JP2011034750A - Composition for conductive film formation and conductive film formation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for conductive film formation capable of forming a practical conductive film with conductivity and a conductive film forming method using the same, without using metal fine particles, in forming a conductive film with copper as a main component. <P>SOLUTION: A conductive film forming composition containing noble metal compounds, copper salt, coordinating compounds, and a reductant is coated on a base material, and then is heated under a non-oxidizing atmosphere to form a conductive film on the base material. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a conductive film forming composition and a conductive film forming method, and can be suitably used as a circuit pattern forming material for a wiring board and a circuit pattern forming method, particularly in the electronics field.

  In recent years, a technique for forming a desired pattern from a metal fine particle dispersion by an ink jet printing method or a screen printing method to form a conductive film such as a wiring on a circuit board has attracted attention. When the average particle size of metal fine particles is about several nanometers to several tens of nanometers, the melting point of the metal particles is significantly lower than that of bulk metal, and the particles are fused at a low temperature. Thus, a conductive film is obtained. At present, such a composition for forming a conductive pattern is mainly one containing silver fine 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 film forming material that can reduce the cost, has a low possibility of causing electromigration, and can form wiring having copper as a main component with high conductivity by a printing method.

  Copper conductive film forming materials include adsorbing organic compounds having nitrogen, oxygen, sulfur and other heteroatoms in the molecular structure on the copper surface, preventing contact with oxygen and water, preventing oxidation, and at the same time copper fine particles Many methods using copper fine 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, such a conductive film forming material using copper fine particles removes an oxidation inhibitor that coats the surface of the copper fine particles and fuses the copper fine particles to each other in the step of forming the conductive film after applying the copper fine particles. Therefore, generally, heating at a high temperature of about 300 ° C. is necessary, and there is a problem that the applicable base materials are limited. In addition, since heating in a reducing atmosphere containing hydrogen is necessary to suppress copper oxidation, there is a serious problem in terms of safety.

  Therefore, a conductive film forming material that forms a copper conductive film without using copper fine 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).

  In addition, by using a metal salt mixture for forming a metal pattern that contains at least a metal salt and a reducing agent and has a viscosity of 3 to 50 mPa · s at 25 ° C., a pattern is drawn on the substrate, and then heated. A method of forming a metal film has been proposed (see, for example, Patent Document 3).

  According to these methods, a copper film or a metal film is formed by heating at a temperature of about 180 ° C. in a non-reducing atmosphere. Heating at a temperature of about 120 ° C., which can be applied to a substrate, has insufficient conductivity of the formed copper film or metal film, and may not be industrially usable.

  As described above, none of the above-described methods is sufficient, and further studies have been demanded for industrial practical use. That is, in the formation of a conductive film mainly composed of copper, development of a conductive film forming composition capable of forming a conductive film having practical conductivity without using metal fine particles has been desired.

JP 2007-32215 A Japanese Patent Laying-Open No. 2005-2471 JP 2008-205430 A

  The present invention has been made in view of the above-described background art, and an object thereof is to form a conductive film having practical conductivity without using metal fine particles in the formation of a conductive film containing copper as a component. It is providing the composition for electrically conductive film formation which can be performed, and the manufacturing method of an electrically conductive film using the same.

  In order to solve the above problems, the present inventors have conducted extensive studies on the composition for forming a conductive film and the method for forming the conductive film, and as a result, the composition contains a noble metal compound, a copper salt, a coordination compound, and a reducing agent. And a conductive film forming composition containing a noble metal compound, a copper salt of a carboxylic acid having a reducing power, and a coordination compound. And it discovers that a favorable electrically conductive film is formed by apply | coating these compositions for electrically conductive film formation to a base material, and heating in non-oxidizing atmosphere and can solve the above-mentioned subject, and completes this invention. It came to.

  That is, this invention is the composition for electrically conductive film formation as shown below, its manufacturing method, and the manufacturing method of an electrically conductive film using the same.

  [1] A conductive film-forming composition containing a noble metal compound, a copper salt, a coordination compound, and a reducing agent.

  [2] The conductive film-forming composition as described in [1] above, wherein the noble metal compound is one or more selected from the group consisting of silver ions, platinum ions, and palladium ions.

  [3] The conductive film formation according to [1] or [2], wherein the noble metal compound is one or more selected from the group consisting of a noble metal salt, a noble metal oxide, and a noble metal sulfide. Composition.

  [4] The composition for forming a conductive film according to [3], wherein the noble metal salt is one or more selected from the group consisting of a noble metal carboxylate and a complex salt of a noble metal and an acetylacetone derivative. object.

  [5] The noble metal compound is silver formate, silver acetate, silver trifluoroacetate, silver propionate, silver butyrate, silver isobutyrate, silver valerate, silver isovalerate, silver pivalate, silver hexanoate, silver heptanoate, Silver cyclohexanecarboxylate, silver octanoate, silver 2-ethylhexanoate, silver nonanoate, silver decanoate, silver undecanoate, silver dodecanoate, silver tridecanoate, silver oleate, silver linoleate, silver linolenate, benzoic acid Silver, palladium formate, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium butyrate, palladium isobutyrate, palladium valerate, palladium isovalerate, palladium pivalate, palladium hexanoate, palladium heptanoate, palladium cyclohexanecarboxylate, Palladium octanoate, silver palladium 2-ethylhexanoate Palladium nonanoate, palladium decanoate, palladium undecanoate, palladium dodecanoate, palladium tridecanoate, palladium oleate, palladium linoleate, palladium linolenate, palladium benzoate, silver acetylacetonato, silver hexafluoroacetylacetonato, acetylaceto The composition for forming a conductive film according to any one of the above [1] to [4], which is one or more selected from the group consisting of natopalladium and hexafluoroacetylacetonatopalladium.

  [6] Any one of the above [1] to [5], wherein the copper salt is one or more selected from the group consisting of a copper carboxylate and a complex salt of copper and an acetylacetone derivative The composition for electrically conductive film formation of description.

  [7] Copper salt is copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper pivalate, copper formate, copper hydroxyacetate, copper glyoxylate, copper oxalate , One or more selected from the group consisting of copper, acetylacetonato, 1,1,1-trifluoroacetylacetonatocopper, and 1,1,1,5,5,5-hexafluoroacetylacetonatocopper The composition for forming a conductive film according to any one of the above [1] to [6], wherein the composition is for forming a conductive film.

  [8] The conductivity according to any one of [1] to [8], wherein the coordination compound is one or more compounds selected from the group consisting of alkanethiols and amines. Film forming composition.

  [9] Alkanethiols are ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, cyclohexanethiol, n -The composition for electrically conductive film formation as described in said [8] characterized by being 1 type, or 2 or more types chosen from the group which consists of heptanethiol, n-octanethiol, and 2-ethylhexanethiol.

  [10] Amines are ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n -Octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecyl Amine, benzylamine, ethylenediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, 1,3 -Propanediamine, , N′-dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N, N′-dimethyl-1, 5-pentanediamine, 1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, isophoronediamine, diethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N— The composition for forming a conductive film as described in [9] above, which is one or more selected from the group consisting of (aminoethyl) piperazine and N- (aminopropyl) piperazine.

  [11] The conductive according to any one of [1] to [10], wherein the reducing agent is one or more selected from the group consisting of diols and carboxylic acids having a reducing power. Film forming composition.

  [12] The diol is ethylene glycol, propylene glycol, 1,2-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,2-hexanediol, 2, 3-hexanediol, 3,4-hexanediol, 2,3-heptanediol, 3,4-heptanediol, 3,4-octanediol, 4,5-octanediol, 3,4-nonanediol, 4,5 Nonanediol, 3,4-decanediol, 4,5-decanediol, 5,6-decanediol, 3-N, N-dimethylamino-1,2-propanediol, 3-N, N-diethylamino-1 , 2-propanediol, 3-N, N-di-n-propylamino-1,2-propanediol, 3-N, N-di-i-propyla No-1,2-propanediol, 3-N, N-di-n-butylamino-1,2-propanediol, 3-N, N-di-i-butylamino-1,2-propanediol, and The composition for forming a conductive film according to [11], wherein the composition is one or more selected from the group consisting of 3-N, N-di-t-butylamino-1,2-propanediol.

  [13] The conductive material according to [11], wherein the carboxylic acid having a reducing power is at least one selected from the group consisting of formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid, and citric acid. Film forming composition.

  [14] The concentration of the noble metal compound is 1 to 50% by weight, the concentration of the copper salt is 0.1 to 80% by weight, and the concentration of the coordinating compound is 0.1 to the total amount of the conductive film forming composition. The composition for forming a conductive film according to any one of the above [1] to [17], wherein 80% by weight and the concentration of the reducing agent is in the range of 0.1 to 80% by weight.

