TW201345352A - Method for producing conductive material, and conductive material - Google Patents

Abstract

The present invention provides a method for producing conductive material, which proceeds with a processing to conductive material including a supporting body formed thereon a silver pattern with a film thickness smaller than 0.3 μm by using triazine with more than two mercapto groups in molecule or its derivatives, and also provides conductive material obtained by the producing method. With the present invention, it is able to provide the method for producing conductive material as follows. That is, it is able to obtain conductive material with which unsatisfactory conductivity of the electrode is alleviated and conductive deviation of each electrode is mitigated. In addition, it also provides conductive material for solving the aforementioned problems.

Description

Method for producing conductive material and conductive material

The present invention relates to a method for producing a conductive material and a conductive material which can be used in applications such as circuits, electromagnetic wave shielding materials, and touch panels.

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

Among such conductive materials, for example, as a method of forming a circuit pattern or the like, the following methods and the like are known. One method is as follows: 1) on a support coated with a conductive material such as silver, copper, gold, ITO or tin oxide; 2) providing a photosensitive layer containing a photoresist such as a photosensitive resin, 3) The photosensitive layer is covered with a mask of a desired pattern to irradiate ultraviolet rays or the like, 4) curing the photoresist, 5) removing the uncured portion of the photosensitive layer, and 6) exposing the conductivity due to chemical etching or the like. The material is partially removed to form a circuit (subtractive method). One method is as follows: 1) adding an electroless plating catalyst to the support, 2) applying a photoresist on the electroless plating catalyst to provide a photosensitive layer, and removing the photosensitive layer of the uncured portion after exposure and development, 3 The electroless plating of the exposed electroless plating catalyst is electrolessly plated to form a conductive pattern, and 4) the photosensitive layer (plating resist) of the cured portion is removed (full additive method). One method is as follows: 1) adding an electroless plating catalyst to the support, performing electroless plating, 2) applying a photoresist to provide a photosensitive layer, and removing the photosensitive layer of the uncured portion after exposure and development, 3) The exposed electroless plating portion is plated to form a conductive pattern, and 4) the photosensitive layer (plating resist) of the cured portion is removed or removed (semi-additive method).

Further, as a simple manufacturing method for forming a circuit pattern or the like, the following is known The metal paste is printed on the support by a screen printing method, an inkjet printing method, or the like, and then heated to sinter the binder component or the like contained in the metal paste. Further, there has been known a method in which a paste containing an electroless plating catalyst is printed on a support by a screen printing method, an inkjet printing method, or the like, and then electroless plating is performed.

For conductive materials used in electromagnetic wave shielding materials, touch panels, etc., The light transmittance is high. As a support of such a conductive material, a light-transmitting support is used. In this case, it is known that, by forming a fine metal wire into a mesh pattern on the light-transmitting support, adjusting the line width or pitch of the metal thin wires, the shape of the pattern, and the like, it is possible to maintain high light transmittance while maintaining high light transmittance. Gives high conductivity.

Regarding the shape of the fine mesh pattern of the metal, various patterns have been introduced. Japanese special Japanese Patent Publication No. Hei 10-41682 discloses a pattern of a triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or the like, an equilateral triangle, an isosceles triangle, or the like, and a (square) hexagonal shape. It is a pattern of a combination of an octagonal shape, a (positive) dodecagonal shape, a (positive) octagonal shape, a (negative) n-angle, a circle, an ellipse, a star, etc., and is a single repetition of these units or two or more types. Combination pattern. Among these patterns, a square, a rhombus, a parallelogram, and a regular hexagon are often used.

Generally speaking, for the metal thin lines of these metal mesh patterns, metal is considered. As the visibility, conductivity, light transmittance, and the like of the fine line, a metal thin wire having a line width of about 1 to 50 μm and a film thickness of about 1 to 50 μm is used as uniformly as possible. For the pitch, set it to about 100~1000μm. The fine line width or pitch of the metal mesh pattern is appropriately adjusted according to the respective uses.

Among the metals forming the circuit or the mesh pattern, since silver has the highest conductivity, it is possible to obtain high conductivity by using a thin wire having a smaller width and a thinner film thickness than other metals. If the line width is small, it is advantageous in terms of light transmittance or visibility of the pattern (difficult to recognize). In addition, if the thickness of the pattern thin line is thin, various functionalities such as an adhesive layer or a hard coat layer are easily obtained. The layer is placed on the pattern. For example, in a touch sensor in which two electrodes are bonded together, or an electromagnetic wave shielding film or the like bonded to a window glass or the like, an adhesive layer is provided on a surface on the side of the metal pattern. In this case, the thinner the thickness of the metal pattern, the less the air is mixed by the unevenness, and it is easy to bond uniformly. Thus, the thinness of the metal pattern is a large advantage. As such, there is an increasing expectation for a conductive material having a silver pattern.

As a method of forming a silver pattern on a support, there is a subtractive method as described above, Full additive method and screen printing method. Further, for example, the use of a silver salt diffusion transfer method as disclosed in the pamphlet of International Publication No. 04/007810, and the use of chemically developed silver as disclosed in Japanese Laid-Open Patent Publication No. 2004-221564 can be used. A method of photosensitive silver halide.

