JP2017191723A - Manufacturing method of conductive member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a conductive member capable of providing the conductive member having excellent conductivity under simple atmosphere such as air and a dry condition at lower temperature than conventional ones even when using micro-sized copper particles.SOLUTION: There is provided a manufacturing method of a conductive member having a substrate and a conductive layer arranged on the substrate, including a process for coating the substrate with a conductive ink composition containing (A) oxycarboxylic acid, (B) a nitrogen-containing compound, (C) copper particles and (D) a dispersant, where the (B) nitrogen-containing compound is at least one selected from a group from a compound having a urine bond, guanidine and a derivative thereof, guanidine salt, a hetero 5-membered compound containing 2 nitrogen atoms as hetero atoms, 1H-triazole and a derivative thereof, a hydrazide compound, a nitrosamine compound, a compound having a nitrile group, melamine and a derivative thereof, ammonium salt, and a process for conducting a compression dry treatment by drying while adding pressure or a pressure reduction dry treatment by drying while reducing pressure to the conductive ink composition on the substrate.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a conductive member, and more particularly to a method for manufacturing a conductive member using a conductive ink composition.

  In recent years, a technique that uses conductive ink obtained by dispersing metal particles to print a desired pattern by a printing method such as inkjet or screen printing, and forms wiring, electrodes, etc. on a circuit board has attracted attention. Yes. Usually, silver particles from which printed matter having high conductivity can be obtained are known as the metal particles of the conductive ink used in such a method.

  However, the conductive ink using silver particles is liable to cause electromigration, and the material silver is an expensive metal, which causes high costs. Therefore, there is a demand for a conductive ink containing copper as a main component that is easily available, low in cost, and less likely to cause electromigration. However, when copper particles are used in the conductive ink, the melting point of copper metal is high, so that it is difficult to completely fuse the copper particles with each other by sintering at a low temperature. Since the surface of the film is easily oxidized, there is a problem that a reducing agent is used to avoid oxidation, and further heat treatment is required under dangerous reducing atmosphere conditions such as hydrogen.

  For example, JP 2010-59535 A (Patent Document 1) includes formic acid or acetic acid and an alcohol or ether having 1 to 3 carbon atoms for the purpose of low-temperature reduction sintering of copper nanoparticles. And a low-temperature sintering method using the same. However, in the method described in Patent Document 1, since the reducing agent is supplied as a reducing atmosphere gas during the sintering process of the copper nanoparticles, it cannot be processed with a simple apparatus, and the copper particles have a particle size of a micro size or more. Then, there was a problem that sintering at a low temperature was difficult.

  In addition, JP 2012-131895 A (Patent Document 2) applies or fills a base material with a conductive ink composition containing an alkanolamine, a carboxylic acid having a reducing power, and copper particles, An electrically conducting portion manufactured by heat-treating the substrate in the atmosphere is described. However, in the method described in Patent Document 2, when sintered at a low temperature, the formation of the electrically conductive portion is insufficient and sufficient conductivity cannot be obtained, and the usable copper particles are also limited to 5 μm or less. There was a problem.

  In addition, in order to form a conductive layer such as a wiring or an electrode on a circuit board using a conductive ink, a method of heat-treating the conductive ink applied to the base as described above is often used. For example, Japanese Unexamined Patent Application Publication No. 2013-128044 (Patent Document 3) describes a method of forming a conductor pattern by heating and pressing after printing a conductive paste on a substrate.

JP 2010-59535 A JP 2012-131895 A JP 2013-128044 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and even when micro-sized copper particles are used, under a simple atmosphere such as air and under drying conditions lower than conventional ones. Another object of the present invention is to provide a method for producing a conductive member that can obtain a conductive member having excellent conductivity.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have included a combination of an oxycarboxylic acid and a specific nitrogen-containing compound in a conductive ink composition using copper particles. It is possible to obtain a conductive member having particularly excellent conductivity by applying a pressure drying process for drying while applying pressure after applying the ink composition to a substrate or a vacuum drying process for drying while reducing pressure. The headline and the present invention were completed.

