WO2014141787A1 - Composition for forming electrically conductive film, and method for producing electrically conductive film using same - Google Patents

Composition for forming electrically conductive film, and method for producing electrically conductive film using same Download PDF

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Publication number
WO2014141787A1
WO2014141787A1 PCT/JP2014/052874 JP2014052874W WO2014141787A1 WO 2014141787 A1 WO2014141787 A1 WO 2014141787A1 JP 2014052874 W JP2014052874 W JP 2014052874W WO 2014141787 A1 WO2014141787 A1 WO 2014141787A1
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group
formula
composition
conductive film
mass
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PCT/JP2014/052874
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French (fr)
Japanese (ja)
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渡辺　徹
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1157—Using means for chemical reduction
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods

Definitions

  • the present invention relates to a composition for forming a conductive film and a method for producing a conductive film using the same.
  • a method of forming a conductive film such as a wiring by applying a dispersion of metal particles or metal oxide particles to a substrate by a printing method and sintering by a heat treatment. Since the above method is simple, energy-saving, and resource-saving compared to the conventional high-heat / vacuum process (sputtering) and plating method for forming a conductive film, it is highly anticipated in the development of next-generation electronics. In particular, in recent years, from the viewpoint of cost reduction, a method of forming a conductive film by using a composition containing metal oxide particles and reducing and sintering the composition by heat treatment has attracted attention.
  • Patent Document 1 sintering by light irradiation (photosintering) is performed to sinter the copper oxide ink on the base material without heating the base material excessively, thereby forming a metal copper film.
  • a method of forming is disclosed (paragraph 0013, Example 1 etc.).
  • the present inventor gives a composition containing copper particles or copper oxide particles and a binder (such as polyvinylpyrrolidone) to a base material with reference to Patent Document 1, and forms a coating film by heating and drying.
  • a binder such as polyvinylpyrrolidone
  • the present invention provides a conductive film-forming composition that can obtain a conductive film that has good adhesion to a substrate and excellent conductivity even by sintering by light irradiation. The purpose is to provide.
  • the present inventor has obtained a polymer containing copper oxide particles and / or copper particles, a repeating unit having a specific reducing group, and a repeating unit having a specific crosslinkable group.
  • the composition containing a curing agent that reacts with the crosslinkable group the conductive film obtained by irradiating the coating film formed from the composition with light has good adhesion to the substrate. And it discovered that it was excellent in electroconductivity, and came to this invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • composition for electrically conductive film formation containing the hardening
  • the polymer includes a repeating unit represented by formula (3) described later and a repeating unit represented by formula (2) described later, a repeating unit represented by formula (4) described later, and the following The composition for electrically conductive film formation as described in said (1) which is a polymer containing the repeating unit represented by Formula (5) to perform or the repeating unit represented by Formula (6) mentioned later.
  • composition for electrically conductive film formation as described in said (2) whose said polymer is a polymer containing the repeating unit represented by the said repeating unit represented by said Formula (3), and said Formula (2).
  • B is a group represented by the above formula (B-1) or (B-7), and the curing agent is an amine or alcohol.
  • B in the formula (2) is a group represented by the formula (B-2), and the curing agent is an epoxide, an aldehyde, or a moiety represented by the formula (13) described later.
  • the composition for forming a conductive film according to any one of the above (1) to (3) which is a compound having two or more structures.
  • composition for forming a conductive film according to any one of (1) to (5) above is applied on a substrate to form a composition layer on the substrate, and then the composition layer A heat treatment is performed on the coating film forming step of forming a coating film, A reduction process which performs light irradiation processing to the above-mentioned paint film, reduces the above-mentioned copper oxide particles and / or copper particles, and forms a conductive film.
  • the manufacturing method of the electrically conductive film as described in said (6) whose said light irradiation process is a pulsed light irradiation process.
  • composition for forming a conductive film which can obtain a conductive film having good adhesion to a substrate and excellent conductivity even by sintering by light irradiation.
  • composition for forming conductive film comprises copper oxide particles and / or copper particles, a repeating unit represented by the formula (1) described later, and a formula (2) described below.
  • the polymer containing the repeating unit represented by this is contained.
  • the repeating unit represented by the formula (1) has a specific reducing group.
  • the repeating unit represented by Formula (2) has a specific crosslinkable group.
  • the composition of this invention contains the hardening
  • the conductive film obtained by irradiating light to the coating film formed from the composition has good adhesion to the base material and is conductive. It will be excellent. This is not clear in detail, but is assumed to be as follows. When a coating obtained from a composition containing copper oxide particles and / or copper particles is irradiated with light and photosintered, components such as solvent and binder in the coating are decomposed and volatilized. It is thought that microscopic or macroscopic destruction occurs in the film itself, and as a result, the obtained conductive film has insufficient adhesion and conductivity to the substrate.
  • the composition of the present invention contains a specific polymer (a polymer having a specific reducing group and a specific crosslinkable group) and a curing agent that reacts with the specific crosslinkable group.
  • a specific polymer a polymer having a specific reducing group and a specific crosslinkable group
  • a curing agent that reacts with the specific crosslinkable group.
  • the coating film formed from the composition a cross-linked structure between the polymers is formed. Therefore, when light is applied to the coating film obtained from the composition of the present invention, the coating film itself is not physically decomposed, and copper oxide particles or copper partially oxidized by a specific reducing group, etc. The particles are reduced and the copper particles are fused to each other, so that a conductive film having excellent adhesion to the substrate can be obtained.
  • the reducing agent when a reducing agent not fixed to the polymer is simply blended separately from the polymer having a crosslinkable group, the reducing agent volatilizes during photo-sintering, so that the reduction of the copper oxide particles and the like proceeds sufficiently.
  • the conductivity of the obtained conductive film is insufficient. That is, it can be said that one feature of the present invention is that a polymer having both reducing and crosslinking functions is used.
  • the composition of the present invention contains copper oxide particles and / or copper particles (preferably copper oxide particles). As described above, when the coating film formed from the composition of the present invention is irradiated with light, the copper oxide particles and the copper particles partially oxidized are rapidly reduced to form a conductive film having excellent conductivity.
  • the copper oxide particle contained in the composition of this invention is a particulate copper oxide, it will not specifically limit.
  • the particulate form refers to a small granular form, and specific examples thereof include a spherical shape and an ellipsoidal shape. It does not have to be a perfect sphere or ellipsoid, and a part may be distorted.
  • the copper oxide particles are preferably copper oxide (I) particles or copper oxide (II) particles, and can be obtained at a low cost.
  • copper oxide ( II) More preferably, it is a particle.
  • the copper oxide particles are preferably nanoparticles.
  • the average particle diameter of the copper oxide particles is not particularly limited, but is preferably 200 nm or less, and more preferably 100 nm or less.
  • the lower limit is not particularly limited, but is preferably 1 nm or more.
  • the average particle size is 1 nm or more, the activity on the particle surface does not become too high, does not dissolve in the composition, and is excellent in handleability.
  • the average particle size is 200 nm or less, it becomes easy to form a pattern such as wiring by a printing method using the composition as an ink-jet ink composition, and when the composition is made into a conductor, it becomes metal copper. This is preferable because the reduction of is sufficient and the conductivity of the resulting conductive film is improved.
  • the average particle diameter in this invention points out an average primary particle diameter.
  • the average particle diameter is obtained by measuring the particle diameter (diameter) of at least 50 or more copper oxide particles by observation with a transmission electron microscope (TEM) and arithmetically averaging them. In the observation diagram, when the shape of the copper oxide particles is not a perfect circle, the major axis is measured as the diameter.
  • the copper oxide particles for example, CuO nanoparticles manufactured by Kanto Chemical Co., Ltd., CuO nanoparticles manufactured by Sigma Aldrich Co., etc. can be preferably used.
  • Copper particles If the copper particle contained in the composition of this invention is particulate copper, it will not specifically limit.
  • the definition of the particle shape is the same as the copper oxide particle described above.
  • the copper particles are preferably nanoparticles.
  • the suitable aspect of the average particle diameter of a copper particle is the same as the copper oxide particle mentioned above.
  • the composition of the present invention contains a polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) (hereinafter also referred to as a specific polymer).
  • the specific polymer contained in the composition of the present invention contains a specific crosslinkable group, so that when the obtained coating film is irradiated with light, the coating film itself is not physically decomposed. A conductive film having excellent adhesion to the substrate can be obtained.
  • the specific polymer contained in the composition of the present invention has a specific reducing group, reduction of copper oxide particles or partially oxidized copper particles occurs quickly during photo-sintering and has excellent conductivity. A conductive film can be obtained.
  • R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group (preferably having 1 to 5 carbon atoms). Of these, a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.
  • L 1 represents a single bond or a divalent organic group.
  • a divalent organic group a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (for example, an arylene group, preferably).
  • A is a reducing group, and specifically represents an organic group containing an amide group (—CON ⁇ ) or a hydroxy group (—OH). Especially, it is preferable that it is an organic group containing an amide group from the reason which the adhesiveness of the electrically conductive film obtained is more excellent.
  • the said reducing group shows a reducibility with respect to the copper oxide particle and the copper particle by which one part was oxidized in the case of light sintering.
  • the organic group containing the amide group is not particularly limited, but a preferable embodiment includes, for example, a group represented by the following formula (7).
  • R 71 represents a hydrocarbon group which may have a hetero atom.
  • a plurality of R 71 may be the same or different.
  • R 71 may form a ring with R 71 .
  • the hetero atom of the hydrocarbon group that may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
  • the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • aliphatic hydrocarbon group examples include a linear or branched alkyl group (particularly 1 to 10 carbon atoms), a linear or branched alkenyl group (particularly 2 to 10 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly 2 to 10 carbon atoms).
  • aromatic hydrocarbon group examples include an aryl group and a naphthyl group.
  • aryl group examples include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group.
  • * represents a bonding position.
  • R 81 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom.
  • a plurality of R 81 may be the same or different.
  • a specific example of R 81 is the same as R 71 described above. Of these, a hydrogen atom is preferable.
  • R 2 is a hydrogen atom or, a substituted or unsubstituted alkyl groups. Specific examples and preferred embodiments of R 2 are the same as those of R 1 described above.
  • L 2 represents a single bond or a divalent organic group. Specific examples and preferred embodiments of L 2 are the same as those of L 1 described above.
  • B is a crosslinkable group and represents a group selected from the group consisting of the following formulas (B-1) to (B-9).
  • R b represents a hydrogen atom or a hydrocarbon group which may have a hetero atom.
  • a plurality of R b may be the same or different. * Represents a bonding position.
  • R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom.
  • R b is preferably a substituted or unsubstituted alkyl group (particularly having 1 to 5 carbon atoms).
  • R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group (particularly one having 1 to 5 carbon atoms), more preferably a methyl group.
  • R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom.
  • R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom.
  • R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom.
  • B represents the formula (B-1), the formula (B-3), the formula (B-4), the formula (B-5) because the adhesiveness of the obtained conductive film is more excellent.
  • groups selected from the group consisting of formula (B-6) and formula (B-7) are represented by formula (B-1), formula (B-3), formula (B-4), formula More preferably, the group is selected from the group consisting of (B-6) and formula (B-7), and the formula (B-1), formula (B-3), formula (B-6) and formula (B) More preferred is a group selected from the group consisting of B-7), and particularly preferred is formula (B-1) or formula (B-7).
  • the crosslinkable group represented by B in the above formula (2) is the above formula (B-2), it is represented by the repeating unit represented by the above formula (1) and the above formula (2).
  • the repeating unit may be the same.
  • the specific polymer may include at least the repeating unit represented by the above formula (2). .
  • the crosslinkable group represented by B in the formula (2) is the formula (B-2)
  • the crosslinkable group also functions as a reducing group.
  • Preferred embodiments of the specific polymer include, for example, a polymer P including a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (2) (same as the above-described formula (2)), Examples thereof include a polymer Q containing a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5), and a polymer R containing a repeating unit represented by the following formula (6).
  • R 3 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred embodiments of R 3 are the same as those of R 1 described above.
  • R 31 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. A plurality of R 31 may be the same or different. A specific example of R 31 is the same as R 71 described above. Of these, a hydrogen atom is preferable.
  • R 4 and R 5 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred embodiments of R 4 and R 5 are the same as those of R 1 described above.
  • the repeating unit represented by the above formula (4) is represented by the above formula (1).
  • R 6 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred embodiments of R 6 are the same as those of R 1 described above.
  • L 6 represents a single bond or a divalent organic group. A specific example of L 6 is the same as L 1 described above. Of these, an alkylene group, —O—, —COO—, —CO— or a combination thereof is preferable, and —CO— is more preferable.
  • R61 represents a bivalent aliphatic hydrocarbon group.
  • an alkylene group having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and an ethylene group is further preferable.
  • p represents an integer of 1 to 100. Among these, an integer of 5 to 30 is preferable.
  • the repeating unit represented by the above formula (6) is also the repeating unit represented by the above formula (1). It corresponds also to the repeating unit represented by these. That is, the OH group at the end of the side chain in the formula (6) is A (reducing group) in the formula (1) and B (crosslinkable group) in the formula (2). But there is.
  • the above-mentioned specific polymer is preferably water-soluble from the viewpoint of good particle dispersibility and improved uniformity of the resulting conductive film.
  • the molecular weight of the specific polymer is not particularly limited, but is preferably from 1,000 to 1,000,000, and more preferably from 10,000 to 500,000 from the viewpoints of preparation of the composition, coating properties, and improvement in film properties.
  • the weight average molecular weight of the specific polymer is measured in terms of polystyrene using N-methylpyrrolidone as a solvent using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation.
  • a desired vinyl polymer can be obtained by performing radical polymerization, cationic polymerization, or anionic polymerization using a vinyl monomer that forms a desired repeating unit.
  • various initiators such as radical polymerization initiators
  • the content of the specific polymer is the total content of the copper oxide particles and the copper particles from the viewpoint of the balance between the conductivity of the obtained conductive film and the storage stability of the composition.
  • it is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 15% by mass.
  • the composition of the present invention contains a curing agent that reacts with the crosslinkable group represented by B in the formula (2).
  • a curing agent is not particularly limited as long as it reacts with the crosslinkable group represented by B in the above formula (2).
  • amine amino group-containing compound
  • alcohol chain formula or Compound in which hydrogen atom of alicyclic hydrocarbon is substituted with hydroxy group
  • epoxide epoxy group-containing compound
  • aldehyde aldehyde group-containing compound
  • radical initiator vinyl compound (vinyl group-containing compound)
  • acid catalyst examples thereof include carboxylic acid.
  • the amine is not particularly limited, but is preferably an amine having a plurality (particularly two) amino groups.
  • examples of such amines include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, and aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
  • aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
  • it is preferable that it is a compound represented by following formula (16).
  • L 16 represents a single bond or a divalent organic group.
  • a specific example of L 16 is the same as L 1 described above.
  • an alkylene group or a group obtained by combining an alkylene group and —NH— is preferable.
  • the alcohol is not particularly limited, but is preferably an aliphatic hydrocarbon which may have a hetero atom having a plurality of (particularly two) hydroxyl groups.
  • aliphatic hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, diethanolamine, triethanolamine, and bishydroxymethylurea.
  • a compound having a secondary amino group (—NR—: R is a hydrogen atom or a hydrocarbon group) or a tertiary amino group (—N ⁇ ) is preferable, and is represented by the following formula (9). More preferably, it is a compound.
  • R 91 represents a divalent aliphatic hydrocarbon group.
  • R 91 is the same as R 61 described above. Of these, an alkylene group having 1 to 5 carbon atoms is preferable.
  • s is 0 or 1.
  • t is 2 or 3.
  • R131 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • a specific example of R 131 is the same as R 1 described above.
  • R 131 is preferably a hydrogen atom.
  • a preferred embodiment of the compound having two or more partial structures represented by the above formula (13) includes, for example, a compound represented by the following formula (14).
  • R141 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • a specific example of R 141 is the same as R 1 described above.
  • R 141 is preferably a hydrogen atom.
  • the epoxide is not particularly limited as long as it is a compound containing an epoxy group, but is preferably a compound containing a plurality (particularly two) of epoxy groups. Especially, it is preferable that it is a compound represented by following formula (10).
  • L 10 represents a single bond or a divalent organic group. Specific examples and preferred embodiments of L 10 are the same as those of L 1 described above.
  • the aldehyde is not particularly limited as long as it is a compound containing an aldehyde group, but is preferably a compound containing a plurality (particularly two) aldehyde groups. Especially, it is preferable that it is a compound represented by following formula (11).
  • L 11 represents a single bond or a divalent organic group.
  • a specific example of L 11 is the same as L 1 described above. Of these, a single bond is preferable.
  • the aldehyde is preferably glyoxal.
  • the radical initiator is not particularly limited, and examples thereof include acetophenones, benzoins, benzophenones (1-hydroxy-1,2,3,4,5,6-hexahydrobenzophenone, etc.), phosphine oxides, ketals.
  • the vinyl compound is not particularly limited as long as it is a compound containing a vinyl group, but is preferably a compound containing a plurality (particularly two) vinyl groups. Especially, it is preferable that it is a compound represented by following formula (12).
  • L 12 represents a single bond or a divalent organic group.
  • a specific example of L 12 is the same as L 1 described above.
  • an organic group having a sulfur atom is preferable, —S— or —SO 2 — is more preferable, and —SO 2 — is still more preferable.
  • the acid catalyst is not particularly limited, and a known acid catalyst can be used. Specific examples include oxalic acid, tartaric acid, succinic acid, citric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like.
  • the carboxylic acid is not particularly limited as long as it is a compound having a carboxy group, but is preferably a compound containing a plurality (particularly two) of carboxy groups. Especially, it is preferable that it is a compound represented by following formula (15).
