JP5118824B2 - Conductive expression method - Google Patents

Description

  The present invention relates to a method of developing conductivity using ultrafine metal particles, and more particularly, to a method of developing conductivity and a conductive member capable of obtaining high conductivity without the need for a firing step that was conventionally required. It is to provide.

  Conductive members are CRT electromagnetic shielding, building materials, infrared shielding for automobiles, antistatic materials for electronic devices and mobile phones, frosted glass heat rays, wiring for circuit boards and IC cards, and coatings for imparting conductivity to resins. It is used in a wide range of fields such as through holes and circuits.

  In particular, in a manufacturing process of a semiconductor device, a liquid crystal display device, a plasma display display device, or the like, a conductive metal thin film may be formed in order to form electrodes and wirings. In these manufacturing processes, the metal thin film is generally formed by a thin film forming method such as vacuum deposition, sputtering, or CVD. Since such a thin film forming method is generally performed under a reduced pressure atmosphere, it is necessary to perform the method by installing a substrate or the like in a reaction vessel such as a vacuum chamber. Therefore, when the object for forming the metal thin film becomes large, a vacuum chamber capable of storing such a large object is required, which makes it difficult to manufacture.

  In the production of a flexible substrate, for example, a silver paste in which silver particles of about 1 μm are kneaded with a resin may be used to form a conductive member in a recess such as a contact hole or a via hole. Since the conductivity is ensured by the contact, there is a problem that the conductivity is low.

  Japanese Patent Application Laid-Open No. 3-281784 (Patent Document 1) discloses a method of forming a metal thin film by applying a paste in which ultrafine metal particles are dispersed and firing the paste at a temperature of about 900 ° C. ing. According to such a method, since a metal thin film can be formed by applying a paste, it is suitable for forming a metal thin film having a large area or forming a metal thin film on a substrate having a complicated surface shape. ing.

  Japanese Patent Laid-Open No. 2001-35255 (Patent Document 2) includes an organic solvent that evaporates in a drying / firing process when a silver wiring is formed on a semiconductor substrate, and a silver content of 0.01 μm or less. Independent dispersion of silver ultrafine particles, characterized in that ultrafine particles are mixed, the surfaces of the ultrafine particles are covered with the organic solvent and are individually dispersed, and the viscosity is 50 mPa · s or less at room temperature. A liquid is disclosed, and an extremely high conductivity is obtained by baking at a temperature of 300 ° C. to form a silver thin film.

  However, the metal colloidal solution in which these ultrafine metal particles are dispersed in a liquid is manufactured by evaporating the metal under a reduced pressure atmosphere, and has a high monodispersity, for example, nozzle type pattern formation such as an ink jet method. Although suitable for an apparatus, in order to obtain conductivity, a temperature of at least 200 ° C. is necessary, and usable substrates are limited to heat-resistant substrates such as glass, polyimide, and ceramic.

  On the other hand, a method is known in which an aqueous silver nitrate solution or the like is reduced with a reducing agent in the presence of a dispersant called a protective colloid to produce ultrafine metal particles coated with the dispersant.

  For example, American Journal of Science, Vol. 37, P476-491, 1889, M Carey Lea. In (Non-patent Document 1), a colloidal metal solution is obtained by adding citric acid or a salt thereof as a dispersant to a metal salt aqueous solution, adding a reducing agent such as ferrous ion, then desalting and concentrating. How to get it has been reported. In addition, Experiments in Colloid Chemistry, 1940, p. 19, Hauser, E .; A. and lynn, J. et al. E. (Non-Patent Document 2) reports a method of obtaining a metal colloid solution using dextrin as a dispersant and a reducing agent. However, since the dispersant is not easily volatilized even after firing, the resulting conductivity is low.

  In addition, as ultrafine metal particles reduced in an aqueous solution exhibiting good conductivity, for example, JP 2002-338050 A (Patent Document 3) is produced using a multimer of (thio) phenol derivatives, Although a metal colloid solution capable of obtaining a conductive film by firing under mild conditions and a method for producing the same have been disclosed, the metal colloid solution exhibits only a high resistance value when fired at less than 100 ° C. Japanese Patent Application Laid-Open No. 2005-081501 (Patent Document 4) discloses stable metal ultrafine particles that can achieve practical electrical conductivity by low-temperature firing and a method for producing the same, and firing at 140 to 220 ° C. Although it is possible to achieve a sufficiently practical conductivity, a firing process is still necessary.

  Since the metal ultrafine particles contained in these metal colloid solutions are generally coated with a dispersing agent, the interconnection between the metal ultrafine particles is not formed in the state where the dispersion medium such as water is evaporated by the drying process. In order to obtain good conductivity for use as a conductive member, the dispersant is decomposed and volatilized, and the metal superoxide is not exhibited. In order to form an interconnection by fusing fine particles, a firing step is required, and not only energy for that is required, but also a base material that can be used is limited in terms of heat resistance.

In order to develop conductivity by heating at a low temperature that does not require heating, the substrate side has also been devised. For example, in Japanese Patent Application Laid-Open No. 2004-127851 (Patent Document 5), the metal colloid is dried. In the conductive film composite formed by laminating the conductive film formed by the method, a conductive film composite characterized by using an image receiving layer containing at least a porous inorganic filler is disclosed, and In JP-A-2005-32458 (Patent Document 6), a conductive film composite formed by laminating conductive films formed by drying a metal colloid solution is made of a water-soluble resin or a hydrophilic resin. An intermediate layer having a 10-point average surface roughness Rz of 3 μm or less according to JIS B 0601 is interposed, and the volume resistivity is 10 × 10 ⁻⁵ Ω · cm or less. A conductive coating composite characterized by the above is disclosed.
JP-A-3-281784 JP 2001-35255 A American Journal of Science, Vol. 37, P476-491, 1889, M Carey Lea. Experiments in Colloid Chemistry, 1940, p. 19, Hauser, E .; A. and lynn, J. et al. E. JP 2002-338850 A Japanese Patent Laying-Open No. 2005-081501 JP 2004-127851 A JP 2005-32458 A

  An object of the present invention is to provide a conductive expression method and a conductive member capable of obtaining high conductivity without requiring a firing step, which has been conventionally required, in a method of expressing conductivity using ultrafine metal particles. It is to provide.

The above object of the present invention has been basically achieved by the following invention.
1. Conductivity characterized in that ultrafine metal particles dispersed as metal colloids in water and / or an organic solvent and a compound having a halogen in the molecule by ionic bonds act to obtain conductivity on the substrate. Sexual expression method.
2. 2. The conductivity developing method as described in 1 above, wherein the ultrafine metal particles are mainly composed of silver.
3. 3. The method of developing conductivity as described in 1 or 2 above, comprising a porous layer composed of inorganic fine particles and a binder of 80% by mass or less based on the inorganic fine particles on the substrate.

  According to the present invention, it is possible to obtain high conductivity without requiring a firing step that has been conventionally required, and a conductive member can be obtained.

  Hereinafter, the present invention will be described in detail. The present inventor causes a metal ultrafine particle dispersed as a metal colloid in water and / or an organic solvent to react with a compound having a halogen in the molecule by ionic bonding, thereby providing a firing step that has been conventionally required. Thus, the inventors have found that high conductivity is exhibited, and have reached the present invention.

  The conductive member in the present invention is, for example, a conductive pattern such as a fine wiring, an antenna, an electromagnetic wave shield, an address electrode, a terminal such as a bump, a wiring pattern in a printed wiring board composed of a plurality of layers, and a contact hole or via hole between wiring layers, Examples thereof include, but are not limited to, battery electrodes and electrodes of electronic components. Moreover, regarding electroconductivity, the electroconductive member obtained by the electroconductivity expression method of the present invention can be further subjected to electroless plating or electroplating to enhance it.

  In the present invention, a compound having halogen in the molecule by ionic bond is used to develop conductivity. In the state in which the dispersion medium contained in the metal colloid solution is volatilized, the many ultrafine metal particles contained are separated by the dispersant or have very little contact with each other. There is no or very low electrical conductivity. When a compound having a halogen in the molecule by ionic bonding is used, a phenomenon that is presumed to be the growth of the ultrafine metal particles and the formation of interconnections associated therewith is observed, and conductivity is exhibited. The growth of the ultrafine metal particles reaches several to several tens of times in particle diameter, and when the conductivity is good, no clear particles are observed and the bulk metal-like shape with a slight gap is reached. This expression of conductivity may show high conductivity in a few seconds, or may show high conductivity over a few tens of days, for example, very slowly.

  In the present invention, the metal colloid solution generally refers to a dispersion in which ultrafine metal particles having an average primary particle size of 200 nm or less are dispersed in a dispersion medium composed of water and / or an organic solvent. The content of the metal ultrafine particles contained in the metal colloid solution is preferably 1% by mass to 95% by mass, and more preferably 3% by mass to 90% by mass with respect to the total mass of the metal colloid solution.