That is, the method for producing a conductive member of the present invention is a method for producing a conductive member comprising a base material and a conductive layer disposed on the base material,
(A) an oxycarboxylic acid, (B) a nitrogen-containing compound, (C) copper particles, and (D) a dispersion medium, wherein the (B) nitrogen-containing compound has a urea bond, guanidine and derivatives thereof, From the group consisting of guanidine salts, hetero 5-membered ring compounds containing 2 nitrogen atoms as hetero atoms, 1H-triazole and derivatives thereof, hydrazide compounds, nitrosamine compounds, compounds having nitrile groups, melamine and derivatives thereof, and ammonium salts A step of applying a conductive ink composition, which is at least one selected, on a substrate, and a pressure drying process for applying pressure to the conductive ink composition on the substrate, or drying while reducing pressure. The method includes a step of forming a conductive layer by performing a drying process under reduced pressure.

  Furthermore, in the manufacturing method of the electroconductive member of this invention, the said electroconductive ink composition is (E) following general formula (i):

[In general formula (i), X ¹ represents a residue obtained by removing active hydrogen (H ^* ) of an amino group and / or imino group from a polyamine, and p + q represents the number of active hydrogens possessed by the polyamine. P + q = 2 to 16 and p = 1 to 16, each AO independently represents an alkyleneoxy group having 2 to 4 carbon atoms, and each r independently represents an added mole number of the alkyleneoxy group represented by AO. R = 1 to 25. ]
It is preferable that the polyamine alkylene oxide adduct represented by these is further contained.

  In addition, even when micro-sized copper particles are used by the method for producing a conductive member of the present invention, the conductive material has excellent conductivity under a simple atmosphere such as air and under dry conditions lower than conventional. The reason why it is possible to obtain a sex member is not necessarily clear, but the present inventors speculate as follows. That is, in the conductive ink composition according to the present invention, by containing copper particles, oxycarboxylic acid, and the specific nitrogen-containing compound in combination, copper is reacted by the reaction of the specific nitrogen-containing compound and the copper particles. Since the copper ammonium salt is formed on the surface of the particles, and the formed copper ammonium salt is reduced to copper by oxycarboxylic acid, the present inventors believe that the adjacent copper particles are fused. I guess. Further, when the specific conductive ink composition is used and dried to form a conductive layer, the porosity of the obtained conductive layer is sufficiently reduced by applying pressure or reducing the pressure. The present inventors infer that the conductivity of the conductive member having such a conductive layer is remarkably improved.

  According to the present invention, even when micro-sized copper particles are used, a conductive member having excellent conductivity can be obtained under a simple atmosphere such as air and under drying conditions lower than conventional ones. It becomes possible to provide the manufacturing method of the electroconductive member which can do.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Conductive ink composition]
First, the conductive ink composition according to the present invention will be described. The conductive ink composition according to the present invention contains (A) an oxycarboxylic acid, (B) a nitrogen-containing compound, (C) copper particles, and (D) a dispersion medium. Compound having urea bond, guanidine and derivatives thereof, guanidine salt, hetero 5-membered ring compound containing 2 nitrogen atoms as hetero atoms, 1H-triazole and derivatives thereof, hydrazide compound, nitrosamine compound, compound having nitrile group, melamine And a derivative thereof, and at least one selected from the group consisting of ammonium salts.

  (A) Oxycarboxylic acid (hereinafter referred to as “component (A)”) will be described. The component (A) used in the present invention is a compound having a hydroxy group and a carboxy group. For example, glycolic acid, lactic acid, glyceric acid, tartronic acid, malic acid, tartaric acid, hydroxybutyric acid, citric acid, isocitric acid, Examples thereof include oxycarboxylic acids having 2 to 20 carbon atoms such as salicylic acid, mandelic acid and benzylic acid, and acid anhydrides thereof. Among these, as the component (A) used in the present invention, oxycarboxylic acids having 2 to 14 carbon atoms and acid anhydrides thereof are preferable from the viewpoint of promoting fusion of copper particles, glycolic acid, lactic acid, Malic acid, citric acid, and acid anhydrides thereof are more preferable, and lactic acid, malic acid, and acid anhydrides thereof are even more preferable. (A) A component can be used 1 type or in mixture of 2 or more types.

  The content of the component (A) is preferably 0.1 to 100 parts by mass and more preferably 0.1 to 75 parts by mass based on 100 parts by mass of the (C) copper particles described later. Preferably, it is 1-60 mass parts. Further, the content of the component (A) is preferably 0.1 to 30% by mass and 1 to 30% by mass based on 100% by mass of the conductive ink composition according to the present invention. Is more preferable. If the content of the component (A) is less than the lower limit, the fusion of the copper particles tends to be insufficient. On the other hand, if the content exceeds the upper limit, the stability tends to decrease.