On the other hand, a circuit pattern formed using a silver pattern is liable to cause migration. As A technique for adsorbing benzotriazole, a benzotriazole derivative, or a fluorenyl compound as a metal ion trapping agent is disclosed in Japanese Laid-Open Patent Publication No. 2009-188360 (Patent Document 1). In the case of the silver-based anti-tarnishing agent, it is disclosed in JP-A-2007-88218 (Patent Document 2) that the metal silver obtained by subjecting the metal silver portion to physical development or plating treatment is prevented by the organic fluorenyl compound. Discoloration technology.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-188360

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-88218

The silver pattern obtained as described above can obtain high conductivity even if the width of the thin line is small or the thickness is small, but in the case where the film thickness of the thin line is, for example, 0.3 μm or less, in the manufacturing step or the disposal of the product. Or accidental disconnection sometimes occurs when the product is used. For example, if a transparent silver electrode used as a touch sensor uses a metallic silver pattern obtained by a silver salt diffusion transfer method, when the electrodes are bonded together or as a touch sensor In the middle of use, unexpected disconnection sometimes occurs. As a result, there is a case where conduction failure of the electrodes or variation in conductivity of each electrode occurs, and improvement is desired. In Patent Documents 1 and 2, there is a description about prevention of migration or discoloration, but there is no concept or description of an unexpected disconnection of a silver image pattern.

An object of the present invention is to provide a method for producing a conductive material, which can A conductive material which improves the conduction failure of the electrode and the deviation of the conductivity of each electrode is obtained, and a conductive material which improves these problems is also provided.

The above problems of the present invention can be achieved by the following invention.

(1) A method for producing a conductive material, comprising the step of using a conductive material having a support and a silver pattern having a film thickness of 0.3 μm or less formed thereon, and having three or more thiol groups in the molecule (triazine) or a derivative thereof is treated.

(2) The method for producing a conductive material according to the above aspect, wherein the silver pattern has a line width of 20 μm or less.

(3) The method for producing a conductive material according to the above (1) or (2), wherein the silver pattern is a silver pattern obtained by a method using a silver salt diffusion transfer method.

(4) The method for producing a conductive material according to any one of the above aspects, further comprising the step of performing a post-treatment of 2 θ in the X-ray diffraction method of the silver pattern. The half value width of the peak of 38.2° was set to 0.41 or less.

(5) A conductive material obtained by the method for producing a conductive material according to any one of the above (1) to (4).

According to the present invention, it is possible to provide a method for producing a conductive material, and it is possible to obtain a conductive material which is improved in conduction failure of an electrode and variation in conductivity of each electrode even if the film thickness of the metal pattern is thin, and an improvement can be provided. Conductive materials for these problems.

a‧‧‧Silver mesh pattern (conducting part)

b‧‧‧Electrode terminal

c‧‧‧Non-image section (non-conductive part)

Fig. 1 is an electrode pattern used in the embodiment.

The conductive material obtained by the present invention has a support and a silver pattern formed thereon. Examples of the conductive material include a light-transmitting conductive material in which silver is drawn in a mesh pattern on a support, and a circuit made of a conductive material in which a wiring portion is drawn with metallic silver.

Examples of the support used in the present invention include a film composed of various resins, various glasses, paper, nonwoven fabric, cloth, various metals, various ceramics, and the like. As various resins, polyethylene can be cited. Polyolefin resin such as polypropylene, polyvinyl chloride. Vinyl chloride resin such as vinyl chloride copolymer, epoxy resin, polyarylate, polyfluorene, polyether oxime, polyimide, fluororesin, phenoxy resin, triethylene fluorene cellulose, polyterephthalic acid Acrylic resins such as ethylene glycol, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, glass paper, nylon, polystyrene resin, ABS resin, and the like. Examples of various glasses include quartz glass, alkali-free glass, crystallized transparent glass, and Pyrex (registered trademark).

When the conductive material of the present invention is a light-transmitting conductive material, the support used is preferably a light-transmitting support. The total light transmittance of the light-transmitting support is preferably 80% or more, more preferably 85% or more. Examples of the light-transmitting support include a film composed of the above various resins and various types of glass.

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

For example, as disclosed in JP-A-55-91199, a metal silver ink or a paste is printed by a method such as screen printing, and is contained in order to impart conductivity. A method of firing a binder component, and a method of imparting a conductive pattern by electroless plating of silver after printing a resin coating material containing an electroless plating catalyst, etc., as disclosed in the pamphlet of International Publication No. 04/39138.

In the lithography method, the following manner may be used, that is, the subtraction method, After applying a photoresist on a support having a uniform metallic silver layer, exposing and developing, a metal silver layer exposed by peeling off the photoresist is etched away to obtain a conductive pattern; and, as in Japanese Patent Laid-Open No. 11-170421 In the additive method disclosed in the publication, a photoresist containing an electroless plating catalyst is applied onto a substrate, exposed, developed, and the photoresist of the unexposed portion is removed, and then the exposed electroless plating catalyst portion is rendered non-ferrous. Silver is electroplated to obtain a conductive pattern.

As a silver salt method using photosensitive silver halide, it can be used like International Publications The use of the silver salt diffusion transfer method and the like, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The use of chemically developed silver as disclosed in Japanese Laid-Open Patent Publication No. 2001/51276 and Japanese Laid-Open Patent Publication No. 2004-221564.

The way to use chemically developed silver is as follows, that is, it can be exposed The silver halide in the portion is made of a chemically-developed silver (silver pattern) reduced by a developing agent present in the developer as a catalyst core, and electroless plating is applied to the chemically-developed silver portion to make conductivity.

The method of using the silver salt diffusion transfer method is as follows, that is, using a support, a catalyst core layer (referred to as a physical development core layer) for reducing a silver complex by a development main agent to become metallic silver, and a material of a silver halide emulsion layer formed on the upper layer thereof . Moreover, the silver halide emulsion layer can also be applied to other supports. Exposure was carried out using the above materials, followed by development treatment. At the time of development processing, a developing solution containing a compound (silver halide solvent) in which silver halide is dissolved in addition to the developing main agent acts. When the material is exposed and developed, when the silver halide emulsion layer contains negative silver halide emulsion particles, the silver halide emulsion particles in the exposed portion are reduced to chemically developed silver and remain in the silver halide emulsion layer. On the other hand, the silver halide emulsion particles in the unexposed portion are dissolved in the silver halide solvent in the developing solution to become a silver complex. The silver complex moves and diffuses to the physical development core layer on the support, and is deposited by the development main agent in the developer to precipitate conductive metal silver. That is, development processing The subsequent silver halide emulsion layer has a silver halide emulsion layer containing chemically developed silver at an exposed portion, and a silver halide emulsion layer after diffusion of silver halide in an unexposed portion. Thereafter, the silver halide emulsion layer after the development treatment is removed by scouring to expose conductive metallic silver. Further, the silver halide emulsion layer after development treatment does not actually contain silver halide emulsion particles, but in the present invention, it is referred to as a silver halide emulsion layer for convenience.

