WO2019131378A1

WO2019131378A1 - Copper powder manufacturing method, copper powder obtained using said manufacturing method, resin composition containing said copper powder, method for forming cured product of said resin composition, and said cured product

Info

Publication number: WO2019131378A1
Application number: PCT/JP2018/046782
Authority: WO
Inventors: 祐介縫田; 仁細川; 森田　博
Original assignee: 株式会社Adeka
Priority date: 2017-12-28
Filing date: 2018-12-19
Publication date: 2019-07-04
Also published as: JP7162617B2; TW201936297A; TWI801476B; JPWO2019131378A1

Abstract

The present invention provides: a method for manufacturing copper powder that can be used as a starting material for a coating, which, when cured, exhibits a low volume resistance value; said copper powder; a resin composition containing said copper powder; a method for forming a cured product; and a cured product. More specifically, the present invention provides: a copper powder manufacturing method comprising a step for subjecting copper particles to a reduction treatment in water using at least one substance selected from the group consisting of potassium borohydride, sodium borohydride, and lithium borohydride, a step for treating the copper particles with at least one substance selected from the group consisting of water, methanol and ethanol, a step for treating the copper particles with at least one substance selected from the group consisting of ether compounds and alcohol compounds, and a step for bringing the copper particles into contact with a compound represented by general formula (1); a copper powder obtained using said manufacturing method; a resin composition containing said copper powder; a method for forming a cured product of said resin composition; and a cured product. (1): (In the formula, X1 represents an alkenyl group or an alkyl group having 14-20 carbon atoms, X2 represents an alkyl group having 1-5 carbon atoms, M represents a titanium atom, a zirconium atom, or a hafnium atom, and a represents an integer of 1-3.)

Description

Method for producing copper powder, copper powder obtained by the method, resin composition containing the copper powder, method for forming a cured product of the resin composition, and the cured product

The present invention relates to a method for producing a copper powder, a copper powder obtained by the method, a resin composition containing the copper powder and a specific resin, a method for forming a cured product of the resin composition, and the resin composition It relates to the cured product. More specifically, the copper powder of the present invention can be used as a conductive material for various applications such as, for example, a conductive filler for conductive paste used for forming an electric circuit or forming an external electrode of a ceramic capacitor. It is a powder.

Copper powder is used as a conductive material for various applications, for example, a material for forming electrodes and circuits of electronic parts and the like, and various proposals have been made for a method of producing copper powder.
For example, in Patent Document 1, a copper oxide slurry obtained by adding a hydrazine and / or a hydrazine compound to a copper hydroxide slurry is reductively precipitated on a copper powder with the hydrazine and / or the hydrazine compound, and the copper powder is alcohol A process for producing copper powder is disclosed by treating with and then treating with a fatty acid-containing solution.

Further, Patent Document 2 discloses a suspension containing copper suboxide particles by adding an alkali hydroxide to a mixture of a copper salt aqueous solution having divalent copper ions and a reducing saccharide which is a first reducing agent. Obtaining the first step, adding a second reducing agent to the suspension containing the copper suboxide particles to obtain a suspension containing the copper suboxide particles and the copper ultrafine particles, the copper suboxide particles Discloses a method for producing a copper powder including a step 2-2 of forming copper fine particles by adding one or more reducing agents selected from a hydrazine compound or ascorbic acid to a suspension containing copper and ultrafine copper particles. . Further, paragraph [0058] of Patent Document 2 discloses that sodium borohydride is preferably used as the second reducing agent used in the step 2-1.

Japanese Patent Application Laid-Open No. 62-099406 International Publication No. 2014/104032

However, a copper powder produced using a conventionally known method for producing copper powder as disclosed in Patent Documents 1 and 2 is combined with a resin such as a phenol resin to obtain a resin composition, When a coating film is formed using this and cured, the volume resistance value of the coating film is high, and there is a problem that the conductivity becomes worse.

Therefore, an object of the present invention is to produce a cured resin having a low volume resistance of the coating film, containing at least one resin selected from the group consisting of copper powder and phenol resin, epoxy resin, polyester resin and acrylic resin. It is an object of the present invention to provide a resin composition that can be used and a method for producing a copper powder.

