JP2011034749A - 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 conductive film and a conductive film forming method using the same by heating at temperature which can allow use of a non-heat-resistant base material such as general-purpose resin or paper, instead of hydrogen gas of high risk in a conductive film forming process. <P>SOLUTION: A conductive film forming composition containing noble metal fine particles, copper ion, a reductant, and monoamines 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&INPIT

Description

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

  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, since the conductive film forming material using such copper fine particles needs to be heated in a reducing atmosphere containing hydrogen in order to suppress copper oxidation in the step of forming the conductive film after coating, There is a big safety problem. Moreover, in order to remove the oxidation inhibitor which coat | covers the copper fine particle surface and to fuse | melt the copper fine particles, generally the heating at high temperature of about 300 degreeC is required, and the problem that the base material which can be applied is restricted is also a problem. there were.

  Therefore, a conductive film forming material that can form a copper conductive film by heating at a relatively low temperature in a non-reducing atmosphere not containing hydrogen 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.

  Furthermore, the formation of the conductive film by these methods requires a heating time of about 1 hour, which may be industrially disadvantageous from the viewpoint of production efficiency.

  As described above, none of the above-described methods is sufficient, and further studies have been demanded for industrial practical use. In other words, the conductive film is formed by heating in a relatively short time at a temperature at which a non-heat-resistant base material made of a general-purpose resin or paper can be used without using highly dangerous hydrogen gas in the conductive film formation process. Development of a conductive film forming composition and a conductive film forming method that can be formed 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 its object is to use a non-heat-resistant group made of a general-purpose resin or paper without using a highly dangerous hydrogen gas in the conductive film forming step. An object of the present invention is to provide a conductive film forming composition capable of forming a conductive film by heating at a temperature at which the material can be used, and a method for producing a conductive film using the composition.

  As a result of intensive studies on the composition for forming a conductive film and a method for forming a conductive film, the present inventors have found a composition for forming a conductive film containing noble metal fine particles, a copper salt, a reducing agent, and monoamines, noble metal fine particles, and reduction. The present inventors have found a copper salt with a powerful carboxylic acid and a composition for forming a conductive film containing monoamines. 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 composition for forming a conductive film containing noble metal fine particles, a copper salt, a reducing agent, and monoamines.

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

  [3] The conductive film-forming composition as described in [1] or [2] above, wherein the noble metal fine particles have an average particle size in the range of 1 to 400 nm.

  [4] The above [1] to [3], 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 description of description.

  [5] 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 [4], which is characterized in that:

  [6] The conductive material according to any one of [1] to [5], wherein the reducing agent is one or more selected from the group consisting of hydrazines and a carboxylic acid having a reducing power. Film forming composition.

  [7] The hydrazines are 1,2-di-n-butylhydrazine, 1,2-di-t-butylhydrazine, 1,2-di-n-pentyldrazine, 1,2-di-n-hexyl. Hydrazine, 1,2-dicyclohexylhydrazine, 1,2-di-n-heptylhydrazine, 1,2-di-n-octylhydrazine, 1,2-di- (2-ethylhexyl) hydrazine, 1,2-diphenylhydrazine And the composition for forming a conductive film according to the above [6], which is one or more selected from the group consisting of 1,2-dibenzylhydrazine.

  [8] The conductive film according to [6], wherein the carboxylic acid having a reducing power is one or more selected from the group consisting of formic acid, hydroxyacetic acid, glyoxylic acid, and oxalic acid. Forming composition.

[9] Monoamines 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 The composition for forming a conductive film according to any one of the above [1] to [8], which is one or more selected from the group consisting of an amine and benzylamine [10] For forming a conductive film The concentration of noble metal fine particles is 1 wt ppm to 50 wt%, and the concentration of copper salt is 0.1 wt% with respect to the total amount of the composition. Any one of [1] to [9] above, wherein the concentration of the reducing agent is in the range of 0.1 to 80% by weight, and the concentration of the monoamines is in the range of 0.1 to 80% by weight. A composition for forming a conductive film according to claim 1.

  [11] A composition for forming a conductive film, comprising noble metal fine particles, a copper salt with a reducing carboxylic acid, and monoamines.

  [12] The conductive film-forming composition as described in [11] above, wherein the noble metal fine particles are one or more selected from the group consisting of gold fine particles, silver fine particles, platinum fine particles, and palladium fine particles. .

  [13] The conductive film-forming composition as described in [11] or [12] above, wherein the noble metal fine particles have an average particle diameter in the range of 1 to 400 nm.

  [14] The copper salt with a carboxylic acid having reducing power is one or more selected from the group consisting of copper formate, copper hydroxyacetate, copper glyoxylate, and copper oxalate. The composition for electrically conductive film formation in any one of [11] thru | or [13].

[15] Monoamines 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 The composition for forming a conductive film according to any one of the above [11] to [14], which is one or more selected from the group consisting of an amine and benzylamine [16] For forming a conductive film The concentration of precious metal fine particles is 1 ppm by weight to 50% by weight with respect to the total amount of the composition, and has a reducing power. Any of [11] to [15] above, wherein the concentration of the copper salt with the carboxylic acid is 0.1 to 80% by weight and the concentration of the monoamines is 0.1 to 80% by weight. A composition for forming a conductive film according to claim 1.

  [17] The method for producing a conductive film-forming composition as described in any one of [1] to [10] above, wherein noble metal fine particles, a copper salt, a reducing agent, and monoamines are mixed.

  [18] Production of the composition for forming a conductive film according to any one of [11] to [16], wherein noble metal fine particles, a copper salt with a carboxylic acid having a reducing power, and monoamines are mixed. Method.

  [19] Forming a conductive film on a substrate by applying the conductive film forming composition according to any one of [1] to [16] to a base material and heating in a non-oxidizing atmosphere. A method for producing a conductive film.

  [20] The method for producing a conductive film according to [19], wherein the substrate is a non-heat resistant substrate.

  [21] The method for producing a conductive film according to [19] or [20], wherein the non-oxidizing atmosphere is selected from the group consisting of a helium atmosphere, a nitrogen atmosphere, and an argon atmosphere.

