JP2010174313A - Copper particulate dispersion and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper particulate dispersion which contains copper particulates with the average particle diameter of 10 nm or less, and a polymer that can be decomposed or can be converted to a compound with a lower molecular weight as a dispersing agent which works as an oxidation-inhibiting agent as well, in a calcination step, and to provide a method for producing the same. <P>SOLUTION: The method for producing the copper particulate dispersion includes the steps of: (a) mixing a hydrazine derivative, a polyhydrazone compound and a copper particulate precursor; and (b) reducing and depositing copper particulates. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a copper fine particle dispersion and a method for producing the same.

  The copper fine particle dispersion of the present invention can be suitably used as a conductive ink or a conductive paste which is a circuit pattern forming material for a wiring board 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 wirings 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 thin film is obtained. At present, such a composition for forming a conductive pattern is mainly one containing silver nanoparticles, but silver has a problem that electromigration occurs. 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, it is desired to use copper fine particles that can be reduced in cost and less likely to cause electromigration in an ink or paste form. However, copper is easily oxidized, and the tendency becomes more remarkable with nano-sized copper fine particles. Oxidized copper has a significant decrease in electrical conductivity. Therefore, in order to use it as an ink or paste, suppressing oxidation while maintaining dispersibility is a major issue.

  In order to solve such a problem, by utilizing adsorption of a polymer having a hetero atom such as a nitrogen atom or an oxygen atom in a molecular structure to copper metal and coexisting such a polymer with copper fine particles, Studies have been made on a method for preventing contact between oxygen and water, preventing oxidation of copper fine particles, and at the same time suppressing aggregation of copper fine particles and maintaining dispersibility.

  As such a polymer, for example, a method using polyethyleneimine (for example, see Patent Document 1), a method using a cellulose derivative (for example, see Patent Document 2), or an organic compound having a 1,4-glucoside bond is used. A method (for example, see Patent Document 3) has been proposed.

  Patent Document 1 discloses a method in which palladium ions for nucleation are added, polyethyleneimine is added as a dispersant, and copper oxides are heated and reduced in a polyol such as ethylene glycol to obtain copper fine particles. It is disclosed.

  By the way, in order to form a circuit on a base material such as a resin substrate, it is necessary to perform firing at a temperature lower than about 300 ° C. which is a heat resistant temperature of the resin substrate. In order to descend, a particle diameter of about 10 nm or less is required (see, for example, Non-Patent Document 1).

  The average particle diameter of the copper fine particles obtained by the method described in Patent Document 1 is in the range of 10 to 50 nm, and the firing at a temperature of 300 ° C. or lower does not sufficiently promote the fusion between the particles, and the formed conductive pattern. However, good conductivity may not be ensured. Moreover, addition of metals other than copper, such as palladium, is required for nucleation, and there also exists a problem that the purity as copper falls.

  In Patent Document 2, a reducing agent is added to a liquid containing copper ions and a water-soluble resin composed of a cellulose derivative (for example, hydroxypropyl cellulose) to reduce and precipitate metal fine particles, and the water-soluble resin is heated by heating. A method for obtaining copper microparticles by gelling is disclosed. However, the average particle diameter of the copper fine particles obtained by this method is in the range of 10 to 50 nm, and the above-described problems may occur.

  In Patent Document 3, a compound having a 1,4-glucoside bond such as starch, dextrin, amylose, amylopectin and derivatives thereof and a copper compound are dissolved in a solvent, and copper ions in the obtained solution are reduced. Discloses a method for obtaining copper fine particles. Although the average particle diameter of the copper fine particles obtained by this method is 10 nm or less, the copper concentration at the time of production is very low at 0.5% by weight or less, so the production amount of copper fine particles per batch is small, and the production efficiency There is a problem that it is low.

  In addition, when forming a conductive pattern using a dispersion containing such a polymer and copper fine particles, in order to ensure good conductivity, the polymer adsorbed on the copper fine particles is decomposed and the copper fine particles are mutually bonded. Must be brought into contact with each other sufficiently to promote fusion. However, in Patent Documents 1 to 3, no consideration is given to the decomposability of the polymer used, and there is a possibility that the polymer will not sufficiently decompose in the firing step, and the formed wiring has good conductivity. May not be secured.

JP 2005-330552 A JP 2001-93414 A JP 2003-213111 A

Phys. Rev. A13, (1976), 2287

  The present invention has been made in view of the above-described background art, and its object is to suppress the dispersion and oxidization of copper fine particles having an average particle diameter of 10 nm or less and decomposition and reduction in molecular weight during the firing process. It is providing the copper fine particle dispersion containing the polymer which functions as an agent, and its manufacturing method.

  As a result of intensive studies on a copper fine particle dispersion and a method for producing the same, the present inventors produce a copper fine particle dispersion containing copper fine particles having an average particle size of 10 nm or less and a specific polyhydrazone compound by a specific process. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

  That is, the present invention relates to a copper fine particle dispersion and a method for producing the same, a copper fine particle and a method for producing the same, a composition for forming a conductive pattern using the copper fine particle, and a method for forming a conductive pattern. .

  [1] The following general formula (1)

［上記一般式（１）中、Ｘ、Ｙ、Ｒ_１、Ｒ_２は各々独立して、水素原子、炭素数が１〜１８のアルキル基、炭素数５〜１０の芳香族基、炭素数が１〜４のアルキ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、又は炭素数５〜１０の芳香族基で水素原子が１〜３置換された炭素数１〜４のアルキル基を表す。］
で示される構造単位を含み、数平均分子量（Ｍｎ）がポリスチレン換算で１００〜１，０００，０００の範囲であるポリヒドラゾン化合物と、平均粒子径が１０ｎｍ以下である銅微粒子とを含有する銅微粒子分散体。

[In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a carbon number. 1 to 4 alkyl groups having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 5 to 10 carbon atoms having 1 to 3 hydrogen atoms substituted An alkyl group having 1 to 4 carbon atoms is represented. ]
A copper fine particle comprising a polyhydrazone compound having a structural unit represented by formula (I) and having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene and copper fine particles having an average particle diameter of 10 nm or less. Dispersion.

[2] In the above general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic group having 3 to 18 carbon atoms. Alkyl groups, aromatic groups having 5 to 10 carbon atoms, aromatic groups having 5 to 10 carbon atoms in which hydrogen atoms on the aromatic ring are substituted with methyl groups by 1 to 3, and hydrogen atoms having 1 to 3 substituents in phenyl groups The copper fine particle dispersion according to the above [1], wherein the copper fine particle dispersion represents an ethyl group in which a hydrogen atom is substituted by 1 to 3 with a methyl group or a phenyl group.

[3] In the general formula (1), X, Y, and R ₁ each independently represent a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, i- Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i- Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group, benzyl group, or 2 -The copper fine particle dispersion according to the above [1] or [2], which represents a phenylethyl group.

  [4] The copper fine particle dispersion according to any one of the above [1] to [3], wherein an average particle size of the copper fine particles is in a range of 0.1 to 10 nm.

  [5] The copper fine particle dispersion according to any one of [1] to [4], wherein the polyhydrazone compound is contained in an amount of 5 to 1000% by weight based on the copper fine particles.

  [6] The following general formula (1)

［上記一般式（１）中、Ｘ、Ｙ、Ｒ_１、Ｒ_２は各々独立して、水素原子、炭素数が１〜１８のアルキル基、炭素数５〜１０の芳香族基、炭素数が１〜４のアルキ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、又は炭素数５〜１０の芳香族基で水素原子が１〜３置換された炭素数１〜４のアルキル基を表す。］
で示される構造単位を含み、数平均分子量（Ｍｎ）がポリスチレン換算で１００〜１，０００，０００の範囲であるポリヒドラゾン化合物、下記一般式（２）

[In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a carbon number. 1 to 4 alkyl groups having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 5 to 10 carbon atoms having 1 to 3 hydrogen atoms substituted An alkyl group having 1 to 4 carbon atoms is represented. ]
A polyhydrazone compound having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene, the structural unit represented by the general formula (2):

［上記一般式（２）中、Ｒ_１〜Ｒ_４は各々独立して、水素原子、炭素数が１〜１８のアルキル基、炭素数５〜１０の芳香族基、炭素数が１〜４のアルキ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、又は炭素数５〜１０の芳香族基で水素原子が１〜３置換された炭素数１〜４のアルキル基を表す。ただし、Ｒ_１〜Ｒ_４が全て水素原子となることはない。］
で示されるヒドラジン誘導体、及び銅微粒子前駆体を混合し、さらに還元剤を添加して、銅微粒子を還元析出させることを特徴とする上記［１］乃至［５］のいずれかに記載の銅微粒子分散体の製造方法。

[In General Formula (2), R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted with an alkyl group, or 1 to 3 carbon atoms in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms 4 represents an alkyl group. However, R _{1 to} R ₄ are not all hydrogen atoms. ]
The copper fine particles according to any one of the above [1] to [5], wherein a hydrazine derivative represented by the formula (1) and a copper fine particle precursor are mixed and a reducing agent is further added to reduce and precipitate the copper fine particles. A method for producing a dispersion.

[7] In the general formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, An aromatic group having 5 to 10 carbon atoms, an aromatic group having 5 to 10 carbon atoms in which a hydrogen atom on the aromatic ring is substituted by 1 to 3 with a methyl group, and a methyl group in which 1 to 3 hydrogen atoms are substituted with a phenyl group Or an ethyl group in which a hydrogen atom is substituted by 1 to 3 with a phenyl group (provided that R ₁ and R ₂ do not become a hydrogen atom at the same time), and that R ₃ and R ₄ represent a hydrogen atom. The method for producing a copper fine particle dispersion as described in [6] above,

[8] In the general formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group, benzyl group, or 2-phenylethyl group (wherein R ₁ , R ₂ is not a hydrogen atom at the same time.), The method for producing a copper fine particle dispersion according to the above [6], wherein R ₃ and R ₄ represent a hydrogen atom.

  [9] The copper fine particle precursor is one or more compounds selected from the group consisting of copper oxide, copper hydroxide, copper halide, copper inorganic acid salt, copper organic acid salt and copper chelate complex. The method for producing a copper fine particle dispersion according to any one of the above [6] to [8], wherein:

  [10] The copper fine particle precursor is cuprous oxide, copper oxide, copper hydroxide, copper nitrate, basic copper carbonate, copper formate, copper acetate, copper propionate, copper butyrate, copper isobutyrate, copper valerate, The above-mentioned [6, which is one or more selected from the group consisting of copper isovalerate, copper pivalate, copper oxalate, copper malonate, copper benzoate, copper citrate and copper acetylacetonate ] The manufacturing method of the copper fine particle dispersion in any one of [8].

  [11] The reducing agent comprises hydrazine, sodium hydrophosphate, tetrabutylammonium borohydride, lithium borohydride, sodium borohydride, potassium borohydride, borane, diborane, formaldehyde, acetaldehyde, formic acid, hydroxyacetone, and hydroxylamine. The method for producing a copper fine particle dispersion according to any one of the above [6] to [10], which is one or two or more compounds selected from the group.

