WO2015037512A1

WO2015037512A1 - Electroconductive pattern and electronic circuit

Info

Publication number: WO2015037512A1
Application number: PCT/JP2014/073383
Authority: WO
Inventors: 村川　昭; 白髪　潤; 亘冨士川; 公恵斉藤
Original assignee: Dic株式会社
Priority date: 2013-09-10
Filing date: 2014-09-04
Publication date: 2015-03-19
Also published as: TW201515016A

Abstract

　The present invention provides: an electroconductive pattern in which a fluid body (b) containing an electroconductive substance and a polymer dispersant is applied on a support body (A) and an electroconductive layer (B) is formed, wherein in the cross-section of the electroconductive layer (B), the polymer dispersant is disproportionately distributed towards the support body (A)-side (substrate interface); and an electronic circuit in which the electroconductive pattern is used. In this electroconductive pattern, the separation of the electroconductive layer containing the electroconductive substance from the support body surface over time is inhibited.

Description

Conductive pattern and electronic circuit

The present invention relates to a conductive pattern used for an electronic circuit such as a printed circuit board, an electromagnetic wave shield, an integrated circuit, or an organic transistor.

In recent years, as electronic devices become more sophisticated, smaller and thinner, there is a strong demand for higher density, smaller and thinner electronic circuits and integrated circuits used therein.

Examples of conductive patterns that can be used in the above-described electronic circuits include, for example, applying (printing) conductive ink containing a conductive substance to the surface of the support by various printing methods, and firing it if necessary. Manufactured by is known.

However, when the conductive layer formed from the conductive ink has insufficient adhesion to the surfaces of various supports, the conductive layer peels off from the surface of the support, and finally the conductive circuit such as an electronic circuit is obtained. There was a problem of causing deterioration of the characteristics and disconnection.

As the support, a film or sheet made of a resin such as polyimide or polyethylene terephthalate is flexible, and has attracted attention as being usable for the production of a foldable flexible device.

However, since the support made of resin such as polyimide is particularly difficult to adhere to the conductive ink, the conductive ink is easily peeled off when the support is bent, and as a result, an electronic circuit finally obtained There is also a problem that there is a higher possibility of causing disconnection such as.

As a method for solving the above problem, for example, a conductive pattern is produced by drawing a pattern by a predetermined method using a conductive ink on an ink receiving substrate provided with a latex layer on the surface of a support. It is known that an acrylic resin can be used as the latex layer (see, for example, Patent Document 1).

However, since the conductive pattern obtained by the above method may not yet be sufficient in terms of the adhesion between the latex layer and the conductive ink, the conductivity due to the peeling of the conductive material contained in the conductive ink is not sufficient. There was a problem that caused a drop or disconnection.

JP 2009-49124 A

The problem to be solved by the present invention is to provide a conductive pattern having adhesiveness that can prevent a conductive layer containing a conductive substance from peeling from the surface of a support.

As a result of diligent research to solve the above problems, the present inventors have formed a conductive pattern having a conductive layer on a support using a fluid containing a conductive substance and a polymer dispersant. As a result of paying attention to the concentration of the polymer dispersant in the cross section of the conductive layer, the polymer dispersant is unevenly distributed on the support (A) side (substrate interface), and the concentration thereof is The inventors have found that the adhesiveness with the conductive layer is improved and completed the present invention.

That is, the present invention is a conductive pattern in which a conductive layer (B) is formed by applying a fluid (b) containing a conductive substance and a polymer dispersant on a support (A), In the cross section of the conductive layer (B), the polymer dispersant is unevenly distributed on the support (A) side (base material interface). The present invention also relates to an electronic circuit using this conductive pattern.

The conductive pattern of the present invention has extremely excellent adhesion between the support and the conductive layer, so that the conductivity of the conductive layer does not deteriorate with time, and the conductive layer is patterned finely. There is no disconnection. Therefore, for example, conductive patterns, electronic circuits, organic solar cells, electronic terminals, organic EL, organic transistors, flexible printed circuit boards, non-contact IC cards and other peripheral wiring forming RFID, plasma display electromagnetic shielding In general, it can be suitably used as various members in the field of printed electronics, such as production of wiring, integrated circuits, and organic transistors.

FIG. 1 is a chart showing the elemental analysis of the conductive layer (silver layer) of the conductive pattern obtained in Example 2 in the depth direction by glow discharge emission spectroscopy (GD-OES).

The conductive pattern of the present invention is a conductive pattern in which a conductive layer (B) is formed by applying a fluid (b) containing a conductive substance and a polymer dispersant on a support (A). In the cross section of the conductive layer (B), the polymer dispersant is unevenly distributed on the support (A) side (base material interface).

The support (A) serves as a base material for the conductive pattern of the present invention. Examples of the material of the support (A) include polyimide, polyamideimide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS resin), acrylic resin, polyvinylidene fluoride, polyvinyl chloride, Examples thereof include polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, cellulose nanofiber, silicon, ceramics, glass, glass / epoxy resin, glass polyimide, and paper phenol.

In addition, since the support (A) preferably has insulating properties, phenol resin, fluorine resin, polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, glass / epoxy resin, glass polyimide, paper phenol, Cellulose nanofibers, alumina, mullite, steatite, forsterite, zirconia and the like are preferable.

Further, as the support (A), for example, a substrate made of synthetic fibers such as polyester fibers, polyamide fibers, and aramid fibers; natural fibers such as cotton and hemp can be used. The fibers may be processed in advance.

As the support (A), a flexible and flexible support is preferably used when the conductive pattern of the present invention is used for an application where bending flexibility is required. Specifically, it is preferable to use a film or sheet-like support.

Examples of the film or sheet-like support include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.

Moreover, in order to improve the adhesiveness with the conductive layer (B) or the primer layer (C) described later, the support (A) is subjected to a surface blasting by a sandblasting method, a solvent treatment method or the like, if necessary. It is possible to use those processed by roughening treatment, electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet / electron beam irradiation treatment, oxidation treatment, etc. it can.