  [22] The method for producing a conductive film according to any one of [19] to [21], wherein the heating temperature is in the range of 60 ° C to 180 ° C.

  The composition for forming a conductive film of the present invention can be obtained at a low price, using a copper salt, a reducing agent, and monoamines as raw materials, and it is not necessary to use a large amount of expensive noble metal fine particles. Excellent productivity.

  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.

  Furthermore, the composition for forming a conductive film of the present invention does not require the installation of a special reaction apparatus such as high temperature, high pressure, and high vacuum in the production thereof, so that the capital investment and utility cost can be reduced. .

  On the other hand, the conductive film forming method of the present invention can form a conductive film or a conductive pattern on a substrate by a simple method such as coating and heating, and can achieve energy saving, low cost, and low environmental load. .

  In the conductive film forming method of the present invention, the conductive film can be formed by heating in a relatively short time at a temperature at which a general-purpose resin or a non-heat resistant substrate made of paper can be used. Excellent in productivity and productivity.

  Furthermore, the conductive film formation method of the present invention does not require heating in a reducing atmosphere containing hydrogen in the conductive film formation step, and is excellent in safety.

  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 composition for forming a conductive film of the present invention contains noble metal fine particles, copper salt, a reducing agent, and monoamines, or contains noble metal fine particles, a copper salt with a reducing carboxylic acid, and monoamines. It is.

  The method for producing the composition for forming a conductive film of the present invention is not particularly limited. For example, the noble metal fine particles, the copper salt, the reducing agent, and monoamines are added to the solvent and dissolved, and then the solvent is removed. In addition, the precious metal fine particles, the copper salt with a carboxylic acid having a reducing power, and monoamines are added to the solvent, dissolved, and then the solvent is removed.

  In the composition for forming a conductive film of the present invention, the noble metal fine particle is a catalyst that promotes reduction of copper ions contained in the copper salt when the composition for forming a conductive film is applied to a substrate and heated in a non-oxidizing atmosphere. To play a role.

  In the composition for forming a conductive film of the present invention, the noble metal fine particles are not particularly limited, but for example, one kind selected from the group consisting of gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium or The thing containing 2 or more types of metal seed | species is mentioned. These metal species may be simple substances or alloys with other metals. Among these, it is preferable to contain one or more metal species selected from the group consisting of gold, silver, platinum, and palladium from the viewpoint of cost, availability, and catalytic ability at the time of forming a conductive film, More preferably, it contains silver and / or palladium.

  In the composition for forming a conductive film of the present invention, fine particles of metal other than these noble metals may be used, but the fine metal particles are not oxidized by the copper ions contained in the copper salt, and the catalytic ability is not exhibited. There is a possibility that the reduction and precipitation rate from copper ions to metallic copper may decrease.

  In the conductive film forming composition of the present invention, the noble metal fine particles have an average particle diameter in the range of 1 to 400 nm. When the particle diameter of the noble metal fine particle is less than 1 nm, the activity of the fine particle surface becomes very high, and there is a possibility of being oxidized or dissolved. On the other hand, if it exceeds 400 nm, noble metal fine particles may settle when stored for a long time. Therefore, it is desirable to be within the above range.

  In the present invention, as a method for measuring the particle diameter of the noble metal fine particles, a general particle measuring method can be used. For example, a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a field emission scanning electron microscope (FE-SEM), or the like can be used as appropriate. The value of the average particle diameter is measured using the above-mentioned apparatus, and three locations where the particle diameters are relatively uniform are selected from the observed field of view, and images are taken at the magnification most suitable for the particle size measurement. From each photo, select the 100 most likely particles, measure the diameter with a ruler, calculate the particle size by dividing the measurement magnification, and obtain these values by arithmetically averaging them. Can do.

  In the composition for forming a conductive film of the present invention, the noble metal fine particles may be commercially available or may be synthesized by a known method, and is not particularly limited. As a known synthesis method, for example, a gas phase method (dry method) in which a synthesis reaction is performed by a physical method such as a sputtering method or a vapor deposition method in gas, or a base metal compound solution is reduced in the presence of a surface protective agent. A liquid phase method (wet method) or the like for precipitating fine metal particles is generally known. Among these, as an example of a generally used liquid phase method, noble metal fine particles are obtained by heating metal complex ions dissolved in a mixed solvent of water containing polyvinyl alcohol as a protective agent and methanol, ethanol, or the like. (E.g., “Journal of Macromolecular Science: Part A. Pure & Applied Chemistry”, 1979, Vol. 13, p. 727), and near the boiling point thereof using a polyol such as ethylene glycol or diethylene glycol. Alternatively, a method of slowly reducing and precipitating metal ions to obtain noble metal fine particles by heating at a lower temperature (see, for example, “MRS Bulletin”, 1989, Vol. 14, p. 29), and the like can be given.

  In the composition for forming a conductive film of the present invention, the purity of the noble metal fine particles as a metal is not particularly limited, but if the purity is too low, there is a risk of adversely affecting the conductivity when the conductive thin film is formed. Therefore, 95% or more is preferable, and 99% or more is more preferable.

  As the noble metal fine particles, those in which a coordinating compound is coordinated to the metal surface are generally used in order to suppress aggregation of the noble metal fine particles and oxidation of the noble metal fine particles. Therefore, even if such a coordinating compound is mixed in the composition for forming a conductive film of the present invention, there is no problem.

  Examples of the coordination compound described above include monomolecular compounds having one or more polar functional groups selected from the group consisting of thiol groups, nitrile groups, amino groups, hydroxyl groups, or hydroxycarbonyl groups, and nitrogen. Examples thereof include polymers having in the molecular structure one or more heteroatoms selected from the group consisting of atoms, oxygen atoms, or sulfur atoms.

  Examples of the monomolecular compound described above include alkanethiol, aliphatic amine, aromatic amine, and alicyclic carboxylic acid. Examples of the polymer described above include polyhydrazone compound, polyvinylpyrrolidone, polyethyleneimine, Examples include polyaniline, polypyrrole, polythiophene, polyacrylamide, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, and polyethylene oxide.