  The dispersion medium of metal ultrafine particles is composed of water and / or an organic solvent, and examples thereof include water alone, a mixture of water and an organic solvent, and an organic solvent alone. As organic solvents used, methanol, ethanol, 1-propanol, 2-propanol, t-butyl alcohol, glycerin, dipropylene glycol, ethylene glycol, diethylene glycol, polyethylene glycol, hexanol, heptanol, octanol, decanol, cyclohexanol, terpineol Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, etc., cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol dimethyl ether , Glycol ethers such as diethylene glycol diethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, butoxycarbitol acetate, etc. Glycol ether esters, amides such as 2-pyrrolidone and N-methylpyrrolidone, long-chain alkanes such as hexane, heptane, octane, decane, tridecane, tetradecane and trimethylpentane, and cyclic such as cyclohexane, cycloheptane and cyclooctane Alkanes, benzene, toluene, xylene, trimethylbenzene, dodecylbenzene, etc. It can be mentioned aromatic hydrocarbons, and the like. The organic solvents can be used alone or in combination of two or more. Also, petroleum distillates, for example, a fraction of 150 ° C. to 190 ° C. (a mixture of aromatic hydrocarbons and aliphatic hydrocarbons) known as mineral spirits can be used. Preferred examples of the dispersion medium suitable for the ink jet method include a mixture of water and glycerin, ethylene glycol, diethylene glycol, and 2-pyrrolidone, and tetradecane and mineral spirit alone. Examples of the dispersion medium suitable for the spin coating method include acetone and toluene. Examples of the dispersion medium suitable for the screen printing method include terpineol, ethylene glycol monomethyl ether acetate, and cyclohexanone. One preferred embodiment is to use an organic solvent that swells or dissolves the undercoat layer described later.

  Ultrafine metal particles are evaporated in an inert gas, cooled and condensed by collision with the gas, recovered in a gas, a metal vapor synthesis method in which a metal is evaporated in a vacuum and recovered together with an organic solvent, laser irradiation Laser ablation method that evaporates and condenses in liquid with energy and recovers, chemical reduction method that reduces and generates and recovers metal ions in aqueous solution, method by pyrolysis of organometallic compound, gas phase of metal chloride Products prepared by various known methods such as a method using reduction in hydrogen and a method of reducing oxides in hydrogen can be preferably used.

  The particle diameter of the ultrafine metal particles is preferably 200 nm or less from the viewpoint of the stability of the colloidal solution, more preferably 100 nm or less, and even more preferably 50 nm or less. Here, the particle diameter means the average particle diameter of the ultrafine metal particles when observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

  The ultrafine metal particles in the present invention are preferably mainly composed of silver from the viewpoint of high conductivity, cost, productivity, ease of handling, and the like. Moreover, it is preferable that 50 mass% or more of all the metal ultrafine particles contained in a metal colloid solution is silver, More preferably, it is 70 mass% or more. Examples of preferable metals other than silver include gold, copper, platinum, palladium, rhodium, ruthenium, iridium, osmium, nickel, and bismuth. In order to suppress migration specific to silver, gold, copper, Platinum and palladium are preferred. As a method for incorporating a metal other than silver, for example, as disclosed in Japanese Patent Application Laid-Open No. 2000-090737, silver ultrafine particles may contain palladium, which is disclosed in Japanese Patent Application Laid-Open No. 2001-35255. Alternatively, a mixture of ultrafine silver particles and ultrafine palladium particles produced separately may be used. Moreover, a metal colloid containing copper, such as a silver nanoparticle ink manufactured by Cima NanoTech, can also be exemplified.

  The ultrafine metal particles are preferably coated with a dispersant in order to form a stable metal colloid solution. For example, American Journal of Science, Vol. 37, P476-491, 1889, M Carey Lea. Citric acid is a dispersing agent in the method described in Experiments in Colloid Chemistry, 1940, p. 19, Hauser, E .; A. and lynn, J. et al. E. In the method described in 1), dextrin is a dispersant. In addition, various ionic compounds such as disodium malate, disodium tartrate and sodium glycolate; various surfactants such as sodium dodecylbenzenesulfonate, sodium oleate, polyoxyethylene alkyl ether, perfluoroalkylethylene oxide adduct Water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, gelatin, carrageenan, gum arabic, albumin, polyethyleneimine, carboxylmethylcellulose, hydroxylpropylcellulose, various organometallic compounds having fatty acids, amines, etc. Can be used. The content of these dispersants is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the content of the ultrafine metal particles contained in the metal colloid solution.

  Various additives such as thickeners, antistatic agents, UV absorbers, plasticizers, and polymer binders may be added to the metal colloid solution depending on the purpose. For example, by adding a UV curable resin component. Further, it is possible to provide characteristics (UV curing characteristics) suitable for pattern formation by UV printing or UV inkjet method.

  In the present invention, the metal colloid solution is adjusted in any form from a low viscosity solution state to a high viscosity paste state. Specifically, the viscosity, the surface tension, the size / content ratio of the ultrafine metal particles, and the like suitable for the apparatus for forming the conductive member are adjusted. For example, when using gravure printing or an inkjet method, the viscosity is preferably adjusted to a range of 1 to 100 mPa · s, and when using relief printing or screen printing, the viscosity is adjusted to a range of 10 to 500 Pa · s. It is preferable.

  When adjusting to a high-viscosity paste state, it is difficult to obtain a desired viscosity simply by increasing the concentration of ultrafine metal particles. Therefore, as a polymer binder, for example, cellulose resin, phenol resin, epoxy resin, acrylic It is preferable to include a resin, a polyester resin, a polyimide resin, or the like.

  As the metal colloid solution used in the present invention, colloids, inks or pastes containing known or commercially available metal ultrafine particles can be widely used.

  In the compound having halogen in the molecule by ionic bond used in the present invention, halogen means fluorine, chlorine, bromine, iodine or astatine, preferably chlorine, bromine or iodine, particularly preferably chlorine or bromine. It is.

  Examples of the compound having halogen in the molecule by ionic bonding include hydrogen halide, inorganic salts, inorganic polymer halide, and organic polymer halide.

  Examples of the hydrogen halide include hydrochloric acid and hydrobromic acid.

  Examples of inorganic salts include sodium salt, potassium salt, ammonium salt, zirconium salt, aluminum salt, calcium salt, ammonium salt and the like. For example, preferred embodiments include sodium chloride, potassium chloride, calcium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, ammonium bromide, sodium iodide, potassium iodide and the like.

  As the inorganic polymer halide, for example, polyaluminum hydroxide containing a basic and high molecular polynuclear condensed ion stably can be used, and those having halogen as a counter ion are used. It is marketed as Polyaluminum Chloride (PAC) by Taki Chemical Co., Ltd. under the name of Purachem WT from Riken Green Co., Ltd., and from other manufacturers for the same purpose. Things are readily available. The degree of polymerization is arbitrary.

  As the organic polymer halide, a cationic polymer compound having halogen as a counter ion can be widely used. The composition and degree of polymerization are arbitrary. For example, cationic polyvinyl alcohol, diallyldimethylammonium chloride polymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-acrylamide copolymer, diallyldimethylammonium chloride-diallylamine hydrochloride derivative copolymer, diallylamine hydrochloride Salt-sulfur dioxide copolymer, diallylmethylamine hydrochloride polymer, diallylamine polymer such as polyallylamine hydrochloride, hydrochloride of allylamine polymer, ammonium salt, polyamine polymer, allyl polymer, alkylamine Examples thereof include a polymer based polymer, a dimethylamine epichlorohydrin polycondensate, and a polyamide epichlorohydrin polymer.

  The compounds mentioned above can be used alone or in combination of two or more. From the convenience of use, sodium chloride, potassium chloride, calcium chloride, and ammonium chloride are preferable.

  The amount of the compound having halogen in the molecule due to ionic bonding is determined by the type and particle size of the metal ultrafine particles contained in the metal colloid solution to be used, the type of substrate, the method of addition, the speed of development of conductivity, and the target conductivity. For example, when it is preliminarily contained on the porous substrate, the number of moles of halogen contained is 0.1 mol% to the number of moles of ultrafine metal particles. The amount is preferably about 500 mol%, more preferably 1 mol% to 200 mol%, and particularly preferably 5 mol% to 100 mol%.

Base materials for forming conductive members include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, polyarylate, polysulfone, polyethersulfone, and polyimide. , Fluororesin, phenoxy resin, triacetate, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, and other acrylic resins, cellophane, nylon, styrene resin, ABS resin, and other resins, quartz glass , alkali-free glass, crystallized clear glass, Pyrex (registered trademark) glass, various glass such as _{sapphire, AIN, Al 2 O 3,} SiC, SiN, MgO, BeO, ZrO 2, Y 2 O 3, hO _2, CaO, GGG (gadolinium gallium garnet) single crystal silicon, an inorganic material such as polycrystalline silicon, paper, various metals can be mentioned, may be used in combination thereof as needed. Depending on the application, these materials can be appropriately selected to form a flexible substrate such as a film or a rigid substrate. The base material may have any shape such as a disk shape, a card shape, or a sheet shape. Also, for example, it may be an electrical terminal portion such as a lead wire or bump of an electronic component, a multilayer capacitor or a tantalum capacitor, a junction portion of a thin film resistor, a TFT electrode, a collector electrode of a solar cell, a gate electrode of an organic FET Any part that requires electrical conductivity can be used as the base material of the present invention. Moreover, these base materials can be appropriately combined depending on the application, and for example, a flexible printed circuit board material in which copper foil and polyimide are laminated, or a polyolefin resin-coated paper in which paper and a polyolefin resin are laminated can be used. Further, for example, a green sheet for a substrate produced by casting a mixture slurry of alumina powder and a binder, a green sheet for a multilayer ceramic capacitor produced by casting a mixture slurry of barium titanate powder and a binder, etc. are also preferable. Can be used.