  Next, (B) a nitrogen-containing compound (hereinafter referred to as “component (B)”) will be described. In the present invention, as component (B), (i) a compound having a urea bond, (ii) guanidine and its derivatives, (iii) guanidine salt, (iv) a hetero 5-membered member containing two nitrogen atoms as hetero atoms A ring compound, (v) 1H-triazole and derivatives thereof, (vi) hydrazide compounds, (vii) nitrosamine compounds, (viii) compounds having a nitrile group, (ix) melamine and derivatives thereof, and (x) ammonium salts At least one nitrogen-containing compound selected from the group is used.

  (I) As a compound having a urea bond, a compound having 1 to 4 urea bonds in the compound and having a cyclic structure or a non-cyclic structure having 1 to 20 carbon atoms in total is exemplified. ), Urazole, 4-methylurazole, 1-methylurazole, hydrazodicarbonamide, azodicarbonamide, and 1,1′-azobis (N, N-dimethylformamide).

[In the general formula ^(1), R 1 ~R ⁴ are each independently a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1-4. ]
(Ii) Examples of guanidine and derivatives thereof include guanidine and derivatives thereof represented by the following general formula (2).

[In General Formula (2), R ^{5 to} R ⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a nitro group, and R ⁹ represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms Represents a group or a nitrile group. ]
Examples of such guanidine derivatives include cyanoguanidine, 1,1,3,3-tetramethylguanidine, and 1-methyl-3-nitroguanidine.

  (Iii) Examples of the guanidine salt include a salt of the guanidine and an acid and a salt of the guanidine derivative and an acid. The acid for forming such a salt is not particularly limited, and examples thereof include hydrochloric acid, sulfamic acid, carbonic acid, and nitric acid. Examples of such guanidine salts include guanidine hydrochloride, guanidine sulfamate (guanidine sulfamate), guanidine carbonate, guanidine nitrate, and 1-methylguanidine hydrochloride.

  (Iv) Examples of the hetero 5-membered ring compound containing two nitrogen atoms as hetero atoms include pyrazole, pyrazolidine, pyrazolone, 2-pyrazolin, 2-imidazoline, 3-imidazoline, 4-imidazoline, imidazolidine and imidazole. Can be mentioned. In addition, (iv) a hetero 5-membered ring compound containing two nitrogen atoms as a hetero atom may have 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent of the hetero 5-member ring. Examples of such compounds include 3,5-dimethylpyrazole and 3-methyl-5-pyrazolone.

  (V) As 1H-triazole and derivatives thereof, for example, 1,2,4-triazole, 1,2,3-triazole, 4-amino-1,2,4-triazole, 1,2,3-benzotriazole , 1-hydroxybenzotriazole, and 5-methylbenzotriazole.

  (Vi) Examples of the hydrazide compound include adipic acid dihydrazide, dodecanediohydrazide, isophthalic acid dihydrazide, benzophenone hydrazone, 3-hydroxy-2-naphthoic acid hydrazide, 4,4′-oxybis (benzenesulfonylhydrazide), and p-toluene. A sulfonyl hydrazide is mentioned.

  (Vii) Examples of the nitrosamine compound include N, N′-dinitrosopentamethylenetetramine.

  (Viii) The compound having a nitrile group is (ii) a compound other than guanidine and its derivatives, and examples thereof include 2,2'-azoisobutyronitrile and isobutyronitrile.

  Examples of (ix) melamine and derivatives thereof include melamine, (iso) cyanuric acid, ammelin, and ammelide.

  Examples of (x) ammonium salt include ammonium chloride, ammonium nitrate, and ammonium carbonate.

Among these, the component (B) used in the present invention is preferably (i) a compound having a urea bond, more preferably a compound represented by the general formula (1), from the viewpoint of promoting fusion of copper particles. A compound in which R ^{1 to} R ⁴ in the general formula (1) are hydrogen atoms and n is 1 or 2 is more preferable, and urea is particularly preferable. (B) A component can be used 1 type or in mixture of 2 or more types.

  The content of the component (B) is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 75 parts by mass, based on 100 parts by mass of the (C) copper particles described later. Preferably, it is 1-60 mass parts. Further, the content of the component (B) is preferably 0.1 to 30% by mass, and 0.1 to 25% by mass based on 100% by mass of the conductive ink composition according to the present invention. More preferably. When the content of the component (B) is less than the lower limit, the fusion of the copper particles tends to be insufficient. On the other hand, when the content exceeds the upper limit, the stability tends to decrease.

