JP6018389B2 - Manufacturing method of conductive material - Google Patents

Description

The present invention, electrical circuits, electromagnetic wave shielding material, those concerning the manufacturing how the conductive material can be used in applications such as 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 of 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; 3) A photoresist agent such as a photosensitive resin is provided, 3) a mask having a desired pattern is irradiated with ultraviolet rays, 4) the photoresist agent is cured, 5) an uncured portion is removed, and 6) chemical etching is performed. A method of forming an electric circuit by removing unnecessary conductive material portions (such as a subtractive method) by 1) applying an electroless plating catalyst on a support, 2) applying a photoresist agent, exposure and development 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 2) Applying a photoresist agent, exposing and developing, 3) applying electroplating, forming a conductive pattern, 4) stripping the plating resist, etc. (semi-additive method) ing.

  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, touch panels, etc., and a light transmissive support is used as a support for such a conductive material. 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.

  Various patterns have been introduced regarding the shape of the metal fine wire mesh pattern. In JP-A-10-41682, a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid or other quadrangle, a (positive) hexagon, a (positive) octagon, ( (Positive) Dodecagon, (Positive) N-gonal such as Dodecagon, Circle, Ellipse, Star, etc. are combined, and these units are repeated independently or two or more combinations are disclosed. Has been. Among these patterns, square, rhombus, parallelogram, and regular hexagon patterns are frequently used.

  Usually, the fine line width and film thickness of these metal mesh patterns are generally about 1 to 50 μm and about 1 to 50 μm in consideration of the visibility, conductivity, light transmittance, etc. of the fine metal lines. A thin metal wire that is as uniform as possible is used. 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 that is thinner and thinner. A narrow line width is advantageous in terms of light transmittance and pattern visibility. Moreover, if the thickness of the pattern fine wire is thin, it becomes easy to provide various functional layers such as an adhesive layer and a hard coat layer 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 electroconductive material which has a silver pattern has increased.

  As a method for forming a silver pattern on a support, in addition to the subtractive method, the full additive method and the screen printing method as described above, for example, a silver salt as disclosed in International Publication No. 04/007810 pamphlet A method using a photosensitive silver halide using a chemically developed silver as disclosed in Japanese Patent Application Laid-Open No. 2004-221564 can be used.

  The silver pattern obtained as described above is highly conductive even if the width of the fine line is thin or thin, but if the thickness of the fine line is 0.3 μm or less, There has been a problem that unintentional disconnection may occur during the process, when handling the product, or when using the product. For example, if a metal silver pattern using a silver salt diffusion transfer method is used as the transparent electrode of the touch sensor, an unintended disconnection may occur when the electrodes are bonded together or while being used as a touch sensor. There has been a need for improvement in some cases, such as defective conduction of electrodes, conductive fluctuations within the electrodes, and conductive fluctuations for each electrode.

  On the other hand, migration of silver circuit electric circuit patterns is likely to occur, and as a technique for preventing these, Japanese Patent Application Laid-Open No. 2009-188360 (Patent Document 1) describes benzotriazole, benzotriazole derivatives, and mercapto compounds as metal ion traps. A technique for adsorbing as an agent is disclosed. In addition, as a silver discoloration preventing agent, Japanese Patent Application Laid-Open No. 2007-88218 (Patent Document 2) discloses a technique for preventing discoloration of a metallic silver portion subjected to physical development or plating treatment with an organic mercapto compound. Has been. In the techniques disclosed in these documents, there is a description about prevention of migration and discoloration, but there is no concept or description about unintentional disconnection of the silver image pattern.

JP 2009-188360 A JP 2007-88218 A

Accordingly, an object of the present invention is to provide a conductive frame or manufacturing how the conductive material conductive material conductive frame is improved for each electrode is obtained in the electrode.

The above object of the present invention is achieved by the following invention.
(1) A method for producing a conductive material having an adhesive layer on the surface on the metal pattern side , wherein two or more silver patterns having a film thickness of 0.3 μm or less formed on a support are formed in a molecule. A method for producing a conductive material, comprising treating with a triazine having a mercapto group or a derivative thereof.

The present invention can provide a conductive frame or manufacturing how the conductive material conductive material conductive frame is improved for each electrode is obtained in the electrode.

Electrode patterns used in the examples

  The form of the conductive material obtained by the present invention has a silver pattern on the support. As an example, a light-transmitting conductive material in which silver is drawn in a mesh pattern, an electric circuit in which a wiring portion is drawn with metallic silver, and the like can be given.

  A method for forming a silver pattern on the support will be described. In the present invention, various methods can be used. For example, a printing method, a photolithography method, a silver salt method using photosensitive silver halide, or the like can be used.

