JP2012126814A - Conductive ink composition, and method for producing electrically conductive site - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive ink composition for forming electrically conductive sites containing copper as a main component, which can form the electrically conductive sites at a temperature enabling to use a resin as a substrate, can form patterns by a screen printing method, contains the copper in a high concentration, and does not deteriorate the conductivity, even when contacted with the atmosphere for a long time, and to provide a method for producing the electrically conductive site using the same.SOLUTION: There is provided the conductive ink composition comprising at least one of a specific alkoxyamino compound and a specific alkoxydiamino compound, metal particles, and copper formate particles, and an electrically conductive site is formed with the same.

Description

  The present invention relates to a conductive ink composition and a method for producing an electrically conductive portion. The conductive ink of the present invention can be suitably used as a circuit pattern forming material for a wiring board in the electronics field.

  2. Description of the Related Art In recent years, a technique that uses a metal particle dispersion as a conductive ink, forms a desired pattern by an ink jet printing method or a screen printing method, and forms an electrically conductive portion such as a wiring in a circuit board has attracted attention. . When the average particle diameter of the metal particles is about several nanometers to several tens of nanometers, the melting point is remarkably lowered than that of the bulk metal, and the metal particles are sintered at a low temperature by utilizing the fusion of the particles at a low temperature. To obtain an electrically conductive portion. At present, such conductive ink mainly contains silver particles.

  However, silver has a problem that electromigration tends to occur, and silver itself is an expensive metal. Here, electromigration is a phenomenon in which a metal component (for example, a metal used for a wiring or an electrode) moves across or inside a non-metallic medium (for example, an insulator) due to the influence of an electric field.

  Therefore, there is a demand for a conductive ink that can reduce the cost, is less likely to cause electromigration, and can form wiring having copper as a main component with high conductivity by a printing method.

  As copper conductive ink, organic compounds having hetero atoms such as nitrogen, oxygen, sulfur, etc. in the molecular structure are adsorbed on the surface of metal copper, preventing contact with oxygen and water, preventing oxidation, and at the same time, metal copper particles Many methods using copper particles having an average particle diameter of about several nanometers to several hundred nanometers that suppress mutual aggregation have been proposed. For example, a method using alkylamine as an oxidation inhibitor has been proposed (see, for example, Patent Document 1).

  However, the conductive ink using such metal copper particles removes the oxidation inhibitor that coats the surface of the metal copper particles in the process of applying the metal copper particles and then forming the electrically conductive portion, and the metal copper particles In general, heating at a high temperature of about 300 ° C. is necessary to fuse the substrate, and there is a problem that applicable substrates are limited. Moreover, since there are many cases where heating in a reducing atmosphere containing hydrogen is required in order to suppress oxidation of metallic copper, there has been a serious problem in terms of safety.

  Therefore, a conductive ink that can form an electrically conductive portion of copper by heating at a relatively low temperature in a non-reducing atmosphere not containing hydrogen without using metal copper particles has been studied.

  For example, there is a method of depositing a copper layer on a substrate by bringing a mixed product composed of copper (II) formate and an alkoxyalkylamine into contact with the substrate at 80 to 200 ° C. and 0.1 to 5 bar. It has been proposed (see, for example, Patent Document 2).

Further, for example, (A) copper formate (II) or a hydrate thereof, and (B) formula: NR ₁ R ₂ R ₃ (wherein R ₁ is composed of a hydroxyl group, a methoxy group, an ethoxy group, and an amino group. Represents a C2-C4 linear or branched alkyl group substituted with one of the substituents selected from the group, wherein R ₂ and R ₃ are each independently hydrogen; Or an amino compound having 1 to 3 carbon atoms which may be substituted with a hydroxyl group or an amino group.) And (C) a saturated fatty acid having 5 to 11 carbon atoms, and component (A) A layer of a conductive paste characterized in that the component (C) is 0.1 to 1 mol with respect to 1 mol is formed on a substrate and heated at 200 to 550 ° C. in a non-oxidizing atmosphere. A method of manufacturing a copper film has been proposed. (For example, refer to Patent Document 3).

  However, in the method of Patent Document 2, since it is a solution in which copper (II) formate is completely dissolved in an alkoxyalkylamine, in the screen printing method in which the viscosity is low and a viscosity of about 10 to 500 Pa · s is necessary, There is a problem that it is difficult to form, and there is a problem that the volume change is large during the heat treatment after application to the substrate, and there is a problem that the pattern shape and film thickness change greatly after application and after heating. There was a fear.

  Moreover, in the method of patent document 3, although pattern formation by a screen printing method is possible, copper concentration is about 15 weight% or less with respect to the weight of the whole electrically conductive paste. When the copper content is low, there is a problem that, when forming the electrically conductive part, it is necessary to repeatedly apply the film to obtain the desired film thickness, and there is a problem that the work efficiency is lowered. There was a risk of not being able to.

  As described above, none of the conventional methods can be said to be sufficient, and further studies have been demanded for industrial practical use. That is, in a conductive ink composition for forming an electrically conductive portion mainly composed of copper, the electrically conductive portion can be formed at a temperature at which a resin can be used as a substrate, and pattern formation by a screen printing method is possible. Therefore, there has been a demand for the development of a conductive ink composition that contains a high concentration of copper and does not deteriorate in conductivity even when exposed to the atmosphere for a long time.

JP 2007-32215 A Japanese Patent Laying-Open No. 2005-2471 JP 2009-158441 A

  The present invention has been made in view of the above-described background art, and an object of the present invention is to use a resin as a base material in a conductive ink composition for forming an electrically conductive portion mainly composed of copper. An electrically conductive ink composition that can form an electrically conductive portion at a temperature, can be patterned by a screen printing method, contains a high concentration of copper, and has no decrease in conductivity even when in contact with the atmosphere, And it is providing the manufacturing method of the electrical conduction | electrical_connection site | part using the same.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and found a conductive ink composition containing an amine compound, metal particles, and copper formate particles. The conductive ink composition can form an electrically conductive portion at a temperature at which a resin can be used as a substrate, can be formed by a screen printing method, contains a high concentration of copper, and is contained in the atmosphere. It has been found that there is no decrease in conductivity even after a long contact, and the present invention has been completed.

That is, the present invention relates to a conductive ink composition and a method for producing an electrically conductive portion as described below.
[1] A conductive ink composition comprising at least one amine compound represented by the following general formula (1) and general formula (2), metal particles, and copper formate particles.

[R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, or a 2-ethoxyethyl group, and R ₃ and R ₄ each independently represent A hydrogen atom or a methyl group, and R ₅ is a hydrogen atom, a straight chain having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a 2-hydroxyethyl group, A 2-methoxyethyl group or a 2-ethoxyethyl group is represented, and X represents a methylene group, an ethylene group, or a propylene group. ]