When the shape of the support (A) is a film or sheet, the thickness of the film or sheet support is usually preferably about 1 to 5,000 μm, and preferably about 1 to 300 μm. More preferably. When the conductive pattern of the present invention is used for a flexible printed circuit board or the like that requires flexibility, a film having a thickness of about 1 to 200 μm may be used as the support (A). preferable.

The conductive layer (B) is a layer containing a conductive substance and a polymer dispersant, and is formed using a fluid (b) containing these.

The fluid (b) contains a conductive substance and a polymer dispersant, and specific examples include conductive ink. Moreover, instead of the conductive substance, a plating nucleating agent used for forming a plating layer (D) described later may be contained.

The content ratio of the polymer dispersant in the fluid (b) is preferably in the range of 0.01 to 10% by mass. Further, the content ratio of the conductive substance in the fluid (b) is preferably in the range of 5 to 90% by mass, more preferably in the range of 10 to 60% by mass, and still more preferably in the range of 10 to 40% by mass. .

Examples of the polymer dispersant contained in the fluid (b) include a copolymer of a (meth) acrylic acid ester having a polyoxyalkylene glycol chain and a chain transfer agent having a sulfur atom, and a phosphate ester residue. A copolymer of a (meth) acrylate ester having a sulfur atom and a chain transfer agent having a sulfur atom, a (meth) acrylate ester having a polyoxyalkylene glycol chain, and a (meth) acrylate ester having a phosphate residue Examples thereof include a copolymer with a chain transfer agent having a sulfur atom, a polyalkyleneimine such as polyethyleneimine and polypropyleneimine, and a compound obtained by adding polyoxyalkylene to the polyalkyleneimine. Among these, the dispersion stability of the conductive substance in the fluid (b) is improved, and in the conductive layer (B), it tends to be unevenly distributed on the support (A) side (substrate interface). Copolymer of (meth) acrylic acid ester having polyoxyalkylene glycol chain, (meth) acrylic acid ester having phosphate residue and chain transfer agent having sulfur atom, adding polyoxyalkylene to polyalkyleneimine The compounds obtained are preferred. The “(meth) acrylic acid ester” means one or both of “methacrylic acid ester” and “acrylic acid ester”.

Examples of the polyoxyalkylene include random structures such as polyoxyethylene and poly (oxyethylene-oxypropylene) or block structures.

As the polyoxyalkylene, those having an oxyethylene unit are preferable because the dispersion stability of the conductive substance in the fluid (b) is further improved, and 10% of the oxyethylene unit is contained in the whole polyoxyalkylene. Those having a content in the range of ˜100 mass% are more preferred.

Examples of the (meth) acrylic acid ester having a polyoxyalkylene glycol chain include polyethylene glycol having a polymerization degree of 2 to 50, and a block copolymer of ethylene oxide and propylene oxide having 2 to 50 repeating units as ethylene oxide ( (Meth) acrylate, or polyethylene glycol having a degree of polymerization of 2 to 50 capped with an alkyl group having 1 to 6 carbon atoms at the end, or a block copolymer of ethylene oxide and propylene oxide having 2 to 50 repeating units as ethylene oxide (Meth) acrylates and the like.

Examples of the S atom-containing chain transfer agent include -SR (R is an alkyl group having 1 to 18 carbon atoms, a phenyl group optionally having a substituent on the benzene ring, a hydroxy group, a carbon An alkoxy group having 1 to 18 atoms, an aralkyloxy group having 1 to 18 carbon atoms, a phenyloxy group optionally having a substituent on the benzene ring, a carboxyl group, a salt of a carboxy group, 1 to 1 carbon atom 1 to 8 carbon atoms having one or more functional groups selected from the group consisting of 18 monovalent or polyvalent alkylcarbonyloxy groups and monovalent or polyvalent alkoxycarbonyl groups having 1 to 18 carbon atoms An alkyl group) having a functional group represented by:

Examples of the (meth) acrylic acid ester having a phosphate ester residue include commercially available monomers such as “Light Ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd., “Phosmer M”, “Phosmer PE” manufactured by Unichemical Co., Ltd. Is mentioned. Moreover, (meth) acrylic acid ester can be easily obtained by reacting (meth) acrylic acid hydroxy ester with a phosphoric acid esterifying reagent such as phosphorus oxychloride or phenyl dichlorophosphate. These can also be used. These may be used alone or in combination of two or more.

Examples of the compound in which polyoxyalkylene is added to the polyalkyleneimine include those having a structure composed of polyethyleneimine and the polyoxyalkylene structure such as a polyethylene oxide structure.

The polyethyleneimine and the polyoxyalkylene may be linearly bonded, and the polyoxyalkylene is grafted and bonded to the side chain of the main chain composed of the polyethyleneimine. There may be.

Specific examples of the compound in which polyoxyalkylene is added to the polyalkyleneimine include a copolymer of polyethyleneimine and polyoxyethylene, a part of imino group present in the main chain, and an ethylene oxide addition reaction. And the like. They are preferably block copolymers.

Further, the compound obtained by adding polyoxyalkylene to the polyalkyleneimine was obtained by reacting an amino group possessed by polyalkyleneimine, a hydroxyl group possessed by polyoxyethylene glycol, and an epoxy group possessed by an epoxy resin. Things can also be used.

Specific examples of the polyalkyleneimine include “PAO2006W”, “PAO306”, “PAO318”, “PAO718” and the like of “Epomin (registered trademark) PAO series” manufactured by Nippon Shokubai Co., Ltd.

The polyalkyleneimine preferably has a number average molecular weight in the range of 3,000 to 30,000.

In addition, examples of the conductive material include transition metals or compounds thereof, and ionic transition metals are preferable among the transition metals. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, and cobalt. Among the ionic transition metals, copper, silver, and gold are preferable, and silver is more preferable because a conductive pattern with low electrical resistance and resistance to corrosion can be formed.