Among the methods of forming a silver pattern on a support, it can be easily and stably It is preferable to use a silver salt diffusion transfer method in order to produce a uniform metallic silver thin film pattern having a film thickness of 0.3 μm or less. The silver pattern produced by the silver salt diffusion transfer method is substantially only patterned by metallic silver. Thereby, a uniform silver pattern having a film thickness of 0.3 μm or less can be easily and stably produced. In addition, high conductivity can be obtained even if the film thickness is as thin as 0.3 μm or less. If the film thickness of the silver pattern is not uniform, there is a case where a conductive material which cannot obtain stable performance is obtained, and the thinner the film thickness of the silver pattern, the more obvious the phenomenon.

For example, a touch sensor that bonds two electrodes together, and is attached to a window glass, etc. When an adhesive layer is provided on the surface of the metal pattern on the electromagnetic wave shielding film or the like, the thinner the thickness of the metal pattern, the less the air is mixed by the unevenness, and the easier it is to bond uniformly. Therefore, the film thickness of the silver pattern in the conductive material of the present invention is preferably 0.3 μm or less. In order to achieve the high light transmittance and the low visibility of the silver pattern required for the sensor electrode of the touch panel or the like, it is preferable to use a line width of 1 to 50 μm and a pitch of 100 to 1000 μm. Thin line patterns (such as mesh patterns). In the present invention, the line width of the silver pattern is preferably 20 μm or less. The silver pattern obtained by the method using the silver salt diffusion transfer method is uniform and high in fineness. Therefore, the silver salt diffusion transfer method is suitable for a case where a fine line pattern having a line width of 20 μm or less, more preferably 15 μm or less is required.

On the other hand, the silver pattern obtained by the method using the silver salt diffusion transfer method is Since it is not reinforced with a binder or the like, unexpected disconnection may occur in the manufacturing step, in the disposal of the product, or as the product is being used. The thinner the thickness of the silver pattern drawn, Then the phenomenon is more obvious.

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

Method for forming a silver pattern on a support by a silver salt diffusion transfer method A typical embodiment of the present invention is to apply a developer containing a soluble silver salt forming agent and a reducing agent to at least a support, a physical development core layer formed thereon, and a silver halide emulsion layer formed thereon. A conductive material precursor forms a silver pattern on the support. Further, the form in which the silver pattern is formed on the support is a conductive material before the DM treatment as described in detail below.

The conductive material precursor used in the present invention has at least a support and is formed on A physical development core layer thereon, and a silver halide emulsion layer formed thereon. The support of the conductive material precursor is a support of the conductive material of the present invention. The conductive material precursor may also have a layer containing gelatin or the like as an undercoat layer between the support and the physical development core layer. In addition, the conductive material precursor may also have a non-photosensitive layer as the outermost layer from the support, and/or an intermediate layer between the physical development core layer and the silver halide emulsion layer, or a support and a physical development core layer. The undercoat layer between. Further, the conductive material precursor may have a back coat layer on the other surface side of the support in which the physical development core layer or the like is not provided.

The physical development core layer of the conductive material precursor contains a physical development core. As the physical development nucleus, fine particles composed of a heavy metal or a sulfide thereof (having a particle size of about 1 to several tens of nm) are used. Specific examples of the physical development nucleus include a metal colloid such as gold or silver, or a metal sulfide obtained by mixing a water-soluble metal salt such as palladium or zinc with a sulfide. The physical development core layer containing these physical development nuclei can be provided on the support by a coating method or an immersion treatment method. An undercoat layer may also be provided on the support. From the viewpoint of production efficiency, it is preferred to use a coating method. The content of the physical development nucleus in the physical development core layer is suitably about 0.1 to 10 mg per 1 m ² in terms of solid content.

The physical development core layer of the conductive material precursor may also contain water soluble high scores Sub-compound. The amount of addition of the water-soluble polymer compound is preferably from about 0 to about 500% by mass based on the amount of the physical development core. As the water-soluble polymer compound, gum arabic, cellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polypropylene decylamine, a copolymer of acrylamide and vinylimidazole, or the like can be used. .

The physical development core layer of the conductive material precursor may also contain a crosslinking agent. As the crosslinking agent, for example, an inorganic compound such as chrome alum, formaldehyde, a monoaldehyde such as acrolein, glyoxal, malealdehyde, glutaraldehyde, 3-methylglutaraldehyde, or succinaldehyde can be used. N-hydroxymethyl compounds such as dialdehydes such as adipaldehyde, urea or ethylene urea, chloric acid, 2,3-dihydroxy-1,4-di Aldehyde equivalents such as alkanes, 2,4-dichloro-6-hydroxy-s-three Salt, 2,4-dihydroxy-6-chloro-three An active halogen compound such as a salt, divinyl fluorene, divinyl ketone, N, N, N-tripropylene decyl hexahydro three One or more kinds of various compounds such as a compound having two or more active three-membered ring of ethyleneimine group and/or epoxy group in the molecule, and a dialdehyde starch as a polymer hardener . Among the crosslinking agents, dialdehydes such as glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, and adipaldehyde are preferred, and a more preferred crosslinking agent is glutaraldehyde. The amount of the crosslinking agent in the physical development core layer is preferably from 0.1 to 30% by mass, particularly preferably from 1 to 20% by mass, based on the amount of the water-soluble polymer compound contained in the physical development core layer.