[R _{6 to} R ₉ each independently represents a hydrogen atom, a methyl group, or an ethyl group. ]
[2] The amine compound represented by general formula (1) and general formula (2) is ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, 2-methoxyethylamine, N-methyl-2- Methoxyethylamine, N, N-dimethyl-2-methoxyethylamine, bis (2-methoxyethyl) amine, 2-ethoxyethylamine, N-methyl-2-ethoxyethylamine, N, N-dimethyl-2-ethoxyethylamine, bis ( 2-ethoxyethyl) amine, 2-n-propoxyethylamine, N-methyl-2-n-propoxyethylamine, N, N-dimethyl-2-n-propoxyethylamine, 2-i-propoxyethylamine, N-methyl-2 -I-propoxyethylamine, N, N-dimethyl-2-i-propoxye Ruamine, 2-n-butoxyethylamine, N-methyl-2-n-butoxyethylamine, N, N-dimethyl-2-n-butoxyethylamine, 2- (2-hydroxyethyloxy) ethylamine, N-methyl-2- (2-hydroxyethyloxy) ethylamine, N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine, 2- (2-methoxyethyloxy) ethylamine, N-methyl-2- (2-methoxyethyloxy) Ethylamine, N, N-dimethyl-2- (2-methoxyethyloxy) ethylamine, 2- (2-ethoxyethyloxy) ethylamine, N-methyl-2- (2-ethoxyethyloxy) ethylamine, N, N-dimethyl -2- (2-Ethoxyethyloxy) ethylamine, 1,1-dimethyl-2-hydroxy Roxyethylamine, N-methyl-1,1-dimethyl-2-hydroxyethylamine, N, N-dimethyl-1,1-dimethyl-2-hydroxyethylamine, 1,1-dimethyl-2-methoxyethylamine, N-methyl- 1,1-dimethyl-2-methoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-methoxyethylamine, 1,1-dimethyl-2-ethoxyethylamine, N-methyl-1,1-dimethyl-2 -Ethoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-ethoxyethylamine, 3-hydroxypropylamine, N-methyl-3-hydroxypropylamine, N, N-dimethyl-3-hydroxypropylamine, 3 -Methoxypropylamine, N-methyl-3-methoxypropylamine, N, N-dimethyl Tyl-3-methoxypropylamine, 3-ethoxypropylamine, N-methyl-3-ethoxypropylamine, N, N-dimethyl-3-ethoxypropylamine, 3-n-propoxypropylamine, 3-i-propoxypropyl Amine, N-methyl-3-i-propoxypropylamine, N, N-dimethyl-3-i-propoxypropylamine, 3-n-butoxypropylamine, N-methyl-3-n-butoxypropylamine, N, N-dimethyl-3-n-butoxypropylamine, N, N ′, N′-trimethyl-N- (2-hydroxyethyl) ethylenediamine, N, N ′, N′-trimethyl-N- (2-methoxyethyl) From ethylenediamine and N, N ', N'-trimethyl-N- (2-ethoxyethyl) ethylenediamine Conductive ink composition according to [1], wherein the at least one selected from the group that.
[3] The metal particles are at least one metal species selected from the group consisting of gold particles, silver particles, copper particles, platinum particles, palladium particles, rhodium particles, iridium particles, ruthenium particles, silver-coated copper particles, and osmium particles. The conductive ink composition as described in [1] or [2] above, which is contained.
[4] The above [1] to [3], wherein the metal particles are at least one selected from the group consisting of gold particles, silver particles, copper particles, platinum particles, palladium particles, and silver-coated copper particles. The conductive ink composition according to any one of the above.
[5] The conductive ink composition according to any one of [1] to [4], wherein the average particle diameter of the metal particles is in the range of 0.01 to 100 μm.
[6] The conductive ink composition as described in any one of [1] to [5] above, wherein the average particle diameter of the copper formate particles is in the range of 1 nm to 5 μm.
[7] The concentration of the metal particles is 0.1 to 99% by weight and the concentration of the amine compound represented by the general formula (1) or (2) is 0.1 to 80% by weight with respect to the total amount of the conductive ink composition. The conductive ink composition according to any one of [1] to [6] above, wherein the concentration of the copper formate particles is 0.1 wt% to 80 wt%.
[8] The conductive ink composition as described in any one of [1] to [7] above, further containing a dispersion medium.
[9] The above-mentioned [8], wherein the dispersion medium is at least one selected from the group consisting of alcohols, ethers, esters, aliphatic hydrocarbons, and aromatic hydrocarbons. Conductive ink composition.
[10] The above [8], wherein the dispersion medium is at least one selected from the group consisting of hexanol, terpineol, methyl-t-butyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, n-hexane, and γ-butyrolactone. The conductive ink composition according to [9].
[11] The conductive ink according to any one of [8] to [10] above, wherein the concentration of the dispersion medium is in the range of 1 to 90% by weight with respect to the weight of the entire conductive ink composition. Composition.
[12] The conductive ink composition as described in any one of [1] to [11] above, wherein the viscosity of the conductive ink composition is in the range of 1 to 1000 Pa · s.
[13] A conductive ink composition according to any one of the above [1] to [12] is applied or filled on a base material, and the base material is heat-treated. Method.
[14] The base material is one or two or more composite base materials selected from the group consisting of resin, paper, glass, silicon-based semiconductor, compound semiconductor, metal oxide, metal nitride, and wood. The method for producing an electrically conductive portion according to [13] above, which is characterized in that
[15] The method for producing an electrically conductive part according to [13] or [14] above, wherein the temperature of the heat treatment is in a range of 60 to 300 ° C.
[16] The method for producing an electrically conductive portion according to any one of [13] to [15], wherein the heat treatment is performed in a non-oxidizing atmosphere.

  The present invention has the following effects.

  (1) Since the conductive ink composition of the present invention can form an electrically conductive portion such as a conductive pattern by a simple method such as coating, filling, and heating, energy saving, low cost, and low environment. The load can be achieved and is extremely useful industrially.

  The conductive ink composition of the present invention contains copper formate particles as a copper precursor, and this becomes metallic copper, which is the main component of the electrical conduction site. Therefore, the electrical conduction site having excellent characteristics of copper is provided. It can be formed.

  In addition, since the conductive ink composition of the present invention contains copper formate particles as a solid, the metal concentration is high, and there is no need for recoating to increase the film thickness, or the number of times can be reduced, and work efficiency can be reduced. Excellent. In addition, since it contains metal particles, it plays a role as a filler and is less affected by changes in viscosity and surface tension during heating after coating, so changes in wiring width and wiring shape during coating and after heating are small and dimensional. Excellent accuracy.

  In addition, the conductive ink composition of the present invention is excellent in workability because of a small decrease in conductivity even when handled in the air for a long time.

  In addition, since the conductive ink composition of the present invention can be easily adjusted to a desired viscosity by containing a dispersion medium as required, a pattern can be formed by a screen printing method.

  (2) The method for producing an electrically conductive portion of the present invention uses the conductive ink composition of the present invention, so that a reducing atmosphere containing hydrogen is not required in the step of forming the electrically conductive portion, such as nitrogen. Electrically conductive sites can be formed by heating in an inert atmosphere, and the safety is excellent.

  Moreover, according to the manufacturing method of the electrical conduction site | part of this invention, formation of an electrical conduction site | part is possible at the temperature which can utilize resin as a base material, and it is excellent in versatility.

  The present invention is described in further detail below.

  First, the conductive ink composition of the present invention will be described.

  The conductive ink composition of the present invention includes at least one amine compound represented by the following general formula (1) and general formula (2), metal particles, and copper formate particles.

[R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, or a 2-ethoxyethyl group, and R ₃ and R ₄ each independently represent A hydrogen atom or a methyl group, and R ₅ is a hydrogen atom, a straight chain having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a 2-hydroxyethyl group, A 2-methoxyethyl group or a 2-ethoxyethyl group is represented, and X represents a methylene group, an ethylene group, or a propylene group. ]

[R _{6 to} R ₉ each independently represents a hydrogen atom, a methyl group, or an ethyl group. ]
The conductive ink composition of the present invention plays a role of developing the electrical conductivity of the electrically conductive site formed by heat treatment, whereby copper ions contained in the copper formate particles are reduced by formic acid to become metallic copper. . In addition, the metal particles play a role of promoting reduction of copper ions contained in the copper formate particles when the conductive ink composition is applied on a substrate and subjected to heat treatment. And the processing time can be shortened. Furthermore, the metal particles function as fillers, suppress changes in viscosity and surface tension during heating after application, and reduce changes in the shape of the electrically conductive portion during application and after heating. On the other hand, the amine compound represented by the general formula (1) or (2) has an effect of improving the dispersibility of the metal particles and the copper formate particles and stabilizing the reduction reaction of the copper ions at the time of forming the electrically conductive site. Have.

R ₅ in the general formula (1) is a hydrogen atom or a straight chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, and a straight chain alkyl group having 1 to 6 carbon atoms. Examples of the group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Examples of the branched alkyl group having 3 to 6 carbon atoms include i -Propyl group, i-butyl group, sec-butyl group, t-butyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neo-pentyl group, i-hexyl group and the like. Examples of the 3-6 cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