  Next, (C) copper particles (hereinafter referred to as “component (C)”) will be described. The component (C) used in the present invention is not particularly limited as long as it is metal particles containing at least copper as a main component, and may be copper alone or an alloy of copper and other metals. As (C) component used in this invention, in order to express the outstanding characteristic of copper, it is preferable that content of copper is 90 mass% or more, and it is more preferable that it is 95 mass% or more. .

  The average particle size of “component (C)” in the conductive ink composition according to the present invention is not particularly limited, but is preferably 0.01 to 100 μm, more preferably 0.01 to 50 μm. preferable. If the average particle diameter is less than the lower limit, the copper particles tend to be expensive, whereas if the average particle diameter exceeds the upper limit, thin film formation tends to be difficult. In the present invention, even when micro-sized copper particles having an average particle diameter of 1 to 100 μm are used, sufficient conductivity is maintained under a simple atmosphere such as air and under drying conditions lower than conventional ones. It becomes possible to obtain a conductive member having a property.

  In the present invention, the average particle diameter of the aforementioned copper particles is the particle diameter (diameter) of each of 50 or more arbitrary copper particles by observation with a transmission electron microscope (TEM) or scanning electron microscope (SEM). Are calculated and arithmetically averaged. In the observation photograph (figure), when the shape of the copper particle is not a perfect circle, the diameter of the maximum circumscribed circle of the cross section of the particle is measured as the particle diameter (diameter).

  In addition, the form of “component (C)” is not particularly limited, and examples thereof include a spherical shape, a square shape, and a needle shape. The “component (C)” used in the present invention is a commercially available product or can be obtained by production using a known technique.

  The content of the component (C) is 0.7 to 99% by mass based on 100% by mass of the conductive ink composition according to the present invention, from the viewpoint of the conductivity of the conductive member obtained. Preferably, it is 0.8-99 mass%, More preferably, it is 1-90 mass%.

  Next, (D) the dispersion medium (hereinafter referred to as “component (D)”) will be described. The component (D) used in the present invention is not particularly limited as long as it does not react with the components (A) and (B) described above, and is a known one that has been conventionally used in conductive ink compositions. A dispersion medium may be used. Such component (D) may be liquid or pasty, for example, water; ketones, esters, alcohols, glycol ethers, aromatic hydrocarbons, aliphatic hydrocarbons And hydrocarbon compounds such as petroleum hydrocarbons and waxes.

  Examples of water include ion exchange water and distilled water. Examples of the ketones include ketones having 3 to 20 carbon atoms, and examples include isophorone and diisobutyl ketone. Examples of the esters include esters having 3 to 20 carbon atoms such as methyl acetate, butyl acetate, isobutyl acetate, propyl acetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monobutyl ether acetate. Examples of alcohols include linear or branched saturated alcohols having 1 to 22 carbon atoms, linear or branched unsaturated alcohols having 3 to 22 carbon atoms, and cyclic alcohols having 6 to 22 carbon atoms. , Methanol, ethanol, propanol, secondary butyl alcohol, octanol, nonanol, decanol, phenol, terpineol, 1-methoxy-2-propanol, ethylene glycol, propylene glycol. Examples of glycol ethers include glycol ethers having 3 to 20 carbon atoms, such as ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol monomethyl ether. Aromatic hydrocarbons include aromatic hydrocarbons having 6 to 20 carbon atoms, and examples include benzene, toluene, xylene, and styrene. Examples of the aliphatic hydrocarbons include saturated or unsaturated aliphatic hydrocarbons having 3 to 18 carbon atoms, such as tridecane, tetradecane, pentadecane, and hexadecane. Examples of petroleum hydrocarbons include mineral spirit, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha, petroleum benzine, and turpentine oil. Examples of waxes include plant-based wax (eg, wax wax, urushi wax), animal-type wax (eg, beeswax, spermaceti), mineral-type wax (eg, montan wax), petroleum-type wax (eg, paraffin wax), synthetic A wax is mentioned. (D) A component can be used 1 type or in mixture of 2 or more types.

  The content of the component (D) is 0.7 to 99% by mass on the basis of 100% by mass of the conductive ink composition according to the present invention from the viewpoint of handleability of the obtained conductive ink composition. It is preferably 0.8 to 99% by mass, and more preferably 10 to 99% by mass.

  In the manufacturing method of the electroconductive member of this invention, the said electroconductive ink composition is (E) following general formula (i):

It is preferable to further contain a polyamine alkylene oxide adduct represented by (hereinafter referred to as “component (E)”).

