JP2010160989A - Method of manufacturing conductive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a conductive film excellent in adhesion with a base layer and capable of exhibiting a superb conductivity at low temperature and short-time heating. <P>SOLUTION: In the method of manufacturing the conductive film, a conductive layer (A) containing conductive fine particles, and an ion exchange layer (E) containing a copolymer (D) made by copolymerizing a monomer (B) containing a tertiary amino group and/or a quaternary ammonium group, and a monomer (C) capable of copolymerizing with the monomer (B) are laminated on a base layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a conductive film using a conductive ink.

Conductive coating is conductive to electromagnetic wave shielding for cathode ray tubes, plasma display panels, etc., infrared shielding for building materials or automobiles, antistatic coating for electronic devices and mobile phones, anti-fogging hot wires for glass, wiring for circuit boards, etc. It has a wide range of uses such as coating for imparting. As a method for forming these conductive films, there are methods by metal vacuum deposition, chemical vapor deposition, ion sputtering, etc., but the above method requires a vacuum treatment, and therefore has a problem of high production cost and low conductivity. there were.
Therefore, a method using silver paste (silver particle diameter of 1 μm or more) has been proposed as an inexpensive manufacturing method. However, this method requires that a conductive circuit such as a wiring be created by screen printing, and is practically used. In order to obtain the required conductivity, it is necessary to heat at a high temperature after printing, and the volume resistance value is limited to the order of 10 ⁻⁵ Ω · cm, which is not satisfactory (Non-Patent Documents 1 and 2). reference).

Therefore, by using a silver nano-dispersion using silver nanoparticles (particle diameter is 1 to 100 nm), even if the conductive film has a film thickness of about 0.1 to 5 μm, the volume is on the order of 10 ⁻⁶ Ω · cm. It is known that a resistance value can be obtained (see Non-Patent Documents 1 and 2). However, in order to develop this volume resistance value, it is necessary to heat and sinter the silver nanodispersion at a high temperature of about 200 ° C. for several tens of minutes. It is difficult to use it for a base material or a plastic film base material such as polyester. In addition, this method has a drawback that the conductive circuit and the conductive film formed using the silver nano-dispersion are poor in adhesion to the base material and easily crack. (See Patent Documents 1 and 2).

JP 2004-273205 A JP 2005-81501 A

Journal of Japan Institute of Electronics Packaging, Vol. 5, no. 6 (2002), 523-528 Nikkei Nano Business, Vol. 22 (2005. 9.26), pages 2-7

  An object of this invention is to provide the manufacturing method of the electroconductive film which is excellent in close_contact | adherence with a foundation | substrate and can express favorable electroconductivity by low temperature and short time heating.

The present invention comprises a conductive layer (A) containing conductive fine particles on a base;
Ions including a copolymer (D) obtained by copolymerizing a monomer (B) containing a tertiary amino group and / or a quaternary ammonium group and a monomer (C) copolymerizable with the monomer (B). It is related with the manufacturing method of the electroconductive film characterized by laminating | stacking an exchange layer (E).

  In the present invention, the monomer (C) is a monomer containing one or more organic groups selected from the group consisting of an alkyl group having a chain or ring structure having 6 to 20 carbon atoms and a phenyl group. It is related with the manufacturing method of the conductive film of the said invention characterized by the above.

  In the present invention, the proportion of the monomer (B) is 25 to 75% by weight and the proportion of the monomer (C) is 25 to 75% by weight in the total 100% by weight of the monomer (B) and the monomer (C). The present invention relates to a method for producing a conductive film according to any one of the above inventions.

  The present invention also relates to the method for producing a conductive film according to any one of the above inventions, wherein the copolymer (D) comprises water and an alcohol having 1 to 3 carbon atoms as a polymerization solvent.

  The present invention also relates to the method for producing a conductive film according to any one of the above inventions, wherein the conductive layer (A) is formed by an ink jet method.

  Moreover, this invention relates to the electroconductive film obtained by the manufacturing method of one of the said inventions.

  Moreover, this invention relates to the printed wiring board which has the electroconductive film of the said invention as an electroconductive circuit.

  The present invention also relates to a touch panel using the printed wiring board of the above invention.

  According to the present invention, it was possible to provide a conductive film that is excellent in adhesion to a base and can exhibit good conductivity by low-temperature and short-time heating.

  Therefore, the conductive film obtained by the present invention includes a non-contact IC media antenna circuit, a printed circuit board conductive circuit, a printed electronics conductive material, various electrode materials, an electromagnetic shielding mesh formation, an electromagnetic shielding conductive thin film, It can be used as an antistatic film or a film for imparting conductivity to a nonconductive material. Furthermore, the conductive film obtained by the present invention is excellent in terms of appearance and film strength such as film smoothness and color uniformity, and can also be used for applications that require specularity, such as display reflectors. .

  The present invention will be described below. However, the present invention is not limited to the following description or embodiments without departing from the technical idea of the present invention.

  First, the conductive layer (A) containing the conductive fine particles of the present invention (hereinafter also referred to as “conductive layer (A)”) will be described. The conductive layer (A) is preferably formed of a conductive ink.

The conductive ink preferably contains conductive fine particles, a resin, and a liquid medium.
The conductive fine particles are for imparting conductivity to the obtained conductive film. Examples of such conductive fine particles include conductive metal substances. Specifically, for example, metals such as gold, silver, copper, nickel, platinum, palladium, iron, cobalt, tungsten, titanium, indium, iridium, rhodium, and amorphous copper. Alloys of these metals, such as silver-copper alloys. Metal composites of these metals, such as silver-copper composites. The thing which coat | covered the metal with another electroconductive metal, for example, silver plating copper, etc. are mentioned. Among these, gold, silver, copper, nickel, platinum, palladium, and iron are preferable, gold, silver, copper, and nickel are more preferable, and silver is still more preferable in terms of conductivity and cost. Other conductive fine particles include, for example, metal oxides such as inorganic powders coated with the above metal substances, silver oxide, indium oxide, antimony oxide, zinc oxide, tin oxide, antimony-doped tin oxide, and indium-tin composite oxide. Carbon black, graphite, metal complexes, organic conductive fine particles and the like can also be used. The conductive fine particles may be used alone or in combination of two or more. When two or more kinds of conductive materials are used in combination, the plurality of materials may be in any form such as a mixture, a melt, a dispersion, and a coating.

  Examples of methods for obtaining conductive fine particles include production methods such as a wet method, an atomizing method, and an electrolytic method. As a result, conductive fine particles having various shapes such as flakes, scales, plates, spheres, substantially spheres, agglomerated spheres, dendrites and foils are obtained. Any shape can be used in the present invention.

