JP2017119814A - Conductive ink composition, conductive member produced using the same, and conductive member production method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive ink composition which can provide a conductive member with sufficient conductivity even when microsized copper particles are used in a simple atmosphere such as air under a colder dry condition than the prior art without adding an additional dispersion medium.SOLUTION: A conductive ink composition comprises (A) an oxycarbonic acid, (B) an amide compound represented by the general formula (1) in the figure, and (C) copper particles. [In the general formula (1), Rrepresents a hydrogen atom, or a C1-18 straight or branched, saturated or unsaturated hydrocarbon group; and Rand Rare each independently a hydrogen atom, methyl group or ethyl group.]SELECTED DRAWING: None

Description

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

  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 has a problem in that electromigration is likely to occur, and the material silver is an expensive metal, resulting in an increase in cost. 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 copper metal has a high melting point, so it is difficult to completely fuse the copper particles with each other by sintering at a low temperature. Since it 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) is characterized by containing formic acid or acetic acid and an alcohol or ether having 1 to 3 carbon atoms for low-temperature reduction sintering of copper nanoparticles. A reducing agent and a low-temperature sintering method using the same are described. 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 micro size or larger. Then, there was a problem that sintering at 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 an electrically conductive portion is insufficient and sufficient conductivity cannot be obtained, and the usable copper particles are limited to 5 μm or less. was there.

JP 2010-59535 A JP 2012-131895 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. A conductive ink composition that makes it possible to obtain a conductive member having sufficient conductivity without blending an additional dispersion medium, a conductive member produced using the conductive ink composition, and the conductive member It aims at providing the manufacturing method of an electroconductive member.

  As a result of intensive studies to achieve the above object, the present inventors have obtained the above object by including a combination of oxycarboxylic acid and a specific amide compound in a conductive ink composition using copper particles. It has been found that this can be achieved, and the present invention has been completed.

  That is, the conductive ink composition of the present invention comprises (A) oxycarboxylic acid, (B) the following general formula (1):

[In General Formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may be linear or branched and may be saturated or unsaturated, and R ² and R ³ are each independently hydrogen. An atom, a methyl group, or an ethyl group is represented. ]
It contains the amide compound represented by these, and (C) copper particle, It is characterized by the above-mentioned.

  In the conductive ink composition of the present invention, as the amide compound (B), N, N-dimethylformamide, N, N-diethylformamide, N-methyl-N-ethylformamide, N, N-dimethylacetamide, N , N-diethylacetamide, N-methyl-N-ethylacetamide, N-methylformamide, N-ethylformamide, N-methylacetamide, N-ethylacetamide, oleic acid amide, stearic acid amide, palmitic acid amide, myristic acid amide And at least one selected from the group consisting of lauric acid amides.

  In the conductive ink composition of the present invention, the (A) oxycarboxylic acid is preferably at least one selected from the group consisting of oxycarboxylic acids having 2 to 14 carbon atoms.

  Furthermore, in the conductive ink composition of the present invention, the (C) copper particles preferably have an average particle diameter in the range of 0.01 to 100 μm.

  In the conductive ink composition of the present invention, the content of the (A) oxycarboxylic acid is within a range of 0.1 to 30% by mass based on 100% by mass of the conductive ink composition. It is preferable that the content of the (B) amide compound is in the range of 1 to 99% by mass and the content of the (C) copper particles is in the range of 0.8 to 98.9% by mass.

  Furthermore, the conductive member of the present invention is obtained by applying the conductive ink composition of the present invention to a substrate and drying it.

  Moreover, the manufacturing method of the electroconductive member of this invention is a method characterized by apply | coating the electroconductive ink composition of the said this invention to a base material, and drying-processing, and obtaining an electroconductive member.

  In the conductive member and the method for producing the same of the present invention, the drying treatment is preferably a pressure drying treatment for drying while applying pressure or a vacuum drying treatment for drying while reducing pressure.

  In addition, by using the conductive ink composition of the present invention, even when micro-sized copper particles are used, an additional atmosphere can be added under a simple atmosphere such as air and under drying conditions lower than conventional ones. The reason why it is possible to obtain a conductive member having sufficient conductivity without adding a dispersion medium is not necessarily clear, but the present inventors speculate as follows. That is, in the conductive ink composition using the copper particles of the present invention, by containing the oxycarboxylic acid and the specific amide compound in combination, the reaction of the specific amide compound and the copper particles causes the copper particles to react. The inventors speculate that a copper ammonium salt is formed on the surface, and then the formed copper ammonium salt is reduced to copper by oxycarboxylic acid, and at that time, adjacent copper particles are fused. Furthermore, in the conductive ink composition of the present invention, since the specific amide compound also functions as a so-called dispersion medium, the present inventors speculate that it is not necessary to add another dispersion medium. .