  [15] A conductive film-forming composition comprising a noble metal compound, a copper salt with a reducing carboxylic acid, and a coordination compound.

  [16] The conductive film-forming composition as described in [15] above, wherein the noble metal compound is one or more selected from the group consisting of silver ions, platinum ions, and palladium ions.

  [17] The conductive film formation according to [15] or [16], wherein the noble metal compound is one or more selected from the group consisting of a noble metal salt, a noble metal oxide, and a noble metal sulfide. Composition.

  [18] The composition for forming a conductive film according to [17], wherein the noble metal salt is one or more selected from the group consisting of a noble metal carboxylate and a complex salt of a noble metal and an acetylacetone derivative. object.

  [19] The noble metal compound is silver formate, silver acetate, silver trifluoroacetate, silver propionate, silver butyrate, silver isobutyrate, silver valerate, silver isovalerate, silver pivalate, silver hexanoate, silver heptanoate, Silver cyclohexanecarboxylate, silver octanoate, silver 2-ethylhexanoate, silver nonanoate, silver decanoate, silver undecanoate, silver dodecanoate, silver tridecanoate, silver oleate, silver linoleate, silver linolenate, benzoic acid Silver, palladium formate, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium butyrate, palladium isobutyrate, palladium valerate, palladium isovalerate, palladium pivalate, palladium hexanoate, palladium heptanoate, palladium cyclohexanecarboxylate, Palladium octoate, silver 2-ethylhexanoate , Palladium nonanoate, palladium decanoate, palladium undecanoate, palladium dodecanoate, palladium tridecanoate, palladium oleate, palladium linoleate, palladium linolenate, palladium benzoate, silver acetylacetonate, silver hexafluoroacetylacetonate, acetyl The composition for forming a conductive film according to any one of the above [15] to [18], which is one or more selected from the group consisting of acetonatopalladium and hexafluoroacetylacetonatopalladium.

  [20] The copper salt with a carboxylic acid having reducing power is selected from the group consisting of copper formate, copper hydroxyacetate, copper glyoxylate, copper lactate, copper oxalate, copper tartrate, copper malate, and copper citrate. The composition for forming a conductive film according to any one of the above [15] to [19], which is at least one kind.

  [21] The coordination compound according to any one of [15] to [20], wherein the coordination compound is one or more compounds selected from the group consisting of alkanethiols and amines. A composition for forming a conductive film.

  [22] Alkanethiols are ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, cyclohexanethiol, n -The composition for forming a conductive film according to [21], wherein the composition is one or more selected from the group consisting of heptanethiol, n-octanethiol, and 2-ethylhexanethiol.

  [23] Amines are ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n -Octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecyl Amine, benzylamine, ethylenediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, 1,3 -Propanediamine, , N′-dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N, N′-dimethyl-1, 5-pentanediamine, 1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, isophoronediamine, diethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N— The composition for forming a conductive film as described in [21] above, which is one or more selected from the group consisting of (aminoethyl) piperazine and N- (aminopropyl) piperazine.

  [24] The concentration of the noble metal compound is 1 ppm by weight to 50% by weight, the concentration of the copper salt with the reducing carboxylic acid is 0.1 to 80% by weight, and the coordination with respect to the total amount of the conductive film forming composition. The conductive film-forming composition as described in any one of [15] to [23] above, wherein the concentration of the conductive compound is in the range of 0.1 to 80% by weight.

  [25] The method for producing a conductive film-forming composition as described in any one of [1] to [14], wherein a noble metal compound, a copper salt, a coordination compound, and a reducing agent are mixed. .

  [26] For forming a conductive film according to any one of the above [15] to [24], wherein the noble metal fine particles, a copper salt with a reducing carboxylic acid, and a coordination compound are mixed. A method for producing the composition.

  [27] Applying the composition for forming a conductive film according to any one of [1] to [24] to a base material and heating in a non-oxidizing atmosphere to form a conductive film on the substrate. The manufacturing method of the electrically conductive film characterized.

  [28] The method for producing a conductive film according to [27], wherein the non-oxidizing atmosphere is selected from the group consisting of a helium atmosphere, a nitrogen atmosphere, and an argon atmosphere.

  [29] The method for producing a conductive film according to the above [27] or [28], wherein the heating temperature is in the range of 60 ° C to 300 ° C.

  The composition for forming a conductive film of the present invention uses a noble metal compound, a copper salt, a coordination compound, and a reducing agent as raw materials, which can be obtained at a lower price than metal fine particles. Excellent in properties.

  Moreover, since the composition for electrically conductive film formation of this invention uses copper salt as a raw material, it can form the electrically conductive film and conductive pattern which have the characteristic which was excellent in copper.

  On the other hand, the conductive film formation method of the present invention can form a conductive film and a conductive pattern by a simple method such as coating and heating, and can achieve energy saving, low cost, low environmental load, and industrially. Very useful.

  In addition, the conductive film formation method of the present invention does not require a reducing atmosphere containing hydrogen in the conductive film formation step, and the conductive film can be formed by heating in an inert atmosphere such as nitrogen, which is excellent in safety.

  Furthermore, the composition for forming a conductive film of the present invention can form a conductive film at a temperature at which the resin base material can be used, and is excellent in versatility.

  The present invention is described in further detail below.

  First, the composition for forming a conductive film of the present invention will be described.

  The conductive film forming composition of the present invention includes a noble metal compound, a copper salt, a coordination compound, and a conductive film forming composition containing a reducing agent, or a noble metal compound, a copper salt with a reducing carboxylic acid, And a conductive film-forming composition containing a coordination compound.

  Here, when the noble metal compound and the reducing agent are present in the same system, the noble metal compound has a high standard electrode potential, and therefore is easily reduced by the reducing component to generate noble metal particles. And since such a noble metal particle coarsens and settles, it was conventionally considered that it was difficult to set it as the composition for electrically conductive film formation in which uniformity is requested | required.

  The present inventor has found that the problems described above can be solved by appropriately selecting each component constituting the composition for forming a conductive film, and has completed the present invention.

  In the conductive film forming composition of the present invention, the noble metal compound is reduced before the copper salt when the conductive film forming composition is applied to a substrate and heated in a non-oxidizing atmosphere. And plays the role of a catalyst that promotes the subsequent reduction of the copper salt.

  In the composition for forming a conductive film of the present invention, the noble metal compound is not particularly limited. For example, one or two selected from the group consisting of gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium. Examples thereof include compounds containing at least one metal species. Among these metal species, a compound containing one or two or more metal species selected from the group consisting of silver, platinum, and palladium is preferable in terms of cost and availability.

  Further, the noble metal compound is not particularly limited as long as it is a compound containing noble metal ions. For example, noble metal salts composed of noble metal ions and inorganic anion species and / or organic anion species, noble metal oxidation And noble metal sulfides. Among these, noble metal salts are preferable, and in terms of solubility, it is preferable to use noble metal carboxylates and / or complex salts of noble metals and acetylacetone derivatives.

  For example, specific examples of noble metal carboxylates include silver formate, silver acetate, silver trifluoroacetate, silver propionate, silver butyrate, silver isobutyrate, silver valerate, silver isovalerate, silver pivalate, hexane Silver, silver heptanoate, silver cyclohexanecarboxylate, silver octanoate, silver 2-ethylhexanoate, silver nonanoate, silver decanoate, silver undecanoate, silver dodecanoate, silver tridecanoate, silver oleate, silver linoleate Silver linolenate, silver benzoate, palladium formate, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium butyrate, palladium isobutyrate, palladium valerate, palladium isovalerate, palladium pivalate, palladium hexanoate, heptanoic acid Palladium, palladium cyclohexanecarboxylate, palladium octoate, 2-e Ruhekisan silver palladium, nonanoic acid, palladium decanoic acid, palladium undecanoic acid, palladium dodecanoic acid, tridecanoic acid, palladium oleic acid, palladium linoleic acid, palladium linolenic acid, benzoic acid palladium and the like as preferred.

  Moreover, as a complex salt of a noble metal and an acetylacetone derivative, for example, acetylacetonato silver, hexafluoroacetylacetonato silver, acetylacetonatopalladium, hexafluoroacetylacetonatopalladium and the like are preferable.

  Among these, from the viewpoint of cost and solubility, noble metal carboxylates such as silver acetate, silver propionate, silver butyrate, silver isobutyrate, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium butyrate, palladium isobutyrate, etc. Is particularly preferred.