Other methods for producing conductive fine particles include, for example, a gas phase method such as a gas evaporation method, and a liquid phase method in which a metal compound is reduced using ultrasonic waves, ultraviolet rays, or a reducing agent in a liquid phase (Japanese Patent Application Laid-Open No. Hei 11). -80647 and JP-A-61-276907), a melting method, an electrolytic method, and the like. In the present invention, it is preferable to produce by using a liquid phase method in which the production cost is low and the production process is small and the metal compound is reduced in the liquid phase using ultrasonic waves, ultraviolet rays or a reducing agent.
The obtained conductive fine particles preferably have an average particle size of 0.001 to 10 μm, and more preferably 0.001 to 0.05 μm. By using conductive fine particles in this range, it becomes possible to form a conductive film having excellent conductivity by heating at a low temperature for a short time.

  The average particle size of the conductive fine particles in the present invention is measured by a particle size distribution measuring apparatus using a dynamic light scattering method, and particles less than 1 μm are generally 1 μm or more by Nanotrack (manufactured by Nikkiso Co., Ltd.). These particles are measured with a microtrack (manufactured by Nikkiso Co., Ltd.).

  The conductive fine particles of the present invention are preferably coated with a protective substance. The protective substance is used for preventing aggregation of the conductive fine particles and improving the dispersion stability of the conductive fine particles in the conductive ink when prepared into a conductive ink containing the conductive fine particles. Examples of such a protective substance include compounds having one or more affinity groups in the compound for conductive fine particles. The affinity group for the conductive fine particles varies depending on the type of the conductive fine particles, but generally, an amino group, a quaternary ammonium group, a hydroxyl group, a cyano group, a carboxyl group, a thiol group, a sulfonic acid group, and phosphoric acid. And polar groups such as a phosphate group. Furthermore, the polar group is preferably an anionic carboxyl group.

  In the present invention, the conductive fine particles preferably further contain a dispersant as a protective substance, and the dispersant is preferably a fatty acid. This is because the use of conductive fine particles coated with a protective substance containing a fatty acid makes it possible to produce a conductive film at a lower temperature and in a shorter time. As the protective substance, a dispersant such as a pigment dispersant, a surfactant, a coupling agent, or a fatty acid can be used.

  As a method of coating these protective substances on conductive fine particles, a method of coating conductive fine particles with a protective substance by mixing conductive fine particles prepared in advance and a protective substance dry or wet, etc., conductive fine particles In the production of conductive fine particles in the presence of a protective substance to obtain conductive fine particles coated with the protective substance, a metal salt of a substance that functions as a protective substance, such as a fatty acid metal salt, with a reducing agent, etc. A method for obtaining conductive fine particles coated with a protective substance by reduction using the same is known. Any of these methods is a known method, and an appropriate method may be used.

In the present invention, the protective substance is preferably used in an amount of 1 to 2000 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the conductive fine particles. When the amount of the protective substance used is less than 1 part by weight, dispersion stability cannot be obtained, and the conductive fine particles may aggregate. On the other hand, when the amount exceeds 2000 parts by weight, an excessive protective substance that does not contribute to dispersion stability may adversely affect the conductivity of the conductive film and other physical properties.
The conductive ink preferably contains a resin and a liquid medium in addition to the conductive fine particles.

  The resin contained in the conductive ink is selected in consideration of adhesion to the base, adhesion to the ion exchange layer (E), and ease of formation of the conductive layer (A). Specifically, for example, polyurethane resin, (unsaturated) polyester resin, alkyd resin, butyral resin, acetal resin, polyamide resin, (meth) acrylic resin, styrene / (meth) acrylic resin, polystyrene resin, nitrocellulose, benzyl Cellulose, cellulose (tri) acetate, casein, shellac, gelatin, gilsonite, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, carboxy Methylcellulose, carboxymethylethylcellulose, carboxymethylnitrocellulose, Rene / vinyl alcohol resin, styrene / maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl acetate resin, ethylene / vinyl acetate resin, vinyl chloride / vinyl acetate resin, chloride Vinyl / vinyl acetate / maleic acid resin, fluorine resin, silicone resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin, benzoguanamine resin, ketone resin, petroleum resin, chlorinated polyolefin resin, modified chlorine Polyolefin resin, chlorinated polyurethane resin and the like.

  It is also preferable to use an ethylenically unsaturated group-containing compound instead of the resin or in combination with the resin. Examples of the ethylenically unsaturated group-containing compound include compounds such as (meth) acrylic acid, (meth) acrylate compounds, and vinyl ether compounds. These compounds having an ethylenically unsaturated double bond may be monofunctional or polyfunctional. These compounds can also be used individually by 1 type, and can also be used in combination of 2 or more type. In the present invention, “(meth) acrylic acid” is used to include acrylic acid and methacrylic acid. Similarly, the term “(meth) acrylate” is used to mean including acrylate and methacrylate. The same applies to other (meth) acryloyl.

  These resins and ethylenically unsaturated group-containing compounds are preferably 0.01 to 99% by weight, more preferably 0.1 to 95% by weight, out of 100% by weight of the conductive ink. By using within the said range, it can be used, without inhibiting the electroconductivity of an electroconductive film.

  Examples of the liquid medium contained in the conductive ink include ester solvents, ketone solvents, ether solvents, glycol ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, water, and the like. . Hereinafter, each of these solvents will be described in more detail.

  Examples of the ester solvent include ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate. , (Iso) amyl acetate, cyclohexyl acetate, ethyl lactate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, methyl monochloroacetate, monochloro Examples thereof include ethyl acetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl propionate, isoamyl propionate, γ-butyrolactone, dihydroterpineol acetate and the like.

  Examples of ketone solvents include acetone, acetophenone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, acetonyl acetone, isophorone, cyclohexanone, methyl Examples include cyclohexanone and 2- (1-cyclohexenyl) cyclohexanone.

  Examples of ether solvents include ethyl ether, isopropyl ether, dioxane, dibutyl ether, methyl-t-butyl ether, terpinyl methyl ether, dihydroterpinyl methyl ether, and cyclic ether solvents such as tetrahydrofuran, 1, Examples include 3-dioxolane.

  Examples of the glycol ether solvent include ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono n-propyl ether acetate , Dipropylene glycol mono n-butyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol mono n-propyl ether acetate, triethylene glycol mono-n-butyl ether acetate, tripropylene glycol Acetic acid ester of glycol monoether such as monoethyl ether acetate, tripropylene glycol mono-n-propyl ether acetate, tripropylene glycol mono-n-butyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl isobutyl ether, dipropylene glycol dimethyl ether , Zip Dialkyl ethers such as propylene glycol diethyl ether.