In the above coating method, the physical development core layer can be coated, for example, by dip coating or slope coating. Coating by coating, spray coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, etc.

The above conductive material precursor has a silver halide emulsion layer as a photo sensor. halogen The silver emulsion layer contains a silver halide emulsion. The silver halide emulsion is an emulsion in which silver halide grains are suspended in an aqueous gelatin solution. The technique used in the silver salt photo film, the printing paper, the film for printing plate, the emulsion mask for photomask, and the like, which are related to silver halide, can also be used as it is in the present invention. Moreover, the silver halide emulsion contained in the silver halide emulsion layer of the present invention is not necessarily negatively photosensitive, according to If necessary, it may be set as a direct reversal emulsion having positive photosensitivity. The direct reversal emulsion can be produced by the method described in Japanese Patent Publication No. Hei 8-17120, and the Japanese Patent Publication No. Hei 8-202041.

When forming silver halide grains contained in the silver halide emulsion layer, it is possible to use A well-known method as described in Research Disclosure Item 17643 (December 1978), 18716 (November 1979), and 308119 (December 1989), such as mixing, reverse mixing, and simultaneous mixing. Among them, from the viewpoint of obtaining silver halide particles having a uniform particle diameter, it is preferable to use a so-called double-control (controlled double jet) in which one type of the simultaneous mixing method is used and the pAg in the liquid phase in which the particles are formed is kept constant. law. In the conductive material precursor of the present invention, the preferred silver halide particles have an average particle diameter of 0.25 μm or less, more preferably 0.05 to 0.2 μm. The halide composition of the silver halide emulsion used in the present invention preferably contains 80 mol% or more of chloride, more preferably 90 mol% or more of chloride.

In the manufacture of a silver halide emulsion, it may also be in the form of silver halide particles as needed In the process of physical or physical ripening, a sulfite, a lead salt, a phosphonium salt, a phosphonium salt or a salt thereof, a phosphonium salt or a salt thereof, and a salt of a metal element of a Group VIII or a salt thereof are allowed to coexist. In addition, silver halide emulsions can also be sensitized using various chemical sensitizers. As the sensitization method, a method generally known in the art such as a sulfur sensitization method, a selenium sensitization method, a noble metal sensitization method, or the like can be used singly or in combination. Further, the silver halide emulsion can also be dye-sensitized as needed.

The ratio of the amount of silver halide to the amount of gelatin contained in the silver halide emulsion layer is preferably 1.2 or more, more preferably 1.5 or more, in mass ratio (silver/gelatin) of silver halide (in terms of silver) to gelatin. Further, 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, well-known photographs may also be included for various purposes. Use additives. These additives are described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989), or in the cited documents.

The conductive material precursor may be in the silver halide emulsion layer and the physical development core layer The upper layer of the interlayer, and/or silver halide emulsion layer has a non-photosensitive layer. These non-photosensitive layers are layers in which a water-soluble polymer compound is used as a main binder. Here, the term "a water-soluble polymer compound as a main binder" means that a non-photosensitive layer contains 50 to 100% by mass of a water-soluble polymer compound as a binder. The water-soluble polymer compound as described herein can be selected as long as it is a compound which is easily swelled by a developing solution and can easily permeate the non-photosensitive layer from the non-photosensitive layer to the lower silver halide emulsion layer and the physical development nucleus layer. compound of.

Specific examples of the water-soluble polymer compound which is a non-photosensitive layer include Proteins such as gelatin, albumin and casein, and polyvinyl alcohol. More preferred water-soluble polymer compounds are proteins such as gelatin, albumin, and casein. In order to sufficiently obtain the effect of the present invention, the total amount of the binder of the non-photosensitive layer is preferably from 20 to 100% by mass, particularly preferably from 30 to 80% by mass, based on the total amount of the binder of the silver halide emulsion layer.

In these non-photosensitive layers, as needed, can contain like Research Known photographic additives as described in Disclosure Item 17643 (December 1978), 18716 (November 1979), and 308119 (December 1989). Further, the non-photosensitive layer may be hardened by a crosslinking agent as long as it does not interfere with the peeling of the silver halide emulsion layer after the treatment.

The conductive material precursor is preferably a non-sensitizing dye or pigment containing a maximum absorption in the photosensitive wavelength region of the silver halide emulsion layer as an anti-smoothing agent or a light-proofing agent for improving image quality. The non-sensitizing dye or pigment as the anti-corona agent may preferably be provided in the above-mentioned undercoat layer or physical development core layer, or as an intermediate layer between the physical development core layer and the silver halide emulsion layer, or It is contained in the back coat layer that is sandwiched by the support. The non-sensitizing dye or pigment as a light-proofing agent is preferably contained in the silver halide emulsion layer. The amount of addition of the non-sensitizing dye or pigment can be varied over a wide range as long as the target effect can be obtained. For example, when it is contained in the back coat layer as an antifogging agent, it is preferably in the range of about 20 mg to about 1 g per 1 m ² , and preferably the absorbance at the maximum absorption wavelength is 0.5 or more.

A method of drawing a silver pattern using the above-described conductive material precursor will be described.

The exposure of the conductive material precursor will be described. Conductive material precursor The silver halide emulsion layer is exposed as an image (e.g., the mesh pattern). As the exposure method, there is a method of exposing a transmissive original of a desired pattern to a silver halide emulsion layer, or a method of scanning and exposing a desired pattern using various types of laser light. In the above method of exposing by laser light, for example, a blue semiconductor laser having an excitation wavelength of 400 to 430 nm (also referred to as a violet laser diode) can be used.