  • L 15 represents a single bond or a divalent organic group.
  • a specific example of L 15 is the same as L 1 described above. Of these, an alkylene group (particularly having 1 to 5 carbon atoms) is preferable.
  • the curing agent is preferably the amine or the alcohol, and more preferably the amine.
  • the curing agent is the above acid catalyst or the above alcohol because the adhesion and conductivity of the resulting conductive film are more excellent. It is preferable that the acid catalyst is more preferable.
  • B (crosslinkable group) in the above formula (2) is the above formula (B-5)
  • the curing agent is the above carboxylic acid because the adhesion and conductivity of the resulting conductive film are more excellent.
  • B (crosslinkable group) in the formula (2) is the formula (B-2)
  • the curing agent is the epoxide
  • the formula (B) because the adhesion and conductivity of the resulting conductive film are more excellent.
  • It is preferably a compound having two or more partial structures represented by 13), the vinyl compound or the aldehyde, and the epoxide, a compound having two or more partial structures represented by the formula (13) or the vinyl. It is more preferably a compound, more preferably a compound having two or more partial structures represented by the epoxide or the formula (13), and particularly preferably the epoxide.
  • the curing agent may be the above alcohol because the adhesion and conductivity of the resulting conductive film are more excellent.
  • a compound having two or more partial structures represented by the above formula (13) is more preferable.
  • the curing agent is the above radical initiator because the resulting conductive film has better adhesion and conductivity. It is preferable.
  • the content of the curing agent is preferably 0.01 to 30% by mass with respect to the content of the specific polymer, from the viewpoint of efficiently crosslinking the polymer, More preferably, it is ⁇ 20% by mass.
  • the composition of the present invention preferably contains a solvent from the viewpoint of easy viscosity adjustment and printability.
  • the solvent functions as a dispersion medium for copper oxide particles and / or copper particles.
  • the type of the solvent is not particularly limited.
  • water, organic solvents such as alcohols, ethers, and esters can be used. Among them, a homogeneous film is formed, and as a result, the conductivity of the formed conductive film is superior, so water, an aliphatic alcohol having a monovalent to trivalent hydroxyl group, and an alkyl ether derived from this aliphatic alcohol.
  • An alkyl ester derived from the aliphatic alcohol, or a mixture thereof is preferably used.
  • the main solvent is a solvent having the highest content in the solvent.
  • the content of the solvent is not particularly limited, but is preferably 5 to 90% by mass, and preferably 8 to 80% by mass with respect to the total mass of the composition, from the viewpoint of suppressing an increase in viscosity and being excellent in handleability. It is more preferable.
  • the composition of the present invention may contain components other than the above components.
  • the composition of the present invention may contain a surfactant.
  • the surfactant plays a role of improving the dispersibility of the copper oxide particles and / or the copper particles.
  • the type of the surfactant is not particularly limited, and examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a fluorine surfactant, and an amphoteric surfactant. These surfactants can be used alone or in combination of two or more.
  • the viscosity of the composition of the present invention is preferably adjusted to a viscosity suitable for printing applications such as inkjet and screen printing.
  • the pressure is preferably 1 to 50 cP, and more preferably 1 to 40 cP.
  • screen printing it is preferably 1000 to 100,000 cP, and more preferably 10,000 to 80,000 cP.
  • the preparation method in particular of the composition of this invention is not restrict
  • an ultrasonic method for example, treatment with an ultrasonic homogenizer
  • a mixer method for example, a mixer method
  • the composition can be obtained by dispersing the components by a known means such as a ball mill method.
  • the manufacturing method of the electrically conductive film of this invention has a coating-film formation process and a reduction process at least. Below, each process is explained in full detail.
  • ⁇ Coating film formation process> the composition for forming a conductive film described above is applied on a substrate, a composition layer is formed on the substrate, and then a heat treatment is applied to the composition layer to form a coating film. It is a process to do.
  • the precursor film before the reduction treatment is obtained in this step.
  • the composition for forming a conductive film used is as described above.
  • a well-known thing can be used as a base material used at this process.
  • the material used for the substrate include resin, paper, glass, silicon-based semiconductor, compound semiconductor, metal oxide, metal nitride, wood, or a composite thereof. More specifically, low density polyethylene resin, high density polyethylene resin, ABS resin, acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate), polyacetal resin, polysulfone resin, polyetherimide resin, polyether ketone Resin base materials such as resin and cellulose derivatives; uncoated printing paper, fine coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper ( Paper substrates such as double kraft paper for heavy bags, double kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coated balls, chip balls, corrugated cardboard; soda glass, borosilicate glass, silica glass, Glass substrates such as quartz glass; silicon-based semiconductor
  • the method for forming the composition layer by applying the composition for forming a conductive film on the substrate is not particularly limited, and a known method can be adopted.
  • coating the composition for electrically conductive film formation to a base material, etc. are mentioned. From the viewpoint of easily controlling the thickness of the conductive film, a method of applying the conductive film forming composition on the substrate is preferable.
  • Application methods include, for example, double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, doctor coater, squeeze coater, reverse roll coater, transfer roll coater, extrusion roll coater, curtain Examples include a coater, dip coater, die coater, gravure roll coating method, screen printing method, dip coating method, spray coating method, spin coating method, and ink jet method.
  • the screen printing method and the ink jet method are preferable because they are simple and easy to produce a large conductive film.
  • the shape of application is not particularly limited, and may be a surface covering the entire surface of the substrate or a pattern (for example, a wiring or a dot).
  • the coating amount of the composition for forming a conductive film on the substrate may be appropriately adjusted according to the desired film thickness of the conductive film.
  • the film thickness of the coating film is preferably 0.01 to 5000 ⁇ m, 0.1 to 1000 ⁇ m is more preferable.
  • the heat treatment conditions for the composition layer are not particularly limited, but the heating temperature is preferably 80 to 200 ° C.
  • the heat treatment for example, an air dryer, an oven, an infrared dryer, a heating drum, or the like can be used.
  • This step is a step of forming a conductive film by performing light irradiation treatment on the coating film formed in the coating film forming step to reduce the copper oxide particles and / or the copper particles.
  • the light source used in the light irradiation treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon (Xe) lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
  • Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon (Xe) discharge lamp, and infrared lamp exposure.
  • the light irradiation process is preferably a light irradiation process using a flash lamp (particularly a Xe flash lamp), and more preferably a pulsed light irradiation process using a flash lamp (particularly a Xe flash lamp).
  • Irradiation with high-energy pulsed light can concentrate and heat the surface of the portion to which the coating film has been applied in a very short time, so that the influence of heat on the substrate can be extremely reduced.
  • Irradiation energy of the pulse light is preferably 1 ⁇ 100J / cm 2, more preferably 1 ⁇ 50J / cm 2, further preferably 1 ⁇ 30J / cm 2.
  • the pulse width of the pulsed light is preferably 1 ⁇ sec to 100 msec, and more preferably 10 ⁇ sec to 10 msec.
  • the irradiation time of the pulsed light is preferably 1 ⁇ sec to 1000 msec, more preferably 1 msec to 500 msec, and further preferably 1 msec to 200 msec.
  • the atmosphere for performing the light irradiation treatment is not particularly limited, and examples thereof include an air atmosphere, an inert atmosphere, and a reducing atmosphere.
  • the inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen.
  • the reducing atmosphere is a reduction of hydrogen, carbon monoxide, formic acid, alcohol, or the like. It refers to the atmosphere in which sex gas exists.
  • a conductive film is obtained by carrying out the above steps.
  • the film thickness of the conductive film is not particularly limited, and an optimum film thickness is appropriately adjusted according to the intended use. Of these, 0.01 to 1000 ⁇ m is preferable and 0.1 to 100 ⁇ m is more preferable from the viewpoint of printed wiring board use.
  • the film thickness is a value (average value) obtained by measuring three or more thicknesses at arbitrary points on the conductive film and arithmetically averaging the values.
  • the volume resistance value of the conductive film is preferably 2.0 ⁇ 10 ⁇ 4 ⁇ cm or less from the viewpoint of conductive characteristics. The volume resistance value can be calculated by multiplying the obtained surface resistance value by the film thickness after measuring the surface resistance value of the conductive film by the four-probe method.
  • the conductive film may be provided on the entire surface of the base material or in a pattern.
  • the patterned conductive film is useful as a conductor wiring (wiring) such as a printed wiring board.
  • wiring conductor wiring
  • the above-mentioned composition for forming a conductive film is applied to a substrate in a pattern and the light irradiation treatment is performed, or the conductive film provided on the entire surface of the substrate is patterned. And a method of etching.
  • the etching method is not particularly limited, and a known subtractive method, semi-additive method, or the like can be employed.
  • an insulating layer (insulating resin layer, interlayer insulating film, solder resist) is further laminated on the surface of the patterned conductive film, and further wiring (metal) is formed on the surface. Pattern) may be formed.
  • the material of the insulating film is not particularly limited.
  • epoxy resin epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated amorphous resin, etc.) , Polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal resin and the like.
  • an epoxy resin a polyimide resin, or a liquid crystal resin, and more preferably an epoxy resin.
  • Specific examples include ABF GX-13 manufactured by Ajinomoto Fine Techno Co., Ltd.
  • solder resist which is a kind of insulating layer material used for wiring protection, is described in detail in, for example, Japanese Patent Application Laid-Open No. 10-204150 and Japanese Patent Application Laid-Open No. 2003-222993. These materials can also be applied to the present invention if desired.
  • solder resist commercially available products may be used. Specific examples include PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.
  • the base material (base material with a conductive film) having the conductive film obtained above can be used for various applications.
  • a printed wiring board, TFT, FPC, RFID, etc. are mentioned.
  • N-vinylpyrrolidone 62 parts by mass of N-vinylpyrrolidone and 188 parts by mass of DMAc were added and heated to 75 ° C. under a nitrogen stream. Thereto, a solution of N-vinylpyrrolidone 62 parts by mass, monomer 6 (37 parts by mass), and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 3.7 parts by mass of DMAc (163 parts by mass) was dropped over 3 hours. did. It stirred for 3 hours after completion
  • Polymer 8 (Polymer 8) PVA500 (manufactured by Kanto Chemical Co., Inc.) is designated as polymer 8.
  • the repeating units contained in the polymer are summarized below.
  • the polymers 1 to 8 correspond to specific polymers.
  • the polymer 9 is a polymer that includes the repeating unit represented by the above formula (2) but does not include the repeating unit represented by the above formula (1), and does not correspond to a specific polymer.
  • the left repeating unit of the repeating units shown corresponds to the repeating unit represented by the above formula (1)
  • the right repeating unit is represented by the above formula (2).
  • the repeating unit shown corresponds to the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2).
  • the left-hand repeating unit of the repeating units shown corresponds to the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2).
  • Example 1 65 parts by mass of CuO nanoparticles (manufactured by Kanto Chemical Co., Inc .: particle size 27 to 95 nm) and 35 parts by mass of pure water are dispersed with Nertaro (manufactured by Sinky) (2200 rpm, 3 minutes) to obtain a CuO paste (CuO: 65% by mass).
  • composition for forming a conductive film 115 parts by weight of the CuO paste, 8 parts by weight of the above aqueous solution 1 (26 parts by weight), 40% by weight BYK-425 (by Big Chemie Japan) propylene glycol solution, and 0.4 parts by weight of triethylenetetramine as a curing agent And kneaded with Nertaro (2200 rpm, 3 minutes) to obtain a composition (composition for forming a conductive film).
  • the obtained composition was apply
  • a conductive film (copper film) was obtained by applying a Xe flash lamp (irradiation energy: 4.9 J / cm 2 , pulse width: 2 msec) to the obtained copper oxide film.
  • Example 2 A conductive composition was obtained according to the same procedure as in Example 1 except that 0.4 parts by mass of diethanolamine was used instead of 0.4 parts by mass of triethylenetetramine. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 3 Implemented except that the above aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.3 parts by mass of p-toluenesulfonic acid was used instead of 0.4 parts by mass of triethylenetetramine.
  • a conductive composition was obtained according to the same procedure as in Example 1.
  • the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 4 Example 1 except that the aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of diethanolamine was used instead of 0.4 parts by mass of triethylenetetramine.
  • a conductive composition was obtained according to the procedure described above.
  • the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 5 A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 3 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass). Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 6 Example 1 except that the above aqueous solution 4 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of succinic acid was used instead of 0.4 parts by mass of triethylenetetramine.
  • a conductive composition was obtained according to the same procedure.
  • the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 7 The aqueous solution 5 (26 parts by mass) was used in place of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of 1,4-butanediol diglycidyl ether was used in place of 0.4 parts by mass of triethylenetetramine. Except for the above, a conductive composition was obtained according to the same procedure as in Example 1. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 8 Example except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of bishydroxymethylurea was used instead of 0.4 parts by mass of triethylenetetramine. According to the same procedure as in No. 1, a conductive composition was obtained. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 9 Example 1 except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of diethanolamine was used instead of 0.4 parts by mass of triethylenetetramine.
  • a conductive composition was obtained according to the procedure described above.
  • the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 10 The above aqueous solution 7 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.1 part by mass of VA-080 (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 0.4 parts by mass of triethylenetetramine.
  • a conductive composition was obtained according to the same procedure as in Example 1 except that it was used.
  • the electrically conductive composition was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 11 The aqueous solution 8 (26 parts by mass) was used in place of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of 1,4-butanediol diglycidyl ether was used in place of 0.4 parts by mass of triethylenetetramine. Except for the above, a conductive composition was obtained according to the same procedure as in Example 1. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 12 Example except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of bishydroxymethylurea was used instead of 0.4 parts by mass of triethylenetetramine. According to the same procedure as in No. 1, a conductive composition was obtained. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 13 Example 1 except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of divinylsulfone was used instead of 0.4 parts by mass of triethylenetetramine.
  • a conductive composition was obtained according to the same procedure.
  • the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 14 Example 1 except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and that 0.5 parts by mass of glyoxal was used instead of 0.4 parts by mass of triethylenetetramine.
  • a conductive composition was obtained according to the procedure described above.
  • the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 1 A conductive composition was obtained according to the same procedure as in Example 1 except that no curing agent was added. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 2 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 3 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 3 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 4 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 4 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 5 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 5 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 6 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 7 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 7 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added. Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
  • Example 8 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added. Moreover, when it was going to obtain an electrically conductive film according to the procedure similar to Example 1 using the obtained electrically conductive composition, a film
  • Example 9 A conductive composition was obtained according to the same procedure as in Example 1 except that the ethanol solution 9 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass). Moreover, the film
  • volume resistivity was measured using the four-probe method resistivity meter. The measurement results are shown in Table 1. The smaller the volume resistivity, the better the conductivity. Practically, it is preferably 20 ⁇ 10 ⁇ 5 ⁇ ⁇ cm or less.
  • ⁇ Adhesion> The obtained conductive film was cut into 5 mm ⁇ 5 mm with a cutter to produce 25 grids (1 mm square). Then, cellotape (registered trademark) was applied and peeled off, and the number of grids remaining without peeling was examined. As a result, the number of remaining grids of 20-25 is evaluated as “AA”, 15-19 is evaluated as “A”, and 10-14 is evaluated as “B”. 1 to 9 were evaluated as “C”, and 0 (completely peeled) were evaluated as “D”. The results are shown in Table 1.
  • the polymer containing the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) and the crosslinkable group represented by B in the above formula (2) Each of the conductive films obtained from the compositions of Examples 1 to 14 containing a curing agent that reacts with the polymer exhibited excellent adhesion and conductivity. Among them, Examples 1 to 6 and 8 to 10 in which A in the formula (1) is an organic group containing an amide group showed better adhesion. Among them, Example 1 in which B in the above formula (2) is the above formula (B-7) (alicyclic epoxy group) and the curing agent is an amine is particularly excellent in adhesion and conductivity. Showed sex.
  • Examples 1 and 5 using an amine as a curing agent showed better adhesion and conductivity.
  • the polymer contains a repeating unit represented by the above formula (1) and a repeating unit represented by the above formula (2), but reacts with the crosslinkable group represented by B in the above formula (2).
  • the curing agent is not contained, the film is scattered and a conductive film cannot be obtained (Comparative Example 8), or even when the conductive film is obtained, the adhesion is insufficient (Comparative Examples 1 to 7). became.

Abstract

The present invention addresses the problem of providing a composition for forming an electrically conductive film, which enables the production of an electrically conductive film having good adhesion to a base and excellent electrical conductivity even by sintering through the irradiation with light. The composition for forming an electrically conductive film according to the present invention comprises: copper oxide particles and/or copper particles; a polymer which contains a repeating unit represented by a specific formula and having a reducing group and a repeating unit represented by a specific formula and having a crosslinking group; and a curing agent which can react with the crosslinking group.

Description

導電膜形成用組成物及びこれを用いる導電膜の製造方法Conductive film forming composition and method for producing conductive film using the same
　本発明は、導電膜形成用組成物及びこれを用いる導電膜の製造方法に関する。 The present invention relates to a composition for forming a conductive film and a method for producing a conductive film using the same.
　金属粒子または金属酸化物粒子の分散体を印刷法により基材に塗布し、加熱処理により焼結させることによって配線等の導電膜を形成する方法が知られている。
　上記方法は、従来の高熱・真空プロセス（スパッタ）やめっき処理による導電膜形成方法に比べて、簡便・省エネ・省資源であることから次世代エレクトロニクス開発において大きな期待を集めている。なかでも、近年、低コスト化の観点から、金属酸化物粒子を含む組成物を用いて、これを加熱処理により還元させるとともに焼結させることで導電膜を形成する方法が注目されている。
　一方、上記のように加熱処理により焼結する場合、基材は高温に曝される。そのため、基材が熱により変形し、均一な導電膜が得ることが難しいという問題がある。 There is known a method of forming a conductive film such as a wiring by applying a dispersion of metal particles or metal oxide particles to a substrate by a printing method and sintering by a heat treatment.