  For example, as disclosed in Japanese Patent Application Laid-Open No. 55-91199, metallic silver ink or paste is printed by means such as screen printing and then baked to impart conductivity, or International Publication No. 04/39138. For example, a method of applying a conductive pattern by applying electroless silver plating after printing a resin paint containing an electroless plating catalyst or the like as disclosed in the No. pamphlet 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. 2001/512276 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 unexposed silver halide is dissolved by the silver halide solvent added in the developer to form a silver complex that moves and diffuses to the physical development nucleus layer on the support, where it is reduced by the developing agent. Thus, conductive metallic silver is deposited. Thereafter, the emulsion layer containing chemically developed silver at the exposed site is removed by washing off.

  Among the methods for forming a silver pattern on a support, a method using a silver salt diffusion transfer method capable of easily and stably producing a uniform metal silver thin film pattern of 0.3 μm or less of the present invention is particularly preferred. . If the film thickness of the silver pattern is not uniform, a conductive material having stable performance may not be obtained, and this phenomenon becomes more prominent as the film thickness of the silver pattern becomes thinner.

  The metal silver fine wire pattern produced by a method using a silver salt diffusion transfer system is almost entirely formed of metal 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 thickness of the metal silver is 0.3 μm or less.

  Further, in order to achieve the high transmittance required for sensor electrodes for touch panels and the visibility of low silver patterns, a fine line width pattern of 15 μm or less (for example, a mesh pattern) may be required. Since the silver pattern obtained by the method using the method is uniform and high-definition, it can be easily and stably realized.

  On the other hand, since it is not reinforced with a binder or the like, an unintended disconnection may occur during the manufacturing process, during the handling of the product, or during use as a product. This phenomenon becomes more prominent as the drawn silver pattern becomes thinner.

  The silver salt diffusion transfer method, which is the most preferable method for forming a silver pattern on a support in the method for producing a conductive material and the conductive material of the present invention, will be described in detail below.

  As a typical form, a conductive material precursor having at least a physical development nucleus layer and a silver halide emulsion layer on a support is allowed to act in an alkaline developer containing a soluble silver salt forming agent and a reducing agent. A form in which a silver pattern is formed on a support to produce a conductive material can be mentioned.

  The conductive material precursor has at least a physical development nucleus layer and a silver halide emulsion layer on the support in this order from the side closer to the support. Further, the non-photosensitive layer is the outermost layer farthest from the support and / or an intermediate layer between the physical development nucleus layer and the silver halide emulsion layer, or an undercoat layer between the support and the physical development nucleus layer. You may have as.

As the physical development nuclei contained in the physical development nuclei layer of the conductive material precursor, fine particles (particle size is about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. The fine particle layer of these physical development nuclei can be provided on the support on which the undercoat layer is formed by a coating method or an immersion treatment method. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg per m ^{2 in} terms of solid content.

  The physical development nucleus layer used for the conductive material precursor can also contain a water-soluble polymer compound. When the water-soluble polymer compound is used, the addition amount is preferably about 0 to 500% by mass with respect to the physical development nucleus. Examples of the water-soluble polymer compound include gum arabic, cellulose, sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like.

  The physical development nucleus layer of the conductive material precursor can also contain a crosslinking agent. Examples of the crosslinking agent include inorganic compounds such as chromium alum, aldehydes such as formaldehyde, glyoxal, malealdehyde, and glutaraldehyde, N-methylol compounds such as urea and ethyleneurea, mucochloric acid, and 2,3-dihydroxy. Aldehyde equivalents such as -1,4-dioxane, compounds having an active halogen such as 2,4-dichloro-6-hydroxy-s-triazine salt and 2,4-dihydroxy-6-chloro-triazine salt, Divinyl sulfone, divinyl ketone, N, N, N-triacryloyl hexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups and epoxy groups in the molecule, and dimers as polymer hardeners One or more of various compounds such as aldehyde starch can be used. Among the crosslinking agents, dialdehydes such as glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, and adipaldehyde are preferable, and glutaraldehyde is more preferable. The crosslinking agent is preferably contained in the physical development nucleus layer in an amount of 0.1 to 30% by mass, particularly preferably 1 to 20% by mass, based on the water-soluble polymer compound contained in the physical development nucleus layer.

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

  In the conductive material precursor, 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 silver halide emulsion capable of obtaining the above-described excellent effects by the subexposure of the present invention is a negative type silver halide emulsion.