  If high conductivity is not required between the base material and the conductive member according to the present invention, an undercoat layer may be formed for the purpose of improving the adhesive force between the base material and the conductive member. Since the undercoat layer is generally insulating, it lowers the conductivity between the base material and the conductive member. Examples of the material for the undercoat layer include gelatin, carrageenan, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, various urethane resins, polyvinyl alcohol, polyvinyl acetal polyvinyl pyrrolidone, carboxyl methyl cellulose, hydroxylpropyl cellulose. , Alcohol-soluble nylon, N-methylolacrylamide, polyvinylidene chloride, vinyl acetate / vinyl chloride copolymer, high molecular weight materials such as ethylene / vinyl acetate copolymer, thermosetting or photo / electron beam curable resin, silane coupling Surface modifiers such as an agent, a titanate coupling agent, a germanium coupling agent, an aluminum coupling agent, and an imidazolesilane coupling agent, and the like. That it is possible.

  When using a water-soluble resin such as gelatin, polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, carrageenan, carboxyl methyl cellulose, hydroxyl propyl cellulose in the undercoat layer, use a suitable hardener for the purpose of improving water resistance, It is also preferable to harden. Hardeners include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1,3,5 triazine N-methylol compounds, isocyanates, aziridine compounds, carbodiimide compounds, epoxy compounds, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid and borates There are such inorganic hardeners, and these can be used alone or in combination of two or more.

  The density of the ultrafine metal particles that form the conductive member at the stage where the compound having a halogen in the molecule due to ionic bonding acts on the ultrafine metal particles is preferably high, and the conductive colloidal solution is prevented from spreading and finely conductive. In order to facilitate the formation of the adhesive member, it is one of the more preferable embodiments that the undercoat layer has a function of absorbing the dispersion medium in the metal colloid solution. For example, when water is used as the dispersion medium for the metal colloidal solution, water resistance is imparted to the subbing layer and various water-soluble resins such as gelatin, carrageenan, polyvinyl alcohol, polyvinyl acetal, polyvinylpyrrolidone, carboxylmethylcellulose, and hydroxylethylcellulose. One or more hardeners can be used in combination. In the case where an organic solvent is used as the dispersion medium for the metal colloid solution, cellulose resin, polyvinyl butyral resin, acrylic resin, acrylic ester resin, amorphous polyester resin, or the like can be used for the undercoat layer. . A preferable layer thickness (when dried) of the undercoat layer is generally preferably from 0.01 to 50 μm, more preferably from 1 to 40 μm, particularly preferably from 5 to 30 μm.

  Further, in addition to absorbing the dispersion medium in the metal colloid solution by swelling or dissolution of the resin, it is further preferable to absorb by using a capillary phenomenon due to the fine voids of the porous layer. In general, the porous layer is more preferable than the case of swelling due to the resin, because the absorption rate of the dispersion medium is faster and the type of the dispersion medium does not matter.

  The undercoat layer made of a porous layer comprises fine particles and a resin binder, and known fine particles can be widely used as the fine particles used. For example, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zirconia, cerium, antimony oxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth , Calcium silicate, magnesium silicate, amorphous synthetic silica, colloidal silica, alumina, colloidal alumina, alumina hydrate, lithopone, zeolite, hydrous halloysite, magnesium hydroxide, inorganic fine particles, acrylic or methacrylic resin, vinyl chloride Resin, vinyl acetate resin, polyester resin, styrene / acrylic resin, styrene / butadiene resin, polystyrene / acrylic resin, polystyrene / isoprene resin, methyl methacrylate / butyl methacrylate Spherical or amorphous nonporous material comprising at least one resin such as acrylate resin, polycarbonate resin, silicone resin, urea resin, melamine resin, epoxy resin, phenol resin, diallyl phthalate resin, etc. Or a porous organic fine particle etc. can be mention | raise | lifted. Of course, it is also possible to use a mixture of one or more inorganic fine particles and one or more organic fine particles.

  Among the above fine particles, inorganic fine particles such as amorphous synthetic silica, alumina, and alumina hydrate having an average secondary particle diameter of 500 nm or less, and organic fine particles having an average particle diameter of 200 nm or less are preferably used. I can do it. In particular, when these inorganic fine particles are used, a porous layer having a high porosity can be formed. Since the porosity is high, the refractive index is lowered and the surface reflectance can be reduced. For example, it is easy to set the gloss value specified in JIS-Z-8741 to 25 or less (indicating that the reflectance is 1/4 compared to standard glass).

  Amorphous synthetic silica can be roughly classified into wet method silica, gas phase method silica, and others depending on the production method. Wet method silica is further classified into precipitation method silica, gel method silica, and sol method silica according to the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica particles that have grown are agglomerated and settled, and are then commercialized through the steps of filtration, washing, drying, pulverization and classification. Precipitated silica is commercially available, for example, from Tosoh Silica Co., Ltd. as a nip seal, from Tokuyama Co., Ltd. as Tokuseal, and from Mizusawa Chemical Co., Ltd. as Mizukasil. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During aging, the microparticles dissolve and reprecipitate so as to bind the other primary particles, so that the distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure. For example, it is commercially available from Tosoh Silica Co., Ltd. as nip gel, from Grace Japan Co., Ltd. as syloid and silo jet, and from Mizusawa Chemical Industry Co., Ltd. as Mizukasil. The sol method silica is also called colloidal silica, and is obtained by heating and aging a silica sol obtained through metathesis of sodium silicate acid or through an ion exchange resin layer. For example, it is commercially available as Snowtex from Nissan Chemical Industries, Ltd. Yes.

  Vapor phase silica is also called a dry method as opposed to a wet method, and is generally made by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. Vapor phase silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd.

The average primary particle size of the vapor-phase process silica used in the present invention is preferably 30 nm or less, and when higher transparency is required, 15 nm or less is preferred. More preferably, those having an average primary particle diameter of 3 to 15 nm and a specific surface area by the BET method of 200 m ² / g or more (preferably 250 to 500 m ² / g) are used. The average primary particle diameter as used in the present invention is an average particle diameter obtained by measuring the diameter of a circle equal to the projected area of each of the 100 primary particles existing within a certain area by observation with an electron microscope. The BET method referred to in the present invention is one of the powder surface area measurement methods by the vapor phase adsorption method, and is a method for obtaining the total surface area, that is, the specific surface area of a 1 g sample from the adsorption isotherm. Usually, as the adsorbed gas, a large amount of nitrogen gas is used, and the most frequently used method is to measure the amount of adsorption from the pressure or volume change of the gas to be adsorbed. The most prominent expression for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, and Teller formula, called the BET formula, which is widely used for determining the surface area. The adsorption amount is obtained based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.

  For dispersion of the vapor phase method silica, various known methods can be used. For example, as described in JP-A-2002-144701, a method of dispersing in the presence of an alkaline compound and a dispersant are used at all. It is possible to preferably carry out either a method of dispersing using only mechanical shearing force or a method of dispersing in the presence of a cationic compound.

  Also, dispersion in the presence of a silane coupling agent can be preferably performed. In particular, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, 3- (trimethoxysilyl) propyldimethyl A silane coupling agent having a quaternary ammonium group such as hydroxyethylammonium chloride can be preferably used.

  The average secondary particle diameter of the dispersed vapor phase method silica is 500 nm or less, preferably 10 to 300 nm, more preferably 20 to 200 nm. As a dispersion method, pre-mixing a dispersion medium mainly composed of gas phase silica and water by ordinary propeller stirring, turbine type stirring, homomixer type stirring, etc., and then a media mill such as a ball mill, a bead mill, a sand grinder, It is preferable to perform dispersion using a pressure disperser such as a high-pressure homogenizer or an ultra-high pressure homogenizer, an ultrasonic disperser, a thin film swirl disperser, or the like. The average secondary particle diameter in the present invention can be determined by photography using a transmission electron microscope. For simplicity, a laser scattering particle size distribution meter (for example, LA910, manufactured by Horiba, Ltd.) is used. Thus, it can be measured as the number median diameter.

  In the present invention, wet process silica pulverized to an average secondary particle diameter of 500 nm or less can also be preferably used. As the wet method silica used here, precipitation method silica or gel method silica is preferable, and precipitation method silica is particularly preferable. The wet process silica particles used in the present invention are preferably wet process silica particles having an average primary particle diameter of 50 nm or less, preferably 3 to 40 nm, and an average aggregate particle diameter of 5 to 50 μm.