In the conductive ink composition of the present invention, the amine compound represented by the general formula (1) and the general formula (2) has a coordination ability with respect to metal particles and / or copper formate particles and is dispersed. There is no particular limitation as long as it is an effect that stabilizes the reduction reaction of copper ions at the time of forming an electrically conductive site, and, for example, in the amine compound represented by the above general formula (1), R ₃ and R ₄ are both hydrogen atoms and X is a methylene group, specifically, ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N-ethylethanolamine, N, N-diethylethanolamine, diethanolamine, triethanolamine, N- (2-methoxyethyl) ethanolamine, N, N-bis (2-methoxyethyl) ethanol Ruamine, N- (2-ethoxyethyl) ethanolamine, N, N-bis (2-ethoxyethyl) ethanolamine, 2-methoxyethylamine, N-methyl-2-methoxyethylamine, N, N-dimethyl-2-methoxy Ethylamine, N-ethyl-2-methoxyethylamine, N, N-diethyl-2-methoxyethylamine, N- (2-hydroxyethyl) -2-methoxyethylamine, N, N-bis (2-hydroxyethyl) -2- Methoxyethylamine, bis (2-methoxyethyl) amine, tris (2-methoxyethyl) amine, N- (2-ethoxyethyl) -2-methoxyethylamine, N, N-bis (2-ethoxyethyl) -2-methoxy Ethylamine, 2-ethoxyethylamine, N-methyl-2-ethoxyethylamine N, N-dimethyl-2-ethoxyethylamine, N-ethyl-2-ethoxyethylamine, N, N-diethyl-2-ethoxyethylamine, N- (2-hydroxyethyl) -2-ethoxyethylamine, N, N-bis (2-hydroxyethyl) -2-ethoxyethylamine, N- (2-methoxyethyl) -2-ethoxyethylamine, N, N-bis (2-methoxyethyl) -2-ethoxyethylamine, bis (2-ethoxyethyl) Amine, tris (2-ethoxyethyl) amine, 2-n-propoxyethylamine, N-methyl-2-n-propoxyethylamine, N, N-dimethyl-2-n-propoxyethylamine, N-ethyl-2-n- Propoxyethylamine, N, N-diethyl-2-n-propoxyethylamine, N- (2-hydride Roxyethyl) -2-n-propoxyethylamine, N, N-bis (2-hydroxyethyl) -2-n-propoxyethylamine, N- (2-methoxyethyl) -2-n-propoxyethylamine, N, N-bis (2-methoxyethyl) -2-n-propoxyethylamine, N- (2-ethoxyethyl) -2-n-propoxyethylamine, N, N-bis (2-ethoxyethyl) -2-n-propoxyethylamine, 2 -I-propoxyethylamine, N-methyl-2-i-propoxyethylamine, N, N-dimethyl-2-i-propoxyethylamine, N-ethyl-2-i-propoxyethylamine, N, N-diethyl-2-i -Propoxyethylamine, N- (2-hydroxyethyl) -2-i-propoxyethylamine, N, N-bi (2-hydroxyethyl) -2-i-propoxyethylamine, N- (2-methoxyethyl) -2-i-propoxyethylamine, N, N-bis (2-methoxyethyl) -2-i-propoxyethylamine, N -(2-Ethoxyethyl) -2-i-propoxyethylamine, N, N-bis (2-ethoxyethyl) -2-i-propoxyethylamine, 2-n-butoxyethylamine, N-methyl-2-n-butoxy Ethylamine, N, N-dimethyl-2-n-butoxyethylamine, N-ethyl-2-n-butoxyethylamine, N, N-diethyl-2-n-butoxyethylamine, N- (2-hydroxyethyl) -2- n-butoxyethylamine, N, N-bis (2-hydroxyethyl) -2-n-butoxyethylamine, N- (2-methyl Xylethyl) -2-n-butoxyethylamine, N, N-bis (2-methoxyethyl) -2-n-butoxyethylamine, N- (2-ethoxyethyl) -2-n-butoxyethylamine, N, N-bis (2-Ethoxyethyl) -2-n-butoxyethylamine, 2-t-butoxyethylamine, N-methyl-2-t-butoxyethylamine, N, N-dimethyl-2-t-butoxyethylamine, N-ethyl-2 -T-butoxyethylamine, N, N-diethyl-2-t-butoxyethylamine, N- (2-hydroxyethyl) -2-t-butoxyethylamine, N, N-bis (2-hydroxyethyl) -2-t -Butoxyethylamine, N- (2-methoxyethyl) -2-t-butoxyethylamine, N, N-bis (2-methoxyethyl)- 2-t-butoxyethylamine, N- (2-ethoxyethyl) -2-t-butoxyethylamine, N, N-bis (2-ethoxyethyl) -2-t-butoxyethylamine, 2- (2-hydroxyethyloxy) ) Ethylamine, N-methyl-2- (2-hydroxyethyloxy) ethylamine, N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine, N-ethyl-2- (2-hydroxyethyloxy) ethylamine, N, N-diethyl-2- (2-hydroxyethyloxy) ethylamine, N- (2-hydroxyethyl) -2- (2-hydroxyethyloxy) ethylamine, N, N-bis (2-hydroxyethyl) -2 -(2-hydroxyethyloxy) ethylamine, N- (2-methoxyethyl) -2- (2-hydroxy Tiloxy) ethylamine, N, N-bis (2-methoxyethyl) -2- (2-hydroxyethyloxy) ethylamine, N- (2-ethoxyethyl) -2- (2-hydroxyethyloxy) ethylamine, N, N -Bis (2-ethoxyethyl) -2- (2-hydroxyethyloxy) ethylamine, 2- (2-methoxyethyloxy) ethylamine, N-methyl-2- (2-methoxyethyloxy) ethylamine, N, N- Dimethyl-2- (2-methoxyethyloxy) ethylamine, N-ethyl-2- (2-methoxyethyloxy) ethylamine, N, N-diethyl-2- (2-methoxyethyloxy) ethylamine, N- (2- Hydroxyethyl) -2- (2-methoxyethyloxy) ethylamine, N, N-bis (2-hydroxy) Til) -2- (2-methoxyethyloxy) ethylamine, N- (2-methoxyethyl) -2- (2-methoxyethyloxy) ethylamine, N, N-bis (2-methoxyethyl) -2- (2 -Methoxyethyloxy) ethylamine, N- (2-ethoxyethyl) -2- (2-methoxyethyloxy) ethylamine, N, N-bis (2-ethoxyethyl) -2- (2-methoxyethyloxy) ethylamine, 2- (2-ethoxyethyloxy) ethylamine, N-methyl-2- (2-ethoxyethyloxy) ethylamine, N, N-dimethyl-2- (2-ethoxyethyloxy) ethylamine, N-ethyl-2- ( 2-ethoxyethyloxy) ethylamine, N, N-diethyl-2- (2-ethoxyethyloxy) ethylamine, N- (2- Hydroxyethyl) -2- (2-ethoxyethyloxy) ethylamine, N, N-bis (2-hydroxyethyl) -2- (2-ethoxyethyloxy) ethylamine, N- (2-methoxyethyl) -2- ( 2-Ethoxyethyloxy) ethylamine, N, N-bis (2-methoxyethyl) -2- (2-ethoxyethyloxy) ethylamine, N- (2-ethoxyethyl) -2- (2-ethoxyethyloxy) ethylamine N, N-bis (2-ethoxyethyl) -2- (2-ethoxyethyloxy) ethylamine and the like.

In the amine compound represented by the general formula (1), for example, when R ₃ and R ₄ are both methyl groups and X is a methylene group, specifically, 1,1-dimethyl-2 -Hydroxyethylamine, N-methyl-1,1-dimethyl-2-hydroxyethylamine, N, N-dimethyl-1,1-dimethyl-2-hydroxyethylamine, N-ethyl-1,1-dimethyl-2-hydroxyethylamine N, N-diethyl-1,1-dimethyl-2-hydroxyethylamine, 1,1-dimethyl-2-methoxyethylamine, N-methyl-1,1-dimethyl-2-methoxyethylamine, N, N-dimethyl- 1,1-dimethyl-2-methoxyethylamine, N-ethyl-1,1-dimethyl-2-methoxyethylamine, N, N-diethyl-1 1-dimethyl-2-methoxyethylamine, 1,1-dimethyl-2-ethoxyethylamine, N-methyl-1,1-dimethyl-2-ethoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-ethoxy Ethylamine, N-ethyl-1,1-dimethyl-2-ethoxyethylamine, N, N-diethyl-1,1-dimethyl-2-ethoxyethylamine, 1,1-dimethyl-2-n-propoxyethylamine, N-methyl -1,1-dimethyl-2-n-propoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-n-propoxyethylamine, N-ethyl-1,1-dimethyl-2-n-propoxyethylamine, N, N-diethyl-1,1-dimethyl-2-n-propoxyethylamine, 1,1-dimethyl-2-i-propoxy Ethylamine, N-methyl-1,1-dimethyl-2-i-propoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-i-propoxyethylamine, N-ethyl-1,1-dimethyl-2- i-propoxyethylamine, N, N-diethyl-1,1-dimethyl-2-i-propoxyethylamine, 1,1-dimethyl-2-n-butoxyethylamine, N-methyl-1,1-dimethyl-2-n -Butoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-n-butoxyethylamine, N-ethyl-1,1-dimethyl-2-n-butoxyethylamine, N, N-diethyl-1,1- Dimethyl-2-n-butoxyethylamine, 1,1-dimethyl-2-tert-butoxyethylamine, N-methyl-1,1-dimethyl-2-tert-butoxy Cyethylamine, N, N-dimethyl-1,1-dimethyl-2-tert-butoxyethylamine, N-ethyl-1,1-dimethyl-2-tert-butoxyethylamine, N, N-diethyl-1,1-dimethyl Examples include 2-t-butoxyethylamine.