  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. In the conductive material precursor of the present invention, the preferred silver halide emulsion grains have an average grain size of 0.25 μm or less, particularly preferably 0.05 to 0.2 μm. There is a preferred range for the halide composition of the silver halide emulsion used in the present invention, and it is preferable to contain 80 mol% or more of chloride, particularly preferably 90 mol% or more of 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.

  In the conductive material precursor, a non-photosensitive layer can be provided between the silver halide emulsion layer and the physical development nucleus layer 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, 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 is preferably provided with the above-described undercoat layer or physical development nucleus layer, or an intermediate layer provided as necessary between the physical development nucleus layer and the silver halide emulsion layer, or a support. It 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.

  A method for drawing a silver pattern using the conductive material precursor will be described.

  The exposure of the conductive material precursor will be described. The silver halide emulsion layer of the conductive material precursor is exposed imagewise. As an exposure method, a method of exposing a transmission original having a desired pattern and the silver halide emulsion layer in close contact with each other, or using various laser beams. And a method of scanning exposure of a desired pattern. 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 using a silver salt diffusion transfer developer of a conductive material precursor will be described. The silver halide emulsion layer of the conductive material precursor exposed imagewise as described above undergoes physical development by processing with a silver salt diffusion transfer developer, and has latent image nuclei that can be developed. Silver halide is dissolved in a soluble silver complex salt forming agent to form a silver complex salt, which is reduced on the physical development nuclei to precipitate 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 a layer provided on a physical development nucleus layer such as a silver halide emulsion layer after development, there is a method of removing by washing with water or transferring 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 solution (silver complex diffusion transfer developer) on the silver halide emulsion layer in advance with a roller or the like, and remove the silver halide emulsion layer and the release paper. In this method, the silver halide emulsion layer and the like are transferred from a plastic resin film to a release paper 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.

  A developing solution for silver salt diffusion transfer development used in the development treatment of the conductive material precursor will be described. The developer is an alkaline solution containing a soluble silver complex salt forming agent and a reducing agent. The soluble silver complex salt forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a compound for reducing the soluble silver complex salt to deposit metallic silver on the physical development nucleus. .

  Soluble silver complex forming agents used in the developer include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and sulfites such as sodium sulfite and potassium hydrogen sulfite. Salts, 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. 5,200,294 Thioethers, 5,5-dialkylhydantoins, alkylsulfones, and others described in the specification, “The Theory of the Photographic Process (4th edition, p474-475)”, T. et al. H. Examples include compounds described in James.

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

  The reducing agent used in the developer is a development known in the field of photographic development as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989). The main drug 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 salt forming agent is preferably 0.001 to 5 mol, more preferably 0.005 to 1 mol, per liter of the 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 developer is preferably 10 or more, and 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 developer of the present invention 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 may be a method of immersing or applying the developer. In the dipping method, for example, the exposed conductive material precursor is conveyed while dipped in a large amount of developer stored in a tank, and the coating method is, for example, the developer on the silver halide emulsion layer side. About 40 to 120 ml per square meter. Specific examples of the dipping method include a processing method and a processing apparatus as disclosed in JP-A-2006-190535, but based on non-contact processing of the silver pattern surface of the conductive material. Therefore, it is preferable because disconnection of the silver pattern hardly occurs. 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 method for producing a conductive material of the present invention, the conductive material precursor is developed with a silver salt diffusion transfer developer as described above, and the conductive material on which the silver pattern is drawn has two or more mercapto groups in the molecule. (Hereinafter, referred to as DM treatment).

  The treatment method is not particularly specified. For example, a conductive material on which a silver pattern is drawn is immersed in a solution of triazine or a derivative thereof having two or more mercapto groups in the molecule (hereinafter referred to as a DM treatment solution). And a method of applying a DM treatment liquid to a conductive material on which a silver pattern is drawn. 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.

  Specific examples of the triazine or a derivative thereof containing two or more mercapto groups used in the present invention include, for example, thiocyanuric acid, 2,4-dimercaptotriazine, 2,4-dimercapto-6-dibutylaminotriazine, 2,4 -Dimercapto-6-phenylaminotriazine, 2,4-dimercapto-6-benzyltriazine and the like can be mentioned, but not limited thereto.

  As a solvent for the DM treatment solution, 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 may be used. it can.

  The content of the triazine or derivative thereof containing two or more mercapto groups in the molecule contained in the DM treatment liquid used in the present invention is preferably 0.01 to 20 g, more preferably 0.05 to 5 g. .