  As the pulverization method, a wet dispersion method in which silica dispersed in an aqueous medium is mechanically pulverized is preferably used. In this case, an increase in the initial viscosity of the dispersion liquid is suppressed, and high concentration dispersion is possible. It is preferable to use precipitated silica having an average agglomerated particle diameter of 5 μm or more because the particle size rises and can be pulverized into fine particles. Productivity is also improved by using a high-concentration dispersion.

  For dispersing the wet method silica, various known methods can be used. For example, as described in JP-A-2005-1117, a method of dispersing in the presence of an alkaline compound and a dispersant are not used. Any of a method of dispersing using only mechanical shearing force, a method of dispersing in the presence of a cationic compound, a method of using a silane coupling agent, etc. can be preferably used.

  The average secondary particle diameter of the dispersed wet process silica is 500 nm or less, preferably 10 to 300 nm, and more preferably 20 to 200 nm from the viewpoint of transparency. As a dispersion method, silica particles and a cationic compound are mixed in a dispersion medium mainly composed of water, and at least a dispersion device such as a sawtooth blade type disperser, a propeller blade type disperser, or a rotor stator type disperser is used. One is used to obtain a preliminary dispersion. If necessary, an appropriate low boiling point solvent or the like may be added to the aqueous dispersion medium. The higher the solid content concentration of the silica pre-dispersion liquid, the more preferable, but when the concentration is too high, it becomes impossible to disperse, so the preferable range is 15 to 40% by mass, and more preferably 20 to 35% by mass. Next, the silica particles are pulverized by applying the silica pre-dispersion to mechanical means having a stronger shearing force to obtain a wet process silica fine particle dispersion having an average secondary particle size of 500 nm or less. As a mechanical means, a known method can be adopted, for example, a media mill such as a ball mill, a bead mill, a sand grinder, a high pressure homogenizer, a pressure disperser such as an ultra high pressure homogenizer, an ultrasonic disperser, a thin film swirl disperser, etc. Can be used.

  As the cationic compound used for the dispersion of the gas phase method silica and the wet method silica, a cationic polymer can be preferably used. As the cationic polymer, polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, JP-A-59-33176, JP-A-59-33177, JP-A-59-155088, Sho 60-11389, Sho 60-49990, Sho 60-83882, Sho 60-109894, Sho 62-198493, Sho 63-49478, Sho 63-115780, Shosho 63-280681, No. 1-40371, No. 6-234268, No. 7-125411, No. 10-193976, etc. The polymer having is preferably used. In particular, diallylamine derivatives are preferably used as the cationic polymer. In terms of dispersibility and dispersion viscosity, the weight average molecular weight of these cationic polymers is preferably about 2,000 to 100,000, and particularly preferably about 2,000 to 30,000.

  As the alumina used in the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable, and among them, a δ group crystal is preferable. γ-alumina can make primary particles as small as about 10 nm. Usually, secondary particles of thousands to tens of thousands of nanometers are averaged by ultrasonic, high-pressure homogenizer, counter collision type jet crusher, etc. It is preferable to grind the particle size to 500 nm or less, preferably about 20 to 300 nm.

The alumina hydrate of the present invention is represented by a constitutive formula of Al ₂ O ₃ .nH ₂ O (n = 1 to 3). The case where n is 1 represents an alumina hydrate having a boehmite structure, and the case where n is greater than 1 and less than 3 represents an alumina hydrate having a pseudo boehmite structure. It can be obtained by a known production method such as hydrolysis of an aluminum alkoxide such as aluminum isopropoxide, neutralization of an aluminum salt with an alkali, or hydrolysis of an aluminate. The average secondary particle size of the alumina hydrate is 500 nm or less, preferably 20 to 300 nm.

  The above-mentioned alumina and alumina hydrate used in the present invention are used in the form of a dispersion dispersed by a known dispersant such as acetic acid, lactic acid, formic acid, nitric acid and the like.

  In the present invention, examples of the resin binder used together with the inorganic fine particles constituting the undercoat layer of the porous layer include, for example, polyvinyl alcohol, silanol-modified polyvinyl alcohol, polyvinyl acetate, oxidized starch, etherified starch, carboxymethylcellulose, and hydroxyethylcellulose. Cellulose derivatives such as casein, gelatin, acidic gelatin, soybean protein, silyl-modified polyvinyl alcohol, etc .; conjugated diene copolymer latex such as maleic anhydride resin, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer; Acrylic polymer latex such as acrylic acid or methacrylic acid ester polymer or copolymer, acrylic acid or methacrylic acid polymer or copolymer; ethylene vinyl acetate copolymer Vinyl polymer latex such as polymer; or functional group-modified polymer latex with functional group-containing monomers such as carboxyl groups of these various polymers; aqueous adhesive such as thermosetting synthetic resin systems such as melamine resin and urea resin Agents: Synthetic resin adhesives such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, alkyd resin, etc. can be used alone or in combination. In addition, the use of known natural or synthetic resin binders alone or in combination is not particularly limited.

  Particularly preferred among the polyvinyl alcohols are those having a degree of saponification of 80% or more or those completely saponified. Those having an average degree of polymerization of 200 to 5000 are preferred.

  Although the content of the resin binder with respect to these inorganic fine particles or organic fine particles is not particularly limited, in order to form a porous layer using inorganic fine particles, the content of the resin binder is 3 to 80% by mass with respect to the inorganic fine particles. Is preferable, more preferably in the range of 5 to 60% by mass, and particularly preferably in the range of 10 to 40% by mass. In the organic fine particles, since it is possible to form a porous layer by binding organic fine particles, there is no lower limit on the content of the resin binder, and the range of 0 to 80% by mass is preferable, and more preferably 0. It is the range of -60 mass%, Most preferably, it is the range of 0-40 mass%.

  In the present invention, if necessary, a hardening agent can be used together with the above-mentioned resin binder constituting the undercoat layer of the porous layer. Specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1 , 3,5 triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, N-methylol compounds as described in Japanese Patent No. 2,732,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,983,611 described Aziridines such as carbodiimide compounds as described in US Pat. No. 3,100,704, Epoxy compounds as described in No. 3,091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, borax, boric acid and borates These may be used alone or in combination of two or more. Although the usage-amount of a hardening agent is not specifically limited, 50 mass% or less is preferable with respect to a resin binder, More preferably, it is 40 mass% or less, Most preferably, it is 30 mass% or less.

  When a partially saponified polyvinyl alcohol having a saponification degree of 80% or more is used as the hydrophilic binder, borax, boric acid and borates are preferable, boric acid is particularly preferable, and the amount used is polyvinyl alcohol. On the other hand, 40 mass% or less is preferable, More preferably, it is 30 mass% or less, Most preferably, it is 20 mass% or less.

  Further, a resin binder having a keto group can also be used as a hydrophilic binder constituting the undercoat layer made of a porous layer. The resin binder having a keto group can be synthesized by a method of copolymerizing a monomer having a keto group and another monomer. Specific examples of the monomer having a keto group include acrolein, diacetone acrylamide, diacetone methacrylate, acetoacetoxyethyl methacrylate, 4-vinylacetoacetanilide, acetoacetylallylamide and the like. Further, a keto group may be introduced by a polymer reaction. For example, an acetoacetyl group can be introduced by a reaction of a hydroxy group or an amino group with a diketene. Specific examples of the resin binder having a keto group include acetoacetyl-modified polyvinyl alcohol, acetoacetyl-modified cellulose derivatives, acetoacetyl-modified starch, diacetone acrylamide-modified polyvinyl alcohol, and resin binders described in JP-A-10-157283. Can be mentioned. In the present invention, modified polyvinyl alcohol having a keto group is particularly preferable. Examples of the modified polyvinyl alcohol having a keto group include acetoacetyl-modified polyvinyl alcohol and diacetone acrylamide-modified polyvinyl alcohol.

  The acetoacetyl-modified polyvinyl alcohol can be produced by a known method such as a reaction between polyvinyl alcohol and diketene. The degree of acetoacetylation is preferably from 0.1 to 20 mol%, more preferably from 1 to 15 mol%. The saponification degree is preferably 80 mol% or more, more preferably 85 mol% or more. The degree of polymerization is preferably 500 to 5000, more preferably 2000 to 4500.

  The diacetone acrylamide modified polyvinyl alcohol can be produced by a known method such as saponification of a diacetone acrylamide-vinyl acetate copolymer. As content of a diacetone acrylamide unit, the range of 0.1-15 mol% is preferable, and also the range of 0.5-10 mol% is preferable. The saponification degree is preferably 85 mol% or more, and the polymerization degree is preferably 500 to 5000.

  In the present invention, the resin binder having a keto group contained in the undercoat layer made of a porous layer is preferably crosslinked with the crosslinking agent. Such a crosslinking agent is preferably a polyhydrazide compound or a polyvalent metal salt. Among the polyhydrazide compounds, dihydrazide compounds are particularly preferable, and adipic acid dihydrazide and succinic acid dihydrazide are more preferable. As the polyvalent metal salt, a zirconium salt is particularly preferable, and zirconium oxychloride and zirconium nitrate are more preferable.

  In the present invention, it is also preferable to use a resin curable with ultraviolet rays or an electron beam as the resin binder contained in the undercoat layer of the porous layer. In particular, when the porous layer is partially formed on the substrate, it is preferable because the porous layer can be fixed by irradiating ultraviolet rays or electron beams immediately after coating.

