and then allowed to act in an alkaline developer containing a soluble silver complex forming agent and a reducing agent, a silver patterning layer is formed on the undercoat layer. It is formed.

As the physical development nucleus contained in the undercoat layer together with the polymer compound having an amino group, fine particles (particle size is about 1 to several tens of nm) made of heavy metal or sulfide thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. The content of physical development nuclei is suitably about 0.1 to 10 mg per 1 m ^{2 in} terms of solid content.

  In the conductive material precursor described above, a silver halide emulsion layer is provided 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 be used as they are.

  The formation of silver halide emulsion grains used in the silver halide emulsion layer is performed by Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (forward mixing, reverse mixing, simultaneous mixing, etc.). (December 1989) can be 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. The average grain size of preferable silver halide emulsion grains is 0.25 μm or less, particularly preferably 0.05 to 0.2 μm. Moreover, there exists a preferable range in the halide composition, it is preferable to contain 80 mol% or more of chloride, and 90 mol% or more is particularly preferably chloride.

  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 forming silver halide grains or physical ripening as 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. In the conductive material precursor used in the present invention, the silver halide emulsion can be dye-sensitized as necessary.

The ratio of the amount of silver halide and the amount of gelatin contained in the silver halide emulsion layer is such that the mass ratio of silver halide (silver equivalent) to gelatin (silver / gelatin) is 1.2 or more, more preferably 1. 5 or more. The amount of silver halide contained in the silver halide emulsion layer is preferably ² to 10 g / m ² in terms of silver.

  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.

  As described above, the conductive material precursor can be provided with a non-light-sensitive layer between the silver halide emulsion layer and the undercoat layer containing physical development nuclei or on the silver halide emulsion layer. These non-photosensitive layers are layers containing a water-soluble polymer compound as a main binder. As the water-soluble polymer compound mentioned here, any compound can be selected as long as it easily swells with the developer and allows the developer to easily penetrate into the lower silver halide emulsion layer and the physical development nucleus layer.

  Specifically, gelatin, albumin, casein, polyvinyl alcohol, or the like can be used. Particularly preferred water-soluble polymer compounds are proteins such as gelatin, albumin and casein. In order to sufficiently obtain the effects of the present invention, the amount of the binder in the non-photosensitive layer is preferably in the range of 20 to 100% by mass, particularly 30 to 80% by mass, based on the total amount of binder in the silver halide emulsion layer. % Is preferred.

  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 included. Further, the film can be hardened with a crosslinking agent as long as the peeling of the silver halide emulsion layer after the treatment is not prevented.

As the conductive material precursor, a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer is preferably used as a halation for improving image quality or as an irradiation inhibitor. As the antihalation agent, preferably provided as an undercoat layer containing the above-mentioned physical development nuclei, or an intermediate layer provided between the undercoat layer and the silver halide emulsion layer, or a support. Can be contained in the backing layer. 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, it is preferably in the range of about 20 mg to about 1 g per m ² , preferably The absorbance at the maximum absorption wavelength is 0.5 or more.

  The exposure for drawing a silver pattern on the conductive material precursor will be described. The silver halide emulsion layer of the conductive material precursor is exposed imagewise, and as an exposure method, there are various methods such as a method in which a transparent original having a desired pattern and the surface having the silver halide emulsion layer are in close contact with each other. There is a method of scanning exposure of a desired pattern using laser light. 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.

  A development process of the exposed conductive material precursor will be described. The silver halide emulsion layer of the conductive material precursor exposed imagewise as described above is processed in an alkali developer (silver salt diffusion transfer developer) containing a soluble silver complex-forming agent and an alkali agent. Silver halide that has physical development and does not have developable latent image nuclei is dissolved by a soluble silver complex-forming agent to form a silver complex, which is reduced on the physical development nuclei in the undercoat layer to form metallic silver. For example, a silver thin film having a mesh pattern can be obtained. On the other hand, silver halide having latent image nuclei that can be developed by exposure is chemically developed in the silver halide emulsion layer to become blackened silver. After development, unnecessary silver halide emulsion layers (including blackened silver), intermediate layers, protective layers and the like are removed, and a silver thin film is exposed on the surface.