As the aliphatic hydrocarbon solvent, for example, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane as normal paraffin solvents, isohexane, , 2,3-trimethylpentane, isooctane, 2,2,5-trimethylhexane, cycloparaffinic solvents include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane,
Examples of the aromatic hydrocarbon solvent include toluene, xylene, styrene, ethylbenzene, naphthalene, tetralin, solvent naphtha, aromatic mixed hydrocarbon, and the like.

  Other liquid media include dimethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, and furfural. You may use the said liquid medium individually or in combination of 2 or more types.

  The liquid medium is preferably used in an amount of 0.01 to 99% by weight, more preferably 0.1 to 95% by weight, in 100% by weight of the conductive ink.

It is also preferable that the conductive ink uses a compound (F) having 10 to 18 carbon atoms (hereinafter also simply referred to as “compound (F)”) having 1 to 4 hydroxyl groups as a liquid medium.
When the conductive ink contains the compound (F), the conductivity of the conductive film is greatly improved. Specifically, the volume resistance value of the conventional conductive film is on the order of 10 ⁻⁵ Ω · cm or more, whereas the conductive film of the present invention contains the compound (F) to increase the volume resistance. A resistance value as low as 10 ⁻⁶ Ω · cm can be achieved. A low resistance value indicates high conductivity. The conductive film of the present invention has greatly improved adhesion to the base. This is a remarkable effect not found in the past. In addition, the volume resistance value and the measuring method of the adhesiveness with the foundation | substrate are demonstrated in an Example.

  Specific examples of the compound (F) include C10-18 monohydric alcohols, polyhydric alcohols, glycol ethers, alkanolamines, and the like.

As a monohydric alcohol having 10 to 18 carbon atoms, for example, a monohydric alcohol having a linear saturated alkyl group includes 1-decanol, 2-decanol, 1-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol. 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol Etc.

  Examples of monohydric alcohols having a branched saturated alkyl group include 3,7-dimethyl-1-octanol, 3,7-dimethyl-3-octanol, 2-heptylundecanol, isomyristyl alcohol, and isocetyl alcohol. And isostearyl alcohol. In addition, cyclic alcohols such as dicyclohexylmethanol, tricyclodecane monomethylol, water-added rosin alcohol and dihydroterpineol are also used.

  The monohydric alcohol having an unsaturated double bond in the molecule includes an alkene group having one unsaturated double bond, an alkadiene group having two unsaturated double bonds, and three unsaturated double bonds. A monohydric alcohol having an alkatriene group having four or more unsaturated double bonds, oleyl alcohol, linolyl alcohol, 11-hexadecene-1-ol, 7-tetradecene-1-ol, 9-tetradecen-1-ol, 11-tetradecen-1-ol, 7-dodesen-1-ol, 10-undecen-1-ol, 9-decene-1-ol, citronellol, dodecadien-1-ol, phytol, Geraniol, rosinol, linanol, terpineol C, α-terpineol, L-α-terpineol, etc. Examples include linear, branched or cyclic unsaturated group-containing monohydric alcohols. These monohydric alcohols can be used singly or in combination in any quantity ratio.

As a polyhydric alcohol having 10 to 18 carbon atoms,
For example, 1,2-decanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol 1,16-hexadecanediol, 1,2-hexadecanediol and other alkylene dihydric alcohols, trimethylol octane, dipentaerythritol, tripentaerythritol cellulose and other polyhydric alcohols.

As glycol ether having 10 to 18 carbon atoms, for example,
Examples include glycol ether solvents such as dipropylene glycol n-butyl ether, triethylene glycol mono n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether, and tripropylene glycol butyl ether.

In the present invention, it is preferable to use a monohydric alcohol or a polyhydric alcohol having 10 to 18 carbon atoms from the viewpoint of the conductivity of the conductive film and the adhesion to the ground, and the monovalent having a branched saturated alkyl group. More preferably, alcohol or cyclic alcohol is used. In the present invention, compound (F) may be used alone or in combination of two or more.
These compounds having 10 to 18 carbon atoms having 1 to 4 hydroxyl groups (F) are preferably used in an amount of usually 0.01 to 99 parts by weight, based on 100 parts by weight of the conductive ink, and 0.1 to 95 parts by weight. It is more preferable to use it.

  In order to produce the conductive ink, conductive fine particles and other raw materials are mixed and dispersed using a conventionally known method such as a ball mill, an attritor, a sand mill, a jet mill, a three-roll mill, or a paint shaker. Alternatively, stirring and mixing may be performed using a conventionally known method such as a mixer or a dissolver.

The obtained conductive ink can form a conductive layer (A) by printing on a foundation | substrate or an ion exchange layer (E). As the printing method, known printing methods such as gravure printing, flexographic printing, and ink jet printing can be used.
Next, the ion exchange layer (E) will be described.
The ion exchange layer (E) is in contact with the conductive layer (A) on the base. Then, the protective substance covering the conductive fine particles triggered by heating is deprived by the anion exchange substance contained in the ion exchange layer (E) or activated by the exchange of the protective substance with other ions. The surface of the conductive fine particles having high energy is exposed. As a result, the conductive fine particles lose their dispersion stability, aggregate and adhere to each other, whereby the coating progresses rapidly. By this coating, the volume resistance value of the coating is low, and high conductivity can be realized.
The ion exchange layer (E) is formed of a coating liquid (G) containing a copolymer (D), a resin, and a liquid medium.

  The copolymer (D) is produced by copolymerizing a monomer (B) containing a tertiary amino group and / or a quaternary ammonium group and a monomer (C) that can be copolymerized with the monomer (B). Is done. As the synthesis method, solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like can be performed. The polymerization can be performed by an ionic polymerization method such as anionic polymerization or cationic polymerization, or a radical polymerization method. Further, the form of the copolymer (D) solution is preferably an aqueous dispersion or an emulsion.

First, a monomer (B) containing a tertiary amino group and / or a quaternary ammonium group (hereinafter referred to as monomer (B)) will be described.
The tertiary amino group or quaternary ammonium group of the monomer (B) is used for the purpose of an ion exchange reaction with the conductive layer (A) after the formation of the ion exchange layer (E). Ammonium groups are preferred. Therefore, when a tertiary amino group-containing monomer is used, it may be converted into a quaternary ammonium salt with a cationizing agent in the state of the monomer before copolymerization or with a cationizing agent after copolymerization. it can.

Examples of the tertiary amino group-containing monomer (B-1) include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
Examples of the cationizing agent include methyl chloride, ethyl chloride, benzyl chloride, ethyl monochloroacetate, ethyl dichloroacetate, methyl sulfate, ethyl sulfate, and p-toluene sulfonate.