  Examples of the ultraviolet curable resin used in the present invention include compounds having an ethylenically unsaturated bond, and specific examples include the following compounds.

(1) Aliphatic, alicyclic, aromatic, araliphatic polyhydric alcohol and poly (meth) acrylate of polyalkylene glycol (2) Aliphatic, alicyclic, aromatic, araliphatic polyhydric alcohol (3) Polyester poly (meth) acrylate (4) Polyurethane poly (meth) acrylate (5) Epoxy poly (meth) acrylate (6) Polyamide poly (meta) ) Acrylate (7) Poly (meth) acryloyloxyalkyl phosphate ester (8) Vinyl-based or diene-based compound having (meth) acryloyloxy group at the side chain or terminal (9) Monofunctional (meth) acrylate, vinylpyrrolidone , (Meth) acryloyl compounds (10) have ethylenically unsaturated bonds Cyano compounds (11) Mono- or polycarboxylic acids having an ethylenically unsaturated bond, and alkali metal salts, ammonium salts, amine salts thereof, etc. (12) Ethylenically unsaturated (meth) acrylamide or alkyl-substituted (meth) acrylamide and (13) Vinyl lactam and polyvinyl lactam compounds (14) Polyethers having ethylenically unsaturated bonds and esters thereof (15) Esters of alcohols having ethylenically unsaturated bonds (16) Having ethylenically unsaturated bonds Polyalcohol and its ester (17) Aromatic compound having one or more ethylenically unsaturated bonds such as styrene and divinylbenzene (18) Polyorganosiloxane compound having (meth) acryloyloxy group at side chain or terminal 19) silicone compounds having an ethylenically unsaturated bond (20) above (1) to (19) multimeric or oligoester (meth) acrylate modified compounds of the compounds described

  These resins can be used alone or in combination with other resins. Moreover, it can also apply | coat without a solvent, can also be diluted with a solvent, can apply | coat, and can also apply | coat, dry and harden and use it in an emulsion state. Among them, the urethane acrylate resin shown in the above (4) is suitable in the present invention because it has a relatively large molecular weight, so that the drying shrinkage is small and there is little possibility of causing warpage of the substrate.

  In the present invention, it is preferable to use a water-soluble UV curable resin in order to obtain affinity with inorganic fine particles dispersed and pulverized in water. In recent years, solvent-free water-based types have been marketed by various manufacturers in consideration of the work environment. For example, Arakawa Chemical Industry Co., Ltd. has a beam set series and Shin Nakamura Chemical Industry Co., Ltd. has an NK oligo series.

  Examples of the photopolymerization initiator used in the present invention include acetophenones such as di- and trichloroacetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyldimethyl ketal, tetramethylthiuram monosulfide, thioxanthones, azo compounds There are various silver salts, and the amount of the photopolymerization initiator used is usually in the range of 0.1 to 10% in terms of solid content with respect to the ultraviolet curable resin. In addition, a storage stabilizer such as hydroquinone may be used as the photopolymerization initiator.

  Also, the ultraviolet curable resin can be cured by irradiation with an electron beam. As the electron beam accelerator, for example, any of an electro curtain system, a scanning type, a double scanning type, or the like may be used, or a silicon foil having a thickness of about 3 μm, which has been put into practical use in recent years, is used for a relatively low energy. For example, it is possible to use an ultra-compact electron beam irradiation device that can extract an electron beam with an acceleration voltage of 100 KV or less with low loss, for example, a device commercially available as Min-EB from American International Technology Co., in addition to the porous layer forming part. It can be used very preferably from the viewpoint of not damaging.

  The content of the resin binder that is cured by ultraviolet rays or electron beams is preferably in the range of 5 to 80% by mass, particularly preferably in the range of 10 to 60% by mass with respect to the fine particles.

  In general, the thickness (when dried) of the porous layer is preferably 1 to 100 μm, more preferably 5 to 70 μm, and particularly preferably 10 to 50 μm.

  Add preservatives, surfactants, colored dyes, UV absorbers, antioxidants, pigment dispersants, antifoaming agents, leveling agents, viscosity stabilizers, pH adjusters, etc. to the undercoat layer as necessary. You can also.

  The undercoat layer may be composed of two or more layers. In this case, the structures of the undercoat layers may be the same or different from each other. An undercoat layer made of a porous layer may be formed on the substrate side).

  The undercoat layer is prepared by dissolving or dispersing one or more of the above materials in an appropriate solvent to prepare a coating solution. The coating solution is a curtain method, an extrusion method, a slot die method, a gravure roll method, a spray method, an air knife. Using various known coating methods such as coating by blade coating method, blade coating method, rod bar coating method, spin coating method, letterpress printing, flexographic printing, gravure printing, screen printing, inkjet printing, etc. It can be formed by selectively applying to the entire surface of the material or to a required portion.

  It is also a preferable aspect of the present invention that a compound having a halogen in the molecule is contained in the undercoat layer by ionic bonds used in the present invention. A compound having halogen in the molecule by ionic bonding may be blended in the coating solution of the undercoat layer, and after forming the undercoat layer, immersion by dipping or the like may be performed by the above various coating apparatuses. .

  Further, in order to improve the adhesion between the base material and the conductive member, the base material may be directly subjected to corona treatment, plasma treatment, etc., and these treatments may be performed after the undercoat layer is formed. .

  As an apparatus for forming a conductive member using the conductivity expression method according to the present invention, for example, filling a concave portion with a dispenser, forming a convex portion, forming a pattern, thermal or piezo, micropump, static electricity, etc. Filling recesses, forming bumps, forming patterns, letterpress printing, flexographic printing, planographic printing, intaglio printing, gravure printing, patterning by screen printing, gravure roll method, slot die It is applied in a desired shape by various known methods such as formation of a coating layer by a method, spin coating method, etc., or partial coating layer formation by an intermittent coating die coater or the like. Moreover, application | coating can also be performed in multiple times so that it may become desired thickness.

For example, the following method can be used as a process for causing a compound having a halogen in the molecule to act on the ultrafine metal particles by ionic bonds.
1. On the base material, a compound itself having a halogen in the molecule by ionic bond, or a layer containing this compound is formed in advance on the entire surface or in a necessary site, and a desired shape is formed on it using a metal colloid solution. How to make.
2. A method of preparing a desired shape using a metal colloid solution on a substrate and then applying or dipping a solution containing a compound having a halogen in the molecule by ionic bonding (for example, by an ink jet method or a dispenser method).
3. A method of preparing a desired shape using a metal colloid solution on a substrate and then leaving it in an environment where a solution in which a compound having a halogen in the molecule is dissolved or dispersed by ionic bonding exists in a mist form.
4). A method of producing a desired shape by mixing a metal colloid solution on a substrate and a solution containing a compound having halogen in the molecule by ionic bonding immediately before.
5. A method in which a metal ultrafine particle and a compound having a halogen in the molecule by ionic bond are dispersed together in a nonpolar organic solvent not containing water to produce a desired shape, and the organic solvent is volatilized or absorbed.

  In order to increase the conductivity of the member formed by the methods 1 to 5, it is also preferable to supply moisture. For supplying water, for example, there are a method of applying water droplets by an ink jet method and a spray of mist water by a spray nozzle, but a method by humidity can also be preferably used.

  For example, by lowering the substrate temperature below the ambient temperature, a large amount of moisture can be present on the substrate surface. Condensation may be performed, but it is more preferable that the condensation is not caused. The humidity of the surrounding atmosphere may be simply increased without controlling the temperature of the substrate surface. In this case, the temperature is preferably 10 ° C. to 80 ° C., and the weight absolute humidity H is 0.01 kg / kg D.D. A. It is preferable that there is more.

  After forming the conductive member, it is also preferable to remove the compound having halogen in the molecule by ionic bonding by washing. In addition, a coating liquid containing a resin component for sealing the conductive member (for example, a component used for the undercoat layer described above) is applied to the entire surface of the substrate on which the conductive member is formed or to a necessary portion (for example, an inkjet method or It is also preferable to perform application (by a dispenser system or the like) to protect the produced conductive member.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example. In addition, a part and% show a mass part and mass%.

Example 1
<Preparation of aqueous silver colloid solution 1>
An aqueous solution in which 3.5 g of dextrin is dissolved in 31.5 g of ion-exchanged water and an aqueous solution in which 8.5 g of silver nitrate is dissolved in 41.5 g of ion-exchanged water are mixed, and 38 g of 2N aqueous sodium hydroxide solution is added while stirring. The solution was slowly added dropwise over a period of minutes. After 1 hour, stirring was stopped and left for 12 hours. Thereafter, decantation was performed, 25 g of ion-exchanged water was added to 25 g of the obtained precipitate, redispersion was performed, and centrifugation was performed to obtain a solid precipitate. 7 g of ion exchange water was added to the solid precipitate to obtain a silver colloid liquid having a solid content of 38% and a specific gravity of 1.4.