  In the composition for forming a conductive film of the present invention, a metal compound other than these noble metal compounds may be used, but the catalytic ability is not exhibited, and the reduction deposition rate from copper ions to metallic copper may be reduced. .

  In the composition for forming a conductive film of the present invention, the noble metal compound may be a commercially available one or synthesized by a known method, and further, a compound containing a noble metal ion, an inorganic anion species, and / or an organic anion species. Even if formed in the system by mixing, etc., it can be used without any limitation, and is not particularly limited. Moreover, even if it is reduced in the system by heating or the like in a mixed state with a reducing agent to form a zero-valent complex or nano-sized ultrafine particles, it does not form aggregates and cause precipitation, If the uniform dispersibility can be maintained, there is no problem.

  In the composition for forming a conductive film of the present invention, the purity of the noble metal compound is not particularly limited. However, if the purity is too low, the conductive film may be adversely affected when the conductive film is formed. 95% or more is preferable, and 99% or more is more preferable.

  In the composition for forming a conductive film of the present invention, the copper ions contained in the copper salt are reduced by a reducing agent, become copper metal, and play a role of developing the conductivity of the formed conductive film.

  In the composition for forming a conductive film of the present invention, the copper salt may be any compound containing copper ions, and is not particularly limited. For example, copper ions and inorganic anion species and / or organic anion species The copper salt which consists of these is mentioned. Among these, it is preferable to use 1 type, or 2 or more types chosen from the group which consists of a copper carboxylate and the complex salt of copper and an acetylacetone derivative from the surface of solubility.

  For example, specific examples of copper carboxylates include copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper 2-ethylbutyrate, copper valerate, Copper salt with carboxylic acid such as copper valerate, copper pivalate, copper hexanoate, copper heptanoate, copper octoate, copper 2-ethylhexanoate, copper nonanoate, copper malonate, copper succinate, malee Copper salt with dicarboxylic acid such as acid copper, Copper salt with aromatic carboxylic acid such as copper benzoate and copper salicylate, Copper formate, Copper hydroxyacetate, Copper glyoxylate, Copper lactate, Copper oxalate, Copper tartrate, Apple Suitable examples include copper salts with carboxylic acids having a reducing power such as acid copper and copper citrate.

  Examples of complex salts of copper and acetylacetone derivatives include acetylacetonato copper, 1,1,1-trimethylacetylacetonatocopper, 1,1,1,5,5,5-hexamethylacetylacetonatocopper, Suitable examples include 1,1,1-trifluoroacetylacetonato copper, 1,1,1,5,5,5-hexafluoroacetylacetonato copper and the like.

  Among these, copper carboxylates such as copper acetate, copper propionate, copper isobutyrate, copper valerate, copper isovalerate, copper formate, and copper glyoxylate are preferable from the viewpoints of cost and solubility.

  In the composition for forming a conductive film of the present invention, other copper salts may be used, but it may be industrially disadvantageous because it is difficult to obtain or expensive. Moreover, as a copper salt, it may be a commercially available one or one synthesized by a known method, and further, by mixing a compound containing copper ions with an inorganic anion species and / or an organic anion species, The formed one can be used without any limitation, and is not particularly limited. In addition, when a copper salt with a carboxylic acid having a reducing power is used as the copper salt, a carboxylic acid having a reducing power as a counter anion acts as a reducing agent, so that it is not necessary to add a reducing agent separately.

  In the composition for forming a conductive film of the present invention, the purity of the copper salt is not particularly limited. However, if the purity is too low, there is a possibility of adversely affecting the conductivity when the conductive thin film is formed. 95% or more is preferable, and 99% or more is more preferable.

  In the composition for forming a conductive film of the present invention, the coordination compound forms a complex with a noble metal ion and a copper ion, improves the solubility of the noble metal compound and the copper salt, and is mixed with a reducing agent. Suppresses the reduction of noble metal ions and copper ions.

  In the composition for forming a conductive film of the present invention, the coordinating compound is not particularly limited as long as it is a compound having a coordinating ability for noble metal ions and copper ions. A monomolecular compound having one or more polar functional groups selected from the group consisting of nitrile group, amino group, hydroxyl group, and hydroxycarbonyl group, and a group consisting of nitrogen atom, oxygen atom, or sulfur atom And polymers having one or more heteroatoms in the molecular structure.

  Examples of such monomolecular compounds include thiols, amines, or alicyclic carboxylic acids, and examples of polymers include polyvinylpyrrolidone, polyethyleneimine, polyaniline, polypyrrole, polythiophene, polyacrylamide, and polyacrylic acid. , Carboxymethyl cellulose, polyvinyl alcohol, and polyethylene oxide. Among these, considering solubility and removability when forming a conductive film, one or more selected from the group consisting of alkanethiols and amines are preferable.

  Specifically, as alkanethiols, for example, ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol , Cyclohexanethiol, n-heptanethiol, n-octanethiol, 2-ethylhexanethiol and the like.

  Examples of amines include ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, and n-heptylamine. , N-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n- Monoamines such as hexadecylamine and benzylamine, ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N-ethylethylenediamine, N, N'- Diethylethylenediamine 1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N , N′-dimethyl-1,5-pentanediamine, 1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, diamines such as isophoronediamine, diethylenetriamine, N, N, N ′, And triamines such as N ″, N ″ -pentamethyldiethylenetriamine, N- (aminoethyl) piperazine, N- (aminopropyl) piperazine, and the like.

  In the composition for forming a conductive film of the present invention, the coordinating compound may be a commercially available one or a compound synthesized by a known method.

  In the composition for forming a conductive film of the present invention, the purity of the coordination compound is not particularly limited, but is preferably 95% or more, and more preferably 99% or more in consideration of use in the field of electronic materials.

  In the conductive film-forming composition of the present invention, the reducing agent reduces the noble metal compound and the copper salt when the conductive film-forming composition is applied to a substrate and heated in a non-oxidizing atmosphere.

  In the composition for forming a conductive film of the present invention, the reducing agent is not particularly limited as long as it is a compound having a reducing power capable of reducing a noble metal ion and a copper ion to a metal, for example, hydrazine Diols, hydroxylamines, α-hydroxyketones, and carboxylic acids having a reducing power. Among these, it is preferable to use one or two or more selected from the group consisting of diols having a relatively low reducing power and carboxylic acids having a reducing power.

  In the composition for forming a conductive film of the present invention, the diol used as the reducing agent is not particularly limited, but for example, the following general formula (1)

［上記一般式（１）中、Ｒ_１、Ｒ_２は各々独立して、水素原子、炭素数１〜６の直鎖状、分岐状若しくは環式のアルキル基、炭素数５〜１０の芳香族基、メチル基で芳香環上の水素原子が１〜３置換された炭素数５〜１０の芳香族基、又はフェニル基で水素原子が１〜３置換されたメチル基を表す。］
で示される化合物、及び／又は下記一般式（２）

[In the general formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and an aromatic group having 5 to 10 carbon atoms. And a methyl group in which a hydrogen atom on the aromatic ring is substituted with 1 to 3 carbon atoms, or a methyl group in which a hydrogen atom is substituted with a phenyl group. ]
And / or the following general formula (2)

［上記一般式（２）中、Ｒ_３、Ｒ_４は各々独立して、水素原子、炭素数１〜６の直鎖状、分岐状若しくは環式のアルキル基、炭素数５〜１０の芳香族基、メチル基で芳香環上の水素原子が１〜３置換された炭素数５〜１０の芳香族基、又はフェニル基で水素原子が１〜３置換されたメチル基を表す。］
で示される化合物が好適なものとして例示される。

[In General Formula (2), R ₃ and R ₄ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aromatic group having 5 to 10 carbon atoms. And a methyl group in which a hydrogen atom on the aromatic ring is substituted with 1 to 3 carbon atoms, or a methyl group in which a hydrogen atom is substituted with a phenyl group. ]
The compound shown by these is illustrated as a suitable thing.

Among these, considering the solubility of the copper salt and further the removability when forming the conductive film, in the general formula (1), the substituents R ₁ and R ₂ are each independently a hydrogen atom, methyl group, ethyl Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, or phenyl group. 2), the substituents R ₃ and R ₄ are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group. , N-pentyl group, n-hexyl group, phenyl group, or benzyl group.

In the above general formula (1), specific examples of the diols in which the substituent R ₁ is a hydrogen atom include ethylene glycol, propylene glycol, 1,2-butanediol, 1,2-pentanediol, and 3-methyl. -1,2-butanediol, 1,2-hexanediol, 4-methyl-1,2-pentanediol, 3,3-dimethyl-1,2-butanediol, 1,2-heptanediol, 1,2- Examples include octanediol and phenylethylene glycol.