In the amine compound represented by the general formula (1), for example, when R ₃ and R ₄ are both hydrogen atoms and X is an ethylene group, specific examples include 3-hydroxypropylamine, N -Methyl-3-hydroxypropylamine, N, N-dimethyl-3-hydroxypropylamine, N-ethyl-3-hydroxypropylamine, N, N-diethyl-3-hydroxypropylamine, 3-methoxypropylamine, N -Methyl-3-methoxypropylamine, N, N-dimethyl-3-methoxypropylamine, N-ethyl-3-methoxypropylamine, N, N-diethyl-3-methoxypropylamine, 3-ethoxypropylamine, N -Methyl-3-ethoxypropylamine, N, N-dimethyl-3-ethoxypropylamine, N- Tyl-3-ethoxypropylamine, N, N-diethyl-3-ethoxypropylamine, 3-n-propoxypropylamine, N-methyl-3-n-propoxypropylamine, N, N-dimethyl-3-n- Propoxypropylamine, N-ethyl-3-n-propoxypropylamine, N, N-diethyl-3-n-propoxypropylamine, 3-i-propoxypropylamine, N-methyl-3-i-propoxypropylamine, N, N-dimethyl-3-i-propoxypropylamine, N-ethyl-3-i-propoxypropylamine, N, N-diethyl-3-i-propoxypropylamine, 3-n-butoxypropylamine, N- Methyl-3-n-butoxypropylamine, N, N-dimethyl-3-n-butoxypropylamine N-ethyl-3-n-butoxypropylamine, N, N-diethyl-3-n-butoxypropylamine, 3-t-butoxypropylamine, N-methyl-3-t-butoxypropylamine, N, N- Examples thereof include dimethyl-3-t-butoxypropylamine, N-ethyl-3-t-butoxypropylamine, N, N-diethyl-3-t-butoxypropylamine and the like.

  Specific examples of the amine compound represented by the general formula (2) include N- (2-hydroxyethyl) ethylenediamine, N- (2-methoxyethyl) ethylenediamine, and N- (2-ethoxyethyl). ) Ethylenediamine, N, N ', N'-trimethyl-N- (2-hydroxyethyl) ethylenediamine, N, N', N'-trimethyl-N- (2-methoxyethyl) ethylenediamine, N, N ', N' -Trimethyl-N- (2-ethoxyethyl) ethylenediamine, N, N ', N'-triethyl-N- (2-hydroxyethyl) ethylenediamine, N, N', N'-triethyl-N- (2-methoxyethyl) ) Ethylenediamine, N, N ', N'-triethyl-N- (2-ethoxyethyl) ethylenediamine and the like.

  Of the amine compounds represented by the general formula (1) and the general formula (2), in view of the removability when forming an electrically conductive site and the cost at the time of production or acquisition, the amine compound is ethanol. Amine, N-methylethanolamine, N, N-dimethylethanolamine, 2-methoxyethylamine, N-methyl-2-methoxyethylamine, N, N-dimethyl-2-methoxyethylamine, bis (2-methoxyethyl) amine, 2-ethoxyethylamine, N-methyl-2-ethoxyethylamine, N, N-dimethyl-2-ethoxyethylamine, bis (2-ethoxyethyl) amine, 2-n-propoxyethylamine, N-methyl-2-n-propoxy Ethylamine, N, N-dimethyl-2-n-propoxyethylamine, 2-i-propoxy Ethylamine, N-methyl-2-i-propoxyethylamine, N, N-dimethyl-2-i-propoxyethylamine, 2-n-butoxyethylamine, N-methyl-2-n-butoxyethylamine, N, N-dimethyl- 2-n-butoxyethylamine, 2- (2-hydroxyethyloxy) ethylamine, N-methyl-2- (2-hydroxyethyloxy) ethylamine, N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine, 2- (2-methoxyethyloxy) ethylamine, N-methyl-2- (2-methoxyethyloxy) ethylamine, N, N-dimethyl-2- (2-methoxyethyloxy) ethylamine, 2- (2-ethoxyethyl) Oxy) ethylamine, N-methyl-2- (2-ethoxyethyloxy) ethyl Amine, N, N-dimethyl-2- (2-ethoxyethyloxy) ethylamine, 1,1-dimethyl-2-hydroxyethylamine, N-methyl-1,1-dimethyl-2-hydroxyethylamine, N, N-dimethyl -1,1-dimethyl-2-hydroxyethylamine, 1,1-dimethyl-2-methoxyethylamine, N-methyl-1,1-dimethyl-2-methoxyethylamine, N, N-dimethyl-1,1-dimethyl- 2-methoxyethylamine, 1,1-dimethyl-2-ethoxyethylamine, N-methyl-1,1-dimethyl-2-ethoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-ethoxyethylamine, 3- Hydroxypropylamine, N-methyl-3-hydroxypropylamine, N, N-dimethyl-3-hydroxy Cypropylamine, 3-methoxypropylamine, N-methyl-3-methoxypropylamine, N, N-dimethyl-3-methoxypropylamine, 3-ethoxypropylamine, N-methyl-3-ethoxypropylamine, N, N-dimethyl-3-ethoxypropylamine, 3-n-propoxypropylamine, 3-i-propoxypropylamine, N-methyl-3-i-propoxypropylamine, N, N-dimethyl-3-i-propoxypropyl Amine, 3-n-butoxypropylamine, N-methyl-3-n-butoxypropylamine, N, N-dimethyl-3-n-butoxypropylamine, N, N ′, N′-trimethyl-N- (2 -Hydroxyethyl) ethylenediamine, N, N ', N'-trimethyl-N- (2-methoxyethyl) Tylenediamine, N, N ′, N′-trimethyl-N- (2-ethoxyethyl) ethylenediamine and the like are preferable, and ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, 2-methoxyethylamine, 2-ethoxyethylamine, bis (2-ethoxyethyl) amine, 2-n-propoxyethylamine, 2-n-butoxyethylamine, 2- (2-hydroxyethyloxy) ethylamine, N-methyl-2- (2-hydroxyethyl) Oxy) ethylamine, N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine, 2- (2-methoxyethyloxy) ethylamine, 2- (2-ethoxyethyloxy) ethylamine, 1,1-dimethyl-2 -Hydroxyethylamine, 1,1-dimethyl 2-methoxyethylamine, 1,1-dimethyl-2-ethoxyethylamine, 3-hydroxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-n-propoxypropylamine, 3-n-butoxypropylamine N, N ', N'-trimethyl-N- (2-hydroxyethyl) ethylenediamine, N, N', N'-trimethyl-N- (2-methoxyethyl) ethylenediamine, and N, N ', N'- Trimethyl-N- (2-ethoxyethyl) ethylenediamine and the like are preferable, especially ethanolamine, N, N-dimethylethanolamine, 2-methoxyethylamine, 2-ethoxyethylamine, 2-n-propoxyethylamine, 2-n-butoxyethylamine. N, N-dimethyl-2- (2-hydroxy Ethyloxy) ethylamine, 1,1-dimethyl-2-hydroxyethylamine, 3-ethoxypropylamine, 3-n-propoxypropylamine, 3-n-butoxypropylamine, and N, N, N'-trimethyl-N'- It is preferable to use at least one selected from the group consisting of (2-hydroxyethyl) ethylenediamine and the like.

  The conductive ink composition of the present invention may contain an amine compound other than those described above as long as it does not contradict the spirit of the present invention.

  In the conductive ink composition of the present invention, the amine compound represented by the general formula (1) or (2) may be commercially available or synthesized by a known method, and is not particularly limited. As a synthesis method, for example, in the amine compound represented by the general formula (1), as a method of synthesizing a compound in which X is a methylene group, a corresponding amine and ethylene oxide, propylene oxide, or isobutylene oxide are reacted. Examples thereof include a method in which an alkanolamine is used and a hydroxyl group is further modified to obtain a derivative.

  For example, in the amine compound represented by the general formula (1), as a method of synthesizing a compound in which X is an ethylene group, water or a corresponding alcohol and acrylonitrile are reacted, and the resulting cyanoethyl group is reduced to alkanolamine or alkoxy. Examples thereof include a method of obtaining an amine and further modifying it into a derivative.

  For example, a method for synthesizing the amine compound represented by the general formula (2) includes a method in which a corresponding ethylenediamine and ethylene oxide are reacted to form an alkanolamine, and a hydroxyl group is further modified to obtain a derivative.

  The purity of the amine compound represented by the general formula (1) or (2) is not particularly limited, and is preferably 95% or more and particularly preferably 99% or more in consideration of use in the field of electronic materials.