Development of a conductive material precursor by means of a silver salt diffusion transfer developer Let me explain. The following physical development occurs when the silver halide emulsion layer of the conductive material precursor exposed as described above is treated with a silver salt diffusion transfer developer. In the case where a negative-sensitivity silver halide emulsion is used as an example, the silver halide of the halogenated emulsion layer of the exposed portion has a latent image core which can be developed by exposure. On the other hand, the silver halide of the halogenated emulsion layer of the unexposed portion does not have a latent image core which can be developed. The silver halide of the unexposed portion which does not have a latent image core which can be developed is dissolved by a soluble silver stear salt forming agent in the developer to become a silver salt. The silver salt is reduced on the physical development nucleus to precipitate metallic silver, and for example, a silver film of a mesh pattern can be obtained. On the other hand, silver halide having a latent image core which can be developed by exposure is chemically developed in a silver halide emulsion layer to become blackened silver. After the development, the silver halide emulsion layer (blackened silver is also contained therein) which is no longer required, the intermediate layer, the protective layer, and the like are removed, and a silver thin film is exposed on the surface.

a silver halide emulsion layer or the like after development processing, which is provided on a layer on the physical development core layer The removal method is a method in which water is removed by washing or peeling off onto a release paper or the like. The method of removing water while jetting a warm water jet using a scrubbing roller or the like, and the method of removing the warm water by a nozzle or the like while removing the water by the impulsive force of the water. The method of performing transfer peeling by a release paper or the like is a method in which an excess developer on a silver halide emulsion layer is previously extruded by a roll or the like, and a silver halide emulsion layer or the like is adhered to the release paper to form a silver halide. Emulsion layer, etc. The release paper was transferred from the support to the release paper and peeled off. As the release paper, a water-absorbent paper or nonwoven fabric, or a paper using a particulate pigment such as cerium oxide and a binder such as polyvinyl alcohol may be used as the material of the water-absorbent void layer.

Silver salt diffusion to be used in development processing of the above-mentioned conductive material precursor The developer developed by printing will be described. The developer is an alkali solution containing a soluble silver salt-forming agent and a reducing agent. The soluble silver salt-forming agent is a compound that dissolves silver halide to form a soluble silver salt. The reducing agent is a compound for reducing soluble silver mis-salt and precipitating metallic silver on a physical development nucleus.

Examples of the soluble silver stear salt forming agent used in the developing solution include thiosulfate such as sodium thiosulfate and ammonium thiosulfate, thiocyanate such as sodium thiocyanate and ammonium thiocyanate, Sulfite such as sodium sulfite and potassium hydrogen sulfite, a oxazolidinone 2-mercaptobenzoic acid and a derivative thereof, a cyclic quinone imine such as uracil, an alkanolamine, a diamine, a ionic compound described in JP-A-9-171257, and the United States Sulfides, 5,5-dialkylhydantoin, alkyl hydrazines, and "The Theory of the photographic Process (4th edition, p474~475)", as described in the specification of Japanese Patent No. 5,200,294, The compound described by THJames.

These soluble silver salt-forming agents may be used singly or in combination of plural kinds. use.

The reducing agent used in the developer can be used like Research Disclosure A developing main agent known in the field of photo development as described in Item 17643 (December 1978), 18716 (November 1979), and 308119 (December 1989). Specific examples of the reducing agent include polyhydroxybenzenes such as hydroquinone, catechol, gallic phenol, methylhydroquinone, and chlorinated hydroquinone, ascorbic acid and derivatives thereof, and 1-phenyl-4,4. 3-pyridyl-3-pyrazolone, 1-phenyl-3-pyrazolone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone, etc. Oxazolines, p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, p-phenylenediamine, and the like. These reducing agents may be used singly or in combination of plural kinds.

The content of the soluble silver salt-forming agent is preferably in every 1 L of the developer. 0.001~5 moles, more preferably 0.005~1 moles. The content of the reducing agent is preferably from 0.01 to 1 mol, more preferably from 0.05 to 1 mol, per 1 L of the developer.

The pH of the developer is preferably 10 or more, more preferably 11 to 14. In order to adjust to The desired pH may contain an alkali agent such as sodium hydroxide or potassium hydroxide or a buffer such as phosphoric acid or carbonic acid in the developer alone or in combination. Further, the developer of the present invention preferably contains a preservative such as sodium sulfite or potassium sulfite.

The developer for diffusing and developing the above-mentioned conductive material precursor The method may be a method of immersing a conductive material precursor in a developing solution or a method of applying a developing solution to a conductive material precursor. The immersion method is, for example, a method in which a conductive material precursor stored in a can is immersed in a large amount of the developer, and the exposed conductive material precursor is immersed. The coating method is, for example, a method of applying a developer to the silver halide emulsion layer side at about 40 to 120 ml per square meter. As a specific method of the immersion method, a treatment method and a treatment apparatus as disclosed in JP-A-2006-190535 can be cited. Since the immersion method is based on the non-contact treatment of the silver pattern surface of the conductive material, it is preferable that the silver pattern is not easily broken. The use temperature of the developer is preferably 2 to 30 ° C, more preferably 10 to 25 ° C. The developer usage time is suitably from about 20 seconds to about 3 minutes. This method is particularly suitable for the case of the dipping method.

The method for producing a conductive material according to the present invention includes the step of using a conductive material having a support and a silver pattern formed thereon as described above, and having three or more sulfhydryl groups in the molecule. Or its derivatives are processed. Hereinafter, it will also be utilized in the presence of two or more thiol groups in the molecule. The treatment of conductive materials by their derivatives or their derivatives is referred to as DM treatment.

The method of DM treatment is not particularly limited, and for example, a conductive material having a silver pattern is immersed in a molecule containing two or more sulfhydryl groups in the molecule. A method in a treatment liquid of a derivative thereof (hereinafter also referred to as a DM treatment liquid), a method of applying a DM treatment liquid onto a conductive material having a silver pattern, or the like. The treatment temperature is preferably from 10 to 50 ° C, more preferably from 20 to 40 ° C. The treatment time is preferably 10 seconds or more, more preferably 30 seconds or more.