  According to the present invention, even when micro-sized copper particles are used, it is sufficient to add no additional dispersion medium under a simple atmosphere such as air and under drying conditions lower than conventional ones. It is possible to provide a conductive ink composition capable of obtaining a conductive member having excellent conductivity, a conductive member manufactured using the conductive ink composition, and a method of manufacturing a conductive member using the conductive member. Become.

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

[Conductive ink composition]
First, the conductive ink composition of the present invention will be described. That is, the conductive ink composition of the present invention comprises (A) oxycarboxylic acid, (B) the following general formula (1):

[In General Formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may be linear or branched and may be saturated or unsaturated, and R ² and R ³ are each independently hydrogen. An atom, a methyl group, or an ethyl group is represented. ]
It contains the amide compound represented by these, and (C) copper particle, It is characterized by the above-mentioned.

  First, (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 hydroxyl group and a carboxyl 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, and it is still more preferable. In addition, the content of the component (A) is preferably 0.1 to 30% by mass, and preferably 1 to 30% by mass based on 100% by mass of the conductive ink composition of the present invention. More preferred. 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, the (B) amide compound (hereinafter referred to as “component (B)”) will be described. In the present invention, as the component (B), the following general formula (1):

[In General Formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may be linear or branched and may be saturated or unsaturated, and R ² and R ³ are each independently hydrogen. An atom, a methyl group, or an ethyl group is represented. ]
The amide compound represented by these is used.

The “hydrocarbon group having 1 to 18 carbon atoms which may be linear or branched and may be saturated or unsaturated” as R ¹ in the general formula (1) includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. , A butyl group which may be linear or branched, a pentyl group which may be linear or branched, a hexyl group which may be linear or branched, a heptyl group which may be linear or branched, an octyl group which may be linear or branched, and a linear or branched group Nonyl group which may be linear or branched, undecyl group which may be linear or branched, dodecyl group which may be linear or branched, tridecyl group which may be linear or branched, tetradecyl group which may be linear or branched, Linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, straight But good undecene group branched, optionally tridecene group be linear or branched, optionally pentadecene group be linear or branched, include good heptadecene group be linear or branched, among which the number of carbon atoms is preferably from 1 to 12.

  As the amide compound (B) used in the present invention, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-N-ethylformamide, N, N- is used from the viewpoint of promoting fusion of copper particles. Dimethylacetamide, N, N-diethylacetamide, N-methyl-N-ethylacetamide, N-methylformamide, N-ethylformamide, N-methylacetamide, N-ethylacetamide, oleic acid amide, stearic acid amide, palmitic acid amide Myristic acid amide and lauric acid amide are 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 1 to 99% by mass and more preferably 5 to 90% by mass based on 100% by mass of the conductive ink composition of the present invention. If 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, if 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. .

  Further, the average particle size of “component (C)” in the conductive ink composition of the present invention is not particularly limited, but is preferably 0.01 to 100 μm, and more preferably 0.01 to 50 μm. . 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 above-mentioned copper particles is determined by observation with a transmission electron microscope (TEM) or scanning electron microscope (SEM), and the particle diameter of each particle for any 50 or more copper particles ( (Diameter) are measured, and they are obtained by arithmetic averaging. 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 0.8 to 98.9% by mass based on 100% by mass of the conductive ink composition of the present invention from the viewpoint of the conductivity of the conductive member obtained. Is preferable, and it is more preferable that it is 1-90 mass%.

  As described above, the conductive ink composition of the present invention contains the (A) oxycarboxylic acid, the (B) amide compound, and the (C) copper particles, which will be further described below. (D) A dispersion medium and / or (E) a polyamine alkylene oxide adduct may be further blended.

  Such a dispersion medium (D) (hereinafter referred to as “component (D)”) is not particularly limited as long as it does not react with the above-described components (A) and (B), and is conventionally conductive. It may be a known dispersion medium used in the ink composition. 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.

  (D) When mix | blending component, the content is 0.7-99 on the basis of 100 mass% of mass of the conductive ink composition of this invention from a viewpoint of the handleability of the conductive ink composition obtained. It is preferable that it is mass%, it is more preferable that it is 0.8-99 mass%, and it is still more preferable that it is 10-99 mass%.