  The quaternary ammonium group-containing monomer (B-2) is a quaternary ammonium salt compound as a whole monomer. Specifically, for example, (meth) acrylic acid dimethylaminoethylmethyl chloride salt, (meth) acrylic acid dimethylaminoethylbenzyl chloride salt, (meth) acrylic acid diethylaminoethylmethyl chloride salt, (meth) acrylic acid diethylaminoethylbenzyl chloride salt Salt, (meth) acrylic acid aminopropyldimethylammonium methyl chloride salt, (meth) acrylic acid aminopropyldimethylammonium benzyl chloride salt, (meth) acrylic acid aminopropyldiethylammonium methyl chloride salt, (meth) acrylic acid aminopropyldiethylammonium salt Benzyl chloride salt, (meth) acrylic acid trimethylammonium methyl sulfate salt, (meth) acrylic acid triethylammonium methyl sulfate , (Meth) acrylic acid aminopropyldimethylammonium methyl sulfate salt, (meth) acrylic acid aminopropyldimethylammonium ethyl sulfate salt, (meth) acrylic acid trimethylaminoethyl p-toluenesulfonate salt, (meth) acrylic acid aminopropyldimethylethyl Examples thereof include ammonium ethyl sulfate salt.

The monomer (C) used for the copolymer (D) is a monomer other than the monomer (B) and represents an ethylenically unsaturated group-containing monomer copolymerizable with the monomer (B).
Among the ethylenically unsaturated group-containing monomers, a hydrophobic monomer is preferably used in order to improve the water resistance of the ion exchange layer (E). Specifically, it is preferable to use a monomer (C-1) containing one or more organic groups selected from the group consisting of an alkyl group having a chain or ring structure of 6 to 20 carbon atoms and a phenyl group. . Since the monomer (B) has a tertiary amino group or a quaternary ammonium group, it is highly hydrophilic and is preferably polymerized in an aqueous solvent rather than in an organic solvent. This is because when used, the circuit may be corroded by the influence of moisture, and conduction failure may occur due to ion migration.

The alkyl group of the monomer (C-1) may be linear, branched, or may have a ring structure.
Among the monomers (C-1), linear or branched alkyl group-containing monomers are hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate. , Nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, nonadecyl (meth) acrylate, ( (E.g., meta) eicosyl acrylate.

  Among the monomers (C-1), an alkyl group-containing monomer having a ring structure includes cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Etc.

  Among the monomers (C-1), as the monomer having a phenyl group, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, (meth) acrylate nonylphenol EO adduct, Examples thereof include tribromophenyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  Among the monomers (C-1), 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) Benzyl acrylate and phenoxyethyl (meth) acrylate are preferred from the viewpoints of ease of copolymerization with the monomer (B), availability, and low cost.

Among the monomers (C), monomers (C-2) other than the monomer (C-1) are, for example,
Among the (meth) acrylate compounds, examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, butanediol monoacrylate, 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-methoxyethyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, phenol Xyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isooctyl (meth) acrylate, methoxytriethylene glycol acrylate, 2-ethoxy Ethyl acrylate, 3-methoxybutyl acrylate, benzyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, dipropylene glycol (meta ) Acrylate, (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, methoxypolyethylene glycol methacrylate, tetramethylpiperidyl methacrylate, 2-methacryloyloxyethyl isocyanate Etc.

  Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethoxylated 1,6-hexanediol. Diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate, 1, 4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol Acrylate, dimethylol-tricyclodecane diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,3-butylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) Acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate Acrylate, tetramethylol methane triacrylate, pentaerythritol tetraacrylate Caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate , Ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, urethane Acrylate, epoxy Examples include acrylate, polyester acrylate, pentaerythritol diacrylate monostearate, polyethylene glycol dimethacrylate, and rosin-modified acrylate.

  Among the vinyl ether compounds, examples of the monofunctional vinyl ether compound include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, and the like. Examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1 , 4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane divinyl ether, bisphenol A diethoxydivinyl ether, glycerol Trivinyl ether, sorbitol tetravinyl ether, Trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, and ditrimethylolpropane tetra vinyl ether.

  Furthermore, examples of the compound having an ethylenically unsaturated double bond other than the above compounds include N-vinylacetamide, tris (acryloxyethyl) isocyanurate, 2-methallyloyloxyethyl hexahydrophthalate, and the like.

  When the copolymer (D) is polymerized, a hydrophilic quaternary ammonium group-containing monomer (B-2) is used as the monomer (B), and a hydrophobic monomer is used as the monomer (C). If a solvent is used, there is a high possibility that they will be separated, and each of the monomer (B) and the monomer (C) may become a homopolymer and a copolymer may not be obtained. Therefore, it is preferable to use an aqueous solvent as the solvent. Specifically, it is preferable to use water and an alcohol having 1 to 3 carbon atoms. Examples of the alcohol having 1 to 3 carbon atoms include methanol, ethanol, 1-propanol, and 2-propanol.

  About the usage-amount of a monomer, it is preferable to contain 25-75 weight% of monomer (B) and 25-75% of monomer (C) in a total of 100 weight% of monomer (B) and monomer (C). When the monomer (B) is less than 25% by weight, the ion exchange property may be insufficient, and when it exceeds 75% by weight, the film strength of the ion exchange layer (E) may be insufficient. When the monomer (C) is less than 25% by weight, the hydrophilicity of the ion exchange layer (E) may be high and the water resistance may be lowered. When the monomer (C) exceeds 75% by weight, the tertiary amino in the ion exchange layer (E) There are few groups and quaternary ammonium groups, and there is a fear that ion exchange properties are insufficient.

The coating liquid (G) can contain a resin, fine particles, and a liquid medium in addition to the copolymer (D). As the resin and the liquid medium, those similar to the conductive ink can be used.
When the ion exchange layer (F) contains fine particles, the fine particles (1) can uniformly disperse the copolymer (D) having ion exchange ability in the ion exchange layer (F). (2) The contact area between the conductive layer (A) and the ion exchange layer (F) is increased, and the efficiency of ion exchange between the conductive fine particles and the copolymer (D) contained therein is improved. This is preferable.

  The average particle diameter of the fine particles is preferably 0.001 to 20 μm. If fine particles having an average particle diameter exceeding 20 μm are used, the conductivity may be lowered. The fine particles can be used in an amount of 1 to 99% by weight, preferably 5 to 95% by weight, in 100% by weight of the coating liquid (G).

  As the fine particles, organic fine particles or inorganic fine particles having no ion exchange ability are preferably used.

  Examples of organic fine particles include natural products such as starch, acrylics such as polymethyl methacrylate, polystyrenes, styrene / acrylics, nylons such as nylon 6, nylon 12, and nylon 6-12, high density polyethylene, and low density. Examples include olefins such as polyethylene, polypropylene, and tetrafluoroethylene, polyesters, phenols, and benzoguanamines.