As the three containing two or more mercapto groups used in the present invention Specific examples of the derivative thereof or a derivative thereof include, for example, a trimeric thiocyanate and a 2,4-didecyl group. 2,4-dimercapto-6-dibutylamino three 2,4-dimercapto-6-phenylamino three 2,4-dimercapto-6-benzyl three Etc. However, it is not limited to them.

As a solvent of the DM treatment liquid, for example, an alcohol such as water or ethanol can be used. An ketone such as a ketone or an ether such as tetrahydrofuran, an arbitrary substance such as methyl sarbuta, N,N-dimethylformamide or dimethyl hydrazine, or a combination thereof.

Three of DM treatment liquids containing two or more sulfhydryl groups in the molecule The content of the derivative or the derivative thereof is preferably from 0.01 to 20 g, more preferably from 0.05 to 5 g, per 1 liter of the DM treatment liquid.

The DM treatment liquid may contain other compounds as needed. example For example, an alkali or an acid, a buffer, or the like for adjusting the pH of the DM treatment liquid may be contained. For example, a preferred pH of the DM treatment liquid when water is used as a solvent is 8 or more. Further, the DM treatment liquid may further contain an antifoaming agent, a preservative, an enzyme, a surfactant, and the like. The drying of the conductive material after the DM treatment can be carried out by any method such as warm air using a film dryer. It is also possible to wash with tap water or pure water before drying.

In addition, in the case where an adhesive layer is provided on the metallic silver pattern like a touch panel sensor in which two transparent electrodes are bonded together or an electromagnetic wave shielding film attached to the window glass, the above may not be used. The conductive material is impregnated into the DM treatment liquid, but three having two or more sulfhydryl groups are dispersed. The adhesive layer of the derivative or its derivative is placed on the conductive material and brought into contact with the metallic silver for treatment. This aspect is also included in the use of three or more thiol groups in the molecule. Or a derivative thereof in the step of treating the electrically conductive material.

The method for producing a conductive material of the present invention may further comprise performing a silver pattern In the X-ray diffraction method, the half value width of the peak of 2θ=38.2° is set to 0.41 or less (hereinafter also referred to as post-processing). Such post-processing is described, for example, in JP-A-2008-34366. In the newspaper. The contents of Japanese Laid-Open Patent Publication No. 2008-34366 are hereby incorporated by reference.

More specifically, the post-treatment is performed by using a phosphorus-containing phosphorus selected from a reducing substance. The post-treatment liquid of at least one of the oxyacid compound and the water-soluble halogen compound treats the conductive material.

As the reducing substance, a developing main agent well known in the field of photo development can be used. They are described in Research Disclosure Item 17643 (December 1978), 18716 (November 1979), and 308119 (December 1989), or in the cited documents. Specific examples of the reducing substance include polyhydric hydroxybenzenes such as hydroquinone, hydroquinone monosulphonate, catechol, gallic phenol, methylhydroquinone, and chlorinated hydroquinone, ascorbic acid and derivatives thereof, and 1- Phenyl-4,4-dimethyl-3-pyrazolone, 1-phenyl-3-pyrazolone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazole 3-pyrazolone such as morpholinone, aminoaminophenol such as p-methylaminophenol, p-aminophenol or p-hydroxyphenylglycine, polyaminobenzene such as p-phenylenediamine, or hydroxylamine Classes, etc. Among them, ascorbic acid is preferred from the viewpoint of high water solubility and low harmfulness. These reducing substances are preferably used as an aqueous solution of at least 1% by mass or more, preferably 5 to 30% by mass.

Examples of the water-soluble phosphorus oxyacid compound include phosphorus oxyacids such as phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, and hexametaphosphoric acid, and salts thereof, and ester compounds of these phosphorus oxyacids. . The solubility of the water-soluble phosphorus oxyacid compound with respect to water at 25 ° C is at least 0.1% by mass or more, preferably 1% by mass or more. Specific examples of the water-soluble phosphorus oxyacid compound include phosphates such as monosodium phosphate, monopotassium phosphate, and disodium phosphate, hypophosphites such as sodium hypophosphite, pyrophosphates such as disodium dihydrogen pyrophosphate, and trimerization. An ester of a water-soluble phosphorus oxyacid compound such as various known water-soluble phosphorus oxyacid compounds, polyoxyethylene alkyl ether phosphates, alkyl phosphates, and the like, such as phosphates and hexametaphosphates. Among them, inorganic water-soluble phosphorus oxyacid compounds and phosphates are preferred. These water-soluble phosphorus oxyacid compounds are preferably used as an aqueous solution of at least 5% by mass or more, preferably 10 to 30% by mass.

For the halogen used as the water-soluble halogen compound, it may be fluorine, chlorine, bromine or iodine. Meaning one. The water-soluble halogen compound can be used as long as it has a solubility of at least 0.1% by mass or more with respect to water at 25° C. and is a compound capable of releasing a halide ion in an aqueous solution. Specific examples of the water-soluble halogen compound include hydrogen acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid or hydrofluoric acid, chlorides such as sodium chloride, ammonium chloride and barium chloride, sodium bromide and potassium bromide. And various kinds of inorganic halides such as bromide such as lithium bromide and iodide such as sodium iodide, fluorides such as sodium fluoride and potassium fluoride; amine salts such as dimethylamine hydrochloride and trimethylamine bromate; Alginamide, alkylpyridinium hydrochloride, imidazolium hydrochloride, polyallylamine hydrochloride, diallyldimethylammonium chloride polymer, and the like. Among them, preferred are compounds which can liberate chloride ions in an aqueous solution. Among them, water-soluble inorganic chlorides such as sodium chloride and potassium chloride are preferred. These water-soluble halogen compounds are preferably used as an aqueous solution of at least 1% by mass or more, preferably 5 to 30% by mass.