  The (E) polyamine alkylene oxide adduct (hereinafter referred to as “component (E)”) has the following general formula (2):

[In General Formula (2), 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 alkylene oxide group having 2 to 4 carbon atoms, and each r independently represents an added mole number of the alkylene oxide group represented by AO. R = 1 to 25. ]
It is represented by

In the general formula (2), X ¹ is a residue obtained by removing an active hydrogen (H ^* ) of an amino group and / or imino group having two or more per molecule from a polyamine, and is represented by the general formula (2). The polyamine alkylene oxide adduct is a compound obtained by adding 1 mol or more of alkylene oxide to 1 mol of polyamine to the active hydrogen of the amino group and / or imino group in the polyamine molecule. 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 of X ¹ (the total number of amino groups and imino groups in the case of having both amino groups and imino groups) is preferably 2-8, more preferably 2-6, from the viewpoint of fluidity. 2-3 are particularly preferred.

  Furthermore, in the general formula (2), p + q represents the number of active hydrogens that the polyamine had, p + q = 2 to 16 and p = 1 to 16, p + q = 2 to 12 and p = 1 to 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 (2), AO specifically includes an ethylene oxide group, a propylene oxide group, a 1,2-butylene oxide group, a 2,3-butylene oxide group, a 1,3-butylene oxide group, 1,4- Examples include butylene oxide groups, and ethylene oxide groups and propylene oxide groups 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 (2), r represents the addition mole number of the alkylene oxide 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 (2), it is preferable that the number of pxr (r in this case is the average addition mole number of an alkylene oxide group) is 2-100, and it is more preferable that it is 4-70.

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

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

  (E) When mix | blending a component, it is preferable that the content is 0.1-100 mass parts on the basis of 100 mass parts of the above-mentioned (C) copper particle, 0.1-75 mass parts It is more preferable that it is 1-60 mass parts. Moreover, it is preferable that content of (E) component is 0.1-30 mass% on the basis of 100 mass% of the conductive ink composition of this invention, and is 0.1-25 mass%. It is more preferable. 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 of the present invention, a known anti-drying agent, dispersant, antioxidant, concentration adjusting agent, surface tension adjusting agent, viscosity adjusting agent and the like are within the range not impairing the effects of the present invention. Additive components can be added.

  Next, a method for producing the conductive ink composition of the present invention will be described. Although the manufacturing method of the electroconductive ink composition of this invention is not specifically limited, For example, when adding (B) component ((D) component further, (B) component and (D) component) to (A) In the case of further adding the component ((E) component), the (A) component and the (E) component) are stirred and mixed to dissolve, and then the (C) component is stirred and mixed to disperse. In addition, when (B) component ((D) component is added further, (B) component and (D) component) is solid at room temperature, after heating and melting it into a liquid state, A conductive ink composition can be obtained by the above-described production method. 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.

[Conductive member and manufacturing method thereof]
Next, the conductive member of the present invention using the above-described conductive ink composition of the present invention and the manufacturing method thereof will be described. That is, the method for producing the conductive member of the present invention is a method for obtaining a conductive member by applying the conductive ink composition of the present invention to a substrate and drying it.

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.

  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, dispenser Examples of the coating method and inkjet method. The amount of application of the conductive ink composition to the substrate is not particularly limited, and may be adjusted as appropriate according to the desired film thickness of the conductive member. Depending on the application method, the conductive ink composition must be in a liquid state. In that case, if the conductive ink composition is in a solid state, the solid conductive ink composition is heated to heat the liquid. It can be melted into a shape and used.

  Furthermore, the atmospheric conditions in the environment for carrying out the method for producing a conductive member of the present invention are not particularly limited. For example, air atmosphere; inert gas atmosphere such as nitrogen gas or argon gas; hydrogen gas or the like A reducing atmosphere can be mentioned. In the present invention, even when micro-sized copper particles are used, a conductive member having sufficient conductivity is obtained under a simple atmosphere such as air and under dry conditions lower than conventional ones. Therefore, an air atmosphere is preferable from the viewpoint of simplicity of facilities and the like.

  The drying method in the manufacturing method of the electroconductive member of this invention is not specifically limited, For example, room temperature drying, heat drying, warm air drying, cold air drying, and plasma drying are mentioned.