  [12] The following general formula (1)

［上記一般式（１）中、Ｘ、Ｙ、Ｒ_１、Ｒ_２は各々独立して、水素原子、炭素数が１〜１８のアルキル基、炭素数５〜１０の芳香族基、炭素数が１〜４のアルキ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、又は炭素数５〜１０の芳香族基で水素原子が１〜３置換された炭素数１〜４のアルキル基を表す。］
で示される構造単位を含み、数平均分子量（Ｍｎ）がポリスチレン換算で１００〜１，０００，０００の範囲であるポリヒドラゾン化合物が、平均粒子径が１０ｎｍ以下である銅微粒子の表面に吸着している銅微粒子。

[In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a carbon number. 1 to 4 alkyl groups having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 5 to 10 carbon atoms having 1 to 3 hydrogen atoms substituted An alkyl group having 1 to 4 carbon atoms is represented. ]
And a polyhydrazone compound having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene is adsorbed on the surface of copper fine particles having an average particle diameter of 10 nm or less. Copper fine particles.

  [13] The copper fine particles as described in [12] above, wherein the average particle size of the copper fine particles is in the range of 0.1 to 10 nm.

  [14] The production of copper fine particles according to [12] or [13], wherein the copper fine particles are separated from the copper fine particle dispersion according to any one of [1] to [5] by a separation operation. Method.

  [15] The method for producing copper fine particles according to the above [14], wherein the separation operation is distillation of components other than the copper fine particles, centrifugation, or filtration.

  [16] A conductive pattern forming composition comprising the copper fine particle dispersion according to any one of [1] to [5].

  [17] A composition for forming a conductive pattern comprising the copper fine particles according to [12] or [13] and a dispersant.

  [18] A method for forming a conductive pattern, comprising applying the composition for forming a conductive pattern according to [16] or [17] to a substrate and heating the substrate.

  The copper fine particle dispersion of the present invention includes copper fine particles in which oxidation is suppressed while having an extremely fine particle size of an average particle size of 10 nm or less. When the copper fine particle dispersion of the present invention is used as a composition for forming a conductive pattern, when a circuit is formed on a substrate such as a resin substrate, firing is performed at a low temperature of about 300 ° C. which is a heat resistant temperature of the resin substrate. It can be performed.

  In addition, the copper fine particle dispersion of the present invention contains a polyhydrazone compound that functions as a dispersant / oxidation inhibitor. Since this polyhydrazone compound is excellent in decomposability, when the copper fine particle dispersion of the present invention is used as a composition for forming a conductive pattern, the polymer adsorbed on the copper fine particles is decomposed and the copper fine particles are sufficiently brought into contact with each other. , Fusing can be promoted.

  Moreover, the copper fine particle dispersion of the present invention does not need to add a metal species other than copper as a nucleus during production, and contains high-purity copper fine particles.

  The method for producing a copper fine particle dispersion according to the present invention does not require installation of a special reaction apparatus such as high temperature, high pressure, and high vacuum.

  In addition, the copper fine particles separated from the copper fine particle dispersion of the present invention can be easily redispersed in an organic solvent or the like because the polyhydrazone compound that functions as a dispersant / oxidation inhibitor is adsorbed on the surface of the copper fine particles. The dispersion obtained in this way also exhibits the effects described above.

  Furthermore, since the present invention uses a polyhydrazone compound, a hydrazine derivative, a copper precursor, and a reducing agent that can be obtained and manufactured at a low price as raw materials, it is excellent in cost.

  The present invention is described in further detail below.

  First, the copper fine particle dispersion of the present invention will be described.

  The copper fine particle dispersion of the present invention comprises a polyhydrazone compound containing a structural unit represented by the general formula (1) and having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene, And copper fine particles having a particle diameter of 10 nm or less.

  In the copper fine particle dispersion of the present invention, the polyhydrazone compound contains one or more structural units selected from the group consisting of the structural unit represented by the general formula (1).

In the copper fine particle dispersion of the present invention, the polyhydrazone compound has substituents X, Y, R in the structural unit represented by the above general formula (1) in consideration of decomposability during firing for forming a conductive pattern. ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a methyl group. A hydrogen atom on the aromatic ring having 1 to 3 carbon atoms, an aromatic group having 5 to 10 carbon atoms, a methyl group having 1 to 3 hydrogen atoms substituted with a phenyl group, or 1 to 3 hydrogen atoms substituted with a phenyl group It preferably represents an ethyl group. Furthermore, in the structural unit represented by the general formula (1), the substituents X, Y, and R ₁ represent a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group, benzyl group, or More preferably it represents a 2-phenylethyl group.

For example, in the structural unit represented by the general formula (1), examples of the polyhydrazone compound in which the substituents X, Y, and R ₁ are all hydrogen atoms include poly (propenaldehyde hydrazone) and poly (propene). Aldehyde methylhydrazone), poly (propenaldehyde ethylhydrazone), poly (propenaldehyde n-propylhydrazone), poly (propenaldehyde i-propylhydrazone), poly (propenaldehyde n-butylhydrazone), poly (propenaldehyde i-butyl) Hydrazone), poly (propenaldehyde sec-butylhydrazone), poly (propenaldehyde t-butylhydrazone), poly (propenaldehyde n-pentylhydrazone), poly (propenaldehyde i-pentylhydrazone), poly (propene Aldehyde neo-pentylhydrazone), poly (propenaldehyde t-pentylhydrazone), poly (propenaldehyde n-hexylhydrazone), poly (propenaldehyde i-hexylhydrazone), poly (propenaldehyde n-heptylhydrazone), poly ( Propenealdehyde n-octylhydrazone), poly (propenaldehyde n-nonylhydrazone), poly (propenaldehyde n-decylhydrazone), poly (propenaldehyde n-undecylhydrazone), poly (propenaldehyde n-dodecylhydrazone), poly (Propenaldehyde cyclohexylhydrazone), poly (propenaldehyde phenylhydrazone), poly [propenaldehyde (4-methyl) phenylhydrazone], poly (propenal Hydrate benzylhydrazone), poly [propene aldehyde (2-phenyl) ethyl hydrazone] and the like.

In the structural unit represented by the general formula (1), as the polyhydrazone compound in which the substituent X is a hydrogen atom, Y is a methyl group, and R ₁ is a hydrogen atom, specifically, poly (2-methyl- 2-propenaldehyde hydrazone), poly (2-methyl-2-propenaldehyde methylhydrazone), poly (2-methyl-2-propenaldehyde ethylhydrazone), poly (2-methyl-2-propenaldehyde n-propylhydrazone) Poly (2-methyl-2-propenaldehyde i-propylhydrazone), poly (2-methyl-2-propenaldehyde n-butylhydrazone), poly (2-methyl-2-propenaldehyde i-butylhydrazone), poly (2-methyl-2-propenaldehyde sec-butylhydrazone), poly (2-methyl-2 -Propenaldehyde t-butylhydrazone), poly (2-methyl-2-propenaldehyde n-pentylhydrazone), poly (2-methyl-2-propenaldehyde i-pentylhydrazone), poly (2-methyl-2-propene) Aldehyde neo-pentylhydrazone), poly (2-methyl-2-propenaldehyde t-pentylhydrazone), poly (2-methyl-2-propenaldehyde n-hexylhydrazone), poly (2-methyl-2-propenaldehyde i) -Hexylhydrazone), poly (2-methyl-2-propenaldehyde n-heptylhydrazone), poly (2-methyl-2-propenaldehyde n-octylhydrazone), poly (2-methyl-2-propenaldehyde n-nonyl) Hydrazone), poly (2-methyl-2-pro Aldehyde n-decylhydrazone), poly (2-methyl-2-propenaldehyde n-undecylhydrazone), poly (2-methyl-2-propenaldehyde n-dodecylhydrazone), poly (2-methyl-2-propene) Aldehyde cyclohexyl hydrazone), poly (2-methyl-2-propenaldehyde phenylhydrazone), poly [2-methyl-2-propenaldehyde (4-methyl) phenylhydrazone], poly (2-methyl-2-propenaldehyde benzylhydrazone) ), Poly [2-methyl-2-propenaldehyde (2-phenyl) ethylhydrazone] and the like.

Moreover, in the structural unit represented by the general formula (1), for example, as a polyhydrazone compound in which the substituents X and Y are hydrogen atoms and R ₁ is a methyl group, specifically, poly (propenaldehyde-2, 2-dimethylhydrazone), poly (propenaldehyde-2-methyl-2-ethylhydrazone), poly (propenaldehyde-2-methyl-2-n-propylhydrazone), poly (propenaldehyde-2-methyl-2-i) -Propylhydrazone), poly (propenaldehyde-2-methyl-2-n-butylhydrazone), poly (propenaldehyde-2-methyl-2-i-butylhydrazone), poly (propenaldehyde-2-methyl-2-) sec-butylhydrazone), poly (propenaldehyde-2-methyl-2-t-butylhydrazone), poly Li (propenaldehyde-2-methyl-2-n-pentylhydrazone), poly (propenaldehyde-2-methyl-2-i-pentylhydrazone), poly (propenaldehyde-2-methyl-2-neo-pentylhydrazone) , Poly (propenaldehyde-2-methyl-2-t-pentylhydrazone), poly (propenaldehyde-2-methyl-2-n-hexylhydrazone), poly (propenaldehyde-2-methyl-2-i-hexylhydrazone) ), Poly (propenaldehyde-2-methyl-2-n-heptylhydrazone), poly (propenaldehyde-2-methyl-2-n-octylhydrazone), poly (propenaldehyde-2-methyl-2-n-nonyl) Hydrazone), poly (propenaldehyde-2-methyl-2-n-decylhi) Razone), poly (propenaldehyde-2-methyl-2-n-undecylhydrazone), poly (propenaldehyde-2-methyl-2-n-dodecylhydrazone), poly (propenaldehyde-2-methyl-2-cyclohexyl) Hydrazone), poly (propenaldehyde-2-methyl-2-phenylhydrazone), poly [propenaldehyde-2-methyl-2- (4-methyl) phenylhydrazone], poly (propenaldehyde-2-methyl-2-benzyl) Hydrazone), poly [propenaldehyde-2-methyl-2- (2-phenyl) ethylhydrazone] and the like.

In the structural unit represented by the general formula (1), the polyhydrazone compound in which the substituent X is a methyl group, Y, and R ₁ is a hydrogen atom, specifically, poly (methyl vinyl ketone hydrazone), poly (Methyl vinyl ketone methyl hydrazone), poly (methyl vinyl ketone ethyl hydrazone), poly (methyl vinyl ketone n-propyl hydrazone), poly (methyl vinyl ketone i-propyl hydrazone), poly (methyl vinyl ketone n-butyl hydrazone), Poly (methyl vinyl ketone i-butyl hydrazone), poly (methyl vinyl ketone sec-butyl hydrazone), poly (methyl vinyl ketone t-butyl hydrazone), poly (methyl vinyl ketone n-pentyl hydrazone), poly (methyl vinyl ketone i -Pentylhydrazone), poly (meth) Ruvinyl ketone neo-pentyl hydrazone), poly (methyl vinyl ketone t-pentyl hydrazone), poly (methyl vinyl ketone n-hexyl hydrazone), poly (methyl vinyl ketone i-hexyl hydrazone), poly (methyl vinyl ketone n-heptyl hydrazone) , Poly (methyl vinyl ketone n-octyl hydrazone), poly (methyl vinyl ketone n-nonyl hydrazone), poly (methyl vinyl ketone n-decyl hydrazone), poly (methyl vinyl ketone n-undecyl hydrazone), poly (methyl vinyl) Ketone n-dodecylhydrazone), poly (methyl vinyl ketone cyclohexyl hydrazone), poly (methyl vinyl ketone phenylhydrazone), poly [methyl vinyl ketone (4-methyl) phenyl hydrazone], poly (methyl vinyl Ketone benzylhydrazone), poly [methylvinyl ketone (2-phenyl) ethyl hydrazone] and the like.