The present inventors have intensively studied to overcome the above problems, and as a result, they find that the above problems can be solved by using copper powder produced using a specific production method, and reach the present invention. It is
That is, the present invention comprises the first step of reducing copper particles in water using at least one borohydride compound selected from the group consisting of potassium borohydride, sodium borohydride and lithium borohydride; Treating the copper particles obtained in the first step with at least one selected from the group consisting of water, methanol and ethanol; a second step; treating the copper particles obtained in the second step with an ether compound And the third step of treating with at least one solvent selected from the group consisting of alcohol compounds; the copper particles obtained in the third step are brought into contact with a compound represented by the following general formula (1) A process of 4;

(Wherein, X ¹ represents an alkyl or alkenyl group having 14 to 20 carbon atoms, X ² represents an alkyl group having 1 to 5 carbon atoms, and M represents a titanium atom, a zirconium atom or a hafnium atom, a represents an integer of 1 to 3)

The present invention also includes (A) a copper powder obtained by the method for producing a copper powder according to the present invention [hereinafter, sometimes abbreviated as (A) component] and (B) phenolic resin, epoxy resin, polyester resin and acrylic It is a resin composition containing at least one resin selected from the group consisting of resins [hereinafter, may be abbreviated as component (B)].

The coating film formed by the resin composition containing the copper powder obtained by the present invention and at least one resin selected from the group consisting of phenol resin, epoxy resin, polyester resin and acrylic resin has a volume after curing Low resistance and excellent conductivity. And in this invention, the copper powder used in order to manufacture the said resin composition can be manufactured.

Hereinafter, the present invention will be described more specifically.
The method for producing a copper powder according to the present invention comprises the step of reducing copper particles in water using at least one borohydride compound selected from the group consisting of potassium borohydride, sodium borohydride and lithium borohydride A second step of treating the copper particles obtained in the first step with at least one selected from the group consisting of water, methanol and ethanol; a copper particle obtained in the second step; A third step of treating with at least one solvent selected from the group consisting of ether compounds and alcohol compounds; contacting the copper particles obtained in the third step with the compound represented by the above general formula (1) A fourth step of In addition, since a copper powder and a copper particle do not have a clear difference, in this specification, it describes as a copper particle in each process, and describes a final product as a copper powder. In all the processes of the present invention, water refers to tap water, ion-exchanged water, pure water, ultrapure water, RO water (reverse osmosis water) and the like. Among these, it is preferable to use pure water or ultrapure water.

Here, in the production method of the present invention, the first step uses copper particles in water using at least one compound selected from the group consisting of potassium borohydride, sodium borohydride and lithium borohydride. It is a step of reducing treatment.

The copper particles used in the first step are not particularly limited, and known general copper particles can be used. Further, the particle size of the copper particles is not particularly limited. For example, when used as a filler in a composition with a resin such as a phenol resin described later, copper particles having an average particle diameter of about several nm to several hundreds of μm can be used. It is preferred to use μm copper particles. The average particle diameter of the copper particles can be determined as a particle diameter (D ₅₀ ) that is 50% cumulative in the volume-based particle size distribution using a particle size distribution measuring device by laser light diffraction method.

When the copper particles used in the first step are oxidized by air oxidation or the like, it is desirable to treat the copper particles in advance using an aqueous solution in which an inorganic acid or an organic acid is dissolved. As the aqueous solution, for example, an aqueous solution in which sulfuric acid is dissolved is preferably used.

The reduction treatment method using at least one borohydride compound selected from the group consisting of potassium borohydride, sodium borohydride and lithium borohydride in water of copper particles, which is carried out in the first step, Well-known general methods can be used. For example, it is preferable to add copper particles to water beforehand to prepare a 10% by mass to 40% by mass copper slurry, and add at least one selected from the above-mentioned borohydride compounds to this copper slurry.

Further, the reaction temperature during the reduction treatment is preferably 10 ° C. to 80 ° C., more preferably 15 ° C. to 70 ° C., and particularly preferably 20 ° C. to 50 ° C. The reduction treatment time is preferably 10 minutes to 300 minutes, and particularly preferably 30 minutes to 90 minutes. The concentration of the borohydride compound used in the reduction treatment in the aqueous solution is preferably in the range of 0.1 mass% to 5 mass% with respect to the amount of copper particles, and is 0.5 mass% to 2 mass%. Is particularly preferred. Among the above-mentioned borohydride compounds, copper particles reduced with sodium borohydride are after curing of a coating film formed of a resin composition comprising a phenol resin, an epoxy resin, a polyester resin and an acrylic resin described later It is preferable because the volume resistance value of

The second step of the present invention is a step of treating (for example, washing) the copper particles obtained in the first step with at least one selected from the group consisting of water, methanol and ethanol. As a process liquid used for this process, it is preferable to use at least water, and it is particularly preferable to use only water. The processing method performed in the second step is not particularly limited, and can be processed by a known method in general. For example, when water is used as the treatment liquid, the copper particles obtained in the first step can be brought into contact with water at 5 ° C. to 90 ° C. or water vapor. In particular, contact with water at a temperature of 10.degree. C. to 50.degree. C. is desirable. As a contact method, it is preferable to adopt a method of immersing copper particles in water or a method of spraying water on copper particles.

