JP2014191913A - Method for producing conductive film and conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a conductive film, capable of obtaining a conductive film having excellent ejection stability, good conductivity, and good film strength.SOLUTION: The method for producing a conductive film comprises: a coating film forming step of applying a conductive film forming composition containing copper oxide particles (A), an organic binder (B), and resin particles (C) having a glass transition temperature of 50°C or lower onto a substrate by using an inkjet method to form a coating film; and a reduction step of subjecting the coating film to pulse light irradiation treatment to reduce the copper oxide particles (A), thereby forming a conductive film containing copper.

Description

  The present invention relates to a method for manufacturing a conductive film and a conductive film.

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 such as an ink jet method and sintering by heat treatment is known.
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, when a thermoplastic resin base material is used as the base material, the base material melts, and there is a problem that it is difficult to obtain a uniform conductive film.

  Under these circumstances, Patent Document 1 discloses that a pulsed light is used for sintering to form a copper metal ink film by sintering the copper oxide ink on the substrate without overheating the thermoplastic resin substrate. Is disclosed (paragraph 0013, Example 1 etc.).

Special table 2010-528428 gazette

As described above, conventionally, a technique of forming a coating film by applying a composition containing copper oxide particles (copper oxide ink) onto a substrate and irradiating the coating film with pulsed light to obtain a conductive film It has been known.
For example, Patent Document 1 (for example, Example 1) describes blending a polymer (organic binder) such as polyvinyl pyrrolidone or polyethylene glycol with copper oxide ink.

Such an organic binder is used from the viewpoints of coating properties and film-forming properties. However, since it does not have conductivity, it is an unnecessary component from the viewpoint of conductivity in the obtained conductive film. Therefore, the organic binder is desirably decomposed and volatilized during sintering by pulse light irradiation.
However, when the organic binder volatilizes, a void is generated in the coating film, and the conductivity of the obtained conductive film may be lowered.
Moreover, when the pulsed light irradiation is performed with a flash lamp, the coating film becomes very high temperature, so that the organic binder volatilizes explosively, the generation of voids increases, and the conductivity of the obtained conductive film is remarkably high. May decrease.

Ink jet method for ejecting ink from nozzles is an effective means for applying copper oxide ink, but the organic binder may cause nozzle clogging, which may reduce ejection stability.
On the other hand, the organic binder is an effective component from the viewpoint of the film strength of the conductive film formed by pulsed light irradiation, and it is required to satisfy both ejection stability and film strength.

  The present invention has been made in view of the above points, and after applying a composition for forming a conductive film containing copper oxide particles and an organic binder by an inkjet method to form a coating film, a pulsed light irradiation treatment was performed. It is an object of the present invention to provide a method for producing a conductive film, which is a method for producing a conductive film, wherein a conductive film having excellent ejection stability and good conductivity and film strength is obtained. .

  As a result of intensive studies to achieve the above object, the present inventor has excellent discharge stability and good conductivity and film strength by blending specific resin particles with the composition for forming a conductive film. The present invention was completed by finding that a conductive film can be obtained.

That is, the present invention provides the following (1) to (8).
(1) A conductive film-forming composition containing copper oxide particles (A), an organic binder (B), and resin particles (C) having a glass transition temperature of 50 ° C. or less on a base material using an inkjet method. A coating film forming process for forming a coating film, and a reduction process for performing a pulsed light irradiation process on the coating film to reduce the copper oxide particles (A) to form a conductive film containing copper. And a method for producing a conductive film.
(2) The manufacturing method of the electrically conductive film as described in (1) whose glass transition temperature of the resin particle (C) is 0 degreeC or more.
(3) The manufacturing method of the electrically conductive film as described in (1) or (2) whose average particle diameter of resin particle (C) is 10-100 nm.
(4) The content of the resin particles (C) in the composition for forming a conductive film is 30 to 60% by mass with respect to the total content of the organic binder (B) and the resin particles (C). (3) The manufacturing method of the electrically conductive film in any one of.
(5) The manufacturing method of the electrically conductive film in any one of (1)-(4) whose resin particle (C) is a self-dispersing polymer.
(6) The method for producing a conductive film according to any one of (1) to (5), wherein the composition for forming a conductive film further contains a copper complex (D).
(7) The manufacturing method of the electrically conductive film in any one of (1)-(6) whose pulsed light irradiation process is a pulsed light irradiation process by a flash lamp.
(8) The electrically conductive film obtained by the manufacturing method of the electrically conductive film in any one of (1)-(7).

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of an electrically conductive film which is excellent in discharge stability and can obtain the electrically conductive and favorable film | membrane intensity | strength can be provided.

Initially, the characteristic point of the manufacturing method of the electrically conductive film of this invention is demonstrated.
In the present invention, since the resin particles (C) are used in combination with the organic binder (B) as the binder of the copper oxide particles (A), the ink jet nozzle clogging due to the organic binder (B) is reduced, and the discharge stability is reduced. Will improve.
In addition, by using resin particles (C) having a glass transition temperature of 50 ° C. or lower, the conductive film obtained by causing volatilization of organic substances to occur in a certain shape during sintering by pulse light irradiation. In this case, it is considered that a copper network is easily formed and the conductivity is excellent and the film strength is also improved.
Below, the manufacturing method of the electrically conductive film of this invention is explained in full detail.

The manufacturing method of the electrically conductive film of this invention is equipped with two processes, (1) coating-film formation process and (2) reduction process. Moreover, it is preferable that the manufacturing method of the electrically conductive film of this invention is further equipped with a drying process between a process (1) and a process (2) so that it may mention later.
Hereinafter, each process is explained in full detail.

[Step (1): Coating film forming step]
Step (1) is a step of forming a coating film by applying a specific composition for forming a conductive film on a substrate using an inkjet method. First, the materials (base material, conductive film forming composition) used in this step will be described in detail.