In the above general formula (1), the diols in which the substituent R ₁ is a methyl group are specifically 2,3-butanediol, 2,3-pentanediol, 2,3-hexanediol, 4 -Methyl-2,3-pentanediol, 2,3-heptanediol, 5-methyl-2,3-hexanediol, 4,4-dimethyl-2,3-pentanediol, 2,3-octanediol, 2, Examples include 3-nonanediol and 1-phenylpropylene glycol.

In the above general formula (1), specific examples of the diols in which the substituent R ₁ is an ethyl group include 3,4-hexanediol, 3,4-heptanediol, 2-methyl-3,4- Hexanediol, 3,4-octanediol, 6-methyl-3,4-heptanediol, 2,2-dimethyl-3,4-hexanediol, 3,4-nonanediol, 3,4-decanediol, 1- Examples include phenyl-1,2-butanediol.

In the general formula (1), examples of the diols in which the substituent R ₁ is an n-propyl group include 4,5-octanediol, 2-methyl-3,4-heptanediol, 5-nonanediol, 2-methyl-4,5-octanediol, 2,2-dimethyl-3,4-heptanediol, 4,5-decanediol, 4,5-undecanediol, 1-phenyl-1,2 -Pentanediol and the like are exemplified.

In the above general formula (1), specific examples of diols in which the substituent R ₁ is an i-propyl group include 2,5-dimethyl-3,4-hexanediol and 2-methyl-3,4. -Octanediol, 2,6-dimethyl-3,4-heptanediol, 2,2,5-trimethyl-3,4-hexanediol, 2-methyl-3,4-nonanediol, 2-methyl-3,4 -Decanediol, 1-phenyl-3-methyl-1,2-butanediol and the like are exemplified.

In the general formula (1), examples of the diols in which the substituent R ₁ is an n-butyl group include 5,6-decanediol, 2-methyl-4,5-nonanediol, 2, Examples include 2-dimethyl-3,4-octanediol, 5,6-undecanediol, 5,6-dodecanediol, and 1-phenyl-1,2-hexanediol.

In the general formula (1), the diols in which the substituent R ₁ is an i-butyl group are specifically 2,7-dimethyl-4,5-octanediol, 2,2,6-trimethyl. Examples include -3,4-heptanediol, 2-methyl-4,5-decanediol, 2-methyl-4,5-uncandiol, 1-phenyl-1,2-heptanediol, and the like.

In the general formula (1), the diols in which the substituent R ₁ is a t-butyl group are specifically 2,2,5,5-tetramethyl-3,4-hexanediol, 2, Examples include 2-dimethyl-3,4-nonanediol, 2,2-dimethyl-3,4-decanediol, 1-phenyl-3,3-dimethyl-1,2-butanediol and the like.

In the above general formula (1), specific examples of diols in which the substituent R ₁ is an n-pentyl group include 6,7-dodecanediol, 6,7-tridecanediol, and 1-phenyl-1 , 2-heptanediol and the like.

In the above general formula (1), specific examples of diols in which the substituent R ₁ is an n-hexyl group include 7,8-tetradecanediol, 1-phenyl-1,2-octanediol, and the like. Is done.

In the general formula (1), specific examples of the diols in which the substituent R ₁ is a phenyl group include hydrobenzoin.

In the above general formula (2), specific examples of the diol in which the substituent R ₃ is a hydrogen atom include 3-amino-1,2-propanediol, 3-methylamino-1,2-propanediol, 3-ethylamino-1,2-propanediol, 3-n-propylamino-1,2-propanediol, 3-i-propylamino-1,2-propanediol, 3-n-butylamino-1,2 -Propanediol, 3-i-butylamino-1,2-propanediol, 3-t-butylamino-1,2-propanediol, 3-n-pentylamino-1,2-propanediol, 3-n- Examples include hexylamino-1,2-propanediol, 3-phenylamino-1,2-propanediol, 3-benzylamino-1,2-propanediol, and the like.

In the general formula (2), examples of the diols in which the substituent R ₃ is a methyl group include 3-N, N-dimethylamino-1,2-propanediol and 3- (N-ethyl). , N-methyl) amino-1,2-propanediol, 3- (Nn-propyl, N-methyl) amino-1,2-propanediol, 3- (Ni-propyl, N-methyl) amino -1,2-propanediol, 3- (Nn-butyl, N-methyl) amino-1,2-propanediol, 3- (Ni-butyl, N-methyl) amino-1,2-propane Diol, 3- (Nt-butyl, N-methyl) amino-1,2-propanediol, 3- (Nn-pentyl, N-methyl) amino-1,2-propanediol, 3- (N -N-hexyl, N-methyl) amino-1 , 2-propanediol, 3- (N-phenyl, N-methyl) amino-1,2-propanediol, 3- (N-benzyl, N-methyl) amino-1,2-propanediol and the like. .

In the general formula (2), examples of the diols in which the substituent R ₃ is an ethyl group include 3-N, N-diethylamino-1,2-propanediol, 3- (Nn- Propyl, N-ethyl) amino-1,2-propanediol, 3- (Ni-propyl, N-ethyl) amino-1,2-propanediol, 3- (Nn-butyl, N-ethyl) Amino-1,2-propanediol, 3- (N-i-butyl, N-ethyl) amino-1,2-propanediol, 3- (Nt-butyl, N-ethyl) amino-1,2- Propanediol, 3- (Nn-pentyl, N-ethyl) amino-1,2-propanediol, 3- (Nn-hexyl, N-ethyl) amino-1,2-propanediol, 3- ( N-phenyl, N-ethyl) amino- Examples include 1,2-propanediol and 3- (N-benzyl, N-ethyl) amino-1,2-propanediol.

In the general formula (2), examples of the diols in which the substituent R ₃ is an n-propyl group include 3-N, N-di-n-propylamino-1,2-propanediol, 3- (N-i-propyl, Nn-propyl) amino-1,2-propanediol, 3- (Nn-butyl, Nn-propyl) amino-1,2-propanediol, 3- (N-i-butyl, Nn-propyl) amino-1,2-propanediol, 3- (Nt-butyl, Nn-propyl) amino-1,2-propanediol, 3- (N -N-pentyl, Nn-propyl) amino-1,2-propanediol, 3- (Nn-hexyl, Nn-propyl) amino-1,2-propanediol, 3- (N-phenyl) , Nn-propyl) amino-1,2-propa Diol, 3- (N-benzyl, Nn-propyl) amino-1,2-propanediol and the like.

In the general formula (2), examples of the diols in which the substituent R ₃ is an i-propyl group include 3-N, N-di-i-propylamino-1,2-propanediol, 3- (Nn-butyl, Ni-propyl) amino-1,2-propanediol, 3- (Ni-butyl, Ni-propyl) amino-1,2-propanediol, 3- (Nt-butyl, Ni-propyl) amino-1,2-propanediol, 3- (Nn-pentyl, Ni-propyl) amino-1,2-propanediol, 3- (N -N-hexyl, Ni-propyl) amino-1,2-propanediol, 3- (N-phenyl, Ni-propyl) amino-1,2-propanediol, 3- (N-benzyl, N -I-propyl) amino-1,2-propanedi All and the like are exemplified.

In the above general formula (2), the diols in which the substituent R ₃ is an n-butyl group specifically includes 3-N, N-di-n-butylamino-1,2-propanediol, 3- (N-i-butyl, Nn-butyl) amino-1,2-propanediol, 3- (Nt-butyl, Nn-butyl) amino-1,2-propanediol, 3- (Nn-pentyl, Nn-butyl) amino-1,2-propanediol, 3- (Nn-hexyl, Nn-butyl) amino-1,2-propanediol, 3- (N -Phenyl, Nn-butyl) amino-1,2-propanediol, 3- (N-benzyl, Nn-butyl) amino-1,2-propanediol and the like are exemplified.

In the general formula (2), the diols in which the substituent R ₃ is an i-butyl group specifically includes 3-N, N-di-i-butylamino-1,2-propanediol, 3- (Nt-butyl, Ni-butyl) amino-1,2-propanediol, 3- (Nn-pentyl, Ni-butyl) amino-1,2-propanediol, 3- (Nn-hexyl, Ni-butyl) amino-1,2-propanediol, 3- (N-phenyl, Ni-butyl) amino-1,2-propanediol, 3- (N-benzyl) , N-i-butyl) amino-1,2-propanediol and the like.