The third step of the present invention is a step of treating the copper particles obtained in the second step with at least one solvent selected from the group consisting of an ether compound and an alcohol compound. Examples of the ether compound used in the third step include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, dioxane and the like. In addition, examples of the alcohol compound used in the third step include methanol, ethanol, propanol, 2-propanol, 1-butanol, isobutanol, 2-butanol, tert-butanol, pentanol, isopentanol, 2- Pentanol, neopentanol, tertiary pentanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol Methylcyclohexanol, methylcycloheptanol, benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, pro Lengucol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2- (N, N-dimethylamino) ethanol, 3 (N, N-dimethyl) Amino) propanol, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol (3-methyl-1 2,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl-1,3- (1,2-hexane) Hex ), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexane Dimethanol etc. are mentioned. Among these, when tetrahydrofuran, methanol, ethanol, propanol or 2-propanol is used, it comprises the copper powder obtained by the production method of the present invention, and the phenol resin, epoxy resin, polyester resin and acrylic resin described later. It is preferable because it can form a cured product having a low volume resistance value after curing of a coating film and excellent in conductivity, which is formed of a resin composition containing at least one resin selected from the group, and among them, a cured product having excellent conductivity can be produced. It is particularly preferred to use 2-propanol. However, a solvent different from the treatment liquid used in the second step is used.

The treatment (for example, washing) method to be performed in the third step is not particularly limited, and can be treated by a well-known general method. For example, the copper particles obtained in the second step are contacted with at least one solvent selected from the group consisting of an ether compound and an alcohol compound at 5 ° C. to 90 ° C., or these vapors to be present in the copper particles. It is sufficient if water can be removed. Among them, it is desirable to contact with at least one solvent selected from the group consisting of an ether compound and an alcohol compound at 10 ° C. to 50 ° C. As a contact method, it is preferable to adopt a method of immersing copper particles in these solvents, a method of spraying these solvents on copper particles, or the like.

The fourth step of the present invention is a step of bringing the copper particles obtained in the third step into contact with the compound represented by the above general formula (1). In the above general formula (1), X ¹ represents an alkyl group having 14 to 20 carbon atoms or an alkenyl group, X ² represents an alkyl group having 1 to 5 carbon atoms, and M represents a titanium atom, a zirconium atom or hafnium Represents an atom.
Examples of the alkyl group having 14 to 20 carbon atoms represented by X ¹ include hexadecyl group, heptadecyl group, octadecyl group, 2-heptylundecyl group, 16-methylheptadecyl group, 2- (4,4-dimethyl-) 2-pentyl) -5,7,7-trimethyloctyl group etc. can be mentioned. Further, examples of the alkenyl group having 14 to 20 carbon atoms include 9-octadecenyl group, 9-hexadecenyl group, 9,11,13-octadecatrienyl group, 8-heptadecenyl group and the like. Examples of the organic acid (X ¹ COOH) giving a portion of an alkyl group or an alkenyl group having 14 to 20 carbon atoms represented by X ¹ in the general formula (1) include, for example, palmitic acid, margaric acid, stearic acid, isostearine Acid, oleic acid, palmitoleic acid, eleostearic acid and the like can be mentioned. Among them, when the organic acid has 18 carbon atoms, that is, when X ¹ is an alkyl group having 17 carbon atoms or an alkenyl group, the resin composition containing the obtained copper powder was used. It is particularly preferable because a cured product having a low volume resistance after curing of the coating film and excellent conductivity can be produced.

Examples of the alkyl group having 1 to 5 carbon atoms represented by X ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, secondary butyl group, tertiary butyl group, isobutyl group, etc. Can be mentioned.
The alcohol compound (X ² OH) giving a part of the alkyl group having 1 to 5 carbon atoms represented by X ² in the general formula (1) is methanol, ethanol, n-propanol, 2-propanol, n-butanol And secondary butanol, tertiary butanol, isobutyl alcohol and the like. Among them, when X ² is an alkyl group having 3 or 4 carbon atoms, the volume resistance value after curing of the coating film formed of the obtained resin composition containing copper powder is low, and the conductivity is improved. It is particularly preferable because excellent cured products can be produced.