  Generally, the above-mentioned coordination compound is coordinated to the surface of the noble metal fine particles in the range of 0 to 200% by weight with respect to the weight of the noble metal fine particles. The amount of the coordinated compound mixed may be in the range of 0 to 200% by weight with respect to the added weight of the noble metal fine particles.

  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 by heat treatment to become metallic copper, and play a role in expressing 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 Among them, it is preferable to use one or more selected from the group consisting of a copper carboxylate and a complex salt of copper and an acetylacetone derivative from the viewpoint 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 salts with aliphatic carboxylic acids 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.

  Specific examples of complex salts of copper and acetylacetone derivatives include acetylacetonate copper, 1,1,1-trimethylacetylacetonate copper, 1,1,1,5,5,5-hexamethylacetylacetate. Suitable examples include sodium copper, 1,1,1-trifluoroacetylacetonatocopper, 1,1,1,5,5,5-hexafluoroacetylacetonatocopper, and the like.

  Among these, in terms of cost, solubility, and removability during heating, copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper pivalate, formic acid Copper, copper hydroxyacetate, copper glyoxylate, copper oxalate, copper acetylacetonate, 1,1,1-trifluoroacetylacetonatocopper, 1,1,1,5,5,5-hexafluoroacetylacetonatocopper Copper salts such as are preferred.

  In the manufacturing method described above, other copper salts may be used, but they may be industrially disadvantageous because they are difficult to obtain or expensive. Moreover, as a copper salt, what was synthesize | combined by the commercially available thing and the well-known method may be sufficient, and also it forms in a system by mixing the compound containing a copper ion, inorganic anion species, and / or organic anion species. Any of these 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 there is no need to add a reducing agent separately. .

  In the manufacturing method described above, the purity of the copper salt is not particularly limited, but if it is too low purity, there is a possibility of adversely affecting the conductivity when it is used as a conductive film, so 95% or more is preferable. 99% or more is more preferable.

  In the conductive film forming composition of the present invention, the reducing agent reduces the copper salt and deposits metallic copper 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 enough to reduce copper ions to metallic copper by heat treatment. Examples include hydrazines, diols, hydroxylamines, α-hydroxy ketones, carboxylic acids having a reducing power, etc. Among these, hydrazines having a high reducing power even at relatively low temperatures, having a reducing power Carboxylic acid is preferred.

  In the composition for forming a conductive film of the present invention, hydrazines used as a reducing agent are not particularly limited, and examples thereof include 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１〜１２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。ただし、Ｒ_１、Ｒ_２が同時に水素原子となることはない。］
で示される化合物が好適なものとして挙げられる。

[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 12 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. However, R ₁ and R ₂ are not simultaneously hydrogen atoms. ]
The compound shown by these is mentioned as a suitable thing.

Among these, considering the solubility and reducing power of the copper salt, and also the removability when forming the conductive film, in the general formula (1), the groups R ₁ and R ₂ are each independently a hydrogen atom, a 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, cyclohexyl group, n-heptyl group, n-octyl Group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, phenyl group, 4-methylphenyl group, or benzyl group (provided that R ₁ and R ₂ are It does not become a hydrogen atom at the same time.) A compound is more preferable.

Specific examples of hydrazines in which the substituent R ₁ is a hydrogen atom in the general formula (1) include methyl hydrazine, ethyl hydrazine, n-propyl hydrazine, i-propyl hydrazine, n-butyl hydrazine, i- Butyl hydrazine, t-butyl hydrazine, n-pentyl hydrazine, n-hexyl hydrazine, cyclohexyl hydrazine, n-heptyl hydrazine, n-octyl hydrazine, 2-ethylhexyl hydrazine, n-nonyl hydrazine, n-decyl hydrazine, n-undecyl Examples include hydrazine, n-dodecyl hydrazine, phenyl hydrazine, 4-methylphenyl hydrazine, benzyl hydrazine and the like.

In the general formula (1), the hydrazines in which the substituent R ₁ is a methyl group are specifically 1,2-dimethylhydrazine, 1-ethyl-2-methylhydrazine, 1-n-propyl. 2-methylhydrazine, 1-i-propyl-2-methylhydrazine, 1-n-butyl-2-methylhydrazine, 1-i-butyl-2-methylhydrazine, 1-t-butyl-2-methylhydrazine, 1-n-pentyl-2-methylhydrazine, 1-n-hexyl-2-methylhydrazine, 1-cyclohexyl-2-methylhydrazine, 1-n-heptyl-2-methylhydrazine, 1-n-octyl-2- Methyl hydrazine, 1- (2-ethylhexyl) -2-methyl hydrazine, 1-n-nonyl-2-methyl hydrazine, 1-n-decyl-2-methyl hydrazine Dorazine, 1-n-undecyl-2-methylhydrazine, 1-n-dodecyl-2-methylhydrazine, 1-phenyl-2-methylhydrazine, 1- (4-methyl) phenyl-2-methylhydrazine, 1-benzyl Examples include 2-methylhydrazine.

In the general formula (1), the hydrazines in which the substituent R ₁ is an ethyl group are specifically 1,2-diethylhydrazine, 1-n-propyl-2-ethylhydrazine, 1-i. -Propyl-2-ethylhydrazine, 1-n-butyl-2-ethylhydrazine, 1-i-butyl-2-ethylhydrazine, 1-t-butyl-2-ethylhydrazine, 1-n-pentyl-2-ethyl Hydrazine, 1-n-hexyl-2-ethylhydrazine, 1-cyclohexyl-2-ethylhydrazine, 1-n-heptyl-2-ethylhydrazine, 1-n-octyl-2-ethylhydrazine, 1- (2-ethylhexyl) ) -2-ethylhydrazine, 1-n-nonyl-2-ethylhydrazine, 1-n-decyl-2-ethylhydrazine, 1-n-undecyl-2- Examples include ethyl hydrazine, 1-n-dodecyl-2-ethyl hydrazine, 1-phenyl-2-ethyl hydrazine, 1- (4-methyl) phenyl-2-ethyl hydrazine, 1-benzyl-2-ethyl hydrazine and the like. .