In the general formula (2), the diols in which the substituent R ₃ is a t-butyl group are specifically 3-N, N-di-t-butylamino-1,2-propanediol, 3- (Nn-pentyl, Nt-butyl) amino-1,2-propanediol, 3- (Nn-hexyl, Nt-butyl) amino-1,2-propanediol, 3- (N-phenyl, Nt-butyl) amino-1,2-propanediol, 3- (N-benzyl, Nt-butyl) amino-1,2-propanediol and the like are exemplified.

In the general formula (2), the diols in which the substituent R ₃ is an n-pentyl group, specifically, 3-N, N-di-n-pentylamino-1,2-propanediol, 3- (Nn-hexyl, Nn-pentyl) amino-1,2-propanediol, 3- (N-phenyl, Nn-pentyl) amino-1,2-propanediol, 3- (N -Benzyl, Nn-pentyl) amino-1,2-propanediol and the like.

In the above general formula (2), the diols in which the substituent R ₃ is an n-hexyl group, specifically, 3-N, N-di-n-hexylamino-1,2-propanediol, Examples include 3- (N-phenyl, Nn-hexyl) amino-1,2-propanediol, 3- (N-benzyl, Nn-hexyl) amino-1,2-propanediol, and the like.

In the general formula (2), examples of the diols in which the substituent R ₃ is a phenyl group include 3-N, N-diphenylamino-1,2-propanediol and 3- (N-benzyl). , N-phenyl) amino-1,2-propanediol and the like.

In the general formula (2), specific examples of diols whose substituent R ₃ is a benzyl group include 3-N, N-dibenzylamino-1,2-propanediol. .

Among these diols, in the general formula (1), those in which the substituents R ₁ and R ₂ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms are preferable. In the general formula (2), The substituents R ₃ and R ₄ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When the number of carbon atoms of these substituents exceeds 4, the boiling point of the decomposition product during heating during the formation of the conductive film increases, and there is a risk that it cannot remain evaporated or diffused in the conductive film. In some cases, the purity of metallic copper and the conductivity of the formed conductive film are adversely affected. Further, in consideration of production or availability costs, the diols represented by the general formula (1) are preferably linear alkanediols, and in the general formula (2), the substituents R ₃ and R ₄ are the same substituents. It is preferably a group.

  Considering the above points, in the composition for forming a conductive film of the present invention, examples of the diol include ethylene glycol, propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 2,3-butanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 3,4-hexanediol, 3,4-heptanediol, 3,4-octanediol, 3 , 4-nonanediol, 3,4-decanediol, 4,5-octanediol, 4,5-nonanediol, 4,5-decanediol, 5,6-decanediol, 3-N, N-dimethylamino- 1,2-propanediol, 3-N, N-diethylamino-1,2-propanediol, 3-N, N-di-n-propylamino- , 2-propanediol, 3-N, N-di-i-propylamino-1,2-propanediol, 3-N, N-di-n-butylamino-1,2-propanediol, 3-N, Use one or more selected from the group consisting of N-di-i-butylamino-1,2-propanediol and 3-N, N-di-t-butylamino-1,2-propanediol Is more preferable.

The diols used in the conductive film forming composition of the present invention may be commercially available or may be synthesized by a known method, and are not particularly limited. Known synthesis methods include, for example, a method of reductively coupling a carbonyl compound with Zn—TiCl ₄ or Mg (Hg) —TiCl ₄ , a method of oxidizing an olefin with an organic peracid such as peracetic acid, and an epoxide compound. Examples thereof include a method of ring opening with trifluoroacetic acid, perchloric acid or the like.

  The purity of the diol used in the composition for forming a conductive film of the present invention is not particularly limited, but is preferably 95% or more, and more preferably 99% or more in consideration of use in the field of electronic materials.

  In the composition for forming a conductive film of the present invention, the carboxylic acid having a reducing power used as a reducing agent is not particularly limited. For example, formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid It is preferable to use 1 type, or 2 or more types selected from the group consisting of malic acid and citric acid.

  The carboxylic acid having a reducing power used in the composition for forming a conductive film of the present invention may be a commercially available one or one synthesized by a known method, and is not particularly limited.

  The purity of the carboxylic acid having a reducing power used in the composition for forming a conductive film of the present invention is not particularly limited, but considering use in the field of electronic materials, it is preferably 95% or more, and 99% or more. Further preferred.

  In the composition for forming a conductive film of the present invention, the composition ratio of the noble metal compound, the copper salt, the coordination compound, and the reducing agent is not particularly limited depending on the amount applied to the substrate. The concentration of the noble metal compound is in the range of 1 ppm by weight to 10% by weight, the concentration of the copper salt is in the range of 0.1 to 80% by weight, and the concentration of the coordinating compound is 0.1% with respect to the total amount of the conductive film forming composition. It is preferable that the concentration of the reducing agent ranges from 0.1 to 80% by weight, the concentration of the noble metal compound ranges from 0.1 to 5% by weight, and the concentration of the copper salt ranges from 1 to More preferably, the range is 60% by weight, the concentration of the coordinating compound is 0.1 to 60% by weight, and the concentration of the reducing agent is 0.1 to 60% by weight.

  If the concentration of the noble metal compound is less than 1 ppm by weight, the catalytic ability may not be exhibited, and the reduction from the copper salt to the metallic copper may not occur, or the precipitation rate may be significantly reduced. In some cases, the composition for forming a conductive film increases in viscosity or solidifies, resulting in a decrease in workability.

  Moreover, if the concentration of the copper salt is less than 0.1% by weight, the amount of metallic copper produced from the copper salt is small, and a conductive film having a sufficient film thickness may not be formed. The viscosity of the forming composition may increase or solidify, and workability may decrease.

  In addition, when the concentration of the coordinating compound is less than 0.1% by weight, although depending on the concentration of the copper salt, the copper salt may not be sufficiently dissolved. Not only the effect is not obtained, but the concentration of copper in the total amount of the composition for forming a conductive film is reduced, and the coating amount of the composition for forming a conductive film for obtaining a conductive film with a desired film thickness is increased. There is a risk of industrial disadvantage.

  Moreover, even if the concentration of the reducing agent exceeds 80% by weight, not only the effect of use is not obtained, but also the content of metallic copper per unit weight of the composition for forming a conductive film is reduced. There is a risk of industrial disadvantage.

  Further, in the composition for forming a conductive film of the present invention, the composition ratio of the noble metal compound, the copper salt with a reducing carboxylic acid, and the coordination compound is particularly limited depending on the amount applied to the substrate. Although not intended, for example, the concentration of the noble metal compound is in the range of 1 ppm by weight to 10% by weight and the concentration of the copper salt with the carboxylic acid having a reducing power is 0.1 to 80 with respect to the total amount of the conductive film forming composition. It is preferable that the concentration of monoamines is in the range of 0.1 to 80% by weight, the concentration of precious metal fine particles is in the range of 1 to 5% by weight, copper with a carboxylic acid having a reducing power. More preferably, the concentration of the salt is in the range of 1 to 60% by weight, and the concentration of the coordination compound is in the range of 0.1 to 60% by weight.

  The composition for forming a conductive film of the present invention may contain additives such as a conductive film smoothing agent, a concentration adjusting agent, a surface tension adjusting agent, a viscosity adjusting agent in addition to the above components.

  In the composition for forming a conductive film of the present invention, the conductive film smoothing agent is not particularly limited. For example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, ethylene Glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol Zimechi Ethers, mention may be made of oxygen-containing compounds such as pentaethylene glycol dimethyl ether, it is preferable to use one or two or more selected from these.

  In the composition for forming a conductive film of the present invention, the concentration adjusting agent, the surface tension adjusting agent, and the viscosity adjusting agent are not particularly limited, but examples include an organic solvent in which each component is dissolved and does not react, What is necessary is just to add it suitably so that it may become a desired density | concentration, surface tension, and a viscosity. Examples of such an organic solvent include one selected from the group consisting of alcohols, glycols, ethers, esters, aliphatic hydrocarbons, and aromatic hydrocarbons, or two or more compatible types. Of the mixture.

  Specifically, as alcohols, for example, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, Examples include cyclohexanol, benzyl alcohol, and terpineol.

  Examples of glycols include ethylene glycol, propylene glycol, butylene glycol, pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol.

  Examples of ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane.

  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.

  Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, decalin and the like.

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

  The concentration of the additive described above in the conductive film forming composition of the present invention is not particularly limited, but the additive concentration may be in the range of 0 to 50% by weight with respect to the total amount of the conductive film forming composition. A range of 0 to 20% by weight is more preferable. Even if the concentration of the additive exceeds 50% by weight, not only the effect of using it is obtained, but also the content of metallic copper per unit weight of the composition for forming a conductive film is reduced. May be disadvantageous.