In addition, when a plating nucleating agent is used instead of the conductive substance contained in the fluid (b), the oxide of the transition metal, a metal whose surface is coated with an organic substance, or the like can be used. These conductive substances or plating nucleating agents can be used alone or in combination of two or more.

The transition metal oxide is usually in an inactive (insulating) state. For example, the metal is exposed by treatment with a reducing agent such as dimethylaminoborane to impart activity (conductivity). be able to.

Further, examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state. However, for example, by removing the organic substance using a laser or the like, the metal can be exposed to impart activity (conductivity).

As the conductive material, particles having an average particle diameter of about 1 to 100 nm are preferably used, and those having an average particle diameter of 1 to 50 nm are preferably used. Compared to the case of using a conductive material having a diameter, it is more preferable because a fine conductive pattern can be formed and the resistance value after firing described later can be further reduced. The “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance with a good dispersion solvent. For this measurement, “Nanotrack UPA-150” manufactured by Microtrack Co. can be used.

Examples of the solvent that can be used for the fluid (b) include organic media such as alcohols, ethers, esters, and ketones, as well as aqueous media such as distilled water, ion-exchanged water, pure water, and ultrapure water. Can be mentioned.

Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, heptanol, hexanol, octanol, and nonanol. , Decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Butyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tri And propylene glycol monobutyl ether.

In addition, the fluid (b) can be used in combination with a ketone solvent such as acetone, cyclohexanone, methyl ethyl ketone, etc., for adjusting the physical properties. Other examples include ester solvents such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate and 3-methoxy-3-methyl-butyl acetate, hydrocarbon solvents such as toluene, especially hydrocarbon solvents having 8 or more carbon atoms. .

Examples of the hydrocarbon solvent having 8 or more carbon atoms include nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane. They can also be used in combination as needed. Furthermore, a solvent such as mineral spirit or solvent naphtha, which is a mixed solvent, can be used in combination.

Examples of the solvent include 2-ethyl 1,3-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, and 1,3-butane. Diol, 1,4-butanediol, 2,3-butanediol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Glycol monomethyl ether acetate, glycerol, and the like.

The fluid (b) can be produced, for example, by mixing the polymer dispersant, the conductive substance, and, if necessary, the solvent. Specifically, it has a polyoxyalkylene glycol chain, a phosphate ester residue and an acrylic acid ester copolymer having a sulfur atom at the terminal, or a branched polyalkyleneimine chain, a hydrophilic segment, and a hydrophobic segment. It can be produced by adding a previously prepared ion solution of the conductive substance to a medium in which the compound is dispersed, and reducing the metal ions.

Examples of the composition containing the conductive substance and the solvent include a dispersion in which the conductive substance is dispersed in a solvent such as the aqueous medium or the organic solvent.

The dispersion can be produced by mixing and stirring the conductive substance and the solvent. Specific examples of the dispersion include “SW1000” (manufactured by Bando Chemical Co., Ltd.), “Silk Auto A-1” (manufactured by Mitsubishi Materials Corporation), “MDot-SLP” (manufactured by Mitsuboshi Belting Co., Ltd.), etc. Is mentioned.

The fluid (b) can also be produced by adding the polymer dispersant to a dispersion in which a conductive substance is dispersed in the solvent. In this production, they can be mixed at room temperature, and when mixing, a stirrer such as a three-one motor can be used as necessary.

In addition, the fluid (b) may include a surfactant, if necessary, in order to improve the dispersion stability of the conductive substance in a solvent such as an aqueous medium or an organic solvent and the wettability to the coated surface. An antifoaming agent, a rheology adjusting agent, etc. may be added.

Furthermore, as the fluid (b), in order to remove impurities mixed in in the manufacturing process, a fluid filtered using a micropore filter or the like, or a material processed using a centrifuge, or the like, should be used. You can also.

The viscosity of the fluid (b) (value measured with a B-type viscometer at 25 ° C.) is preferably in the range of 0.1 to 500,000 mPa · s, and in the range of 0.5 to 10,000 mPa · s. Is more preferable. In addition, when the fluid (b) is applied (printed) by a method such as an ink jet printing method or letterpress reverse printing described later, the viscosity is preferably in the range of 5 to 20 mPa · s.

Examples of the method for applying the fluid (b) on the support (A) include an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, and a bar coating. Method, die coating method, slit coating method, roll coating method, dip coating method and the like.

Among these coating methods, in the case of forming the conductive layer (B) patterned in a thin line shape having a width of about 0.01 to 100 μm, which is required when realizing a high density of an electronic circuit or the like, It is preferable to use an inkjet printing method or a reverse printing method.

As the ink jet printing method, what is generally called an ink jet printer can be used. Specifically, “Konica Minolta EB100, XY100” (manufactured by Konica Minolta Co., Ltd.), “Dimatics Material Printer DMP-3000, DMP-2831” (manufactured by FUJIFILM Corporation), and the like can be mentioned.

Further, as the reversal printing method, a letterpress reversal printing method and an intaglio reversal printing method are known. For example, the fluid (b) is applied to the surface of various blankets, and a non-image portion is in contact with the projected plate The pattern is formed on the surface of the blanket or the like by selectively transferring the fluid (b) corresponding to the non-image area to the surface of the plate, and then the pattern is transferred to the support. The method of making it transfer on the layer (A) (surface) is mentioned.

The conductive layer (B) is formed on the support (A). In order to further improve the adhesion between the surface of the support (A) and the conductive layer (B), the support After the primer is applied to the surface of (A) and dried to form the primer layer (C), the conductive layer (B) may be formed on the primer layer (C).

Examples of the primer include urethane resin, vinyl resin, urethane-vinyl composite resin, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, polyvinyl alcohol, polyvinyl pyrrolidone, and various resins and solvents. Is mentioned.

Among the resins used as the primer, urethane resin, vinyl resin, and urethane-vinyl composite resin are preferably used. Urethane resin having a polyether structure, urethane resin having a polycarbonate structure, urethane resin having a polyester structure, acrylic resin And one or more resins selected from the group consisting of urethane-acrylic composite resins are more preferable, and urethane-acrylic composite resins are more preferable because a conductive pattern having excellent adhesion, electrical conductivity, and fine wire properties can be obtained. .