a reducing substance, water-soluble as a component of the post-treatment liquid used in the present invention The phosphorus oxyacid compound or the water-soluble halogen compound may be used singly or in combination with a plurality of the same kinds of components such as a reducing substance and other reducing substances, or a reducing substance and a water-soluble halogen may be used. Other types of components such as compounds are used in combination. Among them, a water-soluble halogen compound having high efficiency of use of the post-treatment liquid, storage stability of the post-treatment liquid, and high treatment stability is preferable. The higher the temperature of the post-treatment, the better, but if it is not used below the Tg of the substance used as the support of the conductive material, the conductive material will elongate or break during the treatment, so at a temperature below Tg Process it. The preferred treatment temperature is preferably 30 ° C or higher when a water-soluble halogen compound is used, and preferably 40 ° C or higher when using other materials, whichever is better. The treatment is carried out at 50 to 70 ° C, more preferably at 60 to 70 ° C. Although the processing time depends on the composition of the post-treatment, by processing for 10 seconds or more, preferably for 30 seconds to 3 minutes, the half-value width of 2 θ = 38.2 ° in the X-ray diffraction can be set as Good range. As the treatment method, a immersion treatment, a method of applying a post-treatment liquid by spraying, a coating, or the like can be used. From the viewpoint of stability of temperature and crystallization of components of the post-treatment liquid, it is preferred to be impregnated Reason. Further, it is preferred to carry out a water washing treatment after the post-treatment, and to treat the surface of the conductive material to prevent crystallization of the components of the post-treatment liquid.

Although post-treatment improves conductivity, it is sometimes more likely to cause manufacturing or Broken line in use, etc. In the present invention, since the DM process is performed, disconnection can be prevented. Although the post-processing can be performed in either case before or after the DM process of the present invention, it is preferable to prevent the disconnection which may occur during the post-processing step, for example, the transport of the processing device. Implementation.

Hereinafter, the present invention will be specifically described by way of examples, but the invention is of course Not subject to this description.

[Examples]

(Example 1)

As the support, a polyethylene terephthalate film having a total light transmittance of 90% and a thickness of 100 μm which was easily processed by a layer containing vinylidene chloride was used. An undercoat layer containing 500 mg/m ² of gelatin was applied to the film before the physical development of the core layer was applied.

Then, a palladium sulfide sol was produced as follows. Using the obtained sol, a physical development nuclear liquid was produced.

<Preparation of palladium sulfide sol>

The liquid A and the liquid B having the above composition were mixed while stirring, and after 30 minutes, a column packed with an ion exchange resin was passed to obtain a palladium sulfide sol. A physical development nucleus having the following composition was produced.

<Physical development nuclear composition / per 1m ² >

(Polyethyleneimine manufactured by Nippon Shokubai Co., Ltd.; average molecular weight 10,000)

The physical development core liquid was applied onto the undercoat layer so that palladium sulfide was 0.4 mg/m ² in terms of solid content, and dried.

Next, a back coat layer having the following composition was applied to the surface opposite to the side on which the above-described physical development core layer was applied.

<Back coating composition / per 1m ² >

Dye 1 represented by the formula of Formula 1

Surfactant represented by Formula 2 (S-1)

Next, on the above-mentioned physical developing core layer, an intermediate layer having the following composition, a silver halide emulsion layer on the intermediate layer, and an outermost layer on the silver halide emulsion layer are applied. Silver halide emulsions are produced by the usual two-injection mixing process using photographic silver halide emulsions. The silver halide emulsion was prepared by using 95% by mole of silver chloride and 5 % by mole of silver bromide so that the average particle diameter of the silver halide grains was 0.15 μm. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a usual method. The silver halide emulsion thus obtained contained 0.5 g of gelatin per 1 g of silver.

<Intermediate layer composition / per 1m ² >

<Brown silver emulsion layer composition / per 1m ² >

<Outer layer composition / per 1m ² >

The conductive material precursor thus obtained was exposed by a close-contact printer having a mercury lamp as a light source and a permeated document having the pattern of FIG. In the pattern of Fig. 1, the silver mesh pattern portion (conductive portion) a is composed of a mesh having a line width of 10 μm and a thin line interval of 300 μm. b is an electrode terminal portion. c is a non-image portion (non-conductive portion). The exposure is performed such that the mesh fine line width of the conductive material is the same as the exposure amount of the fine line width of the original.

Thereafter, the exposed conductive material precursor is in a developing solution having the following composition Immerse at 20 ° C for 60 seconds. Thereafter, the silver halide emulsion layer, the intermediate layer, the outermost layer, and the back coat layer were washed with warm water of 40° C., and dried to obtain a conductive material in which a silver thin film was formed in a mesh pattern. The fine line width and pitch of the silver pattern image of Fig. 1 were confirmed by an optical microscope, and as a result, the thin line width and pitch of the exposure mask were reproduced. In addition, the film thickness of the thin line portion was examined by a confocal microscope (manufactured by LASERTEC Co., Ltd., OPTELICS C130), and as a result, it was 0.15 μm.

<developer composition>

[Measurement of resistance before film bonding]

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

[DM treatment]

The conductive material on which the silver pattern of Fig. 1 was obtained as described above was treated with a DM treatment liquid having the following composition at 30 ° C for 60 seconds. Thereafter, the conductive material was washed with warm water of 35 ° C for 30 seconds, and dried with a film dryer at 60 ° C for 2 minutes.