Since the above method is simple, energy-saving, and resource-saving compared to the conventional high-heat / vacuum process (sputtering) and plating method for forming a conductive film, it is highly anticipated in the development of next-generation electronics. In particular, in recent years, from the viewpoint of cost reduction, a method of forming a conductive film by using a composition containing metal oxide particles and reducing and sintering the composition by heat treatment has attracted attention.
On the other hand, when sintering by heat processing as mentioned above, a base material is exposed to high temperature. Therefore, there exists a problem that a base material deform | transforms with a heat | fever and it is difficult to obtain a uniform electrically conductive film.
　このようななか、特許文献１には、光照射による焼結（光焼結）を行うことで、基材を加熱し過ぎることなく、基材上の酸化銅インクを焼結して金属銅フィルムを形成する方法が開示されている（００１３段落、実施例１など）。 Under such circumstances, in Patent Document 1, sintering by light irradiation (photosintering) is performed to sinter the copper oxide ink on the base material without heating the base material excessively, thereby forming a metal copper film. A method of forming is disclosed (paragraph 0013, Example 1 etc.).
特表２０１０－５２８４２８号公報Special table 2010-528428
　しかしながら、本発明者が、特許文献１を参考に、基材に銅粒子または酸化銅粒子とバインダー（ポリビニルピロリドンなど）とを含有する組成物を付与、加熱乾燥させて塗膜を形成し、形成した塗膜に光を照射して導電膜を形成したところ、基材と導電膜との間の密着性が不十分となることが明らかになった。このように基材と導電膜との間の密着性が不十分であると、配線等を形成したときに断線やショートなどの不具合が生じやすくなるため問題である。また、得られる導電膜の導電性が不十分となる場合があることも明らかになった。
　そこで、本発明は、上記実情を鑑みて、光照射による焼結でも、基材との密着性が良好で、かつ、導電性に優れる導電膜を得ることのできる、導電膜形成用組成物を提供することを目的とする。 However, the present inventor gives a composition containing copper particles or copper oxide particles and a binder (such as polyvinylpyrrolidone) to a base material with reference to Patent Document 1, and forms a coating film by heating and drying. When the conductive film was formed by irradiating the coated film with light, it became clear that the adhesion between the substrate and the conductive film was insufficient. As described above, inadequate adhesion between the base material and the conductive film is a problem because defects such as disconnection and short circuit are likely to occur when wiring and the like are formed. Moreover, it became clear that the electroconductivity of the electrically conductive film obtained may become inadequate.
Therefore, in view of the above circumstances, the present invention provides a conductive film-forming composition that can obtain a conductive film that has good adhesion to a substrate and excellent conductivity even by sintering by light irradiation. The purpose is to provide.
　本発明者は、上記課題を達成すべく鋭意研究した結果、酸化銅粒子および／または銅粒子と、特定の還元性基を有する繰り返し単位と特定の架橋性基を有する繰り返し単位とを含むポリマーと、上記架橋性基と反応する硬化剤とを含有する組成物とすることで、組成物から形成される塗膜に光を照射して得られる導電膜が、基材との密着性が良好で、かつ、導電性に優れることを見出し、本発明に至った。
　すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of earnest research to achieve the above-mentioned problems, the present inventor has obtained a polymer containing copper oxide particles and / or copper particles, a repeating unit having a specific reducing group, and a repeating unit having a specific crosslinkable group. By making the composition containing a curing agent that reacts with the crosslinkable group, the conductive film obtained by irradiating the coating film formed from the composition with light has good adhesion to the substrate. And it discovered that it was excellent in electroconductivity, and came to this invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.
（１）　酸化銅粒子および／または銅粒子と、後述する式（１）で表される繰り返し単位および後述する式（２）で表される繰り返し単位を含むポリマーと、後述する式（２）中のＢで表される架橋性基と反応する硬化剤とを含有する、導電膜形成用組成物。
（２）　上記ポリマーが、後述する式（３）で表される繰り返し単位および後述する式（２）で表される繰り返し単位を含むポリマー、後述する式（４）で表される繰り返し単位および後述する式（５）で表される繰り返し単位を含むポリマー、または、後述する式（６）で表される繰り返し単位を含むポリマーである、上記（１）に記載の導電膜形成用組成物。
（３）　上記ポリマーが、上記式（３）で表される繰り返し単位および上記式（２）で表される繰り返し単位を含むポリマーである、上記（２）に記載の導電膜形成用組成物。
（４）　上記式（２）中のＢが、上記式（Ｂ－１）または（Ｂ－７）で表される基であり、上記硬化剤が、アミンまたはアルコールである、上記（１）～（３）のいずれかに記載の導電膜形成用組成物。
（５）　上記式（２）中のＢが、上記式（Ｂ－２）で表される基であり、上記硬化剤が、エポキシド、アルデヒド、または、後述する式（１３）で表される部分構造を２つ以上有する化合物である、上記（１）～（３）のいずれかに記載の導電膜形成用組成物。
（６）　上記（１）～（５）のいずれかに記載の導電膜形成用組成物を基材上に付与して、上記基材上に組成物層を形成し、その後、上記組成物層に対して加熱処理を施して、塗膜を形成する塗膜形成工程と、
　上記塗膜に対して光照射処理を行い、上記酸化銅粒子および／または銅粒子を還元して、導電膜を形成する還元工程とを備える、導電膜の製造方法。
（７）　上記光照射処理が、パルス光照射処理である、上記（６）に記載の導電膜の製造方法。 (1) Copper oxide particles and / or copper particles, a polymer containing a repeating unit represented by formula (1) described later and a repeating unit represented by formula (2) described later, and formula (2) described later The composition for electrically conductive film formation containing the hardening | curing agent which reacts with the crosslinkable group represented by B of this.
(2) The polymer includes a repeating unit represented by formula (3) described later and a repeating unit represented by formula (2) described later, a repeating unit represented by formula (4) described later, and the following The composition for electrically conductive film formation as described in said (1) which is a polymer containing the repeating unit represented by Formula (5) to perform or the repeating unit represented by Formula (6) mentioned later.
(3) The composition for electrically conductive film formation as described in said (2) whose said polymer is a polymer containing the repeating unit represented by the said repeating unit represented by said Formula (3), and said Formula (2).
(4) In the above formula (2), B is a group represented by the above formula (B-1) or (B-7), and the curing agent is an amine or alcohol. (3) The composition for electrically conductive film formation in any one.
(5) B in the formula (2) is a group represented by the formula (B-2), and the curing agent is an epoxide, an aldehyde, or a moiety represented by the formula (13) described later. The composition for forming a conductive film according to any one of the above (1) to (3), which is a compound having two or more structures.
(6) The composition for forming a conductive film according to any one of (1) to (5) above is applied on a substrate to form a composition layer on the substrate, and then the composition layer A heat treatment is performed on the coating film forming step of forming a coating film,
A reduction process which performs light irradiation processing to the above-mentioned paint film, reduces the above-mentioned copper oxide particles and / or copper particles, and forms a conductive film.
(7) The manufacturing method of the electrically conductive film as described in said (6) whose said light irradiation process is a pulsed light irradiation process.
　本発明によれば、光照射による焼結でも、基材との密着性が良好で、かつ、導電性に優れる導電膜を得ることのできる、導電膜形成用組成物を提供することができる。 According to the present invention, it is possible to provide a composition for forming a conductive film, which can obtain a conductive film having good adhesion to a substrate and excellent conductivity even by sintering by light irradiation.
［導電膜形成用組成物］
　本発明の導電膜形成用組成物（以下、本発明の組成物ともいう）は、酸化銅粒子および／または銅粒子と、後述する式（１）で表される繰り返し単位および後述する式（２）で表される繰り返し単位を含むポリマーを含有する。ここで、後述するとおり、式（１）で表される繰り返し単位は特定の還元性基を有する。また、式（２）で表される繰り返し単位は特定の架橋性基を有する。また、本発明の組成物は、上記式（２）中のＢで表される架橋性基と反応する硬化剤を含有する。 [Composition for forming conductive film]
The conductive film-forming composition of the present invention (hereinafter also referred to as the composition of the present invention) comprises copper oxide particles and / or copper particles, a repeating unit represented by the formula (1) described later, and a formula (2) described below. The polymer containing the repeating unit represented by this is contained. Here, as described later, the repeating unit represented by the formula (1) has a specific reducing group. Moreover, the repeating unit represented by Formula (2) has a specific crosslinkable group. Moreover, the composition of this invention contains the hardening | curing agent which reacts with the crosslinkable group represented by B in the said Formula (2).
　本発明の組成物はこのような構成をとることにより、組成物から形成される塗膜に光を照射して得られる導電膜が、基材との密着性が良好で、かつ、導電性に優れたものとなる。
　これは詳細には明らかではないが、およそ以下のとおりと推測される。
　酸化銅粒子および／または銅粒子を含有する組成物から得られる塗膜に光を照射して光焼結させた場合、塗膜中の溶媒やバインダーなどの成分が分解・揮発することで、塗膜自体に微視的または巨視的な破壊が生じ、結果として、得られる導電膜は基材との密着性や導電性が不十分となると考えられる。
　上述のとおり、本発明の組成物は、特定のポリマー（特定の還元性基および特定の架橋性基を有するポリマー）と上記特定の架橋性基と反応する硬化剤とを含有するため、本発明の組成物から形成される塗膜中ではポリマー同士の架橋構造が形成されている。そのため、本発明の組成物から得られる塗膜に光を照射した場合、塗膜自体が物理的に分解されることなく、特定の還元性基等により酸化銅粒子や一部が酸化された銅粒子が還元されて銅粒子同士が融着し、基材との密着性に優れた導電膜が得られる。このことは後述する比較例が示すように、特定のポリマーを含有するが硬化剤を含有しない場合（比較例１～８）や、硬化剤を含有するが特定のポリマーを含有しない（特定の架橋性基を有するが特定の還元性基を有さないポリマーを含有する）場合（比較例９）には、密着性が不十分となることからも推測される。
　また、上述のとおり、本発明の組成物に含有されるポリマーは特定の還元性基を有するため、光焼結時に酸化銅粒子や一部が酸化された銅粒子の還元が速やかに起こり、導電性に優れた導電膜が得られるものと考えられる。
　なお、架橋性基を有するポリマーとは別にポリマーに固定されていない還元剤を単に配合した場合には、還元剤が光焼結時に揮発してしまうため、酸化銅粒子等の還元が十分に進まず、得られる導電膜の導電性は不十分となってしまう。すなわち、本発明の１つの特徴は還元性と架橋性の機能を併せ持ったポリマーを使用する点にあると言える。 With the composition of the present invention having such a configuration, the conductive film obtained by irradiating light to the coating film formed from the composition has good adhesion to the base material and is conductive. It will be excellent.
This is not clear in detail, but is assumed to be as follows.
When a coating obtained from a composition containing copper oxide particles and / or copper particles is irradiated with light and photosintered, components such as solvent and binder in the coating are decomposed and volatilized. It is thought that microscopic or macroscopic destruction occurs in the film itself, and as a result, the obtained conductive film has insufficient adhesion and conductivity to the substrate.
As described above, the composition of the present invention contains a specific polymer (a polymer having a specific reducing group and a specific crosslinkable group) and a curing agent that reacts with the specific crosslinkable group. In the coating film formed from the composition, a cross-linked structure between the polymers is formed. Therefore, when light is applied to the coating film obtained from the composition of the present invention, the coating film itself is not physically decomposed, and copper oxide particles or copper partially oxidized by a specific reducing group, etc. The particles are reduced and the copper particles are fused to each other, so that a conductive film having excellent adhesion to the substrate can be obtained. As shown in the comparative examples described later, this indicates a case where a specific polymer is contained but no curing agent is contained (Comparative Examples 1 to 8), or a curing agent is contained but no specific polymer is contained (specific crosslinking). In the case of (containing a polymer having a functional group but not having a specific reducing group) (Comparative Example 9), it is presumed that the adhesion is insufficient.
Further, as described above, since the polymer contained in the composition of the present invention has a specific reducing group, the reduction of the copper oxide particles or the partially oxidized copper particles occurs quickly during photo-sintering. It is considered that a conductive film having excellent properties can be obtained.
In addition, when a reducing agent not fixed to the polymer is simply blended separately from the polymer having a crosslinkable group, the reducing agent volatilizes during photo-sintering, so that the reduction of the copper oxide particles and the like proceeds sufficiently. First, the conductivity of the obtained conductive film is insufficient. That is, it can be said that one feature of the present invention is that a polymer having both reducing and crosslinking functions is used.
　以下では、まず、導電膜形成用組成物の各種成分（酸化銅粒子等、ポリマー、硬化剤など）について詳述し、その後、導電膜の製造方法について詳述する。 In the following, first, various components (copper oxide particles, polymer, curing agent, etc.) of the conductive film forming composition will be described in detail, and then the method for manufacturing the conductive film will be described in detail.
＜酸化銅粒子および／または銅粒子＞
　本発明の組成物には、酸化銅粒子および／または銅粒子（好ましくは酸化銅粒子）が含有される。上述のとおり、本発明の組成物から形成される塗膜に光を照射した場合、酸化銅粒子や一部が酸化された銅粒子が速やかに還元されて導電性に優れた導電膜が形成される。 <Copper oxide particles and / or copper particles>
The composition of the present invention contains copper oxide particles and / or copper particles (preferably copper oxide particles). As described above, when the coating film formed from the composition of the present invention is irradiated with light, the copper oxide particles and the copper particles partially oxidized are rapidly reduced to form a conductive film having excellent conductivity. The
（酸化銅粒子）
　本発明の組成物に含有される酸化銅粒子は粒子状の酸化銅であれば特に限定されない。
　粒子状とは小さい粒状を指し、その具体例としては、球状、楕円体状などが挙げられる。完全な球や楕円体である必要は無く、一部が歪んでいても良い。 (Copper oxide particles)
If the copper oxide particle contained in the composition of this invention is a particulate copper oxide, it will not specifically limit.
The particulate form refers to a small granular form, and specific examples thereof include a spherical shape and an ellipsoidal shape. It does not have to be a perfect sphere or ellipsoid, and a part may be distorted.
　酸化銅粒子は、酸化銅（Ｉ）粒子または酸化銅（ＩＩ）粒子であることが好ましく、安価に入手可能であり、また、得られる導電膜の導電性が良好である理由から、酸化銅（ＩＩ）粒子であることがより好ましい。 The copper oxide particles are preferably copper oxide (I) particles or copper oxide (II) particles, and can be obtained at a low cost. In addition, since the conductivity of the obtained conductive film is good, copper oxide ( II) More preferably, it is a particle.
　酸化銅粒子はナノ粒子であることが好ましい。
　酸化銅粒子の平均粒子径は特に制限されないが、２００ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましい。下限も特に制限されないが、１ｎｍ以上が好ましい。
　平均粒子径が１ｎｍ以上であると、粒子表面の活性が高くなりすぎず、組成物中で溶解することがなく、取扱い性に優れるため好ましい。また、平均粒子径が２００ｎｍ以下であると、組成物をインクジェット用インク組成物として用い、印刷法により配線等のパターン形成を行うことが容易となり、組成物を導体化する際に、金属銅への還元が十分となり、得られる導電膜の導電性が良好となるため好ましい。
　なお、本発明における平均粒子径は、平均一次粒径のことを指す。平均粒子径は、透過型電子顕微鏡（ＴＥＭ）観察により、少なくとも５０個以上の酸化銅粒子の粒子径（直径）を測定し、それらを算術平均して求める。なお、観察図中、酸化銅粒子の形状が真円状でない場合、長径を直径として測定する。
　酸化銅粒子としては、例えば、関東化学社製のＣｕＯナノ粒子、シグマアルドリッチ社製のＣｕＯナノ粒子などを好ましく使用することができる。 The copper oxide particles are preferably nanoparticles.
The average particle diameter of the copper oxide particles is not particularly limited, but is preferably 200 nm or less, and more preferably 100 nm or less. The lower limit is not particularly limited, but is preferably 1 nm or more.
When the average particle size is 1 nm or more, the activity on the particle surface does not become too high, does not dissolve in the composition, and is excellent in handleability. In addition, when the average particle size is 200 nm or less, it becomes easy to form a pattern such as wiring by a printing method using the composition as an ink-jet ink composition, and when the composition is made into a conductor, it becomes metal copper. This is preferable because the reduction of is sufficient and the conductivity of the resulting conductive film is improved.
In addition, the average particle diameter in this invention points out an average primary particle diameter. The average particle diameter is obtained by measuring the particle diameter (diameter) of at least 50 or more copper oxide particles by observation with a transmission electron microscope (TEM) and arithmetically averaging them. In the observation diagram, when the shape of the copper oxide particles is not a perfect circle, the major axis is measured as the diameter.
As the copper oxide particles, for example, CuO nanoparticles manufactured by Kanto Chemical Co., Ltd., CuO nanoparticles manufactured by Sigma Aldrich Co., etc. can be preferably used.
（銅粒子）
　本発明の組成物に含有される銅粒子は粒子状の銅であれば特に限定されない。
　粒子状の定義は上述した酸化銅粒子と同じである。
　銅粒子はナノ粒子であることが好ましい。
　銅粒子の平均粒子径の好適な態様は上述した酸化銅粒子と同じである。 (Copper particles)
If the copper particle contained in the composition of this invention is particulate copper, it will not specifically limit.