The content ratio of the resin in the primer is preferably in the range of 10 to 70% by mass and more preferably in the range of 10 to 50% by mass in consideration of ease of application.

Also, examples of the solvent used for the primer include organic solvents and aqueous media.

Examples of the organic solvent include toluene, ethyl acetate, and methyl ethyl ketone, and examples of the aqueous medium include water, organic solvents that are miscible with water, and mixtures thereof.

Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; ketones such as acetone and methyl ethyl ketone; and polymers such as ethylene glycol, diethylene glycol, and propylene glycol. Examples include alkylene glycols; alkyl ethers of polyalkylene glycols; and lactams such as N-methyl-2-pyrrolidone.

The content ratio of the solvent in the primer is preferably in the range of 25 to 85% by mass and more preferably in the range of 45 to 85% by mass in consideration of ease of application.

If necessary, additives such as a crosslinking agent, a pH adjuster, a film forming aid, a leveling agent, a thickener, a water repellent, and an antifoaming agent may be added to the primer.

The primer layer (C) may be formed by applying a primer to part or all of the surface of the support (A), and removing a solvent such as an aqueous medium or an organic solvent contained in the primer. it can.

Examples of the method for applying the primer to the surface of the support (A) include a gravure method, a coating method, a screen method, a roller method, a rotary method, and a spray method.

The surface of the primer layer (C) is improved in adhesion to the conductive layer (B). For example, plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet treatment, water, acidic Alternatively, the surface treatment may be performed by a wet treatment method using an alkaline chemical solution, an organic solvent, or the like.

As a method for removing the solvent contained in the coating layer after coating the primer on the surface of the support (A), for example, a method of drying using a dryer and volatilizing the solvent is common. . The drying temperature is preferably set to a temperature that allows the solvent to be volatilized and does not adversely affect the support (A).

Although the thickness of the primer layer (C) formed using the primer varies depending on the use of the conductive pattern of the present invention, the adhesion between the support (A) and the conductive layer (B) is further improved. Therefore, the range of 10 to 300 μm is preferable, and the range of 10 to 500 nm is more preferable.

Moreover, when providing a primer layer (C) on the said support body (A), since the adhesiveness of the said support body (A) and the said primer layer (C) can be improved, the said support body (A) Surface treatment for forming fine irregularities, cleaning dirt adhering to the surface, and introducing a functional group such as a hydroxyl group, a carbonyl group, or a carboxyl group may be performed on the surface. Specifically, a plasma discharge treatment such as a corona discharge treatment, a dry treatment such as an ultraviolet treatment, a wet treatment using water, an aqueous solution of an acid / alkali, or an organic solvent may be applied.

In order to form the conductive layer (B), the baking step performed after applying the fluid (b) containing a conductive substance brings the conductive substances contained in the fluid (b) into close contact with each other. This is performed in order to form a conductive layer (B) having conductivity by bonding. The firing can be performed at a temperature range of 80 to 300 ° C. for about 2 to 200 minutes. Here, in order to disperse the polymer dispersant efficiently on the support (A) side (base material interface), it is preferable to set the firing temperature in the range of 150 to 300 ° C.

Although the firing may be performed in the air, part or all of the firing step may be performed in a reducing atmosphere in order to prevent all of the metal powder from being oxidized.

The baking step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, microwave, flash irradiation apparatus, or the like.

The conductive layer (B) formed using the fluid (b) by the above method contains a conductive substance in the range of 80 to 99.9% by mass in the conductive layer (B). In addition, the polymer dispersant is preferably contained in the range of 0.1 to 20% by mass.

That the polymer dispersant is unevenly distributed on the support (A) side (substrate interface) in the cross section of the conductive layer (B) is the depth by glow discharge emission spectroscopy (GD-OES). It can be confirmed from elemental analysis of the base material interface of the conductive layer by elemental analysis of the direction and X-ray photoelectron spectroscopy (XPS).

The conductive layer (B) may be provided on the entire surface of the support (A), or may be provided on a part of the surface of the support (A). Specific examples of the conductive layer (B) provided on a part of the surface of the support (A) include fine wires formed on the surface of the support (A). . By making the said conductive layer (B) into a thin wire | line, it is suitable when using the conductive pattern of this invention for an electrical circuit etc.

The width of the fine line (line width) is preferably about 0.01 to 200 μm, and more preferably about 0.01 to 150 μm because the conductive pattern can be densified.

The thickness of the conductive layer (B) is preferably in the range of 0.01 to 100 μm because a conductive pattern having low resistance and excellent conductivity can be formed. In addition, when the conductive layer (B) has a thin line shape, the thickness is preferably in the range of 0.1 to 50 μm.

The conductive pattern of the present invention is formed on the conductive layer (B) for the purpose of forming a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time. A plating layer (D) may be formed.

The formation method of the plating layer (D) is preferably a method of forming by plating. Examples of the plating treatment include wet plating methods such as electrolytic plating methods and electroless plating methods, and dry plating methods such as sputtering methods and vacuum deposition methods. Further, the plating layer (D) may be formed by combining two or more of these plating methods.

Among the above plating treatments, the adhesion between the conductive layer (B) and the plating layer (D) is further improved, and a conductive pattern having excellent conductivity can be obtained. A wet plating method such as an electrolytic plating method is preferable, and an electrolytic plating method is more preferable.

In the electroless plating method, for example, the metal constituting the conductive layer (B) is brought into contact with an electroless plating solution, thereby depositing a metal such as copper contained in the electroless plating solution from the metal film. This is a method of forming an electroless plating layer (film).

Examples of the electroless plating solution include those containing a metal such as copper, nickel, chromium, cobalt, and tin, a reducing agent, and a solvent such as an aqueous medium and an organic solvent.

Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol and the like.