As preferable specific examples of the compound represented by the above general formula (1), for example, the following compound No. 1 to No. 108 can be mentioned. "IPr" represents an isopropyl group, and "nBu" represents an n-butyl group.

The compound represented by the said General formula (1) can be manufactured by a well-known general manufacturing method. For example, it can be obtained by reacting tetrakis alkoxide titanium, tetrakis alkoxide zirconium, tetrakis alkoxide hafnium or the like with a carboxylic acid having a corresponding structure at an arbitrary molar ratio. As commercially available products, for example, S-151 (the above compound No. 91), S-152, (the above compound No. 92), ZR-152 (the above compound No. 106) (made by Nippon Soda Co., Ltd.), etc. may be mentioned. it can.

The method for bringing the copper particles obtained in the third step into contact with the compound represented by the general formula (1) is not particularly limited. For example, the copper particles obtained in the third step And the compound represented by the above general formula (1) are directly combined (method I) or obtained in the third step in a solution in which the compound represented by the above general formula (1) is dissolved in a solvent Method of immersing copper particles (method II) or method of spraying a solution obtained by dissolving a compound represented by the above general formula (1) in a solvent onto copper particles obtained in the third step (method III) And immersing the copper particles obtained in the third step in at least one liquid selected from the group consisting of water, ether and alcohol, and then represented by the above general formula (1) in the liquid And the like (Method IV) of adding a compound. Among them, method II and method IV are preferable because copper powder of high productivity and stable quality can be produced, and copper powder produced using method IV is obtained. It is preferable because the volume resistance value after curing of the coating film formed from the resin composition of the copper powder and the phenol resin, epoxy resin, polyester resin and acrylic resin described later is particularly low.

The copper powder [component (A)] produced through the above-described first to fourth steps is selected from the group consisting of the copper powder, and the phenol resin, epoxy resin, polyester resin and acrylic resin described later. When a coating film is formed of a resin composition containing at least one resin [component (B)], the volume resistance value after curing of the coating compounded the copper powder obtained by another manufacturing method It has a specific feature that is lower than that of the above and has excellent conductivity. In order to investigate this reason, the present applicant attempted to specify the characteristics of copper powder by performing surface analysis and electrical property analysis on the copper powder obtained by the manufacturing method of the present invention described above. However, the difference with the copper powder obtained by the other manufacturing method as shown in the below-mentioned comparative example can not be found, and it is obtained by the manufacturing method of the present invention in the present powder analysis technology which the applicant has. It was not possible to define the properties, properties, shape, etc. of the copper powder itself, and it was not possible to find out the reason why only the copper powder obtained by the production method of the present invention has specific properties.

Next, the resin composition of the present invention will be described.
The resin composition of the present invention is selected from the group consisting of the copper powder [component (A)] produced through the above-mentioned first to fourth steps and a phenol resin, an epoxy resin, a polyester resin and an acrylic resin. It is characterized in that it contains at least one resin [component (B)].

The component (A) used in the resin composition of the present invention is a copper powder produced by the above-mentioned production method. The concentration of the component (A) in the resin composition of the present invention is not particularly limited and can be suitably changed according to the shape and thickness of the desired cured resin, but the conductivity is good. Therefore, the concentration of the component (A) in the resin composition of the present invention is preferably 20% by mass to 95% by mass, more preferably 50% by mass to 95% by mass, and 75% by mass to 95% by mass. % Is particularly preferred.