<Resin substrate>
In the step (2) described later, the substrate used in the present invention is preferably a thermoplastic resin substrate because the substrate is softened and fused with the conductive film to improve adhesion. .
If the thermoplastic resin base material used by this invention is a base material comprised by a thermoplastic resin, it will not specifically limit.
Examples of the thermoplastic resin constituting the thermoplastic resin substrate include polyolefin resins such as polyethylene, polypropylene, and polybutylene; methacrylic resins such as polymethyl methacrylate; polystyrene resins such as polystyrene, ABS, and AS; polyethylene terephthalate ( PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate, polyethylene naphthalate (PEN), poly 1,4-cyclohexyldimethylene terephthalate (PCT) and other polyester resins; polycaproamide (nylon 6), polyhexa Methylene adipamide (nylon 66), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydodecanamide (nylon 12), Rihexamethylene terephthalamide (nylon 6T), polyhexanemethylene isophthalamide (nylon 6I), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalate Polyamide resin selected from nylon resin and nylon copolymer resin such as amide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I); polyvinyl chloride resin; Oxymethylene (POM); Polycarbonate (PC) resin; Polyphenylene sulfide (PPS) resin; Modified polyphenylene ether (PPE) resin; Polyetherimide (PEI) resin; Polysulfone (P F) resin; polyethersulfone (PES) resin; polyketone resin; polyethernitrile (PEN) resin; polyetherketone (PEK) resin; polyetheretherketone (PEEK) resin; polyetherketoneketone (PEKK) resin; (PI) resin; polyamideimide (PAI) resin; fluororesin; modified resin obtained by modifying these resins or a mixture of these resins;

The glass transition temperature (Tg) of the thermoplastic resin constituting the thermoplastic resin substrate is not particularly limited, but is preferably 160 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 100 ° C. or lower. The lower limit of the glass transition temperature is not particularly limited, but is preferably 50 ° C. or higher.
Here, the glass transition temperature refers to a glass transition temperature measured by DSC (differential scanning calorimetry).

  The thickness of the base material used for this invention is not specifically limited, For example, 1-100 micrometers is mentioned.

<Composition for forming conductive film>
The conductive film-forming composition used in the present invention (hereinafter also referred to as the conductive film-forming composition of the present invention) has a copper oxide particle (A), an organic binder (B), and a glass transition temperature of 50 ° C. or lower. Contains certain resin particles (C).
Moreover, it is preferable that the composition for electrically conductive film formation of this invention contains a copper complex (D) from viewpoints, such as electroconductivity, and also contains a solvent (E) substantially from viewpoints, such as printability. Is preferred.
Hereinafter, each component of the composition for electrically conductive film formation of this invention is explained in full detail.

(Copper oxide particles (A))
If the copper oxide particle (A) contained in the composition for electrically conductive film formation of this invention is a particulate copper oxide, it will not specifically limit.
Note that the particulate form means a small granular form, and specific examples thereof include a spherical shape and an ellipsoidal shape. It is not necessary to be a perfect sphere or ellipsoid, and a part may be distorted.
The “copper oxide” in the present invention is a compound substantially free of unoxidized copper. Although not containing copper substantially, it means that content of copper is 1 mass% or less with respect to copper oxide particles. The copper content relative to the copper oxide particles is measured by XRD.

  As the copper oxide particles (A), copper oxide (I) particles or copper oxide (II) particles are preferable, available at low cost, and because the conductivity of the resulting conductive film becomes better, Copper (II) oxide particles are more preferred.

The average particle diameter of the copper oxide particles (A) is not particularly limited, but is preferably 200 nm or less, and more preferably 100 nm or less. Although a minimum is not specifically limited, 1 nm or more is preferable.
When the average particle diameter is 1 nm or more, the activity on the particle surface does not become too high, and it does not dissolve in the composition for forming a conductive film of the present invention, and is excellent in handleability. Further, when the average particle diameter is 200 nm or less, it becomes easy to form a pattern such as wiring by a printing method using the composition for forming a conductive film of the present invention as an ink composition for inkjet, and the conductive film of the present invention. When making the composition for formation into a conductor, reduction to metallic copper is sufficient, and the conductivity of the resulting conductive film becomes better, which is preferable.
In addition, the average particle diameter of a copper oxide particle (A) points out an average secondary 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, CuO manufactured by CI Kasei Co., Ltd. and the like can be preferably used.

  The content of the copper oxide particles (A) with respect to the total amount of the conductive film-forming composition of the present invention is preferably 5 to 50% by mass and more preferably 10 to 30% by mass because the conductivity of the obtained conductive film becomes better. % Is more preferable.

(Organic binder (B))
The organic binder (B) acts as a binder for the copper oxide particles (A), imparts toughness to the resulting conductive film, and enhances the film strength.
As the organic binder (B), for example, an acrylic polymer (for example, a polymer or copolymer of an acrylic monomer such as (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylamide, (meth) acrylonitrile) ), Polyvinylpyrrolidone (PVP), polyethyleneimine (PEI), polyvinyl alcohol (PVA), polyvinyl acetal, polyethylene glycol (PEG), polyester, polyamide, polyimide, etc., and these may be used alone. Two or more kinds may be used in combination.

The weight average molecular weight of an organic binder (B) is not specifically limited, For example, about 5,000-500,000 is mentioned, 10,000-220,000 are preferable and 12,000-150,000 are more preferable.
The weight average molecular weight is a polystyrene equivalent value obtained by the GPC method (solvent: N-methylpyrrolidone).

  In the composition for forming a conductive film of the present invention, the content of the organic binder (B) is not particularly limited, but is preferably 0.5 to 10% by mass with respect to the content of the copper oxide particles (A). -5 mass% is more preferable.

(Resin particles (C))
The resin particles (C) also act as a binder for the copper oxide particles (A) as with the organic binder (B). However, the composition for forming a conductive film of the present invention is used in combination with the organic binder (B). By containing the resin particles (C) having a glass transition temperature of 50 ° C. or lower, the ejection stability by the ink jet method is improved, and the conductivity and film strength of the obtained conductive film are improved.

In the present invention, the glass transition temperature of the resin particles (C) is 50 ° C. or lower, but is preferably 0 ° C. or higher, more preferably 10 to 45 ° C., because the film strength of the obtained conductive film is more excellent. More preferred is ˜45 ° C.
In addition, the measurement Tg obtained by actual measurement is applied to the glass transition temperature of the resin particles (C). Specifically, the measurement Tg means a value measured under normal measurement conditions using a differential scanning calorimeter (DSC) EXSTAR 6220 manufactured by SII Nano Technology.