  In the conductive ink composition of the present invention, the metal particles are not particularly limited. For example, gold particles, silver particles, copper particles, platinum particles, palladium particles, rhodium particles, iridium particles, ruthenium particles, silver coats. What contains the 1 type (s) or 2 or more types of metal seed | species chosen from the group which consists of a copper particle and an osmium particle | grain is mentioned. These metal species may be simple substances or alloys with other metals. Among them, one or two selected from the group consisting of gold particles, silver particles, copper particles, platinum particles, palladium particles, and silver-coated copper particles because of cost, availability, and catalytic ability at the time of forming an electrically conducting site. More than species are preferred. Here, the silver-coated copper particles represent copper particles whose surfaces are coated (coated) with silver.

  In the conductive ink composition of the present invention, metal particles other than these may be used as the metal particles, and in particular, the metal particles are oxidized by the copper ions contained in the copper formate particles, or the catalytic ability is reduced, or It is preferable to use the above-described metal particles because they may not be expressed, and the rate of reduction and precipitation from copper formate particles to metal copper may be reduced.

  In the conductive ink composition of the present invention, the metal particles have a very high activity on the metal surface, there is no risk of being oxidized or dissolved, and the ink can pass through the mesh when printing by screen printing. Therefore, the average particle diameter is preferably in the range of 0.01 to 100 μm.

  In the present invention, as a method for measuring the average particle diameter of metal particles, a transmission electron microscope (TEM) or a scanning electron microscope (SEM) is used, and the particle diameters are relatively uniform from the observed field of view. Select three locations and shoot at the most suitable magnification for particle size measurement. From each photograph, 100 particles that seemed to be the most abundant were selected, the diameter was measured with a ruler, the particle size was calculated by dividing the measurement magnification, and these values were obtained by arithmetic averaging. .

  In the conductive ink composition of the present invention, the metal particles may be commercially available or may be synthesized by a known method, and is not particularly limited. Moreover, there is no limitation in particular as a shape of a metal particle, The thing of arbitrary shapes, such as spherical shape, scale shape, needle shape, and dendritic shape, can be used. As a known synthesis method, for example, mechanical pulverization method, atomization method, gas phase reduction method, CVD method, PVD method, electrolytic deposition method, chemical reduction method and the like are generally known. As a method for synthesizing silver-coated copper particles, for example, a method of plating silver on the copper particles themselves or a method of depositing silver salts such as silver nitrate mixed with copper particles is generally known.

  In the conductive ink composition of the present invention, the purity of the metal particles is not particularly limited, and is preferably 95% or more and particularly preferably 99% or more from the viewpoint of imparting conductivity.

  In the conductive ink composition of the present invention, the copper formate particles are not particularly limited as long as they are copper salt particles having a copper ion as a cation species and formic acid as an anion species. For example, at least one selected from the group consisting of monovalent copper ions, divalent copper ions, and trivalent copper ions, and particles of copper salts made of formic acid can be given. Among these, from the viewpoint of stability and availability, copper salt particles composed of divalent copper ions and formic acid are preferable.

  In the conductive ink composition of the present invention, the purity of the copper formate particles is not particularly limited, and is preferably 95% or more and particularly preferably 99% or more from the viewpoint of imparting conductivity.

  In the conductive ink composition of the present invention, the average particle size of the copper formate particles is not particularly limited, and is preferably in the range of 1 nm or more and less than 10 μm. By setting the amount within this range, when dissolved, when reprecipitated, other particles are deposited as nuclei, and there is no risk of coarsening of the particles, and a conductive ink composition that can form patterns such as wiring by a printing method When it becomes difficult to adapt to an object or forms an electrically conductive part, it does not react completely to the inside of the particle, the reduction to metallic copper becomes insufficient, and the conductivity of the formed electrically conductive part There is no risk of adverse effects.

  In the conductive ink composition of the present invention, the copper formate particles may be commercially available or produced by a known method, and further, by mixing a compound containing copper ions and formic acid in the system. The formed one can be used without any limitation, and is not particularly limited.

  The method for producing the copper formate particles is not particularly limited. For example, a method of pulverizing a coarse powder of copper formate particles by mechanical pulverization, or a method of depositing copper formate particles from a solution containing copper ions and formic acid. Etc. Among these, the method of pulverizing the coarse powder of copper formate particles by mechanical pulverization is preferable because the reproducibility of the particle size is good and a large amount of solvent and large-scale equipment are not required.

  The mechanical pulverization is not particularly limited. For example, it may be dry or wet. Specifically, a ball mill, a bead mill, a sand mill, a jet mill, a cutter mill, a hammer mill, One or more of the group consisting of a vibration mill, a colloid mill, a roll mill, a mortar, and a stone mortar can be used. Among them, it is preferable to use a bead mill because fine particles can be obtained efficiently.

  In the present invention, as a method for measuring the average particle size of copper formate particles, a transmission electron microscope (TEM) or a scanning electron microscope (SEM) is used. Select three locations and shoot at the most suitable magnification for particle size measurement. From each photograph, 100 particles that seemed to be the most abundant were selected, the diameter was measured with a ruler, the particle size was calculated by dividing the measurement magnification, and these values were obtained by arithmetic averaging. .

  In the conductive ink composition of the present invention, the concentration of each component is not particularly limited, and the concentration of metal particles is 0.1 to 99% by weight relative to the total amount of the conductive ink composition, the general formula (1), or It is preferable that the concentration of the amine compound represented by (2) is 0.1 to 80% by weight and the concentration of the copper formate particles is in the range of 0.1 to 80% by weight. The total amount of the amine compound, metal particles, and copper formate particles represented by 1) or (2) does not exceed 100% by weight. ].

  By setting the concentration of the amine compound represented by the general formula (1) or (2) within the above range, the metal particles and / or the copper formate particles are sufficiently dispersed, and the copper in the total amount of the conductive ink composition. Thus, the coating amount of the conductive ink composition for obtaining an electrically conducting portion having a desired film thickness does not increase.

  In addition, by setting the concentration of the metal particles within the above range, the catalytic ability is manifested, and the metal particles function as a filler for improving the film thickness, and the viscosity or solidification of the conductive ink composition may occur. Absent.

  Furthermore, by setting the concentration of the copper formate particles within the above range, the amount of metallic copper generated from the copper formate particles can be reduced, and an electrically conductive portion having a sufficient film thickness can be formed. No increase in viscosity or solidification occurs.

  The conductive ink composition of the present invention may contain a dispersion medium in addition to the above components.

  In the conductive ink composition of the present invention, the dispersion medium can easily adjust the viscosity of the conductive ink composition to a desired viscosity by changing the concentration thereof.

  In the conductive ink composition of the present invention, the dispersion medium is not particularly limited as long as it does not react with the amine compound represented by the general formula (1) or (2), the metal particles, and the copper formate particles. For example, 1 type, or 2 or more types chosen from the group which consists of alcohols, ethers, ester, aliphatic hydrocarbons, and aromatic hydrocarbons are mentioned.

  Specific examples of alcohols include hexanol, heptanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, and terpineol.

  Specific examples of ethers include diethyl ether, diisobutyl ether, dibutyl ether, methyl-t-butyl ether, methyl cyclohexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran, Examples include tetrahydropyran and 1,4-dioxane.

  Specific examples of the esters include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and γ-butyrolactone.

  Specific examples of the aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, decalin and the like. Is exemplified.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, dichlorobenzene, and the like.

  Among these, from the viewpoint of cost and safety, it may be one or more selected from the group consisting of hexanol, terpineol, methyl-t-butyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, n-hexane, and γ-butyrolactone. preferable.

  In the conductive ink composition of the present invention, the dispersion medium may be a commercially available one or one synthesized by a known method.

  In the conductive ink composition of the present invention, the purity of the dispersion medium is not particularly limited, and is preferably 95% or more and particularly preferably 99% or more in consideration of use in the field of electronic materials.

  In the conductive ink composition of the present invention, the concentration of the dispersion medium is not particularly limited, and the concentration of copper in the total amount of the conductive ink composition decreases, and the conductivity for obtaining an electrically conductive portion with a desired film thickness. Since the coating amount of the conductive ink composition does not increase, the concentration of the dispersion medium is preferably in the range of 1 to 90% by weight based on the total amount of the conductive ink composition [however, the general formula (1) Or the total amount of the amine compound, metal particles, copper formate particles, and dispersion medium represented by (2) does not exceed 100% by weight. ].

  In the conductive ink composition of the present invention, the viscosity of the conductive ink composition may be appropriately adjusted according to a desired application method, and is not particularly limited. For example, the conductive ink composition is applied by a screen printing method to form a pattern. When performing, it is preferable to adjust to the range of 1-1000 Pa.s normally.