The definition of the particle shape is the same as the copper oxide particle described above.
The copper particles are preferably nanoparticles.
The suitable aspect of the average particle diameter of a copper particle is the same as the copper oxide particle mentioned above.
＜ポリマー＞
　本発明の組成物には、下記式（１）で表される繰り返し単位および下記式（２）で表される繰り返し単位を含むポリマー（以下、特定ポリマーともいう）が含有される。
　上述のとおり、本発明の組成物に含有される特定ポリマーは特定の架橋性基を含有するため、得られる塗膜に光を照射した場合に、塗膜自体が物理的に分解されることなく、基材との密着性に優れた導電膜が得られる。また、本発明の組成物に含有される特定ポリマーは特定の還元性基を有するため、光焼結時に酸化銅粒子や一部が酸化された銅粒子の還元が速やかに起こり、導電性に優れた導電膜が得られる。 <Polymer>
The composition of the present invention contains a polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) (hereinafter also referred to as a specific polymer).
As described above, the specific polymer contained in the composition of the present invention contains a specific crosslinkable group, so that when the obtained coating film is irradiated with light, the coating film itself is not physically decomposed. A conductive film having excellent adhesion to the substrate can be obtained. In addition, since the specific polymer contained in the composition of the present invention has a specific reducing group, reduction of copper oxide particles or partially oxidized copper particles occurs quickly during photo-sintering and has excellent conductivity. A conductive film can be obtained.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　上記式（１）中、Ｒ1は、水素原子、または、置換若しくは無置換のアルキル基（好ましくは、炭素数１～５のもの）を表す。なかでも、水素原子、メチル基が好ましく、水素原子がより好ましい。 In the above formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group (preferably having 1 to 5 carbon atoms). Of these, a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.
　上記式（１）中、Ｌ1は、単結合または２価の有機基を表す。
　２価の有機基としては、置換若しくは無置換の脂肪族炭化水素基（例えば、アルキレン基。好ましくは炭素数１～８）、置換若しくは無置換の芳香族炭化水素基（例えば、アリーレン基。好ましくは炭素数６～１２）、－Ｏ－、－Ｓ－、－ＳＯ2－、－Ｎ(Ｒ)－（Ｒ：アルキル基）、－ＣＯ－、－ＮＨ－、－ＣＯＯ－、－ＣＯＮＨ－、またはこれらを組み合わせた基（例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など）などが挙げられる。なかでも、アルキレン基、－Ｏ－、－ＣＯＯ－、またはこれらを組み合わせた基が好ましい。 In the above formula (1), L 1 represents a single bond or a divalent organic group.
As the divalent organic group, a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (for example, an arylene group, preferably). Is carbon number 6-12), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, Alternatively, a group in which these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, or the like) can be given. Of these, an alkylene group, —O—, —COO—, or a combination thereof is preferable.
　上記式（１）中、Ａは還元性基であり、具体的には、アミド基（－ＣＯＮ＜）を含有する有機基、または、ヒドロキシ基（－ＯＨ）を表す。なかでも、得られる導電膜の密着性がより優れる理由から、アミド基を含有する有機基であることが好ましい。なお、上記還元性基は、光焼結の際に、酸化銅粒子や一部が酸化された銅粒子に対して還元性を示す。 In the above formula (1), A is a reducing group, and specifically represents an organic group containing an amide group (—CON <) or a hydroxy group (—OH). Especially, it is preferable that it is an organic group containing an amide group from the reason which the adhesiveness of the electrically conductive film obtained is more excellent. In addition, the said reducing group shows a reducibility with respect to the copper oxide particle and the copper particle by which one part was oxidized in the case of light sintering.
　上記アミド基を含有する有機基としては特に制限されないが、好適な態様として、例えば、下記式（７）で表される基が挙げられる。 The organic group containing the amide group is not particularly limited, but a preferable embodiment includes, for example, a group represented by the following formula (7).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記式（７）中、Ｒ71は、ヘテロ原子を有していてもよい炭化水素基を表す。複数あるＲ71はそれぞれ同一であっても異なっていてもよい。Ｒ71は、Ｒ71同士で環を形成していてもよい。
　上記ヘテロ原子を有していてもよい炭化水素基のヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、リン原子などが挙げられる。
　上記ヘテロ原子を有していてもよい炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、またはこれらを組み合わせた基などが挙げられる。
　上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状または分岐状のアルキル基（特に、炭素数１～１０）、直鎖状または分岐状のアルケニル基（特に、炭素数２～１０）、直鎖状または分岐状のアルキニル基（特に、炭素数２～１０）などが挙げられる。
　上記芳香族炭化水素基としては、例えば、アリール基、ナフチル基などが挙げられる。上記アリール基としては、例えば、フェニル基、トリル基、キシリル基などの炭素数６～１８のアリール基などが挙げられる。
　上記式（７）中、＊は結合位置を表す。 In the above formula (7), R 71 represents a hydrocarbon group which may have a hetero atom. A plurality of R 71 may be the same or different. R 71 may form a ring with R 71 .
Examples of the hetero atom of the hydrocarbon group that may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
Examples of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 10 carbon atoms), a linear or branched alkenyl group (particularly 2 to 10 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly 2 to 10 carbon atoms).
Examples of the aromatic hydrocarbon group include an aryl group and a naphthyl group. Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group.
In the above formula (7), * represents a bonding position.
　上記式（７）で表される基の好適な態様として、例えば、Ｒ71同士で環を形成した態様が挙げられる。なかでも、下記式（８）で表される基であることが好ましい。 As a preferred embodiment of the group represented by the formula (7), for example, embodiments that form a ring R 71 together. Especially, it is preferable that it is group represented by following formula (8).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記式（８）中、Ｒ81は、水素原子、または、ヘテロ原子を有していてもよい炭化水素基を表す。複数あるＲ81はそれぞれ同一であっても異なっていてもよい。Ｒ81の具体例は上述したＲ71と同様である。なかでも、水素原子であることが好ましい。 In the formula (8), R 81 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. A plurality of R 81 may be the same or different. A specific example of R 81 is the same as R 71 described above. Of these, a hydrogen atom is preferable.
　上記式（２）中、Ｒ2は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｒ2の具体例および好適な態様は上述したＲ1と同様である。
　上記式（２）中、Ｌ2は、単結合または２価の有機基を表す。Ｌ2の具体例および好適な態様は上述したＬ1と同様である。
　上記式（２）中、Ｂは架橋性基であり、下記式（Ｂ－１）～（Ｂ－９）からなる群より選択される基を表す。 In the formula (2), R 2 is a hydrogen atom or, a substituted or unsubstituted alkyl groups. Specific examples and preferred embodiments of R 2 are the same as those of R 1 described above.
In the above formula (2), L 2 represents a single bond or a divalent organic group. Specific examples and preferred embodiments of L 2 are the same as those of L 1 described above.
In the above formula (2), B is a crosslinkable group and represents a group selected from the group consisting of the following formulas (B-1) to (B-9).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記式（Ｂ－１）～（Ｂ－９）中、Ｒbは、水素原子、または、ヘテロ原子を有していてもよい炭化水素基を表す。複数あるＲbはそれぞれ同一であっても異なっていてもよい。＊は結合位置を表す。 In the above formulas (B-1) to (B-9), R b represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. A plurality of R b may be the same or different. * Represents a bonding position.
　上記式（Ｂ－１）中、Ｒbは、水素原子または置換若しくは無置換のアルキル基であることが好ましく、水素原子であることがより好ましい。
　上記式（Ｂ－３）中、Ｒbは、置換若しくは無置換のアルキル基（特に炭素数１～５のもの）であることが好ましい。
　上記式（Ｂ－６）中、Ｒbは、水素原子または置換若しくは無置換のアルキル基（特に炭素数１～５のもの）であることが好ましく、メチル基であることがより好ましい。
　上記式（Ｂ－７）中、Ｒbは、水素原子または置換若しくは無置換のアルキル基であることが好ましく、水素原子であることがより好ましい。ｍは０～１１の整数を表す。ｎは０～２の整数を表す。ただし、ｎが０の場合、ｍは０～７の整数を表し、ｎが１の場合、ｍは０～９の整数を表し、ｎが２の場合、ｍは０～１１の整数を表す。
　上記式（Ｂ－８）中、Ｒbは、水素原子または置換若しくは無置換のアルキル基であることが好ましく、水素原子であることがより好ましい。
　上記式（Ｂ－９）中、Ｒbは、水素原子または置換若しくは無置換のアルキル基であることが好ましく、水素原子であることがより好ましい。 In the above formula (B-1), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom.
In the above formula (B-3), R b is preferably a substituted or unsubstituted alkyl group (particularly having 1 to 5 carbon atoms).
In the above formula (B-6), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group (particularly one having 1 to 5 carbon atoms), more preferably a methyl group.
In the above formula (B-7), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom. m represents an integer of 0 to 11. n represents an integer of 0-2. However, when n is 0, m represents an integer of 0 to 7, when n is 1, m represents an integer of 0 to 9, and when n is 2, m represents an integer of 0 to 11.
In the above formula (B-8), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom.
In the above formula (B-9), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and more preferably a hydrogen atom.
上記式（２）中、Ｂは、得られる導電膜の密着性がより優れる理由から、式（Ｂ－１）、式（Ｂ－３）、式（Ｂ－４）、式（Ｂ－５）、式（Ｂ－６）および式（Ｂ－７）からなる群より選択される基であることが好ましく、式（Ｂ－１）、式（Ｂ－３）、式（Ｂ－４）、式（Ｂ－６）および式（Ｂ－７）からなる群より選択される基であることがより好ましく、式（Ｂ－１）、式（Ｂ－３）、式（Ｂ－６）および式（Ｂ－７）からなる群より選択される基であることがさらに好ましく、式（Ｂ－１）または式（Ｂ－７）であることが特に好ましい。 In the above formula (2), B represents the formula (B-1), the formula (B-3), the formula (B-4), the formula (B-5) because the adhesiveness of the obtained conductive film is more excellent. Are preferably groups selected from the group consisting of formula (B-6) and formula (B-7), and are represented by formula (B-1), formula (B-3), formula (B-4), formula More preferably, the group is selected from the group consisting of (B-6) and formula (B-7), and the formula (B-1), formula (B-3), formula (B-6) and formula (B) More preferred is a group selected from the group consisting of B-7), and particularly preferred is formula (B-1) or formula (B-7).
　なお、上記式（２）中のＢで表される架橋性基が上記式（Ｂ－２）である場合、上記式（１）で表される繰り返し単位と上記式（２）で表される繰り返し単位とは同一であってもよい。また、上記式（２）中のＢで表される架橋性基が上記式（Ｂ－２）である場合、上記特定ポリマーは、少なくとも上記式（２）で表される繰り返し単位を含めばよい。
　その理由は、上記式（２）中のＢで表される架橋性基が上記式（Ｂ－２）である場合、上記架橋性基が還元性基としても機能するからである。 When the crosslinkable group represented by B in the above formula (2) is the above formula (B-2), it is represented by the repeating unit represented by the above formula (1) and the above formula (2). The repeating unit may be the same. In the case where the crosslinkable group represented by B in the above formula (2) is the above formula (B-2), the specific polymer may include at least the repeating unit represented by the above formula (2). .
The reason is that when the crosslinkable group represented by B in the formula (2) is the formula (B-2), the crosslinkable group also functions as a reducing group.
　上記特定ポリマーの好適な態様としては、例えば、下記式（３）で表される繰り返し単位および下記式（２）（上述した式（２）と同じ）で表される繰り返し単位を含むポリマーＰ、下記式（４）で表される繰り返し単位および下記式（５）で表される繰り返し単位を含むポリマーＱ、および、下記式（６）で表される繰り返し単位を含むポリマーＲが挙げられる。なかでも、得られる導電膜の密着性がより優れる理由から、ポリマーＰまたはポリマーＲであることが好ましく、ポリマーＰであることがより好ましい。 Preferred embodiments of the specific polymer include, for example, a polymer P including a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (2) (same as the above-described formula (2)), Examples thereof include a polymer Q containing a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5), and a polymer R containing a repeating unit represented by the following formula (6). Especially, it is preferable that it is the polymer P or the polymer R from the reason which the adhesiveness of the electrically conductive film obtained is more excellent, and it is more preferable that it is the polymer P.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記式（３）中、Ｒ3は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｒ3の具体例および好適な態様は上述したＲ1と同様である。
　上記式（３）中、Ｒ31は、水素原子、または、ヘテロ原子を有していてもよい炭化水素基を表す。複数あるＲ31はそれぞれ同一であっても異なっていてもよい。Ｒ31の具体例は上述したＲ71と同様である。なかでも、水素原子であることが好ましい。 In the above formula (3), R 3 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred embodiments of R 3 are the same as those of R 1 described above.
In the above formula (3), R 31 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. A plurality of R 31 may be the same or different. A specific example of R 31 is the same as R 71 described above. Of these, a hydrogen atom is preferable.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記式（４）および（５）中、Ｒ4およびＲ5は、それぞれ独立して、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｒ4およびＲ5の具体例および好適な態様は上述したＲ1と同様である。
　なお、上記式（４）で表される繰り返し単位および下記式（５）で表される繰り返し単位を含むポリマーＱにおいて、上記式（４）で表される繰り返し単位は、上記式（１）で表される繰り返し単位にも上記式（２）で表される繰り返し単位にも該当する。すなわち、上記式（４）中のＯＨ基は、上記式（１）中のＡ（還元性基）であり、かつ、上記式（２）中のＢ（架橋性基）でもある。 In the above formulas (4) and (5), R 4 and R 5 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred embodiments of R 4 and R 5 are the same as those of R 1 described above.
In addition, in the polymer Q including the repeating unit represented by the above formula (4) and the repeating unit represented by the following formula (5), the repeating unit represented by the above formula (4) is represented by the above formula (1). This also applies to the repeating unit represented by the above formula (2). That is, the OH group in the above formula (4) is A (reducing group) in the above formula (1) and B (crosslinkable group) in the above formula (2).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記式（６）中、Ｒ6は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｒ6の具体例および好適な態様は上述したＲ1と同様である。
　上記式（６）中、Ｌ6は、単結合または２価の有機基を表す。Ｌ6の具体例は上述したＬ1と同様である。なかでも、アルキレン基、－Ｏ－、－ＣＯＯ－、－ＣＯ－またはこれらを組み合わせた基であることが好ましく、－ＣＯ－であることがより好ましい。
　上記式（６）中、Ｒ61は、２価の脂肪族炭化水素基を表す。なかでも、炭素数１～５のアルキレン基であることが好ましく、１～３のアルキレン基であることがより好ましく、エチレン基であることがさらに好ましい。
　上記式（６）中、ｐは１～１００の整数を表す。なかでも、５～３０の整数であることが好ましい。
　なお、上記式（６）で表される繰り返し単位を含むポリマーＲにおいて、上記式（６）で表される繰り返し単位は、上記式（１）で表される繰り返し単位にも上記式（２）で表される繰り返し単位にも該当する。すなわち、上記式（６）中の側鎖の末端にあるＯＨ基は、上記式（１）中のＡ（還元性基）であり、かつ、上記式（２）中のＢ（架橋性基）でもある。 In the above formula (6), R 6 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred embodiments of R 6 are the same as those of R 1 described above.
In the above formula (6), L 6 represents a single bond or a divalent organic group. A specific example of L 6 is the same as L 1 described above. Of these, an alkylene group, —O—, —COO—, —CO— or a combination thereof is preferable, and —CO— is more preferable.
In said formula (6), R61 represents a bivalent aliphatic hydrocarbon group. Among these, an alkylene group having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and an ethylene group is further preferable.
In the above formula (6), p represents an integer of 1 to 100. Among these, an integer of 5 to 30 is preferable.
In addition, in the polymer R containing the repeating unit represented by the above formula (6), the repeating unit represented by the above formula (6) is also the repeating unit represented by the above formula (1). It corresponds also to the repeating unit represented by these. That is, the OH group at the end of the side chain in the formula (6) is A (reducing group) in the formula (1) and B (crosslinkable group) in the formula (2). But there is.
　上記特定ポリマーは、粒子分散性がよく、得られる導電膜の均一性が向上する観点から、水溶性であることが好ましい。 The above-mentioned specific polymer is preferably water-soluble from the viewpoint of good particle dispersibility and improved uniformity of the resulting conductive film.
　上記特定ポリマーの分子量は特に制限されないが、組成物の調製、塗布性、膜性向上などの観点から、１０００～１００００００であることが好ましく、１００００～５０００００であることがより好ましい。
　なお、本願において、上記特定ポリマーの重量平均分子量は、東ソー社製ゲル透過クロマトグラフ（ＧＰＣ）を用いて、Ｎ－メチルピロリドンを溶媒としてポリスチレン換算で測定したものである。 The molecular weight of the specific polymer is not particularly limited, but is preferably from 1,000 to 1,000,000, and more preferably from 10,000 to 500,000 from the viewpoints of preparation of the composition, coating properties, and improvement in film properties.
In the present application, the weight average molecular weight of the specific polymer is measured in terms of polystyrene using N-methylpyrrolidone as a solvent using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation.
　上記特定ポリマーの製造方法は特に制限されず、公知の方法を採用できる。例えば、所望の繰り返し単位を形成するビニル系モノマーを用いて、ラジカル重合、カチオン重合またはアニオン重合を行うことにより、所望のビニル系ポリマーを得ることができる。
　なお、各重合様式においては、必要に応じて各種開始剤（例えば、ラジカル重合開始剤など）を使用することができる。 The manufacturing method in particular of the said specific polymer is not restrict | limited, A well-known method is employable. For example, a desired vinyl polymer can be obtained by performing radical polymerization, cationic polymerization, or anionic polymerization using a vinyl monomer that forms a desired repeating unit.