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is an n-propyl group include 1,2-di-n-propylhydrazine, 1-i-propyl-2- n-propylhydrazine, 1-n-butyl-2-n-propylhydrazine, 1-i-butyl-2-n-propylhydrazine, 1-t-butyl-2-n-propylhydrazine, 1-n-pentyl- 2-n-propylhydrazine, 1-n-hexyl-2-n-propylhydrazine, 1-cyclohexyl-2-n-propylhydrazine, 1-n-heptyl-2-n-propylhydrazine, 1-n-octyl- 2-n-propylhydrazine, 1- (2-ethylhexyl) -2-n-propylhydrazine, 1-n-nonyl-2-n-propylhydrazine, 1-n-decyl-2-n -Propyl hydrazine, 1-n-undecyl-2-n-propyl hydrazine, 1-n-dodecyl-2-n-propyl hydrazine, 1-phenyl-2-n-propyl hydrazine, 1- (4-methyl) phenyl- Examples include 2-n-propyl hydrazine, 1-benzyl-2-n-propyl hydrazine and the like.

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is an i-propyl group include 1,2-di-i-propylhydrazine, 1-n-butyl-2- i-propylhydrazine, 1-i-butyl-2-i-propylhydrazine, 1-t-butyl-2-i-propylhydrazine, 1-n-pentyl-2-i-propylhydrazine, 1-n-hexyl- 2-i-propylhydrazine, 1-cyclohexyl-2-i-propylhydrazine, 1-n-heptyl-2-i-propylhydrazine, 1-n-octyl-2-i-propylhydrazine, 1- (2-ethylhexyl) ) -2-i-propylhydrazine, 1-n-nonyl-2-i-propylhydrazine, 1-n-decyl-2-i-propylhydrazine, 1-n-undecyl-2- i-propylhydrazine, 1-n-dodecyl-2-i-propylhydrazine, 1-phenyl-2-i-propylhydrazine, 1- (4-methyl) phenyl-2-i-propylhydrazine, 1-benzyl-2 -I-propylhydrazine and the like are exemplified.

In the general formula (1), the hydrazines in which the substituent R ₁ is an n-butyl group are specifically 1,2-di-n-butylhydrazine, 1-i-butyl-2- n-butylhydrazine, 1-t-butyl-2-n-butylhydrazine, 1-n-pentyl-2-n-butylhydrazine, 1-n-hexyl-2-n-butylhydrazine, 1-cyclohexyl-2- n-butylhydrazine, 1-n-heptyl-2-n-butylhydrazine, 1-n-octyl-2-n-butylhydrazine, 1- (2-ethylhexyl) -2-n-butylhydrazine, 1-n- Nonyl-2-n-butylhydrazine, 1-n-decyl-2-n-butylhydrazine, 1-n-undecyl-2-n-butylhydrazine, 1-n-dodecyl-2-n-butylhydrazine, 1 -Phenyl-2-n-butylhydrazine, 1- (4-methyl) phenyl-2-n-butylhydrazine, 1-benzyl-2-n-butylhydrazine and the like are exemplified.

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is an i-butyl group include 1,2-di-i-butylhydrazine, 1-t-butyl-2- i-butylhydrazine, 1-n-pentyl-2-i-butylhydrazine, 1-n-hexyl-2-i-butylhydrazine, 1-cyclohexyl-2-i-butylhydrazine, 1-n-heptyl-2- i-butylhydrazine, 1-n-octyl-2-i-butylhydrazine, 1- (2-ethylhexyl) -2-i-butylhydrazine, 1-n-nonyl-2-i-butylhydrazine, 1-n- Decyl-2-i-butylhydrazine, 1-n-undecyl-2-i-butylhydrazine, 1-n-dodecyl-2-i-butylhydrazine, 1-phenyl-2-i-butylhydrazine, 1- (4-Methyl) phenyl-2-i-butylhydrazine, 1-benzyl-2-i-butylhydrazine and the like are exemplified.

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is a t-butyl group include 1,2-di-t-butylhydrazine, 1-n-pentyl-2- t-butylhydrazine, 1-n-hexyl-2-t-butylhydrazine, 1-cyclohexyl-2-t-butylhydrazine, 1-n-heptyl-2-t-butylhydrazine, 1-n-octyl-2- t-butylhydrazine, 1- (2-ethylhexyl) -2-t-butylhydrazine, 1-n-nonyl-2-t-butylhydrazine, 1-n-decyl-2-t-butylhydrazine, 1-n- Undecyl-2-t-butylhydrazine, 1-n-dodecyl-2-t-butylhydrazine, 1-phenyl-2-t-butylhydrazine, 1- (4-methyl) phenyl-2-t-butylhydride Examples include azine, 1-benzyl-2-t-butylhydrazine and the like.

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is an n-pentyl group include 1,2-di-n-pentylhydrazine and 1-n-hexyl-2- n-pentylhydrazine, 1-cyclohexyl-2-n-pentylhydrazine, 1-n-heptyl-2-n-pentylhydrazine, 1-n-octyl-2-n-pentylhydrazine, 1- (2-ethylhexyl)- 2-n-pentylhydrazine, 1-n-nonyl-2-n-pentylhydrazine, 1-n-decyl-2-n-pentylhydrazine, 1-n-undecyl-2-n-pentylhydrazine, 1-n- Dodecyl-2-n-pentylhydrazine, 1-phenyl-2-n-pentylhydrazine, 1- (4-methyl) phenyl-2-n-pentylhydrazine, 1-benzyl Examples include ru-2-n-pentylhydrazine.

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is an n-hexyl group include 1,2-di-n-hexylhydrazine, 1-cyclohexyl-2-n- Hexylhydrazine, 1-n-heptyl-2-n-hexylhydrazine, 1-n-octyl-2-n-hexylhydrazine, 1- (2-ethylhexyl) -2-n-hexylhydrazine, 1-n-nonyl- 2-n-hexylhydrazine, 1-n-decyl-2-n-hexylhydrazine, 1-n-undecyl-2-n-hexylhydrazine, 1-n-dodecyl-2-n-hexylhydrazine, 1-phenyl- Examples include 2-n-hexylhydrazine, 1- (4-methyl) -2-n-hexylphenylhydrazine, 1-benzyl-2-n-hexylhydrazine and the like.