In addition, as the electroless plating solution, if necessary, monocarboxylic acids such as acetic acid and formic acid; dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid; malic acid, lactic acid, glycol Hydroxycarboxylic acid compounds such as acid, gluconic acid and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid; Use organic acids such as carboxylic acid compounds, or soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), and those containing complexing agents such as amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine. You It is possible.

The electroless plating solution is preferably used in the range of 20 to 98 ° C.

In the electrolytic plating method, for example, electricity is supplied in a state where an electrolytic plating solution is in contact with the surface of the metal constituting the conductive layer (B) or the electroless plating layer (coating) formed by the electroless treatment. Thus, a metal such as copper contained in the electrolytic plating solution is used to form a conductive material constituting the conductive layer (B) placed on the negative electrode or an electroless plating layer (coating) formed by the electroless treatment. This is a method of depositing on the surface and forming an electrolytic plating layer (metal coating).

Examples of the electrolytic plating solution include those containing metal sulfides such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specifically, what contains copper sulfate, sulfuric acid, and an aqueous medium is mentioned.

The electrolytic plating solution is preferably used in the range of 20 to 98 ° C.

In the above electrolytic plating treatment method, since workability is good without using a highly toxic substance, it is preferable to form a plating layer (D) made of copper using the electrolytic plating method.

Further, as the dry plating process, a sputtering method, a vacuum deposition method, or the like can be used. In the sputtering method, an inert gas (mainly argon) is introduced in a vacuum, a voltage is applied to the material for forming the plating layer (D) to generate a glow discharge, and then the inert gas atoms are removed. Ionized, vigorously struck gas ions against the surface of the material for forming the plating layer (D) at high speed, and ejects atoms and molecules constituting the material for forming the plating layer (D) to the surface of the conductive layer (B). In this method, the plating layer (D) is formed by adhering.

Examples of the material for forming the plating layer (D) by sputtering include chrome, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, copper-zinc alloy, indium tin oxide (ITO), and silicon dioxide. , Titanium dioxide, niobium oxide, zinc oxide and the like.

When performing the plating process by the sputtering method, for example, a magnetron sputtering apparatus or the like can be used.

The thickness of the plating layer (D) is preferably in the range of 1 to 50 μm. The thickness of the plating layer (D) can be adjusted by controlling the processing time, the current density, the usage amount of the plating additive, and the like in the plating process when forming the plating layer (D). .

The conductive pattern of the present invention obtained by the above method is a fluid containing the conductive substance (B) in order to form the conductive layer (B) at a position corresponding to a desired pattern shape to be formed. By applying and baking b), a conductive pattern having a desired pattern can be produced.

Further, the conductive pattern can be manufactured by, for example, a photolithographic etching method such as a subtractive method or a semi-additive method, or a method of plating on the printed pattern of the conductive layer (B).

The subtractive method is an etching process having a shape corresponding to a desired pattern shape on the conductive layer (B) manufactured in advance or on the plating layer (D) provided on the conductive layer (B). In a method of forming a resist layer and then dissolving and removing the plating layer (D) and the conductive layer (B) in the removed portion of the resist with a chemical solution by a subsequent development process, thereby forming a desired pattern. is there. As the chemical solution, a chemical solution containing copper chloride, iron chloride or the like can be used.

In the semi-additive method, the conductive layer (B) is formed on the support (A), and the surface of the conductive layer (B) is treated by plasma discharge treatment or the like as necessary. A plating resist layer having a shape corresponding to a desired pattern is formed on the surface of (B), and then a plating layer (D) is formed by an electrolytic plating method and an electroless plating method. This is a method of forming a desired pattern by dissolving and removing the contacted conductive layer (B) in a chemical solution or the like.

Also, the method of plating on the printed pattern of the conductive layer (B) is to print the pattern of the conductive layer (B) on the support (A) by an ink jet method, a reverse printing method or the like, and if necessary, plasma After the surface of the conductive layer (B) is treated by discharge treatment or the like, the plating layer (D) is formed on the surface of the conductive layer (B) by an electrolytic plating method or an electroless plating method. This is a method of forming a pattern.

In the conductive layer (B), the conductive pattern obtained by the above method is in contact with the unevenly distributed portion of the conductive dispersant (B) due to the uneven distribution of the polymer dispersant on the support (A) side. Adhesion with the surface of (A) or the surface of the primer layer (C) is greatly improved. Thereby, since the adhesiveness between the support (A) and the conductive layer (B) is extremely high, delamination can be suppressed and excellent durability capable of maintaining good electrical conductivity is obtained. Therefore, formation of circuit forming substrates used for electronic circuits, integrated circuits, etc., formation of organic solar cells, electronic terminals, organic EL, organic transistors, flexible printed circuit boards, peripheral wiring constituting RFID, etc., plasma display It can be used for electromagnetic shield wiring. In particular, it can be suitably used for applications requiring high durability. For example, for printed wiring boards (PWB), flexible printed boards (FPC), automatic tape bonding (TAB), chip-on-film (COF), etc. It is possible to use.

Hereinafter, the present invention will be described in detail by way of examples.

[Preparation of fluid (1)]
[Synthesis of an acrylic ester copolymer having a polyoxyalkylene glycol chain, a phosphate ester residue, and a terminal sulfur atom]
A four-necked flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 32 parts by mass of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and 32 parts by mass of ethanol, and stirred at 80 ° C. in a nitrogen stream. The temperature was raised to. Next, 20 parts by mass of phosphooxyethyl methacrylate (“Light Ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd.), methoxypolyethyleneglycol methacrylate (Nippon Co., Ltd. “Blemmer (registered trademark) PME-1000”, molecular weight 1,000) A mixture of 80 parts by mass, methyl mercaptopropionate 4.1 parts by mass and MEK 80 parts by mass, and a polymerization initiator “2,2′-azobis (2,4-dimethylvaleronitrile) (“ Wako Pure Chemical Industries, Ltd. ”“ V −65 ”) and 0.5 parts by mass and a mixture of 5 parts by mass of MEK were added dropwise over 2 hours. After completion of the dropwise addition, 0.3 parts by mass of a polymerization initiator (“Perbutyl (registered trademark) O” manufactured by NOF Corporation) was added twice every 4 hours and stirred at 80 ° C. for 12 hours. Water was added to the obtained resin solution for phase inversion emulsification, and after desolvation under reduced pressure, water was added to add a non-volatile 76.8% by mass polyoxyalkylene glycol chain, a phosphate residue, and a sulfur atom at the terminal. An aqueous solution of an acrylic acid ester copolymer (hereinafter abbreviated as “polymer dispersing agent (1)”) was obtained. The weight average molecular weight measured by gel permeation chromatography of the obtained polymer dispersant (1) was 4,300 in terms of polystyrene, and the acid value was 97.5.