  As a method for removing the silver halide emulsion layer and the like after the development processing, there are a method of removing by washing or transferring and peeling to a release paper. There are two methods for removing the water washing: a method of removing hot water using a scrubbing roller or the like while jetting it with a nozzle or the like, and a method of removing hot water by jetting with a nozzle or the like. In addition, the method of transferring and peeling with a release paper or the like is to squeeze the excess alkali developer on the silver halide emulsion layer with a roller or the like in advance, and the silver halide emulsion layer or the like and the release paper are brought into close contact with each other. Is transferred to a release paper from a plastic resin film and peeled off. 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.

  The soluble silver complex forming agent contained in the silver salt diffusion transfer developer is a compound that dissolves silver halide to form a soluble silver complex, and the reducing agent reduces the soluble silver complex to form a metal on the physical development nucleus. It is a compound for precipitating silver.

  Soluble silver complex forming agents contained in the silver salt diffusion transfer developer include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sodium sulfite and potassium bisulfite. Sulfites such as oxazolidones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, US Pat. No. 200,294, thioethers, 5,5-dialkylhydantoins, alkyl sulfones, and other “The Theory of the Photographic Process (4th edition, p474-475)”, T. et al. H. Examples include compounds described in James.

  These soluble silver complex forming agents can be used alone or in combination.

  The reducing agent contained in the silver salt diffusion transfer developer is used in the field of photographic development as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989). A known developing agent can be used. For example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, ascorbic acid and its derivatives, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1- Examples include 3-pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, and the like. These reducing agents can be used alone or in combination.

  The content of the soluble silver complex forming agent is preferably 0.001 to 5 mol, more preferably 0.005 to 1 mol, per liter of the silver salt diffusion transfer developer. The content of the reducing agent is preferably from 0.01 to 1 mol, more preferably from 0.05 to 1 mol, per liter of the developer.

  The pH of the silver salt diffusion transfer developer is preferably 10 or more, more preferably 11-14. In order to adjust to a desired pH, an alkali agent such as sodium hydroxide or potassium hydroxide, or a buffering agent such as phosphoric acid or carbonic acid is contained alone or in combination. The silver salt diffusion transfer developer preferably contains a preservative such as sodium sulfite or potassium sulfite.

  The application of the developer for diffusion transfer development of the conductive material precursor described above may be a method of immersing the developer or a method of coating. In the dipping method, for example, the exposed conductive material precursor is conveyed while dipping in a developer stored in a large amount in a tank. In the coating method, for example, the developer is applied to the silver halide emulsion layer side. About 40 to 120 mL is applied per square meter. Specific examples of the dipping method include a treatment method and a treatment apparatus as disclosed in JP-A-2006-190535. The method described in this publication is preferable because the surface of the conductive material on the side where the silver patterning layer is provided is basically transported in a non-contact manner, so that the silver pattern is not easily broken. The application temperature of the developer is preferably 2 to 30 ° C, more preferably 10 to 25 ° C. The application time of the developer is suitably about 20 seconds to 3 minutes. This embodiment is particularly suitable in the case of the immersion method.

  In the present invention, the silver patterning layer preferably has a mesh pattern as the conductive portion. In the present invention, the mesh pattern means a pattern having a geometric shape in which a plurality of unit lattices are arranged in a mesh shape. Examples of the shape of the unit lattice include triangles such as regular triangles, isosceles triangles, right triangles, Examples include squares, rectangles, rhombuses, parallelograms, trapezoids and other quadrangles, hexagons, octagons, dodecagons, decagons and other n-gons, and combinations of stars, etc. Or a combination of two or more shapes. Among them, the shape of the unit cell is preferably a square or a rhombus. Irregular geometric shapes represented by Voronoi graphics, Delaunay graphics, pen tile graphics, etc. are also one of the preferred mesh mesh patterns in the present invention.

  The line width of the fine lines constituting the mesh pattern is preferably 1 to 50 μm, more preferably 2 to 20 μm. Moreover, it is preferable that the repeating space | interval of the unit cell which comprises a mesh pattern is 100-1000 micrometers, More preferably, it is 100-600 micrometers.