In the general formula (1), the hydrazines in which the substituent R ₁ is a cyclohexyl group are specifically 1,2-dicyclohexylhydrazine, 1-n-heptyl-2-cyclohexylhydrazine, 1-n. -Octyl-2-cyclohexylhydrazine, 1- (2-ethylhexyl) -2-cyclohexylhydrazine, 1-n-nonyl-2-cyclohexylhydrazine, 1-n-decyl-2-cyclohexylhydrazine, 1-n-undecyl-2 -Cyclohexylhydrazine, 1-n-dodecyl-2-cyclohexylhydrazine, 1-phenyl-2-cyclohexylhydrazine, 1- (4-methyl) phenyl-2-cyclohexylhydrazine, 1-benzyl-2-cyclohexylhydrazine and the like are exemplified The

In the general formula (1), the hydrazines in which the substituent R ₁ is an n-heptyl group are specifically 1,2-di-n-heptylhydrazine, 1-n-octyl-2-n. -Heptylhydrazine, 1- (2-ethylhexyl) -2-n-heptylhydrazine, 1-n-nonyl-2-n-heptylhydrazine, 1-n-decyl-2-n-heptylhydrazine, 1-n-undecyl 2-n-heptylhydrazine, 1-n-dodecyl-2-n-heptylhydrazine, 1-phenyl-2-n-heptylhydrazine, 1- (4-methyl) phenyl-2-n-heptylhydrazine, 1- Examples include benzyl-2-n-heptylhydrazine.

In the general formula (1), the hydrazines in which the substituent R ₁ is an n-octyl group are specifically 1,2-di-n-octylhydrazine, 1- (2-ethylhexyl)- 2-n-octylhydrazine, 1-n-nonyl-2-n-octylhydrazine, 1-n-decyl-2-n-octylhydrazine, 1-n-undecyl-2-n-octylhydrazine, 1-n- Examples include dodecyl-2-n-octylhydrazine, 1-phenyl-2-n-octylhydrazine, 1- (4-methyl) phenyl-2-n-octylhydrazine, 1-benzyl-2-n-octylhydrazine and the like. The

In the general formula (1), the hydrazines in which the substituent R ₁ is a 2-ethylhexyl group are specifically 1,2-bis- (2-ethylhexyl) hydrazine, 1-n-nonyl- 2- (2-ethylhexyl) hydrazine, 1-n-decyl-2- (2-ethylhexyl) hydrazine, 1-n-undecyl-2- (2-ethylhexyl) hydrazine, 1-n-dodecyl-2- (2- Examples include ethylhexyl) hydrazine, 1-phenyl-2- (2-ethylhexyl) hydrazine, 1- (4-methyl) phenyl-2- (2-ethylhexyl) hydrazine, 1-benzyl-2- (2-ethylhexyl) hydrazine and the like. Is done.

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is an n-nonyl group include 1,2-di-n-nonylhydrazine and 1-n-decyl-2- n-nonylhydrazine, 1-n-undecyl-2-n-nonylhydrazine, 1-n-dodecyl-2-n-nonylhydrazine, 1-phenyl-2-n-nonylhydrazine, 1- (4-methyl) phenyl Examples include 2-n-nonyl hydrazine and 1-benzyl-2-n-nonyl hydrazine.

In the general formula (1), the hydrazines in which the substituent R ₁ is an n-decyl group are specifically 1,2-di-n-decylhydrazine, 1-n-undecyl-2-n. -Decylhydrazine, 1-n-dodecyl-2-n-decylhydrazine, 1-phenyl-2-n-decylhydrazine, 1- (4-methyl) phenyl-2-n-decylhydrazine, 1-benzyl-2- Examples include n-decylhydrazine.

In the general formula (1), the hydrazines in which the substituent R ₁ is an n-undecyl group are specifically 1,2-di-n-undecylhydrazine and 1-n-dodecyl-2. -N-undecylhydrazine, 1-phenyl-2-n-undecylhydrazine, 1- (4-methyl) phenyl-2-n-undecylhydrazine, 1-benzyl-2-n-undecylhydrazine, etc. Is done.

In the above general formula (1), specific examples of hydrazines in which the substituent R ₁ is an n-dodecyl group include 1,2-di-n-dodecylhydrazine, 1-phenyl-2-n- Examples include dodecylhydrazine, 1- (4-methyl) phenyl-2-n-dodecylhydrazine, 1-benzyl-2-n-dodecylhydrazine and the like.

In the general formula (1), the hydrazines in which the substituent R ₁ is a phenyl group are specifically 1,2-diphenylhydrazine, 1- (4-methyl) phenyl-2-phenylhydrazine, Examples include 1-benzyl-2-phenylhydrazine.

In the general formula (1), the hydrazines in which the substituent R ₁ is a (4-methyl) phenyl group are specifically 1,2-bis (4-methyl) phenylhydrazine, 1-benzyl. Examples include -2- (4-methyl) phenylhydrazine.

In the general formula (1), specific examples of hydrazines in which the substituent R ₁ is a benzyl group include 1,1-dibenzylhydrazine.

Among these hydrazines, those having 4 to 8 carbon atoms in the substituents R ₁ and R _{2 in} the general formula (1) are more preferable. If the number of carbon atoms of the substituents R ₁ and R ₂ is less than 4, the reducing power is too strong, so when mixed with a copper salt, the copper ions may be reduced before heating and metal copper may be deposited. is there. In addition, when the number of carbon atoms of the substituents R ₁ and R ₂ exceeds 8, the boiling point of hydrocarbons, which are decomposition products at the time of heating when forming the conductive film, becomes high, and can evaporate and dissipate. May remain in the copper thin film without adversely affecting the purity of the copper metal and the conductivity of the formed copper thin film. Further, in consideration of production or availability costs, among these hydrazines, in the above general formula (1), the substituents of the substituents R ₁ and R ₂ are preferably the same substituent.