In the general formula (i), X ¹ represents a residue obtained by removing active hydrogen (H ^* ) of an amino group and / or imino group from a polyamine, and p + q represents the number of active hydrogens possessed by the polyamine. P + q = 2 to 16 and p = 1 to 16, each AO independently represents an alkyleneoxy group having 2 to 4 carbon atoms, and each r independently represents an added mole number of the alkyleneoxy group represented by AO. R = 1 to 25.

In general formula (i), X ¹ is a residue obtained by removing active hydrogen (H ^* ) of an amino group and / or imino group from a polyamine having two or more amino groups and / or imino groups in one molecule. The polyamine alkylene oxide adduct represented by the general formula (i) is an addition of 1 mol or more of alkylene oxide to 1 mol of the polyamine to the active hydrogen of the amino group and / or imino group in the polyamine molecule. Compound. The active hydrogen is a hydrogen atom bonded to the nitrogen atom of the amino group and / or imino group, and the amino group includes two active hydrogens and the imino group includes one active hydrogen.

The number of carbon atoms of X ¹ is not particularly limited, but is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 to 4 from the viewpoint of fluidity.

  In addition, the number of amino groups and / or imino groups possessed by the polyamine (the total number of both when amino groups and imino groups are included) is preferably 2 to 8, from the viewpoint of fluidity. 6 is more preferable, and 2-3 is particularly preferable.

  Furthermore, in the general formula (i), p + q represents the number of active hydrogens that the polyamine had, p + q = 2-16 and p = 1-16, p + q = 2-12 and p = 1-12. It is more preferable that

X ¹ includes, for example, ethylenediamine residue, propylenediamine residue, tetramethylenediamine residue, hexamethylenediamine residue, methylaminoethylamine residue, ethylaminoethylamine residue, 2,5-dimethylhexamethylenediamine residue. , Trimethylhexamethylenediamine residue, 1,3-propanediamine residue, methylaminopropylamine residue, ethylaminopropylamine residue, diethylenetriamine residue, dipropylenetriamine residue, methyliminobispropylamine residue, bis (Hexamethylene) triamine residue, triethylenetetramine residue, tetraethylenepentamine residue, aliphatic polyamine residue such as pentaethylenehexamine residue; alicyclic diamine residue such as cyclohexanediamine residue; Echile Diamine residue, propylenediamine residue, tetramethylenediamine residue, hexamethylenediamine residue, methylaminoethylamine residue, ethylaminoethylamine residue, 1,3-propanediamine residue, methylaminopropylamine residue, ethyl An aminopropylamine residue, a diethylenetriamine residue, a dipropylenetriamine residue, and a triethylenetetramine residue are preferable, and an ethylenediamine residue, a propylenediamine residue, a tetramethylenediamine residue, and a diethylenetriamine residue are more preferable.

In the general formula (i), AO is specifically an ethyleneoxy group, a propyleneoxy group, a 1,2-butyleneoxy group, a 2,3-butyleneoxy group, a 1,3-butyleneoxy group, 1,4- Examples include butyleneoxy group, and ethyleneoxy group and propyleneoxy group are preferable from the viewpoint of fluidity. Further, when there are a plurality of AOs in one molecule, these AOs may be the same or different. If they are different, block addition, random addition, or alternate addition may be used. Further, when p is 2 or more, p (AO) _{r s} may be the same or different.

  In general formula (i), r represents the addition mole number of the alkyleneoxy group each independently represented by AO, and is r = 1-25. The number of r is preferably 1 to 20 independently from the viewpoint of fluidity, and more preferably 1 to 15 independently. Moreover, in general formula (i), it is preferable that the number of pxr (r is an average addition mole number of an alkyleneoxy group in this case) is 2-100, and it is more preferable that it is 4-70.

In the present invention, it is preferable that all the alkyleneoxy group of the amino group and / or imino group derived from an active hydrogen X ¹ has is added. For example, when the polyamine is ethylenediamine, it is preferable that an alkyleneoxy group is added to four active hydrogens of ethylenediamine.

  Such component (E) can be obtained by adding alkylene oxide to the polyamine. The addition of the alkylene oxyside can be carried out by a usual method of adding an alkylene oxide corresponding to the above AO to an amine compound such as a polyamine.