The component (B) used in the resin composition of the present invention is at least one resin selected from the group consisting of phenol resins, epoxy resins, polyester resins and acrylic resins.
Here, the phenol resin is not particularly limited, and a well-known general phenol resin can be used. For example, a novolac type phenol resin, a resol type phenol resin, or the like can be used. Among them, it is preferable to use a resol type phenolic resin. In addition, a commercial item can also be used, for example, powdery phenol resin (manufactured by Gunei Chemical Co., Ltd., trade name: Resin top, PGA-4528, PGA-2473, PGA-4704, PGA-4504, Sumitomo Bakelite Co., Ltd., Brand name: Sumilight resin PR-UFC-504, PR-EPN, PR-ACS-100, PR-ACS-150, PR-12687, PR-13355, PR-16382, PR-217, PR-310, PR- 311, PR-50064, PR-50099, PR-50102, PR-50252, PR-50395, PR-50590, PR-50590B, PR-50699, PR-50869, PR-51316, PR-51326B, PR-51350B, PR-5510, PR-51541 B, PR-5179 , PR-51820, PR-51939, PR-53153, PR-53364, PR-53497, PR-53724, PR-53769, PR-53804, PR-54364, PR-54458A, PR-5545, PR-55170, PR -8000, PR-FTZ-1, PR-FTZ-15), flaky phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name: SUMILITE RESIN PR-12686R, PR-13349, PR-50235A, PR-51363F, PR- 51494G, PR-51618G, PR-53194, PR-53195, PR-54869, PR-F-110, PR-F-143, PR-F-151F, PR-F-85G, PR-HF-3, PR- HF-6), liquid phenolic resin (Sumitomo Bakelite Product name: SUMILITE RESIN PR-50087, PR-50607B, PR-50702, PR-50781, PR-51138C, PR-51206, PR-51663, PR-51947A, PR-53123, PR-53338, PR- 53365, PR-53717, PR-54135, PR-54313, PR-54562, PR-55345, PR-940, PR-9400, PR-967), resol type liquid phenolic resin (manufactured by Gunei Chemical Co., Ltd., trade name: Product name: Sumi Top PL-4826, PL-2390, PL-4690, PL-3630, PL-4222, PL-4246, PL-2211, PL-3224, PL-4329, PL-5208, manufactured by Sumitomo Bakelite Co., Ltd. Light resin PR-50273, PR-512 06, PR-51781, PR-53056, PR-53311, PR-53416, PR-53570, PR-54387), fine-grained phenolic resin (manufactured by Air Water Co., Ltd., trade name: Bellpearl, R800, R700, R600, R200, R100, S830, S870, S890, S895, S290, S190), spherical spherical resin (manufactured by Gunei Chemical Co., Ltd., trade name: Marilyn GU-200, FM-010, FM-150, HF-008, HF-015, HF-075, HF-300, HF-500, HF-1500) Solid phenol resin (manufactured by Gunei Chemical Co., Ltd., trade name: Resin top PS-2601, PS-2607, PS-2655, PS-2768, PS-2608 , PS-4609, PSM-2222, PSK-2320, PS-61 2), and the like.

Moreover, an epoxy resin is not specifically limited, either, A well-known epoxy resin can be used. Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcine, pyrocatechol, phloroglucinol and the like; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (ortho cresol) , Ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (ortho cresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumyl) Benzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as xybisphenol, phenol novolak, ortho cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol , Polyglycidyl ethers of polyhydric alcohols such as polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid Suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid and the like Homopolymers or copolymers of glycidyl methacrylate; epoxy compounds having a glycidyl amino group such as N, N-diglycidyl aniline, bis (4- (N-methyl-N-glycidyl amino) phenyl) methane, diglycidyl ortho toluidine, etc. Vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexene Epoxides of cyclic olefin compounds such as sun carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, tri Heterocyclic compounds such as glycidyl isocyanurate can be mentioned. In addition, even if these epoxy resins are internally crosslinked by a prepolymer having an isocyanate group at an end, polyvalent active hydrogen compounds such as polyhydric phenols, polyamines, carbonyl group-containing compounds, and polyphosphates are used. It may be of high molecular weight.

Further, the polyester resin is not particularly limited as long as it is an esterification reaction of a polybasic acid component and a polyhydric alcohol component. Examples of the polybasic acid component include one or more dibasic acids such as diphenolic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, dimer acid, etc. In addition, lower alkyl esters of these acids are mainly used, and, if necessary, monobasic acids such as benzoic acid, crotonic acid, p-tert-butylbenzoic acid, trimellitic anhydride, methylcyclohexenic carboxylic acid, anhydride A trivalent or higher polybasic acid such as pyromellitic acid is used in combination. Commercially available products may also be used. For example, Toyobo Co., Ltd., trade names: Byron 300, 500, 560, 600, 630, 650, 670, Byron GK130, 140, 150, 190, 330, 590, 680, 780, 810, 890, 200, 226, 240, 245, 270, 280, 290, 296, 660, 660 Same as 885, Byron GK 250, 360, 640, 880, Unitika Co., Ltd., trade name: Erie Ter UE-3220, 3500, 3210, 3215, 3216, 3620, 3240, 3250, 3300, UE-3200, 9200, 3201, 3203, 3350, 3370, 3380, 3600, 3980, 660, the 3690, the 9600, the 9800, manufactured by Toagosei Co., Ltd., product name: Aron Melt PES-310, the 318, the 334, the 316, such as the 360, and the like.