In each polymerization mode, various initiators (such as radical polymerization initiators) can be used as necessary.
　本発明の組成物において、上記特定ポリマーの含有量は、得られる導電膜の導電性と組成物の保存安定性とのバランスの観点から、上記酸化銅粒子と上記銅粒子の合計の含有量に対して、１～５０質量％であることが好ましく、３～３０質量％であることがより好ましく、５～１５質量％であることがさらに好ましい。 In the composition of the present invention, the content of the specific polymer is the total content of the copper oxide particles and the copper particles from the viewpoint of the balance between the conductivity of the obtained conductive film and the storage stability of the composition. On the other hand, it is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 15% by mass.
＜硬化剤＞
　本発明の組成物には、上記式（２）中のＢで表される架橋性基と反応する硬化剤が含有される。
　そのような硬化剤としては、上記式（２）中のＢで表される架橋性基と反応するものであれば特に制限されないが、例えば、アミン（アミノ基含有化合物）、アルコール（鎖式または脂環式の炭化水素の水素原子をヒドロキシ基で置換した化合物）、エポキシド（エポキシ基含有化合物）、アルデヒド（アルデヒド基含有化合物）、ラジカル開始剤、ビニル化合物（ビニル基含有化合物）、酸触媒、カルボン酸などが挙げられる。 <Curing agent>
The composition of the present invention contains a curing agent that reacts with the crosslinkable group represented by B in the formula (2).
Such a curing agent is not particularly limited as long as it reacts with the crosslinkable group represented by B in the above formula (2). For example, amine (amino group-containing compound), alcohol (chain formula or Compound in which hydrogen atom of alicyclic hydrocarbon is substituted with hydroxy group), epoxide (epoxy group-containing compound), aldehyde (aldehyde group-containing compound), radical initiator, vinyl compound (vinyl group-containing compound), acid catalyst, Examples thereof include carboxylic acid.
　上記アミンとしては特に制限されないが、複数（特に２つ）のアミノ基を有するアミンであることが好ましい。そのようなアミンとしては、例えば、ジエチレントリアミンやトリエチレンテトラミン等の脂肪族ポリアミン、メタフェニレンジアミンやジアミノジフェニルメタンやジアミノジフェニルスルホン等の芳香族ポリアミンなどが挙げられる。なかでも、下記式（１６）で表される化合物であることが好ましい。 The amine is not particularly limited, but is preferably an amine having a plurality (particularly two) amino groups. Examples of such amines include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, and aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Especially, it is preferable that it is a compound represented by following formula (16).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記式（１６）中、Ｌ16は、単結合または２価の有機基を表す。Ｌ16の具体例は上述したＬ1と同様である。なかでも、アルキレン基、または、アルキレン基と－ＮＨ－とを組み合わせた基であることが好ましい。 In the above formula (16), L 16 represents a single bond or a divalent organic group. A specific example of L 16 is the same as L 1 described above. Among these, an alkylene group or a group obtained by combining an alkylene group and —NH— is preferable.
　上記アルコールとしては特に制限されないが、複数（特に２つ）の水酸基を有するヘテロ原子を有していてもよい脂肪族炭化水素であることが好ましい。そのような脂肪族炭化水素としては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ジエタノールアミン、トリエタノールアミン、ビスヒドロキシメチル尿素などが挙げられる。なかでも、第２級アミノ基（－ＮＲ－：Ｒは水素原子または炭化水素基）または第３級アミノ基（－Ｎ＜）を有する化合物であることが好ましく、下記式（９）で表される化合物であることがより好ましい。 The alcohol is not particularly limited, but is preferably an aliphatic hydrocarbon which may have a hetero atom having a plurality of (particularly two) hydroxyl groups. Examples of such aliphatic hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, diethanolamine, triethanolamine, and bishydroxymethylurea. Among these, a compound having a secondary amino group (—NR—: R is a hydrogen atom or a hydrocarbon group) or a tertiary amino group (—N <) is preferable, and is represented by the following formula (9). More preferably, it is a compound.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　上記式（９）中、Ｒ91は、２価の脂肪族炭化水素基を表す。Ｒ91の具体例は上述したＲ61と同様である。なかでも、炭素数１～５のアルキレン基であることが好ましい。
　上記式（９）中、ｓは０または１である。
　上記式（９）中、ｔは２または３である。
　上記式（９）中、ｓおよびｔは、ｓ＋ｔ＝３の関係式を満たす。 In the above formula (9), R 91 represents a divalent aliphatic hydrocarbon group. A specific example of R 91 is the same as R 61 described above. Of these, an alkylene group having 1 to 5 carbon atoms is preferable.
In the above formula (9), s is 0 or 1.
In the above formula (9), t is 2 or 3.
In the above formula (9), s and t satisfy the relational expression of s + t = 3.
　また、上記アルコールの好適な態様として、例えば、下記式（１３）で表される部分構造を２つ以上有する化合物が挙げられる。 Moreover, as a suitable aspect of the alcohol, for example, a compound having two or more partial structures represented by the following formula (13) can be mentioned.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記式（１３）中、Ｒ131は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｒ131の具体例は上述したＲ1と同様である。Ｒ131は水素原子であることが好ましい。 In said formula (13), R131 represents a hydrogen atom or a substituted or unsubstituted alkyl group. A specific example of R 131 is the same as R 1 described above. R 131 is preferably a hydrogen atom.
　上記式（１３）で表される部分構造を２つ以上有する化合物の好適な態様としては、例えば、下記式（１４）で表される化合物が挙げられる。 A preferred embodiment of the compound having two or more partial structures represented by the above formula (13) includes, for example, a compound represented by the following formula (14).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記式（１４）中、Ｒ141は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｒ141の具体例は上述したＲ1と同様である。Ｒ141は水素原子であることが好ましい。 In said formula (14), R141 represents a hydrogen atom or a substituted or unsubstituted alkyl group. A specific example of R 141 is the same as R 1 described above. R 141 is preferably a hydrogen atom.
　上記エポキシドとしてはエポキシ基を含有する化合物であれば特に制限されないが、複数（特に２つ）のエポキシ基を含有する化合物であることが好ましい。なかでも、下記式（１０）で表される化合物であることが好ましい。 The epoxide is not particularly limited as long as it is a compound containing an epoxy group, but is preferably a compound containing a plurality (particularly two) of epoxy groups. Especially, it is preferable that it is a compound represented by following formula (10).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記式（１０）中、Ｌ10は、単結合または２価の有機基を表す。Ｌ10の具体例および好適な態様は上述したＬ1と同様である。 In the above formula (10), L 10 represents a single bond or a divalent organic group. Specific examples and preferred embodiments of L 10 are the same as those of L 1 described above.
　上記アルデヒドとしてはアルデヒド基を含有する化合物であれば特に制限されないが、複数（特に２つ）のアルデヒド基を含有する化合物であることが好ましい。なかでも、下記式（１１）で表される化合物であることが好ましい。 The aldehyde is not particularly limited as long as it is a compound containing an aldehyde group, but is preferably a compound containing a plurality (particularly two) aldehyde groups. Especially, it is preferable that it is a compound represented by following formula (11).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記式（１１）中、Ｌ11は、単結合または２価の有機基を表す。Ｌ11の具体例は上述したＬ1と同様である。なかでも単結合であることが好ましい。
　上記アルデヒドは、グリオキサールであることが好ましい。 In the above formula (11), L 11 represents a single bond or a divalent organic group. A specific example of L 11 is the same as L 1 described above. Of these, a single bond is preferable.
The aldehyde is preferably glyoxal.
　上記ラジカル開始剤としては、特に制限されず、例えば、アセトフェノン類、ベンゾイン類、ベンゾフェノン類（１－ヒドロキシ－１,２,３,４,５,６－ヘキサヒドロベンゾフェノンなど）、ホスフィンオキシド類、ケタール類、アントラキノン類、チオキサントン類、アゾ化合物、過酸化物類、２，３－ジアルキルジオン化合物類、ジスルフィド化合物類、フルオロアミン化合物類、芳香族スルホニウム類、ロフィンダイマー類、オニウム塩類、ボレート塩類、活性エステル類、活性ハロゲン類、無機錯体、クマリン類、有機あるいは無機過酸化物、有機アゾまたはジアゾ化合物（例えば、後述するＶＡ－０８０）などを用いることができる。 The radical initiator is not particularly limited, and examples thereof include acetophenones, benzoins, benzophenones (1-hydroxy-1,2,3,4,5,6-hexahydrobenzophenone, etc.), phosphine oxides, ketals. , Anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, activity Esters, active halogens, inorganic complexes, coumarins, organic or inorganic peroxides, organic azo or diazo compounds (for example, VA-080 described later) and the like can be used.
　上記ビニル化合物としてはビニル基を含有する化合物であれば特に制限されないが、複数（特に２つ）のビニル基を含有する化合物であることが好ましい。なかでも、下記式（１２）で表される化合物であることが好ましい。 The vinyl compound is not particularly limited as long as it is a compound containing a vinyl group, but is preferably a compound containing a plurality (particularly two) vinyl groups. Especially, it is preferable that it is a compound represented by following formula (12).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記式（１２）中、Ｌ12は、単結合または２価の有機基を表す。Ｌ12の具体例は上述したＬ1と同様である。なかでも硫黄原子を有する有機基であることが好ましく、－Ｓ－または－ＳＯ2－であることがより好ましく、－ＳＯ2－であることがさらに好ましい。 In the above formula (12), L 12 represents a single bond or a divalent organic group. A specific example of L 12 is the same as L 1 described above. Among these, an organic group having a sulfur atom is preferable, —S— or —SO 2 — is more preferable, and —SO 2 — is still more preferable.
　上記酸触媒としては特に制限されず、公知の酸触媒を用いることができる。具体例としては、シュウ酸、酒石酸、コハク酸、クエン酸、塩酸、硫酸、ｐ－トルエンスルホン酸などが挙げられる。 The acid catalyst is not particularly limited, and a known acid catalyst can be used. Specific examples include oxalic acid, tartaric acid, succinic acid, citric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like.
　上記カルボン酸としては特に制限されず、カルボキシ基を有する化合物であれば特に制限されないが、複数（特に２つ）のカルボキシ基を含有する化合物であることが好ましい。なかでも、下記式（１５）で表される化合物であることが好ましい。 The carboxylic acid is not particularly limited as long as it is a compound having a carboxy group, but is preferably a compound containing a plurality (particularly two) of carboxy groups. Especially, it is preferable that it is a compound represented by following formula (15).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記式（１５）中、Ｌ15は、単結合または２価の有機基を表す。Ｌ15の具体例は上述したＬ1と同様である。なかでもアルキレン基（特に炭素数１～５）であることが好ましい。 In the above formula (15), L 15 represents a single bond or a divalent organic group. A specific example of L 15 is the same as L 1 described above. Of these, an alkylene group (particularly having 1 to 5 carbon atoms) is preferable.
　上記式（２）中のＢ（架橋性基）が上記式（Ｂ－１）または（Ｂ－７）～（Ｂ－９）である場合、得られる導電膜の密着性および導電性がより優れる理由から、硬化剤は上記アミンまたは上記アルコールであることが好ましく、上記アミンであることがより好ましい。
　上記式（２）中のＢ（架橋性基）が上記式（Ｂ－４）である場合、得られる導電膜の密着性および導電性がより優れる理由から、硬化剤は上記酸触媒または上記アルコールであることが好ましく、上記酸触媒であることがより好ましい。
　上記式（２）中のＢ（架橋性基）が上記式（Ｂ－５）である場合、得られる導電膜の密着性および導電性がより優れる理由から、硬化剤は上記カルボン酸であることが好ましい。
　上記式（２）中のＢ（架橋性基）が上記式（Ｂ－２）である場合、得られる導電膜の密着性および導電性がより優れる理由から、硬化剤は上記エポキシド、上記式（１３）で表される部分構造を２つ以上有する化合物、上記ビニル化合物または上記アルデヒドであることが好ましく、上記エポキシド、上記式（１３）で表される部分構造を２つ以上有する化合物または上記ビニル化合物であることがより好ましく、上記エポキシドまたは上記式（１３）で表される部分構造を２つ以上有する化合物であることがさらに好ましく、上記エポキシドであることが特に好ましい。
　上記式（２）中のＢ（架橋性基）が上記式（Ｂ－３）である場合、得られる導電膜の密着性および導電性がより優れる理由から、硬化剤は上記アルコールであることが好ましく、上記式（１３）で表される部分構造を２つ以上有する化合物であることがより好ましい。
　上記式（２）中のＢ（架橋性基）が上記式（Ｂ－６）である場合、得られる導電膜の密着性および導電性がより優れる理由から、硬化剤は上記ラジカル開始剤であることが好ましい。 When B (crosslinkable group) in the above formula (2) is the above formula (B-1) or (B-7) to (B-9), the adhesion and conductivity of the resulting conductive film are more excellent. For the reason, the curing agent is preferably the amine or the alcohol, and more preferably the amine.
When B (crosslinkable group) in the above formula (2) is the above formula (B-4), the curing agent is the above acid catalyst or the above alcohol because the adhesion and conductivity of the resulting conductive film are more excellent. It is preferable that the acid catalyst is more preferable.
When B (crosslinkable group) in the above formula (2) is the above formula (B-5), the curing agent is the above carboxylic acid because the adhesion and conductivity of the resulting conductive film are more excellent. Is preferred.
When B (crosslinkable group) in the formula (2) is the formula (B-2), the curing agent is the epoxide, the formula (B) because the adhesion and conductivity of the resulting conductive film are more excellent. It is preferably a compound having two or more partial structures represented by 13), the vinyl compound or the aldehyde, and the epoxide, a compound having two or more partial structures represented by the formula (13) or the vinyl. It is more preferably a compound, more preferably a compound having two or more partial structures represented by the epoxide or the formula (13), and particularly preferably the epoxide.
When B (crosslinkable group) in the above formula (2) is the above formula (B-3), the curing agent may be the above alcohol because the adhesion and conductivity of the resulting conductive film are more excellent. A compound having two or more partial structures represented by the above formula (13) is more preferable.
When B (crosslinkable group) in the above formula (2) is the above formula (B-6), the curing agent is the above radical initiator because the resulting conductive film has better adhesion and conductivity. It is preferable.
　本発明の組成物において、上記硬化剤の含有量は、ポリマーを効率よく架橋する観点から、上記特定ポリマーの含有量に対して、０．０１～３０質量％であることが好ましく、０．１～２０質量％であることがより好ましい。 In the composition of the present invention, the content of the curing agent is preferably 0.01 to 30% by mass with respect to the content of the specific polymer, from the viewpoint of efficiently crosslinking the polymer, More preferably, it is ˜20% by mass.
＜溶媒＞
　本発明の組成物は、粘度調節のし易さ、および、印刷性の観点から、溶媒を含有するのが好ましい。溶媒は、酸化銅粒子および／または銅粒子の分散媒として機能する。
　溶媒の種類は特に制限されないが、例えば、水や、アルコール類、エーテル類、エステル類などの有機溶媒などを使用することができる。なかでも、均質な膜が形成され、結果として、形成される導電膜の導電性がより優れる理由から、水、１～３価のヒドロキシル基を有する脂肪族アルコール、この脂肪族アルコール由来のアルキルエーテル、この脂肪族アルコール由来のアルキルエステル、またはこれらの混合物が好ましく用いられる。なかでも、沸点が高すぎないことから、特に水を主溶媒として用いることが好ましい。主溶媒とは、溶媒の中で含有率が最も多い溶媒である。 <Solvent>
The composition of the present invention preferably contains a solvent from the viewpoint of easy viscosity adjustment and printability. The solvent functions as a dispersion medium for copper oxide particles and / or copper particles.
The type of the solvent is not particularly limited. For example, water, organic solvents such as alcohols, ethers, and esters can be used. Among them, a homogeneous film is formed, and as a result, the conductivity of the formed conductive film is superior, so water, an aliphatic alcohol having a monovalent to trivalent hydroxyl group, and an alkyl ether derived from this aliphatic alcohol. An alkyl ester derived from the aliphatic alcohol, or a mixture thereof is preferably used. Among these, since the boiling point is not too high, it is particularly preferable to use water as the main solvent. The main solvent is a solvent having the highest content in the solvent.
　溶媒の含有量は特に制限されないが、粘度の上昇が抑制され、取扱い性により優れる点から、組成物全質量に対して、５～９０質量％であることが好ましく、８～８０質量％であることがより好ましい。 The content of the solvent is not particularly limited, but is preferably 5 to 90% by mass, and preferably 8 to 80% by mass with respect to the total mass of the composition, from the viewpoint of suppressing an increase in viscosity and being excellent in handleability. It is more preferable.
＜その他成分＞
　本発明の組成物には、上記各成分以外の成分が含まれていてもよい。
　例えば、本発明の組成物には、界面活性剤が含まれていてもよい。界面活性剤は、酸化銅粒子および／または銅粒子の分散性を向上させる役割を果たす。界面活性剤の種類は特に制限されず、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤、フッ素系界面活性剤、両性界面活性剤などが挙げられる。これら界面活性剤は、１種を単独、または２種以上を混合して用いることができる。 <Other ingredients>
The composition of the present invention may contain components other than the above components.
For example, the composition of the present invention may contain a surfactant. The surfactant plays a role of improving the dispersibility of the copper oxide particles and / or the copper particles. The type of the surfactant is not particularly limited, and examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a fluorine surfactant, and an amphoteric surfactant. These surfactants can be used alone or in combination of two or more.