  The DM treatment liquid may contain other compounds as necessary. For example, an alkali, an acid, a buffering agent, or the like for adjusting the pH of the DM treatment liquid can be contained. For example, the preferred pH of the DM 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 the DM treatment can be carried out 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 addition, when an adhesive layer is provided on a metal silver image, such as a touch panel sensor that bonds two transparent electrodes or an electromagnetic wave shielding film that is bonded to a window glass, it is not immersed in the DM treatment liquid as described above. However, it is also possible to provide a pressure-sensitive adhesive layer in which triazine having two or more mercapto groups or a derivative thereof is dispersed, and to contact and treat the metal silver.

  In the present invention, as described in Japanese Patent Application Laid-Open No. 2008-34366, post-treatment (hereinafter referred to as “half-width of 2θ = 38.2 °” in the X-ray diffraction method of silver pattern is 0.41 or less) In this case, the DM treatment of the present invention is preferably used in combination.

  Although the post-treatment improves conductivity, disconnection or the like at the time of manufacture or use is more likely to occur, but disconnection can be prevented by using the DM treatment of the present invention in combination. The post-treatment can be performed either before or after the DM treatment of the present invention. However, the post-treatment is performed in the point of preventing a disconnection that may occur during the post-processing step, for example, when the processing apparatus is transported. preferable.

  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. Before the physical development nucleus layer was applied, an undercoat layer containing 500 mg / m ^{2 of} gelatin was applied to the film and dried.

  Next, a palladium sulfide sol solution was prepared as follows, and a physical development nucleus solution was prepared using the obtained sol.

<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.

<Physical development nuclei solution composition / 1 m ² per>
The palladium sulfide sol 0.4mg
0.08 mL of 2% glutaraldehyde solution
10 mass% SP-200 aqueous solution 0.5 mg
(Nippon Shokubai Co., Ltd. polyethyleneimine; average molecular weight 10,000)

This physical development nuclei solution was applied on the undercoat layer so that palladium sulfide was 0.4 mg / m ² in solid content, and dried.

Subsequently, a backing layer having the following composition was applied to the surface opposite to the side on which the physical development nucleus 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 physical development nucleus layer in order from the side closer to the support. The silver halide emulsion was prepared by a general double jet mixing method for 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.

<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 silver mesh pattern portion (conductive portion) a is made of a mesh whose unit figure having a line width of 10 μm and a fine line interval of 300 μm is formed, b is an electrode terminal portion, and c is a non-image portion (nonconductive portion). It is. The exposure amount was such that the mesh fine line width of the conductive material was the same as that of the transparent original.

  Thereafter, the exposed conductive material precursor was immersed in the following developer at 20 ° C. for 60 seconds, and then the silver halide emulsion layer, intermediate layer, outermost layer and backing layer were removed by washing with warm water at 40 ° C. And dried. A conductive material having a silver thin film formed in a mesh pattern was obtained from the exposed sample. 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 exposure mask 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).

<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.
Adjust to pH = 12.2.

  The electrical resistance between the electrode terminals of the conductive material formed with the silver pattern of FIG. 1 obtained as described above was measured with a tester (part b in FIG. 1). The outermost terminal was 1, the innermost terminal was 7, and the electrical resistance between the electrode terminals of terminals 1 to 7 was measured with a tester. These results are shown in Table 1 (before bonding in the table).

  The conductive material on which the silver pattern of FIG. 1 obtained as described above was formed was treated with the following DM treatment liquid at 30 ° C. for 60 seconds. 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.

<DM treatment liquid>
Sodium hydroxide 1.4g
2,4-dimercapto-6-dibutylaminotriazine 0.7 g
Dipotassium hydrogen phosphate 8.3g
85% by mass phosphoric acid 3.7 g
Bring the total volume to 1000 mL with water.

  1 was subjected to a post-treatment at 60 ° C. for 60 seconds using a 3% by mass aqueous sodium chloride 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.

  A transparent adhesive sheet for optics (LUCIACS CS9622T manufactured by Nitto Denko Corporation) is applied to the conductive material having the silver pattern of FIG. The pressure was adjusted while being conveyed at a speed of 1 m per minute, and the laminate was laminated on the silver pattern. At this time, in the silver pattern of FIG. 1, the optical transparent adhesive sheet was bonded so that the terminal portion b was not covered and the lowermost electrode to the uppermost electrode were covered. After the conductive material with the adhesive sheet bonded was stored at 60 ° C. and 90% for 200 hours, the electrical resistance between the electrode terminals of the conductive material was measured with a tester in the same manner as before bonding. These results are shown in Table 1 (after bonding in the table).