The average particle diameter of the resin particles (C) is preferably 10 nm to 1 μm (1000 nm) in terms of volume average particle diameter, more preferably 10 to 200 nm, and further preferably 10 to 100 nm for the reason described below. That is, if the average particle diameter exceeds 100 nm, the conductivity may decrease, and if it is less than 10 nm, the film strength may decrease, but if the average particle diameter is 10 to 100 nm, the resulting conductive film Excellent conductivity and film strength.
The particle size distribution of the resin particles (C) is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution. Two or more kinds of resin particles having a monodispersed particle size distribution may be mixed.
The average particle size and particle size distribution of such resin particles (C) are measured by a dynamic light scattering method using a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). Is required.

  Further, the difference in average particle diameter between the resin particles (C) and the copper oxide particles (A) is preferably 50 nm or less, and more preferably 40 nm or less. If the resin particles (C) are too large, the conductivity may be deteriorated. If the copper oxide particles (A) are too large, the film strength may be deteriorated, but the difference between the average particle diameters is within the above range. If it exists, the electroconductivity and film | membrane intensity | strength of the electrically conductive film obtained are more excellent.

  The weight average molecular weight (Mw) of the resin particles (C) is not particularly limited, is preferably 10,000 to 200,000, and more preferably 100,000 to 200,000. The weight average molecular weight is measured by gel permeation chromatography (GPC).

Although content of the resin particle (C) with respect to the composition for electrically conductive film formation of this invention is not specifically limited, 0.5-20 mass% is preferable, 3-20 mass% is more preferable, From 5-15 mass% preferable.
Further, the content of the resin particles (C) with respect to the total content of the organic binder (B) and the resin particles (C) is preferably 10 to 80% by mass, and more preferably 30 to 60% by mass for the reason described below. . That is, when the content exceeds 60% by mass, the film strength may be reduced, and when it is less than 30% by mass, the ejection stability may be inferior. And the film strength is more excellent.

Such resin particles (C) are not particularly limited as long as the glass transition temperature is 50 ° C. or lower, and may be used alone or in combination of two or more.
For example, as the resin particles (C), latex in which a particulate resin is dispersed in an aqueous medium can be used. Specific examples of this resin include acrylic resins, vinyl acetate resins, styrene-butadiene resins, Acrylonitrile-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin, benzoguanamine resin, phenol resin, silicone resin, epoxy resin, urethane resin, Examples thereof include paraffinic resins and fluorine resins.
Of these, acrylic resins, styrene-butadiene resins, acrylonitrile-butadiene resins, acrylic-styrene resins, styrene resins, crosslinked acrylic resins, and crosslinked styrene resins are preferred.

The resin particles (C) are preferably self-dispersing polymer particles, more preferably self-dispersing polymer particles having a carboxy group, from the viewpoint of ejection stability.
Self-dispersing polymer particles (hereinafter, also referred to as “self-dispersing polymer particles”) are water-based in the absence of other surfactants due to functional groups (particularly acidic groups or salts thereof) possessed by the polymer itself. It means water-insoluble polymer particles which can be dispersed in a medium and do not contain a free emulsifier.

Here, the dispersed state refers to an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in an aqueous medium in a liquid state, and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in an aqueous medium in a solid state. It includes both states.
The dispersion state of the self-dispersing polymer particles refers to a solution in which 30 g of a water-insoluble polymer is dissolved in 70 g of an organic solvent (for example, methyl ethyl ketone), a neutralizing agent that can neutralize 100% of the salt-forming group of the water-insoluble polymer ( After mixing and stirring (device: stirring device with stirring blade, rotation speed 200 rpm, 30 minutes, 25 ° C.) It means a state in which even after removing the organic solvent from the mixed solution, it can be visually confirmed that the dispersed state exists stably at 25 ° C. for at least one week.
The water-insoluble polymer refers to a polymer having a dissolution amount of 10 g or less when the polymer is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C. The above dissolution amount is the dissolution amount when 100% neutralized with sodium hydroxide or acetic acid depending on the type of salt-forming group of the water-insoluble polymer.
Moreover, the aqueous medium is comprised including water, and may contain the hydrophilic organic solvent as needed. In the present invention, it is preferably composed of water and 0.2% by mass or less of a hydrophilic organic solvent with respect to water, and more preferably composed of water.

  Hereinafter, self-dispersing polymer particles will be described as a suitable example of the resin particles (C). However, the resin particles (C) in the present invention are not limited thereto, and the above-described latex and the like are preferably used. it can.

  From the viewpoint of self-dispersibility, the self-dispersing polymer particles include a hydrophilic constituent unit, a constituent unit derived from an aromatic group-containing monomer as a hydrophobic constituent unit, and / or a constituent unit derived from an alicyclic monomer. And a water-insoluble polymer.

The hydrophilic structural unit is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and may be derived from one type of hydrophilic group-containing monomer, or two or more types of hydrophilic groups. It may be derived from the contained monomer.
The hydrophilic group is not particularly limited and may be a dissociable group or a nonionic hydrophilic group, but is preferably a dissociable group, and more preferably an anionic dissociable group. Examples of the dissociable group include a carboxy group, a phosphoric acid group, and a sulfonic acid group, and among them, a carboxy group is preferable.
The hydrophilic group-containing monomer is preferably a dissociable group-containing monomer from the viewpoint of self-dispersibility and the like, and is preferably a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond.
Examples of the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.
Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid. Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, and bis- (3-sulfopropyl) -itaconate.
Examples of unsaturated phosphoric acid monomers include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyl Examples include roxyethyl phosphate. The dissociable group-containing monomer is preferably an unsaturated carboxylic acid monomer, and more preferably acrylic acid or methacrylic acid, from the viewpoints of dispersion stability and ejection stability.

Examples of the monomer having a nonionic hydrophilic group include 2-methoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-methoxyethoxy) ethyl methacrylate, ethoxytriethylene glycol methacrylate, and methoxy. Ethylenically unsaturated monomers containing (poly) ethyleneoxy groups or polypropyleneoxy groups such as polyethylene glycol (molecular weight 200-1000) monomethacrylate, polyethylene glycol (molecular weight 200-1000) monomethacrylate; hydroxymethyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate Rate, ethylenically unsaturated monomer having a hydroxy group such as hydroxy hexyl (meth) acrylate; and the like.
In addition, as a monomer having a nonionic hydrophilic group, the ethylenically unsaturated monomer having a terminal alkyl ether is more stable than the ethylenically unsaturated monomer having a terminal hydroxy group, and the content of the water-soluble component is increased. From the viewpoint of

As the hydrophilic structural unit, an embodiment containing only a hydrophilic unit having an anionic dissociable group, and a hydrophilic structural unit having an anionic dissociative group and a hydrophilic having a nonionic hydrophilic group Any of the embodiments containing both sex structural units is preferred.
The content of the hydrophilic structural unit in the self-dispersing polymer is preferably 25% by mass or less, and more preferably 1 to 25% by mass.
The content of the structural unit having an anionic dissociable group in the self-dispersing polymer is preferably in a range where the acid value is in a suitable range described later. Moreover, 0-25 mass% is preferable from a viewpoint of discharge stability, and, as for content of the structural unit which has a nonionic hydrophilic group, 0-20 mass% is more preferable.