In the structural unit represented by the general formula (1), the polyhydrazone compound in which the substituents X and Y are methyl groups and R ₁ is a hydrogen atom, specifically, poly (methyl isopropenyl ketone hydrazone), Poly (methyl isopropenyl ketone methyl hydrazone), poly (methyl isopropenyl ketone ethyl hydrazone), poly (methyl isopropenyl ketone n-propyl hydrazone), poly (methyl isopropenyl ketone i-propyl hydrazone), poly (methyl isopropenyl ketone) n-butylhydrazone), poly (methyl isopropenyl ketone i-butyl hydrazone), poly (methyl isopropenyl ketone sec-butyl hydrazone), poly (methyl isopropenyl ketone t-butyl hydrazone), poly (methyl isopropenyl ketone n- Bae Nylhydrazone), poly (methyl isopropenyl ketone i-pentyl hydrazone), poly (methyl isopropenyl ketone neo-pentyl hydrazone), poly (methyl isopropenyl ketone t-pentyl hydrazone), poly (methyl isopropenyl ketone n-hexyl) Hydrazone), poly (methyl isopropenyl ketone i-hexyl hydrazone), poly (methyl isopropenyl ketone n-heptyl hydrazone), poly (methyl isopropenyl ketone n-octyl hydrazone), poly (methyl isopropenyl ketone n-nonyl hydrazone) , Poly (methyl isopropenyl ketone n-decyl hydrazone), poly (methyl isopropenyl ketone n-undecyl hydrazone), poly (methyl isopropenyl ketone n-dodecyl hydrazone), poly ( Til isopropenyl ketone cyclohexyl hydrazone), poly (methyl isopropenyl ketone phenyl hydrazone), poly [methyl isopropenyl ketone (4-methyl) phenyl hydrazone], poly (methyl isopropenyl ketone benzyl hydrazone), poly [methyl isopropenyl ketone ( 2-phenyl) ethylhydrazone] and the like.

Further, in the structural unit represented by the general formula (1), the polyhydrazone compound in which the substituents X, Y, and R ₁ are all methyl groups is specifically exemplified by poly (methyl isopropenyl ketone-2,2- Dimethyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-ethyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n-propyl hydrazone), poly (methyl isopropenyl ketone-2-methyl) -2-i-propyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n-butyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-i-butyl hydrazone), poly (methyl Isopropenyl ketone-2-methyl-2-sec-butylhydrazone), poly (methylisopropenyl) Ketone-2-methyl-2-t-butylhydrazone), poly (methylisopropenylketone-2-methyl-2-n-pentylhydrazone), poly (methylisopropenylketone-2-methyl-2-i-pentylhydrazone) ), Poly (methyl isopropenyl ketone-2-methyl-2-neo-pentylhydrazone), poly (methyl isopropenyl ketone-2-methyl-2-t-pentylhydrazone), poly (methyl isopropenyl ketone-2-methyl) -2-n-hexylhydrazone), poly (methyl isopropenyl ketone-2-methyl-2-i-hexyl hydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n-heptyl hydrazone), poly (methyl Isopropenyl ketone-2-methyl-2-n-octylhydrazone), poly ( Til isopropenyl ketone-2-methyl-2-n-nonylhydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n-decylhydrazone), poly (methyl isopropenyl ketone-2-methyl-2-n) -Undecylhydrazone), poly (methylisopropenylketone-2-methyl-2-n-dodecylhydrazone), poly (methylisopropenylketone-2-methyl-2-cyclohexylhydrazone), poly (methylisopropenylketone-2) -Methyl-2-phenylhydrazone), poly [methylisopropenylketone-2-methyl-2- (4-methyl) phenylhydrazone], poly (methylisopropenylketone-2-methyl-2-benzylhydrazone), poly [ Methyl isopropenyl ketone-2-methyl-2- (2-phenyl ) Ethyl hydrazone] and the like.

  Of these, taking into account the effect of inhibiting oxidation, degradability and cost, poly (propenaldehyde hydrazone), poly (propenaldehyde phenylhydrazone), poly (2-methyl-2-propenaldehyde hydrazone), poly (2-methyl) -2-propenaldehyde phenylhydrazone), poly (propenaldehyde-2,2-dimethylhydrazone), poly (methyl vinyl ketone hydrazone), poly (methyl vinyl ketone phenyl hydrazone), poly (methyl isopropenyl ketone hydrazone), poly ( More preferably, one kind selected from the group consisting of methyl isopropenyl ketone phenylhydrazone) and poly (methyl isopropenyl ketone-2,2-dimethylhydrazone), or a combination of two or more kinds.

  In the copper fine particle dispersion of the present invention, the polyhydrazone compound described above has a number average molecular weight in the range of 100 to 1,000,000 in terms of polystyrene, preferably a number average molecular weight of 1000 to 50,000. Is in range. When the number average molecular weight is less than 100, the adsorptive power to the copper fine particles may be reduced, and the effect as a dispersant or an oxidation inhibitor may not be exhibited. When the number average molecular weight exceeds 1,000,000, firing is performed. During the treatment, the polymer may not be decomposed smoothly, and the time required for the decomposition may be too long to be industrial, or the polymer may be carbonized and remain in the copper thin film.

  In the copper fine particle dispersion of the present invention, the polyhydrazone compound described above may have only one type as a repeating unit having the structure represented by the general formula (1), or may have two or more types, In addition to the structure represented by the general formula (1) as a repeating unit, another structure may be included as a repeating unit. Other structural units are not particularly limited. For example, ethylene, propylene, isobutylene, styrene, α-methylstyrene, acrylic esters, methacrylic esters, maleimides, acrylonitrile, vinyl ethers, vinyl alcohol And structural units derived from monomers such as vinyl acetate.

  In the copper fine particle dispersion of the present invention, the polyhydrazone compound described above may be commercially available or may be synthesized by a known method. As a known synthesis method of a polyhydrazone compound, for example, a polycarbonyl compound can be synthesized by dehydration condensation with hydrazines.

  In the copper fine particle dispersion of the present invention, the purity of the polyhydrazone compound described above is not particularly limited, but is preferably 95% or more, and more preferably 99% or more because it is premised on use in the field of electronic materials. .

  When synthesizing the above polyhydrazone compound, dehydration condensation can be performed by a conventionally known method, and is not particularly limited. For example, the following general formula (3), which is a raw material, is used.

［上記一般式（３）中、Ｘ、Ｙは各々独立して、水素原子、炭素数が１〜１８のアルキル基、炭素数５〜１０の芳香族基、炭素数が１〜４のアルキ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、又は炭素数５〜１０の芳香族基で水素原子が１〜３置換された炭素数１〜４のアルキル基を表す。］
で示される構造単位を一種又は二種以上含有するポリカルボニル化合物からなる群より選ばれる一種又は二種以上と、下記一般式（４）

[In the general formula (3), X and Y are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. In which the hydrogen atom on the aromatic ring is substituted with 1 to 3 carbon atoms, or the aromatic group having 5 to 10 carbon atoms with 1 to 3 hydrogen atoms substituted with 1 to 3 carbon atoms. Represents an alkyl group. ]
And one or more selected from the group consisting of polycarbonyl compounds containing one or more structural units represented by the following general formula (4):

［上記一般式（４）中、Ｒ_１、Ｒ_２は各々独立して、水素原子、炭素数が１〜１８のアルキル基、炭素数５〜１０の芳香族基、炭素数が１〜４のアルキ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、又は炭素数５〜１０の芳香族基で水素原子が１〜３置換された炭素数１〜４のアルキル基を表す。］
で示される構造単位を一種又は二種以上含有するヒドラジン類からなる群より選ばれる一種又は二種以上とを同時に溶剤に溶解させた後、加熱する方法により行うことができる。この際、反応を短時間で完結させるために、副生物として生成する水を留去しながら行うことが好ましい。

[In General Formula (4), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted with an alkyl group, or 1 to 3 carbon atoms in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms 4 represents an alkyl group. ]
It can carry out by the method of heating, after simultaneously dissolving 1 type or 2 types or more selected from the group which consists of 1 type or 2 types or more which contain the structural unit shown by a solvent in a solvent. At this time, in order to complete the reaction in a short time, it is preferable to carry out while distilling off the water produced as a by-product.

  In addition, a catalyst for promoting dehydration condensation may be added during the above synthesis. The catalyst may be appropriately selected according to various conditions such as the type and amount of the polycarbonyl compound and hydrazine used, and is not particularly limited. For example, hydrochloric acid, hydrogen chloride gas, hydrobromic acid , Sulfuric acid, phosphoric acid, phosphorus oxychloride, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, chlorosulfonic acid, formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, benzoic acid, etc. Can be mentioned.

  In the synthesis described above, the polycarbonyl compound containing one or more of the structural units represented by the general formula (3) as a raw material may be a commercially available product or a compound synthesized by a known method. As a known synthesis method, for example, any method such as radical polymerization, anionic polymerization, and cationic polymerization may be used, and it is not particularly limited, but radical polymerization and anionic polymerization are preferably used (for example, AR Lyons, J. Polym. Sci. Part D, 6, 251 (1972), Yoshio Okamoto, “Polymer Experimental Studies 4 Addition Polymerization / Ring-Opening Polymerization”, Kyoritsu Shuppan (1983), p. (See Kaihei 10-45837).

  Moreover, the hydrazines containing one or more of the structural units represented by the above general formula (4) as a raw material may be commercially available or may be synthesized by a known method. As a known synthesis method, 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, reduction of acylhydrazine, Examples thereof include reduction of N-nitrosamine, reductive coupling of aromatic nitro compounds, alkylation and arylation of hydrazine and azine, reaction of amine and chloramine (Reaching reaction), and the like.

  The above-described polyhydrazone compound contained in the copper fine particle dispersion of the present invention is decomposed by the baking treatment to lower the molecular weight. The temperature at which the decomposition of the polyhydrazone compound occurs is usually in the range of 100 to 400 ° C., and can be sufficiently decomposed and reduced in molecular weight even at a relatively low temperature such as 300 ° C. or less which is the heat resistant temperature of the resin substrate. .

  The copper fine particles contained in the copper fine particle dispersion of the present invention have an average particle size of 10 nm or less, but those having an average particle size in the range of 0.1 to 10 nm are preferred. When the average particle diameter of the copper fine particles is less than 0.1 nm, the activity on the copper surface becomes very high, and the oxidation may not be suppressed. Further, when the average particle diameter of the copper fine particles exceeds 10 nm, as described above, the degree of melting point decrease may be reduced, and the fusion between the particles may hardly occur.

  In the present invention, a general particle measuring method can be used as a method for measuring the particle diameter of the copper fine particles. 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 photograph, select 100 particles that are most likely to be present, measure the diameter with a ruler, and calculate the particle size by dividing the measurement magnification. These values can be obtained by arithmetic averaging. The standard deviation can be obtained from the particle size and number of individual copper fine particles during the observation. The coefficient of variation can be calculated by the following equation based on the above average particle diameter and its standard deviation.