  Concentrated nitric acid was added to the obtained silver colloid solution to form silver nitrate, and titration was performed using an aqueous potassium iodide solution to determine the silver concentration. The obtained silver concentration is 32%, and 6% corresponding to the difference from the solid content of 38% corresponds to the content of a dispersant other than silver. As a result of observation with an electron microscope, the particle diameter of the ultrafine silver particles was about 20 nm.

<Preparation of aqueous silver colloid solution 2>
An aqueous solution in which 43 g of ferrous sulfate heptahydrate was dissolved in 100 g of ion-exchanged water and an aqueous solution in which 66 g of sodium citrate dihydrate was dissolved in 100 g of ion-exchanged water were mixed, and the pH was adjusted with a 5N aqueous sodium hydroxide solution. Was adjusted to 6. While stirring, an aqueous solution in which 11 g of silver nitrate was dissolved in 100 g of ion exchange water was gradually added to obtain an aqueous metal colloid solution containing silver ultrafine particles having iron citrate as a protective colloid. After this metal colloid aqueous solution was left overnight and decanted, 300 g of 1N ammonium nitrate aqueous solution was added, decantation was performed three times, excess salts were removed, and centrifugation was performed to obtain a solid precipitate. I got a thing. 5 g of ion-exchanged water was added to the solid precipitate to obtain a silver colloid liquid having a solid content of 55% and a specific gravity of 1.7.

  Concentrated nitric acid was added to the obtained silver colloid solution to form silver nitrate, and titration was performed using an aqueous potassium iodide solution to determine the silver concentration. The obtained silver concentration is 45%, and 10% corresponding to the difference from the solid content of 55% corresponds to the content of a dispersant other than silver. As a result of observation with an electron microscope, the particle diameter of the ultrafine silver particles was about 10 nm.

<Preparation of aqueous silver colloid solution 3>
An aqueous solution in which 43 g of ferrous sulfate heptahydrate was dissolved in 100 g of ion-exchanged water and an aqueous solution in which 66 g of sodium citrate dihydrate was dissolved in 100 g of ion-exchanged water were mixed, and the pH was adjusted with a 5N aqueous sodium hydroxide solution. Was adjusted to 6. While stirring, an aqueous solution in which 10.5 g of silver nitrate and 0.68 g of palladium nitrate were dissolved in 100 g of ion-exchanged water was gradually added to obtain an aqueous metal colloid solution containing silver palladium ultrafine particles having iron citrate as a protective colloid. . After this metal colloid aqueous solution was left overnight and decanted, 300 g of 1N ammonium nitrate aqueous solution was added, decantation was performed three times, excess salts were removed, and centrifugation was performed to obtain a solid precipitate. I got a thing. 5 g of ion-exchanged water was added to the solid precipitate to obtain a silver colloid liquid having a solid content of 52% and a specific gravity of 1.6.

  Concentrated nitric acid was added to the obtained silver colloid solution to form silver nitrate, and titration was performed using an aqueous potassium iodide solution to determine the silver concentration. The determined silver concentration was 41%. Furthermore, when the concentration of palladium was measured using a fluorescent X-ray analyzer (RIX1000 manufactured by Rigaku Corporation), a result of 2% was obtained. The total of both is 43%, and 9% corresponding to the difference from the solid content of 52% corresponds to the content of a dispersant other than silver and palladium. As a result of observation with an electron microscope, the particle diameter of the silver palladium ultrafine particles was about 10 nm.

<Preparation of substrate 1>
Using polyfix 601 (manufactured by Showa Polymer Co., Ltd.) as a polyamine resin having chlorine ions as counter ions, a dry film thickness is formed on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm and subjected to easy adhesion treatment. Was applied and dried so as to be 2 μm.

<Preparation of base material 2>
On a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm and using PAS-H-1L (manufactured by Nittobo) as diallyldimethylammonium chloride-polymer having chlorine ions as counter ions. And dried so that the dry film thickness was 2 μm.

<Preparation of base material 3>
PAA-HCL-3L (manufactured by Nittobo) is used as a polyallylamine polymer having chlorine ions as a counter ion, and is dried on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm and subjected to easy adhesion treatment. It was applied and dried so that the film thickness was 2 μm.

<Preparation of base material 4>
As a polyallylamine-based polymer having a hydroxyl group as a counter ion, PAA-10C (manufactured by Nittobo) is used, and a dry film thickness is 2 μm on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm and subjected to easy adhesion treatment. It was applied and dried so that

<Preparation of base material 5>
10 g of polyvinyl alcohol PVA405 (manufactured by Kuraray Co., Ltd.) was dissolved in 90 g of ion-exchanged water. On top of this was added 4g of Purachem WT (manufactured by Riken Green Co., Ltd.) as polyaluminum hydroxide having chlorine ions as counter ions, and then a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) with a thickness of 100μm that had been subjected to easy adhesion treatment. And dried so that the dry film thickness was 5 μm.

<Preparation of substrate 6>
10 g of polyvinyl alcohol PVA405 (manufactured by Kuraray Co., Ltd.) was dissolved in 90 g of ion-exchanged water. After 2 g of sodium chloride was added thereto, it was applied and dried on a 100 μm-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd.) that had been subjected to easy adhesion treatment so that the dry film thickness was 5 μm.

<Preparation of base material 7>
10 g of polyvinyl alcohol PVA405 (manufactured by Kuraray Co., Ltd.) was dissolved in 90 g of ion-exchanged water. After 2 g of sodium bromide was added thereto, it was applied and dried on a 100 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd.) that had been subjected to an easy adhesion treatment so that the dry film thickness was 5 μm.

<Preparation of base material 8>
10 g of polyvinyl alcohol PVA405 (manufactured by Kuraray Co., Ltd.) was dissolved in 90 g of ion-exchanged water. After 2 g of ammonium chloride was added thereto, it was applied and dried on a 100 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd.) that had been subjected to an easy adhesion treatment so that the dry film thickness was 5 μm.

<Preparation of base material 9>
10 g of polyvinyl alcohol PVA405 (manufactured by Kuraray Co., Ltd.) is dissolved in 90 g of ion-exchanged water, and the dry film thickness is 5 μm on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm subjected to easy adhesion treatment. , Applied and dried.

<Preparation of substrate 10>
10 g of polyvinyl alcohol PVA405 (manufactured by Kuraray Co., Ltd.) is dissolved in 90 g of ion-exchanged water, and a dry film thickness of 15 μm is formed on a 100 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) subjected to easy adhesion treatment. , Applied and dried.

<Preparation of substrate 11>
10 g of polyvinyl alcohol PVA-117 (manufactured by Kuraray Co., Ltd.) is dissolved in 90 g of ion-exchanged water, and the dry film thickness is 15 μm on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm that has been subjected to easy adhesion treatment. Thus, it was applied and dried.

<Preparation of sodium chloride coating solution 1>
A 5% aqueous solution of sodium chloride was prepared using pure water, and 0.1% of an alkylene glycol nonionic surfactant was added thereto to obtain a sodium chloride coating solution 1.

<Preparation of substrate 12>
The sodium chloride coating solution 1 was applied onto the substrate 10 using a # 6 wire bar. The amount of sodium chloride applied was 0.6 g / m ² .

<Preparation of base material 13>
3g of alkali-treated gelatin (made by Nitta Gelatin Co., Ltd.), 4g of polyvinylpyrrolidone PVP-K90 (made by ISP), and 0.3g of epoxy crosslinker Denacol EX-521 (made by Nagase ChemteX Corporation) as a hardening agent It was applied and dried so as to have a dry film thickness of 15 μm on a 100 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd.) dissolved in 90 g of exchange water and subjected to easy adhesion treatment.

<Preparation of the base material 14>
The sodium chloride coating solution 1 was applied onto the substrate 13 using a # 6 wire bar. The amount of sodium chloride applied was 0.6 g / m ² .

<Preparation of base material 15>
Precipitation dispersion using a sawtooth-type blade disperser (blade peripheral speed 30 m / sec) with precipitation method silica (oil absorption 200 ml / 100 g, average primary particle size 16 nm, average secondary particle size 9 μm) added to water. A liquid was prepared. Next, the obtained preliminary dispersion was treated with a bead mill (using 0.3 mmφ zirconia beads) to obtain an inorganic fine particle dispersion 1 having a solid content concentration of 30% by mass. The average secondary particle diameter of the dispersed silica was 250 nm.

  The inorganic fine particle dispersion 1 and other chemicals were mixed at 50 ° C. to prepare a porous layer forming coating solution 1 having the following composition.

<Porous layer forming coating solution 1>
Inorganic fine particle dispersion 1 (as silica solid content) 100 g
Polyvinyl alcohol 16g
(Saponification degree 88%, average polymerization degree 3500)
Boric acid 3g
Nonionic surfactant 0.3g
(Polyoxyethylene alkyl ether)
The solid concentration was adjusted with water so as to be 12%.

  The porous layer forming coating solution 1 was coated and dried as inorganic fine particles on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm that had been subjected to an easy adhesion treatment so as to be 20 g per square meter.

<Preparation of the base material 16>
4 μg of polyfix 601 (manufactured by Showa Polymer Co., Ltd.) as a polyamine resin having chlorine ions as counter ions in the porous layer forming coating solution 1 and 100 μm thick polyethylene terephthalate which has been subjected to easy adhesion treatment On a film (manufactured by Teijin DuPont Films Co., Ltd.), it was coated and dried as inorganic fine particles so as to be 20 g per square meter.