Examples of inorganic fine particles having no ion exchange capacity include, for example, barium sulfate, magnesium sulfate, iron (II) sulfate, calcium sulfate, magnesium hydroxide, zinc oxide, zinc hydroxide, zinc sulfide, lead oxide, magnesium phosphate, Examples include aluminum chloride, synthetic amorphous silica, colloidal silica, aluminum hydroxide, lithopone, and the like. Among these inorganic fine particles, amorphous silica and colloidal silica are preferable. Further, the inorganic fine particles are preferably subjected to treatment with an organic substance (for example, silane coupling agent treatment) according to the purpose of use.
These fine particles can be used alone or in combination of two or more.

  Mixing of the raw material of the coating liquid (G) can be performed by the same method as the conductive ink described above.

Since the method for producing a conductive film of the present invention is characterized in that the conductive layer (A) and the ion exchange layer (E) are brought into contact with each other, a method for forming a conductive film, a substrate, and a film of a conductive film The shape and the like are not particularly limited. As an aspect of bringing the conductive layer (A) and the ion exchange layer (E) into contact,
(1) A method in which an ion exchange layer (E) and a conductive layer (A) are sequentially formed on a base to form a conductive film.
(2) A method in which a conductive layer (A) and an ion exchange layer (E) are sequentially formed on a base to form a conductive film.
Can be mentioned. The conductive layer (A) and the ion exchange layer (E) are prepared by, for example, applying a conductive ink for the conductive layer (A) and a coating liquid (G) for the ion exchange layer (E) by wet-on-wet. It is also preferable to heat and heat the layer to form a conductive film.

The conductive layer (A) changes into a conductive film by ion exchange with the ion exchange layer (E).
In the present invention, even if any of the above methods (1) to (2) is used, desired conductivity of the conductive film can be obtained by heating at a low temperature for a short time.
Further, for the purpose of protecting the conductive film, an overprint varnish, various coating agents and the like may be applied on the conductive film. These varnishes and coating agents can be used in either normal heat drying type or active energy ray curable type.

  Various functional layers can be laminated on the conductive coating of the present invention depending on the application. For example, when forming a protective layer on a conductive film, the case where an adhesive layer is formed on the opposite surface of the base can be mentioned.

  Examples of the method for protecting the conductive coating include a method in which paper or a plastic film is bonded onto the conductive coating through an adhesive, and a method in which the conductive coating is laminated on the conductive coating by melt extrusion of plastic. Furthermore, it can also protect by providing a resist layer on a conductive film.

  In order for the conductive film to obtain higher conductivity, it is preferable to perform heating and pressurization as well as heating. Heating and pressing can be performed with a press roll machine, a press machine, a laminator, or the like. The conditions for heating and heating and pressurization may be performed in a range that does not adversely affect the substrate, but the heating temperature is 50 to 150 ° C., the pressing condition is 0.5 to 2.0 MPa, and the pressing time is 10 seconds to 10 seconds. It is preferable to carry out within a range of minutes. For example, when a press roll machine is used, the linear pressure of the roll is preferably in the range of 1 to 25 kg / cm. Moreover, it is preferable to carry out the conveyance speed at the time of a press in the range of 0.1-30 m / min.

  As the base, paper, plastic, glass, fiber, or the like can be used. The base may be a film, sheet or plate. In addition, a substrate in which another layer is previously formed on the substrate may be used as the substrate. As the paper system, for example, various processed papers such as synthetic paper, polyethylene coated paper, impregnated paper, water-resistant processed paper, insulating processed paper, and stretch processed paper can be used in addition to coated paper and uncoated paper. Among these, coated paper and processed paper are preferable from the viewpoint of obtaining stable conductivity as the conductive film. In the case of coated paper, the higher the smoothness, the more preferable because the volume resistance value of the conductive coating is stably expressed.

  Examples of plastics that can be used include plastics such as polyester, polyethylene, polypropylene, cellophane, vinyl chloride, vinylidene chloride, polystyrene, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, nylon, polyimide, and polycarbonate. On the surface of the plastic film, corona discharge treatment or plasma treatment is performed as necessary for the purpose of improving the adhesion of the conductive film to be formed or improving the print reproducibility of the conductive circuit to be applied and printed. Or a resin coating agent such as polyurethane, polyisocyanate, organic titanate, polyethyleneimine, or polybutadiene can be applied.

  As the glass system, any of those generally used as glass for substrates can be used. For example, soda lime glass, micro sheet glass, non-alkali glass, heat resistant glass, Vycor glass, quartz glass and the like can be mentioned.

  Examples of the fiber system include plant fibers such as cotton and hemp, animal fibers such as silk and wool, polyester, acrylic, nylon, vinylon, polypropylene, polyvinyl chloride, polyethylene, polyvinylidene chloride, polyurethane and other chemical fibers, rayon And recycled fibers such as polynosic and cupra. In addition, as the fiber structure, for example, any of woven fabric, knit, non-woven fabric and the like can be used.

  In order to improve the adhesion with the conductive film, for example, when forming a conductive circuit of a printed wiring circuit by printing, for example, in order to enable printing with a fine circuit width, corona discharge treatment or plasma treatment is performed. It is also preferable to carry out an anchor treatment by a dry treatment such as a wet treatment by applying a resin coating agent such as polyurethane, polyisocyanate, organic titanate, polyethyleneimine or polybutadiene.

  The conductive layer (A) and the ion exchange layer (E) formed in the method for producing a conductive film of the present invention are preferably formed by printing or coating. For example, various printing methods such as gravure printing, flexographic printing, screen printing, inkjet printing, dispenser printing, spray coating, spin coating, die coating, lip coating, knife coating, dip coating, curtain coating, roll coating, bar coating, etc. A coating method can be used. Also, the printing form may be solid coating or pattern printing such as a wiring circuit.

  The thickness of the conductive coating is preferably 0.01 to 30 μm, more preferably 0.05 to 10 μm. For example, when the conductive film is used as an electromagnetic wave shielding layer, it is preferably 0.05 to 10 μm, and when it is used as a conductive circuit, 0.5 to 30 μm is preferable. When the thickness of the conductive coating is less than 0.01 μm, the conductivity may be insufficient, and when it exceeds 30 μm, it may be difficult to reduce the cost.

  The conductive film of the present invention can be preferably used as a conductive circuit of a printed wiring board. The conductive circuit of the printed wiring board is used as an electrode for a touch panel, an electrode for a membrane switch, an antenna circuit for a non-contact type IC medium, or a film for imparting conductivity to a mesh non-conductive material for electromagnetic shielding, such as a conductive cloth. It can also be used for FPC wiring circuits.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”.