  Considering the above points, in the composition for forming a conductive film of the present invention, hydrazines include 1,2-di-n-butylhydrazine, 1,2-di-t-butylhydrazine, 1,2-dihydride. -N-pentyldrazine, 1,2-di-n-hexylhydrazine, 1,2-dicyclohexylhydrazine, 1,2-di-n-heptylhydrazine, 1,2-di-n-octylhydrazine, 1,2 It is particularly preferable to use one or more selected from the group consisting of -di- (2-ethylhexyl) hydrazine, 1,2-diphenylhydrazine, and 1,2-dibenzylhydrazine.

  In the composition for forming a conductive film of the present invention, hydrazines may be commercially available or synthesized by a known method, and are not particularly limited. Moreover, what substituted the hydrogen atom of hydrazine with protecting groups, such as an acyl group, t-butoxycarbonyl group, benzyloxycarbonyl group, n-butylaminocarbonyl group, is also contained in the hydrazine in this invention.

  Known synthesis methods of hydrazines include, for example, a method of reducing an aromatic diazonium salt with a reducing agent such as sulfite or tin (II) chloride, a method of catalytic reduction of hydrazone or azine using a platinum catalyst, an acyl hydrazine Reduction, N-nitrosamine reduction, reductive coupling of highly subsequent nitro compounds, alkylation and arylation of hydrazine and azine, reaction of amine and chloramine (Reasching reaction), and the like.

  In the composition for forming a conductive film of the present invention, the purity of hydrazines 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 , Malic acid, citric acid and the like.

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

  In the composition for forming a conductive film of the present invention, the purity of the carboxylic acid having a reducing power is not particularly limited, but is preferably 95% or more, more preferably 99% or more in consideration of use in the field of electronic materials. preferable.

  In the composition for forming a conductive film of the present invention, monoamines form a complex with copper ions contained in the copper salt, stabilize the copper ions, and improve the solubility of the copper salt.

  In the composition for forming a conductive film of the present invention, examples of monoamines include aliphatic monoamines, aromatic monoamines, cyclic monoamines, and the like. Among these, aliphatic monoamines are particularly preferred. Specific examples of such aliphatic monoamines include ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, n-hexylamine, and cyclohexylamine. N-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-penta Examples include decylamine, n-hexadecylamine, benzylamine and the like.

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

  In the composition for forming a conductive film of the present invention, the purity of monoamines 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 composition ratio of the noble metal fine particles, the copper salt, the reducing agent, and the monoamines is not particularly limited depending on the amount applied to the substrate. The concentration of the noble metal fine particles is in the range of 1 ppm to 50% by weight, the concentration of the copper salt is in the range of 0.1 to 80% by weight, and the concentration of the reducing agent is 0.1 to 80% by weight with respect to the total amount of the forming composition. Preferably, the concentration of monoamines is in the range of 0.1 to 80% by weight, the concentration of noble metal fine particles is in the range of 1 to 20% by weight, and the concentration of copper salt is 1 to 60% by weight. More preferably, the range, the concentration of the reducing agent is in the range of 0.1 to 60% by weight, and the concentration of the monoamines is in the range of 0.1 to 60% by weight.

  If the concentration of the noble metal fine particles is less than 1 ppm by weight, the catalytic ability may not be exhibited, and the reduction precipitation rate from copper ions to metal copper may not occur or may be significantly reduced. In some cases, the composition for forming a conductive film is increased in viscosity or solidified and the workability is decreased.

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

  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. May be disadvantageous.

  If the concentration of monoamines is less than 0.1% by weight, although depending on the concentration of the copper salt, there is a possibility that the copper salt cannot be sufficiently dissolved. Not only can the concentration of copper in the total amount of the composition for forming a conductive film be reduced, the amount of coating of the composition for forming a conductive film for obtaining a conductive film having a desired film thickness is increased, which is industrially disadvantageous. There is a risk.

  Further, in the composition for forming a conductive film of the present invention, the composition ratio of the noble metal fine particles, the copper salt with a reducing carboxylic acid, and the monoamines is not particularly limited by the amount applied to the substrate. However, for example, the concentration of the noble metal fine particles is in the range of 1 ppm by weight to 50% by weight and the concentration of the copper salt with the carboxylic acid having a reducing power is 0.1 to 80% by weight with respect to the total amount of the conductive film forming composition. Preferably, the concentration of monoamines is in the range of 0.1 to 80% by weight, the concentration of noble metal fine particles is in the range of 1 to 20% by weight, and the copper salt with a carboxylic acid having a reducing power. More preferably, the concentration is in the range of 1 to 60% by weight, and the concentration of monoamines is in the range of 0.1 to 60% by weight.

  In addition to the said component, in the composition for electrically conductive film formation of this invention, even if it contains additives, such as an electrically conductive film smoothing agent, a concentration regulator, a surface tension regulator, a viscosity modifier, it does not interfere.

  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.

  Examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, cyclohexanol, and benzyl alcohol. , Terpineol and the like.

  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 hydrocarbons 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.

  In the composition for forming a conductive film of the present invention, the concentration of the additive is not particularly limited, but the concentration of the additive is in the range of 0 to 50% by weight with respect to the total amount of the composition for forming a conductive film. It is preferable that the range is 0 to 20% by weight. 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 includes, for example, the above-mentioned noble metal fine particles, a copper salt, a reducing agent, and a monoamine mixed, and the above-mentioned noble metal fine particles and a copper salt with a carboxylic acid having a reducing power. , And monoamines can be easily prepared.

  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 copper salt is not sufficiently dissolved in the coordinating compound, when the reducing agent is added, the coordinating compound causes the unstabilized dissolved residue to react with the reducing agent to form coarse particles, resulting in uniform dispersibility May be damaged.

  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, a conductive film forming method using the conductive film forming composition 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 fine particles and the copper salt are reduced by the reducing agent, and at the same time, the organic matter is removed by decomposition and volatilization.