Among the above polyester resins, the number average molecular weight is 10,000 to 50,000 and the glass transition point is -35 ° C to 35 ° C in vapor pressure osmometry (VPO method). The polyester resin, which is formed by the resin composition with the copper particles obtained according to the present invention, has a low volume resistance after curing of the coating film and can produce a cured product excellent in conductivity. A polyester resin having a number average molecular weight in the range of 15,000 to 40,000 and a glass transition temperature in the range of 0 ° C. to 35 ° C. is particularly preferable. The glass transition temperature is a temperature which can be measured by a DSC method (Suggested Scanning Calorimetry) according to ASTM 3418/82.

Furthermore, the acrylic resin is also not particularly limited, and known general acrylic resins can be used. It may be synthesized by a polymerization reaction using an acrylate compound or a methacrylate compound as a raw material, or may be obtained from a commercial product. As a commercial item of acrylic resin, for example, Mitsubishi Rayon Co., Ltd. product name: Acripet MD, VH, MF, V, Negami Industrial Co., Ltd. product name: Brand name: HYPER M-4003, M-4005, M -4006, M-4202, M-5000, M-5001, M-4501, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-50, BR-52, BR-53, BR-60, BR-64 , BR-73, BR-75, BR-77, BR-79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR -95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117 , BR Such as 118 and the like, but not limited thereto.

Among the above-mentioned acrylic resins, acrylic resins having a weight average molecular weight of 10,000 to 100,000 and a glass transition temperature in the range of 0 ° C. to 100 ° C. are the same as copper particles obtained by the present invention. The number average molecular weight is preferably in the range of 20,000 to 80,000 because a cured product having a low volume resistance after curing of the coating film formed of the resin composition and excellent conductivity can be produced. An acrylic resin having a glass transition temperature in the range of 10 ° C. to 90 ° C. is particularly preferable. The glass transition temperature is a temperature which can be measured by a DSC method (Suggested Scanning Calorimetry) according to ASTM 3418/82. In addition, the weight average molecular weight in this specification means the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography analysis which used tetrahydrofuran as a solvent. The "weight average molecular weight" in the present specification is sometimes referred to as "mass average molecular weight" in the technical field to which the present invention belongs, but is the same.

The concentration of the component (B) in the resin composition of the present invention is not particularly limited and can be suitably changed according to the shape and thickness of the desired cured resin, but the conductivity is good. Therefore, the concentration of the component (B) in the resin composition of the present invention is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 50% by mass, and 5% by mass to 25% by mass. % Is particularly preferred.

In addition, other solvents, an antioxidant, a silane coupling agent, etc. can be mix | blended with said resin composition, unless the effect of this invention is impaired.

As the solvent, for example, water or an organic solvent can be used. Here, as an organic solvent, for example, alcohol solvents, diol solvents, ketone solvents, ester solvents, ether solvents, aliphatic or alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, cyano group Hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, other solvents, and the like.

Examples of alcohol solvents include methanol, ethanol, propanol, 2-propanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, 3Pentanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcyclohepta Nord, benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2- (N, N-dimethylamino) ethanol, 3 (N, N-dimethylamino) propanol, etc. It can be mentioned.

Examples of diol solvents include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol (3 -Methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl- 1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like.

Examples of ketone solvents include acetone, ethyl methyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl hexyl ketone, ethyl butyl ketone, diethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl Ketone, cyclohexanone, methyl cyclohexanone and the like can be mentioned.

As ester solvents, for example, methyl formate, ethyl formate, methyl acetate, ethyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, tert-butyl acetate, amyl acetate, iso-amyl acetate, tert-amyl acetate, Phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, sec-butyl propionate, tert-butyl propionate, amyl propionate, isoamyl propionate, iso-amyl propionate, tert-amyl propionate Acid phenyl, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhexanoate, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate, Methyl toxoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono Butyl ether acetate, ethylene glycol monosecondary butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol monosecondary butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monosecondary butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono tertiary butyl ether acetate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether Acetate, butylene glycol monopropyl ether acetate, butylene glycol monoisopropyl ether acetate, butylene glycol monobutyl ether acetate, butylene glycol mono-secondary butyl ether acetate, butylene glycol monoisobutyl ether acetate, butylene glycol mono-first 3 butyl ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutanoate, ethyl oxobutanoate, γ-lactone, dimethyl malonate, dimethyl succinate, propylene glycol diacetate, δ-lactone and the like.

Examples of the ether solvents include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, dioxane and the like.