[Production of silver dispersion (1)]
A reducing agent solution comprising 463 g (4.41 mol) of 85% by mass of N, N-diethylhydroxylamine, the polymer dispersant (1) obtained above (equivalent to 23.0 g of non-volatiles), and 1,250 g of water. Prepared. Separately, the polymer dispersant (1) obtained above corresponding to 11.5 g of non-volatiles was dissolved in 333 g of water, and a solution of 500 g (2.94 mol) of silver nitrate in 833 g of water was added thereto and stirred well. did. The reducing agent solution was added dropwise to this mixture at room temperature (25 ° C.) over 2 hours. The obtained reaction mixture was filtered with a membrane filter (pore size 0.45 μm), and the filtrate was in a hollow fiber type ultrafiltration module (“MOLSEP module FB-02 type” manufactured by Daisen Membrane Systems Co., Ltd., molecular weight cut off 150,000). The amount of water corresponding to the amount of the filtrate flowing out was added at any time for purification. After confirming that the electric conductivity of the filtrate was 100 μS / cm or less, water injection was stopped and the filtrate was concentrated. The concentrate was recovered to obtain 742.9 g (dispersion medium: water) of a silver dispersion (1) of 36.7 parts by mass of nonvolatiles.

A mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added to the silver dispersion liquid (1) obtained above and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes. After removing the supernatant, a mixed solvent of 50 ml of isopropyl alcohol and 50 ml of hexane was added to the precipitate and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes. After removing the supernatant, 20 g of water was further added to the precipitate, followed by stirring for 2 minutes, and the organic solvent was removed under reduced pressure. Further, add 10 g of water and disperse with stirring, then leave it in a freezer at −40 ° C. for 24 hours to freeze it, and treat it with a freeze dryer (“FDU-2200” manufactured by Tokyo Rika Kikai Co., Ltd.) for 24 hours. As a result, a silver-containing powder (1) composed of a flake-like lump having a grayish green metallic luster was obtained.

To 25.9 g of the silver-containing powder (1) obtained above, 45 g of ethylene glycol and 55 g of ion-exchanged water are added and stirred for 3 hours to obtain a fluid (1) that can be used for conductive ink for inkjet printing. Obtained. The content of silver in the obtained fluid (1) was 20% by mass, and the content of the polymer dispersant (1) was 1% by mass. Moreover, the viscosity of the fluid (1) was 10 mPa · s.

[Preparation of fluid (2)]
Under a nitrogen atmosphere, 30 ml of a chloroform solution containing 9.6 g of p-toluenesulfonic acid chloride was added to a mixture of 20 g of methoxypolyethylene glycol (number average molecular weight 2,000), 8.0 g of pyridine and 20 ml of chloroform while stirring with ice cooling. After dropwise addition for 30 minutes, the mixture was stirred at a bath temperature of 40 ° C. for 4 hours, and 50 ml of chloroform was mixed.

The product obtained above was washed with 100 ml of 5% by mass aqueous hydrochloric acid solution, then with 100 ml saturated aqueous sodium hydrogen carbonate solution, and further with 100 ml saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate and filtered. And concentrated under reduced pressure. The product concentrated under reduced pressure was washed several times with hexane, filtered, and dried under reduced pressure at 80 ° C. to obtain methoxypolyethylene glycol having p-toluenesulfonyloxy group.

5.39 g of methoxypolyethylene glycol having p-toluenesulfonyloxy group obtained above, 20 g of polyethyleneimine (manufactured by Aldrich, molecular weight 25,000), 0.07 g of potassium carbonate and 100 ml of N, N-dimethylacetamide were mixed. The mixture was stirred at 100 ° C. for 6 hours in a nitrogen atmosphere.

Next, 300 ml of a mixed solution of ethyl acetate and hexane (volume ratio of ethyl acetate / hexane = 1/2) was added, and after vigorous stirring at room temperature, the solid product was filtered. The solid was washed with 100 ml of a mixed solution of ethyl acetate and hexane (ethyl acetate / hexane volume ratio = 1/2) and then dried under reduced pressure, whereby a compound in which polyethylene glycol was bound to polyethyleneimine (hereinafter referred to as “polyethyleneimine”). , Abbreviated as “polymer dispersing agent (2)”).

138.8 g of an aqueous solution containing 0.592 g of the polymer dispersant (2) obtained above and 10 g of silver oxide were mixed and stirred at 25 ° C. for 30 minutes. Next, 46 g of dimethylethanolamine was gradually added with stirring, and the mixture was stirred at 25 ° C. for 30 minutes. Thereafter, 15.2 g of a 10% by mass ascorbic acid aqueous solution was gradually added with stirring, and stirring was continued for 20 hours to obtain a silver dispersion (2).

To the silver dispersion (2) obtained above, a mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes. After removing the supernatant, a mixed solvent of 50 ml of isopropyl alcohol and 50 ml of hexane was added to the precipitate and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes. After removing the supernatant, 20 g of water was further added to the precipitate, followed by stirring for 2 minutes, and the organic solvent was removed under reduced pressure. Further, 10 g of water was added and stirred and dispersed, and then the dispersion was left to stand in a freezer at −40 ° C. for 24 hours to freeze, and this was frozen with a freeze dryer (“FDU-2200” manufactured by Tokyo Rika Kikai Co., Ltd.). By performing the time treatment, a silver-containing powder (2) composed of flaky lumps having a grayish green metallic luster was obtained.