[Conductive ink production example 1]
Attach 200 parts of toluene and 38.9 parts of silver oleate to a separable four-necked flask with a condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer, and stir at room temperature in a nitrogen atmosphere. 3 parts (a ratio of 0.2 mol to 1 mol of metal) were added and dissolved. Thereafter, when 73.1 parts of a 20% succinic acid dihydrazide (hereinafter abbreviated as SUDH) aqueous solution (a ratio of 2 mol of hydrazide group to 1 mol of metal) was dropped, the liquid color changed from pale yellow to dark brown. In order to further promote the reaction, the temperature was raised to 40 ° C. to advance the reaction. When the solution was allowed to stand after completion of the reaction, it was separated into an upper layer and a lower layer. The excess reducing agent and impurities were removed by removing the lower aqueous layer. Therefore, distilled water was added to the oil layer, and washing and separation were repeated several times to obtain a conductive ink. In the obtained conductive ink, the average particle diameter of silver fine particles was 0.007 μm, the silver concentration was 73%, and the particle diameter did not change even after being stored at 40 ° C. for one month and was stable.

[Conductive ink production example 2]
A separable four-necked flask was equipped with a condenser, thermometer, nitrogen gas inlet tube, and stirring device. While stirring at room temperature in a nitrogen atmosphere, 200 parts of toluene and 18.1 parts of silver propionate were charged, and diethylaminoethanol 2 was used as a dispersant. .3 parts (0.2 mol / mol of metal) and 2.8 parts of oleic acid (0.1 mol / mol of metal) were added and dissolved. Thereafter, when 73.1 parts of 20% SUDH aqueous solution (2 mol times of hydrazide group with respect to 1 mol of metal) was added, the liquid color changed from light yellow to dark brown. In order to further promote the reaction, the temperature was raised to 40 ° C. to advance the reaction. When the solution was allowed to stand after completion of the reaction, it was separated into an upper layer and a lower layer. The excess reducing agent and impurities were removed by removing the lower aqueous layer. Therefore, distilled water was added to the oil layer, and washing and separation were repeated several times to obtain a conductive ink. In the obtained conductive ink, the average particle diameter of silver fine particles was 0.005 μm, the silver concentration was 75%, and the particle diameter did not change and was stable even after storage at 40 ° C. for one month.

[Conductive ink production example 3]
A conductive ink was obtained in the same manner as in Synthesis Example 2 except that the starting metal salt was changed to 22.3 parts of silver hexanoate. In the obtained conductive ink, the average particle diameter of silver fine particles was 0.005 μm, the silver concentration was 80%, and the particle diameter did not change and was stable even after being stored at 40 ° C. for one month.

[Conductive ink production example 4]
A conductive ink was obtained in the same manner as in Synthesis Example 2 except that the starting metal salt was changed to 39.1 parts of silver stearate. The average particle diameter of the silver fine particles of the obtained conductive ink was 0.008 μm, the silver concentration was 65%, and the particle diameter did not change and was stable even after storage at 40 ° C. for one month.

[Conductive ink production example 5]
With respect to 100 parts of the ink obtained in Conductive Ink Production Example 3, 20 parts of dihydroterpineol is added as a compound of 10 to 18 carbon atoms (F) having 1 to 4 hydroxyl groups and stirred to obtain a conductive ink. It was. The average particle size of the silver fine particles was 0.005 μm, the silver concentration was 66.7%, and the particle size did not change even after storage at 40 ° C. for one month and was stable.

[Conductive ink production example 6]
To 100 parts of the ink obtained in Conductive Ink Production Example 3, 20 parts of isotetradecanol is added as a compound of 10 to 18 carbon atoms (F) having 1 to 4 hydroxyl groups and stirred, and the conductive ink is stirred. Got. The average particle size of the silver fine particles was 0.005 μm, the silver concentration was 66.7%, and the particle size did not change even after storage at 40 ° C. for one month and was stable.

[Copolymer solution production example 1]
In a separable four-necked flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube, and stirring device, 25.0 parts of dimethylaminoethyl methacrylate (DM), 226.7 parts of ion-exchanged water, 340.0 parts of methanol, benzyl After weighing 20.1 parts of chloride and stirring at room temperature for 30 minutes, 75.0 parts of n-butyl methacrylate (n-BMA) was added and the temperature was raised to 60 ° C. When the temperature reached 60 ° C., 5.0 parts of water-soluble azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was added and reacted for 3 hours. 1 hour and 2 hours after the end of the reaction, 0.5 parts of V-50 was added and a post reaction was performed. Then, a vacuum pump was attached to the flask, and the solvent was removed at a reduced pressure of 600 torr. After distilling 370 parts of a mixed solution of methanol and water, the mixture was diluted with water and adjusted so that the nonvolatile content became 20%. Thus, a solution of copolymer (D) was obtained.

[Copolymerization solution production example 2]
Weighed 35.0 parts of dimethylaminoethyl methacrylate (DM), 226.7 parts of ion-exchanged water, and 340.0 parts of ethanol in a separable four-necked flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube, and stirring device. After being collected and stirred at room temperature for 30 minutes, 65.0 parts of cyclohexyl methacrylate (CHMA) was added and the temperature was raised to 60 ° C. When the temperature reached 60 ° C., 5.0 parts of water-soluble azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was added and reacted for 3 hours. After 1 hour and 2 hours from the end of the reaction, 0.5 parts of V-50 was added in an amount of 0.5 parts, followed by a reaction. Then, a vacuum pump was attached to the flask, and the solvent was removed at a reduced pressure of 600 torr. After distilling 350 parts of the ethanol / water mixture, it was diluted with water and adjusted so that the non-volatile content was 20%. Thus, a solution of copolymer (D) was obtained.

[Copolymerization solution production example 3]
In a separable four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer, 50.0 parts of methyl chloride salt (DMC) of dimethylaminoethyl methacrylate, 226.7 parts of ion-exchanged water, 340. After weighing out 0 parts and stirring at room temperature for 30 minutes, 50.0 parts of 2-ethylhexyl methacrylate (2-EHMA) was added and the temperature was raised to 60 ° C. When the temperature reached 60 ° C., 5.0 parts of water-soluble azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was added and reacted for 3 hours. 1 hour and 2 hours after the completion of the reaction, 0.5 parts of V-50 was added and the post reaction was carried out. Then, a vacuum pump was attached to the flask, the solvent was removed at a reduced pressure of 600 torr, 350 parts of methanol / water mixture was distilled off, and then diluted with water to adjust the non-volatile content to 20%. Thus, a solution of copolymer (D) was obtained.