Examples of aliphatic or alicyclic hydrocarbon solvents include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decalin, solvent naphtha, turpentine oil, D-limonene, pinene, and mineral spirits. And Cosmo Matsuyama Oil Co., Ltd., trade name: Swazole # 310, Exxon Chemical Co., Ltd., trade name: Solvesso # 100, and the like.

Examples of aromatic hydrocarbon solvents include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, cymene and tetralin.

Examples of hydrocarbon solvents having a cyano group include acetonitrile, 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1 And 6,6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene and the like.

Examples of the halogenated aromatic hydrocarbon solvents include carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and the like.

Other organic solvents include, for example, N-methyl-2-pyrrolidone, dimethylsulfoxide, dimethylformamide, aniline, triethylamine and pyridine.

A commercial item can also be used for the said antioxidant, for example, dibutyl hydroxytoluene, Irganox 1010, Irganox 1035FF, Irganox 565 [BASF Japan KK-made] etc. are mentioned. The amount of the antioxidant used is preferably 0.0001% by mass to 10% by mass.

A commercial item can also be used for the said silane coupling agent, For example, epoxy-type [KBM403, KBM303: Shin-Etsu Chemical Co., Ltd. product made], vinyl-type [KBM1003: Shin-Etsu Chemical Co., Ltd. product], acrylic system silane Coupling agents [KBM 503: manufactured by Shin-Etsu Chemical Co., Ltd.], 3-ethyl (triethoxysilylpropoxymethyl) oxetane [TESOX: manufactured by Toagosei Co., Ltd.], and the like. The amount of the silane coupling agent used is preferably 0.0001% by mass to 10% by mass.

Next, a method of forming a cured product using the above-described resin composition of the present invention will be described.
The method of forming the cured product of the present invention comprises the steps of applying the resin composition of the present invention described above onto a substrate, and heating the substrate coated with the resin composition of the present invention to cure the cured product. And a curing step to form. The temperature of the curing step is preferably in the range of 50 ° C. to 200 ° C. because a cured product having good conductivity can be obtained, and the range of 100 ° C. to 200 ° C. is particularly preferable. The heating time in the curing step is preferably in the range of 1 minute to 300 minutes, and more preferably in the range of 10 minutes to 60 minutes. In addition, before the curing step, the substrate or the substrate coated with the resin composition of the present invention is maintained at 50 ° C. to 150 ° C. as needed, and a drying step of volatilizing low boiling point components such as organic solvents is further included. You may

Examples of the substrate in the present invention include resin substrates, glass substrates, ceramic substrates and the like. Examples of the material of the resin substrate include polyimide, polyester, aramid, polyethylene terephthalate (PET), Teflon (registered trademark) and the like, and examples of the material of the ceramic substrate include alumina and alumina-zirconia. Moreover, as a kind of glass substrate, a glass epoxy substrate, a glass composite substrate, etc. are mentioned.

As a coating method in the above-mentioned coating process, a spin coat method, a dip method, a spray coat method, a mist coat method, a flow coat method, a curtain coat method, a roll coat method, a knife coat method, a bar coat method, a slit coat method, a screen A printing method, a gravure printing method, an offset printing method, an inkjet method, a brush coating etc. can be mentioned.

Moreover, in order to obtain a required film thickness, the above-mentioned application process to an arbitrary process can be repeated multiple times. For example, all the steps from the coating step to the curing step may be repeated a plurality of times, and the coating step and the drying step may be repeated a plurality of times.

As a use of the cured | curing material of this invention formed as mentioned above, a conductive layer, an electrode film, wiring etc. can be mentioned.

Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples, but it should be understood that the present invention is not limited thereto.

[Production of copper powder]
Example 1
Copper particles [volume cumulative average particle size (D ₅₀ ): 1.6 μm] were added to pure water to make a 20 mass% copper slurry. Then, 1 mass% of sodium borohydride was added with respect to a copper particle, and it stirred at 25 degreeC for 1 hour (1st process). After that, washing with pure water at a temperature of 20 ° C. (second step) and further washing with 2-propanol at a temperature of 20 ° C., the pure water is replaced with 2-propanol, and 20 mass% copper slurry (3rd step). Here, the compound No. No. 91 was added as it is to 1.0% by mass with respect to the mass of the copper particles, whereby the copper particles were added to the compound No. 91 was contacted (fourth step). Thereafter, the copper particles are separated and dried to obtain an example copper powder No. 1 powder. I got one.

Example 2
The compound used in the fourth step is No. Example copper powder No. 1 was prepared in the same manner as in Example 1 except that the No. 92 was used. I got two.