＜導電膜形成用組成物の粘度＞
　本発明の組成物の粘度は、インクジェット、スクリーン印刷等の印刷用途に適するような粘度に調整させることが好ましい。インクジェット吐出を行う場合、１～５０ｃＰであることが好ましく、１～４０ｃＰであることがより好ましい。スクリーン印刷を行う場合は、１０００～１０００００ｃＰであることが好ましく、１００００～８００００ｃＰであることがより好ましい。 <Viscosity of composition for forming conductive film>
The viscosity of the composition of the present invention is preferably adjusted to a viscosity suitable for printing applications such as inkjet and screen printing. When inkjet discharge is performed, the pressure is preferably 1 to 50 cP, and more preferably 1 to 40 cP. When screen printing is performed, it is preferably 1000 to 100,000 cP, and more preferably 10,000 to 80,000 cP.
＜導電膜形成用組成物の調製方法＞
　本発明の組成物の調製方法は特に制限されず、公知の方法を採用できる。例えば、上記溶媒中に上記酸化銅粒子および／または銅粒子、上記特定ポリマー、および、上記硬化剤を添加した後、超音波法（例えば、超音波ホモジナイザーによる処理）、ミキサー法、３本ロール法、ボールミル法などの公知の手段により成分を分散させるによって、組成物を得ることができる。 <Method for Preparing Composition for Forming Conductive Film>
The preparation method in particular of the composition of this invention is not restrict | limited, A well-known method is employable. For example, after adding the copper oxide particles and / or copper particles, the specific polymer, and the curing agent to the solvent, an ultrasonic method (for example, treatment with an ultrasonic homogenizer), a mixer method, a three-roll method The composition can be obtained by dispersing the components by a known means such as a ball mill method.
［導電膜の製造方法］
　本発明の導電膜の製造方法は、少なくとも塗膜形成工程と還元工程とを有する。以下に、それぞれの工程について詳述する。 [Method for producing conductive film]
The manufacturing method of the electrically conductive film of this invention has a coating-film formation process and a reduction process at least. Below, each process is explained in full detail.
＜塗膜形成工程＞
　本工程は、上述した導電膜形成用組成物を基材上に付与して、基材上に組成物層を形成し、その後、組成物層に対して加熱処理を施して、塗膜を形成する工程である。本工程により還元処理が施される前の前駆体膜が得られる。
　使用される導電膜形成用組成物については、上述のとおりである。 <Coating film formation process>
In this step, the composition for forming a conductive film described above is applied on a substrate, a composition layer is formed on the substrate, and then a heat treatment is applied to the composition layer to form a coating film. It is a process to do. The precursor film before the reduction treatment is obtained in this step.
The composition for forming a conductive film used is as described above.
　本工程で使用される基材としては、公知のものを用いることができる。基材に使用される材料としては、例えば、樹脂、紙、ガラス、シリコン系半導体、化合物半導体、金属酸化物、金属窒化物、木材、またはこれらの複合物が挙げられる。
　より具体的には、低密度ポリエチレン樹脂、高密度ポリエチレン樹脂、ＡＢＳ樹脂、アクリル樹脂、スチレン樹脂、塩化ビニル樹脂、ポリエステル樹脂（ポリエチレンテレフタレート）、ポリアセタール樹脂、ポリサルフォン樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂、セルロース誘導体等の樹脂基材；非塗工印刷用紙、微塗工印刷用紙、塗工印刷用紙（アート紙、コート紙）、特殊印刷用紙、コピー用紙（ＰＰＣ用紙）、未晒包装紙（重袋用両更クラフト紙、両更クラフト紙）、晒包装紙（晒クラフト紙、純白ロール紙）、コートボール、チップボール、段ボール等の紙基材；ソーダガラス、ホウケイ酸ガラス、シリカガラス、石英ガラス等のガラス基材；アモルファスシリコン、ポリシリコン等のシリコン系半導体基材；ＣｄＳ、ＣｄＴｅ、ＧａＡｓ等の化合物半導体基材；銅板、鉄板、アルミ板等の金属基材；アルミナ、サファイア、ジルコニア、チタニア、酸化イットリウム、酸化インジウム、ＩＴＯ（インジウム錫酸化物）、ＩＺＯ（インジウム亜鉛酸化物）、ネサ（酸化錫）、ＡＴＯ（アンチモンドープ酸化錫）、フッ素ドープ酸化錫、酸化亜鉛、ＡＺＯ（アルミドープ酸化亜鉛）、ガリウムドープ酸化亜鉛、窒化アルミニウム基材、炭化ケイ素等のその他無機基材；紙－フェノール樹脂、紙－エポキシ樹脂、紙－ポリエステル樹脂等の紙－樹脂複合物、ガラス布－エポキシ樹脂、ガラス布－ポリイミド系樹脂、ガラス布－フッ素樹脂等のガラス－樹脂複合物等の複合基材等が挙げられる。これらの中でも、ポリエステル樹脂基材、ポリエーテルイミド樹脂基材、紙基材、ガラス基材、ガラス布－エポキシ樹脂、が好ましく使用される。 A well-known thing can be used as a base material used at this process. Examples of the material used for the substrate include resin, paper, glass, silicon-based semiconductor, compound semiconductor, metal oxide, metal nitride, wood, or a composite thereof.
More specifically, low density polyethylene resin, high density polyethylene resin, ABS resin, acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate), polyacetal resin, polysulfone resin, polyetherimide resin, polyether ketone Resin base materials such as resin and cellulose derivatives; uncoated printing paper, fine coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper ( Paper substrates such as double kraft paper for heavy bags, double kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coated balls, chip balls, corrugated cardboard; soda glass, borosilicate glass, silica glass, Glass substrates such as quartz glass; silicon-based semiconductor substrates such as amorphous silicon and polysilicon; Compound semiconductor substrates such as dS, CdTe, GaAs; metal substrates such as copper plate, iron plate, aluminum plate; alumina, sapphire, zirconia, titania, yttrium oxide, indium oxide, ITO (indium tin oxide), IZO (indium zinc) Oxides), Nesa (tin oxide), ATO (antimony-doped tin oxide), fluorine-doped tin oxide, zinc oxide, AZO (aluminum-doped zinc oxide), gallium-doped zinc oxide, aluminum nitride substrate, silicon carbide, and other inorganic materials Substrate: Paper-phenolic resin, paper-epoxy resin, paper-polyester resin and other paper-resin composite, glass cloth-epoxy resin, glass cloth-polyimide resin, glass cloth-fluorine resin-glass-resin composite And the like, and the like. Among these, polyester resin base materials, polyetherimide resin base materials, paper base materials, glass base materials, and glass cloth-epoxy resins are preferably used.
　導電膜形成用組成物を基材上に付与して、組成物層を形成する方法は特に制限されず、公知の方法を採用できる。例えば、導電膜形成用組成物中に基材を浸漬する方法や、導電膜形成用組成物を基材に塗布する方法などが挙げられる。導電膜の厚みを制御しやすい点から、導電膜形成用組成物を基材上に塗布する方法が好ましい。
　塗布の方法としては、例えば、ダブルロールコータ、スリットコータ、エアナイフコータ、ワイヤーバーコータ、スライドホッパー、スプレーコーチィング、ブレードコータ、ドクターコータ、スクイズコータ、リバースロールコータ、トランスファーロールコータ、エクストロージョンコータ、カーテンコータ、ディップコーター、ダイコータ、グラビアロールによる塗工法、スクリーン印刷法、ディップコーティング法、スプレー塗布法、スピンコーティング法、インクジェット法などが挙げられる。なかでも、簡便であり、また、サイズの大きい導電膜を製造することが容易であることから、スクリーン印刷法、インクジェット法であることが好ましい。
　塗布の形状は特に制限されず、基材全面を覆う面状であっても、パターン状（例えば、配線状、ドット状）であってもよい。
　基材上への導電膜形成用組成物の塗布量としては、所望する導電膜の膜厚に応じて適宜調整すればよいが、通常、塗膜の膜厚は０．０１～５０００μｍが好ましく、０．１～１０００μｍがより好ましい。 The method for forming the composition layer by applying the composition for forming a conductive film on the substrate is not particularly limited, and a known method can be adopted. For example, the method of immersing a base material in the composition for electrically conductive film formation, the method of apply | coating the composition for electrically conductive film formation to a base material, etc. are mentioned. From the viewpoint of easily controlling the thickness of the conductive film, a method of applying the conductive film forming composition on the substrate is preferable.
Application methods include, for example, double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, doctor coater, squeeze coater, reverse roll coater, transfer roll coater, extrusion roll coater, curtain Examples include a coater, dip coater, die coater, gravure roll coating method, screen printing method, dip coating method, spray coating method, spin coating method, and ink jet method. Among these, the screen printing method and the ink jet method are preferable because they are simple and easy to produce a large conductive film.
The shape of application is not particularly limited, and may be a surface covering the entire surface of the substrate or a pattern (for example, a wiring or a dot).
The coating amount of the composition for forming a conductive film on the substrate may be appropriately adjusted according to the desired film thickness of the conductive film. Usually, the film thickness of the coating film is preferably 0.01 to 5000 μm, 0.1 to 1000 μm is more preferable.
　組成物層に対する加熱処理の条件は特に制限されないが、加熱温度は８０～２００℃であることが好ましい。
　加熱処理には、例えば、送風乾燥機、オーブン、赤外線乾燥機、加熱ドラムなどを用いることができる。 The heat treatment conditions for the composition layer are not particularly limited, but the heating temperature is preferably 80 to 200 ° C.
For the heat treatment, for example, an air dryer, an oven, an infrared dryer, a heating drum, or the like can be used.
＜還元工程＞
　本工程は、上記塗膜形成工程で形成された塗膜に対して光照射処理を行い、酸化銅粒子および／または銅粒子を還元して、導電膜を形成する工程である。 <Reduction process>
This step is a step of forming a conductive film by performing light irradiation treatment on the coating film formed in the coating film forming step to reduce the copper oxide particles and / or the copper particles.
　光照射処理で使用される光源は特に制限されず、例えば、水銀灯、メタルハライドランプ、キセノン（Ｘｅ）ランプ、ケミカルランプ、カーボンアーク灯等がある。放射線としては、電子線、Ｘ線、イオンビーム、遠赤外線などがある。また、ｇ線、ｉ線、Ｄｅｅｐ－ＵＶ光、高密度エネルギービーム（レーザービーム）も使用される。
　具体的な態様としては、赤外線レーザーによる走査露光、キセノン（Ｘｅ）放電灯などの高照度フラッシュ露光、赤外線ランプ露光などが好適に挙げられる。 The light source used in the light irradiation treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon (Xe) lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon (Xe) discharge lamp, and infrared lamp exposure.
　光照射処理は、フラッシュランプ（特にＸｅフラッシュランプ）による光照射処理であることが好ましく、フラッシュランプ（特にＸｅフラッシュランプ）によるパルス光照射処理であることがより好ましい。高エネルギーのパルス光の照射は、塗膜を付与した部分の表面を、極めて短い時間で集中して加熱することができるため、基材への熱の影響を極めて小さくすることができる。
　パルス光の照射エネルギーは、１～１００Ｊ／ｃｍ2であることが好ましく、１～５０Ｊ／ｃｍ2であることがより好ましく、１～３０Ｊ／ｃｍ2であることがさらに好ましい。パルス光のパルス幅は、１μ秒～１００ｍ秒であることが好ましく、１０μ秒～１０ｍ秒であることがより好ましい。パルス光の照射時間は、１μ秒～１０００ｍ秒であることが好ましく、１ｍ秒～５００ｍ秒であることがより好ましく、１ｍ秒～２００ｍ秒であることがさらに好ましい。 The light irradiation process is preferably a light irradiation process using a flash lamp (particularly a Xe flash lamp), and more preferably a pulsed light irradiation process using a flash lamp (particularly a Xe flash lamp). Irradiation with high-energy pulsed light can concentrate and heat the surface of the portion to which the coating film has been applied in a very short time, so that the influence of heat on the substrate can be extremely reduced.
Irradiation energy of the pulse light is preferably 1 ~ 100J / cm 2, more preferably 1 ~ 50J / cm 2, further preferably 1 ~ 30J / cm 2. The pulse width of the pulsed light is preferably 1 μsec to 100 msec, and more preferably 10 μsec to 10 msec. The irradiation time of the pulsed light is preferably 1 μsec to 1000 msec, more preferably 1 msec to 500 msec, and further preferably 1 msec to 200 msec.
　上記光照射処理を実施する雰囲気は特に制限されず、大気雰囲気下、不活性雰囲気下、または還元性雰囲気下などが挙げられる。なお、不活性雰囲気とは、例えば、アルゴン、ヘリウム、ネオン、窒素等の不活性ガスで満たされた雰囲気であり、また、還元性雰囲気とは、水素、一酸化炭素、ギ酸、アルコール等の還元性ガスが存在する雰囲気を指す。 The atmosphere for performing the light irradiation treatment is not particularly limited, and examples thereof include an air atmosphere, an inert atmosphere, and a reducing atmosphere. The inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen. The reducing atmosphere is a reduction of hydrogen, carbon monoxide, formic acid, alcohol, or the like. It refers to the atmosphere in which sex gas exists.
＜導電膜＞
　上記工程を実施することにより、導電膜が得られる。
　導電膜の膜厚は特に制限されず、使用される用途に応じて適宜最適な膜厚が調整される。なかでも、プリント配線基板用途の点からは、０．０１～１０００μｍが好ましく、０．１～１００μｍがより好ましい。
　なお、膜厚は、導電膜の任意の点における厚みを３箇所以上測定し、その値を算術平均して得られる値（平均値）である。
　導電膜の体積抵抗値は、導電特性の点から、２．０×１０-4Ωｃｍ以下であることが好ましい。
　体積抵抗値は、導電膜の表面抵抗値を四探針法にて測定後、得られた表面抵抗値に膜厚を乗算することで算出することができる。 <Conductive film>
A conductive film is obtained by carrying out the above steps.
The film thickness of the conductive film is not particularly limited, and an optimum film thickness is appropriately adjusted according to the intended use. Of these, 0.01 to 1000 μm is preferable and 0.1 to 100 μm is more preferable from the viewpoint of printed wiring board use.
The film thickness is a value (average value) obtained by measuring three or more thicknesses at arbitrary points on the conductive film and arithmetically averaging the values.
The volume resistance value of the conductive film is preferably 2.0 × 10 −4 Ωcm or less from the viewpoint of conductive characteristics.
The volume resistance value can be calculated by multiplying the obtained surface resistance value by the film thickness after measuring the surface resistance value of the conductive film by the four-probe method.
　導電膜は基材の全面、または、パターン状に設けられてもよい。パターン状の導電膜は、プリント配線基板などの導体配線（配線）として有用である。
　パターン状の導電膜を得る方法としては、上記導電膜形成用組成物をパターン状に基材に付与して、上記光照射処理を行う方法や、基材全面に設けられた導電膜をパターン状にエッチングする方法などが挙げられる。
　エッチングの方法は特に制限されず、公知のサブトラクティブ法、セミアディティブ法などを採用できる。 The conductive film may be provided on the entire surface of the base material or in a pattern. The patterned conductive film is useful as a conductor wiring (wiring) such as a printed wiring board.
As a method of obtaining a patterned conductive film, the above-mentioned composition for forming a conductive film is applied to a substrate in a pattern and the light irradiation treatment is performed, or the conductive film provided on the entire surface of the substrate is patterned. And a method of etching.
The etching method is not particularly limited, and a known subtractive method, semi-additive method, or the like can be employed.
　パターン状の導電膜を多層配線基板として構成する場合、パターン状の導電膜の表面に、さらに絶縁層（絶縁樹脂層、層間絶縁膜、ソルダーレジスト）を積層して、その表面にさらなる配線（金属パターン）を形成してもよい。 When a patterned conductive film is configured as a multilayer wiring board, an insulating layer (insulating resin layer, interlayer insulating film, solder resist) is further laminated on the surface of the patterned conductive film, and further wiring (metal) is formed on the surface. Pattern) may be formed.
　絶縁膜の材料は特に制限されないが、例えば、エポキシ樹脂、アラミド樹脂、結晶性ポリオレフィン樹脂、非晶性ポリオレフィン樹脂、フッ素含有樹脂（ポリテトラフルオロエチレン、全フッ素化ポリイミド、全フッ素化アモルファス樹脂など）、ポリイミド樹脂、ポリエーテルスルフォン樹脂、ポリフェニレンサルファイド樹脂、ポリエーテルエーテルケトン樹脂、液晶樹脂など挙げられる。
　これらの中でも、密着性、寸法安定性、耐熱性、電気絶縁性等の観点から、エポキシ樹脂、ポリイミド樹脂、または液晶樹脂を含有するものであることが好ましく、より好ましくはエポキシ樹脂である。具体的には、味の素ファインテクノ（株）製、ＡＢＦ　ＧＸ－１３などが挙げられる。 The material of the insulating film is not particularly limited. For example, epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated amorphous resin, etc.) , Polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal resin and the like.
Among these, from the viewpoints of adhesion, dimensional stability, heat resistance, electrical insulation, and the like, it is preferable to contain an epoxy resin, a polyimide resin, or a liquid crystal resin, and more preferably an epoxy resin. Specific examples include ABF GX-13 manufactured by Ajinomoto Fine Techno Co., Ltd.