Fluid (2) usable for conductive ink for inkjet printing by adding 45 g of ethylene glycol and 55 g of ion exchange water to 25.9 g of the silver-containing powder (2) obtained above and stirring for 3 hours. Got. The content of silver in the obtained fluid (2) was 20% by mass, and the content of the polymer dispersant (2) was 1% by mass. Moreover, the viscosity of the fluid (2) was 10 mPa · s.

[Synthesis Example 1: Production of urethane-acrylic composite resin]
100 parts by mass of polyester polyol (polyester obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer Polyol, hydroxyl group equivalent 1000 g / equivalent), 17.4 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane diisocyanate, and 178 parts by mass of methyl ethyl ketone. By mixing and reacting in the part, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

Next, 13.3 parts by mass of triethylamine was added to the organic solvent solution of the urethane prepolymer obtained above to neutralize part or all of the carboxyl groups of the urethane resin, and 277 parts by mass of water was further added. By sufficiently stirring, an aqueous dispersion of urethane resin having a carboxyl group was obtained.

Next, 8 parts by mass of a 25% by mass ethylenediamine aqueous solution was added to the aqueous dispersion of the urethane resin obtained above, and the urethane resin was chain-extended by stirring, followed by aging and desolvation to obtain a solid content. An aqueous dispersion of urethane resin (B) -2 having a concentration of 30% by mass was obtained. The urethane resin obtained here had an acid value of 30 and a weight average molecular weight of 55,000.

In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping the monomer mixture and dropping funnel for dropping the polymerization catalyst, 280 parts by mass of deionized water, water of the urethane resin obtained above 333 parts by mass of the dispersion was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

In order to obtain a vinyl polymer constituting the core layer under stirring in a reaction vessel heated to 80 ° C., 46 parts by mass of methyl methacrylate, 46 parts by mass of n-butyl acrylate, 4 parts by mass of 2-hydroxyethyl methacrylate And a vinyl monomer mixture containing 4 parts by mass of Nn-butoxymethylacrylamide and 20 parts by mass of an aqueous ammonium persulfate solution (concentration: 0.5% by mass) from separate dropping funnels, and the temperature in the reaction vessel was set to 80. While maintaining at ± 2 ° C., polymerization was carried out by dropping over 120 minutes.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, then the temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content was 20% by mass. By filtering with a cloth, an aqueous dispersion of composite resin particles composed of a shell layer made of the urethane resin and a core layer made of a vinyl polymer having an Nn-butoxymethylacrylamide group was obtained.

Example 1
A non-alkali glass (“OA-10” manufactured by Nippon Electric Glass Co., Ltd.) was used as the support, and the fluid (1) obtained above was applied to the surface of the inkjet printing machine (an inkjet testing machine manufactured by Konica Minolta Co., Ltd. “ EB100 ”, evaluation printer head KM512L, discharge amount 42 pl), a straight line having a line width of 100 μm and a film thickness of 0.5 μm is printed by about 1 cm, and then baked at 200 ° C. for 30 minutes. A conductive pattern having a conductive layer laminated thereon was obtained.

(Example 2)
Instead of the fluid (1) used in Example 1, a conductive pattern was obtained in the same manner as in Example 1 except that the fluid (2) obtained above was used.

Example 3
Instead of the alkali-free glass used as the support in Example 1, a polyimide film (“Kapton 150ENC” manufactured by Toray DuPont Co., Ltd., thickness 50 μm) was used instead of the fluid (1) used in Example 1. A conductive pattern was obtained in the same manner as in Example 1 except that the fluid (2) obtained above was used.

Example 4
An alkali-free glass (“OA-10” manufactured by Nippon Electric Glass Co., Ltd.) was used as the support, and the urethane-acrylic composite resin aqueous dispersion obtained in Synthesis Example 1 was dried on the surface to a dry film thickness of 1 μm. Thus, a support made of an alkali-free glass having a primer layer obtained by coating with a spin coater and drying at 120 ° C. for 3 minutes using a hot air dryer was obtained. On the surface of the primer layer of the obtained support, apply the fluid (1) obtained above to an inkjet printer (ink tester “EB100” manufactured by Konica Minolta, Inc., evaluation printer head KM512L, discharge amount 42 pl). Using this, a straight line having a line width of 100 μm and a film thickness of 0.5 μm was printed by about 1 cm, and then fired at 200 ° C. for 30 minutes to obtain a conductive pattern in which a conductive layer was laminated on a support.

(Example 5)
A conductive pattern was obtained in the same manner as in Example 4 except that instead of the fluid (1) used in Example 4, the fluid (2) obtained above was used.

(Example 6)
A polyimide film (“Kapton 150ENC” manufactured by Toray DuPont Co., Ltd., thickness 50 μm) was used as a support, and the urethane-acrylic composite resin aqueous dispersion obtained in Synthesis Example 1 was dried on the surface with a dry film thickness of 1 μm. Thus, a support comprising a polyimide film having a primer layer obtained by coating with a spin coater and drying at 120 ° C. for 3 minutes using a hot air dryer was obtained. On the surface of the primer layer of the obtained support, apply the fluid (1) obtained above to an inkjet printer (ink tester “EB100” manufactured by Konica Minolta, Inc., evaluation printer head KM512L, discharge amount 42 pl). Using this, a straight line having a line width of 100 μm and a film thickness of 0.5 μm was printed by about 1 cm, and then fired at 200 ° C. for 30 minutes to obtain a conductive pattern in which a conductive layer was laminated on a support.

(Comparative Example 1)
[Preparation of fluid (3)]
In 70 parts by mass of tetradecane, silver particles having an average particle size of 30 nm are dispersed using oleic acid, and the viscosity is adjusted to 10 mPa · s, whereby a fluid that can be used for conductive ink for inkjet printing (3 ) Was prepared.

Conductivity is obtained in the same manner as in Example 1 except that alkali-free glass is used as the support and the fluid (3) obtained above is used instead of the fluid (1) used in Example 1. Got a pattern.