      Coefficient of variation = standard deviation / volume average particle diameter × 100 (%).

  In the copper fine particle dispersion of the present invention, the composition ratio of the polyhydrazone compound and the copper fine particles is not particularly limited, but the polyhydrazone compound is preferably 5 to 1000% by weight, and 10 to 200% by weight with respect to the amount of metallic copper. % Is more preferable. If the amount of the polyhydrazone compound is less than 5% by weight with respect to the amount of copper metal, the oxidation may not be suppressed. This is not preferable because the content of metallic copper per unit weight in the fine particle dispersion is lowered.

  The copper fine particle dispersion of the present invention contains the above-mentioned copper fine particles and a polyhydrazone compound, but in addition to them, the polyhydrazone compound may be dissolved and may contain an organic solvent that does not react with the polyhydrazone compound. There is no problem in one direction. Examples of such an organic solvent include one selected from the group consisting of alcohols, glycols, ethers, esters, hydrocarbons, and aromatic hydrocarbons, or a mixture of two or more compatible types. Can be mentioned.

  Specifically, as alcohols, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, cyclohexanol , Benzyl alcohol, terpineol, etc., and glycols include ethylene glycol, propylene glycol, butylene glycol, pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc., and ethers include Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol Examples thereof include diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and the esters include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, propion Examples of hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, and cyclohexane. Decalin and the like, and examples of the aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, dichlorobenzene and the like.

  Among these, from the aspect of cost, safety and water solubility, one selected from the group consisting of ethanol, i-propyl alcohol, terpineol, ethylene glycol, propylene glycol, diethylene glycol dimethyl ether, and γ-butyrolactone, or compatible It is more preferable to use a combination of two or more.

  In the copper fine particle dispersion of the present invention, when the composition contains an organic solvent, the total weight of the polyhydrazone compound and the copper fine particles is in the range of 0.1 to 100% by weight based on the total weight of the copper fine particle dispersion ( The balance is preferably an organic solvent), and more preferably in the range of 10 to 80% by weight (the balance is an organic solvent). When the total weight of the polyhydrazone compound and the copper fine particles is less than 10% by weight with respect to the total weight of the copper fine particle dispersion, an operation such as concentration is required when using as a conductive pattern forming composition, resulting in an increase in work man-hours. If the amount exceeds 80% by weight, the fluidity is almost lost and the workability may be significantly reduced.

  The form of the copper fine particle dispersion of the present invention can be freely selected as necessary. For example, it can be used as a concentrated liquid having a desired concentration by removing a part of the polyhydrazone compound and / or organic solvent in the copper fine particle dispersion, or can be processed into a paste. Furthermore, since the concentrate or paste-like processed product can be redispersed in the presence of a desired organic solvent, the organic solvent can be freely replaced.

  Next, the manufacturing method of the copper fine particle dispersion of this invention is demonstrated.

  The copper fine particle dispersion of the present invention can be produced by bringing a polyhydrazone compound and copper fine particles into contact with each other. For example, a method of adding and mixing a polyhydrazone compound to copper fine particles dispersed in a liquid phase can be mentioned. However, since the copper fine particles are immediately oxidized under the condition where oxygen and water are present, the above method requires a complicated and expensive production apparatus, which is very expensive and is not industrially advantageous. Therefore, a method of contacting the polyhydrazone compound at the same time when the copper fine particles are synthesized is preferable.

  In the method for producing a copper fine particle dispersion of the present invention, the synthesis of copper fine particles is not particularly limited, and any known method can be used, but after mixing the polyhydrazone compound and the copper fine particle precursor, the copper fine particles are mixed. A method of reducing precipitation is preferred. According to this method, the production of copper fine particles and the contact between the copper fine particles and the polyhydrazone compound can be carried out simultaneously and in the same reaction vessel, which is industrially advantageous.

  In the method for producing a copper fine particle dispersion of the present invention, the synthesis of copper fine particles is not particularly limited, but is preferably performed in the presence of a hydrazine derivative. In the presence of a hydrazine derivative, the polyhydrazone compound and the copper fine particle precursor can be dissolved in a uniform and high concentration.

  The method for producing a copper fine particle dispersion of the present invention includes the following two steps.

  a) A step of mixing the polyhydrazone compound represented by the above general formula (1), a hydrazine derivative, and a copper fine particle precursor (hereinafter referred to as a step).

  b) A step of adding a reducing agent to the mixture obtained in step a to reduce and precipitate copper fine particles (hereinafter referred to as step b).

  In the method for producing a copper fine particle dispersion of the present invention, it is only necessary to carry out the step a and the step b, and there may be no problem even if other steps are added. For example, a step of diluting a polyhydrazone compound and / or a copper fine particle precursor, a step of diluting or concentrating a mixture of the polyhydrazone compound and the copper fine particle precursor, and a step of cooling or heating the mixture of the polyhydrazone compound and the copper fine particle precursor. The step of washing the copper fine particle dispersion, the step of diluting or concentrating the copper fine particle dispersion, the step of aggregating and / or precipitating the copper fine particles in the copper fine particle dispersion, and the like can be appropriately performed.

  In the method for producing a copper fine particle dispersion of the present invention, the hydrazine derivative used in step a is the following general formula (2).

［上記一般式（２）中、Ｒ_１〜Ｒ_４は各々独立して、水素原子、炭素数が１〜１８のアルキル基、炭素数５〜１０の芳香族基、炭素数が１〜４のアルキ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、又は炭素数５〜１０の芳香族基で水素原子が１〜３置換された炭素数１〜４のアルキル基を表す。ただし、Ｒ_１〜Ｒ_４が全て水素原子となることはない。］
で示される化合物である。

[In General Formula (2), R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted with an alkyl group, or 1 to 3 carbon atoms in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms 4 represents an alkyl group. However, R _{1 to} R ₄ are not all hydrogen atoms. ]
It is a compound shown by these.

In the method for producing a copper fine particle dispersion of the present invention, the hydrazine derivative used in step a is not particularly limited, but the solubility of the polyhydrazone compound and the copper fine particle precursor and the removability of decomposition products are considered. Then, in the general formula (2), the substituents R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, An aromatic group having 5 to 10 carbon atoms, an aromatic group having 5 to 10 carbon atoms in which hydrogen on the aromatic ring is substituted by 1 to 3 by a methyl group, a methyl group in which hydrogen is substituted by 1 to 3 by a phenyl group, or It represents an ethyl group having 1 to 3 hydrogen atoms substituted with a phenyl group (however, R ₁ and R ₂ do not simultaneously become hydrogen atoms), and consists of a compound in which the substituents R ₃ and R ₄ are hydrogen atoms. One or more selected from the group It is preferably a compound. Further, in the general formula (2), each of the substituents R1 and R2 is independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, n -Represents a nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a cyclohexyl group, a phenyl group, a 4-methylphenyl group, a benzyl group, or a 2-phenylethyl group (provided that R ₁ , R ₂ Are not a hydrogen atom at the same time.), More preferably one or two or more compounds selected from the group consisting of compounds in which the substituents R ₃ and R ₄ are hydrogen atoms.

Specific examples of the hydrazine derivative in which the substituents R ₁ , R ₃ and R ₄ in the general formula (2) are hydrogen atoms include methyl hydrazine, ethyl hydrazine, n-propyl hydrazine, i-propyl hydrazine, n -Butyl hydrazine, i-butyl hydrazine, sec-butyl hydrazine, t-butyl hydrazine, n-pentyl hydrazine, i-pentyl hydrazine, neo-pentyl hydrazine, t-pentyl hydrazine, n-hexyl hydrazine, i-hexyl hydrazine, n -Heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n-undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine, phenylhydrazine, 4-methylphenylhydrazine, benzylhydrazine 2-phenylethyl hydrazine, and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is a methyl group and R ₃ and R ₄ are hydrogen atoms specifically includes 1,1-dimethylhydrazine, 1-methyl-1- Ethyl hydrazine, 1-methyl-1-n-propyl hydrazine, 1-methyl-1-i-propyl hydrazine, 1-methyl-1-n-butyl hydrazine, 1-methyl-1-i-butyl hydrazine, 1-methyl -1-sec-butylhydrazine, 1-methyl-1-t-butylhydrazine, 1-methyl-1-n-pentylhydrazine, 1-methyl-1-i-pentylhydrazine, 1-methyl-1-neo-pentyl Hydrazine, 1-methyl-1-t-pentylhydrazine, 1-methyl-1-n-hexylhydrazine, 1-methyl-1-i-hexylhydrazine, 1-methyl Tyl-1-n-heptylhydrazine, 1-methyl-1-n-octylhydrazine, 1-methyl-1-n-nonylhydrazine, 1-methyl-1-n-decylhydrazine, 1-methyl-1-n- Undecylhydrazine, 1-methyl-1-n-dodecylhydrazine, 1-methyl-1-cyclohexylhydrazine, 1-methyl-1-phenylhydrazine, 1-methyl-1- (4-methyl) phenylhydrazine, 1-methyl Examples include -1-benzylhydrazine, 1-methyl-1- (2-phenyl) ethylhydrazine, and the like.

In the above general formula (2), specific examples of the hydrazine derivative in which the substituent R ₁ is an ethyl group and R ₃ and R ₄ are hydrogen atoms include 1,1-diethylhydrazine, 1-ethyl-1- n-propylhydrazine, 1-ethyl-1-i-propylhydrazine, 1-ethyl-1-n-butylhydrazine, 1-ethyl-1-i-butylhydrazine, 1-ethyl-1-sec-butylhydrazine, 1 -Ethyl-1-t-butylhydrazine, 1-ethyl-1-n-pentylhydrazine, 1-ethyl-1-i-pentylhydrazine, 1-ethyl-1-neo-pentylhydrazine, 1-ethyl-1-t -Pentylhydrazine, 1-ethyl-1-n-hexylhydrazine, 1-ethyl-1-i-hexylhydrazine, 1-ethyl-1-n-heptylhydrazine, 1-ethyl-1-n-octylhydrazine, 1-ethyl-1-n-nonylhydrazine, 1-ethyl-1-n-decylhydrazine, 1-ethyl-1-n-undecylhydrazine, 1-ethyl-1 -N-dodecylhydrazine, 1-ethyl-1-cyclohexylhydrazine, 1-ethyl-1-phenylhydrazine, 1-ethyl-1- (4-methyl) phenylhydrazine, 1-ethyl-1-benzylhydrazine, 1-ethyl Examples include -1- (2-phenyl) ethylhydrazine.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-propyl group, and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-propyl hydrazine, 1-n-propyl-1-i-propylhydrazine, 1-n-propyl-1-n-butylhydrazine, 1-n-propyl-1-i-butylhydrazine, 1-n-propyl-1-sec-butyl Hydrazine, 1-n-propyl-1-t-butylhydrazine, 1-n-propyl-1-n-pentylhydrazine, 1-n-propyl-1-i-pentylhydrazine, 1-n-propyl-1-neo -Pentylhydrazine, 1-n-propyl-1-t-pentylhydrazine, 1-n-propyl-1-n-hexylhydrazine, 1-n-propyl-1-i-hexylhydrazine, 1-n-propyl-1-n-heptylhydrazine, 1-n-propyl-1-n-octylhydrazine, 1-n-propyl-1-n-nonylhydrazine, 1-n-propyl-1-n-decyl Hydrazine, 1-n-propyl-1-n-undecylhydrazine, 1-n-propyl-1-n-dodecylhydrazine, 1-n-propyl-1-cyclohexylhydrazine, 1-n-propyl-1-phenylhydrazine 1-n-propyl-1- (4-methyl) phenylhydrazine, 1-n-propyl-1-benzylhydrazine, 1-n-propyl-1- (2-phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an i-propyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-i-propyl hydrazine, 1-i-propyl-1-n-butylhydrazine, 1-i-propyl-1-i-butylhydrazine, 1-i-propyl-1-sec-butylhydrazine, 1-i-propyl-1-t-butyl Hydrazine, 1-i-propyl-1-n-pentylhydrazine, 1-i-propyl-1-i-pentylhydrazine, 1-i-propyl-1-neo-pentylhydrazine, 1-i-propyl-1-t -Pentylhydrazine, 1-i-propyl-1-n-hexylhydrazine, 1-i-propyl-1-i-hexylhydrazine, 1-i-propyl-1-n-heptylhydrazine, 1-i-propyl-1-n-octylhydrazine, 1-i-propyl-1-n-nonylhydrazine, 1-i-propyl-1-n-decylhydrazine, 1-i-propyl-1-n-un Decylhydrazine, 1-i-propyl-1-n-dodecylhydrazine, 1-i-propyl-1-cyclohexylhydrazine, 1-i-propyl-1-phenylhydrazine, 1-i-propyl-1- (4-methyl ) Phenylhydrazine, 1-i-propyl-1-benzylhydrazine, 1-i-propyl-1- (2-phenyl) ethylhydrazine and the like are exemplified.