　また、配線保護のために用いられる絶縁層の材料の一種であるソルダーレジストについては、例えば、特開平１０－２０４１５０号公報や、特開２００３－２２２９９３号公報等に詳細に記載され、ここに記載の材料を所望により本発明にも適用することができる。ソルダーレジストは市販品を用いてもよく、具体的には、例えば、太陽インキ製造（株）製ＰＦＲ８００、ＰＳＲ４０００（商品名）、日立化成工業（株）製　ＳＲ７２００Ｇ、などが挙げられる。 The solder resist, which is a kind of insulating layer material used for wiring protection, is described in detail in, for example, Japanese Patent Application Laid-Open No. 10-204150 and Japanese Patent Application Laid-Open No. 2003-222993. These materials can also be applied to the present invention if desired. As the solder resist, commercially available products may be used. Specific examples include PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.
　上記で得られた導電膜を有する基材（導電膜付き基材）は、種々の用途に使用することができる。例えば、プリント配線基板、ＴＦＴ、ＦＰＣ、ＲＦＩＤなどが挙げられる。 The base material (base material with a conductive film) having the conductive film obtained above can be used for various applications. For example, a printed wiring board, TFT, FPC, RFID, etc. are mentioned.
　以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
（合成例１：ポリマー１）
　三口フラスコに、Ｎ－ビニルピロリドン８０質量部、ＤＭＡｃ２２０質量部を加え窒素気流下、７５℃まで加熱した。そこへ、Ｎ－ビニルピロリドン（下記構造）８０質量部、サイクロマーＡ（下記構造、ダイセル社製）２９質量部、およびＶ－６０１（和光純薬社製、下記構造）３．７質量部のＤＭＡｃ（２２０質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した。その後、室温まで、反応溶液を冷却した。反応終了後、ヘキサン／酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、３１０００であった。得られたポリマーをポリマー１とする。 (Synthesis Example 1: Polymer 1)
To a three-necked flask, 80 parts by mass of N-vinylpyrrolidone and 220 parts by mass of DMAc were added and heated to 75 ° C. under a nitrogen stream. Thereto, 80 parts by mass of N-vinylpyrrolidone (the following structure), 29 parts by mass of cyclomer A (the following structure, manufactured by Daicel), and 3.7 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, the following structure) DMAc (220 parts by mass) solution was added dropwise over 3 hours. It stirred for 3 hours after completion | finish of dripping. Thereafter, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was performed with hexane / ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 31000. The resulting polymer is referred to as Polymer 1.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
（合成例２：ポリマー２）
　三口フラスコに、Ｎ－ビニルピロリドン６２質量部、ＤＭＡｃ２０２質量部を加え窒素気流下、７５℃まで加熱した。そこへ、Ｎ－ビニルピロリドン６２質量部、ヒドロキシメチルアクリルアミド（下記構造）４９質量部、およびＶ－６０１（和光純薬社製）３．７質量部のＤＭＡｃ（２０２質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した。その後、室温まで、反応溶液を冷却した。反応終了後、酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、３６０００であった。得られたポリマーをポリマー２とする。 (Synthesis Example 2: Polymer 2)
In a three-necked flask, 62 parts by mass of N-vinylpyrrolidone and 202 parts by mass of DMAc were added and heated to 75 ° C. under a nitrogen stream. Thereto was added a DMAc (202 parts by mass) solution of 62 parts by mass of N-vinylpyrrolidone, 49 parts by mass of hydroxymethylacrylamide (the following structure), and 3.7 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) for 3 hours. It was dripped over. It stirred for 3 hours after completion | finish of dripping. Thereafter, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was performed with ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 36000. The obtained polymer is designated as Polymer 2.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
（合成例３：ポリマー３）
　三口フラスコに、Ｎ－ビニルピロリドン６２質量部、ＤＭＡｃ１８３質量部を加え窒素気流下、７５℃まで加熱した。そこへ、Ｎ－ビニルピロリドン６２質量部、４－ヒドロキシブチルアクリレートグリシジルエーテル（下記構造）３２質量部、およびＶ－６０１（和光純薬社製）３．７質量部のＤＭＡｃ（１８３質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した。その後、室温まで、反応溶液を冷却した。反応終了後、酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、３００００であった。得られたポリマーをポリマー３とする。 (Synthesis Example 3: Polymer 3)
In a three-necked flask, 62 parts by mass of N-vinylpyrrolidone and 183 parts by mass of DMAc were added and heated to 75 ° C. under a nitrogen stream. Thereto, 62 parts by mass of N-vinylpyrrolidone, 32 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (the following structure), and 3.7 parts by mass of DMAc (183 parts by mass) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Was added dropwise over 3 hours. It stirred for 3 hours after completion | finish of dripping. Thereafter, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was performed with ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 30000. The obtained polymer is designated as Polymer 3.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（合成例４：ポリマー４）
　三口フラスコに、Ｎ－ビニルピロリドン６２質量部、ＤＭＡｃ１６３質量部を加え窒素気流下、７５℃まで加熱した。そこへ、Ｎ－ビニルピロリドン６２質量部、ビニルオキサゾリン（下記構造）１６質量部、およびＶ－６０１（和光純薬社製）３．７質量部のＤＭＡｃ（１６３質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した。その後、室温まで、反応溶液を冷却した。反応終了後、酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、２４０００であった。得られたポリマーをポリマー４とする。 (Synthesis Example 4: Polymer 4)
In a three-necked flask, 62 parts by mass of N-vinylpyrrolidone and 163 parts by mass of DMAc were added and heated to 75 ° C. under a nitrogen stream. Thereto was added a DMAc (163 parts by mass) solution of 62 parts by mass of N-vinylpyrrolidone, 16 parts by mass of vinyloxazoline (the following structure), and 3.7 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) over 3 hours. And dripped. It stirred for 3 hours after completion | finish of dripping. Thereafter, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was performed with ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 24000. The resulting polymer is designated as Polymer 4.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（合成例５：ポリマー５）
　三口フラスコに、ＤＭＡｃ１８０質量部を入れ、窒素気流下、７５℃まで加熱した。そこへ、ブレンマーＡＥ４００（日油社製、下記構造）１５０質量部、およびＶ－６０１（和光純薬社製）０．７質量部のＤＭＡｃ（１８０質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した後、室温まで反応溶液を冷却した。反応終了後、ヘキサン／酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、４５０００であった。得られたポリマーをポリマー５とする。 (Synthesis Example 5: Polymer 5)
In a three-necked flask, 180 parts by mass of DMAc was placed and heated to 75 ° C. under a nitrogen stream. Thereto, a DMAc (180 parts by mass) solution of 150 parts by mass of Bremer AE400 (manufactured by NOF Corporation, the following structure) and 0.7 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 3 hours. . After completion of the dropwise addition, the reaction solution was cooled to room temperature after stirring for 3 hours. After completion of the reaction, reprecipitation was performed with hexane / ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 45000. The resulting polymer is designated as Polymer 5.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（合成例６：ポリマー６）
　三口フラスコに、カレンズＡＯＩ（和光純薬社製、下記構造）７質量部、２，５－ジ－タ－シャリ－アミルヒドロキノン（下記構造）０．０１質量部、ＴＨＦ３０質量部を加え、氷浴下２－ブタノンオキシム（下記構造）５質量部を滴下した。室温で１時間撹拌した後、酢酸エチルで抽出することでモノマー６（下記構造）を得た。
　三口フラスコに、Ｎ－ビニルピロリドン６２質量部、ＤＭＡｃ１８８質量部を加え窒素気流下、７５℃まで加熱した。そこへ、Ｎ－ビニルピロリドン６２質量部、モノマー６（３７質量部）、およびＶ－６０１（和光純薬社製）３．７質量部のＤＭＡｃ（１６３質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した。その後、室温まで、反応溶液を冷却した。反応終了後、ヘキサン／酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、３７０００であった。得られたポリマーをポリマー６とする。 (Synthesis Example 6: Polymer 6)
To a three-necked flask, 7 parts by weight of Karenz AOI (manufactured by Wako Pure Chemical Industries, Ltd., the following structure), 0.01 part by mass of 2,5-di-tert-amyl-amylhydroquinone (the following structure), and 30 parts by mass of THF are added, and an ice bath is added. 5 parts by mass of lower 2-butanone oxime (the following structure) was added dropwise. After stirring at room temperature for 1 hour, monomer 6 (the following structure) was obtained by extracting with ethyl acetate.
To a three-necked flask, 62 parts by mass of N-vinylpyrrolidone and 188 parts by mass of DMAc were added and heated to 75 ° C. under a nitrogen stream. Thereto, a solution of N-vinylpyrrolidone 62 parts by mass, monomer 6 (37 parts by mass), and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 3.7 parts by mass of DMAc (163 parts by mass) was dropped over 3 hours. did. It stirred for 3 hours after completion | finish of dripping. Thereafter, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was performed with hexane / ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 37000. The resulting polymer is designated as Polymer 6.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（合成例７：ポリマー７）
　三口フラスコに、Ｎ－ビニルピロリドン８０質量部、ＤＭＡｃ２００質量部を加え窒素気流下、７５℃まで加熱した。そこへ、Ｎ－ビニルピロリドン８０質量部、アクリル酸（下記構造）１２質量部、およびＶ－６０１（和光純薬社製）３．７質量部のＤＭＡｃ（２００質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した。その後、室温まで、反応溶液を冷却した。
　この反応液に２，５－ジ－タ－シャリ－アミルヒドロキノン０．０５質量部、およびベンジルトリエチルアンモニウムクロライド（下記構造）５質量部のＤＭＡｃ（５０質量部）溶液を加え、さらにメタクリル酸グリシジル（下記構造）２８質量部を添加した後、１００℃で４時間撹拌した。反応終了後、酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、７００００であった。得られたポリマーをポリマー７とする。 (Synthesis Example 7: Polymer 7)
To a three-necked flask, 80 parts by mass of N-vinylpyrrolidone and 200 parts by mass of DMAc were added and heated to 75 ° C. under a nitrogen stream. Thereto was added a DMAc (200 parts by mass) solution of 80 parts by mass of N-vinylpyrrolidone, 12 parts by mass of acrylic acid (the following structure), and 3.7 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) over 3 hours. And dripped. It stirred for 3 hours after completion | finish of dripping. Thereafter, the reaction solution was cooled to room temperature.
To this reaction solution was added a DMAc (50 parts by mass) solution of 0.05 parts by mass of 2,5-di-tertiary-amylhydroquinone and 5 parts by mass of benzyltriethylammonium chloride (the following structure), and glycidyl methacrylate ( The following structure) After adding 28 parts by mass, the mixture was stirred at 100 ° C. for 4 hours. After completion of the reaction, reprecipitation was performed with ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 70000. The resulting polymer is designated as Polymer 7.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（ポリマー８）
　ＰＶＡ５００（関東化学社製）をポリマー８とする。 (Polymer 8)
PVA500 (manufactured by Kanto Chemical Co., Inc.) is designated as polymer 8.
（ポリマー９）
　三口フラスコに、ＤＭＡｃ１８０質量部を入れ、窒素気流下、７５℃まで加熱した。そこへ、４－ヒドロキシブチルアクリレートグリシジルエーテル（下記構造）１５０質量部、およびＶ－６０１（和光純薬社製）０．７質量部のＤＭＡｃ（１８０質量部）溶液を、３時間かけて滴下した。滴下終了後、３時間攪拌した後、室温まで反応溶液を冷却した。反応終了後、ヘキサン／酢酸エチルで再沈を行い、固形物（ポリマー）を取り出した。得られたポリマーの重量平均分子量Ｍｗは、４００００であった。得られたポリマーをポリマー９とする。 (Polymer 9)
In a three-necked flask, 180 parts by mass of DMAc was placed and heated to 75 ° C. under a nitrogen stream. Thereto, a DMAc (180 parts by mass) solution of 150 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (the following structure) and 0.7 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 3 hours. . After completion of the dropwise addition, the reaction solution was cooled to room temperature after stirring for 3 hours. After completion of the reaction, reprecipitation was performed with hexane / ethyl acetate, and a solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 40000. The resulting polymer is designated as Polymer 9.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　上記ポリマー１～９について、ポリマー中に含まれる繰り返し単位を以下にまとめて示す。ここで、ポリマー１～８は特定ポリマーに該当する。また、ポリマー９は上記式（２）で表される繰り返し単位を含むが上記式（１）で表される繰り返し単位を含まないポリマーであり、特定ポリマーに該当しない。
　なお、ポリマー１～４、６および７は、示される繰り返し単位のうち左側の繰り返し単位が上記式（１）で表される繰り返し単位に相当し、右側の繰り返し単位が上記式（２）で表される繰り返し単位に相当する。また、ポリマー５については、示される繰り返し単位が上記式（１）で表される繰り返し単位および上記式（２）で表される繰り返し単位に相当する。また、ポリマー８については、示される繰り返し単位のうち左側の繰り返し単位が上記式（１）で表される繰り返し単位および上記式（２）で表される繰り返し単位に相当する。 Regarding the above polymers 1 to 9, the repeating units contained in the polymer are summarized below. Here, the polymers 1 to 8 correspond to specific polymers. Further, the polymer 9 is a polymer that includes the repeating unit represented by the above formula (2) but does not include the repeating unit represented by the above formula (1), and does not correspond to a specific polymer.
In the polymers 1 to 4, 6 and 7, the left repeating unit of the repeating units shown corresponds to the repeating unit represented by the above formula (1), and the right repeating unit is represented by the above formula (2). Corresponds to a repeating unit. Further, for polymer 5, the repeating unit shown corresponds to the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2). For polymer 8, the left-hand repeating unit of the repeating units shown corresponds to the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（ポリマーの水溶液およびエタノール溶液の調製）
　上記ポリマー１～８をそれぞれ水に溶かし、ポリマーの水溶液（ポリマー濃度：３５質量％）を得た。得られた水溶液をそれぞれ水溶液１～８とする。
　上記ポリマー９をエタノールに溶かし、ポリマーのエタノール溶液（ポリマー濃度：３５質量％）を得た。得られたエタノール溶液をエタノール溶液９とする。 (Preparation of aqueous polymer solution and ethanol solution)
Each of the above polymers 1 to 8 was dissolved in water to obtain an aqueous polymer solution (polymer concentration: 35% by mass). The obtained aqueous solutions are designated as aqueous solutions 1 to 8, respectively.
The polymer 9 was dissolved in ethanol to obtain a polymer ethanol solution (polymer concentration: 35% by mass). Let the obtained ethanol solution be the ethanol solution 9.
＜実施例１＞
　ＣｕＯナノ粒子（関東化学社製：粒径２７～９５ｎｍ）６５質量部、純水３５質量部を練太郎（シンキー社製）（２２００ｒｐｍ、３分）で分散させ、ＣｕＯペースト（ＣｕＯ：６５質量％）を得た。
　次に、上記ＣｕＯペースト１１５質量部に上記水溶液１（２６質量部）、４０質量％ＢＹＫ－４２５（ビックケミー・ジャパン社製）プロピレングリコール溶液８質量部、硬化剤としてトリエチレンテトラミン０．４質量部を加え、練太郎（２２００ｒｐｍ、３分）で混練し、組成物（導電膜形成用組成物）を得た。
　なお、上記組成物の組成は、質量比で、ＣｕＯ／ポリマー／ＢＹＫ－４２５／トリエチレンテトラミン／溶媒＝５０．０／６．１／２．１／０．３／４１．５である。 <Example 1>
65 parts by mass of CuO nanoparticles (manufactured by Kanto Chemical Co., Inc .: particle size 27 to 95 nm) and 35 parts by mass of pure water are dispersed with Nertaro (manufactured by Sinky) (2200 rpm, 3 minutes) to obtain a CuO paste (CuO: 65% by mass). )
Next, 115 parts by weight of the CuO paste, 8 parts by weight of the above aqueous solution 1 (26 parts by weight), 40% by weight BYK-425 (by Big Chemie Japan) propylene glycol solution, and 0.4 parts by weight of triethylenetetramine as a curing agent And kneaded with Nertaro (2200 rpm, 3 minutes) to obtain a composition (composition for forming a conductive film).
The composition of the above composition is CuO / polymer / BYK-425 / triethylenetetramine / solvent = 50.0 / 6.1 / 2.1 / 0.3 / 41.5 in terms of mass ratio.
（硬化処理）
　得られた組成物を４０μｍギャップの塗布バーでガラスエポキシ基板上に塗布した。その後、塗布した組成物を１００℃で１０分間加熱乾燥し、さらに１５０℃で１時間加熱して硬化させ、酸化銅膜を得た。 (Curing treatment)
The obtained composition was apply | coated on the glass epoxy board | substrate with the application | coating bar of a 40 micrometer gap. Thereafter, the applied composition was dried by heating at 100 ° C. for 10 minutes, and further cured by heating at 150 ° C. for 1 hour to obtain a copper oxide film.
（光照射処理）
　得られた酸化銅膜にＸｅフラッシュランプ（照射エネルギー：４．９Ｊ／ｃｍ2、パルス幅：２ｍ秒）を当てることで導電膜（銅膜）を得た。 (Light irradiation treatment)
A conductive film (copper film) was obtained by applying a Xe flash lamp (irradiation energy: 4.9 J / cm 2 , pulse width: 2 msec) to the obtained copper oxide film.
＜実施例２＞
　トリエチレンテトラミン０．４質量部の代わりにジエタノールアミン０．４質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 2>
A conductive composition was obtained according to the same procedure as in Example 1 except that 0.4 parts by mass of diethanolamine was used instead of 0.4 parts by mass of triethylenetetramine.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例３＞
　水溶液１（２６質量部）の代わりに上記水溶液２（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにｐ－トルエンスルホン酸０．３質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 3>
Implemented except that the above aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.3 parts by mass of p-toluenesulfonic acid was used instead of 0.4 parts by mass of triethylenetetramine. A conductive composition was obtained according to the same procedure as in Example 1.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例４＞
　水溶液１（２６質量部）の代わりに上記水溶液２（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにジエタノールアミン０．５質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 4>
Example 1 except that the aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of diethanolamine was used instead of 0.4 parts by mass of triethylenetetramine. A conductive composition was obtained according to the procedure described above.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例５＞
　水溶液１（２６質量部）の代わりに上記水溶液３（２６質量部）を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 5>
A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 3 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass).