  Moreover, in the manufacturing method of the electroconductive member of this invention, room temperature drying or heat drying is preferable from a viewpoint of equipment versatility, and the drying temperature is 20-300 from the viewpoint of improving the electroconductivity of the electroconductive member obtained. The range of ° C is preferred, and the range of 40 to 250 ° C is more preferred. If the drying temperature is less than the lower limit, the copper particles tend to be difficult to fuse. On the other hand, if the drying temperature exceeds the upper limit, the substrate or the like tends to be easily damaged by heat, such as melting or deformation. In the present invention, even when micro-sized copper particles are used, a conductive member having sufficient conductivity is obtained under a simple atmosphere such as air and under dry conditions lower than conventional ones. Therefore, a low temperature of 20 to 150 ° C. can be adopted as the drying temperature.

  The drying time in the method for producing a conductive member of the present invention is not particularly limited, and may be appropriately selected in consideration of the desired copper film conductivity (resistance value), drying temperature, etc. Specifically, 10 seconds to 24 hours are preferable. In addition, when drying at room temperature without heat drying, you may dry in the desiccator etc. which put the desiccant in order to accelerate | stimulate drying.

In the method for producing a conductive member of the present invention, the drying treatment will be described below.
(I) a pressure drying process for drying while applying pressure, or
(Ii) reduced pressure drying treatment for drying while reducing pressure;
It is preferable that

  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.

  As pressure conditions in such pressure drying treatment, the pressure is preferably 0.1 to 20 MPa, more preferably 1 to 10 MPa. If the pressure is less than the lower limit, there is a tendency that the effect of improving the conductivity of the conductive member obtained due to insufficient fusion of the copper particles tends to be insufficient. On the other hand, if the pressure exceeds the upper limit, There is a tendency that the cost of the apparatus for pressing increases.

  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).

  As a pressure reduction condition in such a vacuum drying treatment, the pressure is preferably 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. In this case, the effect of improving the electrical conductivity tends to be insufficient.

  Moreover, it does not specifically limit as a drying method in such a pressure drying process and a reduced pressure drying process, For example, room temperature drying, heat drying, warm air drying, cold air drying, and plasma drying are mentioned.

  Furthermore, such pressure drying treatment and reduced pressure drying treatment 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.

  Moreover, the processing time in such a pressure drying process and a reduced pressure drying process is not specifically limited, If it selects suitably considering the electroconductivity (resistance value) of a desired electroconductive member, process temperature, etc. In general, it is generally preferable that the time for maintaining the pressure and temperature is 10 seconds to 24 hours. In addition, as such a pressure drying process and a reduced pressure drying process, when implementing at room temperature, without heating, you may implement in the desiccator etc. which put the desiccant in order to accelerate | stimulate drying.

  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 1-41 and Comparative Examples 1-9)
The conductive ink compositions of Examples 1 to 41 and Comparative Examples 1 to 9 were produced by the following methods so as to be the components and compositions shown in Tables 1 to 7, respectively. That is, in order to obtain the compositions shown in Tables 1 to 7, when (B) component ((D) component is further added, (B) component and (D) component), (A) component is added and mixed. (C) component is added and mixed, and then subjected to ultrasonic treatment (ULTRASONIC CLEANER “SONOQUICK C10” manufactured by Ultrasonic Industry Co., Ltd.) for 30 minutes to form each conductive ink as a uniform dispersion. A composition was obtained. In Examples 9 and 10, after the component (B) was heated and melted into a liquid state, a conductive ink composition was obtained by the above-described production method.

  Next, in Examples 1 to 27 and Comparative Examples 1 to 3, the obtained conductive ink compositions were each a rectangular solid printing portion of 3 cm in length and 1 cm in width on a glass substrate with an applicator in an air atmosphere. (Wet film thickness: 300 μm) and dried at the treatment temperatures and treatment times shown in Tables 1 to 3 and Table 6 respectively to obtain conductive films (conductive members). In Examples 9 and 10, the conductive ink composition obtained by the above method was heated and melted into a liquid state, and then each conductive film (conductive member) was formed by the above coating method. Obtained.

  Further, in Examples 28 to 34 and Comparative Examples 4 to 6, the obtained conductive ink compositions were respectively printed in a rectangular solid printing portion of 3 cm in length and 1 cm in width on a glass substrate with an applicator in an air atmosphere. (Wet film thickness: 300 μm), and dried by using an atmosphere-controlled heating and pressurizing apparatus at the processing temperature, processing time, atmosphere and pressing conditions shown in Table 4 and Table 7, respectively. A film (conductive member) was obtained.