(Example 2)
A conductive material was prepared in the same manner as in Example 1 except that 2,4-dimercapto-6-dibutylaminotriazine in the DM treatment liquid was changed to thiocyanuric acid, and evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Example 3)
A conductive material was prepared in the same manner as in Example 1 except that 2,4-dimercapto-6-dibutylaminotriazine in the DM treatment liquid was changed to 2,4-dimercapto-6-phenylaminotriazine. The evaluation was conducted. 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 treatment with the DM treatment liquid 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 1 except that 2,4-dimercapto-6-dibutylaminotriazine in the DM treatment liquid was changed to 2-amino-4,6-dimercaptopyrimidine. The evaluation was conducted. These results are shown in Table 1.

(Comparative Example 3)
A conductive material was prepared in the same manner as in Example 1 except that 2,4-dimercapto-6-dibutylaminotriazine in the DM treatment liquid was changed to 2-mercaptobenzimidazole, and evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 4)
A conductive material was prepared in the same manner as in Example 1 except that 2,4-dimercapto-6-dibutylaminotriazine in the DM treatment liquid was changed to 1-phenyl-5-mercaptotetrazole, and evaluation was performed in the same manner as in Example 1. Carried out. These results are shown in Table 1.

Example 4
In the pattern of FIG. 1, a transparent original having a silver mesh pattern portion (conductive portion) a made of a mesh having a unit width of 15 μm and a fine line interval of 350 μm made of a square mesh was used. The thickness of the silver mesh pattern measured with a confocal microscope (Latertec Corporation, Optics C130) was 0.15 μm. Others were produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 5)
A conductive material was prepared in the same manner as in Example 4 except that the treatment with the DM treatment liquid was not performed, and the evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Example 5)
In the pattern of FIG. 1, a transparent original in which a silver mesh pattern portion (conductive portion) a is a mesh whose unit graphic having a line width of 20 μm and a fine line interval of 400 μm is a square is used. The thickness of the silver mesh pattern measured with a confocal microscope (Latertec Corporation, Optics C130) was 0.15 μm. Others were produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 6)
A conductive material was prepared in the same manner as in Example 5 except that the treatment with the DM treatment liquid was not performed, and the evaluation was performed in the same manner as in Example 1. These results are shown in Table 1.

(Example 6)
A silver pattern was formed in the same manner as in Example 1 except that the composition of the silver halide emulsion layer in Example 1 was changed as follows.
<Silver halide emulsion layer composition / 1m ² per>
Gelatin 1.0g
Silver halide emulsion 10.0g Equivalent to silver 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg

  The thickness of the silver mesh pattern measured with a confocal microscope (Latertec Corporation, Optics C130) was 0.3 μm. Others were subjected to DM treatment and post-treatment in the same manner as in Example 1 to produce a conductive material, and evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 7)
A conductive material was prepared in the same manner as in Example 6 except that the treatment with the DM treatment liquid 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 8)
Using the following plating solution as the conductive material before being treated with the DM treatment liquid of Example 1, electrolytic silver plating was performed under the conditions of a liquid temperature of 25 ° C., a current density of 1 A / dm ² , and a plating time of 2 minutes. A conductive material was prepared. The electrical resistance between the electrode terminals of the pattern of FIG. 1 after plating was measured with a tester. These results are shown in Table 1 (before bonding in the table). The thickness of the mesh pattern after plating measured with a confocal microscope (Latertec Corp., Optics C130) was 0.5 μm. Thereafter, DM treatment, post-treatment, and adhesive sheet bonding were carried out in the same manner as in Example 1. Evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1 (after bonding in the table). The conductive material bonded with the pressure-sensitive adhesive sheet was mixed with air, and when placed on the liquid crystal screen for confirmation, it was an unacceptable level that could be seen without staring.

<Plating solution>
45g potassium cyanide
115g potassium cyanide
Silver Glow 3K 15ml
Silver Glow TY 5ml
Bring the total volume to 1000 mL with water.

  From the results in Table 1, the effectiveness of the present invention can be understood.

As is apparent from the above results, the present invention, the conductivity in the electrode frame, or the conductive frame for each electrode to obtain a preparation how the conductive material improved conductivity material is obtained, Can do.

Producing how the conductive material of the present invention of the present invention, as a method of manufacturing an electromagnetic wave shielding material such as various displays and windows, also can be a promising preparation how the transparent electrodes for various touch panels.

a. Silver mesh pattern part (conductive part)
b. Electrode terminal part c. Non-image part (non-conductive part)

Claims (1)

A method for producing a conductive material having an adhesive layer on the surface on the metal pattern side, wherein a silver pattern with a film thickness of 0.3 μm or less formed on a support has two or more mercapto groups in the molecule A process for producing a conductive material, characterized by treatment with triazine or a derivative thereof.

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