  Next, a method for producing an electrically conductive portion using the conductive ink composition of the present invention [hereinafter, for the sake of brevity, this is referred to as “the production method of the present invention”. ] Will be described.

  In the present invention, the “electrical conduction part” means a part having electrical conduction formed by the method for producing an electrical conduction part of the present invention. For example, a conductive thin film, a wiring, an electrode, an electrical conduction part between both surfaces and / or multilayers through a through hole, a joint part having electrical conduction between a substrate and an object to be joined, and the like can be given.

  The production method of the present invention is performed by applying or filling the conductive ink composition of the present invention onto a substrate and heat-treating the substrate. For example, after applying the conductive ink composition of the present invention onto a substrate, the copper ion contained in the copper formate particles is reduced by heat treatment, and the general formula (1) or (2) The amine compound shown is volatilized and removed, and an electrical conduction site can be easily formed on the substrate.

  In the production method of the present invention, a known substrate can be used as the substrate, and is not particularly limited. For example, resin, paper, glass, silicon-based semiconductor, compound semiconductor, metal oxide, metal nitride 1 type, 2 types or more, or 2 types or more composite base materials which consist of wood etc. are mentioned.

  Specific examples of the resin include low density polyethylene resin, high density polyethylene resin, ABS resin (acrylonitrile-butadiene-styrene copolymer resin), acrylic resin, styrene resin, vinyl chloride resin, polyester resin, phenol resin, epoxy Examples thereof include resins, polyacetal resins, polysulfone resins, polyimide resins, polyetherimide resins, polyether ketone resins, and cellulose derivatives.

  Specifically, for example, non-coated printing paper, fine-coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unexposed packaging paper ( Examples include heavy-duty kraft paper and double-kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coated balls, chip balls, cardboard and the like.

  Specific examples of the glass include soda glass, borosilicate glass, silica glass, and quartz glass.

  Specific examples of the silicon-based semiconductor include single crystal silicon, polycrystalline silicon, amorphous silicon, and polysilicon.

  Specific examples of the compound semiconductor include CdS, CdTe, GaAs, and the like.

  Specific examples of the metal oxide include alumina, sapphire, zirconia, titania, yttrium oxide, indium oxide, ITO (indium tin oxide), IZO (indium zinc oxide), nesa (tin oxide), ATO ( Examples include antimony-doped tin oxide), fluorine-doped tin oxide, zinc oxide, AZO (aluminum-doped zinc oxide), and gallium-doped zinc oxide.

  Specific examples of the metal nitride include aluminum nitride and silicon nitride.

  Specific examples of the composite base material include, for example, paper-resin composite base materials such as paper-phenol resin, paper-epoxy resin, paper-polyester resin; glass cloth-epoxy resin, glass cloth-polyimide resin. And glass cloth-resin composite base materials such as glass cloth-fluorine resin.

  In the production method of the present invention, the heat treatment is preferably performed in a non-oxidizing atmosphere. Examples of the non-oxidizing atmosphere include helium, nitrogen, and argon. Among these, it is preferable to use nitrogen because it is inexpensive. Further, the non-oxidizing atmosphere may contain oxygen as long as it does not significantly affect the oxidation of the formed electrical conduction site, and its concentration is preferably 5000 ppm or less, particularly preferably 500 ppm or less. .

  In the production method of the present invention, the heat treatment temperature may be any temperature at which the copper ions in the copper formate particles are reduced and the amine compound represented by the general formula (1) or (2) is volatilized and removed. However, there is no particular limitation, and the reduction of the copper ions in the copper formate particles proceeds completely, the amine compound represented by the general formula (1) or (2) does not remain, and an organic base material can be used. 60 to 300 ° C is preferable, and a range of 80 to 200 ° C is particularly preferable.

  Moreover, what is necessary is just to select the time of heat processing suitably with temperature or the electroconductivity desired, and when the heating temperature of about 200 degreeC is set, it is about 10 to 60 minutes normally.

  In the production method of the present invention, the method for applying the conductive ink composition of the present invention to a substrate can be performed by a known method, and is not particularly limited. For example, a screen printing method or a dip coating method is used. , Spray coating method, spin coating method, ink jet method, dispenser coating method and the like. There is no problem even if the shape of application is planar or dot-like, and there is no particular limitation. The coating amount for applying the conductive ink composition to the substrate may be appropriately adjusted according to the desired film thickness of the electrically conductive part, and the film thickness of the conductive ink composition after drying is 0.01 to The range of 5000 μm is preferable, and the coating may be particularly preferably performed in the range of 0.1 to 1000 μm.

  The production method of the present invention can be used as a part of a process for producing various industrial products, and an industrial product having an electrically conductive portion that is partially or wholly produced by the production method of the present invention can be obtained. it can.

  The industrial product having an electrically conducting portion partially or wholly produced by the production method of the present invention is not particularly limited, and for example, an image display device such as an organic electroluminescence panel, a plasma display panel, a liquid crystal panel; Light emitting devices such as LED (Light Emitting Diode) light emitting devices and organic electroluminescence light emitting devices; Circuits such as one-layer (single-sided) printed wiring boards, two-layer (double-sided) printed wiring boards, multilayer printed wiring boards, and flexible printed wiring boards Substrates; capacitors such as multilayer capacitors and solid electrolytic capacitors; solar cells such as silicon solar cells, compound semiconductor solar cells, dye-sensitized solar cells, and organic semiconductor solar cells; lithium secondary batteries, nickel-hydrogen secondary Secondary batteries such as batteries; radio wave type recognition tags; Examples thereof include a magnetic wave shielding shield.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not construed as being limited to these examples.

  In the following reference examples, the average particle diameter of the particles is randomly selected from three points in the field of view using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) depending on the particle size. Select and shoot at an arbitrary magnification in the range of 50,000 to 1,000,000 times, select 100 particles in total from each photo, measure the diameter with a ruler, and divide the measurement magnification The particle diameter was calculated and obtained by arithmetically averaging these values. TEM manufactured by JEOL Ltd., trade name: JEM-2000FX, and SEM used by JEOL Ltd., trade name: JSM T220A.

Elemental analysis was measured by Perkin Elmer, fully automatic elemental analyzer, trade name: 2400II, and ¹ H-NMR was measured by Varian, trade name: Gemini-200.

  Furthermore, the viscosity of the conductive ink composition was measured at a measurement temperature of 30 ° C. using a rheometer (trade name: AR Rheometer AR2000ex, manufactured by TA Instruments Inc.) unless otherwise specified.

[Reference Example 1] Preparation of copper formate particles.
To 40 g of ethanol, 2.24 g of copper formate particle powder (average particle size 21 μm) and 150 g of zirconia beads (made by Nikkato Co., Ltd., trade name: YZT ball, size: Φ0.1 mm) are added, and the stirring is connected to a stirring motor. Using wings, the mixture was stirred for 12 hours at a peripheral speed of 10 m / sec and pulverized.

  Next, this slurry-like mixture was passed through a sieve having an opening of 0.075 mm and further washed with 160 g of ethanol to separate zirconia beads to obtain a copper formate particle dispersion.

  This copper formate particle dispersion was observed with an SEM and the average particle size was determined to be 210 nm. Next, this copper formate particle dispersion was distilled off ethanol and excess water at 40 ° C. under reduced pressure to obtain 1.68 g of copper formate particle powder.

Example 1 Preparation of a conductive ink composition containing copper particles, N, N-dimethylethanolamine and copper formate particles.
To 10 g of tetrahydrofuran, 1.02 g of copper particles (Copper Powder, -625 mesh, APS 0.50-1.5 micron manufactured by Alfa Aesar), N, N-dimethyl which is an amine compound represented by the general formula (1) 1.54 g of ethanolamine and 1.54 g of copper formate particles (average particle size 210 nm) obtained in Reference Example 1 were added, and the mixture was sufficiently kneaded until completely dispersed in a mortar. From this slurry-like mixture, tetrahydrofuran and excess water were distilled off at 25 ° C. under reduced pressure to prepare a paste-like conductive ink composition.

  The resulting conductive ink composition had a viscosity of 178 Pa · s. As a result of elemental analysis, 40.6 wt% copper particles, 21.8 wt% copper formate particles, 37.6 wt% N, N It contained dimethylethanolamine (hereinafter referred to as “conductive ink A” for the sake of brevity).