  Next, the manufacturing method of the composition for electrically conductive film formation of this invention is demonstrated.

  The composition for forming a conductive film of the present invention can be obtained by, for example, mixing the above-described noble metal compound, copper salt, coordination compound, and reducing agent, and also with the above-mentioned noble metal compound and a carboxylic acid having a reducing power. It can be easily prepared by mixing a copper salt and a coordination compound.

  In the manufacturing method of the composition for electrically conductive film formation of this invention, there is no restriction | limiting in particular in a mixing method, A well-known method can be utilized. The order of mixing is not particularly limited, but it is preferable to add a noble metal compound and a copper salt to the coordinating compound and sufficiently dissolve them, and then add and mix the reducing agent. If the precious metal compound and copper salt are not sufficiently dissolved in the coordination compound, when the reducing agent is added, the coordinating compound reacts the unstabilized dissolved residue with the reducing agent to form coarse particles, which are uniform. Dispersibility may be impaired.

  In the manufacturing method of the composition for electrically conductive film formation of this invention, you may add a solvent in the manufacturing process. The solvent to be added is not particularly limited as long as it is a precious metal compound, a copper salt, a coordinating compound, and a reducing agent, and is not particularly limited as long as it dissolves them and does not react with them. Examples thereof include one kind selected from the group consisting of alcohols, ethers, esters, aliphatic hydrocarbons, and aromatic hydrocarbons, or a mixture of two or more kinds having compatibility.

  Specifically, examples of alcohols include hexanol, heptanol, octanol, cyclohexanol, benzyl alcohol, and terpineol.

  Examples of ethers include diethyl ether, diisobutyl ether, dibutyl ether, methyl-t-butyl ether, methyl cyclohexyl ether, and the like.

  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.

  Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, decalin and the like.

  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 is preferable to use one kind selected from the group consisting of hexanol, terpineol, methyl-t-butyl ether, and γ-butyrolactone, or a combination of two or more kinds.

  In the manufacturing method of the composition for electrically conductive film formation of this invention, you may mix a coordination compound, a noble metal compound, and copper salt, heating. The heating temperature is not lower than the temperature at which each component described above is solidified and is not particularly limited as long as it is not higher than the temperature at which each component is decomposed, boiled or reacted. Is in the range of 30-80 ° C.

  On the other hand, when adding the reducing agent, it is preferable to add and mix while cooling. Although cooling temperature is not specifically limited, Usually, it is the range of -50-10 degreeC, Preferably it is the range of -20-0 degreeC. When the cooling temperature exceeds 10 ° C., the reduction reaction proceeds vigorously when the reducing agent is added, coarse particles may be formed, and the uniformity may be impaired. When the cooling temperature is less than −50 ° C., a coordination compound, a noble metal compound, In addition, the copper salt may be completely solidified, making it difficult to mix with the reducing agent.

  In the method for producing a conductive film-forming composition of the present invention, the mixing method is not particularly limited. For example, stirring with a stirring blade, stirring with a stirrer and a stirring bar, stirring with a boiler, ultrasonic ( And agitation with a homogenizer). As stirring conditions, for example, in the case of stirring with stirring blades, the rotation speed of the stirring blades is usually in the range of 1 to 1000 rpm, preferably in the range of 10 to 400 rpm.

  Since the composition for forming a conductive film of the present invention is required to contain as high a concentration of metal as possible (for example, at least 5% by weight or more as an inkjet ink), the composition for forming a conductive film of the present invention is required. Solvent removal may be performed in the manufacturing method of the product.

  Next, the conductive film forming method of the present invention will be described.

  By applying the conductive film-forming composition of the present invention to a substrate and heating it in a non-oxidizing atmosphere, the conductive film can be easily formed on the substrate. By heating, the noble metal compound and the copper salt are reduced by the reducing agent, and at the same time, organic substances are removed by decomposition and volatilization.

  In the conductive film forming method of the present invention, a known material can be used as the base material, and is not particularly limited, and examples thereof include resin, paper, metal, glass, wood, and the like. Low density polyethylene resin, high density polyethylene resin, ABS resin (acrylonitrile-butadiene-styrene copolymer synthetic resin), acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate), polyacetal resin, cellulose derivative, etc. Resin base material, non-coated printing paper, fine coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper (heavy-duty kraft paper for heavy bags) Paper, bifurcated kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coated balls, chipboard cardboard, and other paper base materials Metal substrates such as copper plate, iron plate, aluminum plate, glass substrates such as soda glass, borosilicate glass, silica glass, and quartz glass, bases such as alumina, sapphire, zirconia, titania, yttrium oxide, ITO (indium tin oxide) Materials and the like.

  In the method for forming a conductive film of the present invention, the method for applying the composition for forming a conductive film to a substrate can be performed by a known method, and is not particularly limited. For example, screen printing, dip coating, and the like. Method, spray coating method, spin coating method, ink jet method, dispenser coating method and the like. The shape of the coating film is not particularly limited as long as it is planar or dot-shaped. The coating amount for applying the conductive film-forming composition to the substrate may be appropriately adjusted according to the desired thickness of the conductive film, but the film thickness of the conductive film-forming composition after drying is usually 0. The coating may be performed in the range of 0.01 to 5000 μm, preferably in the range of 0.1 to 1000 μm.

  In the conductive film forming method of the present invention, heating is preferably performed in a non-oxidizing atmosphere. Examples of the non-oxidizing atmosphere include helium, argon, nitrogen, and the like. Among these, it is preferable to use nitrogen because it is inexpensive. Further, the inert gas may contain oxygen as long as it does not significantly affect the oxidation of the noble metal fine particles, and its concentration is usually 2000 ppm or less, and more preferably 500 ppm or less.

  In the method for forming a conductive film of the present invention, the heating temperature is not particularly limited as long as it is a temperature at which the noble metal compound and the copper salt are reduced by the reducing agent, and the organic matter is decomposed and volatilized. The range of 80 to 250 ° C. is more preferable. If the heating temperature is less than 50 ° C., the reduction of the copper salt does not proceed completely, and the remaining organic matter may become prominent. If the heating temperature exceeds 300 ° C., the organic substrate may not be used.

  In the method for forming a conductive film of the present invention, the heating time may be appropriately selected depending on the types of the copper precursor and the reducing agent and the desired conductivity, and is not particularly limited, but a heating temperature of about 200 ° C. is set. In such a case, it is usually about 10 to 60 minutes.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not construed as being limited by these examples.

Example 1 Preparation of a conductive film-forming composition containing silver acetate, copper acetate, N, N, N ′, N′-tetramethylethylenediamine, and 1,2-propanediol.
0.085 g of silver acetate was added to 10 g of tetrahydrofuran, 1.8 g of copper acetate, and 2.2 g of N, N, N ′, N′-tetramethylethylenediamine were sequentially added. After heating to 60 ° C., the mixture was stirred for 10 minutes until it was completely dissolved. Next, the mixture was cooled to 0 ° C., 1.6 g of 1,2-propanediol was added, and the mixture was stirred at 0 ° C. for 30 minutes to obtain a uniform solution. After filtering this solution with a 0.5 μm membrane filter, the tetrahydrofuran in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive film (hereinafter, in order to simplify the notation, Referred to as “Coating Solution A”). When this conductive film-forming composition was stored at 0 ° C. under light-shielding conditions, no precipitate was deposited even after 1 day, and it was a uniform solution.

Example 2 For forming a conductive film containing palladium acetate, copper propionate, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, and 3-N, N-diethylamino-1,2-propanediol Preparation of the composition.
To 10 g of tetrahydrofuran was added 0.11 g of palladium acetate, 2.1 g of copper propionate, and 3.5 g of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine were sequentially added. After heating to 60 ° C., the mixture was stirred for 10 minutes until it was completely dissolved. Next, the mixture was cooled to 0 ° C., 3.5 g of 3-N, N-diethylamino-1,2-propanediol was added, and the mixture was stirred at 0 ° C. for 30 minutes to obtain a uniform solution. After filtering this solution with a 0.5 μm membrane filter, the tetrahydrofuran in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive film (hereinafter, in order to simplify the notation, This is referred to as “Coating liquid B”). When this conductive film-forming composition was stored at 0 ° C. under light-shielding conditions, it was a uniform solution with no precipitation even after one day.