<DM treatment liquid>

The conductive material on which the silver pattern of FIG. 1 was formed by the DM treatment was subjected to post-treatment at 60 ° C for 60 seconds using a 3 mass % sodium chloride aqueous solution. Thereafter, the conductive material was washed with warm water of 35 ° C for 30 seconds, and dried with a film dryer at 60 ° C for 2 minutes.

[Measurement of resistance after film bonding]

The conductive material in which the silver pattern of FIG. 1 was formed, which was subjected to the post-treatment, was adjusted to a pressure of 0.5 MPa/m, and the optical transparent adhesive sheet was conveyed at a speed of 1 m/min. LUCIACS CS9622T) made by Electrician Co., Ltd. is simultaneously pressed and bonded to the silver pattern. At this time, the optical transparent adhesive sheet is bonded to the silver pattern of FIG. 1 so as not to cover the terminal portion b and cover the uppermost electrode from the lowermost electrode. After the conductive material to which the adhesive sheet was bonded was stored at 60 ° C and 90% for 200 hours, the electric resistance between the electrode terminals of the conductive material was measured by a tester in the same manner as before bonding. These results are shown in Table 1 (after lamination in the table).

(Example 2)

In addition to the 2,4-dimercapto-6-dibutylamino group III of the DM treatment solution A conductive material was produced in the same manner as in Example 1 except that the reaction was changed to trimeric thiocyanate, and the evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Example 3)

In addition to the 2,4-dimercapto-6-dibutylamino group III of the DM treatment solution Change to 2,4-dimercapto-6-phenylamino three A conductive material was produced in the same manner as in Example 1 except that the evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 1)

A conductive material was produced in the same manner as in Example 1 except that the treatment with the DM treatment liquid was not carried out, and evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 2)

In addition to the 2,4-dimercapto-6-dibutylamino group III of the DM treatment solution A conductive material was produced in the same manner as in Example 1 except that the compound was changed to 2-amino-4,6-dimercaptopyrimidine, and the evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 3)

In addition to the 2,4-dimercapto-6-dibutylamino group III of the DM treatment solution A conductive material was produced in the same manner as in Example 1 except that it was changed to 2-mercaptobenzimidazole, and evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 4)

In addition to the 2,4-dimercapto-6-dibutylamino group III of the DM treatment solution A conductive material was produced in the same manner as in Example 1 except that it was changed to 1-phenyl-5-mercaptotetrazole, and evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Example 4)

In the pattern of FIG. 1, the silver mesh pattern portion (conductive portion) a is a transmissive document composed of a mesh having a line width of 15 μm and a thin line interval of 350 μm. The thickness of the silver mesh pattern measured by a confocal microscope (manufactured by LASERTEC Co., Ltd., OPTELICS C130) was 0.15 μm. A conductive material was produced in the same manner as in Example 1 except that the evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 5)

A conductive material was produced in the same manner as in Example 4 except that the treatment with the DM treatment liquid was not carried out, and evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Example 5)

In the pattern of FIG. 1, the silver mesh pattern portion (conductive portion) a is a transmissive document composed of a mesh having a line width of 20 μm and a line pattern of 400 μm. The thickness of the silver mesh pattern measured by a confocal microscope (manufactured by LASERTEC Co., Ltd., OPTELICS C130) was 0.15 μm. A conductive material was produced in the same manner as in Example 1 except that the evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 6)

A conductive material was produced in the same manner as in Example 5 except that the treatment with the DM treatment liquid was not carried out, and evaluation was carried out 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 of Example 1 was changed as follows.

<Brown silver emulsion layer composition / per 1m ² >

Confocal microscope (made by LASERTEC, OPTELICS C130) The thickness of the silver mesh pattern measured was 0.3 μm. Otherwise, the DM treatment and the post treatment were carried out in the same manner as in Example 1 to prepare 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 produced in the same manner as in Example 6 except that the treatment with the DM treatment liquid was not carried out, and evaluation was carried out in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 8)

The conductive material before the treatment with the DM treatment liquid of Example 1 was plated with silver at a liquid temperature of 25 ° C, a current density of 1 A/dm ² , and a plating time of 2 minutes to prepare a conductive material. Sexual material. The electric 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 the bonding in the table). The thickness of the mesh pattern after plating measured by a confocal microscope (manufactured by LASERTEC Co., Ltd., OPTELICS C130) was 0.5 μm. Thereafter, DM treatment, post-treatment, and bonding of the adhesive sheets 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 lamination in the table). In the conductive material to which the adhesive sheet was bonded, air was mixed, and it was confirmed after being placed on the liquid crystal screen, and as a result, it was a failure level which was visually recognized even if it was not gazing.

<plating solution>

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

As is apparent from the above results, according to the present invention, it is possible to obtain a method for producing a conductive material in which a conductive material having improved conduction failure of the electrode and variation in conductivity of each electrode can be obtained. Conductive materials that improve these problems can also be obtained.

[Industrial availability]

The method for producing a conductive material and the conductive material of the present invention can be used as electromagnetic wave shielding materials for various displays and windows, and can be used as a transparent electrode for various touch panels, and can be a promising manufacturing method and material.

Claims (5)

A method for producing a conductive material, comprising the steps of: using a conductive material having a support and a silver pattern having a film thickness of 0.3 μm or less formed thereon, and using a metal having two or more sulfhydryl groups in the molecule; The treatment solution of (triazine) or its derivative is treated. The method for producing a conductive material according to the first aspect of the invention, wherein the silver pattern has a line width of 20 μm or less. The method for producing a conductive material according to the first aspect of the invention, wherein the silver pattern is a silver pattern obtained by a method using a silver salt diffusion transfer method. The method for producing a conductive material according to claim 1, further comprising the step of: post-processing the peak value of the peak of 2 θ=38.2° in the X-ray diffraction method of the silver pattern to 0.41 the following. A conductive material obtained by the method for producing a conductive material according to any one of claims 1 to 4.