[Copolymer solution production examples 4 to 8]
Synthesis was performed according to the composition shown in Table 1 in the same manner as in Production Example 3 to obtain a solution of copolymer (D).

[Copolymerization solution production example 9]
In a separable four-necked flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube, and stirring device, 100.0 parts of dimethylaminoethyl methacrylate (DM), 510.0 parts of ion-exchanged water, 56.7 parts of methanol, benzyl After weighing 80.5 parts of chloride and stirring at room temperature for 30 minutes, the temperature was raised to 60 ° C. When the temperature reached 60 ° C., 5.0 parts of water-soluble azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was added and reacted for 3 hours. 1 hour and 2 hours after the completion of the reaction, 0.5 parts of V-50 was added and the post reaction was carried out. Then, a vacuum pump was attached to the flask, the solvent was removed at a reduced pressure of 600 torr, 363.7 parts of a methanol / water mixture was distilled off, and then diluted with water so that the non-volatile content was 20%. The solution of the copolymer was obtained by adjusting.

[Copolymerization solution production example 10]
In a separable four-necked flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube, and stirrer, 100.0 parts of methyl chloride salt (DMC) of dimethylaminoethyl methacrylate, 510.0 parts of ion-exchanged water, 56. 7 parts were weighed and stirred at room temperature for 30 minutes, and then heated to 60 ° C. When the temperature reached 60 ° C., 10.0 parts of water-soluble azo polymerization initiator V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted for 3 hours. 1 hour and 2 hours after the completion of the reaction, 0.5 parts of V-50 was added and the post reaction was carried out. Then, a vacuum pump was attached to the flask, and the solvent was removed at a reduced pressure of 600 torr. After 359.0 parts of a methanol / water mixture was distilled off, the mixture was diluted with water so that the nonvolatile content was 20%. The solution of the copolymer was obtained by adjusting.

[Copolymerization solution production example 11]
In a separable four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer, 60.0 parts of cyclohexyl methacrylate (CHMA), 20.0 parts of methacrylic acid (MAA), 2-hydroxyethyl methacrylate (2 -HEMA) 20.0 parts, 283.4 parts of ion-exchanged water, and 283.3 parts of ethanol were weighed and stirred at room temperature for 30 minutes, and then heated to 60 ° C. When the temperature reached 60 ° C., 5.0 parts of water-soluble azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was added and reacted for 3 hours. 1 hour and 2 hours after the completion of the reaction, 0.5 parts of V-50 was added and the post reaction was carried out. After that, a vacuum pump was attached to the flask, and the solvent was removed at a reduced pressure of 600 torr. After 360.0 parts of the methanol / water mixture was distilled off, it was diluted with water so that the nonvolatile content became 20%. The solution of the copolymer was obtained by adjusting.

[Copolymerization solution production example 12]
In a separable four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer, 40.0 parts of 2-ethylhexyl methacrylate (2-EHMA), 20.0 parts of methyl methacrylate (MMA), n-butyl 40.0 parts of methacrylate (n-BMA) and 566.7 parts of ethanol were weighed and stirred at room temperature for 30 minutes, and then heated to 60 ° C. When the temperature reached 60 ° C., 5.0 parts of water-soluble azo polymerization initiator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was added and reacted for 3 hours. 1 hour and 2 hours after the completion of the reaction, 0.5 parts of V-50 was added and the post reaction was carried out. Then, a vacuum pump was attached to the flask, the solvent was removed at a reduced pressure of 600 torr, 347.2 parts of ethanol was distilled off, and then diluted with ethanol to adjust the non-volatile content to 20%. A combined solution was obtained.
The properties of the copolymer are shown in Table 1.

The meanings of the symbols in the table are shown below.
DM: dimethylaminoethyl methacrylate, DMC: dimethylaminoethyl methyl chloride salt, CHMA: cyclohexyl methacrylate, 2-EHMA: 2-ethylhexyl methacrylate, isodecyl MA: isodecyl methacrylate, lauryl MA: lauryl methacrylate, stearyl MA: stearyl methacrylate, BZMA: benzyl methacrylate, PhEMA: phenoxyethyl methacrylate, MMA: methyl methacrylate, EA: ethyl acrylate, n-BMA: n-butyl methacrylate, MAA: methacrylic acid, 2-HEMA: 2-hydroxyethyl methacrylate, V-50: 2,2′-azobis (2-amidinopropane) dihydrochloride, MeOH: methanol, EtOH: ethanol, IPA: isopropyl alcohol.

"Example 1"
75 parts of the copolymer (D) solution obtained in Copolymer solution production example 1 and 25 parts of a mixed solution of water / isopropyl alcohol = 1/1 (weight ratio) were mixed, and 20 parts were obtained using a dissolver. The mixture was stirred for a minute to obtain a coating liquid (G). Next, it was coated on a polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., 100 μm thick) using a bar coater and dried at 75 ° C. for 5 minutes to obtain an ion exchange membrane having a dried coating film thickness of 6 μm. It was.
Next, using the conductive ink obtained in Conductive Ink Production Example 1, a circuit pattern of a conductive layer having a width of 3 mm was printed on the ion exchange membrane by an ink jet method, and the temperature was 150 ° C. in a hot air drying oven. The film was dried for 30 minutes to obtain a conductive film.

"Examples 2 to 8"
In the same manner as in Example 1, a conductive film was obtained according to Table 2.

"Example 9"
Using the solution of the copolymer (D) obtained in Copolymer Solution Production Example 1, the same method as in Example 1 was used to print an ion exchange layer by an inkjet method instead of coating with a bar coater. Obtained. In the same manner as in Example 1, a conductive film was obtained according to Table 2.

"Examples 10 to 16"
In the same manner as in Example 9, a conductive film was obtained according to Table 2.

"Example 17"
On the polyester film (thickness 100 μm), using the conductive ink obtained in the conductive ink production example 1, a circuit pattern having a width of 3 mm is printed by an ink jet method and dried at 75 ° C. for 3 minutes to form a conductive layer. Formed. Next, on the circuit pattern of the conductive layer, 87.5 parts of the copolymer solution obtained in the copolymer solution production example 1 and a mixed solution 12.5 of water / isopropyl alcohol = 1/1 (weight ratio). Were mixed for 20 minutes using a dissolver to obtain a coating solution. This coating solution was applied onto the conductive layer using a bar coater and dried in a hot air drying oven at 150 ° C. for 30 minutes to form an ion exchange layer, thereby obtaining a conductive coating.

"Examples 18 to 24"
In the same manner as in Example 17, a conductive film was obtained according to Table 3.