Example 2 Preparation of a conductive ink composition containing silver particles, N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine, and copper formate particles.
To 10 g of tetrahydrofuran, 0.64 g of silver particles (Silver Powder, APS 0.7-1.3 micron manufactured by Alfa Aesar), N, N-dimethyl-2- (A) which is an amine compound represented by the general formula (1) 1.33 g of 2-hydroxyethyloxy) ethylamine and 1.54 g of copper formate particles (average particle size 210 nm) obtained in Reference Example 1 were added, and the mixture was sufficiently kneaded until completely dispersed in a mortar. From this slurry-like mixture, tetrahydrofuran and excess water were distilled off at 25 ° C. under reduced pressure to prepare a paste-like conductive ink composition.

The resulting conductive ink composition has a viscosity of 125 Pa · s. As a result of elemental analysis, 18.2 wt% copper particles, 18.1 wt% silver particles, 25.9 wt% copper formate particles, It contained 37.8% by weight of N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine (hereinafter referred to as “conductive ink B” for the sake of brevity).
Example 3 Preparation of a conductive ink composition containing silver-coated copper particles, 2-ethoxyethylamine, and copper formate particles.
In 10 g of tetrahydrofuran, 1.12 g of silver-coated copper particles (Ag / wet copper powder manufactured by Mitsui Kinzoku Co., Ltd.), 1.07 g of 2-ethoxyethylamine, which is an amine compound represented by the general formula (1), and Reference Example 1 1.54 g of the obtained copper formate particles (average particle size 210 nm) was added, and kneaded sufficiently in a mortar until the dispersion was completely dispersed. From this slurry-like mixture, tetrahydrofuran and excess water were distilled off at 25 ° C. under reduced pressure to prepare a paste-like conductive ink composition.

  The resulting conductive ink composition has a viscosity of 205 Pa · s. As a result of elemental analysis, 44.1 wt% copper particles, 3.0 wt% silver particles, 24.1 wt% copper formate particles, 28.8% by weight of 2-ethoxyethylamine was contained (hereinafter referred to as “conductive ink C” for the sake of brevity).

Example 4 Preparation of a conductive ink composition containing copper particles, 1,1-dimethyl-2-hydroxyethylamine, copper formate particles, and decane.
To 1.0 g of tetrahydrofuran, 1.06 g of copper particles (Copper Powder, -625 mesh, APS 0.50-1.5 micron manufactured by Alfa Aesar), 1,1-dimethyl which is an amine compound represented by the general formula (1) 1.28 g of 2-hydroxyethylamine and 1.54 g of copper formate particles (average particle size 210 nm) obtained in Reference Example 1 were added, and the mixture was sufficiently kneaded until completely dispersed in a mortar. Tetrahydrofuran and excess water were distilled off from this slurry-like mixture at 25 ° C. under reduced pressure, and 0.32 g of decane was added as a dispersion medium to the remaining solid to prepare a paste-like conductive ink composition. .

  The resulting conductive ink composition had a viscosity of 147 Pa · s. As a result of elemental analysis, 40.4 wt% copper particles, 21.4 wt% copper formate particles, 30.6 wt% 1,1 -Dimethyl-2-hydroxyethylamine, containing 7.6 wt% decane (hereinafter referred to as "conductive ink D" for the sake of brevity).

Example 5 Preparation of a conductive ink composition containing copper particles, 3-n-butoxypropylamine, and copper formate particles.
To 10 g of tetrahydrofuran, 0.7 g of copper particles (Copper Powder, -625 mesh, APS 0.50-1.5 micron manufactured by Alfa Aesar), 3-n-butoxy which is an amine compound represented by the general formula (1) 1.24 g of propylamine and 1.54 g of the copper formate particles (average particle size 210 nm) obtained in Reference Example 1 were added, and the mixture was sufficiently kneaded until completely dispersed in a mortar. From this slurry-like mixture, tetrahydrofuran and excess water were distilled off at 25 ° C. under reduced pressure to prepare a paste-like conductive ink composition.

  The obtained conductive ink composition had a viscosity of 162 Pa · s. As a result of elemental analysis, it was found that 38.6 wt% copper particles, 25.9 wt% copper formate particles, 35.5 wt% 3-n -It contained butoxypropylamine (hereinafter, for the sake of brevity, this is referred to as "conductive ink E").

Example 6 Preparation of a conductive ink composition containing copper particles, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) ethylenediamine, and copper formate particles.
To 10 g of tetrahydrofuran, 1.03 g of copper particles (Copper Powder, -625 mesh, APS 0.50-1.5 micron manufactured by Alfa Aesar), N, N, N which is an amine compound represented by the general formula (2) 1.46 g of '-trimethyl-N'-(2-hydroxyethyl) ethylenediamine and 1.54 g of copper formate particles (average particle size 210 nm) obtained in Reference Example 1 are added, and the mixture is completely dispersed in a mortar. Kneaded thoroughly. From this slurry-like mixture, tetrahydrofuran and excess water were distilled off at 25 ° C. under reduced pressure to prepare a paste-like conductive ink composition.

  The resulting conductive ink composition had a viscosity of 143 Pa · s. As a result of elemental analysis, 41.3 wt% copper particles, 22.4 wt% copper formate particles, 36.3% wt N, N , N′-trimethyl-N ′-(2-hydroxyethyl) ethylenediamine (hereinafter referred to as “conductive ink F” for the sake of brevity).

Comparative Example 1 Preparation of a conductive ink composition containing copper formate particles and 3-methoxypropylamine. (System without adding metal particles)
2.24 g of copper formate particles and 1.96 g of 3-methoxypropylamine which is an amine compound represented by the general formula (1) were sequentially added to 10 g of tetrahydrofuran. The mixture was stirred at room temperature for 10 minutes until it was completely dissolved to obtain a uniform solution. This solution was filtered through a 0.5 μm membrane filter, and then the tetrahydrofuran in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a conductive ink composition.

  It was 3.9 mPa * s as a result of measuring the viscosity of the obtained electroconductive ink composition with the B-type viscosity meter (the Toki Sangyo company make, brand name: BL II). Further, as a result of elemental analysis, it contained 18.3% by weight of copper particles, 25.7% by weight of copper formate particles, and 56.0% by weight of 3-methoxypropylamine. Therefore, this is referred to as “conductive ink G”).

Comparative Example 2 Preparation of a conductive ink composition containing copper particles, n-octylamine, and copper formate particles. (System using an amine compound that is not an amine compound represented by the general formulas (1) and (2))
To 10 g of tetrahydrofuran, 1.02 g of copper particles (Copper Powder, -625 mesh, APS 0.50-1.5 micron manufactured by Alfa Aesar) is not an amine compound represented by the general formulas (1) and (2). -1.54 g of octylamine and 1.54 g of the copper formate particles (average particle size 210 nm) obtained in Reference Example 1 were added, and the mixture was sufficiently kneaded until completely dispersed in a mortar. From this slurry-like mixture, tetrahydrofuran and excess water were distilled off at 25 ° C. under reduced pressure to prepare a paste-like conductive ink composition.

  The obtained conductive ink composition had a viscosity of 188 Pa · s. As a result of elemental analysis, it was found that 39.8 wt% copper particles, 21.2 wt% copper formate particles, 39.0 wt% octylamine were obtained. (Hereinafter, for the sake of brevity, this is referred to as “conductive ink H”).

[Examples 7 to 12, Comparative Examples 3 and 4] Printability evaluation, conductivity evaluation, and volume change evaluation.
Conductive inks A to H are applied on a glass substrate by a screen printing method (screen specifications: mesh number: 200, wire diameter: 40 μm, weaving thickness: 115 μm, mesh opening: 87 μm, space ratio: 46.9%, paste transmission Volume: 53.94 mg / cm ³ ) was applied to form a uniform coating film having a width of 2 mm × length of 30 mm and a film thickness of 54 μm.

  Next, in a heating furnace in which nitrogen gas was circulated at a flow rate of 6 L / min, the glass substrate coated with these conductive inks was subjected to heat treatment for 30 minutes to obtain an electrically conductive portion. Each heating temperature is shown in Table 1.

The printability is evaluated by visually checking the shape of the printed pattern.
If there is no tearing, chipping or bleeding: ○,
If there is tear, chipping, or bleeding: ×,
It was evaluated.

  The electrical conductivity was evaluated by comparing the volume resistivity calculated by the following formula from the measured surface resistivity and film thickness at each electrically conductive portion.

  Volume resistivity (Ω · cm) = surface resistivity (Ω / □) × film thickness (cm).

  The surface resistivity was measured with a four-probe resistance measuring machine (trade name: Loresta GP, manufactured by Mitsubishi Chemical Corporation).