<Preparation of the base material 17>
The sodium chloride coating solution 1 was applied onto the substrate 15 using a # 6 wire bar. The amount of sodium chloride applied was 0.7 g / m ² .

<Preparation of the base material 18>
Gas phase method silica (average primary particle diameter 7 nm, specific surface area 300 m ² / g) is added to water as inorganic fine particles, and a pre-dispersion liquid is prepared using a sawtooth blade type disperser (blade peripheral speed 30 m / sec). Produced. Next, the obtained preliminary dispersion was treated with a bead mill (using 0.3 mmφ zirconia beads) to obtain an inorganic fine particle dispersion 2 having a solid concentration of 10% by mass. The average secondary particle size was 120 nm.

  Using the inorganic fine particle dispersion 2, a porous layer forming coating solution 2 having the following composition was prepared.

<Porous layer forming coating solution 2>
Inorganic fine particle dispersion 2 (as silica solid content) 100 g
Polyvinyl alcohol 25g
(Saponification degree 88%, average polymerization degree 3500)
Boric acid 4g
Nonionic surfactant 0.3g
(Polyoxyethylene alkyl ether)
The solid content was adjusted with water so that the solid concentration would be 8%.

  The porous layer forming coating solution 2 was coated and dried as inorganic fine particles on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm that had been subjected to an easy adhesion treatment so as to be 20 g per square meter.

<Preparation of the base material 19>
On the substrate 18, 5% of mucochloric acid was dissolved in ethanol as a compound having a halogen in the molecule by a covalent bond, and this was applied using a # 6 wire bar. The amount of mucochloric acid applied was 0.6 g / m ² .

<Preparation of the base material 20>
On the substrate 18, 5-chlorobenzotriazole as a compound having a halogen in the molecule by a covalent bond was dissolved in ethanol by 5%, and this was applied using a # 6 wire bar. The amount of 5-chlorobenzotriazole applied was 0.6 g / m ² .

<Preparation of the base material 21>
4 μg of Purachem WT (manufactured by Riken Green Co., Ltd.) is added to the porous layer forming coating solution 2 as polyaluminum hydroxide having chlorine ions as counter ions, and a polyethylene terephthalate film with a thickness of 100 μm (Teijin DuPont) subjected to easy adhesion treatment. (Manufactured by Film Co., Ltd.) was coated and dried as inorganic fine particles at 20 g per square meter.

<Preparation of the base material 22>
The sodium chloride coating solution 1 was applied onto the substrate 18 using a # 6 wire bar. The amount of sodium chloride applied was 0.7 g / m ² .

<Preparation of base material 23>
8 parts of Charol DC902P (Daiichi Kogyo Seiyaku Co., Ltd.) as diallyldimethylammonium chloride-polymer having chlorine ions as counter ions in water, and gas phase method silica (average primary particle diameter of 7 nm, specific surface area) as inorganic fine particles (300 m ² / g) 100 parts were added, and a pre-dispersion was prepared using a sawtooth blade type disperser (blade peripheral speed 30 m / sec). Next, the obtained preliminary dispersion was treated with a high-pressure homogenizer to produce an inorganic fine particle dispersion 3 having a solid concentration of 20% by mass. The average secondary particle size was 130 nm.

  A porous layer forming coating solution 3 having the following composition was prepared using the inorganic fine particle dispersion 3.

<Porous layer forming coating solution 3>
Inorganic fine particle dispersion 3 (as silica solid content) 100 g
Polyvinyl alcohol 25g
(Saponification degree 88%, average polymerization degree 3500)
Boric acid 4g
Nonionic surfactant 0.3g
(Polyoxyethylene alkyl ether)
The solid concentration was adjusted with water so as to be 13%.

  The porous layer forming coating solution 3 was coated and dried as inorganic fine particles on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd.) having a thickness of 100 μm that had been subjected to an easy adhesion treatment so as to be 10 g per square meter.

<Preparation of the base material 24>
The porous layer forming coating solution 3 was applied and dried as inorganic fine particles on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm that had been subjected to an easy adhesion treatment so as to be 20 g per square meter.

<Preparation of base material 25>
Using the inorganic fine particle dispersion 3, a porous layer forming coating solution 4 having the following composition was prepared. On a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm and subjected to an easy adhesion treatment with a slide bead coating device with the porous layer forming coating solution 4 as the lower layer and the crosslinking agent-containing coating solution 1 having the following composition as the upper layer. In addition, simultaneous multilayer coating and drying were performed so that the inorganic fine particles were 35 g per square meter and adipic acid dihydrazide was 0.8 g per square meter.

<Porous layer forming coating solution 4>
Inorganic fine particle dispersion 3 (as silica solid content) 1000 g
Acetacetyl-modified polyvinyl alcohol 230g
(Acetyacetylation degree 3%, saponification degree 98%, average polymerization degree 2350)
Nonionic surfactant 3g
(Polyoxyethylene alkyl ether)
It adjusted with water so that solid content concentration might be 12%.

<Crosslinking agent-containing coating solution 1>
Adipic acid dihydrazide 1000g
Nonionic surfactant 20g
(Polyoxyethylene alkyl ether)
The total amount was made 20000 g with water.

<Preparation of the base material 26>
Using the inorganic fine particle dispersion 3, a porous layer forming coating solution 5 having the following composition was prepared.

<Porous layer forming coating solution 5>
Inorganic fine particle dispersion 3 (as silica solid content) 100 g
60g urethane acrylate resin
(New Nakamura Chemical Co., Ltd. NK Oligo UA-7100)
Photoinitiator 1g
(2-hydroxy-2-methyl-1-phenyl-propan-1-one)
It adjusted with water so that solid content concentration might be 40%.

  The porous layer forming coating solution 5 is applied as inorganic fine particles on a polyethylene terephthalate film (made by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm that has been subjected to an easy adhesion treatment, and an ultraviolet ray having an irradiation energy of 80 W / cm. It was cured by passing under the lamp at a conveyance speed of 9 m / min and dried.

<Preparation of base material 27>
The following porous forming coating solution 6 was applied and dried on a 100 μm-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd.) that had been subjected to an easy adhesion treatment so that the inorganic fine particles were 20 g per square meter. The wet silica used in the porous forming coating liquid 6 is a so-called gel-type silica, and the average primary particle diameter is 100 nm or less, but the primary particles are firmly fixed and the average secondary particle diameter is 6 μm. It has become. Since the crushing and dispersion treatment using a bead mill was not performed as in the case of the inorganic fine particle dispersion 1, simple mixing was performed, and thus the average secondary particle size in the porous layer forming coating solution 6 was 6 μm.

<Porous layer forming coating solution 6>
Wet silica 100g
(Mizusawa Chemical Co., Ltd. Mizukasil P78A, average secondary particle size 6 μm)
Polyvinyl alcohol 50g
(Saponification degree 98%, average polymerization degree 1700)
Nonionic surfactant 0.3g
(Polyoxyethylene alkyl ether)
It adjusted with water so that solid content concentration might be 15%.

<Preparation of substrate 28>
The sodium chloride coating solution 1 was applied onto the substrate 27 using a # 6 wire bar. The amount of sodium chloride applied was 0.7 g / m ² .

<Preparation of base material 29>
Nitric acid (2.5 parts) and alumina hydrate (average primary particle size 15 nm) are added to water, and an inorganic fine particle dispersion 4 having a solid content concentration of 30% by mass is obtained using a sawtooth blade type disperser. It was. The average secondary particle size was 160 nm.

  Using the inorganic fine particle dispersion 4, a porous layer forming coating solution 7 having the following composition was prepared.

<Porous layer forming coating solution 7>
Inorganic fine particle dispersion 4 (as alumina hydrate solid content) 100 g
Polyvinyl alcohol 12g
(Saponification degree 88%, average polymerization degree 3500)
Boric acid 0.5g
Nonionic surfactant 0.3g
(Polyoxyethylene alkyl ether)
It adjusted with water so that solid content concentration might be 16%.

  The porous layer-forming coating solution 7 was applied and dried as inorganic fine particles on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm that had been subjected to an easy adhesion treatment so as to be 20 g per square meter.

<Preparation of the base material 30>
The sodium chloride coating solution 1 was applied onto the substrate 29 using a # 6 wire bar. The amount of sodium chloride applied was 0.7 g / m ² .

<Preparation of base material 31>
The following porous forming coating solution 8 was applied and dried so as to be 20 g per square meter as organic fine particles on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm subjected to easy adhesion treatment. Since the organic fine particles used in the porous forming coating liquid 8 have a glass transition point of 75 ° C., the temperature of the coating liquid preparation, coating and drying should not exceed 30 ° C., and the porous layer formation should not be inhibited. did.

<Porous layer forming coating solution 8>
Styrene-acrylic resin 100g
(Average primary particle diameter 70 nm, glass transition temperature 75 ° C., minimum film-forming temperature 80 ° C., concentration 30% by mass)
Polyvinyl alcohol 8g
(Saponification degree 98%, average polymerization degree 1700)
Nonionic surfactant 0.3g
(Polyoxyethylene alkyl ether)
It adjusted with water so that solid content concentration might be 25%.