Example 3
The compound used in the fourth step is No. Example copper powder No. 1 was prepared in the same manner as in Example 1 except that it was changed to No. 106. I got three.

Comparative Example 1
Comparative copper powder 1 was obtained in the same manner as in Example 1 except that the compound used in the fourth step was changed to stearic acid.

Comparative Example 2
Example 1 and Example 1 except that the compound used in the fourth step is changed to tetraisopropyl bis (dioctyl phosphite) titanate [product made by Ajinomoto Finetech Co., Ltd., trade name: Prenact 41B), which is a titanate coupling agent. Comparative copper powder 2 was obtained in the same manner.

Comparative Example 3
Example 1 and Example 1 except that the compound used in the fourth step is changed to tetraoctyl bis (ditridecyl phosphite) titanate [Ajinomoto Finetechto Co., Ltd. product name: Prenact 46B], which is a titanate coupling agent. Comparative copper powder 3 was obtained in the same manner.

[Preparation of Resin Composition]
Examples 11 to 23
Each component was mixed so as to obtain the composition shown in Table 1, and resin compositions (Example resin compositions No. 1 to 8) were produced.

Comparative Examples 4 to 9
Each component was mixed so as to obtain the composition shown in Table 1, to produce resin compositions (comparative resin compositions 1 to 6).

In the table,
B-1: Bisphenol A liquid epoxy resin (made by ADEKA, trade name: Adeka resin EP-4005) and resol type phenol resin (made by Sumitomo Bakelite, trade name: PR-50232) were mixed at a weight ratio of 2: 8 blend.
B-2: Resole-type xylene resin modified with phenols (Fudoh, trade name: PR-1440)

Examples 12 to 19
Example Resin Composition No. Using 1 to 8, coating by a bar coating method was performed on a PET film so as to have a film thickness of 10 μm to 20 μm. In addition, diethylene glycol monobutyl ether was used as a solvent for adjusting the film thickness of each composition. Thereafter, heat baking is carried out at 150 ° C. for 30 minutes in the air, whereby a thin film example cured product No. 1 is obtained. I got 1 to 8.

Comparative Examples 11 to 15
Using the comparative compositions 1 to 6, coating by a bar coating method was performed on a PET film so as to have a film thickness of 10 μm to 20 μm. In addition, diethylene glycol monobutyl ether was used as a solvent for adjusting the film thickness of each composition. Thereafter, heat baking was performed at 150 ° C. for 30 minutes in the air to obtain thin film comparative cured products 1 to 6.

<Example of evaluation>
Example Cured product No. The volume resistance values of 1 to 8 and comparative cured products 1 to 6 were measured with a high-precision resistivity meter (Mitsubishi Chemical Analytech Co., Ltd., product name: Loresta GP) using a four-terminal four-probe method. The results are shown in Table 2.

From the results of Table 2, Evaluation Examples 1 to 8 show lower volume resistance than Comparative Evaluation Examples 1 to 6, and Example Cured Product No. 1 was obtained. Nos. 1 to 8 are comparative cured product Nos. It has been found that the conductivity is superior to 1 to 5.

Claims

A first step of reducing the copper particles in water with at least one borohydride compound selected from the group consisting of potassium borohydride, sodium borohydride and lithium borohydride;
A second step of treating the copper particles obtained in the first step with at least one selected from the group consisting of water, methanol and ethanol;
A third step of treating the copper particles obtained in the second step with at least one solvent selected from the group consisting of an ether compound and an alcohol compound; and the copper particles obtained in the third step The 4th process made to contact the compound represented with General formula (1); The manufacturing method of the copper powder.

(Wherein, X 1 represents an alkyl or alkenyl group having 14 to 20 carbon atoms, X 2 represents an alkyl group having 1 to 5 carbon atoms, and M represents a titanium atom, a zirconium atom or a hafnium atom, a represents an integer of 1 to 3)
In the fourth step, in a state in which the copper particles are immersed in the solvent in the third step, the compound represented by the general formula (1) is added, and the copper particles are brought into contact with the compound The manufacturing method of the copper powder of Claim 1.
The copper powder obtained by the manufacturing method of Claim 1.
A resin composition comprising (A) the copper powder according to claim 3; and (B) at least one resin selected from the group consisting of a phenol resin, an epoxy resin, a polyester resin and an acrylic resin.
A coating step of coating the resin composition according to claim 4 on a substrate; and curing by heating the substrate coated with the resin composition in the air at 50 ° C. to 200 ° C., for 1 minute to 300 minutes A curing step;
A cured product obtained by curing the resin composition according to claim 4.