  Moreover, (E) component can use a commercial item, for example, Adeka Pluronic TR701 (made by ADEKA), such as Adekapluronic TR701 and TR702 which are propylene oxide-ethylene oxide block adducts of ethylenediamine, Examples thereof include ADEKA polyether EDP series such as ADEKA polyether EDP300 and EDP450 which are propylene oxide adducts of ethylenediamine.

  The content of the component (E) is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 75 parts by mass, based on 100 parts by mass of the above-mentioned (C) copper particles. Preferably, it is 1-60 mass parts. In addition, the content of the component (E) is preferably 0.1 to 30% by mass, based on 100% by mass of the conductive ink composition according to the present invention, and preferably 0.1 to 25% by mass. More preferably. If the content of the component (E) is less than the lower limit, the fluidity tends to decrease. On the other hand, even if the content exceeds the upper limit, the fluidity tends to decrease.

  Moreover, in this invention, you may use the ionic liquid by oxycarboxylic acid and a polyamine alkylene oxide adduct as a component which serves as both (A) component and (E) component.

  Furthermore, in the conductive ink composition according to the present invention, known anti-drying agents, dispersants, antioxidants, concentration adjusting agents, surface tension adjusting agents, viscosity adjusting agents, and the like, as long as the effects of the present invention are not impaired. The additive component can be added.

  Next, a method for producing the conductive ink composition according to the present invention will be described. The method for producing the conductive ink composition according to the present invention is not particularly limited. For example, when the component (A) and the component (B) (the component (E) are further added to the component (D), the component (D) (A) component, (B) component, and (E) component) are stirred and mixed and dissolved in the component, and then (C) component is stirred and mixed to disperse. The mixer used in the stirring and mixing is appropriately selected and used. For example, a mixer such as an ultrasonic disperser, a homomixer, a disper, an agitator, a planetary mixer, an ajihomo mixer, a universal mixer, an attritor, etc. Can be used. These can select 1 type, or 2 or more types of methods.

[Method for producing conductive member]
Next, the manufacturing method of the electroconductive member of this invention using the said electroconductive ink composition is demonstrated. The method for producing a conductive member of the present invention includes a step of applying the conductive ink composition on a substrate, and a pressure drying process for drying the conductive ink composition on the substrate while applying pressure thereto, or It includes a step of forming a conductive layer by performing a reduced-pressure drying process for drying under reduced pressure. Thereby, the electroconductive member provided with the base material and the electroconductive layer arrange | positioned on the said base material, and having the outstanding electroconductivity can be obtained.

  As the substrate, known materials can be used, and are not particularly limited. Examples thereof include resin, paper, metal, and glass. Specifically, low-density polyethylene resin, high-density polyethylene are used. Resin, acrylonitrile-butadiene-styrene copolymer synthetic resin, acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate), polyacetal resin, Resin base materials such as cellulose derivatives; uncoated printing paper, fine coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached packaging paper (heavy bag) Kraft paper, kraft paper), bleached wrapping paper (bleached kraft) Paper, pure white roll paper), paper base such as coated ball, chipboard corrugated cardboard; metal base such as copper plate, iron plate, aluminum plate; glass base material such as soda glass, borosilicate glass, silica glass, quartz glass; alumina , Sapphire, zirconia, titania, yttrium oxide, ITO (indium tin oxide), and other metal oxide substrates.

  The conductive layer is a layer obtained by drying the conductive ink composition, and may be a sheet shape or a conductor pattern such as a wiring pattern or an electrode. Moreover, the thickness of the said conductive layer, the width | variety of the said conductor pattern, etc. are not specifically limited, According to the objective which uses a conductive member, it can adjust suitably.

  In the environment for carrying out the method for producing a conductive member of the present invention, the atmospheric conditions are not particularly limited. For example, air atmosphere; inert gas atmosphere such as nitrogen gas and argon gas; reduction of hydrogen gas and the like The atmosphere can be mentioned. In the present invention, even when micro-sized copper particles are used, it is possible to obtain a conductive member having excellent conductivity under a simple atmosphere such as air and under dry conditions lower than conventional ones. Since it is possible, an air atmosphere is preferable from the viewpoint of simplicity of facilities and the like.

  Further, the method for applying the conductive ink composition is not particularly limited, for example, gravure printing method, flexographic printing method, screen printing method, dip coating method, slit coating method, spin coating method, Examples thereof include a coating method using a dispenser and an ink jet method. The coating amount for applying the conductive ink composition to the substrate is not particularly limited, and may be appropriately adjusted according to the desired thickness of the conductive layer. Moreover, as said application | coating, conductor patterns, such as a wiring pattern and an electrode, may be printed on the said base material.