  The self-dispersing polymer particles preferably include a polymer having a carboxy group, more preferably include a polymer having a carboxy group and an acid value of 25 to 100 mgKOH / g, and more preferably 25 to 80 mgKOH / g. preferable.

The aromatic group-containing monomer is not particularly limited as long as it is a compound containing an aromatic group and a polymerizable group. The aromatic group may be a group derived from an aromatic hydrocarbon or a group derived from an aromatic heterocycle, but an aromatic group derived from an aromatic hydrocarbon is preferred.
The polymerizable group may be a polycondensable polymerizable group or an addition polymerizable polymerizable group, but an addition polymerizable polymerizable group is preferred, and an ethylenically unsaturated bond. The group containing is more preferable.
The aromatic group-containing monomer is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond. The said aromatic group containing monomer may be used individually by 1 type, and may use 2 or more types together.
Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and styrene-based monomers. Among them, the hydrophilicity and hydrophobicity of the polymer chain From the viewpoint of balance and the like, an aromatic group-containing (meth) acrylate monomer is preferable, and phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are more preferable.
The self-dispersing polymer particles include a structural unit derived from the aromatic group-containing (meth) acrylate monomer, and the content thereof is preferably 10 to 95% by mass, more preferably 15 to 90% by mass, and 15 to 80%. More preferred is mass%.

The alicyclic monomer is not particularly limited as long as it is a compound containing an alicyclic hydrocarbon group and a polymerizable group, but alicyclic (meth) acrylate is preferred from the viewpoint of dispersion stability.
The alicyclic (meth) acrylate includes a structural site derived from (meth) acrylic acid and a structural site derived from alcohol, and the structural site derived from alcohol is unsubstituted or substituted. It has a structure containing at least one hydrocarbon group. In addition, the said alicyclic hydrocarbon group may be couple | bonded with the structural site | part derived from alcohol through the coupling group, even if it is the structural site | part derived from alcohol itself.
The alicyclic hydrocarbon group is not particularly limited as long as it contains a cyclic non-aromatic hydrocarbon group. For example, a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or higher ring Specific examples thereof include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a cycloalkenyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclo group. A pentenyl group, an adamantyl group, a decahydronaphthalenyl group, a perhydrofluorenyl group, and the like, and those having 5 to 20 carbon atoms are preferable, and may further have a substituent to form a condensed ring. It may be.
Examples of the linking group that connects the alicyclic hydrocarbon group and the structural portion derived from the alcohol include, for example, an alkyl group, an alkenyl group, an alkylene group, an aralkyl group, an alkoxy group, a mono- or mono-carbon group having 1 to 20 carbon atoms. Oligoethylene glycol group, mono- or oligopropylene glycol group and the like can be mentioned.
Although the specific example of the said alicyclic (meth) acrylate is shown below, it is not limited to these, Moreover, these may be used individually by 1 type and may use 2 or more types together. Monocyclic (meth) acrylates include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, and cyclononyl. Examples thereof include cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in the cycloalkyl group such as (meth) acrylate. Examples of the bicyclic (meth) acrylate include isobornyl (meth) acrylate and norbornyl (meth) acrylate. Examples of the tricyclic (meth) acrylate include adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
As a content rate of the structural unit derived from the said alicyclic (meth) acrylate contained in the said self-dispersing polymer particle, 20-90 mass% is preferable, 40-90 mass% is more preferable, 50-80 mass% Is more preferable.

The self-dispersing polymer particles may further contain other structural units.
The monomer that forms the other structural unit (hereinafter, also referred to as “other copolymerizable monomer”) is not particularly limited, and examples thereof include alkyl group-containing monomers.
Examples of the alkyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, alkyl (meth) acrylates such as t-butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Ethylenically unsaturated monomers having a hydroxy group such as acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; Dialkylaminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate; N-hydroxyalkyl (meta) such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide and N-hydroxybutyl (meth) acrylamide ) Acrylamide; N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (n-, iso) butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl ( N-alkoxyalkyl (meth) acrylamides such as meth) acrylamide and N- (n-, iso) butoxyethyl (meth) acrylamide; and the like. These may be used alone or in combination of two or more. Do it .
Of these, (meth) acrylates containing a linear (straight or branched) alkyl group having 1 to 8 carbon atoms are preferred, more preferably 1 to 4 carbon atoms, methyl (meth) acrylate, ethyl ( More preferred is (meth) acrylate.
When the self-dispersing polymer particles contain other structural units, the content is preferably 10 to 80% by mass, and more preferably 15 to 75% by mass.

  The self-dispersing polymer may be a random copolymer in which each constituent unit is irregularly introduced, or may be a block copolymer that is regularly introduced.

The weight average molecular weight of the resin particles (C) is as described above, but the weight average molecular weight (Mw) of the self-dispersing polymer is preferably 3,000 to 200,000, more preferably 5,000 to 150,000. 10,000 to 100,000 are more preferable. At this time, the acid value is preferably 25 to 100, and more preferably 25 to 95.
The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (4.6 mm ID × 15 cm, Tosoh Corporation) as columns, and THF (tetrahydrofuran) as an eluent. Is used. As conditions, the sample concentration is 0.35 / min, the flow rate is 0.35 mL / min, the sample injection amount is 10 μL, the measurement temperature is 40 ° C., and an IR detector is used. Moreover, the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500 "," A-1000 ", and" n-propylbenzene ".

  The self-dispersing polymer is a structural unit derived from the aromatic group-containing (meth) acrylate monomer (preferably a structural unit derived from phenoxyethyl (meth) acrylate and / or a structural unit derived from benzyl (meth) acrylate). ) As a copolymerization ratio, it is preferable to contain 15 to 80% by mass of the total mass of the self-dispersing polymer particles.