  In the conductive film forming method of the present invention, a known material can be used as the substrate, and is not particularly limited, and examples thereof include metal, glass, resin, paper, and wood. Specifically, metal substrates such as copper plate, iron plate, aluminum plate, glass substrates such as soda glass, borosilicate glass, silica glass, quartz glass, alumina, sapphire, zirconia, titania, yttrium oxide, ITO (indium tin) The conductive film forming method of the present invention can form a conductive film at a relatively low temperature, and among these, non-heat resistant materials such as resin, paper, and wood are particularly preferable. It can be suitably applied to a conductive substrate.

  In the conductive film forming method of the present invention, the non-heat-resistant substrate is not particularly limited, and examples thereof include those having a heat-resistant temperature of 200 ° C. or less, specifically, 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 kraft paper for heavy bags, both kraft paper), bleached packaging Paper (bleached kraft paper, pure white roll paper), coated ball, chipboard corrugated paper, low density polyethylene resin, high density polyethylene resin, ABS resin (acrylonitrile-butadiene-styrene copolymer synthetic resin), acrylic resin, styrene Non-heat-resistant resins such as resins, vinyl chloride resins, polyester resins (polyethylene terephthalate), polyacetal resins, and cellulose derivatives are preferably used. Kill. These non-heat resistant substrates may be subjected to surface treatment as necessary, and for example, a composition-receiving layer for forming a conductive film can be formed.

  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. There is no problem even if the shape of the coating film is planar or dot-shaped, and there is no particular limitation. 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 method for forming a conductive film 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 the copper ion contained in the copper salt is reduced by the reducing agent and the components other than the metal are decomposed and volatilized. It is the range of 180 degreeC, and the range of 80-150 degreeC is further more preferable. If the heating temperature is less than 60 ° C., the reduction of the copper precursor does not proceed completely, and the remaining organic matter may become prominent. If the heating temperature exceeds 180 ° C., the substrate such as the non-heat-resistant resin described above May become unavailable.

  In the conductive film forming method of the present invention, the heating time is not particularly limited because it depends on the coating amount of the composition for forming a conductive film and the heating temperature, but when a heating temperature of about 150 ° C. is set. Is usually in the range of 1 to 60 minutes, preferably in the range of 10 to 30 minutes. If it is less than 1 minute, copper ions may not be completely reduced, or decomposition and volatilization of organic components may be insufficient, and if it exceeds 60 minutes, there is no effect corresponding to the excess, resulting in a reduction in work efficiency.

  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 examples, the average particle diameter of the noble metal 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 with a fully automatic elemental analyzer “2400II” manufactured by PerkinElmer, and ¹ H-NMR was measured with “Gemini-200” manufactured by Varian.

Preparation Example 1 Preparation of silver fine particles.
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% silver and 54 wt% organic components, and the main component of the organic substance was aniline from the analysis result by ¹ H-NMR.

Preparation Example 2 Preparation of palladium fine particles.
To 10 g of 2-ethylhexylamine was added 1.12 g of palladium acetate, and the mixture was 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 removing the colorless and transparent aqueous phase at the bottom after phase separation, washing with 10 g of ion-exchanged water and removing the lower aqueous phase after phase separation again gave a black palladium fine particle dispersion. When this silver fine particle dispersion was observed with a TEM and the average particle size was determined, it was 7.4 nm (standard deviation 2.2, variation coefficient 30%). The palladium fine particle dispersion was heated to 80 ° C. under reduced pressure (120 Pa) to remove distillate, thereby obtaining 1.19 g of palladium fine particles. As a result of elemental analysis, the obtained palladium fine particles were composed of 42 wt% palladium and 58 wt% organic component, and the main component of the organic substance was 2-ethylhexylamine from the analysis result by ¹ H-NMR.

Example 1 Preparation of a conductive film forming composition containing silver fine particles, copper acetate, n-hexylamine and 1,2-di-n-hexylhydrazine.
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 anhydride and 4.1 g of n-hexylamine were sequentially added. After heating to 40 ° C., the mixture was stirred for 10 minutes until it was completely dissolved. Next, the mixture was cooled to 0 ° C., 2.4 g of 1,2-di-n-hexylhydrazine 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”).

Example 2 Preparation of a conductive film-forming composition containing fine palladium particles, 1,1,1,5,5,5-hexafluoroacetylacetonato copper, n-butylamine, and formic acid.
0.14 g of the palladium fine particles obtained in Example 2 was added to 10 g of tetrahydrofuran, 4.8 g of 1,1,1,5,5,5-hexafluoroacetylacetonatocopper and 3.1 g of n-butylamine were sequentially added. did. After heating to 60 ° C., the mixture was stirred for 10 minutes until it was completely dissolved. Next, it cooled to 0 degreeC, 1.08g of formic acid was added, and it stirred for 30 minutes with 0 degreeC, and was set as the 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”).

Example 3 Preparation of a conductive film-forming composition containing silver fine particles, copper formate, and n-octylamine.
0.14 g of the silver fine particles obtained in Example 1 was added to 10 g of tetrahydrofuran, 1.5 g of copper formate anhydride and 5.2 g of n-octylamine 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 Solution C”).

Comparative Example 1 Preparation of a conductive film forming composition containing silver fine particles, copper acetate, and 1,2-di-n-hexylhydrazine.
0.14 g of the silver fine particles obtained in Example 1 was added to 10 g of tetrahydrofuran, and 1.8 g of copper acetate anhydride was added. After heating to 40 ° C., the mixture was stirred for 10 minutes, but was not completely dissolved. Next, the mixture was cooled to 0 ° C., 2.4 g of 1,2-di-n-hexylhydrazine was added, and the mixture was stirred at 0 ° C. for 30 minutes to obtain an ocher slurry. Tetrahydrofuran in the slurry was desolvated by vacuum concentration to prepare a composition for forming a conductive film (hereinafter, referred to as “coating solution D” for the sake of brevity).

Comparative Example 2 Preparation of a conductive film forming composition containing silver fine particles and copper formate.
0.14 g of the silver fine particles obtained in Example 1 was added to 10 g of tetrahydrofuran, and 1.5 g of copper formate anhydride was added. Although it stirred for 10 minutes at room temperature, it did not become a uniform solution. Tetrahydrofuran in the slurry was removed by vacuum concentration to prepare a composition for forming a conductive film (hereinafter referred to as “coating liquid E” for the sake of brevity).