Further, in the above general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-butyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-butylhydrazine, 1-n-butyl-1-i-butylhydrazine, 1-n-butyl-1-sec-butylhydrazine, 1-n-butyl-1-t-butylhydrazine, 1-n-butyl-1-n-pentyl Hydrazine, 1-n-butyl-1-i-pentylhydrazine, 1-n-butyl-1-neo-pentylhydrazine, 1-n-butyl-1-t-pentylhydrazine, 1-n-butyl-1-n -Hexylhydrazine, 1-n-butyl-1-i-hexylhydrazine, 1-n-butyl-1-n-heptylhydrazine, 1-n-butyl-1-n-octylhydrazine, 1-n-butyl-1 -N- Nonyl hydrazine, 1-n-butyl-1-n-decylhydrazine, 1-n-butyl-1-n-undecylhydrazine, 1-n-butyl-1-n-dodecylhydrazine, 1-n-butyl-1 -Cyclohexylhydrazine, 1-n-butyl-1-phenylhydrazine, 1-n-butyl-1- (4-methyl) phenylhydrazine, 1-n-butyl-1-benzylhydrazine, 1-n-butyl-1- (2-phenyl) ethylhydrazine and the like are exemplified.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an i-butyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-i-butylhydrazine, 1-i-butyl-1-sec-butylhydrazine, 1-i-butyl-1-t-butylhydrazine, 1-i-butyl-1-n-pentylhydrazine, 1-i-butyl-1-i-pentyl Hydrazine, 1-i-butyl-1-neo-pentylhydrazine, 1-i-butyl-1-t-pentylhydrazine, 1-i-butyl-1-n-hexylhydrazine, 1-i-butyl-1-i -Hexylhydrazine, 1-i-butyl-1-n-heptylhydrazine, 1-i-butyl-1-n-octylhydrazine, 1-i-butyl-1-n-nonylhydrazine, 1-i-butyl-1 -N- Decylhydrazine, 1-i-butyl-1-n-undecylhydrazine, 1-i-butyl-1-n-dodecylhydrazine, 1-i-butyl-1-cyclohexylhydrazine, 1-i-butyl-1-phenyl Examples include hydrazine, 1-i-butyl-1- (4-methyl) phenylhydrazine, 1-i-butyl-1-benzylhydrazine, 1-i-butyl-1- (2-phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is a sec-butyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-sec-butylhydrazine, 1-sec-butyl-1-t-butylhydrazine, 1-sec-butyl-1-n-pentylhydrazine, 1-sec-butyl-1-i-pentylhydrazine, 1-sec-butyl-1-neo-pentyl Hydrazine, 1-sec-butyl-1-t-pentylhydrazine, 1-sec-butyl-1-n-hexylhydrazine, 1-sec-butyl-1-i-hexylhydrazine, 1-sec-butyl-1-n -Heptylhydrazine, 1-sec-butyl-1-n-octylhydrazine, 1-sec-butyl-1-n-nonylhydrazine, 1-sec-butyl-1 -N-decylhydrazine, 1-sec-butyl-1-n-undecylhydrazine, 1-sec-butyl-1-n-dodecylhydrazine, 1-sec-butyl-1-cyclohexylhydrazine, 1-sec-butyl- Examples include 1-phenylhydrazine, 1-sec-butyl-1- (4-methyl) phenylhydrazine, 1-sec-butyl-1-benzylhydrazine, 1-sec-butyl-1- (2-phenyl) ethylhydrazine and the like. Is done.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is a t-butyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-t-butylhydrazine, 1-t-butyl-1-n-pentylhydrazine, 1-t-butyl-1-i-pentylhydrazine, 1-t-butyl-1-neo-pentylhydrazine, 1-t-butyl-1-t-pentyl Hydrazine, 1-t-butyl-1-n-hexylhydrazine, 1-t-butyl-1-i-hexylhydrazine, 1-t-butyl-1-n-heptylhydrazine, 1-t-butyl-1-n -Octylhydrazine, 1-t-butyl-1-n-nonylhydrazine, 1-t-butyl-1-n-decylhydrazine, 1-t-butyl-1-n-undecylhydrazine, 1-t-butyl- 1-n- Dodecylhydrazine, 1-t-butyl-1-cyclohexylhydrazine, 1-t-butyl-1-phenylhydrazine, 1-t-butyl-1- (4-methyl) phenylhydrazine, 1-t-butyl-1-benzyl Examples include hydrazine and 1-t-butyl-1- (2-phenyl) ethylhydrazine.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-pentyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-pentylhydrazine, 1-n-pentyl-1-i-pentylhydrazine, 1-n-pentyl-1-neo-pentylhydrazine, 1-n-pentyl-1-t-pentylhydrazine, 1-n-pentyl-1-n-hexyl Hydrazine, 1-n-pentyl-1-i-hexylhydrazine, 1-n-pentyl-1-n-heptylhydrazine, 1-n-pentyl-1-n-octylhydrazine, 1-n-pentyl-1-n -Nonylhydrazine, 1-n-pentyl-1-n-decylhydrazine, 1-n-pentyl-1-n-undecylhydrazine, 1-n-pentyl-1-n-dodecylhydrazine 1-n-pentyl-1-cyclohexylhydrazine, 1-n-pentyl-1-phenylhydrazine, 1-n-pentyl-1- (4-methyl) phenylhydrazine, 1-n-pentyl-1-benzylhydrazine, Examples include 1-n-pentyl-1- (2-phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an i-pentyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-i-pentylhydrazine, 1-i-pentyl-1-neo-pentylhydrazine, 1-i-pentyl-1-t-pentylhydrazine, 1-i-pentyl-1-n-hexylhydrazine, 1-i-pentyl-1-i-hexyl Hydrazine, 1-i-pentyl-1-n-heptylhydrazine, 1-i-pentyl-1-n-octylhydrazine, 1-i-pentyl-1-n-nonylhydrazine, 1-i-pentyl-1-n -Decylhydrazine, 1-i-pentyl-1-n-undecylhydrazine, 1-i-pentyl-1-n-dodecylhydrazine, 1-i-pentyl-1-cyclohexylhydrazine 1-i-pentyl-1-phenylhydrazine, 1-i-pentyl-1- (4-methyl) phenylhydrazine, 1-i-pentyl-1-benzylhydrazine, 1-i-pentyl-1- (2 -Phenyl) ethylhydrazine and the like are exemplified.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is a neo-pentyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-neo-pentylhydrazine, 1-neo-pentyl-1-t-pentylhydrazine, 1-neo-pentyl-1-n-hexylhydrazine, 1-neo-pentyl-1-i-hexylhydrazine, 1-neo-pentyl-1-n-heptyl Hydrazine, 1-neo-pentyl-1-n-octylhydrazine, 1-neo-pentyl-1-n-nonylhydrazine, 1-neo-pentyl-1-n-decylhydrazine, 1-neo-pentyl-1-n -Undecylhydrazine, 1-neo-pentyl-1-n-dodecylhydrazine, 1-neo-pentyl-1-cyclohexylhydrazine 1-neo-pentyl-1-phenylhydrazine, 1-neo-pentyl-1- (4-methyl) phenylhydrazine, 1-neo-pentyl-1-benzylhydrazine, 1-neo-pentyl-1- (2- Examples include phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is a t-pentyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-t-pentylhydrazine, 1-t-pentyl-1-n-hexylhydrazine, 1-t-pentyl-1-i-hexylhydrazine, 1-t-pentyl-1-n-heptylhydrazine, 1-t-pentyl-1-n-octyl Hydrazine, 1-t-pentyl-1-n-nonylhydrazine, 1-t-pentyl-1-n-decylhydrazine, 1-t-pentyl-1-n-undecylhydrazine, 1-t-pentyl-1- n-dodecylhydrazine, 1-t-pentyl-1-cyclohexylhydrazine, 1-t-pentyl-1-phenylhydrazine, 1-t-pentyl-1- (4-methyl) phenylhydra Examples thereof include gin, 1-t-pentyl-1-benzylhydrazine, 1-t-pentyl-1- (2-phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-hexyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-hexyl hydrazine, 1-n-hexyl-1-i-hexylhydrazine, 1-n-hexyl-1-n-heptylhydrazine, 1-n-hexyl-1-n-octylhydrazine, 1-n-hexyl-1-n-nonyl Hydrazine, 1-n-hexyl-1-n-decylhydrazine, 1-n-hexyl-1-n-undecylhydrazine, 1-n-hexyl-1-n-dodecylhydrazine, 1-n-hexyl-1- Cyclohexylhydrazine, 1-n-hexyl-1-phenylhydrazine, 1-n-hexyl-1- (4-methyl) phenylhydrazine, 1-n-hexyl-1-benzylhydrazine 1-n-hexyl-1- (2-phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an i-hexyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-i-hexylhydrazine, 1-i-hexyl-1-n-heptylhydrazine, 1-i-hexyl-1-n-octylhydrazine, 1-i-hexyl-1-n-nonylhydrazine, 1-i-hexyl-1-n-decyl Hydrazine, 1-i-hexyl-1-n-undecylhydrazine, 1-i-hexyl-1-n-dodecylhydrazine, 1-i-hexyl-1-cyclohexylhydrazine, 1-i-hexyl-1-phenylhydrazine 1-i-hexyl-1- (4-methyl) phenylhydrazine, 1-i-hexyl-1-benzylhydrazine, 1-i-hexyl-1- (2-phenyl) ethyl Examples include hydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-heptyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-heptylhydrazine, 1-n-heptyl-1-n-octylhydrazine, 1-n-heptyl-1-n-nonylhydrazine, 1-n-heptyl-1-n-decylhydrazine, 1-n-heptyl-1-n-un Decylhydrazine, 1-n-heptyl-1-n-dodecylhydrazine, 1-n-heptyl-1-cyclohexylhydrazine, 1-n-heptyl-1-phenylhydrazine, 1-n-heptyl-1- (4-methyl) ) Phenylhydrazine, 1-n-heptyl-1-benzylhydrazine, 1-n-heptyl-1- (2-phenyl) ethylhydrazine and the like are exemplified.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-octyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-octylhydrazine, 1-n-octyl-1-n-nonylhydrazine, 1-n-octyl-1-n-decylhydrazine, 1-n-octyl-1-n-undecylhydrazine, 1-n-octyl-1-n- Dodecylhydrazine, 1-n-octyl-1-cyclohexylhydrazine, 1-n-octyl-1-phenylhydrazine, 1-n-octyl-1- (4-methyl) phenylhydrazine, 1-n-octyl-1-benzyl Examples include hydrazine and 1-n-octyl-1- (2-phenyl) ethylhydrazine.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-nonyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-nonylhydrazine, 1-n-nonyl-1-n-decylhydrazine, 1-n-nonyl-1-n-undecylhydrazine, 1-n-nonyl-1-n-dodecylhydrazine, 1-n-nonyl-1-cyclohexylhydrazine 1-n-nonyl-1-phenylhydrazine, 1-n-nonyl-1- (4-methyl) phenylhydrazine, 1-n-nonyl-1-benzylhydrazine, 1-n-nonyl-1- (2- Examples include phenyl) ethylhydrazine and the like.

In addition, as the hydrazine derivative in which the substituent R ₁ is an n-decyl group and R ₃ and R ₄ are hydrogen atoms in the general formula (2), specifically, 1,1-di-n-decylhydrazine, 1-n-decyl-1-n-undecylhydrazine, 1-n-decyl-1-n-dodecylhydrazine, 1-n-decyl-1-cyclohexylhydrazine, 1-n-decyl-1-phenylhydrazine, 1 Examples include -n-decyl-1- (4-methyl) phenylhydrazine, 1-n-decyl-1-benzylhydrazine, 1-n-decyl-1- (2-phenyl) ethylhydrazine and the like.

In the above general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-undecyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-undecylhydrazine 1-n-undecyl-1-n-dodecylhydrazine, 1-n-undecyl-1-cyclohexylhydrazine, 1-n-undecyl-1-phenylhydrazine, 1-n-undecyl-1- (4-methyl) phenyl Examples include hydrazine, 1-n-undecyl-1-benzylhydrazine, 1-n-undecyl-1- (2-phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is an n-dodecyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-di-n-dodecylhydrazine, 1-n-dodecyl-1-cyclohexylhydrazine, 1-n-dodecyl-1-phenylhydrazine, 1-n-dodecyl-1- (4-methyl) phenylhydrazine, 1-n-dodecyl-1-benzylhydrazine, 1 -N-dodecyl-1- (2-phenyl) ethylhydrazine and the like are exemplified.

In the above general formula (2), specific examples of the hydrazine derivative in which the substituent R ₁ is a cyclohexyl group and R ₃ and R ₄ are hydrogen atoms include 1,1-dicyclohexylhydrazine and 1-cyclohexyl-1- Examples include phenylhydrazine, 1-cyclohexyl-1- (4-methyl) phenylhydrazine, 1-cyclohexyl-1-benzylhydrazine, 1-cyclohexyl-1- (2-phenyl) ethylhydrazine and the like.

Further, in the above general formula (2), specific examples of the hydrazine derivative in which the substituent R ₁ is a phenyl group and R ₃ and R ₄ are hydrogen atoms include 1,1-diphenylhydrazine and 1-phenyl-1- Examples include (4-methyl) phenylhydrazine, 1-phenyl-1-benzylhydrazine, 1-phenyl-1- (2-phenyl) ethylhydrazine and the like.

In the general formula (2), the hydrazine derivative in which the substituent R ₁ is a 4-methylphenyl group and R ₃ and R ₄ are hydrogen atoms, specifically, 1,1-bis (4-methyl) Examples include phenylhydrazine, 1- (4-methyl) phenyl-1-benzylhydrazine, 1- (4-methyl) phenyl-1- (2-phenyl) ethylhydrazine and the like.

In the above general formula (2), specific examples of the hydrazine derivative in which the substituent R ₁ is a benzyl group and R ₃ and R ₄ are hydrogen atoms include 1,1-dibenzylhydrazine and 1-benzyl-1 -(2-Phenyl) ethylhydrazine and the like are exemplified.

As the hydrazine derivative in which the substituent R ₁ is a 2-phenylethyl group and R ₃ and R ₄ are hydrogen atoms in the general formula (2), specifically, 1,1-bis (2-phenyl) ) Ethyl hydrazine and the like are exemplified.

Among these hydrazine derivatives, those in which the number of carbon atoms of the substituents R _{1 to} R ₄ does not exceed 12 in the general formula (2) are preferable. When the number of carbon atoms of each of the substituents R _{1 to} R ₄ exceeds 12, the boiling point of hydrocarbons, which are decomposition products during the preparation of the copper fine particle dispersion, increases, and copper cannot be evaporated or diffused. There exists a possibility that it may remain in a fine particle dispersion, and when used as a conductive pattern forming composition, it may adversely affect the purity of metallic copper and the conductivity of the formed copper thin film.

  In consideration of the removability, cost and safety of decomposition products, n-propyl hydrazine, i-propyl hydrazine, n-butyl are used as the hydrazine derivatives used in step a in the method for producing a copper fine particle dispersion of the present invention. Hydrazine, t-butyl hydrazine, n-pentyl hydrazine, n-hexyl hydrazine, n-heptyl hydrazine, n-octyl hydrazine, n-nonyl hydrazine, n-decyl hydrazine, n-undecyl hydrazine, n-dodecyl hydrazine, cyclohexyl hydrazine More preferably, one selected from the group consisting of phenylhydrazine, benzylhydrazine, 1,1-dimethylhydrazine and 1,1-diethylhydrazine, or a combination of two or more.

  In the step a in the method for producing a copper fine particle dispersion of the present invention, hydrazine derivatives other than those described above may be included as long as they do not contradict the spirit of the present invention.

  In the method for producing a copper fine particle dispersion of the present invention, the hydrazine derivative represented by the general formula (2) may be a commercially available product or may be synthesized by a known method, and is not particularly limited. The above-described method can be applied as a synthesis method. Further, the purity of the hydrazine derivative represented by the general formula (2) 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 method for producing a copper fine particle dispersion of the present invention, the copper fine particle precursor used in step a is not particularly limited as long as it is a compound containing copper ions. For example, oxides such as cuprous oxide and copper oxide , Hydroxides such as copper hydroxide (I) and copper hydroxide (II), halides such as copper fluoride, copper chloride, copper bromide, copper iodide, basic copper carbonate, copper nitrite, copper nitrate , Inorganic acid salts such as copper sulfite, copper sulfate, copper phosphate, copper pyrophosphate, copper formate, copper acetate, copper propionate, copper butyrate, copper isobutyrate, copper valerate, copper isovalerate, copper pivalate, One or more selected from the group consisting of organic acid salts such as copper oxalate, copper malonate, copper succinate, copper maleate, copper benzoate, copper citrate, copper tartrate and acetylacetonato copper, ethylenediamine copper, etc. Two or more kinds can be suitably used. Among these, copper acetate is particularly preferable from the viewpoint of cost. Although copper fine particle precursors other than these may be used, they may be industrially disadvantageous because they are difficult to obtain or expensive. Moreover, as a copper fine particle precursor, although the high purity thing marketed for electronic materials can be used, you may use what is distribute | circulated industrially.

  In the method for producing a copper fine particle dispersion of the present invention, the mixing ratio of the polyhydrazone compound and the copper fine particles in step a is not particularly limited, but the polyhydrazone compound is 5 to 1000% by weight with respect to the amount of metallic copper. It is preferably 10 to 200% by weight. If the amount of the polyhydrazone compound is less than 5% by weight relative to the amount of copper metal, oxidation may not be possible when the copper fine particle dispersion is prepared. Is not preferable, and the content of metallic copper per unit weight in the copper fine particle dispersion decreases, which is not preferable.

  In the method for producing a copper fine particle dispersion of the present invention, the mixing ratio of the hydrazine derivative and the copper fine particle precursor in step a is not particularly limited, but the hydrazine derivative is 0 with respect to 1 molar equivalent of the copper fine particle precursor. It is preferably 25 to 1000 molar equivalents, and more preferably 1 to 100 molar equivalents. If the amount of the hydrazine derivative is less than 0.25 molar equivalent relative to 1 molar equivalent of the copper fine particle precursor, the polyhydrazone compound and the copper fine particle precursor may not be completely dissolved. , You can not get the effect just put.

  In the method for producing a copper fine particle dispersion of the present invention, the reducing agent used in step b is not particularly limited as long as it has a reducing power capable of reducing copper ions to metallic copper. For example, hydrazine, sodium hydrophosphate , One or more selected from the group consisting of tetrabutylammonium borohydride, lithium borohydride, sodium borohydride, potassium borohydride, borane, diborane, formaldehyde, acetaldehyde, formic acid, hydroxyacetone, and hydroxylamine are preferably used. be able to. Among these, sodium borohydride is particularly preferable from the viewpoint of safety and cost. Moreover, as a reducing agent, although the high purity thing marketed for electronic materials can be used, you may use what is distribute | circulated industrially.

  In the method for producing a copper fine particle dispersion of the present invention, the amount of the reducing agent used in step b is not particularly limited as long as it is an amount that can completely reduce copper ions to metallic copper, but 1 mol of the copper fine particle precursor. The amount of the reducing agent is preferably 1 to 10 molar equivalents, more preferably 1 to 2 molar equivalents, relative to equivalents. If the amount of the reducing agent is less than 1 molar equivalent relative to 1 molar equivalent of the copper fine particle precursor, there is a possibility that the reduction to metallic copper may not proceed completely. There is no effect.

  In the method for producing a copper fine particle dispersion of the present invention, the temperature in step b is not particularly limited as long as the reducing agent can reduce copper ions to metallic copper, but is usually in the range of −50 to 100 ° C. And a range of 0 to 60 ° C is preferable. If it is less than −50 ° C., the reduction reaction may be extremely slow, and if it exceeds 100 ° C., the reducing agent may decompose, which is not realistic.

  In the method for producing a copper fine particle dispersion of the present invention, pH adjustment may be performed in step b in order to control the reduction reaction. In order to adjust the pH, examples of the base include ammonia water, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and quaternary ammonium salts such as tetramethylammonium hydroxide. Although these can use the highly purified thing marketed for electronic materials, you may use what is distribute | circulated industrially.

  In the method for producing a copper fine particle dispersion of the present invention, a method of precipitating copper fine particles by using the hydrazine derivative used in the step a as a reducing agent without performing the step b can also be used. At this time, in order to increase the reducing power of the hydrazine derivative, it is preferable to add water and heat.

  In consideration of the fact that the copper fine particle dispersion is used as an electronic material, the water to be added is preferably water in which ionic substances such as ion-exchanged water, pure water and ultrapure water, particles, and the like are reduced as much as possible. The heating temperature is not higher than the boiling point of the hydrazine derivative, and the hydrazine derivative is not particularly limited as long as the copper ion can be reduced to metal copper. A range of ˜200 ° C. is preferred. If it is less than 0 ° C., the reduction reaction may be extremely slow, and if it exceeds 300 ° C., the hydrazine derivative may decompose, which is not realistic.

  Since the amount of water to be added depends on the amount of water brought from the hydration state of the copper fine particle precursor, it is difficult to specify, but the copper fine particle precursor is equivalent to 1 molar equivalent of the copper fine particle precursor. It may be added so that the sum of the amount of water derived from the hydrated state and the amount of water to be added is in the range of 2 to 100 molar equivalents, and more preferably in the range of 4 to 10 molar equivalents. . When the sum of the amount of water brought in due to the hydration state of the copper fine particle precursor and the amount of added water is less than 2 molar equivalents relative to 1 molar equivalent of the copper fine particle precursor, the reduction to metallic copper is completely There is a possibility that it does not progress, and even if it is added in excess of 100 molar equivalents, the effect just added cannot be obtained.

  In the method for producing a copper fine particle dispersion of the present invention, an organic solvent may be added in step a and / or step b. As such an organic solvent, the same organic solvent as described above that can be contained in the copper fine particle dispersion of the present invention can be used.

  The copper fine particle dispersion of the present invention can be suitably used as an ink-like or paste-like conductive pattern forming composition as it is or by mixing an additive as necessary.

  Other uses of the copper fine particle dispersion of the present invention include materials such as electrode materials, catalysts, colorants, cosmetics, near infrared absorbers, optical recording materials, polarizing materials, anti-counterfeiting inks, and electromagnetic shielding materials. Etc.

  Next, the copper fine particles of the present invention and the production method thereof will be described.

  The copper fine particles of the present invention are characterized in that the polyhydrazone compound represented by the general formula (1) is adsorbed on the particle surface.

  Although it does not specifically limit as a copper fine particle of this invention, From the meaning of this invention, it is preferable that the average particle diameter is the range of 0.1-10 nm. If the particle diameter of the copper fine particles is less than 0.1 nm, the activity of the copper surface becomes very high, and the oxidation may not be suppressed. In addition, when the thickness exceeds 10 nm as described above, the degree of melting point decrease may be reduced, and fusion between particles may be difficult to occur.

  The copper fine particles of the present invention can be obtained in the form of powder by separating the copper fine particles from the copper fine particle dispersion of the present invention by a separation operation.

  In the method for producing copper fine particles of the present invention, the operation for separating the copper fine particles is not particularly limited, and examples thereof include filtration, centrifugal separation, and distillation of components other than the copper fine particles.

  In the method for producing copper fine particles of the present invention, when the separation operation is filtration, a poor solvent can be added to promote aggregation of the copper fine particles in order to improve the filtration efficiency. As a poor solvent, the 1 type chosen from polar solvents, such as methanol, acetonitrile, and water, or 2 or more types of compatible mixtures can be used conveniently, for example.

  In the method for producing copper fine particles of the present invention, when the separation operation is centrifugation, a known method can be used.

  In the method for producing copper fine particles of the present invention, when the separation operation is distillation of components other than copper fine particles, a known method can be used, and the method is not particularly limited, but is necessary for distillation. When the heating temperature is equal to or higher than the decomposition temperature of the polyhydrazone compound, the heating is preferably performed under reduced pressure.

  The copper fine particles of the present invention can be suitably used as an ink-like or paste-like conductive pattern forming composition by re-dispersing in an organic solvent and mixing additives as necessary.

  Next, the conductive pattern forming composition of the present invention will be described.

  The conductive pattern forming composition of the present invention contains the above-described copper fine particle dispersion of the present invention, or contains the above-described copper fine particles of the present invention and a dispersant for dispersing the copper fine particles.

  In the composition for forming a conductive pattern of the present invention, the dispersant for dispersing the copper fine particles of the present invention is not particularly limited, but the surface of the copper fine particles of the present invention is represented by the general formula (1). Since the polyhydrazone compound shown is adsorbed, its concentration, viscosity and the like can be freely controlled by using an organic solvent as a dispersant.

  Although it does not specifically limit as an organic solvent, For example, it is 1 type chosen from the group which consists of alcohols, glycols, ethers, ester, hydrocarbons, and aromatic hydrocarbons, or compatibility. The mixture of 2 or more types is mentioned.

  Specifically, as alcohols, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, cyclohexanol , Benzyl alcohol, terpineol, and the like. Specific examples of glycols include ethylene glycol, propylene glycol, butylene glycol, pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and the like. Specific examples of ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether. , Triethylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and the like. Specific examples of the esters include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, Examples thereof include methyl propionate, ethyl propionate, butyl propionate, and γ-butyrolactone. Specific examples of hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, and n-nonane. , N-decane, n-undecane, n-dodecane, cyclohexane, decalin and the like. Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propyl. Benzene, n-butylbenzene, mesitylene, chlorobenzene, Examples include dichlorobenzene.

  Among these, from the viewpoint of cost and safety, one kind selected from the group consisting of ethanol, i-propyl alcohol, terpineol, ethylene glycol, propylene glycol, diethylene glycol dimethyl ether, γ-butyrolactone, n-decane, toluene and n-butylbenzene. It is more preferable to use two or more compatible types in combination.

  In the conductive pattern forming composition containing the copper fine particles of the present invention and the dispersant for dispersing the copper fine particles, the amount of the copper fine particles is 0.1 to 100 with respect to the weight of the copper fine particles and the entire dispersant. The balance is preferably an organic solvent in the range of 5% by weight, and the balance is more preferably an organic solvent in the range of 5 to 80% by weight. If the total amount of copper fine particles is less than 5% by weight with respect to the total weight of the copper fine particles and the dispersing agent, an operation such as concentration is required when using the copper fine particles, which may lead to an increase in work man-hours. Then, the fluidity is lowered and the workability may be significantly lowered.

  The composition for forming an electroconductive pattern of the present invention can contain additives such as a viscosity modifier and a surface tension modifier as necessary.

  Next, the formation method of the conductive pattern of this invention is demonstrated.

  The composition for forming a conductive pattern of the present invention can be used for printed wiring by being applied on a substrate and heated, and can be applied to a substrate and dried to be used as a high-density recording material, a light shielding filter, or the like. Can be used.

  In the method for forming a conductive pattern of the present invention, the substrate on which the composition for forming a conductive pattern of the present invention is applied can be a known substrate, and is not particularly limited. Examples include inorganic substrates such as glass plates, ITO (indium tin oxide), and ceramic substrates, and organic substrates such as polyimide, polyethylene terephthalate (PET), aramid resin, and epoxy resin.

  In the method for forming a conductive pattern of the present invention, the method for applying the composition for forming a conductive pattern of the present invention can be performed by a known method, and is not particularly limited. , Dip coating method, spray coating method, spin coating method, ink jet method and the like.

  In the method for forming a conductive pattern of the present invention, the heating is preferably performed in an inert gas atmosphere. As an inert gas, helium, argon, nitrogen etc. are mentioned, for example. Among these, it is preferable to use nitrogen because it is inexpensive. The inert gas may contain oxygen as long as it does not significantly affect the oxidation of the 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 pattern of the present invention, the heating temperature is not particularly limited as long as the copper precursor is reduced by the reducing agent and the organic substance is decomposed and volatilized, but is usually in the range of 50 to 350 ° C. Yes, the range of 50 to 200 ° C is more preferable. When the heating temperature is less than 50 ° C., the reduction of the copper precursor does not proceed completely, and the remaining organic substance may become remarkable. When the heating temperature exceeds 350 ° C., the organic substrate may not be used.

  In the method for forming a conductive pattern of the present invention, the heating time may be appropriately selected depending on the type of the copper precursor and the reducing agent and the desired conductivity, but when a heating temperature of about 250 ° C. is set, Usually about 10 to 60 minutes.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not construed as being limited in any way by these examples.

In the following examples, the average particle diameter of the copper 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. TEM used the product name "JEM-2000FX" made by JEOL. The average molecular weight was calculated in terms of polystyrene by gel permeation chromatography (high-speed GPC system manufactured by Tosoh Corporation). 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.

[Reference Example 1] Preparation of poly (2-methyl-2-propenaldehyde).
In a 50 ml eggplant-shaped flask containing a magnetic stirrer, 7.0 g (100 mmol) of 2-methyl-2-propenaldehyde (methacrolein) produced by distillation was dissolved in 20 g of toluene, and 64 mg of azobisisobutyronitrile (0 .2 mmol) was added, heated to 50 ° C. and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with methanol, and then dried under reduced pressure at room temperature to obtain 5.09 g of poly (2-methyl-2-propenaldehyde) (yield 72.7%).

Number average molecular weight (Mn) = 27.2 × 10 ² , Mw / Mn = 6.8.

[Reference Example 2] Preparation of poly (methyl vinyl ketone).
In a 50 ml eggplant type flask containing a magnetic stirrer, 3.5 g (50 mmol) of methyl vinyl ketone produced by distillation was dissolved in 10 g of toluene, and 32 mg (0.2 mmol) of azobisisobutyronitrile was added, up to 60 ° C. Heat and stir for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with methanol, and dried under reduced pressure at room temperature to obtain 3.03 g of poly (methyl vinyl ketone) (yield: 86.7%).

Number average molecular weight (Mn) = 62.8 × 10 ² , Mw / Mn = 4.03.

[Reference Example 3] Preparation of poly (2-methyl-2-propenaldehyde phenylhydrazone).
In a 50 ml eggplant-shaped flask containing a magnetic stirrer, 1.4 g of poly (2-methyl-2-propenaldehyde) (ketone amount 20 mmol) was dissolved in 40 g of tetrahydrofuran, and 2.38 g (22 mmol) of phenylhydrazine, p- Toluenesulfonic acid 5 mg was added, heated to 60 ° C. and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with a small amount of methanol, and then dried under reduced pressure at room temperature to obtain 2.48 g of poly (2-methyl-2-propenaldehyde phenylhydrazone) (yield 70. 5%).

Number average molecular weight (Mn) = 38.1 × 10 ² , Mw / Mn = 3.05.

Reference Example 4 Preparation of poly (methyl vinyl ketone phenylhydrazone).
In a 50 ml eggplant type flask containing a magnetic stirrer, 1.4 g (ketone amount 20 mmol) of poly (methyl vinyl ketone) was dissolved in 40 g of tetrahydrofuran, and 1.44 g (22 mmol) of dimethylhydrazone and 5 mg of p-toluenesulfonic acid were dissolved. The mixture was added, heated to 60 ° C., and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of methanol, and then the precipitate was collected by filtration. The obtained white solid was washed with water and then with a small amount of methanol, and then dried under reduced pressure at room temperature to obtain 2.12 g of poly (methyl vinyl ketone phenylhydrazone) (yield 82.8%).

Number average molecular weight (Mn) = 58.2 × 10 ² , Mw / Mn = 4.32.

[Example 1] Preparation of copper fine particle dispersion containing poly (2-methyl-2-propenaldehyde phenylhydrazone).
After 2 g of copper (II) acetate monohydrate and 0.48 g of poly (2-methyl-2-propenaldehydephenylhydrazone) were added to 10 g of n-hexylhydrazine and completely dissolved, 0.37 g of sodium borohydride was added. A solution dissolved in 1.63 g of water was added dropwise at room temperature over 30 minutes. Furthermore, the black copper fine particle dispersion was obtained by stirring at room temperature for 30 minutes. When this copper fine particle dispersion was observed with TEM and the average particle size was determined, it was 5.2 nm (standard deviation 1.7, coefficient of variation 33%). Even if the obtained copper fine particle dispersion was left in the atmosphere for 1 hour, no discoloration due to oxidation was observed, and the uniform dispersion state was maintained. To the copper fine particle dispersion, 100 ml of acetonitrile: water = 1: 1 (v / v) solution was added and allowed to stand, and the resulting precipitate was filtered to obtain a copper fine particle powder. As a result of elemental analysis, the obtained copper fine particles were composed of 61% by weight of copper and 39% by weight of organic components. From the analysis result by ¹ H-NMR, the main component of the organic substance was poly (2-methyl-2-propene). Aldehyde phenylhydrazone). The obtained copper fine particle powder was redispersible in terpineol.

[Example 2] Preparation of copper fine particle dispersion containing poly (methyl vinyl ketone phenylhydrazone).
After adding 2 g of copper (II) acetate monohydrate and 0.48 g of poly (methyl vinyl ketone phenylhydrazone) to 10 g of phenylhydrazine and completely dissolving it, 0.37 g of sodium borohydride was dissolved in 1.63 g of water. The solution was added dropwise at room temperature over 30 minutes. Furthermore, the black copper fine particle dispersion was obtained by stirring at room temperature for 30 minutes. When this copper fine particle dispersion was observed with a TEM and the average particle diameter was determined, it was 2.9 nm (standard deviation 1.2, coefficient of variation 41%). Even if the obtained copper fine particle dispersion was left in the atmosphere for 1 hour, no discoloration due to oxidation was observed, and the uniform dispersion state was maintained. To the copper fine particle dispersion, 100 ml of acetonitrile: water = 1: 1 (v / v) solution was added and allowed to stand, and the resulting precipitate was filtered to obtain a copper fine particle powder. As a result of elemental analysis, the obtained copper fine particles are composed of 60% by weight of copper and 40% by weight of organic components. From the analysis result by ¹ H-NMR, the main component of the organic substance is poly (methyl vinyl ketone phenylhydrazone). there were. The obtained copper fine particle powder was redispersible in terpineol. The obtained copper fine particle powder was redispersible in toluene.

[Comparative Example 1] Preparation of a copper fine particle dispersion containing polyvinylpyrrolidone.
To 10 g of phenylhydrazine, 2 g of copper (II) acetate monohydrate and 0.48 g of polyvinylpyrrolidone (trade name: polyvinylpyrrolidone K-30, viscosity average molecular weight 40,000, manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and hydrogenated. A solution prepared by dissolving 0.37 g of sodium boron in 1.63 g of water was added dropwise at room temperature over 30 minutes. Furthermore, the black copper fine particle dispersion was obtained by stirring at room temperature for 30 minutes. When this copper fine particle dispersion was observed with a TEM and the average particle size was determined, it was 8.9 nm (standard deviation 4.2, coefficient of variation 47%). To the copper fine particle dispersion, 100 ml of acetonitrile: water = 1: 1 (v / v) solution was added and allowed to stand, and the resulting precipitate was filtered to obtain a copper fine particle powder.

[Example 3] Preparation of a conductive pattern forming composition containing poly (2-methyl-2-propenaldehyde phenylhydrazone) and copper fine particles.
5.6 g of terpineol and 20 g of toluene were added to 1.0 g of the copper fine particle powder obtained in Example 1, and the mixture was heated and stirred at 60 ° C. for 1 hour to redisperse the copper fine particles. After filtering this uniform dispersion with a 0.5 μm membrane filter, toluene in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive pattern (hereinafter, the notation is simplified). (Referred to as conductive ink A).

Example 4 Preparation of a conductive pattern forming composition containing poly (methyl vinyl ketone phenylhydrazone) and copper fine particles.
5.6 g of terpineol and 20 g of toluene were added to 1.0 g of the copper fine particle powder obtained in Example 2, and the mixture was heated and stirred at 60 ° C. for 1 hour to redisperse the copper fine particles. After filtering this uniform dispersion with a 0.5 μm membrane filter, toluene in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive pattern (hereinafter, the notation is simplified). (Referred to as conductive ink B).

Comparative Example 2 Preparation of a conductive pattern forming composition containing polyvinylpyrrolidone and copper fine particles.
To 1.0 g of the copper fine particle powder obtained in Comparative Example 1, 5.6 g of terpineol and 20 g of toluene were added, and the mixture was heated and stirred at 60 ° C. for 1 hour to redisperse the copper fine particles. After filtering this uniform dispersion with a 0.5 μm membrane filter, toluene in the obtained filtrate was desolvated by concentration under reduced pressure to prepare a composition for forming a conductive pattern (hereinafter, the notation is simplified). (Referred to as conductive ink C).

[Example 5, Example 6, Comparative Example 3] Evaluation of conductivity after baking, amount of organic residue, and degree of polymer degradation.
Each conductive ink was applied onto a glass substrate using a bar coater to form a uniform coating film of 10 mm × 50 mm and a film thickness of 90 μm. Next, heat treatment was performed at 300 ° C. for 1 hour in a hydrogen-nitrogen mixed atmosphere having a hydrogen content of 5% by volume to obtain a copper thin film having a film thickness of about 5 μm. The specific resistance of the copper thin film was measured with a four-point probe resistance measuring device (trade name: Loresta GP, manufactured by Mitsubishi Chemical Corporation).

  In addition, elemental analysis was performed on the copper thin film obtained by scraping to obtain a carbon content. Further, each copper powder was added to 20 ml of dimethylformamide, heated to 160 ° C. and stirred for 30 minutes, and then the molecular weight of the dissolved residual polymer was measured by GPC. The results of these evaluations are shown together in Table 1.

Claims (18)

The following general formula (1)

[In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a carbon number. 1 to 4 alkyl groups having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 5 to 10 carbon atoms having 1 to 3 hydrogen atoms substituted An alkyl group having 1 to 4 carbon atoms is represented. ]
A copper fine particle comprising a polyhydrazone compound having a structural unit represented by formula (I) and having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene and copper fine particles having an average particle diameter of 10 nm or less. Dispersion. In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, An aromatic group having 5 to 10 carbon atoms, an aromatic group having 5 to 10 carbon atoms in which a hydrogen atom on the aromatic ring is substituted by 1 to 3 with a methyl group, and a methyl group in which 1 to 3 hydrogen atoms are substituted with a phenyl group Or an ethyl group in which a hydrogen atom is substituted by 1 to 3 with a phenyl group. In the general formula (1), X, Y, and R ₁ each independently represent a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n -Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group, benzyl group, or 2-phenylethyl group The copper fine particle dispersion according to claim 1 or 2, wherein The copper fine particle dispersion according to any one of claims 1 to 3, wherein an average particle size of the copper fine particles is in a range of 0.1 to 10 nm. The copper fine particle dispersion according to any one of claims 1 to 4, wherein the polyhydrazone compound is contained in an amount of 5 to 1000% by weight based on the copper fine particles. The following general formula (1)

[In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a carbon number. 1 to 4 alkyl groups having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 5 to 10 carbon atoms having 1 to 3 hydrogen atoms substituted An alkyl group having 1 to 4 carbon atoms is represented. ]
A polyhydrazone compound having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene, the structural unit represented by the general formula (2):

[In General Formula (2), R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An aromatic group having 5 to 10 carbon atoms in which 1 to 3 hydrogen atoms on the aromatic ring are substituted with an alkyl group, or 1 to 3 carbon atoms in which 1 to 3 hydrogen atoms are substituted with an aromatic group having 5 to 10 carbon atoms 4 represents an alkyl group. However, R _{1 to} R ₄ are not all hydrogen atoms. ]
The copper fine particle dispersion according to any one of claims 1 to 5, wherein the hydrazine derivative represented by the formula (1) and a copper fine particle precursor are mixed and a reducing agent is further added to reduce and precipitate the copper fine particles. Body manufacturing method. In the general formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, 10 aromatic group, an aromatic group having 5 to 10 carbon atoms in which a hydrogen atom on the aromatic ring is substituted by 1 to 3 by a methyl group, a methyl group in which a hydrogen atom is substituted by 1 to 3 by a phenyl group, or a phenyl group And represents an ethyl group in which 1 to 3 hydrogen atoms are substituted (provided that R ₁ and R ₂ are not hydrogen atoms at the same time), and R ₃ and R ₄ represent a hydrogen atom. Item 7. A method for producing a copper fine particle dispersion according to Item 6. In the general formula (2), 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, sec-butyl. Group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, n-nonyl Represents a group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, phenyl group, 4-methylphenyl group, benzyl group, or 2-phenylethyl group (provided that R ₁ and R ₂ are simultaneously 7. The method for producing a copper fine particle dispersion according to claim 6, wherein R ₃ and R ₄ each represent a hydrogen atom. The copper fine particle precursor is one or two or more compounds selected from the group consisting of copper oxide, copper hydroxide, copper halide, copper inorganic acid salt, copper organic acid salt and copper chelate complex. A method for producing a copper fine particle dispersion according to any one of claims 6 to 8. Copper fine particle precursor is cuprous oxide, copper oxide, copper hydroxide, copper nitrate, basic copper carbonate, copper formate, copper acetate, copper propionate, copper butyrate, copper isobutyrate, copper valerate, copper isovalerate The copper pivalate, the copper oxalate, the copper malonate, the copper benzoate, the copper citrate and the copper acetylacetonate are one or two or more selected from the group consisting of The manufacturing method of the copper fine particle dispersion in any one of these. The reducing agent is selected from the group consisting of hydrazine, sodium hydrophosphate, tetrabutylammonium borohydride, lithium borohydride, sodium borohydride, potassium borohydride, borane, diborane, formaldehyde, acetaldehyde, formic acid, hydroxyacetone, and hydroxylamine. The method for producing a copper fine particle dispersion according to any one of claims 6 to 10, wherein the method is one or two or more compounds. The following general formula (1)

[In the general formula (1), X, Y, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 5 to 10 carbon atoms, or a carbon number. 1 to 4 alkyl groups having 5 to 10 carbon atoms substituted with 1 to 3 hydrogen atoms on the aromatic ring, or 5 to 10 carbon atoms having 1 to 3 hydrogen atoms substituted An alkyl group having 1 to 4 carbon atoms is represented. ]
And a polyhydrazone compound having a number average molecular weight (Mn) in the range of 100 to 1,000,000 in terms of polystyrene is adsorbed on the surface of copper fine particles having an average particle diameter of 10 nm or less. Copper fine particles. The copper fine particles according to claim 12, wherein the average particle diameter of the copper fine particles is in the range of 0.1 to 10 nm. The method for producing copper fine particles according to claim 12 or 13, wherein the copper fine particles are separated from the copper fine particle dispersion according to any one of claims 1 to 5 by a separation operation. The method for producing copper fine particles according to claim 14, wherein the separation operation is distillation of components other than the copper fine particles, centrifugation, or filtration. The composition for electroconductive pattern formation containing the copper fine particle dispersion in any one of Claims 1 thru | or 5. The composition for electroconductive pattern formation containing the copper fine particle of Claim 12 or Claim 13, and a dispersing agent. A method for forming a conductive pattern, comprising applying the composition for forming a conductive pattern according to claim 16 or 17 to a substrate and heating.