  The method for producing the water-insoluble polymer is not particularly limited. For example, a method in which emulsion polymerization is performed in the presence of a polymerizable surfactant to covalently bond the surfactant and the water-insoluble polymer; the hydrophilic group And a method of copolymerizing a monomer mixture containing the monomer containing the aromatic group-containing monomer with a known polymerization method such as a solution polymerization method or a bulk polymerization method. The polymerization method includes a solution polymerization method. Preferably, a solution polymerization method using an organic solvent is more preferable.

The method for producing self-dispersing polymer particles preferably includes a step of synthesizing a polymer in an organic solvent, and a dispersion step of forming an aqueous dispersion in which at least a part of the carboxy group of the polymer is neutralized. .
The dispersion step preferably includes the following step (i) and step (ii).
Step (i): Step of stirring a mixture containing a polymer (water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium Step (ii): Step of removing the organic solvent from the mixture Step (i) ) Is preferably a step in which a polymer (water-insoluble polymer) is first dissolved in an organic solvent, and then a neutralizing agent and an aqueous medium are gradually added and mixed and stirred. There is no restriction | limiting in particular in the stirring method, Dispersers, such as a generally used mixing stirring apparatus and an ultrasonic disperser and a high-pressure homogenizer, can be used as needed. Preferable examples of the organic solvent include alcohol solvents such as isopropyl alcohol, ketone solvents such as methyl ethyl ketone, and ether solvents. For example, the organic solvents exemplified in paragraph 0059 of JP 2010-188661 A can be used. Moreover, as a neutralizing agent, the neutralizing agent illustrated by paragraphs 0060-0061 of Unexamined-Japanese-Patent No. 2010-188661 can be used, for example.
In the step (ii), the self-dispersing polymer is obtained by distilling the organic solvent from the dispersion (mixture) obtained in the step (i) by a conventional method such as distillation under reduced pressure and inversion into an aqueous system. An aqueous dispersion of particles is obtained. The organic solvent in the obtained aqueous dispersion is substantially removed, and the amount of the organic solvent is preferably 0.2% by mass or less, and more preferably 0.1% by mass or less.

(Copper complex (D))
The conductive film-forming composition of the present invention preferably further contains a copper complex (D) because the conductivity of the obtained conductive film is more excellent.
Examples of the copper complex (D) include copper acetylacetonate, quinoline copper, tetrakis (pyridine) copper / perchlorate, bis (ethylenediamine) copper, and the like. A coordinated copper formate complex (also simply referred to as “copper formate complex” in the present specification) is preferably used.

The copper formate complex can be synthesized by mixing copper formate and an amine. Copper formate and amine may be mixed as they are, or may be mixed as an aqueous solution, an organic solvent solution or an organic solvent suspension. The mixing of copper formate and amine is preferably performed using a suitable stirrer or mixer at a temperature of about 0 to 100 ° C. Moreover, it is preferable that copper formate and an amine add 2-4 equivalents of amine with respect to 1 equivalent of copper formate.
In the composition obtained by mixing copper formate and amine, a copper amine complex having a formate anion and an amine as a ligand as main components is formed. A preferred copper formate copper complex is that two molecules of formate anion and amine are coordinated to Cu ²⁺ which is a central metal. The two amines may be of the same type or different types.
Depending on the mixing conditions, the composition formed by mixing copper formate and amine may contain a solvent and unreacted amine in addition to the above copper amine complex. When mixing at an equivalent ratio of 1: 2, a composition consisting essentially of only the copper amine complex is obtained.

(Copper formate)
As said copper formate, anhydrous copper formate (II), copper (II) formate, dihydrate, copper formate (II), tetrahydrate, etc. can be used.

(Amine)
As said amine, a primary-tertiary amine can be used, and a tertiary amine is preferable from the viewpoint that the boiling point of the amine is low. Further, from the viewpoint of increasing the hydrophilicity of the obtained copper formate complex, an amine having one or more hydroxy groups in the molecule is preferable.
Examples of the tertiary amine include N, N-dimethylethanolamine, N, N-dimethyl-2-methoxyethylamine, N, N-dimethyl-2-ethoxyethylamine, N, N-dimethyl-2-n- Propoxyethylamine, N, N-dimethyl-2-i-propoxyethylamine, N, N-dimethyl-2-n-butoxyethylamine, N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine, N, N- Dimethyl-2- (2-methoxyethyloxy) ethylamine, N, N-dimethyl-2- (2-ethoxyethyloxy) ethylamine, N, N-dimethyl-1,1-dimethyl-2-hydroxyethylamine, N, N -Dimethyl-1,1-dimethyl-2-methoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-e Xylethylamine, N, N-dimethyl-3-hydroxypropylamine, N, N-dimethyl-3-methoxypropylamine, N, N-dimethyl-3-ethoxypropylamine, N, N-dimethyl-3-i-propoxy Examples thereof include propylamine, N, N-dimethyl-3-n-butoxypropylamine, and N, N-dimethyl-2-hydroxyethanolamine, and among them, N, N-dimethyl-2-hydroxyethanolamine is preferable.

  In the composition for forming a conductive film of the present invention, the content of the copper complex (D) is preferably 1 to 15% by mass and more preferably 3 to 10% by mass with respect to the content of the copper oxide particles (A).

(Solvent (E))
It is preferable that the composition for electrically conductive film formation of this invention contains a solvent (E) from viewpoints, such as printability. The solvent (E) functions as a dispersion medium for the copper oxide particles (A), the organic binder (B), and the resin particles (C).
Examples of the solvent (E) include water or a hydrophilic alcohol. Specific examples of the hydrophilic alcohol include monohydric alcohols such as methanol, ethanol, 2-propanol, and butyl alcohol; ethylene glycol, diethylene glycol, and triethylene. Polyhydric alcohols such as glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, glycerin, diglycerin, triglycerin, polyglycerin, trimethylolpropane; and the like, and these may be used alone or in two kinds You may use the above together.
The content of the solvent (E) is not particularly limited, but from the viewpoint of suppressing an increase in viscosity and being excellent in handleability, an amount such that the solid content of the composition for forming a conductive film of the present invention is 10 to 60% by mass is preferable. More preferably, the solid content is 20 to 50% by mass.

(Other ingredients)
The composition for forming a conductive film of the present invention may contain components other than the above components.
For example, the conductive film forming composition of the present invention may contain a surfactant. The type of the surfactant is not particularly limited, and examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, fluorosurfactants, and amphoteric surfactants. You may use, and may use 2 or more types together.