Comparative Example 3 Preparation of a conductive film-forming composition containing copper formate and n-octylamine.
To 10 g of tetrahydrofuran, 1.5 g of copper formate anhydride and 2.7 g of n-octylamine 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”).

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, This is referred to as “coating liquid G”).

Example 4 to Example 9, Comparative Example 5 to Comparative Example 8 Formation of conductive film and evaluation of conductive film.
Paper (copy paper, thickness 0.08 mm) or PVC plate (polyvinyl chloride plate, thickness 1 mm) was cut into a size of 30 mm × 80 mm, respectively, to form a substrate. On these base materials, the conductive film forming compositions (coating liquids A to F) prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were applied to a bar coater (number of the line: No. 80). Were applied uniformly to form a uniform coating film of 5 mm × 50 mm and a film thickness of about 180 μm. Next, using a heating furnace in which nitrogen gas was circulated at a flow rate of 6 L / min, each base material coated with each of these conductive film forming compositions was subjected to heat treatment at 110 ° C. for 20 minutes.

  Subsequently, the surface resistance value of each of the formed conductive films was measured with a four-probe resistance measuring machine (trade name “Loresta GP”, manufactured by Mitsubishi Chemical Corporation).

  Moreover, 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. The film thickness of each conductive film was randomly selected from the observed field of view with a scanning electron microscope (SEM), photographed at a magnification of 5000 times, and the film thickness was measured in each photograph. These values were divided by the photographing magnification and obtained by arithmetically averaging the film thicknesses at three locations. SEM used a product name “JSM T220A” manufactured by JEOL Ltd.

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

  The composition for forming a conductive film, the combination of base materials, and the evaluation results are also shown in Table 1.

表１から明らかなとおり、実施例４〜実施例９は、本発明の導電膜形成用組成物を用いて導電膜を形成した例であるが、いずれも良好な導電性を示した。

As is apparent from Table 1, Examples 4 to 9 are examples in which a conductive film was formed using the composition for forming a conductive film of the present invention, and all exhibited 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 that does not contain monoamines, but the conductive film formed in Comparative Example 5 was significantly conductive. In Comparative Example 6, the copper reduction reaction did not proceed at all and a conductive film could not be formed. Moreover, in Comparative Example 7 and Comparative Example 8 using the composition for forming a conductive film not containing noble metal fine particles, the copper reduction reaction did not proceed completely, and a decrease in conductivity was observed.

Claims (22)

A composition for forming a conductive film, comprising noble metal fine particles, a copper salt, a reducing agent, and monoamines. The composition for forming a conductive film according to claim 1, wherein the noble metal fine particles are one or more selected from the group consisting of gold fine particles, silver fine particles, platinum fine particles, and palladium fine particles. The composition for forming a conductive film according to claim 1 or 2, wherein the noble metal fine particles have an average particle diameter in the range of 1 to 400 nm. The conductive film according to any one of claims 1 to 3, 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. 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 4 characterized by the above-mentioned. The conductive film formation according to any one of claims 1 to 5, wherein the reducing agent is one or more compounds selected from the group consisting of hydrazines and a carboxylic acid having a reducing power. Composition. Hydrazines are 1,2-di-n-butylhydrazine, 1,2-di-t-butylhydrazine, 1,2-di-n-pentyldrazine, 1,2-di-n-hexylhydrazine, 1 1,2-dicyclohexylhydrazine, 1,2-di-n-heptylhydrazine, 1,2-di-n-octylhydrazine, 1,2-di- (2-ethylhexyl) hydrazine, 1,2-diphenylhydrazine, and 1 The composition for electrically conductive film formation of Claim 6 which is 1 type, or 2 or more types chosen from the group which consists of 1,2-dibenzylhydrazine. The composition for forming a conductive film according to claim 6, wherein the carboxylic acid having a reducing power is one or more selected from the group consisting of formic acid, hydroxyacetic acid, glyoxylic acid, and oxalic acid. . Monoamines 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, and The composition for forming a conductive film according to any one of claims 1 to 8, wherein the composition is one or more selected from the group consisting of benzylamine. The concentration of the noble metal fine particles is 1 wt ppm to 50 wt%, the concentration of the copper salt is 0.1 to 80 wt%, the concentration of the reducing agent is 0.1 to 80 wt%, and the total amount of the conductive film forming composition The composition for forming a conductive film according to any one of claims 1 to 9, wherein the concentration of monoamines is in the range of 0.1 to 80% by weight. A composition for forming a conductive film, comprising noble metal fine particles, a copper salt with a reducing carboxylic acid, and monoamines. The composition for forming a conductive film according to claim 11, wherein the noble metal fine particles are one or more selected from the group consisting of gold fine particles, silver fine particles, platinum fine particles, and palladium fine particles. The composition for forming a conductive film according to claim 11 or 12, wherein an average particle diameter of the noble metal fine particles is in a range of 1 to 400 nm. The copper salt with a carboxylic acid having a reducing power is one or more selected from the group consisting of copper formate, copper hydroxyacetate, copper glyoxylate, and copper oxalate. The composition for electrically conductive film formation in any one of Claim 13. Monoamines 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, and The composition for forming a conductive film according to any one of claims 11 to 14, wherein the composition is one or more selected from the group consisting of benzylamine. The concentration of the noble metal fine particles 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 concentration of the monoamines 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 11 to 15, wherein the composition 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 10 characterized by mixing precious metal microparticles | fine-particles, copper salt, a reducing agent, and monoamines. The method for producing a composition for forming a conductive film according to any one of claims 11 to 16, wherein noble metal fine particles, a copper salt with a carboxylic acid having a reducing power, and monoamines are mixed. A conductive film is formed on a substrate by applying the conductive film-forming composition according to any one of claims 1 to 16 to a base material and heating in a non-oxidizing atmosphere. A method for producing a membrane. The method for producing a conductive film according to claim 19, wherein the substrate is a non-heat resistant substrate. 21. The method for producing a conductive film according to claim 19, 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 any one of claims 19 to 21, wherein the heating temperature is in the range of 60C to 180C.