  In the pressure drying treatment, pressure is applied to the conductive ink composition on the substrate, and at the same time, the conductive ink composition is dried. As a method of applying pressure, for example, a method of applying pressure using a pressurizing device (atmosphere controlled heating and pressurizing device capable of controlling the atmosphere gas, temperature and pressure, etc.) The method of laminating | stacking a protective sheet and pressing with a pressure roller or a press from the said protective sheet etc. is mentioned.

  In the pressure drying treatment according to the present invention, the pressure condition is preferably a pressure of 0.1 to 20 MPa, and more preferably 1 to 10 MPa. When the pressure is less than the lower limit, there is a tendency that the effect of improving conductivity is not sufficiently achieved in the conductive member obtained by insufficient fusion of the copper particles, and on the other hand, when the upper limit is exceeded, pressurization is performed. However, the cost of the apparatus tends to increase.

  In the reduced-pressure drying treatment, the conductive ink composition on the substrate is depressurized and simultaneously the conductive ink composition is dried. Examples of the method of reducing the pressure include a method of reducing the pressure using a pressure reducing device (atmosphere controlled heating pressure reducing device capable of controlling the atmosphere gas, temperature and pressure).

  In the reduced pressure drying treatment according to the present invention, the reduced pressure condition is preferably a pressure of 0.1 to 1000 Pa, and more preferably 1 to 100 Pa. When the pressure is less than the lower limit, a device for reducing the pressure tends to be large, and the cost tends to increase. On the other hand, when the upper limit is exceeded, the conductive member obtained by insufficient fusion of the copper particles is obtained. There is a tendency that the effect of improving the electrical conductivity is not sufficiently exhibited.

  In the pressure drying process and the vacuum drying process according to the present invention, the drying method is not particularly limited, and examples include room temperature drying, heat drying, hot air drying, cold air drying, and plasma drying.

  The pressure drying treatment and the pressure drying treatment according to the present invention are preferably performed at room temperature or under heating conditions from the viewpoint of facility versatility. As temperature at this time, the range of 20-300 degreeC is preferable from the viewpoint which the electroconductivity of the electroconductive member obtained further improves, and the range of 60-250 degreeC is more preferable. If the temperature is less than the lower limit, it tends to be difficult to fuse the copper particles. On the other hand, if the temperature exceeds the upper limit, the base material tends to be easily damaged by heat, such as melting and deformation. . In the present invention, even when micro-sized copper particles are used, it is possible to obtain a conductive member having excellent conductivity under a simple atmosphere such as air and under dry conditions lower than conventional ones. Since it is possible, it becomes possible to employ | adopt the low temperature of 20-150 degreeC as a temperature of the said pressure drying process and the said pressure reduction drying process.

  Further, in the pressure drying process and the vacuum drying process according to the present invention, the processing time is not particularly limited, and is appropriately selected in consideration of the conductivity (resistance value) of the desired conductive member, the processing temperature, and the like. Generally, the time for maintaining the pressure and temperature is preferably 10 seconds to 24 hours. The pressure drying treatment and the vacuum drying treatment according to the present invention may be carried out in a desiccator or the like containing a desiccant in order to promote drying when carried out at room temperature without heating.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Examples 1 to 16, Comparative Examples 1 to 5, Reference Examples 1 to 8)
[Preparation of conductive ink composition]
The conductive ink compositions used in Examples 1 to 16, Comparative Examples 1 to 5 and Reference Examples 1 to 8 were prepared by the following method so as to have the compositions shown in Tables 1 to 4, respectively. It was prepared by. That is, first, the components (A) and (B) (comparative example 1: (B) component only, comparative example 2, comparative example 5: (A) component only, comparative example 3: acetic acid as comparative component of component (A), comparative example 4: triethanolamine as comparative component of component (B) and (E) component (Example 10, Comparative Example 5 and Reference Example 8 only) was added and mixed to obtain a uniform solution. Next, component (C) is added to and mixed with this solution, and subjected to ultrasonic treatment (ULTRASONIC CLEANER “SONOQUICK C10” manufactured by Ultrasonic Industry Co., Ltd.) for 30 minutes to obtain a uniform dispersion, which is used as each conductive ink. It was set as the composition.