(Viscosity of conductive film forming composition)
It is preferable to adjust the viscosity of the composition for electrically conductive film formation of this invention to the viscosity suitable for inkjet discharge, for example, 1-50 cP is preferable and 1-40 cP is more preferable.

(Method for preparing composition for forming conductive film)
The method for preparing the composition for forming a conductive film of the present invention is not particularly limited, and a known method can be employed. For example, the above-described essential components and optional components can be treated with an ultrasonic method (for example, treatment with an ultrasonic homogenizer), a mixer. The composition for forming a conductive film of the present invention can be obtained by mixing by a known method such as a method, a three-roll method or a ball mill method.

(Inkjet method)
In the step (1), the method for applying (applying) the conductive film forming composition of the present invention on the substrate is performed by dropping the ink (conductive film forming composition) into droplets from a nozzle provided on the inkjet head. This is an inkjet method for discharging. According to the inkjet method, a large conductive film can be easily produced.
The ink jet method is not particularly limited, and a known method can be adopted. For example, a charge control method for ejecting ink using electrostatic attraction force; a drop-on-demand method (pressure pulse using the vibration pressure of a piezo element) Method); acoustic ink jet method that changes the electrical signal into an acoustic beam, irradiates the ink and uses ink to eject the ink; thermal ink jet method that heats the ink to form bubbles and uses the generated pressure; etc. Is mentioned.
In addition, as an inkjet head, a short serial head was used, a shuttle system in which the head was scanned in the width direction of the substrate, and a line head in which elements were arranged corresponding to the entire area of one side of the substrate were used. There is a line system.

In addition, the shape of the coating film apply | coated by the inkjet method is not specifically limited, The surface shape which covers the base-material whole surface may be sufficient, and pattern shape (for example, wiring shape, dot shape) may be sufficient.
The coating amount of the composition for forming a conductive film on the substrate may be adjusted as appropriate according to the desired film thickness of the conductive film, but usually the coating film thickness is preferably 0.01 to 5000 μm, 0.1-1000 micrometers is more preferable.

[Drying process]
It is preferable that the manufacturing method of the electrically conductive film of this invention is further equipped with the drying process which dries the coating film formed at process (1) between process (1) and process (2).
By the drying step, the solvent remaining in the coating film is removed, and in the reduction step, which will be described later, the generation of minute cracks and voids due to the evaporation of the solvent can be reduced.
As a drying method, a hot air dryer or the like can be used.
The drying temperature is preferably a temperature at which the oxide particles (A) are not reduced, specifically 40 to 200 ° C, more preferably 45 to 150 ° C, and further preferably 50 to 120 ° C.
The drying time is not particularly limited, but is preferably 1 to 60 minutes because the adhesion between the base material and the conductive film becomes better and the conductivity of the conductive film becomes better.

[Step (2): Reduction step]
In step (2), the coating film formed in step (1) (or the coating film after drying when the drying step is provided) is subjected to pulsed light irradiation treatment to reduce the copper oxide particles (A), This is a step of forming a conductive film containing copper.
The pulsed light irradiation process is a process of irradiating the coating film with pulsed light for a short time, and since the base material is not heated too much, a thermoplastic resin base material can be used as the base material.
When the pulse light irradiation treatment is performed on the coating film, reduction sintering proceeds on the surface layer of the coating film, and energy absorbed in the surface layer is conducted to a region below the surface layer, and reduction sintering proceeds on the entire coating film. More specifically, the copper particles produced by the reduction of the copper oxide particles (A) are fused to form grains, and the grains are bonded and fused to form a conductive film containing copper.

  The light source used in the pulsed light irradiation process 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. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.

As the pulsed light irradiation process, a pulsed light irradiation process using a flash lamp is preferable, and a pulsed light irradiation process using a Xe flash lamp is more preferable.
Irradiation energy of the pulse light is preferably 1~100J / cm ^2, more preferably 1~50J / cm ^2, more 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 ms, more preferably 1 ms to 500 ms, and further preferably 1 ms to 200 ms.

  The atmosphere for performing the pulsed 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 an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen, for example. The reducing atmosphere is a reducing gas such as hydrogen, carbon monoxide, formic acid, or alcohol. There is an atmosphere that exists.

(Conductive film)
By carrying out the above steps, a conductive film containing copper is obtained.
The film thickness of the conductive film is not particularly limited, and an optimum film thickness is appropriately adjusted according to the intended use. Especially, from the point of a printed wiring board use, 0.01-1000 micrometers is preferable and 0.1-100 micrometers is more preferable.

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 for obtaining a patterned conductive film, a method of applying the composition for forming a conductive film of the present invention to a substrate in a pattern and performing a pulsed light irradiation treatment, or a conductive film provided on the entire surface of the substrate. Examples include a method of etching in a pattern.
The etching method is not particularly limited, and a known subtractive method, semi-additive method, or the like can be employed.

  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 wiring (metal) is further formed on the surface. Pattern) may be formed.

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.

  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, Japanese Patent Application Laid-Open No. 2003-222993, and the like. These materials can 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.

  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.

(Preparation of self-dispersing polymer particles C-1)
In a 2 liter three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 540.0 g of methyl ethyl ketone was charged and heated to 75 ° C. While maintaining the temperature inside the reaction vessel at 75 ° C., 243 g of methyl methacrylate (MMA), 270 g of phenoxyethyl acrylate (PhOEA), 27 g of acrylic acid (AA), 108 g of methyl ethyl ketone, and “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) 2 .16 g of the mixed solution was added dropwise at a constant speed so that the addition was completed in 2 hours. After completion of the dropwise addition, a solution consisting of 1.08 g of “V-601” and 15.0 g of methyl ethyl ketone was added, stirred for 2 hours at 75 ° C., and then a solution consisting of 0.54 g of “V-601” and 15.0 g of methyl ethyl ketone was added. After stirring at 75 ° C. for 2 hours, the temperature was raised to 85 ° C., and stirring was further continued for 2 hours to obtain a polymerization solution containing a copolymer.
Next, 588.2 g of the polymerization solution was weighed, 165 g of isopropanol, 120.8 mL of 1 mol / L NaOH aqueous solution was added, and the temperature in the reaction vessel was raised to 80 ° C. Next, 718 g of distilled water was added dropwise at a rate of 20 mL / min to disperse in water. Then, the solvent was distilled off by keeping the temperature in the reaction vessel at 80 ° C. for 2 hours, 85 ° C. for 2 hours, and 90 ° C. for 2 hours under atmospheric pressure. Furthermore, the pressure in the reaction vessel was reduced, and isopropanol, methyl ethyl ketone, and distilled water were distilled off to obtain an aqueous dispersion of self-dispersing polymer C-1 (resin particles) having a solid content of 26.0% by mass.

The monomer composition (mass ratio) of C-1 is methyl methacrylate (MMA) / phenoxyethyl acrylate (PhOEA) / acrylic acid (AA) = 45/50/5.
For C-1, the measurement Tg was 40 ° C., the average particle size was 26 nm, and the weight average molecular weight (Mw) was 71,000.

(Preparation of self-dispersing polymer particles C-2 to C-8)
Aqueous dispersion of self-dispersing polymers C-2 to C-8 (resin particles) having the following monomer composition in the same manner as above except that the type and mass ratio of the monomer were changed to the following monomer composition. Was prepared.
C-2: methyl methacrylate (MMA) / 2-methoxyethyl methacrylate (MeOEA) / benzyl methacrylate (BzMA) / methacrylic acid (MAA) = (38/20/35/7), measurement Tg: 50 ° C., average particle Diameter: 13 nm, Mw: 120,000
C-3: methyl methacrylate (MMA) / phenoxyethyl methacrylate (PhOEMA) / methacrylic acid (MAA) = 35/58/7, measurement Tg: 41 ° C., average particle size: 5 nm, Mw: 180,000
C-4: methyl methacrylate (MMA) / 2-methoxyethyl methacrylate (MeOEA) / benzyl methacrylate (BzMA) / methacrylic acid (MAA) = (55/4/35/6), measurement Tg: 74 ° C., average particle Diameter: 13 nm, Mw: 46,000
C-5: methyl methacrylate (MMA) / benzyl methacrylate (BzMA) / benzyl acrylate (BzA) / acrylic acid (AA) = (50/21/25/5), measurement Tg: 62 ° C., average particle size: 45 nm , Mw: 60,000

(Synthesis of copper formate complex)
Methanol (100 mL) and copper formate tetrahydrate (11.3 g) were added to a 1 L eggplant flask to prepare a suspension. N, N-dimethyl-2-hydroxyethanolamine (11.9 g) was added to the suspension and stirred at room temperature for 1 hour. The obtained solution was distilled off under reduced pressure to obtain a copper formate complex (22 g).
This copper formate complex was used for the preparation of the following composition for forming a conductive film.

(Preparation of Composition 1)
After adding water and zirconia beads (0.05 mmφ) to copper oxide powder (Cai Kasei Co., Ltd., NanoTek CuO, average primary particle size: 50 nm) and stirring with a batch-type ready mill (AIMEX) for 30 minutes, A dispersion of copper oxide particles having an average particle diameter of 62 nm was prepared by filtering the zirconia beads.
A dispersion of copper oxide particles thus prepared, polyvinylpyrrolidone (weight average molecular weight: 10,000) as an organic binder, and latex “Nipol SX1503” (acrylonitrile-butadiene copolymer, manufactured by Nippon Zeon Co., Ltd. as resin particles, Self-dispersibility: yes, Tg: −20 ° C., average particle size: 50 nm, solid content: 42% by mass), and a copper formate complex as a copper complex in a content shown in Table 1 below, and Water was blended as a solvent so that the total solid content was 30% by mass to obtain a conductive film forming composition. The obtained composition for forming a conductive film is referred to as “composition 1”.

  The content in Table 1 below represents the content of the copper oxide particles relative to the total amount of the composition for forming a conductive film (described in the following Table 1 for convenience as “total content”), and the organic binder. And the copper complex represent the content with respect to the content of the copper oxide particles (in the following Table 1, for convenience, described as “counter (A) content”), and the resin particles are the total content of the organic binder and the resin particles. The content with respect to the amount (in the following Table 1, for the sake of convenience, described as “vs. (B) + (C) content”). All units are “mass%”.

(Preparation of composition 2)
As a resin particle, latex “Nipol LX433C” (modified styrene / butadiene copolymer, self-dispersibility: none, Tg: 50 ° C., average particle size: 100 nm, solid content: 50.0 mass%) manufactured by Nippon Zeon Co., Ltd. A conductive film-forming composition was obtained according to the same procedure as that of the composition 1, except that it was used. The obtained composition for forming a conductive film is referred to as “composition 2”.

(Preparation of composition 3)
As a resin particle, latex “Nipol LX430” (modified styrene / butadiene copolymer, self-dispersibility: none, Tg: 12 ° C., average particle size: 150 nm, solid content: 49.0% by mass) manufactured by ZEON CORPORATION A conductive film-forming composition was obtained according to the same procedure as that of the composition 1, except that it was used. The obtained composition for forming a conductive film is referred to as “composition 3”.

(Preparation of composition 4)
As resin particles, latex “Nipol LX416” (modified styrene / butadiene copolymer, self-dispersibility: none, Tg: 50 ° C., average particle size: 110 nm, solid content: 48.0% by mass) manufactured by Nippon Zeon Co., Ltd. A conductive film-forming composition was obtained according to the same procedure as that of the composition 1, except that it was used. The obtained composition for forming a conductive film is referred to as “composition 4”.

(Preparation of composition 5)
A conductive film forming composition was obtained according to the same procedure as that of the composition 1 except that an aqueous dispersion of the self-dispersing polymer C-1 was used as the resin particles. The obtained composition for forming a conductive film is referred to as “composition 5”.

(Preparation of composition 6)
A conductive film forming composition was obtained according to the same procedure as that of the composition 1 except that an aqueous dispersion of the self-dispersing polymer C-2 was used as the resin particles. The obtained composition for forming a conductive film is referred to as “composition 5”.

(Preparation of composition 7)
A conductive film-forming composition was obtained according to the same procedure as for composition 1, except that an aqueous dispersion of self-dispersing polymer C-2 was used as the resin particles and no copper complex was blended. The obtained composition for forming a conductive film is referred to as “composition 7”.

(Preparation of compositions 8-9)
A conductive film forming composition was obtained according to the same procedure as that of the composition 6 except that the content of the resin particles was changed to the content shown in Table 1 below. Let the obtained composition for electrically conductive film formation be the compositions 8-9, respectively.

(Preparation of composition 10)
A conductive film forming composition was obtained according to the same procedure as that of the composition 1 except that an aqueous dispersion of the self-dispersing polymer C-3 was used as the resin particles. The obtained composition for forming a conductive film is referred to as “composition 10”.

(Preparation of Comparative Composition 1)
A conductive film-forming composition was obtained according to the same procedure as that of the composition 1, except that the resin particles were not blended. Let the obtained composition for electrically conductive film formation be the comparative composition 1 (ratio 1).

(Preparation of comparative compositions 2-3)
A conductive film-forming composition was obtained according to the same procedure as that of the composition 1 except that an aqueous dispersion of the self-dispersing polymer C-4 or C-5 was used as the resin particles. Let the obtained composition for electrically conductive film formation be the comparative composition 2 (ratio 2) and the comparative composition 3 (ratio 3), respectively.

<Example 1>
On a polyimide substrate (Toray DuPont, thickness: 25 μm), using an inkjet printing apparatus (FUJIFILM Dimatix, apparatus name: DMP-2831), composition 1 is formed into a solid film of 5 mm × 20 mm. The coated film was obtained by applying and drying at 100 ° C. for 10 minutes. Then, the electrically conductive film was obtained by performing pulse light irradiation processing (Xenon company light sintering apparatus Sinteron2000, irradiation energy: 5 J / m < ² >, pulse width: 2 msec) to the obtained coating film.

<Examples 2 to 10 and Comparative Examples 1 to 3>
A conductive film was obtained in the same manner as in Example 1 except that the compositions 2 to 10 and the comparative compositions 1 to 3 were used instead of the composition 1, respectively.

<Conductivity>
About the obtained electrically conductive film, volume resistivity was measured using the four-probe method resistivity meter, and electroconductivity was evaluated. The evaluation criteria are as follows. A or B is required for practical use.
A: Volume resistivity is less than 50 μΩ · cm B: Volume resistivity is 50 μΩ · cm or more and less than 100 μΩ · cm C: Volume resistivity is 100Ω · cm or more

<Discharge stability>
The composition (comparative composition) was applied using an inkjet printing apparatus as described above, and the ejection stability was evaluated according to the following criteria. The coating unevenness was visually observed. Practically, if it is A or B, the ejection stability is good, and it can be evaluated as having ink jet aptitude.
(1) Discharge rate after 60 minutes continuous discharge test is 90% or more (2) Discharge rate after 30 minutes rest after 1 minute discharge is 90% or more (3) No coating unevenness If both pass, B: 2 items pass, C: 2 or more items fail

<Folding resistance (evaluation of film strength)>
First, volume resistivity (initial resistivity) of the obtained conductive film (5 mm × 20 mm) was measured using a four-point probe resistivity meter. Next, after conducting a test in which the conductive film was folded in half and a load of 200 g was applied to the fold for 5 minutes, volume resistivity (resistivity after the test) was measured in the same manner. The evaluation criteria are as follows. Practically, if it is A or B, it can be evaluated that the film strength of the conductive film is excellent.
A: The resistivity after the test is an increase rate of less than 1% with respect to the initial resistivity.
B: The resistivity after the test is an increase rate of 1% or more and less than 5% with respect to the initial resistivity.
C: The resistivity after the test is an increase rate of 5% or more with respect to the initial resistivity.

  As can be seen from the results shown in Table 1, in Comparative Example 1 in which the resin particles (C) were not blended, the ejection stability was insufficient, and the Tg of the blended resin particles was more than 50 ° C. In Examples 2 and 3, the film strength of the conductive film was insufficient.

  On the other hand, all of Examples 1 to 10 using the resin particles (C) having a glass transition temperature of 50 ° C. or less were excellent in ejection stability and conductivity and film strength of the conductive film.

At this time, as can be seen from the comparison of Examples 1 to 4, Examples 2 to 4 in which the Tg of the resin particles (C) is 0 ° C. or higher were superior in film strength to Example 1 that deviates from this.
Moreover, Example 1 and 2 whose average particle diameter of a resin particle (C) is 10-100 nm was more excellent in electroconductivity than Example 3 and 4 exceeding this range.
In addition, Example 1 in which the resin particles (C) are self-dispersing was superior in ejection stability to Examples 2 to 4 that were not self-dispersing.

Moreover, as can be seen from the comparison between Example 6 and Example 7, Example 6 in which the copper complex (D) was blended was superior in conductivity to Example 7 in which this was not blended.
Moreover, as can be seen from the comparison between Examples 6, 8, and 9, the content of the resin particles (C) is 30 to 60% by mass with respect to the total content of the organic binder (B) and the resin particles (C). In Example 6, the ejection stability was superior to Example 8 that was less than this range, and the film strength was superior to Example 9 that exceeded this range.
Moreover, as can be seen from the comparison between Example 6 and Example 10, Example 6 in which the average particle diameter of the resin particles (C) is 10 to 100 nm has a film strength that is less than Example 10 that is less than this range. It was excellent.

Claims (8)

The composition for electrically conductive film formation containing the copper oxide particle (A), the organic binder (B), and the resin particle (C) whose glass transition temperature is 50 degrees C or less is provided on a base material using an inkjet method. Coating film forming step for forming a coating film,
A reduction process which performs pulse light irradiation processing to the coating film, reduces the copper oxide particles (A), and forms a conductive film containing copper.   The manufacturing method of the electrically conductive film of Claim 1 whose glass transition temperature of the said resin particle (C) is 0 degreeC or more.   The manufacturing method of the electrically conductive film of Claim 1 or 2 whose average particle diameter of the said resin particle (C) is 10-100 nm.   Content of the said resin particle (C) in the said composition for electrically conductive film formation is 30-60 mass% with respect to the total content of the said organic binder (B) and the said resin particle (C). The manufacturing method of the electrically conductive film of any one of -3.   The manufacturing method of the electrically conductive film of any one of Claims 1-4 whose said resin particle (C) is a self-dispersing polymer.   The manufacturing method of the electrically conductive film of any one of Claims 1-5 in which the said composition for electrically conductive film formation contains a copper complex (D) further.   The manufacturing method of the electrically conductive film of any one of Claims 1-6 whose said pulsed light irradiation process is a pulsed light irradiation process by a flash lamp.   The electrically conductive film obtained by the manufacturing method of the electrically conductive film of any one of Claims 1-7.