  Furthermore, in Examples 35 to 41 and Comparative Examples 7 to 9, the obtained conductive ink compositions were each rectangular solid printing portions having a length of 3 cm and a width of 1 cm on a glass substrate with an applicator in an air atmosphere. (Wet film thickness: 300 μm) and using an atmosphere-controlled heating / depressurization apparatus, and drying at the treatment temperature, treatment time, atmosphere and decompression conditions shown in Table 5 and Table 7, respectively, A conductive member was obtained.

  The volume resistivity (Ω · cm) of the obtained conductive film (conductive member) was measured using a Loresta pointer meter (“MCP-T610” manufactured by Mitsubishi Chemical Corporation). The results are shown in Tables 1-7. In addition, volume resistivity becomes easy to conduct electricity, so that a numerical value is low, and it determines with it being favorable.

In addition, the blank in Tables 1-7 shows 0 (zero). Moreover, the following were used as a copper particle in Tables 1-7.
Copper particles: “Sub-micro copper powder IOXCu750” manufactured by IOX, average particle diameter of 750 nm, and copper content of 99% by mass or more.

  As is clear from the results shown in Tables 1 to 7, when the conductive ink composition of the present invention is used, any copper particles are used under a simple atmosphere of air and conventionally. It was confirmed that even under lower temperature drying conditions, it is possible to form a conductive member having sufficient conductivity stably. In addition, when the conductive member is formed using the conductive ink composition of the present invention, the conductivity of the resulting conductive member tends to be further improved by drying under pressure or reduced pressure. Was confirmed. Furthermore, since the specific amide compound used in the present invention also functions as a so-called dispersion medium, it is possible to form a conductive member that stably has sufficient conductivity without additionally adding another dispersion medium. It was confirmed that it was possible.

  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. A conductive ink composition capable of obtaining a conductive member having sufficient conductivity without adding an additional dispersion medium under a simple atmosphere and under drying conditions lower than conventional ones, and It becomes possible to provide the electroconductive member manufactured using it, and the manufacturing method of the electroconductive member using the same.

  Therefore, when a conductive member is obtained using the conductive ink composition of the present invention, drying at a low temperature of about room temperature to about 300 ° C. is possible, and at that time, the substrate is damaged by heat. Since the problem is solved, the present invention is very useful when manufacturing wiring, electrodes and the like on a circuit board.

Claims (9)

(A) oxycarboxylic acid, (B) the following general formula (1):
[In General Formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may be linear or branched and may be saturated or unsaturated, and R ² and R ³ are each independently hydrogen. An atom, a methyl group, or an ethyl group is represented. ]
A conductive ink composition comprising an amide compound represented by formula (C) and (C) copper particles.   The (B) amide compound is N, N-dimethylformamide, N, N-diethylformamide, N-methyl-N-ethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N. -Selected from the group consisting of ethylacetamide, N-methylformamide, N-ethylformamide, N-methylacetamide, N-ethylacetamide, oleic acid amide, stearic acid amide, palmitic acid amide, myristic acid amide and lauric acid amide The conductive ink composition according to claim 1, wherein the conductive ink composition is at least one kind.   The conductive ink composition according to claim 1, wherein the (A) oxycarboxylic acid is at least one selected from the group consisting of oxycarboxylic acids having 2 to 14 carbon atoms.   4. The conductive ink composition according to claim 1, wherein an average particle diameter of the (C) copper particles is in a range of 0.01 to 100 μm.   Based on 100% by mass of the conductive ink composition, the content of the (A) oxycarboxylic acid is in the range of 0.1 to 30% by mass, and the content of the (B) amide compound is 1 to 99. The content of the (C) copper particles is in the range of 0.8 to 98.9% by mass within the range of mass%, and according to any one of claims 1 to 4. Conductive ink composition.   A conductive member obtained by applying the conductive ink composition according to any one of claims 1 to 5 to a substrate and drying it.   The conductive member according to claim 6, wherein the drying process is a pressure drying process for drying while applying pressure or a vacuum drying process for drying while reducing pressure.   A method for producing a conductive member, comprising: applying a conductive ink composition according to any one of claims 1 to 5 to a base material, followed by drying to obtain a conductive member.   The method for producing a conductive member according to claim 8, wherein the drying process is a pressure drying process for drying while applying pressure or a vacuum drying process for drying while reducing pressure.