<Preparation of the base material 32>
The sodium chloride coating solution 1 was applied onto the substrate 31 using a # 6 wire bar. The amount of sodium chloride applied was 0.7 g / m ² .

<Formation 1 of conductive member>
After applying various metal colloid solutions to the base materials 1 to 32 and using a # 6 wire bar, the metal thin film formed on the base material is cut into 80 mm × 50 mm together with the base material, and this is electrically conductive It was a sex member. The metal colloid solution used is the above-mentioned aqueous silver colloid solution 1 as metal colloid 1, the above-mentioned aqueous silver colloid solution 2 as metal colloid 2, the above-mentioned aqueous silver colloid solution 3 as metal colloid 3, and the aqueous silver nano-ink as metal colloid 4. Sumitomo Electric AGIN-W4A manufactured by Kogyo Co., Ltd. (silver ultrafine particle diameter of about 15 nm), aqueous silver / copper composite nano ink as metal colloid 5, IJ241-4 manufactured by Cima NanoTech (metal ultrafine particles containing 2 parts of copper per 100 parts of silver) The organic colloidal silver nano-ink ULG Materials AG1TeH (silver ultrafine particle diameter of about 10 nm) was used as the metal colloid 6. Application of the metal colloid was performed at 15 ° C. and 27% Rh (weight absolute humidity H = 0.0029 kg / kg DA). Water-based metal colloids 1 to 5 are dried in an environment of 15 ° C. and 27%, and the high boiling point solvent (n-tetradecane) contained in the pattern made with the organic solvent-based metal colloid 6 is volatilized to some extent. Therefore, drying was performed at 100 ° C. (relative humidity 1% Rh or less).

  Each conductive member obtained was evaluated as follows, and the results are shown in Table 1.

<Conductivity>
About each electroconductive member, the amount of silver per square meter was measured using the fluorescent-X-ray-analysis apparatus (RIX1000 by Rigaku Corporation). Under the environment of 23 ° C. and 50% Rh, the sheet resistance value of each conductive member was measured using a measuring instrument (Lorestar GP manufactured by Dia Instruments Co., Ltd.). The theoretical sheet resistance value was calculated from the obtained silver amount per square meter for various metal thin films, and compared with the actually measured sheet resistance value. As an example of theoretical sheet resistance value calculation, for example, in a sample in which the metal colloid 1 is applied to the base material 24, the silver amount per square meter measured by a fluorescent X-ray analyzer is 4.7 g. The thickness is 4.48 × 10 ⁻⁵ cm divided by the specific gravity of 10.5. The sheet resistance value is obtained by dividing the volume resistance value of 1.59 × 10 ⁻⁶ Ω · cm of silver by this thickness, and the value is calculated as 0.0355 Ω / □. The metal colloid 3 and the metal colloid 5 contain palladium or copper but are as small as about 2%. Therefore, in this evaluation, the sheet resistance value is determined only by the silver amount measured by the fluorescent X-ray analyzer. Was calculated.
The theoretical sheet resistance value was evaluated according to the following criteria.
○: Less than 10 times the theoretical sheet resistance value Δ: 10 times or more and less than 10,000 times the theoretical sheet resistance value ×: 10,000 times or more the theoretical sheet resistance value −: No conductivity For example, the metal colloid 1 In the sample applied to the substrate 24, the measured sheet resistance value is less than 0.355Ω, ◯, if it is 0.355Ω or more and less than 355Ω, Δ if it is 355Ω or more, x, overrange display and measurement is impossible. If so, it is evaluated as-.

  As is apparent from the results in Table 1, the base material of the present invention exhibits good conductivity with the metal colloid 1 using dextrin as the reducing agent. The metal colloid 5 has a high resistance value because the particle diameter is as large as 50 nm or more, and the metal colloid 6 did not exhibit conductivity. The thicker the undercoat layer, the better the conductivity, and particularly the better conductivity when a porous layer is formed. From the comparison of the substrates 3 and 4, it can be seen that even if the polymer is a cationic polymer, the conductivity does not appear in the polymer having no chlorine ion. In the comparative example in which the compound having halogen in the molecule due to ionic bond is not present in the base material and the comparative example in which the compound having halogen in the molecule due to covalent bond is present in the base material (base material 19 and base material 20), It does not show conductivity at all.

Example 2
The conductive member of Example 1 was allowed to stand for 1 hour under high humidity conditions of 50 ° C. and 80% Rh (weight absolute humidity H = 0.067 kg / kg DA). Table 2 shows the results obtained by measuring the sheet resistance under the conditions of 23 ° C. and 50% Rh in the same manner as in Example 1.

  As is apparent from the results in Table 2, the conductivity is greatly improved by leaving the substrate of the present invention under high humidity conditions. In the comparative example in which the compound having halogen in the molecule due to ionic bond is not present in the base material and the comparative example in which the compound having halogen in the molecule due to covalent bond is present in the base material (base material 19 and base material 20), It does not show conductivity at all.

Example 3
Using a metal colloid 6, a straight line having a length of 1 cm was drawn on a polyethylene terephthalate film (manufactured by Teijin DuPont Films, Inc.) having a thickness of 100 μm that had been subjected to an easy adhesion treatment, using a dispenser. After drying at 100 ° C. (relative humidity 1% Rh or less), the shape of the drawn linear pattern was measured using a Tokyo Seimitsu Surfcom 1400A model, and the average thickness was 4 μm and the width was 1 mm. The resistance value of this linear pattern was measured according to the following resistance value evaluation method, but an overrange was displayed and no conductivity was observed.

  After immersing the linear pattern in the following treatment liquid 1 for 30 minutes, the resistance value was measured according to the following resistance value evaluation method. Furthermore, after leaving it to stand at 50 ° C. and 80% Rh for 12 hours, the resistance value was measured again.

<Treatment liquid 1> 5% sodium chloride aqueous solution

  Similarly, the same measurement was performed using the following treatment liquids 2 to 3.

<Treatment solution 2> 5% sodium bromide aqueous solution

<Treatment liquid 3> 5% Charol DC902P (Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution

  The evaluation method of the resistance value is shown below.

<Resistance value>
The resistance value between both ends of the linear pattern was measured with a tester (PC500 type, manufactured by Sanwa Denki Keiki Co., Ltd.) in an environment of 23 ° C. and 50% Rh.

  As is apparent from Table 3, the untreated product not immersed in the treatment liquid does not exhibit conductivity. It can be seen that the linear pattern treated with the treatment liquids 1 to 3 of the present invention exhibits high conductivity, and in particular, a sample left under a high humidity condition exhibits an extremely low resistance value.

Example 4
Pigment inks for cyan, magenta, yellow, and black cartridges of an ink jet printer using a commercially available pigment ink (Stylus C82, manufactured by Seiko Epson Corp.) Instead of filling.

<Silver ink 1>
Metal colloid 4 50cm ³
Ion exchange water 60cm ³

  A pattern composed only of 80 mm × 50 mm black was printed on the substrates 15 and 17 produced in Example 1. The print setting was set to Best Photo mode with the paper setting set to Glossy Photo Paper. Printing was performed in an environment of 23 ° C. and 50% Rh.

  The sheet resistance value immediately after printing was measured in the same manner as in Example 1. Further, the sheet resistance value was measured after being left for 2 minutes in an environment of 50 ° C. and 80% Rh, and after being left for 1 hour. The results are shown in Table 4. The amount of silver per square meter in the printed portion measured with a fluorescent X-ray analyzer was 2.02 g. When the theoretical sheet resistance value was calculated in the same manner as in Example 1, it was 0.083Ω / □.

  As is apparent from Table 4, when the base material 17 according to the present invention is used, the theoretical sheet resistance value calculated from the silver amount is 7 times immediately after printing and 2 minutes in an environment of 50 ° C. and 80% Rh. If it is left to stand, it will decrease to a very low resistance value of 3 times and if it is left in an environment of 50 ° C. and 80% Rh for 1 hour, it will be about twice as low. The substrate 15 containing no halogen does not show any conductivity. Since the base material 17 of Example 1 using the same metal colloid 4 showed a resistance value 12 times the theoretical sheet resistance value calculated from the silver amount, the evaluation result was Δ, but in this test The resistance value is 7 times lower. This is because when the silver ink 1 is produced, the metal colloid 4 is diluted, so that the time until the silver ink 1 is dried on the base material 17 becomes long, so that moisture is allowed to act after the conductive member is formed. It is considered that the same effect as in the case of

Claims (3)

  Conductivity characterized in that ultrafine metal particles dispersed as metal colloids in water and / or an organic solvent and a compound having a halogen in the molecule by ionic bonds act to obtain conductivity on the substrate. Sexual expression method.   2. The method of developing conductivity according to claim 1, wherein the metal ultrafine particles are mainly composed of silver.   3. The method of developing conductivity according to claim 1 or 2, further comprising a porous layer comprising inorganic fine particles and a binder of 80% by mass or less based on the inorganic fine particles on the substrate.