  In Tables 1 to 4, the copper particle 1 is “sub-micro copper powder IOXCu750” manufactured by IOX, having an average particle diameter of 750 nm and a copper content of 99% by mass or more, and ethylenediamine-42PO-6EO is ethylenediamine. Propylene oxide 42 mol ethylene oxide 6 mol random adduct was used. In Table 2, the copper particles 2 used were “Copper powder (spheroidal)” manufactured by Aldrich, an average particle diameter of 20 μm, and a copper content of 99% by mass or more.

[Manufacture of conductive members]
Next, each of the obtained conductive ink compositions is formed in a rectangular solid printing portion having a length of 3 cm and a width of 1 cm in a conductive layer obtained on a glass substrate with an applicator in an air atmosphere. After coating (wet film thickness: 300 μm), the atmosphere gas, temperature and pressure are controlled using an atmosphere control heating and pressurizing device or an atmosphere control heating and decompression device, and the processing temperature and processing time shown in Tables 1 to 4, respectively. The conductive layer was formed by drying in an atmosphere and under a pressurized pressure or a reduced pressure to obtain each conductive member having the conductive layer disposed on the substrate. In addition, the thickness of the obtained electroconductive layer is Example 1-Example 8, Example 10-Example 13, Comparative Example 1-Comparative Example 5, Reference Example 1-Reference Example 8: 40 micrometers, Example 9 : 90 μm, Example 14 to Example 16: 50 μm.

[Evaluation of conductivity]
The volume low efficiency (unit: Ω · cm) of the conductive layer of the obtained conductive member was measured using a Loresta pointer meter (“MCP-T610” manufactured by Mitsubishi Chemical Corporation). The results are shown in Tables 1 to 4, respectively. The volumetric efficiency indicates that the smaller the value, the easier it is to conduct electricity and the better the conductivity. In Table 2, “INF” indicates that the volume low efficiency is too large and exceeds the measurement range.

  As is clear from the results shown in Tables 1 to 4, according to the method for producing a conductive member using the conductive ink composition of the present invention, even when micro-sized copper particles are used, It was confirmed that a conductive member having stable and excellent conductivity can be obtained under a simple atmosphere of air and under drying conditions lower than before. Furthermore, in the electroconductive member obtained by the manufacturing method of this invention, compared with the electroconductive member (reference example) obtained by drying the electroconductive ink composition which concerns on this invention, without applying pressure or pressure reduction. Also, it was confirmed that the conductivity was remarkably improved.

  As described above, according to the present invention, even when relatively large micro-sized copper particles are used, air or the like can be used without treatment under dangerous reducing atmosphere conditions such as hydrogen. Thus, it is possible to provide a method for producing a conductive member capable of obtaining a conductive member having excellent conductivity under a simple atmosphere and drying conditions lower than conventional ones.

  Therefore, according to the manufacturing method of the present invention, the conventional problem that the substrate is damaged by heat during drying is solved, and particularly excellent conductivity is achieved in the obtained conductive member. The present invention is very useful when manufacturing wiring, electrodes and the like on a circuit board.

Claims (2)

A method for producing a conductive member comprising a base material and a conductive layer disposed on the base material,
(A) an oxycarboxylic acid, (B) a nitrogen-containing compound, (C) copper particles, and (D) a dispersion medium, wherein the (B) nitrogen-containing compound has a urea bond, guanidine and derivatives thereof, From the group consisting of guanidine salts, hetero 5-membered ring compounds containing 2 nitrogen atoms as hetero atoms, 1H-triazole and derivatives thereof, hydrazide compounds, nitrosamine compounds, compounds having nitrile groups, melamine and derivatives thereof, and ammonium salts A step of applying a conductive ink composition, which is at least one selected, on a substrate, and a pressure drying process for applying pressure to the conductive ink composition on the substrate, or drying while reducing pressure. The manufacturing method of the electroconductive member characterized by including the process of performing a reduced pressure drying process and forming an electroconductive layer. The conductive ink composition is (E) the following general formula (i):
[In general formula (i), X ¹ represents a residue obtained by removing active hydrogen (H ^* ) of an amino group and / or imino group from a polyamine, and p + q represents the number of active hydrogens possessed by the polyamine. P + q = 2 to 16 and p = 1 to 16, each AO independently represents an alkyleneoxy group having 2 to 4 carbon atoms, and each r independently represents an added mole number of the alkyleneoxy group represented by AO. R = 1 to 25. ]
The method for producing a conductive member according to claim 1, further comprising a polyamine alkylene oxide adduct represented by the formula: