TW201232563A - Conductive paste, conductive film-attached base material using the conductive paste, and method for manufacturing conductive film-attached base material - Google Patents

Abstract

Provided is a conductive paste, with which a conductive film that suppresses formation of an oxide film and can maintain a low volume resistivity for a long period of time can be formed. The conductive paste contains: copper particles (A) having a surface oxygen concentration ratio (O/Cu) of 0.5 or less, said surface oxygen concentration ratio being obtained by means of X-ray photoelectron spectroscopy; a chelating agent (B), which is composed of a compound having a stability constant (logKcu) of 5-15 with copper ions at 25 DEG C and an ion strength of 0.1 mol/L; and a thermosetting resin (C).

Description

201232563 6. Technical Field of the Invention The present invention relates to a conductive paste, a conductive film substrate using the same, and a method for manufacturing a conductive film substrate, in particular, the oxidation of a metal component is suppressed. A conductive paste, a conductive film substrate using the same, and a method of producing a conductive film substrate. [Prior Art] Conventionally, a method of using a conductive paste in the formation of a wiring conductor such as an electronic component or a printed wiring board (printed substrate) has been known. Here, for example, the printing substrate is produced by applying a conductive paste to a desired pattern shape on an insulating substrate containing glass, ceramics or the like and baking it to form a wiring pattern. As the conductive paste, a silver paste containing silver (Ag) as a main component is mainly used from the viewpoint of ensuring high conductivity. However, if the silver paste is energized in a high-temperature and high-humidity environment, it is easy to cause ionization of silver atoms and migration of ions by the electric field (electrodeposition of silver). When ion migration occurs in the wiring pattern, there is a problem that a short circuit occurs between the wirings, which hinders the reliability of the wiring substrate. From the viewpoint of improving the reliability of an electronic device or a wiring board, a technique of using a copper paste instead of a silver paste as a conductive paste has been proposed. Since the copper paste is difficult to cause migration, the connection reliability of the electronic circuit can be improved. ..., and the copper is easy to oxidize, so if it is placed in the high humidity environment, it is easy to produce copper telluride due to the reaction with water or oxygen in the atmosphere. The formed conductive film has a problem that the volume resistivity tends to become high due to the influence of the oxide film 160003.doc: 201232563. In order to solve such a problem, a technique of producing a copper powder formulated in a copper paste by a wet reduction method is employed. For example, in the patent document, a surface treatment method for treating a conductive powder containing a conductive powder of steel or a copper alloy using an aqueous solution containing an acid, a reducing agent, and an alkali metal salt of a fatty acid having 8 or more carbon atoms is disclosed. Further, Patent Document 2 discloses a copper-based conductive coating composition in which an antioxidant is contained together with a copper powder and a binder resin for a coating material. Further, it is disclosed that at least one of salicylic acid and a derivative thereof or benzotriazole carboxylic acid is used as the antioxidant. However, the actual situation is that even with the technique of the above cited documents, the problem of an increase in the volume resistivity caused by the formation of the oxide film in the conductive paste for wiring conductors cannot be sufficiently improved. [Prior Art] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-1 84143 [Patent Document 2] Japanese Patent Laid-Open Publication No. 〇58〇8丨 No. [Invention] [Invention Problem to be Solved The present invention has been made to solve the above problems. That is, an object of the present invention is to provide a conductive paste capable of forming a conductive film capable of suppressing formation of an oxide film and maintaining a low volume resistivity for a long period of time. Further, the present invention has been made in an effort to provide a conductive film substrate comprising a conductive film using the above conductive paste. [Technical means for solving the problem] That is, the conductive paste of the present invention is characterized by containing copper particles (A) whose surface oxygen concentration ratio 〇/(: is obtained by X-ray photoelectron spectroscopy. 11 is 〇5 to T; chelating agent (B), which is contained in 25. (:, ionic strength 〇·ι m〇l/L and copper ion stability constant l〇gKCu is 5 to 15 compounds; Thermosetting resin (C). In addition, 'the following will also be 25. (:, ionic strength oj mol / L and copper ion stability constant logKCu only expressed as "the stability with copper ions logKCuJ ° above the conductive In the paste, the copper particles (A) are preferably surface-modified copper particles having a KpH of 3 or less in the ruthenium. The copper particles (A) may also be composite metal copper particles. And heating the copper composite particles containing the metal primary copper particles having an average primary particle diameter of 0.3 to 20 μm, and the copper hydride fine particles having an average primary particle diameter of 丨2 to 〇nm adhered to the surface of the metal copper particles, and the hydrogenation is performed. The copper particles are converted into metal steel particles to form. The pH adjusting agent for the dispersion medium is preferably at least one selected from the group consisting of citric acid, citric acid, maleic acid, malonic acid, acetic acid, propionic acid, sulfuric acid, nitric acid, and hydrochloric acid. Preferably, the pH adjusting agent for forming the water-soluble copper compound solution of the copper hydride fine particles is selected from the group consisting of citric acid, citric acid, maleic acid, malonic acid, acetic acid, propionic acid, sulfuric acid, nitric acid, and hydrochloric acid. At least one of the above-mentioned chelating agents (B) is preferably a functional group (a) containing a nitrogen atom and a functional group (b) having an atom having an isolated electron pair other than a nitrogen atom, 160003.doc 201232563 = = adjacent MW compound ' and the above nitrogen atom and the above gas atom ΓΓ have an isolated electron pair of atoms separated by two or three atoms and the bond two or two of the atoms having an isolated electron pair other than the nitrogen atom are (four) or Further, the nitrogen atom and the atom having an isolated electron pair other than the gas atom are preferably bonded by two or three carbon atoms t. Further, the sound bonding agent (8) is preferably selected from the water (four). Acid, water aldehyde aldehyde #, o-amino phenol The thermosetting resin (C) is preferably selected from the group consisting of bismuth resin, diallyl phthalate (tetra) phthalate, unsaturated alkyd resin, epoxy resin, (iv) resin, and biscision The at least one of the resin, the polysulfide resin, the acrylic resin, the melamine resin, and the urea resin. The conductive paste is preferably 00 parts by mass relative to the copper particles. The amount of the conductive paste (B) is preferably 5 parts by weight to 50 parts by mass based on 100 parts by mass of the steel particles (4), and the amount of the thermosetting resin (c) is 5 to 50 parts by mass. The conductive film substrate is characterized in that a conductive film formed by curing the above-described conductive paste of the present invention is provided on a substrate. In the above-mentioned conductive film substrate, the volume resistivity of the conductive film is preferably (3) 〇-4 Qcm or less. The method for producing a conductive film substrate according to the present invention is characterized in that after the conductive paste of the present invention is applied onto a substrate, the conductive paste is cured to form a conductive film. [Effect of the Invention] According to the present invention, it is possible to form an I film which can suppress the formation of copper oxide even in a high humidity environment, and can maintain the formation of a lower volume resistivity for a long period of time. Conductive paste. Further, according to the present invention, it is possible to produce a conductive film substrate which is highly reliable as a wiring board and the like, and which is capable of suppressing an increase in volume change rate due to formation of an oxide film, by using such a conductive paste. [Embodiment] Hereinafter, the present invention will be described in detail.

The conductive paste of the present invention is characterized by comprising: steel particles (4) having a surface oxygen concentration ratio determined by X-ray photoelectron spectroscopy. /(10)^以下; The meal mixture (8)' is contained in the hunger, ionic strength 01 secret and copper ion stability constant 1 (> a compound of 5 to 15; and a thermosetting resin (C). According to the present invention By compounding the stability constant of the copper ion in the 2nd generation and the ionic strength of 01 mol/L, the compound in the specific range is used as the meal mixture (8), and the amount of copper ions reacted with the oxygen contained in the atmosphere can be reduced. Therefore, it is possible to form a conductive paste in which the formation of copper oxide is suppressed. It is difficult to form an oxide film containing copper oxide as a main component in the conductive film formed of such a conductive paste, so that it can be made even under high humidity. The conductive film substrate can also be suppressed from increasing in volume resistivity. The copper particles (4) are conductive components of the conductive paste, and the surface oxygen concentration determined by X-ray photoelectron spectroscopy is 0.5 or less. The surface oxygen concentration ratio 〇/Cu obtained by X-ray photoelectron spectroscopy is only expressed as "surface oxygen concentration ratio O/Cu". "· Surface oxygen concentration ratio 0/Cu" is based on X-ray photoelectrons. Spectroscopic analysis of copper particles as determined by 160003.doc 201232563 The surface oxygenity (atomic %) of the sub-surface is expressed by the ratio of the surface copper concentration (atoms. /.). In the present specification, 'the surface steel concentration (atoms.) and the surface oxygen concentration (atomic %) The measured values obtained by X-ray photoelectron spectroscopy of the surface region of the particle from the surface of the steel particle toward the center to a depth of about 3 nm, respectively, range from the surface of the copper particle toward the center to a depth of about hm. By measuring the concentration of each component in the particle region in the range, the surface state of the copper particles is sufficiently grasped. If the surface oxygen concentration of the copper particles (4) exceeds 〇/Cu exceeds 〇5, the surface of the copper particles (4) is oxidized. When the amount of copper is too large, when the conductive film is formed, the contact resistance between the particles becomes large, and the volume resistivity becomes high. By using the copper particles (4) having a surface oxygen concentration ratio of O/Cu of not more than 0.5. The contact resistance between the copper particles can be lowered, and the conductivity at the time of forming the conductive film can be improved. The surface oxygen concentration ratio 〇/Cu of the copper particles (A) is preferably 〇3 or less. Further, the 'copper particles (4) are preferably Contained by the particle as a whole The concentration of the copper particles is not less than 700 ppm. The oxygen concentration of the copper particles can be measured by, for example, an oxygen concentration meter. As the copper particles (4), various copper particles can be used as long as the surface oxygen concentration ratio O/Cu is 0.5 or less. The metal steel particles may be copper hydride fine particles or metal copper microparticles (hereinafter also referred to as copper microparticles) obtained by heating copper hydride microparticles. As the copper particles (4), the metal copper particles may be composited with the copper microparticles. A composite particle of the form: as a composite particle, for example, a form in which copper microparticles are attached or bonded to the surface of a metallic copper particle, and the details of the multifilament are further described below. Next 160003.doc 201232563 Copper particles The average particle diameter of (4) is preferably 0. 〇1 to 2 〇μιη The average particle diameter can be appropriately adjusted according to the copper particles (sub-(Α)). If the copper seat is in the range of 〇.01~2〇 _ 八...4 The average diameter of the copper (4) is 〇_〇1 (four) or more, the flow characteristics of the conductive paste become good. Further, when the average particle diameter of the copper particles (Α) is 2 〇 S, the fine wiring can be easily produced by the conductive paste containing the steel particles. The gray copper particles (4) contain metallic copper particles, and the average particle size (pound:: diameter) is preferably 0.33 to 2~. Further, in the case where the copper particles (4) are only included; in the case of copper, the average particle diameter of the aggregated particles is preferably (iv) (i) μπι ‘ more preferably 〇.02 〇 4 μηι. When the secondary copper particles (Α) contain metallic copper particles, when the average particle size is one, the conductivity of the copper particles is good. Further, when the copper particles (Α) contain only copper fine particles, when the average particle diameter of the aggregated particles is G (n _ or more, the flow characteristics of the conductive paste containing the copper particles become good. In the case where the metal copper particles are contained, when the average particle diameter (average-secondary particle diameter) is 20 μm or less, the fine wiring can be easily produced by the conductive paste containing the copper particles. Further, the copper particles (4) contain only steel. In the case of the fine particles, when the average particle diameter of the aggregated particles is 丨 or less, the fine wiring can be easily produced by the conductive paste containing the copper particles. The steel particles having a surface oxygen concentration ratio of O/Cu of 0.5 or less (Α) For example, the following copper particles (Α1) to (Α5丨. (Α1) are metal copper particles, and the average primary particle diameter is 〇3 to 2 〇. (A2) is a copper composite particle. Including: metal steel particles, the average one; 160003.doc 201232563 ^仫 is 0.3~2〇μιη; and copper hydride microparticles attached to the surface of the above metal ball, and the average particle diameter of the agglomerated particles is 20~400 nm (A3) is hydrogenated copper microparticles' and it is agglomerated The average particle diameter of the particles is nm~1 μη^ 〇 (4) is a composite metal copper particle comprising: metallic copper particles, the average-subgranular 35 is 〇.3~2G μηι; and metallic copper microparticles, The hydrogenated copper microparticles adhering to the surface of the metal copper particles are heated, and the aggregated particles have an average particle diameter of 20 to 400 nm. * (4)) is a metal steel microparticle, and the average particle diameter of the agglomerated particles is (4) nm~ 1 μηι. In addition, 'composite metal copper particles (Α4) are copper composite particles (A. The hydrogenated copper microparticles are converted into metal steel particles by heat treatment. Further, the metal copper particles (Α5) are converted by heat treatment) The copper hydride microparticles (A3 0 in the present specification 'average particle diameters are obtained as follows. That is, = metal steel particles average - secondary particle diameter pair self-scanning electron microscope

:^^ "SEM" (SeanningEle_nMie_pe)) M (four) « The particle of the Fruid (F(10)) diameter of the particle is calculated by averaging the particle diameters. Further, the average particle diameter of the aggregated particles including the copper microparticles is measured by an electron microscope (hereinafter referred to as "French" (Transmissi〇n Eiectr〇n Μ (10) coffee (4)), which is randomly selected from the particles (10) (10). In addition, for example, copper composite particles (A2) include copper particles 160003.doc 201232563, and composite particles of copper hydride microparticles attached to the surface of the copper particles. In the case of the average particle diameter, the entire particle size is observed by SEM, and the whole particle of the particle including the copper microparticles is measured, and the Fe diameter is calculated by averaging the obtained particle diameter. The copper particles (A) 'is, for example, "surface-modified copper particles" obtained by subjecting the surface of copper particles to reduction treatment, or "composite metal copper particles to which at least part of the surface of the metal copper particles adheres to metallic copper particles". The "surface-modified copper particles" are obtained by reducing the surface of copper particles in a dispersion medium having a positive value of 3 or less. "Surface-modified copper particles" can be, for example, It is produced by the following step (1) to (3) wet reduction method: (1) dispersing copper particles in a dispersion medium to form a "copper fraction step, (2) adjusting the pH of the copper dispersion to a specific value. The following two steps, and (3) a step of adding a reducing agent to the copper dispersion. The surface-modified copper particles obtained by the above steps (1) to (3) are mainly composed of metallic copper particles. The average-secondary particle diameter of the copper particles is preferably 0.3 to 20 (four) metal copper particles (4))). The average-minor particle diameter of the surface-modified steel particles is 0.3 or more, and the flow characteristics of the conductive paste containing the copper particles are included. It is also good. Moreover, the surface of the copper particles is changed to the average of the secondary particles, and the sub-grain size is ~〇, and the following is the case where the conductive wiring containing the copper particles can be easily fabricated to make the fine wiring 0 t or less. Steps (1) to (3) of the particles are described. (1) Preparation of Steel Dispersion Copper particles which are usually used as a conductive paste in which copper is dispersed in a copper dispersion can disperse particles dispersed in copper by J60003.doc 201232563. The particle shape of the steel particles in the liquid may be spherical or plate-shaped. The average particle diameter of the copper particles in the dispersion is preferably ο·μη - more preferably ho μηι. If the average particle diameter of the copper particles is not 3 (four), the fluidity of the conductive paste is lowered. When the average particle diameter of the copper particles exceeds 20, it is difficult to form fine wiring by using the obtained conductive paste. By setting the average particle diameter of the copper particles to G3 to 2 g, fluidity can be improved, and fine wiring can be suitably produced. Further, the average particle diameter of the copper particles is obtained by measuring the Feret diameter of the metal copper particles randomly selected from the SEM image, and calculating the mean value thereof. The copper particles are made into a *end-shaped dispersion medium, and the copper particle concentration of the copper knives is preferably "% by mass". If the copper == concentration does not reach 〇.1 mass% ’, there is a dispersion contained in the copper dispersion. “There is too much disposal, and the production efficiency cannot be maintained at a sufficient level. On the other hand, if the concentration of the steel particles exceeds 5 G mass%, there is a case where the particles of the particles are too loud and the yield of the surface-modified copper particles is lowered. The surface-modified copper particles can be obtained in a yield by setting the copper particle concentration of the copper dispersion to a range of 0.1 to 50% by mass. The dispersion medium of the steel particle dispersion liquid is not particularly limited as long as it is a dispersible copper particle, and those having high polarity can be preferably used. As the dispersion medium of the high electrode, for example, an alcohol such as water, methanol, ethanol or 2-propanol or a glycol such as ethylene glycol; and a mixed medium obtained by mixing the same can be used as the dispersion of the polarity. Medium, especially suitable for use with water. 160003.doc 201232563 In order to prevent oxidation of the surface of the particles, the copper particles dispersed in the dispersion medium are also surface treated by surface treatment agents. As the surface treatment agent, long-chain carboxylic acid such as stearic acid, palmitic acid or myristic acid can be used. In the case where a long-chain carboxylic acid is used as the surface treatment agent, it is preferred to remove the long-chain carboxylic acid (surface treatment agent) from the surface of the copper particles and then disperse it in the dispersion medium. By removing the long-chain carboxylic acid (surface treatment agent) from the surface of the copper particles and dispersing them in a dispersion medium, the following reduction reaction can be smoothly carried out. Further, in the case where a long-chain carboxylic acid is used as the surface treating agent, the copper particles can also be directly used for the reduction treatment. The removal of the long-chain carboxylic acid can be carried out, for example, by a method such as washing with an acid. Further, in order to improve the dispersibility of the steel particles to the dispersion medium, it is preferred to pretreat the copper particles. By performing the pretreatment, the surface of the copper particles can be made hydrophilic, and therefore, the dispersibility of the copper particles with respect to a highly polar dispersion medium such as water can be improved. As the pretreatment agent, for example, an aliphatic carboxy group such as an aliphatic carboxy oxime having 6 or less carbon atoms, an aliphatic hydroxy monocarboxylic acid or an aliphatic amino acid, and an aliphatic polycarboxylic acid can be preferably used. As the aliphatic polycarboxylic acid, J may be an aliphatic polycarboxylic acid having 10 or less turns or an aliphatic hydroxypolycarboxylate. —uj An aliphatic polycarboxylic acid having a horse number of 8 or less. As the pretreatment agent, specifically, glycine, alanine, citric acid, succinic acid, cis-butyl, s---J-acid, malonic acid and the like can be preferably used. Preferably, a dispersing agent is added to the copper dispersion obtained by the above method in rabbit, ° X. As a dispersing agent, various kinds of water-soluble compounds which are adsorptive to copper particles can be used, 160003.doc -13- 201232563. As the dispersing agent, specifically, for example, a water-soluble polymer compound such as polyethylene glycol, polyacrylic acid, polyvinylpyrrolidone, hydroxypropylcellulose, propylcellulose or ethylcellulose can be used; & ethylenediamine Chelating compounds such as tetraacetic acid and iminodiacetic acid. The amount of the surface treatment agent, the pre-treatment (4), and the sub-(4) present on the surface of the steel particles after the respective treatments described above are (1) by mass relative to the copper particles. The treatment of the steel particles using the pretreatment agent or the dispersant adds copper particles to the solution obtained by adding a pretreatment agent or the like to a solvent such as water and imparts a drop. Further, in the solution, the surface of the copper particles is supported by a pretreatment agent or the like. In order to increase the processing speed, it is preferred to carry out the pretreatment, while heating the copper dispersion on one side. The heating temperature is preferably 50. (It is carried out at a temperature lower than or equal to the boiling point of the dispersion medium such as water. Further, when a surface treatment agent or a dispersant such as an acid is added to the dispersion medium, the heating temperature is preferably such a compound. Heating is performed at a boiling point or lower. The heat treatment time is preferably 5 minutes or longer and 3 hours or shorter. If the heating time is less than 5 minutes, the effect of improving the treatment speed cannot be sufficiently obtained. In the case of more than 3 hours, the cost is too high, and it is economically unsatisfactory. Further, in order to prevent oxidation of the surface of the steel particles during pretreatment, etc., it is preferable to be inert to nitrogen or argon. The gas is replaced in the processing vessel. After the pretreatment, the solvent is removed, and it is washed with water or the like as needed, thereby obtaining copper particles dispersed in the dispersion. (2) Copper dispersion Adjustment of pH The pH of the steel dispersion obtained in the above (1) is adjusted. The pH value can be adjusted by adding a pH adjuster to the copper dispersion. As the whole agent, an acid can be used. As the pH adjuster of the copper dispersion, for example, a carboxylic acid such as formic acid, citric acid, maleic acid, malonic acid, acetic acid or propionic acid; or sulfuric acid or nitric acid can be preferably used; An inorganic acid such as hydrochloric acid, etc. As the acid, a compound similar to the above-described citric acid used as a pretreatment agent can be used. Among the four or the like, a carboxylic acid can be preferably used as the pH adjuster. As a pH adjuster, the carboxylic acid can be adsorbed on the surface of the copper particles and remain on the surface of the surface-modified copper particles after the reduction treatment to protect the surface of the particles, thereby suppressing the oxidation reaction of copper. In particular, the formic acid contains a reducing property. The acid group (·〇Η〇), (4) remains on the surface of the copper particles modified on the surface of the crucible, and inhibits oxidation of the surface of the particles. By using a conductive paste prepared with such copper particles, it is difficult to form an oxide film and the volume is formed. The conductive film which suppresses the increase in the resistivity is not necessarily limited to the acid component. For example, when the dispersion is low, a base may be used as the pH adjuster. The pH value is preferably set to 3. If the pH of the copper dispersion is set to 3 or less, the oxide film on the surface of the particle can be smoothly removed in the subsequent reduction treatment step, and the surface-modified copper particles obtained can be reduced. When the pH of the dispersion exceeds 3, the effect of removing the oxide film on the surface of the copper particles cannot be sufficiently obtained, and the oxygen concentration of the surface of the copper particles 160003.doc 201232563 cannot be sufficiently reduced. On the other hand, the pH of the dispersion liquid is preferably 0.5 or more. When the value of the dispersion liquid is less than 〇5, copper ions are excessively eluted, and it is difficult to smoothly reform the surface of the copper particles. The pH is more preferably 5% or more and 2 or less. Further, when the positive value of the dispersion is 3 or less, the dispersion may be directly subjected to reduction treatment. (3) Reduction treatment of copper dispersion A reducing agent is added to the copper dispersion whose pH has been adjusted to carry out reduction treatment. As the reducing agent to be added to the copper dispersion, a metal hydride reducing agent, a hypophosphite such as hypophosphite or sodium hypophosphite, an amine group such as dimethylamine (tetra), and formic acid can be used. At least - kind. Examples of the metal nitrides include a hydrogenation clock, potassium hydride, and hydrogenation. The hydrogenation reducing agent is exemplified by hydrogenation, hydrogenation side, and nitriding. Among them, sub squaric acid and sodium hyposulfite can be preferably used. Further, as described above, the acid can also be used as a positive value adjusting agent. Therefore, when formic acid is added to the dispersion medium, it functions as a reducing agent and also functions as a pH adjuster. The reduction test added to the copper dispersion is excessively added to the amount of copper atoms on the surface of the particles. Specifically, it is preferable to add a reducing agent having a total molar number of copper particles contained in the eight-dispersion liquid to a molar amount of more than # molar amount, and to add a total number of copper atoms in the molar amount relative to the copper particles. The ear ratio is 1.2 to 10 times the amount of the reducing agent. : Adding a reduction of the total number of moles relative to copper by more than 1〇 is present in terms of cost. The production cost becomes too high. Further, there is a J2063.doc -16-201232563 which is more complicated to remove and the amount of decomposition products derived from the reducing agent is excessive. The reversion reaction is preferably carried out by setting the temperature of the dispersion medium to 5 to 6 Gt, more preferably 35 to 5 Gt. By setting the temperature of the dispersion to :) 〇C or less, the influence of the concentration change of the entire dispersion liquid when the dispersion medium is evaporated from the copper dispersion can be reduced. As described above, the reduction of the copper particles can be carried out by adding a reducing agent to the copper dispersion, or by dispersing the copper particles in the dispersion medium to which the reducing agent is added, and the positive value of the copper dispersion after adding the reducing agent is higher. It is preferably maintained at a state of 3 or less from the start of the reaction to the end of the reaction. Thereby, the removal of the oxide film on the surface of the copper particles can be smoothly performed. * The oxidation-reduction potential of the steel dispersion can be appropriately adjusted depending on the amount or type of the reducing agent added. The redox potential of the copper dispersion is preferably from 100 to 300 mV, more preferably from 100 to 300 mV, relative to a standard hydrogen electrode (SHE, Standard Hydrogen (10) (four). By reducing the redox potential of the copper dispersion The potential of the standard hydrogen electrode (SHE) is set to 1 〇〇 to 3 〇〇 mV ', and the reduction reaction of copper ions can be smoothly performed. Further, the oxidation-reduction potential can be obtained as a potential difference from the standard electrode. The 'redox potential> is expressed by a potential difference measured using a standard hydrogen electrode as a standard electrode. After the decomposition of the reducing agent is substantially completed, the surface-modified copper particles are separated from the dispersion, and water is required as needed. It is cleaned and dried to obtain a surface-modified copper with a surface oxygen concentration ratio of O/Cu of 0.5 or less. 160003.doc -17- 201232563 Particles are copper particles (4) powder. Surface oxygen concentration ratio of copper particles (4) is O/Cu In the above steps (1) to (3), for example, by adjusting the pH of the copper dispersion or adjusting the oxidation-reduction potential of the copper dispersion, it is adjusted to the desired range. The surface treatment of the steps (1) to (3) can reduce the presence of copper oxide (CU2〇, Cu(7)) which is present on the surface of the copper particles as a starting material to copper atoms, and can reduce the amount of copper oxide which is a major factor hindering conductivity. Further, by-products such as a reducing agent decomposition product are usually components which are soluble in the dispersion medium. The copper particles can be separated from the components by filtration or centrifugation. Further, in the above steps (1) to (1) 3) The surface of the copper particles after surface treatment, sometimes a part of the copper atoms is reduced by the reducing agent to form copper hydride. Therefore, the surface treated copper particles may also be separated from the dispersion after 40~12 (The heat treatment is carried out under TC, whereby copper hydride is converted into copper. As described above, the "composite metal copper particles" in the present invention are those in which at least a part of the surface of the metal copper particles adheres to the metal copper particles. "Copper particles" are "copper composite particles" obtained by heating copper hydride fine particles on the surface of metallic copper particles, and converting copper hydride fine particles into metallic copper fine particles and & The presence or absence of the attached particles on the surface of the copper particles can be observed by observing the SEM image. Further, the identification of the copper chloride fine particles adhering to the surface of the copper metal particles can be performed by an X-ray diffraction apparatus (manufactured by Rigaku Corporation, TTR-III). As the metal copper particles, known copper particles which are generally used for the conductive paste can be used. The particle shape of the metal copper particles may be spherical or may be in the form of a plate 160003.doc 201232563. The average particle diameter of the particles is preferably 〇3 to 2 The metal copper particles μιη of the beryllium copper composite particles are more preferably 1 to 1 〇μιη. If the average particle diameter of the metal copper particles is 揸 仏 仏 运 0 0J μηι, the conductive paste can not be obtained to obtain sufficient flow characteristics. On the other hand, if the average particle diameter of the right metal copper particles exceeds 20 Å, it is difficult to make fine wiring by using the obtained conductive paste. The average particle size of the metal copper particles is more preferably the same. The average particle size of the metal copper particles is determined by the Feret diameter of 1GG metal copper particles randomly selected from the self-bribery image or the Wei image. The value of the Measured value is calculated on average. The copper hydride fine particles of the copper composite particles are mainly present in the form of primary particle agglomerated Me-order particles. The particles of the hydrogen (tetra) fine particles may have a spherical shape or a plate shape. The average particle diameter of the agglomerated particles of the copper hydride fine particles is preferably 20 to 4 Å, more preferably 2 (9) (10), still more preferably - Δ 00 nm. More preferably, it is 8〇~15〇nn^ If the average particle size of the agglomerated particles F of the copper hydride fine particles is less than 2〇nm, the fusion and growth of the copper hydride microparticles are likely to occur, and the volume shrinkage occurs when the conductive film is formed. The crack is equal to the shape of the bad It. On the other hand, if the average particle diameter of the agglomerated particles of the copper hydride fine particles exceeds 400 nm, the surface area of the particles is insufficient, and it is difficult to cause a surface smelting phenomenon, which makes it difficult to form a dense conductive film. The average particle diameter of the hydrogenated steel micro-soak was measured by measuring the Feret diameter of 100 hydrogenated copper fine particles randomly selected from the TEM image or the SEM image, and averaging the measured values. As the copper composite particles, it is preferable to include metal steel particles having an average primary particle diameter of 〇_3 to 20 160003.doc •19 to 201232563 μη, and an average particle size of the aggregated particles attached to the surface of the metal copper particles. Composite particles (copper composite particles (A2)) of copper hydride fine particles of 2 〇 to 4 〇〇 nm. The amount of the copper hydride fine particles attached to the surface of the metal steel particles is preferably 5 to 50 mass% of the amount of the metal copper particles. More preferably, it is 10 to 35 mass%. When the amount of the copper hydride fine particles is less than 5% by mass based on the amount of the metal copper particles, the conductive channels are not sufficiently formed between the metal copper particles, and the effect of lowering the volume resistivity of the conductive film cannot be sufficiently obtained. On the other hand, when the amount of the copper hydride fine particles is more than 50% by mass based on the amount of the metal copper particles, it is difficult to ensure sufficient fluidity as the conductive paste. Further, the amount of the copper hydride fine particles adhering to the surface of the metal copper particles is, for example, the concentration of the steel ions in the water-soluble copper compound solution to which the reducing agent is added, and the concentration of the copper ions remaining in the reaction liquid after the formation of the copper hydride fine particles is completed. Calculated by the difference. The copper composite particles can be produced, for example, by a wet reduction method including the following steps (i) to (iii): (1) a step of forming copper hydride fine particles in the reaction system (R), and (11) a reaction system (R) a step in which metal copper particles are introduced to cause the copper hydride fine particles to adhere to the surface of the metal copper particles to form "copper composite particles" (iii) a step of separating the "copper composite particles" from the reaction system (R). Heating the copper composite particles 'converts copper hydride fine particles into metal copper fine particles, whereby "composite metal steel particles" can be obtained. In the present specification, the term "reaction system (R) J refers to a system for generating copper nitride fine particles. The reaction system (foot) includes not only (01) unreacted addition of a reducing agent to a water-soluble copper compound solution. The system of the state also includes 160003.doc -20· 201232563 (β) a system in which the formation of hydrogenated steel fine particles is being performed by the reaction of the water-soluble copper compound and the reducing agent, and the formation reaction of the (γ) copper hydride fine particles is completed. The system in which the hydrogenated copper particles are formed in a dispersed state. The term "reaction system (R)" means that a water-soluble copper compound, copper ions, various anions, and copper chloride particles are present in a solvent such as water. Various ions, other residues, reducing agents or decomposition products thereof remaining in the solvent after the formation. Therefore, the dispersion liquid obtained by separating the generated copper hydride fine particles from the solution and dispersing them in a new dispersion medium does not conform to the reaction system (R) in the present specification. Hereinafter, the steps (1) to (out) for producing copper composite particles and the method for producing composite metal copper particles from the copper composite particles will be described. (1) Formation of copper hydride fine particles The reaction system (R) can be formed by adding at least a reducing agent to a water-soluble copper compound solution formed by adding a water-soluble steel compound to a solvent. As the water-soluble copper compound forming the reaction system (R), a copper salt is preferred. As the copper salt, a copper (11) ion and a mineral acid or a salt of a tickic acid are more preferably used. As the slow acid forming the copper salt, it is preferred that the carbon atom having a plurality of carbon atoms in the internal carbon number is preferably a formic acid, acetic acid or propionic acid. As the water-soluble copper compound, copper sulfate, copper lithate, copper formate, copper acetate, vaporized copper, evolved copper, moth copper, and the like are particularly preferably used. Further, the solvent of the water-soluble steel compound solution is not particularly limited as long as it is a water-soluble copper compound. As the solvent of the water-soluble steel compound solution, water is particularly preferably used. (4) Concentration phase of water-soluble copper compound contained in the solution of the copper compound 160003.doc 201232563 For solution _ mass%, difficult state ~ 3Gf4%. If the concentration of the water-soluble copper compound is less than (M mass% ', the amount of water in the solution is too large, and the production efficiency of the copper hydride fine particles is lowered. On the other hand, if the concentration of the water-soluble copper compound exceeds 30% by mass, the copper hydride fine particles are present. The yield is decreased. 2 The addition of a reducing agent to the water-soluble copper compound solution preferably adjusts the p Η value to a specific value or less. As a water-soluble copper compound solution, the pH value adjusting agent can be used as a surface-modified copper. In the description of the production steps of the particles, the acid components exemplified as the ruthenium adjusting agent for the copper dispersion are the same. Specifically, for example, citric acid, citric acid, cis-succinic acid, malonic acid, acetic acid, or C can be used. Acid, sulfuric acid, nitric acid, hydrochloric acid, etc.. As a 11-value adjusting agent for a water-soluble copper compound solution, especially formic acid, it is preferable to use formic acid because it contains a reducing brewing base (-CHO). Therefore, it is possible to remain on the surface of the particles and suppress oxidation of the copper particles. The pH of the water-soluble copper compound solution is preferably set to 3. The pH of the water-soluble copper compound solution is set to 3 or less, the production efficiency of copper hydride fine particles can be improved. It is presumed that the reduction can be carried out in a state where copper ions and hydrogen ions are mixed in a solution. If the pH of the water-soluble copper compound solution exceeds 3, it is easy. The metal copper microparticles are formed, and the formation ratio of the copper chloride microparticles is lowered. From the viewpoint of increasing the formation ratio of the copper hydride microparticles, it is more preferable to set the value of the water-soluble steel compound solution to 0.5 to 2. At least one selected from the group consisting of metal hydride 'hydrogenation reducing agent, hypophosphite, sodium hypophosphite, and the like, and at least one of amine boron, 22- 160003.doc 201232563, and formic acid, may be used. Examples of the gold hydride compound include hydrogenated hydrazine, potassium hydride, and hydrogen (IV). Examples of the hydrogenated reduction hydrazine include chlorination (tetra), hydrogenation, and a hydrogenation axis. Among these, it can be preferably used. Sub-subtree, sub-sodium complex. Further, as described above, formic acid can also be used as a valence adjusting agent, so when formic acid is added to the dispersion medium, it functions as a reducing agent. The reducing agent which functions as a ρί1 value adjusting agent is preferably added to the water-soluble copper compound solution with respect to the copper ion in the solution by an equivalent amount of 丨.2~Η). If the amount of the reducing agent is less than 12 times the amount of the copper ion, it is difficult to obtain a sufficient reduction. On the other hand, if the amount of the reduction is more than 1 G times the amount of the copper ion added When the number of the copper nitride fine particles, the content of impurities such as sodium, boron, phosphorus, etc. is increased, the reaction system and the system (R) may be dissolved in a reducing agent solution containing a solvent such as a reducing agent and water. The copper compound solution is mixed and formed. Further, the reaction system (R) can be formed by adding a reducing agent in a solid state to a solution of a water-soluble copper compound. In the reaction system (8) formed in this manner, copper ions are acidic. Under the conditions, it is reduced by a reducing agent to form copper hydride microparticles ' and the particles are grown. (H) Formation of copper composite particles Metal copper particles are introduced into the reaction system (R) formed in the above (1), and hydrogenated copper fine particles are adhered to the surface of the metal copper particles to form "steel composite particles". First, metal copper particles are put into a reaction system (foot). Further, the shape and particle diameter of the metallic copper particles are as described above. 160003.doc • 23- 201232563 Metal steel particles are preferably added to the reverse (R) of the stage in which copper ions are present, or in a solution of a water-soluble steel compound. The core... The copper ion reduction reaction can be carried out in the environment in which the metal steel particles and the copper hydride fine particles coexist in the reaction system (8) in which the steel ions are present. Therefore, the shape of the metal copper particles and the chlorinated steel particles can be combined. The presence or absence of copper ions in the reaction system (8) can be determined by the concentration of the copper ion electrode or the concentration of copper ions in the visible light absorption spectrum. Further, the presence or absence of copper ions can be confirmed by measurement of the oxidation reduction potential of the aqueous solution. Namely, the metal copper particles are preferably added to the reaction system (R) in which the copper hydride fine particles are being formed. Alternatively, it is preferred to add a metal copper particle to the water-soluble copper compound solution before the addition of the reducing agent, and then add a reducing agent to form a reaction system (R). It is preferred to add metal steel particles to the reaction system (R) which is generating hydrogenated steel fine particles. Further, the reaction system (11) to which metal copper particles are added is not limited to the above state. For example, the reaction system (r) in which the amount of copper ions or the amount of reduction in the reaction system (R) is reduced by the reduction reaction, and the growth of the copper hydride fine particles after the formation or formation of the copper hydride fine particles is stopped may be stopped. The addition of metallic copper particles, that is, the reaction system (R) in which the metal copper particles can be supplied to the copper hydride microparticles, or the reaction system (R) which is generating the copper hydride microparticles can be put into the hydrogen hydride microparticles. In the reaction system (R). By adding metallic copper particles to the reaction system (R), the copper-copper particles can be attached to the surface of the metal copper, and 160003.doc -24 * 201232563 "copper composite particles" can be formed in the reaction system (R). The amount of copper ions contained in the reaction system (8) to which the metal copper particles are added is preferably from 1 to 100% by mass, based on the amount of copper ions of the water-soluble copper compound solution before the addition of the reducing agent. More preferably 5 to 100 mass. /. . Further, the copper in the water-soluble copper compound solution is ionized. The temperature of the reaction system (R) is preferably. Hirose, τ, Ping and the residence 60 C U. By setting the temperature of the reaction system (R) to 60 ° C or lower, ότ* female nitlc: also inhibits the decomposition of the copper hydride microparticles in the reaction system (R). The metal copper particles are preferably added in a state where the oxidation-reduction potential of the reaction system (8) is in the range of 100 300 mV aHE, more preferably in the range of 1 〇〇 to 22 〇 mV SHE. "Survey" refers to a standard hydrogen electrode. Further, "claw 乂 she" is an oxidation-reduction potential measured without using a quasi-hydrogen electrode as a reference. In this paper, the measured value of the reduction potential in the Moon is determined by using a standard hydrogen electrode as a reference. (.iii) Separation of copper composite particles The copper composite particles formed in the reaction system (R) are separated from the reaction system (R). The method of separating the copper composite particles from the reaction system (R) is not particularly limited. As a method of separating the copper composite particles from the reaction system (R), for example, powdery copper composite particles can be separated from the reaction system by centrifugal separation or filtration. After the copper composite particles are separated from the reaction system, the cleaning impurities adhering to the surface of the particles are removed by washing with a cleaning liquid such as water. By subjecting the separated copper composite particles to purification treatment in the above-described manner, the powdery copper composite particles having copper hydride fine particles adhered to the surface of the metal copper particles can be obtained by purifying the separated copper composite particles by the above-mentioned method 160003.doc *25-201232563. Further, the solvent of the reaction system (11) may be replaced before the separation of the copper composite particles, and impurities such as decomposition products of the reducing agent may be removed together with the solvent. The copper composite particles separated from the reaction system (R) are subjected to heat treatment to convert the copper hydride fine particles into metal copper fine particles, whereby composite metal copper particles having a surface oxygen concentration ratio of O/Cu of 0.5 or less can be obtained. The composite metal copper particles can form a conductive path reliably by the metal copper particles present between the metal copper particles, thereby reducing the volume resistivity when the conductive film is formed. Further, as described above, by converting the copper hydride fine particles into the metal copper fine particles, it is difficult to cause the metal copper fine particles to be peeled off from the metallic copper particles. Therefore, by dispersing the metallic copper fine particles in the conductive paste, a conductive paste in which the viscosity of the conductive paste is suppressed from rising can be obtained. The heat treatment of the copper composite particles is preferably carried out at a temperature of 6 Torr to 12 Torr. If the heating temperature exceeds 120. (:, the metal steel fine particles are easily fused to each other, and the volume resistivity when the conductive film is formed becomes high. On the other hand, if the heating temperature is less than 60, the time required for the heat treatment becomes long' It is not preferable in terms of manufacturing cost. The heat treatment of the copper composite particles is more preferably carried out at 6 Torr to 1 Torr, and more preferably at 60 to 90. Further, the heat treatment is carried out. The residual moisture content of the composite metal copper particles is preferably 3% by mass or less, more preferably 5% by mass or less. The heat treatment of the copper composite particles is preferably carried out under a reduced pressure of _i〇U ^ under a relative pressure. If the heating is performed under a pressure greater than I60003.doc -26 - 201232563, the time required for drying becomes longer, which is not good in terms of manufacturing cost. Another aspect is that if the pressure during heat treatment is not satisfactory For example, the removal and drying of a multi-audio agent such as water requires the use of a large device, which in turn makes the manufacturing cost high. The surface oxygen concentration ratio o/cu of the "composite metal copper particles" can be adjusted by the steps (1) to (iv) above. Water soluble copper compound The oxidation-reduction potential of the reaction system (8), the temperature of the reaction system (R), or the like, or the partial pressure of oxygen during the heat treatment of the copper composite particles, etc., and adjusted to the required range: obtained by the above steps. The average-secondary particle diameter of the metallic copper particles of the composite metallic copper particles is preferably 〇.3 to 2 〇 (4). Further, the average particle diameter of the particles of the metallic copper fine particles attached to the surface of the metallic copper particles is preferably 20 〜 400 nm (composite metal copper particles (A4)) If the average particle diameter of the metal copper particles of the "composite metal copper particles" is less than (3) Km, sufficient flow characteristics cannot be obtained when the conductive paste is formed. On the other hand, when the average particle diameter of the metal copper particles exceeds 2 pm, it is difficult to form fine wiring by the obtained conductive paste. The average particle diameter of the metal copper particles in the "composite metal steel particles" is preferably 1 to 1 〇μηι. Similarly to the copper hydride microparticles in the copper composite particles, the copper microparticles of the "composite metal copper particles" are mainly in the form of secondary particles in which primary particles of about nm are aggregated. The particle shape of the copper microparticles can be The spherical shape may be a plate shape. If the average particle diameter of the agglomerated particles of the copper microparticles is less than 2 nm, the copper microparticles are likely to be fused and grown, and cracks accompanying volume shrinkage occur when the conductive crucible is formed. In the case of a bad situation. Another 160003.doc -27· 201232563 Aspects: If the average particle size of the agglomerated particles of copper particles exceeds _, the product is not sufficient, and it is difficult to generate the phenomenon of the table (4), so that dense conductive is formed. The film becomes difficult. The average particle diameter of the agglomerated particles of the copper microparticles is more preferably 30 to 3 〇 0 nm, more preferably 5 〇 to 2 〇〇 nm. More preferably, the average particle diameter of the metal steel particles is from the side. The Feret's (FeM) diameter of 100 metal copper particles randomly selected from the image of (4) was measured and averaged. In other words, the average particle diameter of the copper microparticles is calculated by averaging the measured values of the (10) hydrogenated copper microparticles randomly selected from the image or the SEM image. As the other copper particles (A)', hydrogenated copper microparticles (A3) and hydrogenated copper microparticles (A3) having an average particle diameter of aggregated particles of 10 nm to i μm may be preferably used, for example, "Kelly composite particles" It is formed by the solution of the water-soluble copper compound used in the manufacturing process. Specifically, it can be obtained, for example, by a pH of 3 or less and an oxidation-reduction potential of 1 〇〇 to 3 〇〇 mV SHE, preferably 1 〇〇 to 220 mV 81 ^. It is obtained by adding a reducing agent to the solution of the water-soluble copper compound. As the reducing agent, the same as the reducing agent used in the production step of the "copper composite particles" can be used. Further, the average particle diameter of the agglomerated particles of the hydrogenated fine particles can be adjusted by controlling the reaction temperature or the reaction time at the time of the reduction reaction or by adding a dispersing agent. As the copper particles (A)', the metal steel fine particles (A5) obtained by heat-treating the hydrogenated steel fine particles (A3) are preferably used. Namely, as the copper particles (A)', the average particle diameter of the aggregated particles is preferably 1 〇 nm to i ^ claws. 160003.doc • 28 · 201232563 Metallic copper microparticles (A5). Further, the method of obtaining the copper particles (A) having a surface oxygen concentration ratio of O/Cu of 0.5 or less is not limited to the method using wet reduction as described above. As a method of obtaining copper particles having a surface oxygen concentration ratio of 〇/Cu of 0.5 or less, for example, an oxide film formed on the surface of the copper powder may be washed with an acid such as hydrochloric acid, sulfuric acid or nitric acid to dissolve and remove the oxide film. Further, 'as a method for obtaining copper particles (A) having a surface oxygen concentration ratio of O/Cu of 0.5 or less', in addition to the above method, for example, by introducing a reducing gas into the surface of the copper particles, copper may be added to the gas. The particles are subjected to heat treatment or the like. Specifically, for example, first, a reducing gas such as hydrogen gas, carbon monoxide, natural gas, or ammonia decomposition gas is introduced, or the inside is made a vacuum, thereby reducing the inside of the reduction furnace into a reducing atmosphere. Then, copper particles f are added to the reduction furnace, and the steel particles are subjected to a reduction treatment in a temperature range of 120 to 400 C, whereby the oxide on the surface of the particles can be removed. Also as an alternative method of using a reducing gas, it can also be inert

The surface of the copper particles is subjected to a reduction treatment by a plasma treatment method.

160003.doc > The solid dielectric body 6 on the lower electrode 3 is disposed to thereby reduce the surface of the copper particles. -29· 201232563 In addition, as another method of adjusting the surface oxygen concentration of copper particles, a two-roll mill can be used by mixing copper particles, the following chelating agent (B), and thermosetting resin (c). Or the bead mill performs the mixing of the mixture (paste) as a whole. The chelating agent (B) is a compound which can be coordinated to a copper ion to form a complex with copper ions by a reaction represented by the following formula (1). [Equation 1] (1) wherein the symbols in the formula represent the following meanings. Μ : Copper ion Ζ: chelating agent (Β) ΜΖ : wrong salt X: a copper-bonded chelating agent (Β) number chelating agent (Β) is at 25t, ionic strength (M mol / L, When X = 1 of the above formula 〇), the stability constant i 〇 gKcu with copper ions is 5 to 15 compounds. The stability constant logKcu is an index indicating the strength of the bonding force between the integrator and the metal. The stability constant lGgKeu can be obtained as a logarithmic value of the equilibrium constant KCui of the non-reactive formula of the above formula (1). Specifically, KCu can be obtained by the following formula (2). [Number 2] K - ΜΖχ] [Μ]. [Ζ] Χ 160003.doc -30- 201232563 (wherein in the above formula (2), □ indicates the concentration of each component in parentheses). The "stability constant l〇gKCu" in the present invention is described as a specific numerical value of various compounds, for example, in the chemical handbook (Maruzen) and StabiHty Constants of Metal-Ion Complexes (PERGAMON PRESS).

Journal of Chemical Engineering Data (ACS Publications) and other literature. We believe that at least a part of the copper ions generated in the paste and the chelating agent (B) can be formed by blending a compound having a stability constant of 1 〇gKcu of 5 〇gKcu with copper ions as a chelating agent (B). Compound. Therefore, it is possible to reduce the formation of copper oxide in the paste by reducing the amount of water in the large rolling or the copper ions which are reacted with oxygen contained in, for example, ruthenium 2, HW or the like. Further, since the chelating agent (B) is hardly dissociated from the copper ions, the state of the complex compound can be maintained for a long period of time even when placed in a high humidity environment. Therefore, it is possible to form a conductive paste which can form a conductive film which is difficult to form an oxide film and which suppresses an increase in volume resistivity. If the stability constant l〇gKcu of the chelating agent (B) is less than 5, the bonding strength to copper ions is insufficient, and thus the amount of copper ions which react with moisture or oxygen in the atmosphere cannot be sufficiently reduced, and it is difficult to Inhibit the formation of copper oxide. Further, when the stability constant 丨 ogKcu of the condensing agent (B) exceeds 丨5, the bonding force of the chelating agent (b) to the copper ions is too strong, and the contact between the copper particles is inhibited to lower the conductivity. It is presumed that the chelating agent (B) acts not only on the copper ions present on the surface of the copper particles but also on the copper (metal copper). The stability constant logKCu is preferably 7 to 14. a as the integrator (B), it is preferred to use a functional group (4) containing a gas atom to contain an atom having an isolated electron pair other than a nitrogen atom. I60003.doc • 31 - 201232563 (8) is disposed in the ortho position of the aromatic ring. And the "nitrogen atom" of the uterine energy group (4) and the functional group (b) have an atomic group of atoms of an isolated electron pair, which are bonded by two or three shoulders. By compounding the ρ having the above molecular structure as the sound aggregating agent (8), a complex which is stable with copper ions can be formed. σ is an atom between the nitrogen atom of the plant of the uterine energy (4) and the atom of the functional group (8) and having an isolated electron pair, and examples thereof include a carbon atom. As the chelating agent (8), it is suitable to use a nitrogen atom of the sulphur (a) and a functional group which is bonded by two or three carbon atoms. The atomic group of the pair of electrons is a functional group (b) having an atom other than the nitrogen atom of the isolated electron pair, and a hydroxyl group or a carboxyl group is preferable. The acid device as a chelating agent (8)' can be selected, for example, from a water-saving month. At least one of W-o-aminobenzene and salicylic acid: 2: (4) In the case of a sound-mixing agent (8), a complex with copper ions can be formed by the following [?].

Cc

(I) In the conductive paste > X parts, which is more than the content of the inflammatory σ W (B) relative to the copper particles (A) l 〇〇 , 则 别 别 别 1 1 1 1 1 1 若 若 若 若 若 若 若When the content is less than 0.01 protons, when the conductive film is formed, the effect of suppressing the increase in the volume resistance of 160003.doc •32-201232563 cannot be sufficiently obtained. On the other hand, when the content of the chelating agent (B) exceeds t by mass, there is a possibility that the contact between the copper particles is inhibited and the conductivity is lowered. The thermosetting resin (C) can be used as a thermosetting resin (C), as long as it can be sufficiently cured at a normal curing temperature, and a known thermosetting resin used as a resin binder of a conductive paste can be used. For example, a phenol resin, a diallyl phthalate resin, an unsaturated alkyd resin, an epoxy resin, an amine ester resin, a bis-methylene iodide tri-n-resin, and a polyoxyn resin can be preferably used. Acrylic resin, melamine resin, urea resin, and the like. Among these, phenol resins are particularly preferably used. The thermosetting resin (C) can be added within a range in which the resin component after curing does not inhibit conductivity. The content of the thermosetting resin in the conductive paste can be appropriately selected in accordance with the ratio of the volume of the copper particles to the void volume existing between the copper particles. The content of the thermosetting resin (C) in the conductive paste is usually 5 to 5 parts by mass, more preferably 5 to 2 parts by mass, per 100 parts by mass of the copper particles (A) powder. When the content of the thermosetting resin is less than 5 parts by mass, it is difficult to obtain sufficient flow characteristics as a paste. On the other hand, when the content of the thermosetting resin exceeds 50 parts by mass, the contact between the copper particles is hindered by the resin component after the curing, and the volume resistivity of the conductor is increased. In addition to the components (A) to (C) above, the conductive paste of the present invention may contain a solvent or various additives as needed within a range not impairing the effects of the present invention. 160003.doc •33· 201232563 (Leveling agent, even Other ingredients such as mixture, viscosity modifier, antioxidant, etc.). In particular, in order to obtain a paste having moderate fluidity, it is preferred to contain a solvent capable of dissolving the thermosetting resin (c). As the solvent contained in the conductive paste, for example, cyclohexanone, cyclohexanol, terpineol, ethylene glycol, ethylene glycol monoethyl sulphate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether can be preferably used. Acetate's ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene: alcohol monoethyl ether, triethylene glycol monotop, diethylene glycol monoethyl ether, ethyl S, g, monoethyl ether, monobutyl ether Acetate. As a paste for printing, the amount of the solvent contained in the conductive paste is preferably 1 to 3% by mass based on the steel particles from the viewpoint of an appropriate viscosity range. The conductive paste can be obtained by mixing the components of the above (A) to m owing a, v fc a Μ) (l) with other components such as a solvent. When the components of the above (A) and (C) are used, they can be heated while the surface of the thermosetting resin is hardened or the solvent is volatilized. The temperature at the time of mixing and stirring is preferably set to 1 〇 to fu. More preferably set to 2〇~ Fu. By setting the temperature of HTC or higher when the conductive paste is formed, the viscosity of the paste can be sufficiently lowered, and the stirring can be smoothly and sufficiently performed. Further, the hydrogenated steel formed on the surface of the copper particles can be made into a steel atom. On the other hand, if the conductive paste is formed, the temperature exceeds 120. (:, there is a hardening of the thermosetting resin (C) in the paste or a fusion of the particles. Further, in order to prevent oxidation of the copper particles during mixing, it is preferably a container substituted with an inert gas. The present invention is described above. The present invention described above, the conductive paste of the moon is difficult to oxidize even in the atmosphere, and the volumetric electricity caused by the formation of copper oxide can be formed as compared with the previous conductive paste. 34-201232563 Conductive film in which the increase in resistivity is suppressed. The conductive film substrate 1 of the present invention can be produced, for example, in the following manner, that is, as shown in Fig. 2, the conductive paste is applied to the surface of the substrate. A conductive paste film is formed. Then, after removing volatile components such as a solvent, the thermosetting resin (C) is cured to form a lightning conductive to wind conductive film 12 on the substrate 1!, whereby the present invention can be manufactured. The conductive film substrate 10 can be used as the substrate U': a glass substrate, a plastic material, a fiber-reinforced composite material, a ceramic substrate, etc. Examples of the fiber-reinforced composite material include a glass fiber-reinforced resin substrate and the like. For example, a film-form substrate such as a polyimide film or a polyester film can be used. In particular, a glass fiber reinforced resin used in a printed wiring board, an oxy resin substrate, or the like can be preferably used. Cloth method jade scare. 沄 can be enumerated · screen printing method, roll coating method, air knife coating method, knife coating method base, w release coating method, gravure coating method, die coating method, swash plate A well-known method, such as a coating method, is used, and it is effective to form the surface and the unevenness on the side surface of the substrate 11 to obtain a smoothed wiring shape which is suppressed, and a screen printing method is suitably used. The hardening of the thermosetting resin (C) can be carried out by maintaining the substrate 11 on which the conductive paste film is formed at a temperature of from 1 to 0. If the curing temperature is less than 〇c ', it is difficult to make the thermosetting resin. On the other hand, if the hardening temperature exceeds 30 (Tr, it is known that the substrate 11 is deformed when a substrate 11 formed of a thermoplastic resin such as a plastic film is used.作为. As a hardening method, warm air heating and heat can be cited. In addition, 160003.doc. •35· 201232563 It is also possible to carry out the formation of a nitrogen ring conductive film having a small amount of oxygen in the atmosphere. The volume resistivity of the conductive film 12 is preferably electric. When the volume resistivity of the film i2 exceeds 10% & i2cm, there is a possibility that sufficient conductivity can be obtained as a tantalum for an electronic device. To ensure stable conductivity, the electric wire can be easily maintained and the wire shape can be maintained. In view of the above, the thickness of the conductive film 12 on the substrate U is preferably 〜200 μΐΏ, more preferably 5 to 100 μηι. The conductive film substrate of the present invention is formed by the above-described conductive paste of the present invention. The conductive film' can be made to be difficult to form an oxide film caused by copper oxide. Compared with the previous material (four), the volume resistivity is low, and the volume resistivity can be suppressed even if it is used for a long period of time in an environment of humidity. The rising conductive film substrate. In the above, the conductive film substrate of the present invention has been described as an example, and the composition can be appropriately changed as needed within the limits of the gist of the present invention. Further, in the method for producing a conductive film substrate of the present invention, the order of formation of the respective portions or the like may be appropriately changed within the limits of the production of the conductive film substrate. Field [Examples] Hereinafter, the present invention will be described in further detail by way of examples. First, copper particles (surface-modified copper particles) which are subjected to reduction treatment on steel particles are obtained. Namely, a formic acid 3 〇 and a 5 〇 wt% aqueous solution of hypophosphorous acid 9·〇 g were placed in a glass beaker, and the beaker was placed in a water bath and kept at 40 c. Copper particles (made by Mitsui Mining Co., Ltd., 160003.doc -36-201232563, manufactured under the trade name: "1400YP", average primary particle size: 7 μηι) 5.0 g, and stirred for 30 minutes were obtained. liquid". The pellet was centrifuged at a speed of 3 000 rpm for 1 minute using a centrifugal separator, and the precipitate was recovered from the obtained "copper dispersion". The precipitate was dispersed in distilled water 3 〇 g, and the aggregate was again precipitated by centrifugation to separate the precipitate. The resulting precipitate was subjected to a reduced pressure of _3 5 kPa at 8 Torr. (: heating for 60 minutes, volatilizing the residual water to gradually remove it - obtaining copper particles (A-1) whose surface is surface-modified. By X-ray photoelectron spectroscopy apparatus (manufactured by ULVAC-PHI, trade name: "ESCA5500 ") The obtained copper particles (A_1) were subjected to measurement of surface oxygen concentration [atomic %] and surface copper concentration [atomic %] under the following conditions.

• Analysis area: 800 mm2 < D • Pass Energy: 93.9 eV • Energy Step: 0_8 eV/step The surface oxygen concentration of the buckle is divided by the surface copper concentration to calculate the surface oxygen concentration ratio O/ Cu, as a result, the surface oxygen concentration ratio 〇/16 of the copper particles (eight 丨) was found to be 〇.16. In addition, the amount of oxygen in the copper particles (A-1) was measured by an oxygen meter (manufactured by LECO Co., Ltd.), and the product name was "ROH-, and the amount of oxygen was 460 ppm." 1) To a mixed phenol resin (manufactured by Qun Rong Chemical Co., Ltd.)