Example 3 Preparation of a conductive film-forming composition containing silver acetate, 1,1,1,5,5,5-hexafluoroacetylacetonate copper, n-hexanethiol, and glyoxylic acid.
0.085 g of silver acetate was added to 10 g of tetrahydrofuran, 2.4 g of 1,1,1,5,5,5-hexafluoroacetylacetonate copper and 4.8 g of n-hexanethiol were sequentially added. After heating to 60 ° C., the mixture was stirred for 10 minutes until it was completely dissolved. Next, it was cooled to 0 ° C., 1.8 g of glyoxylic acid was added, and the mixture was stirred at 0 ° C. for 30 minutes to obtain a uniform solution. After filtering this solution with a 0.5 μm membrane filter, the tetrahydrofuran in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive film (hereinafter, in order to simplify the notation, Referred to as “Coating Solution C”). When this conductive film-forming composition was stored at 0 ° C. under light-shielding conditions, it was a uniform solution with no precipitation even after one day.

Example 4 Preparation of a conductive film forming composition containing silver acetate, copper formate, and n-hexylamine.
To 10 g of tetrahydrofuran was added 0.085 g of silver acetate, 1.5 g of copper formate and 2.1 g of n-hexylamine were sequentially added. The mixture was stirred at room temperature for 10 minutes until it was completely dissolved to obtain a uniform solution. After filtering this solution with a 0.5 μm membrane filter, the tetrahydrofuran in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive film (hereinafter, in order to simplify the notation, This is referred to as “Coating liquid D”). When this conductive film-forming composition was stored at 0 ° C. under light-shielding conditions, it was a uniform solution with no precipitation even after one day.

Reference Example Preparation of silver fine particle dispersion.
In the following reference examples, the average particle diameter of the silver fine particles was selected at random from the field of view observed with a transmission electron microscope (TEM), and photographed at a magnification of 1,000,000 times. A total of 100 particles were selected from each photograph, 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. As the TEM, a product name “JEM-2000FX” manufactured by JEOL Ltd. was used. Elemental analysis was measured by a Perkin Elmer fully automatic elemental analyzer “2400II”, and ¹ H-NMR was measured by “Gemini-200” manufactured by Varian.

  To 10 g of aniline, 1.67 g of silver acetate was added and stirred at 40 ° C. for about 10 minutes until the solid was completely dissolved and became a homogeneous solution. Subsequently, a solution prepared by dissolving 0.37 g of sodium borohydride in 1.63 g of water was added dropwise at room temperature over 30 minutes. The mixture was further stirred at room temperature for 30 minutes and transferred to a separatory funnel under a nitrogen stream. After the phase-separated lower colorless and transparent aqueous phase was removed, washing with 10 g of ion-exchanged water and again removing the lower aqueous phase after phase separation yielded a black silver fine particle dispersion. When this silver fine particle dispersion was observed with TEM and the average particle diameter was determined, it was 9.2 nm (standard deviation 4.2, coefficient of variation 46%). The silver fine particle dispersion was heated to 80 ° C. under reduced pressure (120 Pa) to remove distillate, thereby obtaining 2.19 g of silver fine particles. As a result of elemental analysis, the obtained silver fine particles were composed of 46 wt% of silver and 54 wt% of an organic component, and the main component of the organic substance was aniline from the analysis result by 1H-NMR.

Comparative Example 1 Preparation of a conductive film-forming composition containing silver fine particles, copper acetate, N, N, N ′, N′-tetramethylethylenediamine and 1,2-propanediol.
0.14 g of the silver fine particles obtained in Example 1 was added to 10 g of tetrahydrofuran, 1.8 g of copper acetate, and 2.2 g of N, N, N ′, N′-tetramethylethylenediamine were sequentially added. After heating to 60 ° C., the mixture was stirred for 10 minutes until it was completely dissolved. Next, the mixture was cooled to 0 ° C., 1.6 g of 1,2-propanediol was added, and the mixture was stirred at 0 ° C. for 30 minutes 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 composition for forming a conductive film. When this composition for forming an electrically conductive film was stored at 0 ° C. under light-shielding conditions, a precipitate was deposited after 1 day.

Comparative Example 2 Preparation of a conductive film-forming composition containing silver acetate, 1,1,1,5,5,5-hexafluoroacetylacetonatocopper, and glyoxylic acid.
0.085 g of silver acetate was added to 10 g of tetrahydrofuran, and 2.4 g of 1,1,1,5,5,5-hexafluoroacetylacetonato copper was added. After heating to 60 ° C., the mixture was stirred for 10 minutes until it was completely dissolved. Next, it was cooled to 0 ° C., 1.8 g of glyoxylic acid was added, and the mixture was stirred at 0 ° C. for 30 minutes 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 composition for forming a conductive film. When this composition for forming an electrically conductive film was stored at 0 ° C. under light-shielding conditions, a precipitate was deposited after 1 day.

Comparative Example 3 Preparation of a conductive film-forming composition containing copper formate and n-hexylamine.
To 10 g of tetrahydrofuran was added 0.085 g of silver acetate, 1.5 g of copper formate and 2.1 g of n-hexylamine were sequentially added. The mixture was stirred at room temperature for 10 minutes until it was completely dissolved to obtain a uniform solution. After filtering this solution with a 0.5 μm membrane filter, the tetrahydrofuran in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive film (hereinafter, in order to simplify the notation, This is referred to as “Coating liquid E”). When this conductive film-forming composition was stored at 0 ° C. under light-shielding conditions, it was a uniform solution with no precipitation even after one day.

Comparative Example 4 Preparation of a conductive film-forming composition containing copper formate and 3-methoxypropylamine.
To 10 g of tetrahydrofuran, 1.5 g of copper formate anhydride and 1.8 g of 3-methoxypropylamine were sequentially added. The mixture was stirred at room temperature for 10 minutes until it was completely dissolved to obtain a uniform solution. After filtering this solution with a 0.5 μm membrane filter, the tetrahydrofuran in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive film (hereinafter, in order to simplify the notation, Referred to as “Coating fluid F”). When this conductive film-forming composition was stored at 0 ° C. under light-shielding conditions, it was a uniform solution with no precipitation even after one day.

Examples 5 to 8, Comparative Example 5, Comparative Example 6 Conductivity evaluation.
On the glass substrate, the coating liquids A to F obtained in the above Examples and Comparative Examples were uniformly applied using each bar coater (number of the wire number: No. 40), and 5 mm × 50 mm, film A uniform coating film having a thickness of about 90 μm was formed. 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 coating solutions was subjected to heat treatment for 30 minutes to obtain a conductive film. In each of the coating solutions described above, the temperature at which the conductive film having the highest conductivity could be formed was defined as “heating temperature”.

  About each formed electrically conductive film, the surface resistance value was measured with the four-point probe resistance measuring device (Brand name "Loresta GP", Mitsubishi Chemical Corporation make).

  Next, each formed electrically conductive film was cut | disconnected, the cross section was observed with the scanning electron microscope (SEM), and the average film thickness of each electrically conductive film was evaluated. Here, “average film thickness” means that each conductive film is randomly selected from the observed field of view with a scanning electron microscope (SEM), and taken at a magnification of 5000 times. The film thickness was measured, and these values were divided by the photographing magnification, and the film thicknesses at three locations were obtained by arithmetic averaging. SEM used a product name “JSM T220A” manufactured by JEOL Ltd.

  The conductivity was evaluated by comparing the volume resistance value calculated from the surface resistance value and the average film thickness obtained from the observation result of a scanning electron microscope (SEM) in each conductive film.

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

実施例１〜実施例４は、本発明の導電膜形成用組成物の例であるが、１日経過後も、沈殿の析出は無く、均一な溶液であり、保存安定性に優れた。

Examples 1 to 4 are examples of the composition for forming a conductive film of the present invention, but after 1 day, there was no precipitation, precipitation was uniform, and storage stability was excellent.

  On the other hand, Comparative Example 1 is an example in which noble metal fine particles are used, and Comparative Example 2 is an example in which no coordinating compound is added.

  Further, as is apparent from Table 1, Examples 5 to 8 are examples in which a conductive film was formed using a conductive film forming composition containing a noble metal compound, a copper salt, a coordination compound, and a reducing agent. However, all of the formed conductive films showed good conductivity.

  On the other hand, Comparative Example 5 and Comparative Example 6 are examples in which a conductive film was formed using a conductive film forming composition not containing a noble metal compound, but the copper reduction reaction did not proceed completely, and the conductive film was not conductive. A decline in sex was observed.