  Next, the compound represented by the general formula (1) for treating the silver patterning layer in the present invention will be described.

  In the formula, Z represents an atomic group necessary for forming an oxazole ring or an oxadiazole ring together with the carbon atom, oxygen atom and nitrogen atom of the compound of the general formula (1). The oxazole ring may be condensed with a benzene ring or a naphthalene ring to form a benzoxazole ring or a naphthoxazole ring. The oxazole ring, oxadiazole ring, benzoxazole ring and naphthoxazole ring may have a substituent. As the substituent, carbon such as methyl group, ethyl group, isopropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-decyl group, n-hexadecyl group, isohexadecyl group, etc. Alkyl groups such as alkyl groups, phenyl groups, naphthyl groups, etc., acetyl groups, butyryl groups, isobutyryl groups, isohexadesilyl groups, benzoyl groups, etc., alkyloxy groups such as methoxy groups, ethoxy groups, etc. Group, an alkylthio group such as a methylthio group, an ethylthio group and an n-pentylthio group, and an aryloxy group such as a phenoxy group. These substituents are further methyl group, ethyl group, isopropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-decyl group, n-hexadecyl group, isohexadecyl group. Alkyl groups having 1 to 20 carbon atoms such as, aryl groups such as phenyl groups and naphthyl groups, acyl groups such as acetyl groups, butyryl groups, isobutyryl groups, isohexadesilyl groups, benzoyl groups, methoxy groups, ethoxy groups, etc. An alkyloxy group such as an alkyloxy group, a methylthio group, an ethylthio group or an n-pentylthio group, or an aryloxy group such as a phenoxy group may be used as a substituent.

  In the present invention, the silver patterning layer is treated with the compound represented by the general formula (1) (hereinafter referred to as MC treatment).

  The MC treatment method is not particularly defined. For example, a method of immersing a conductive material in which a silver patterning layer is formed in a solution containing a compound represented by the general formula (1) (hereinafter referred to as MC treatment solution) And a method of applying an MC treatment liquid to a conductive material on which a silver patterning layer is formed. The treatment temperature is preferably 10 to 50 ° C, more preferably 20 to 40 ° C. The treatment time is preferably 10 seconds or longer, more preferably 30 seconds or longer. The upper limit of the processing time is preferably within 10 minutes.

  Specific examples of the compound represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto.

  As the solvent contained in the MC treatment liquid, for example, water, alcohols such as ethanol, ketones such as acetone, ethers such as tetrahydrofuran, methyl cellosolve, N, N-dimethylformamide, dimethyl sulfoxide and the like are used. be able to.

  The amount of the compound represented by the general formula (1) contained in the MC treatment liquid is preferably 0.01 to 20 g, more preferably 0.05 to 5 g, per liter.

  The aforementioned MC treatment liquid can contain other compounds as necessary. For example, an alkali, an acid, a buffering agent, or the like for adjusting the pH of the MC treatment solution can be contained. For example, the preferred pH of the MC treatment liquid when water is used as a solvent is 8 or more. Furthermore, antifoaming agents, preservatives, enzymes, surfactants and the like can also be contained. Drying after MC treatment can be performed by any method such as using warm air from a film dryer. It can also be washed with tap water or pure water before drying.

  In the present invention, a peak of 2θ = 38.2 ° in the X-ray diffraction method of a silver pattern using a water-soluble halogen compound as described in JP-A-2008-34366 is used for the MC treatment of the present invention. When post-treatment with a half-value width of 0.41 or less is used in combination, it is possible to further reduce the resistance value variation with time required by the present invention. The treatment may be performed before or after the MC treatment, but is preferably performed after.

  The post-treatment used for setting the half width of the peak at 2θ = 38.2 ° in the X-ray diffraction method of the silver pattern to 0.41 or less includes (I) a reducing substance, and (II) a water-soluble phosphorus oxo. A method of immersing a conductive material in which a silver patterning layer is formed in a post-treatment liquid containing either an acid compound or (III) a water-soluble halogen compound, or a conductive material in which a silver patterning layer is formed (I) to (I) to Examples thereof include a method of applying a post-treatment liquid containing the compound (III).

  As the reducing substance (I), 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.