Medium-sized copper particles (A-1) 5.0 g, and trade name: "Resitop butane acetate 0.43 g of resin 5 g' was dissolved. The resin solution was mixed in a mortar to obtain conductive 160003. .doc -37- 201232563 Paste 1 ο The conductive paste 1 is applied to a glass substrate by a screen printing method to form a strip shape having a width of 1 mm and a thickness of 20 μm, and is heated at 15 ° C. The phenol resin was hardened to form a conductive film substrate including the conductive film 1 (Example 2). The conductive paste 2 was obtained in the same manner as in Example 1 except that the amount of the salicylic acid was changed to 0.0125 g. 3) A conductive paste 3 was obtained in the same manner as in Example 1 except that 0.025 g of salicylaldehyde oxime was used instead of 5 g of salicyl hydroxamate ruthenium in the resin/gluten solution. (Example 4) A conductive paste 4 was obtained in the same manner. Example 5) Example except that the amount of salicylaldoxime was changed to 〇〇125 g

§ In addition to (Example 6) G was added to the resin, except that 0.0125 g of salicylic acid was used instead of the salicylhydroxamic acid ruthenium 5 solution, and the conductive paste 6 (Comparative Example 1) g was obtained in the same manner as in Example ,. The conductive paste 7 was obtained in the same manner as in Example 5 except that barium salicylate was added to the resin solution. (Comparative Example 2) 160003.doc •38-201232563 A conductive paste 8 was obtained in the same manner as in Example 1 except that 0.015 g of salicylate was used instead of 0.005 g of salicyl hydroxamic acid in the resin solution. (Comparative Example 3) A conductive paste 9 was obtained in the same manner as in Example 1 except that 0.0125 g of rosin acid was added instead of 0.005 g of salicyl hydroxamic acid in the resin solution. The conductive film substrates 2 to 6 (Examples 2 to 6) were obtained in the same manner as in Example 1 except that the conductive pastes 2 to 6 were applied to the glass substrate instead of the conductive paste 1 to form the conductive films 2 to 6. Further, the conductive film substrates 7 to 9 (Comparative Examples 1 to 3) were obtained in the same manner as in Example 1 except that the conductive pastes 7 to 9 were applied to the glass substrate instead of the conductive paste 1 to form the conductive films 7 to 9. (Resistance of Conductor Wiring) The resistance values of the obtained conductive films 1 to 9 were measured by a resistance meter (manufactured by Keithley Co., Ltd., trade name: "Milliohm HiTester"). (Durability Test) Thereafter, the conductive film substrates 丨 to 9 were subjected to a durability test in a high-temperature and high-humidity environment. In other words, the conductive film substrates 1 to 9 were held in a bath having a temperature of about 7 Å < t and 85% RH for 60 hours, and the electric resistance values of the conductive films 1 to 9 were measured. The volume resistivity of the initial volume resistivity and the volume resistivity after the durability test in the high-temperature and high-humidity environment, and the compound used in the chelating agent (8) 'the compound used in the chelating agent (B) at 251, the ionic strength 0.1 The addition of the stability constant logKCu to the steel ion at m〇l/L and the chelating agent (B) are not shown in Table i. In addition, in the table [integration, the amount of the integrator (8) is added in an amount of 1 part by mass relative to the copper particles (mass parts). Table 160003.doc • 39-201232563 shows 0 [Table 1] Conductive paste Mixture 体积 Volume resistivity (initial) [μΩοηι] Rate of change of volume resistivity (after durability test) Γ%1 Compound stability constant l〇gKcu Addition amount [parts by mass] Example 1 1 Salicyl hydroxy samarium 13 0.1 27 4 Example 2 2 Salicyl Hydroxamic Acid 13 0.25 27 6 Example 3 3 Salicylaldoxime 13 0.5 23 6 Example 4 4 Salicylaldoxime 13 0.25 24 7 Example 5 5 o-Aminophenol 7.8 0.25 28 4 Example 6 6 Acid 11 0.25 36 4 Comparative Example 1 7 - - - 36 9 Comparative Example 2 8 Poplar Brewing 16 0.25 43 12 Comparative Example 3 9 Rosin Acid 2 0.25 35 10 It is clear from Table 1 that it is formulated with copper ions. The stability constant logKCu is a conductive paste of 5 to 15 chelating agent (B) to form a conductive film. The conductive film substrates 1 to 6 have a low volume resistivity and are placed at a high temperature and high environment. The rate of change in resistivity is also suppressed to a low level. On the other hand, in the conductive paste substrate formed by using the unmixed integrator (B) to the conductive film substrate 7 on which the conductive film 7 is formed (Comparative Example 1), the volume resistivity after being placed at a high temperature and high temperature The rate of change is 9% higher, and the long-term car is poor. In addition, the stability constant with copper ions is used in the formulation. The conductive paste of the chelating agent (8) is known as And the surface stability R constant 1 constant (the rosin acid) bamboo is the chelating agent (B) conductive paste 9 and the addition of the electric butterfly 9 to form the conductive film 8 to 9 with the conductive film substrate In 8~9, the initial body φ has a relatively low resistivity, and the volume resistivity after immersion in a high-temperature and high-humidity environment is also increased to 10~12%, and the durability is poor. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a schematic configuration example of wet reduction treatment of steel particles. Apparatus used in the implementation Fig. 2 shows a conductive film base of Fig. 0 of the present invention. Material - Example cross-section [Main component symbol description] 1 Reaction tank 2 Upper electrode 3 Lower electrode 4 Processed material 5 AC power supply 6 Solid dielectric body 7 Gas inlet port 8 Gas discharge port 9 Insulator 10 With conductive film substrate 1 1 Substrate 1:2 Conductive film 160003.doc -41.

Claims (1)

201232563 VII. Patent application scope: i•-type conductive paste, which is characterized by: copper particles (eight), which have a surface oxygen concentration ratio 〇/Cu of 〇5 or less by linear photoelectron spectroscopy; integrator (B) It is a compound containing 5 to 15 of a stability constant of copper ions and a thermosetting resin (C), which is contained at 25 ° C and an ionic strength G.lm. 2. The conductive paste of the request, wherein the copper particles (8) are surface-modified copper particles which have been subjected to reduction treatment in a dispersion medium having a pH of 3 or less. 3. The conductive paste of the request, wherein the copper particles (4) are composite metal copper particles, which are heated to include metal copper particles having an average-order particle size of 〇3 to 2 〇 (4), and agglomerating and adhering to the surface of the metal copper particles. The copper composite particles having a primary primary particle diameter of 1 to 20 legs of copper chloride fine particles are formed by converting the copper nitride fine particles into metallic copper fine particles. 4. The conductive paste of claim 2, wherein the use is selected from the group consisting of formic acid, citric acid, cis-butyl acid, malonic acid, acetic acid, propionic acid, sulfuric acid, tree, hydrochloric acid, and the like pH adjuster for the medium. 5. The conductive paste of claim 3, wherein the use is selected from the group consisting of formic acid, citric acid, maleic acid, malonic acid, acetic acid, propionic acid, sulfuric acid, and diaphoric acid' hydrochloric acid for forming A pH adjuster for the water-soluble copper compound solution of the above copper hydride fine particles. 6. If = item! The conductive paste according to any one of the fifth aspect, wherein the sound-activating agent (8) is disposed in the aromatic ring, and the functional group (b) containing an atom having an isolated electron pair other than the nitrogen atom is disposed in the aromatic ring. An ortho-group aromatic compound in which the above-mentioned nitrogen atom and the atom having the isolated electron pair of the I60003.doc 201232563 are bonded to each other by two or three atoms. 7. A conductive paste according to the item 6, wherein the functional group (b) having an atom having an isolated electron pair other than a nitrogen atom is a hydroxyl group or a carboxyl group. The above-mentioned nitrogen atom in the electroconductive paste of the item 6 or 7 is separated from the above-mentioned gas atom by an atom having an isolated electron pair of two or three carbon atoms. The conductive paste according to any one of claims 1 to 8, wherein the chelating agent is a compound selected from the group consisting of salicylic acid, salicylaldoxime, o-aminophenol, and salicylic acid. The conductive paste according to any one of claim 19, wherein the thermosetting resin (C) is selected from the group consisting of a phenol resin, a diallyl phthalate resin, an unsaturated alkyd resin, and an epoxy resin. At least one of an amine ester resin, a di-n-butylene diimide, a polyoxon resin, an acrylic resin, a melamine resin, and a urea resin. 11. The conductive paste according to any one of claims 1 to 10, wherein the amount of the above chelating agent (B) relative to the copper particles (A) is 〇 〇 i 〜 i parts by mass. The conductive paste according to any one of claims 1 to 11, wherein the amount of the thermosetting resin (c) is from 5 to 5 Å by mass relative to 100 parts by mass of the copper particles (A). 13. A conductive film substrate comprising a conductive film formed by hardening the conductive paste according to any one of claims 1 to 12 on a substrate. 14. The conductive film substrate according to claim 13, wherein the conductive film has a volume resistivity of 1.0 x 1.0 4 cm or less. A method of producing a conductive film substrate, which comprises applying a conductive paste according to any one of claims 1 to 12 to a substrate, and then curing the conductive paste to form a conductive film. 160003.doc