  Regarding the film thickness, each formed electrical conduction site was cut, the cross section was observed with a scanning electron microscope (SEM), and the average film thickness was taken as the value. That is, for each electrical conduction site, three locations were selected at random from the field of view observed with a scanning electron microscope (SEM) and photographed at a magnification of 5000 times. The film thickness was measured, and these values were divided by the photographing magnification, and the value obtained by arithmetically averaging the film thickness at the three locations was taken as the film thickness of each electrically conductive portion.

  Regarding the volume change, there is no difference in the area before and after the heat treatment, that is, the area of the conductive ink coating film and the area of the electrically conductive part, so the coating film thickness at the time of application and the film of the electrically conductive part after the heat treatment Evaluation was based on the rate of change in thickness.

    Volume change rate (%) = [(film thickness of electrically conductive part / conductive ink coating film thickness) −1] × 100.

  The results of these evaluations are also shown in Table 1.

  As is clear from Table 1, in Examples 7 to 12, all of the conductive ink compositions of the present invention exhibited good printability, and no tearing, chipping or bleeding was observed. Moreover, regarding electroconductivity, favorable electroconductivity was shown and the volume change before and behind heat processing was also small.

  On the other hand, since the comparative example 3 did not use metal particles, the wiring could not be applied uniformly due to printing defects such as tearing, chipping and bleeding. Moreover, regarding the conductivity, although there is no great difference, the volume change before and after the heat treatment was large. Moreover, since the comparative example 4 used the amine compound which is not an amine compound shown by General formula (1), (2), it was inferior to printability.

[Example 13, Comparative Example 5] Conductivity evaluation of ink after contact with air.
On the glass substrate, conductive inks A and H were applied by a screen printing method in the same manner as described in Examples 7 to 12, and a uniform coating film having a width of 2 mm × length of 30 mm and a film thickness of 54 μm was obtained. did.

  Next, these coating films were left in the atmosphere for 24 hours, and were sufficiently brought into contact with the atmosphere.

  Next, the same heat treatment as that described in Examples 7 to 12 was performed at a heating temperature of 140 ° C. to obtain an electrically conductive portion. Table 2 shows the evaluation results of the conductivity.

  In addition, evaluation of electroconductivity was performed by the comparison of volume resistivity, and the volume resistivity was computed by the method as described in Examples 7-12.

  As is apparent from Table 2, in Example 13, the conductive ink composition of the present invention showed good conductivity with almost no decrease in volume resistivity even after 24 hours of atmospheric contact.

  On the other hand, in Comparative Example 5, the conductive ink composition using n-octylamine which is an amine compound that is not an amine compound represented by the general formulas (1) and (2) has a volume of 24 hours by atmospheric contact. The resistivity has deteriorated significantly.

Claims (16)

A conductive ink composition comprising at least one amine compound represented by the following general formula (1) and general formula (2), metal particles, and copper formate particles.

[R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, or a 2-ethoxyethyl group, and R ₃ and R ₄ each independently represent A hydrogen atom or a methyl group, and R ₅ is a hydrogen atom, a straight chain having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a 2-hydroxyethyl group, A 2-methoxyethyl group or a 2-ethoxyethyl group is represented, and X represents a methylene group, an ethylene group, or a propylene group. ]

[R _{6 to} R ₉ each independently represents a hydrogen atom, a methyl group, or an ethyl group. ]   The amine compound represented by the general formula (1) and the general formula (2) is ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, 2-methoxyethylamine, N-methyl-2-methoxyethylamine, N, N-dimethyl-2-methoxyethylamine, bis (2-methoxyethyl) amine, 2-ethoxyethylamine, N-methyl-2-ethoxyethylamine, N, N-dimethyl-2-ethoxyethylamine, bis (2-ethoxy Ethyl) amine, 2-n-propoxyethylamine, N-methyl-2-n-propoxyethylamine, N, N-dimethyl-2-n-propoxyethylamine, 2-i-propoxyethylamine, N-methyl-2-i- Propoxyethylamine, N, N-dimethyl-2-i-propoxyethyla , 2-n-butoxyethylamine, N-methyl-2-n-butoxyethylamine, N, N-dimethyl-2-n-butoxyethylamine, 2- (2-hydroxyethyloxy) ethylamine, N-methyl-2- (2-hydroxyethyloxy) ethylamine, N, N-dimethyl-2- (2-hydroxyethyloxy) ethylamine, 2- (2-methoxyethyloxy) ethylamine, N-methyl-2- (2-methoxyethyloxy) Ethylamine, N, N-dimethyl-2- (2-methoxyethyloxy) ethylamine, 2- (2-ethoxyethyloxy) ethylamine, N-methyl-2- (2-ethoxyethyloxy) ethylamine, N, N-dimethyl -2- (2-ethoxyethyloxy) ethylamine, 1,1-dimethyl-2-hydroxy Ethylamine, N-methyl-1,1-dimethyl-2-hydroxyethylamine, N, N-dimethyl-1,1-dimethyl-2-hydroxyethylamine, 1,1-dimethyl-2-methoxyethylamine, N-methyl-1 , 1-dimethyl-2-methoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-methoxyethylamine, 1,1-dimethyl-2-ethoxyethylamine, N-methyl-1,1-dimethyl-2- Ethoxyethylamine, N, N-dimethyl-1,1-dimethyl-2-ethoxyethylamine, 3-hydroxypropylamine, N-methyl-3-hydroxypropylamine, N, N-dimethyl-3-hydroxypropylamine, 3- Methoxypropylamine, N-methyl-3-methoxypropylamine, N, N-dimethyl- 3-methoxypropylamine, 3-ethoxypropylamine, N-methyl-3-ethoxypropylamine, N, N-dimethyl-3-ethoxypropylamine, 3-n-propoxypropylamine, 3-i-propoxypropylamine, N-methyl-3-i-propoxypropylamine, N, N-dimethyl-3-i-propoxypropylamine, 3-n-butoxypropylamine, N-methyl-3-n-butoxypropylamine, N, N- Dimethyl-3-n-butoxypropylamine, N, N ′, N′-trimethyl-N- (2-hydroxyethyl) ethylenediamine, N, N ′, N′-trimethyl-N- (2-methoxyethyl) ethylenediamine, And N, N ', N'-trimethyl-N- (2-ethoxyethyl) ethylenediamine Conductive ink composition according to claim 1, characterized in that more least one selected.   The metal particles contain at least one metal species selected from the group consisting of gold particles, silver particles, copper particles, platinum particles, palladium particles, rhodium particles, iridium particles, ruthenium particles, silver-coated copper particles, and osmium particles. The conductive ink composition according to claim 1 or 2.   The metal particles are at least one selected from the group consisting of gold particles, silver particles, copper particles, platinum particles, palladium particles, and silver-coated copper particles. Conductive ink composition.   5. The conductive ink composition according to claim 1, wherein the average particle diameter of the metal particles is in the range of 0.01 to 100 μm.   The conductive ink composition according to claim 1, wherein the average particle diameter of the copper formate particles is in the range of 1 nm to 5 μm.   The concentration of the metal particles is 0.1 to 99% by weight, the concentration of the amine compound represented by the general formula (1) or (2) is 0.1 to 80% by weight, and formic acid based on the total amount of the conductive ink composition. The conductive ink composition according to claim 1, wherein the concentration of copper particles is 0.1 wt% to 80 wt%.   The conductive ink composition according to claim 1, further comprising a dispersion medium.   9. The conductive ink composition according to claim 8, wherein the dispersion medium is at least one selected from the group consisting of alcohols, ethers, esters, aliphatic hydrocarbons, and aromatic hydrocarbons. object.   The dispersion medium is at least one selected from the group consisting of hexanol, terpineol, methyl-t-butyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, n-hexane, and γ-butyrolactone. Conductive ink composition.   The conductive ink composition according to any one of claims 8 to 10, wherein the concentration of the dispersion medium is in the range of 1 to 90% by weight with respect to the weight of the entire conductive ink composition.   The conductive ink composition according to claim 1, wherein the viscosity of the conductive ink composition is in a range of 1 to 1000 Pa · s.   A method for producing an electrically conductive portion, comprising applying or filling the conductive ink composition according to any one of claims 1 to 12 to a substrate, and subjecting the substrate to heat treatment.   The substrate is one or two or more composite substrates selected from the group consisting of resin, paper, glass, silicon-based semiconductor, compound semiconductor, metal oxide, metal nitride, and wood The manufacturing method of the electrical conduction | electrical_connection site | part of Claim 13.   The method for producing an electrically conductive portion according to claim 13 or 14, wherein the temperature of the heat treatment is in a range of 60 to 300 ° C.   The method for producing an electrically conductive portion according to claim 13, wherein heat treatment is performed in a non-oxidizing atmosphere.