(Comparative Example 2)
A polyimide film (“Kapton 150ENC” manufactured by Toray DuPont Co., Ltd., thickness 50 μm) is used as a support, and instead of the fluid (1) used in Example 1, the fluid (3) obtained above is used. A conductive pattern was obtained in the same manner as in Example 1 except that.

For the conductive patterns obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the adhesion between the conductive layer and the support was evaluated. In addition, about what has a primer layer in a support body, the adhesiveness of a conductive layer and a primer layer was evaluated.

[Evaluation of adhesion between conductive layer and support]
A cellophane adhesive tape (“CT405AP-24” manufactured by Nichiban Co., Ltd., width 24 mm) is pressure-bonded to the surface of the conductive layer of the conductive pattern with a finger, and the pressure-sensitive cellophane adhesive tape is then applied to the surface of the conductive pattern. It peeled in the direction. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesion between the conductive layer and the support was evaluated according to the following criteria.

A: A conductive layer containing silver was not attached to the adhesive surface of the cellophane adhesive tape. B: A conductive layer in a range of less than 3% with respect to the area where the conductive layer and the adhesive tape contacted each other was from the primer layer. Exfoliated and adhered to the adhesive surface of the adhesive tape C: The conductive layer in the range of 3% or more and less than 30% with respect to the area where the conductive layer and the adhesive tape were in contact with each other was separated from the primer layer, and the adhesive surface of the adhesive tape D: The conductive layer of 30% or more of the area where the conductive layer and the adhesive tape contacted peeled off from the primer layer and adhered to the adhesive tape

[Elemental analysis of substrate interface of conductive layer by X-ray photoelectron spectroscopy (XPS)]
The conductive layer was peeled off at the interface between the conductive layer of the conductive pattern and the support, and the surface that was in contact with the support (substrate interface) was placed on an X-ray photoelectron spectrometer (“Kraitos AXIS-HS, manufactured by Shimadzu Corporation” ”, X-ray: monochrome Al—Kα, voltage: 12 KV, current: 10 mA, measurement diameter: 400 μm × 600 μm) was used for elemental analysis of carbon atoms. The carbon atom weight was quantified in atom%.

According to the elemental analysis with an X-ray photoelectron spectrometer, the conductive patterns of Examples 1 to 3 have a high carbon atom content of 80 to 89 atm% at the substrate interface of the conductive layer. It was confirmed that the polymer dispersant was segregated. On the other hand, in the conductive patterns of Examples 1 to 3, the amount of carbon atoms at the base material interface of the conductive layer is as low as 15 to 71 atm%, and the polymer dispersant is not segregated at the base material interface of the conductive layer. I was able to confirm. In Examples 4 to 6, in which the primer layer was formed on the support, the conductive layer could not be peeled off at the interface between the conductive layer and the support, and therefore elemental analysis with an X-ray photoelectron spectrometer was not possible. However, from the results of elemental analysis in Examples 1 to 3 in which the conditions differ only in the presence or absence of the primer layer, it can be estimated that the polymer dispersant is segregated at the base material interface of the conductive layer.

[Elemental analysis of substrate interface of conductive layer by glow discharge emission spectroscopy (GD-OES)]
For the conductive layer (silver layer) having the conductive pattern obtained in Example 2, the Marcus type high-frequency glow discharge luminescent surface analyzer (“GD-Profiler2” manufactured by Horiba, Ltd., gas type: Ar, discharge pressure: FIG. 1 shows a chart of elemental analysis of carbon atoms and silver atoms in the depth direction by 200 Pa, discharge power: 20 W, pulse discharge: On, pulse frequency: 50 Hz, uptake: every 5 ms, measurement diameter: 4 mm). From this chart, it can be seen that, in the cross section of the conductive layer, the signal side of the carbon atom is high and the signal intensity of the silver atom is low on the support side (base material interface) and the opposite side (air interface side). It was confirmed that the polymer dispersant was segregated at the material interface.

Table 1 summarizes the results evaluated above.

* “Presence / absence of uneven distribution of polymer dispersant” in Examples 4 to 6 in Table 1 above was determined to be “Yes” based on the estimation of the carbon atom weight at the substrate interface of the conductive layers in Examples 1 to 3.

In the cross section of the conductive layer, the conductive pattern of the present invention of Examples 1 to 6 in which the polymer dispersant is unevenly distributed on the support (A) side (substrate interface) is the adhesion between the support and the conductive layer. It was confirmed that the property is very high.

On the other hand, the conductive patterns of Comparative Examples 1 and 2 have a small amount of oleic acid, which is a surfactant corresponding to a dispersant, on the support side (base material interface) of the conductive layer. It was confirmed that the adhesion with the conductive layer was insufficient.

Claims

A conductive pattern in which a fluid (b) containing a conductive substance and a polymer dispersant is applied on a support (A) to form a conductive layer (B), wherein the conductive layer (B) In the cross section of the conductive pattern, the polymer dispersant is unevenly distributed on the support (A) side (substrate interface).
The polymer dispersant is a copolymer of a (meth) acrylic acid ester having a polyoxyalkylene glycol chain and a chain transfer agent having a sulfur atom, a (meth) acrylic acid ester having a phosphoric acid ester residue and a sulfur atom. Copolymer of a chain transfer agent having a chain, a (meth) acrylate having a polyoxyalkylene glycol chain, a (meth) acrylate having a phosphate residue, and a chain transfer agent having a sulfur atom The conductive pattern according to claim 1, wherein the conductive pattern is at least one selected from the group consisting of a coalescence, a polyalkyleneimine, or a polyalkyleneimine having a polyoxyalkylene structure containing an oxyethylene unit.
The conductive pattern according to claim 1, wherein a primer layer (C) is provided between the support (A) and the conductive layer (B).
The conductive pattern according to claim 1, wherein a plating layer (D) is further laminated on the surface of the conductive layer (B).
An electronic circuit having the conductive pattern according to any one of claims 1 to 4.