  (II) Examples of water-soluble phosphorus oxoacid compounds include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid and the like, and salts thereof, and ester compounds of these phosphorus oxoacids Is mentioned. The solubility of these water-soluble phosphorus oxoacid compounds in water at 25 ° C. is at least 0.1% by mass, preferably 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. Of the ester. 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.

  (III) 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, and a halide in an aqueous solution. Any compound that can release ions can be used. Specific examples of these water-soluble halogen compounds include hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid and other hydroacids, chlorides such as sodium chloride, ammonium chloride and rubidium chloride, sodium bromide, Various inorganic halides such as bromides such as potassium bromide and lithium bromide, iodides such as sodium iodide, fluorides such as sodium fluoride and potassium fluoride, and amines such as dimethylamine hydrochloride and trimethylamine bromide Examples thereof include salts, benzalkonium chloride, 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.

  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.

Example 1
As a support, a polyethylene terephthalate film having a total light transmittance of 90% and a thickness of 100 μm, which was subjected to easy adhesion processing with a layer containing vinylidene chloride, was used.

  Next, physical development nuclei (palladium sulfide sol) were prepared according to the following formulation, an undercoat layer coating solution containing the physical development nuclei was prepared, applied onto the support and dried to provide an undercoat layer. Thereafter, the mixture was heated at 50 ° C. for 1 day.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40mL
Distilled water 1000mL
B liquid sodium sulfide 8.6g
Distilled water 1000mL
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. The following undercoat layer coating solution 1 was prepared using this palladium sulfide sol.

<Undercoat layer coating liquid 1> per 1 m ^{2 of the} palladium sulfide sol 0.4 mg
0.2% aqueous 2 mass% glyoxal solution
Surfactant (S-1) 4mg
Denacol EX-830 5mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
10 mass% SP-200 aqueous solution 0.5g
(Nippon Shokubai polyethyleneimine)

Subsequently, a backing layer having the following composition was applied to the surface opposite to the side where the undercoat layer was applied.
<Undercoat 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

  Subsequently, an intermediate layer, a silver halide emulsion layer, and an outermost layer having the following composition were coated on the undercoat layer in order from the side closer to the support. The silver halide emulsion was prepared by the double jet mixing method common to photographic silver halide emulsions. This silver halide emulsion was prepared with 95 mol% of silver chloride and 5 mol% of silver bromide, and an average grain size of 0.15 μm. 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 0.5 g of gelatin per gram of silver. The amount of the amino group of polyethyleneimine contained in the undercoat layer is estimated to be 90.3% or more with respect to the molar ratio before the bonding reaction with the crosslinking agent.

<Intermediate layer composition / per 1 m ² >
Gelatin 0.5g
Surfactant (S-1) 5mg

<Silver halide emulsion layer composition / 1m ² per>
Gelatin 1.0g
Silver halide emulsion 6.0g silver equivalent 1-phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg

<Outermost layer composition / per 1 m ² >
1g of gelatin
Amorphous silica matting agent (average particle size 3.5μm) 10mg
Surfactant (S-1) 10mg

  The conductive material precursor thus obtained was exposed by closely contacting a transparent original having the pattern of FIG. 1 with a contact printer using a mercury lamp as a light source. In the pattern of FIG. 1, the mesh pattern portion (conductive portion) a is made of a square mesh with a unit figure having a fine line width of 10 μm and a fine line interval of 300 μm, b is an electrode terminal portion, and c is a non-image portion (non-conductive portion). is there. The exposure amount was such that the thin line width of the conductive material obtained after development was the same as the thin line width of the transparent original.

  Thereafter, the exposed conductive material precursor was immersed in a silver salt diffusion transfer developer having the following composition at 20 ° C. for 60 seconds, and then the silver halide emulsion layer, the intermediate layer, the outermost layer and the backing layer were heated to 40 ° C. It was washed with warm water and dried. When the fine line width and pitch of the obtained silver pattern image of FIG. 1 were confirmed with an optical microscope, the fine line width and pitch of the transparent original were reproduced. Moreover, it was 0.15 micrometer when the film thickness of the thin wire | line part was investigated with the confocal microscope (Lasertec company make, Optics C130).