"Example 25"
After forming a conductive layer by the same method as in Example 17, a coating liquid was printed on a circuit pattern having a width of 3 mm to a width of 5 mm using an ink jet method instead of a bar coater, and was heated at 150 ° C. in a hot air drying oven. An ion exchange layer was formed by drying for 30 minutes to obtain a conductive film.

"Examples 26 to 32"
In the same manner as in Example 25, a conductive film was obtained according to Table 3.

“Comparative Example 1”
50 parts of the copolymer solution obtained in Copolymer solution production example 9 and 50 parts of a mixed solution of water / isopropyl alcohol = 1/1 (weight ratio) were mixed and stirred for 20 minutes using a dissolver. To obtain a coating solution. Then, it was coated on a polyester film (thickness: 100 μm) using a bar coater and dried at 75 ° C. for 5 minutes to obtain an ion exchange layer having a dried coating film thickness of 6 μm.
Next, using the conductive ink obtained in Conductive Ink Production Example 1, a circuit pattern of a conductive layer having a width of 3 mm was printed on the ion exchange layer by an inkjet method, and the temperature was 150 ° C. in a hot air drying oven. The film was dried for 30 minutes to obtain a conductive film.

"Comparative Examples 2-4"
In the same manner as in Comparative Example 1, a conductive film was obtained according to Table 4.

“Comparative Example 5”
A circuit pattern of a conductive layer having a width of 3 mm was printed on a polyester film (thickness: 100 μm) by the inkjet method using the conductive ink obtained in Conductive Ink Production Example 5 and dried at 75 ° C. for 3 minutes. . Next, 50 parts of the copolymer solution obtained in the copolymer solution production example 9 and 50 parts of a mixed solution of water / isopropyl alcohol = 1/1 (weight ratio) were mixed, and the mixture was used for 20 minutes using a dissolver. The coating liquid was obtained by stirring.
Next, the coating liquid was applied onto the circuit pattern of the conductive layer using a bar coater, and dried in a hot air drying oven at 150 ° C. for 30 minutes to form an ion exchange layer to obtain a conductive film.

"Comparative Examples 6-8"
A conductive film was obtained according to Table 4 in the same manner as in Comparative Example 5.

"Comparative Example 9"
A circuit pattern of a conductive layer having a width of 3 mm was printed on a polyester film (thickness: 100 μm) by the inkjet method using the conductive ink obtained in Conductive Ink Production Example 3, and dried at 75 ° C. for 3 minutes. . Next, 50 parts of the copolymer solution obtained in the copolymer solution production example 9 and 50 parts of a mixed solution of water / isopropyl alcohol = 1/1 (weight ratio) were mixed, and the mixture was used for 20 minutes using a dissolver. The coating liquid was obtained by stirring.
Next, the coating liquid was printed on the circuit pattern of the conductive layer by the ink jet method, but the nozzles were clogged and printing was not possible.

"Comparative Examples 10-12"
Using the copolymer solution of Production Examples 10 to 12 for the copolymer solution, printing was attempted by the inkjet method in the same manner as in Comparative Example 9, but printing was not possible because the nozzles were clogged.

In addition, the layer structure of the electroconductive film obtained by the Example and the comparative example is the following two patterns.
(1) Base / ion exchange layer / conductive film (2) Base / conductive film / ion exchange layer

  The following items were evaluated for the conductive films obtained in Examples and Comparative Examples.

[Film thickness]
The film thicknesses of the conductive film and the ion exchange layer were measured with a film thickness meter “MH-15M type” manufactured by Sendai Nikon Corporation.

[Base adhesion]
A cellophane tape was affixed to the conductive film formed on the ground or the ion exchange layer, and the cellophane tape was abruptly peeled off. The degree of peeling of the conductive film at that time was evaluated according to the following evaluation criteria. In the case of the layer configuration (2), a cellophane tape was stuck on the ion exchange layer for evaluation.
○: Almost no peeling. (Peeling area less than 10%)
Δ: Partially peeled off. (Peeling area 10% or more and less than 50%)
X: Almost peeled. (Peeling area 50% or more)

(Volume resistance value)
The obtained conductive circuit pattern having a width of 3 mm was sandwiched at four points at intervals of 30 mm, and the resistance value of the circuit was measured with a four-probe resistance measuring instrument (“DR-1000CU type” manufactured by Sanwa Denki Keiki Co., Ltd.). The volume resistance value was calculated from the value and the film thickness.
In addition, the base, the conductive film (conductive layer), and the ion exchange layer were laminated in this order in the production of the conductive film [corresponding to the layer structure (2)]. The conductive film partially peeled off the ion exchange layer, and the conductive film The volume resistance value was calculated by measuring the resistance value and the film thickness. Furthermore, about what overcoated on the conductive layer, a part of overcoat layer was peeled, the conductive film was exposed, and resistance value was measured.

[Bending resistance]
After measuring the volume resistance value of the obtained conductive film, bend it 180 degrees with the conductive film side inside, and then bend it 180 degrees with the conductive film side outside, and measure the volume resistance value again. The change in resistance value before and after bending was evaluated.
○: Change in volume resistance value is less than 20% Δ: Change in volume resistance value is 20% or more and less than 30% ×: Change in volume resistance value is 30% or more

〔water resistant〕
The surface of the conductive coating was rubbed with absorbent cotton soaked in water, and the number of times of rubbing until the conductive coating was peeled was evaluated. In the case of the layer configuration (2), a cellophane tape was stuck on the ion exchange layer for evaluation.

Claims (8)

On the ground, a conductive layer (A) containing conductive fine particles,
Ions including a copolymer (D) obtained by copolymerizing a monomer (B) containing a tertiary amino group and / or a quaternary ammonium group and a monomer (C) copolymerizable with the monomer (B). A method for producing a conductive coating, comprising laminating an exchange layer (E).   The monomer (C) is a monomer containing one or more organic groups selected from the group consisting of an alkyl group having a chain or ring structure of 6 to 20 carbon atoms and a phenyl group. 2. A method for producing a conductive film according to 1.   The ratio of the monomer (B) is 25 to 75% by weight and the ratio of the monomer (C) is 25 to 75% by weight in a total of 100% by weight of the monomer (B) and the monomer (C). Item 3. A method for producing a conductive coating according to Item 1 or 2.   The method for producing a conductive film according to any one of claims 1 to 3, wherein the copolymer (D) comprises water and an alcohol having 1 to 3 carbon atoms as a polymerization solvent.   The method for producing a conductive film according to any one of claims 1 to 4, wherein the conductive layer (A) is formed by an inkjet method.   The electroconductive film obtained by the manufacturing method in any one of Claims 1-5.   A printed wiring board having the conductive film according to claim 6 as a conductive circuit.   A touch panel using the printed wiring board according to claim 7.