Claims (29)

A composition for forming a conductive film, comprising a noble metal compound, a copper salt, a coordination compound, and a reducing agent. The composition for forming a conductive film according to claim 1, wherein the noble metal compound is one or more selected from the group consisting of silver ions, platinum ions, and palladium ions. The composition for forming a conductive film according to claim 1 or 2, wherein the noble metal compound is one or more selected from the group consisting of a noble metal salt, a noble metal oxide, and a noble metal sulfide. The composition for forming a conductive film according to claim 3, wherein the noble metal salt is one or more selected from the group consisting of a noble metal carboxylate and a complex salt of a noble metal and an acetylacetone derivative. Noble metal compounds are silver formate, silver acetate, silver trifluoroacetate, silver propionate, silver butyrate, silver isobutyrate, silver valerate, silver isovalerate, silver pivalate, silver hexanoate, silver heptanoate, cyclohexanecarboxylic acid Silver, silver octanoate, silver 2-ethylhexanoate, silver nonanoate, silver decanoate, silver undecanoate, silver dodecanoate, silver tridecanoate, silver oleate, silver linoleate, silver linolenate, silver benzoate, formic acid Palladium, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium butyrate, palladium isobutyrate, palladium valerate, palladium isovalerate, palladium pivalate, palladium hexanoate, palladium heptanoate, palladium cyclohexanecarboxylate, palladium octanoate , Silver palladium 2-ethylhexanoate, Nona Palladium acid, palladium decanoate, palladium undecanoate, palladium dodecanoate, palladium tridecanoate, palladium oleate, palladium linoleate, palladium linolenate, palladium benzoate, silver acetylacetonate, silver hexafluoroacetylacetonate, acetylacetonato The composition for forming a conductive film according to any one of claims 1 to 4, wherein the composition is one or more selected from the group consisting of palladium and hexafluoroacetylacetonato palladium. 6. The conductive according to claim 1, wherein the copper salt is one or more selected from the group consisting of a copper carboxylate and a complex salt of copper and an acetylacetone derivative. Film forming composition. Copper salt is copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper pivalate, copper formate, copper hydroxyacetate, copper glyoxylate, copper oxalate, acetylacetate It is one or more selected from the group consisting of copper nato, copper 1,1,1-trifluoroacetylacetonato, and copper 1,1,1,5,5,5-hexafluoroacetylacetonato The composition for electrically conductive film formation in any one of Claim 1 thru | or 6 characterized by the above-mentioned. The composition for forming a conductive film according to any one of claims 1 to 8, wherein the coordination compound is one or more compounds selected from the group consisting of alkanethiols and amines. object. Alkanethiols are ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, cyclohexanethiol, n-heptanethiol The composition for forming a conductive film according to claim 8, wherein the composition is one or more selected from the group consisting of n-octanethiol and 2-ethylhexanethiol. Amines are ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n-octylamine 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, benzyl Amine, ethylenediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine , N, N ' Dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N, N′-dimethyl-1,5-pentanediamine 1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, isophoronediamine, diethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N- (aminoethyl) The composition for forming a conductive film according to claim 9, wherein the composition is one or more selected from the group consisting of piperazine and N- (aminopropyl) piperazine. The composition for forming a conductive film according to any one of claims 1 to 10, wherein the reducing agent is one or more selected from the group consisting of diols and carboxylic acids having a reducing power. object. Diols are ethylene glycol, propylene glycol, 1,2-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,2-hexanediol, 2,3-hexane Diol, 3,4-hexanediol, 2,3-heptanediol, 3,4-heptanediol, 3,4-octanediol, 4,5-octanediol, 3,4-nonanediol, 4,5-nonanediol 3,4-decanediol, 4,5-decanediol, 5,6-decanediol, 3-N, N-dimethylamino-1,2-propanediol, 3-N, N-diethylamino-1,2- Propanediol, 3-N, N-di-n-propylamino-1,2-propanediol, 3-N, N-di-i-propylamino-1 2-propanediol, 3-N, N-di-n-butylamino-1,2-propanediol, 3-N, N-di-i-butylamino-1,2-propanediol, and 3-N, The composition for electrically conductive film formation of Claim 11 which is 1 type, or 2 or more types chosen from the group which consists of N-di-t-butylamino-1, 2-propanediol. The composition for forming a conductive film according to claim 11, wherein the carboxylic acid having a reducing power is at least one selected from the group consisting of formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid, and citric acid. object. The concentration of the noble metal compound is 1 to 50% by weight, the concentration of the copper salt is 0.1 to 80% by weight, and the concentration of the coordination compound is 0.1 to 80% by weight with respect to the total amount of the conductive film forming composition. The composition for forming a conductive film according to any one of claims 1 to 17, wherein the concentration of the reducing agent is in the range of 0.1 to 80% by weight. A conductive film-forming composition comprising a noble metal compound, a copper salt with a reducing carboxylic acid, and a coordination compound. The composition for forming a conductive film according to claim 15, wherein the noble metal compound is one or more selected from the group consisting of silver ions, platinum ions, and palladium ions. 17. The composition for forming a conductive film according to claim 15, wherein the noble metal compound is one or two or more selected from the group consisting of a noble metal salt, a noble metal oxide, and a noble metal sulfide. The composition for forming a conductive film according to claim 17, wherein the noble metal salt is one or more selected from the group consisting of a noble metal carboxylate and a complex salt of a noble metal and an acetylacetone derivative. Noble metal compounds are silver formate, silver acetate, silver trifluoroacetate, silver propionate, silver butyrate, silver isobutyrate, silver valerate, silver isovalerate, silver pivalate, silver hexanoate, silver heptanoate, cyclohexanecarboxylic acid Silver, silver octanoate, silver 2-ethylhexanoate, silver nonanoate, silver decanoate, silver undecanoate, silver dodecanoate, silver tridecanoate, silver oleate, silver linoleate, silver linolenate, silver benzoate, formic acid Palladium, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium butyrate, palladium isobutyrate, palladium valerate, palladium isovalerate, palladium pivalate, palladium hexanoate, palladium heptanoate, palladium cyclohexanecarboxylate, palladium octanoate , Silver palladium 2-ethylhexanoate, Nona Palladium acid, palladium decanoate, palladium undecanoate, palladium dodecanoate, palladium tridecanoate, palladium oleate, palladium linoleate, palladium linolenate, palladium benzoate, silver acetylacetonate, silver hexafluoroacetylacetonate, acetylacetonato The composition for forming a conductive film according to any one of claims 15 to 18, wherein the composition is one or more selected from the group consisting of palladium and hexafluoroacetylacetonato palladium. The copper salt with a reducing carboxylic acid is at least one selected from the group consisting of copper formate, copper hydroxyacetate, copper glyoxylate, copper lactate, copper oxalate, copper tartrate, copper malate, and copper citrate. The composition for electrically conductive film formation in any one of Claim 15 thru | or 19. 21. The conductive film forming material according to claim 15, wherein the coordination compound is one or more compounds selected from the group consisting of alkanethiols and amines. Composition. Alkanethiols are ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, cyclohexanethiol, n-heptanethiol The composition for forming a conductive film according to claim 21, wherein the composition is one or more selected from the group consisting of n-octanethiol and 2-ethylhexanethiol. Amines are ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n-octylamine 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, benzyl Amine, ethylenediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine , N, N ' Dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N, N′-dimethyl-1,5-pentanediamine 1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, isophoronediamine, diethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N- (aminoethyl) The conductive film-forming composition according to claim 21, wherein the composition is one or more selected from the group consisting of piperazine and N- (aminopropyl) piperazine. The concentration of the noble metal compound is 1 wt ppm to 50 wt%, the concentration of the copper salt with the reducing carboxylic acid is 0.1 to 80 wt%, and the coordination compound is based on the total amount of the conductive film forming composition. The composition for forming a conductive film according to any one of claims 15 to 23, wherein the concentration is in the range of 0.1 to 80% by weight. The manufacturing method of the composition for electrically conductive film formation in any one of the Claims 1 thru | or 14 characterized by mixing a noble metal compound, copper salt, a coordination compound, and a reducing agent. 25. The process for producing a conductive film-forming composition according to claim 15, comprising mixing noble metal fine particles, a copper salt with a reducing carboxylic acid, and a coordination compound. Method. A conductive film is formed on a substrate by applying the conductive film-forming composition according to any one of claims 1 to 24 to a base material and heating in a non-oxidizing atmosphere. Manufacturing method of membrane. 28. The method for producing a conductive film according to claim 27, wherein the non-oxidizing atmosphere is selected from the group consisting of a helium atmosphere, a nitrogen atmosphere, and an argon atmosphere. The method for producing a conductive film according to claim 27 or 28, wherein the heating temperature is in the range of 60C to 300C.