<Silver salt diffusion transfer developer composition>
Potassium hydroxide 40g
Hydroquinone 28g
1-phenyl-3-pyrazolidone 3g
125g potassium sulfite
24g of N-methylethanolamine
Potassium bromide 2g
Bring the total volume to 1000 mL with water.

  The conductive material on which the silver patterning layer having the pattern shape of FIG. 1 obtained as described above was formed was treated with the following MC treatment solution at 30 ° C. for 60 seconds (MC treatment). Thereafter, it was washed with warm water at 35 ° C. for 30 seconds and dried with warm air at 60 ° C. for 2 minutes using a film dryer.

<MC treatment solution>
Sodium hydroxide 4.0g
Compound M1 0.7g
Dipotassium hydrogen phosphate 2.5g
Bring the total volume to 1000 mL with water.
The pH was 12.

  The electrical resistance between the electrode terminals of the outermost terminals of the conductive material on which the pattern of FIG. 1 obtained as described above was formed was measured with a tester (part b in FIG. 1). These results are shown in Table 1 (before aging in Table 1).

  The conductive material having the pattern shown in FIG. 1 formed as described above was stored under conditions of 85 ° C. and 85% RH for up to 200 hours. During this time, the electrical resistance between the electrode terminals of the conductive material was measured with a tester at 16 hours, 38 hours, and 200 hours. These results are shown in Table 1.

(Example 2)
The conductive material having the pattern shown in FIG. 1 after the MC treatment in Example 1 was subjected to a post treatment at 60 ° C. for 60 seconds using a 10% sodium chloride aqueous solution. Thereafter, it was washed with warm water at 35 ° C. for 30 seconds and dried with warm air at 60 ° C. for 2 minutes using a film dryer. Thereafter, the treatment and evaluation after the MC treatment were carried out in the same manner as in Example 1. These results are shown in Table 1.

(Examples 3 to 5)
A conductive material was prepared in the same manner as in Example 2 except that the compound M1 used in the MC treatment liquid was changed to the compound M4, compound M13, and compound M16, and evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Example 6)
In Example 1, the 10 mass% SP-200 aqueous solution contained in the undercoat layer coating solution 1 was changed to 0.17 g of 30 mass% Acryt UW-223SX (Taisei Fine Chemical Co., Ltd. alkylamino-modified polyacrylic acid) Produced a conductive material in the same manner as in Example 2, and evaluated in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 1)
A conductive material was prepared in the same manner as in Example 1 except that the MC treatment was not performed, and the evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 2)
A conductive material was prepared in the same manner as in Example 2 except that the MC treatment was not performed, and evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Examples 3-5)
A conductive material was prepared in the same manner as in Example 2 except that the compound M1 used in the MC treatment liquid was changed to the following compound RM1, compound RM2, and compound RM3, and evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 6)
A conductive material 2 was prepared using an undercoat layer coating liquid 2 having the following formulation as an undercoat layer, and a conductive material of Comparative Example 3 was prepared in the same manner as in Example 2 except that this was used. Evaluation was carried out in the same manner as above. These results are shown in Table 1.

<Preparation of undercoat layer coating solution 2> per 1 m ^{2 of the} palladium sulfide sol 0.4 mg
0.2% aqueous 2 mass% glyoxal solution
Surfactant (S-1) 4mg
Denacol EX-830 50mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
10% by mass PVA117 aqueous solution 0.5g
(Kuraray polyvinyl alcohol)

  As is clear from the results in Table 1, a conductive material with improved conductivity variation can be obtained according to the present invention.

  The conductive material of the present invention of the present invention can be a promising material as an electromagnetic shielding material for various displays and windows, and as a light transmissive electrode for various touch panels.

a. Mesh pattern part b. Electrode terminal part c. Non-image part

Claims (1)

An undercoat layer containing a polymer compound having an amino group on a support, and a silver patterning layer treated with at least one compound represented by the following general formula (1) on the undercoat layer Conductive material.

(In the formula, Z represents an atomic group necessary to form an oxazole ring or an oxadiazole ring together with the carbon atom, oxygen atom, and nitrogen atom of the compound of the general formula (1).)

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