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例６＞
　水溶液１（２６質量部）の代わりに上記水溶液４（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにコハク酸０．４質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 6>
Example 1 except that the above aqueous solution 4 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of succinic acid was used instead of 0.4 parts by mass of triethylenetetramine. A conductive composition was obtained according to the same procedure.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例７＞
　水溶液１（２６質量部）の代わりに上記水溶液５（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりに１，４－ブタンジオールジグリシジルエーテル０．５質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 7>
The aqueous solution 5 (26 parts by mass) was used in place of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of 1,4-butanediol diglycidyl ether was used in place of 0.4 parts by mass of triethylenetetramine. Except for the above, a conductive composition was obtained according to the same procedure as in Example 1.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例８＞
　水溶液１（２６質量部）の代わりに上記水溶液６（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにビスヒドロキシメチル尿素０．４質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 8>
Example except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of bishydroxymethylurea was used instead of 0.4 parts by mass of triethylenetetramine. According to the same procedure as in No. 1, a conductive composition was obtained.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例９＞
　水溶液１（２６質量部）の代わりに上記水溶液６（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにジエタノールアミン０．４質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 9>
Example 1 except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of diethanolamine was used instead of 0.4 parts by mass of triethylenetetramine. A conductive composition was obtained according to the procedure described above.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例１０＞
　水溶液１（２６質量部）の代わりに上記水溶液７（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにＶＡ－０８０（和光純薬工業社製）０．１質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 10>
The above aqueous solution 7 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.1 part by mass of VA-080 (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 0.4 parts by mass of triethylenetetramine. A conductive composition was obtained according to the same procedure as in Example 1 except that it was used.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例１１＞
　水溶液１（２６質量部）の代わりに上記水溶液８（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりに１，４－ブタンジオールジグリシジルエーテル０．５質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 11>
The aqueous solution 8 (26 parts by mass) was used in place of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of 1,4-butanediol diglycidyl ether was used in place of 0.4 parts by mass of triethylenetetramine. Except for the above, a conductive composition was obtained according to the same procedure as in Example 1.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例１２＞
　水溶液１（２６質量部）の代わりに上記水溶液８（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにビスヒドロキシメチル尿素０．５質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 12>
Example except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of bishydroxymethylurea was used instead of 0.4 parts by mass of triethylenetetramine. According to the same procedure as in No. 1, a conductive composition was obtained.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例１３＞
　水溶液１（２６質量部）の代わりに上記水溶液８（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにジビニルスルホン０．５質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 13>
Example 1 except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of divinylsulfone was used instead of 0.4 parts by mass of triethylenetetramine. A conductive composition was obtained according to the same procedure.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜実施例１４＞
　水溶液１（２６質量部）の代わりに上記水溶液８（２６質量部）を使用し、トリエチレンテトラミン０．４質量部に代わりにグリオキサール０．５質量部を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Example 14>
Example 1 except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and that 0.5 parts by mass of glyoxal was used instead of 0.4 parts by mass of triethylenetetramine. A conductive composition was obtained according to the procedure described above.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例１＞
　硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Comparative Example 1>
A conductive composition was obtained according to the same procedure as in Example 1 except that no curing agent was added.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例２＞
　水溶液１（２６質量部）の代わりに上記水溶液２（２６質量部）を使用し、硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Comparative example 2>
A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例３＞
　水溶液１（２６質量部）の代わりに上記水溶液３（２６質量部）を使用し、硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Comparative Example 3>
A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 3 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例４＞
　水溶液１（２６質量部）の代わりに上記水溶液４（２６質量部）を使用し、硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Comparative example 4>
A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 4 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例５＞
　水溶液１（２６質量部）の代わりに上記水溶液５（２６質量部）を使用し、硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Comparative Example 5>
A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 5 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例６＞
　水溶液１（２６質量部）の代わりに上記水溶液６（２６質量部）を使用し、硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Comparative Example 6>
A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例７＞
　水溶液１（２６質量部）の代わりに上記水溶液７（２６質量部）を使用し、硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜（銅膜）を得た。 <Comparative Example 7>
A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 7 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added.
Moreover, the electrically conductive composition (copper film) was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
＜比較例８＞
　水溶液１（２６質量部）の代わりに上記水溶液８（２６質量部）を使用し、硬化剤を加えなかった以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って導電膜を得ようとしたところ、膜が飛散し、導電膜が得られず、後述する体積低効率および密着性を評価することができなかった。 <Comparative Example 8>
A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass) and no curing agent was added.
Moreover, when it was going to obtain an electrically conductive film according to the procedure similar to Example 1 using the obtained electrically conductive composition, a film | membrane scattered, an electrically conductive film was not obtained, but the volume low efficiency and adhesiveness which are mentioned later Could not be evaluated.
＜比較例９＞
　水溶液１（２６質量部）の代わりに上記エタノール溶液９（２６質量部）を使用した以外は、実施例１と同様の手順に従って導電性組成物を得た。
　また、得られた導電性組成物を用いて、実施例１と同様の手順に従って膜を得た。
　なお、得られた膜について後述する体積抵抗率を測定しようとしたところ、体積抵抗率が測定上限値を超えたため体積抵抗率を測定できなかった。 <Comparative Example 9>
A conductive composition was obtained according to the same procedure as in Example 1 except that the ethanol solution 9 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass).
Moreover, the film | membrane was obtained according to the procedure similar to Example 1 using the obtained electroconductive composition.
In addition, when it was going to measure the volume resistivity mentioned later about the obtained film | membrane, since the volume resistivity exceeded the measurement upper limit, volume resistivity could not be measured.
　各実施例で使用した硬化剤の構造を以下にまとめて示す。 The structure of the curing agent used in each example is summarized below.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
＜体積抵抗率＞
　得られた導電膜について、四探針法抵抗率計を用いて体積抵抗率を測定した。測定結果を第１表に示す。体積抵抗率が小さいほど導電性に優れる。実用上、２０×１０-5Ω・ｃｍ以下であることが好ましい。 <Volume resistivity>
About the obtained electrically conductive film, the volume resistivity was measured using the four-probe method resistivity meter. The measurement results are shown in Table 1. The smaller the volume resistivity, the better the conductivity. Practically, it is preferably 20 × 10 −5 Ω · cm or less.
＜密着性＞
　得られた導電膜の５ｍｍ×５ｍｍの中にカッターで切り込みを入れて２５個の碁盤目（１ｍｍ角）を作製した。そして、セロテープ（登録商標）を貼り付けてから剥離し、剥離せずに残った碁盤目の個数を調べた。
　その結果、残った碁盤目の個数が、２０～２５個のものを「ＡＡ」と評価し、１５～１９個のものを「Ａ」と評価し、１０～１４個のものを「Ｂ」と評価し、１～９個のものを「Ｃ」と評価し、０個のもの（完全に剥がれたもの）を「Ｄ」と評価した。
　結果を第１表に示す。 <Adhesion>
The obtained conductive film was cut into 5 mm × 5 mm with a cutter to produce 25 grids (1 mm square). Then, cellotape (registered trademark) was applied and peeled off, and the number of grids remaining without peeling was examined.
As a result, the number of remaining grids of 20-25 is evaluated as “AA”, 15-19 is evaluated as “A”, and 10-14 is evaluated as “B”. 1 to 9 were evaluated as “C”, and 0 (completely peeled) were evaluated as “D”.
The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
　第１表から分かるように、上記式（１）で表される繰り返し単位および上記式（２）で表される繰り返し単位を含むポリマーと上記式（２）中のＢで表される架橋性基と反応する硬化剤とを含有する本願実施例１～１４の組成物から得られた導電膜は、いずれも優れた密着性および導電性を示した。なかでも、上記式（１）中のＡがアミド基を含有する有機基である実施例１～６および８～１０はより優れた密着性を示した。そのなかでも、上記式（２）中のＢが上記式（Ｂ－７）（脂環式エポキシ基）であり、かつ、硬化剤がアミンである実施例１は、特に優れた密着性および導電性を示した。
　また、上記式（２）中のＢが上記式（Ｂ－１）（エポキシ基）または上記式（Ｂ－７）（脂環式エポキシ基）である実施例１、２および５の対比から、硬化剤としてアミンを使用する実施例１および５の方がより優れた密着性および導電性を示した。
　一方、上記式（１）で表される繰り返し単位および上記式（２）で表される繰り返し単位を含むポリマーを含有するが、上記式（２）中のＢで表される架橋性基と反応する硬化剤を含有しない場合、膜が飛散して導電膜が得られない（比較例８）か、導電膜が得られても密着性が不十分となる（比較例１～７）という結果になった。
　また、上記式（１）で表される繰り返し単位および上記式（２）で表される繰り返し単位を含むポリマーを含有しない（上記式（１）で表される繰り返し単位を含まず上記式（２）で表される繰り返し単位を含むポリマーを含有する）場合には、たとえ上記式（２）中のＢで表される架橋性基と反応する硬化剤を含有しても、得られる膜の密着性および導電性は不十分となった（比較例９）。 As can be seen from Table 1, the polymer containing the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) and the crosslinkable group represented by B in the above formula (2) Each of the conductive films obtained from the compositions of Examples 1 to 14 containing a curing agent that reacts with the polymer exhibited excellent adhesion and conductivity. Among them, Examples 1 to 6 and 8 to 10 in which A in the formula (1) is an organic group containing an amide group showed better adhesion. Among them, Example 1 in which B in the above formula (2) is the above formula (B-7) (alicyclic epoxy group) and the curing agent is an amine is particularly excellent in adhesion and conductivity. Showed sex.
Further, from the comparison of Examples 1, 2 and 5 in which B in the above formula (2) is the above formula (B-1) (epoxy group) or the above formula (B-7) (alicyclic epoxy group), Examples 1 and 5 using an amine as a curing agent showed better adhesion and conductivity.
On the other hand, the polymer contains a repeating unit represented by the above formula (1) and a repeating unit represented by the above formula (2), but reacts with the crosslinkable group represented by B in the above formula (2). When the curing agent is not contained, the film is scattered and a conductive film cannot be obtained (Comparative Example 8), or even when the conductive film is obtained, the adhesion is insufficient (Comparative Examples 1 to 7). became.
Further, it does not contain a polymer containing the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) (not containing the repeating unit represented by the above formula (1) and the above formula (2). In the case of containing a polymer containing a repeating unit represented by formula (2), even if a curing agent that reacts with the crosslinkable group represented by B in the above formula (2) is contained, adhesion of the resulting film And conductivity were insufficient (Comparative Example 9).

Claims (7)

  1. 　酸化銅粒子および／または銅粒子と、下記式（１）で表される繰り返し単位および下記式（２）で表される繰り返し単位を含むポリマーと、下記式（２）中のＢで表される架橋性基と反応する硬化剤とを含有する、導電膜形成用組成物。
    Figure JPOXMLDOC01-appb-C000001
    （式（１）中、Ｒ1は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｌ1は、単結合または２価の有機基を表す。Ａは還元性基であり、アミド基を含有する有機基、または、ヒドロキシ基を表す。
    　式（２）中、Ｒ2は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｌ2は、単結合または２価の有機基を表す。Ｂは架橋性基であり、下記式（Ｂ－１）～（Ｂ－９）からなる群より選択される基を表す。）
    Figure JPOXMLDOC01-appb-C000002
    （式（Ｂ－１）～（Ｂ－９）中、Ｒbは、水素原子、または、ヘテロ原子を有していてもよい炭化水素基を表す。複数あるＲbはそれぞれ同一であっても異なっていてもよい。ｍは０～１１の整数を表す。ｎは０～２の整数を表す。＊は結合位置を表す。）     Represented by copper oxide particles and / or copper particles, a polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and B in the following formula (2) The composition for electrically conductive film containing the hardening | curing agent which reacts with a crosslinkable group.
    Figure JPOXMLDOC01-appb-C000001
    (In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. L 1 represents a single bond or a divalent organic group. A represents a reducing group, an amide An organic group containing a group or a hydroxy group is represented.
    In formula (2), R 2 represents a hydrogen atom or a substituted or unsubstituted alkyl group. L 2 represents a single bond or a divalent organic group. B is a crosslinkable group and represents a group selected from the group consisting of the following formulas (B-1) to (B-9). )
    Figure JPOXMLDOC01-appb-C000002
    (In the formula (B-1) ~ (B -9), R b is a hydrogen atom, or, also respectively. Plurality of R b representing a hydrocarbon group which may have a hetero atom either the same (M represents an integer of 0 to 11. n represents an integer of 0 to 2. * represents a bonding position.)
  2. 　前記ポリマーが、下記式（３）で表される繰り返し単位および下記式（２）で表される繰り返し単位を含むポリマー、下記式（４）で表される繰り返し単位および下記式（５）で表される繰り返し単位を含むポリマー、または、下記式（６）で表される繰り返し単位を含むポリマーである、請求項１に記載の導電膜形成用組成物。
    Figure JPOXMLDOC01-appb-C000003
    （式（３）中、Ｒ3は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｒ31は、水素原子、または、ヘテロ原子を有していてもよい炭化水素基を表す。複数あるＲ31はそれぞれ同一であっても異なっていてもよい。
    　式（２）中、Ｒ2は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｌ2は、単結合または２価の有機基を表す。Ｂは架橋性基であり、前記式（Ｂ－１）～（Ｂ－９）からなる群より選択される基を表す。）
    Figure JPOXMLDOC01-appb-C000004
    （式（４）および（５）中、Ｒ4およびＲ5は、それぞれ独立して、水素原子、または、置換若しくは無置換のアルキル基を表す。）
    Figure JPOXMLDOC01-appb-C000005
    （式（６）中、Ｒ6は、水素原子、または、置換若しくは無置換のアルキル基を表す。Ｌ6は、単結合または２価の有機基を表す。Ｒ61は、２価の脂肪族炭化水素基を表す。ｐは１～１００の整数を表す。）     The polymer includes a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (4), and the following formula (5). The composition for electrically conductive film formation of Claim 1 which is a polymer containing the repeating unit represented by following formula (6) or the polymer containing the repeating unit.
    Figure JPOXMLDOC01-appb-C000003
    (In Formula (3), R 3 represents a hydrogen atom or a substituted or unsubstituted alkyl group. R 31 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. A plurality of R 31 may be the same or different.
    In formula (2), R 2 represents a hydrogen atom or a substituted or unsubstituted alkyl group. L 2 represents a single bond or a divalent organic group. B is a crosslinkable group and represents a group selected from the group consisting of the formulas (B-1) to (B-9). )
    Figure JPOXMLDOC01-appb-C000004
    (In formulas (4) and (5), R 4 and R 5 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.)
    Figure JPOXMLDOC01-appb-C000005
    (In the formula (6), R 6 represents a hydrogen atom or a substituted or unsubstituted alkyl group. L 6 represents a single bond or a divalent organic group. R 61 represents a divalent aliphatic group. Represents a hydrocarbon group, and p represents an integer of 1 to 100.)
  3. 　前記ポリマーが、前記式（３）で表される繰り返し単位および前記式（２）で表される繰り返し単位を含むポリマーである、請求項２に記載の導電膜形成用組成物。 The composition for electrically conductive film formation of Claim 2 whose said polymer is a polymer containing the repeating unit represented by the said repeating unit represented by the said Formula (3), and the said Formula (2).
  4. 　前記式（２）中のＢが、前記式（Ｂ－１）または（Ｂ－７）で表される基であり、前記硬化剤が、アミンまたはアルコールである、請求項１～３のいずれか１項に記載の導電膜形成用組成物。 The B in the formula (2) is a group represented by the formula (B-1) or (B-7), and the curing agent is an amine or an alcohol. The composition for electrically conductive film formation of 1 item | term.
  5. 　前記式（２）中のＢが、前記式（Ｂ－２）で表される基であり、前記硬化剤が、エポキシド、アルデヒド、または、下記式（１３）で表される部分構造を２つ以上有する化合物である、請求項１～３のいずれか１項に記載の導電膜形成用組成物。
    Figure JPOXMLDOC01-appb-C000006
    （式（１３）中、Ｒ131は、水素原子、または、置換若しくは無置換のアルキル基を表す。）     B in the formula (2) is a group represented by the formula (B-2), and the curing agent has two partial structures represented by epoxide, aldehyde, or the following formula (13). The composition for forming a conductive film according to any one of claims 1 to 3, which is a compound having the above.
    Figure JPOXMLDOC01-appb-C000006
    (In formula (13), R 131 represents a hydrogen atom or a substituted or unsubstituted alkyl group.)
  6. 　請求項１～５のいずれか１項に記載の導電膜形成用組成物を基材上に付与して、前記基材上に組成物層を形成し、その後、前記組成物層に対して加熱処理を施して、塗膜を形成する塗膜形成工程と、
    　前記塗膜に対して光照射処理を行い、前記酸化銅粒子および／または銅粒子を還元して、導電膜を形成する還元工程とを備える、導電膜の製造方法。     A composition for forming a conductive film according to any one of claims 1 to 5 is applied onto a substrate to form a composition layer on the substrate, and then heated to the composition layer. Applying a treatment to form a coating film,
    A reduction process which performs light irradiation processing to the coating film, reduces the copper oxide particles and / or copper particles, and forms a conductive film.
  7. 　前記光照射処理が、パルス光照射処理である、請求項６に記載の導電膜の製造方法。 The method for producing a conductive film according to claim 6, wherein the light irradiation process is a pulsed light irradiation process.
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