JPH04268381A - Copper alloy composition - Google Patents

Abstract

PURPOSE:To provide a conductive paste excellent in electric conductivity. oxidation resistance, and migration resistance at a low cost, and a product containing the paste. CONSTITUTION:The title compsn. comprises 100 pts.wt. copper alloy powder of the general formula: AgxCuy (wherein 0.001<=x<=0.999, 0.001<=y<=0.999, and x+y=1) wherein the silver content at the surface of the particle of the alloy powder is higher than that in the central part of the particle, 5-200 pts.wt. org. binder, and 0.01-100 pts.wt. additive which can remove copper oxide. The compsn. is used for producing a printed circuit board and as a paste for screen printing, electromagnetic wave shielding, a conductive circuit, a conductive adhesive, an electrode, and through hole coating.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention has excellent conductivity and
It relates to a copper alloy composition paste with good oxidation resistance and excellent migration resistance, and a conductor using the paste, and is useful for electromagnetic shielding, conductive adhesives, Paste for conductive circuits, paste for electrodes, screen
It can be used as a paste for printing, a paste for printed resistor terminals, a paste for through-holes, a contact material, etc.

BACKGROUND ART Conventionally, conductive pastes or conductive compositions have been made of noble metals such as gold, platinum, palladium, silver, silver-palladium, etc. (for example, JP-A-56-70064;
-124655, 59-45355, JP-A-1-9
No. 8674), nickel (for example, JP-A No. 58-539
66), silver-plated copper (for example, JP-A-56-8892
Copper (e.g., JP 56-163166, JP 62-74967, 6)
No. 3-89577, No. 57-55974, JP-A-2-1
No. 6172), etc., in which an organic binder, optionally a solvent, and additives are added and dispersed are known.

[0002] The known conductive pastes used have the following drawbacks. Copper is inexpensive, but its conductivity tends to decrease due to oxidation. In addition, attempts have been made to add antioxidants to pastes using copper powder, but initially the copper oxide on the powder surface was removed and conductivity was obtained, but it was still difficult to form a coating. After that, contact resistance gradually increases at high temperatures or high humidity, impairing conductivity. Furthermore, conductive pastes using silver powder are known, but they have the problem of migration. Conductive pastes that use copper powder plated with silver are also known, but it is difficult to uniformly plate the fine powder with silver, and there are also problems with peeling of the plated silver and migration. The problem still arises. Moreover, local batteries are likely to occur between silver and copper, and the copper is more likely to be oxidized. A method of mechanically forcibly bonding silver and copper has been disclosed (for example, Japanese Patent Application Laid-open No. 56-155259, 57).
98572), it has the disadvantage that it is not very effective in preventing silver migration because it is a mechanical bond.

[Problems to be Solved by the Invention] The present invention provides an inexpensive conductive paste that has excellent conductivity, long-term oxidation resistance, and migration resistance, and products using the same. This is what I am trying to do.

0003

[Means for Solving the Problems] The structure of the present invention for solving the above problems is a copper alloy composition and a product using the same as described in the claims. These will be explained in detail below. The copper alloy powder used in the present invention is produced by an atomization method. The gas atomization method and the water atomization method are preferred, and the inert gas atomization method is particularly preferred. Regarding the inert gas atomization method used in the present invention, the method already disclosed by the present inventors and disclosed in Application No. USP 395,531 is preferred. For example, copper, silver mixtures, or alloys of such composition are melted in a crucible in an inert atmosphere or in vacuum using high frequency induction heating. At this time, the inert atmosphere means an atmosphere that does not react with the melt at all or reacts only very slowly. For example, an atmosphere containing nitrogen, helium, hydrogen, or argon as a main component is preferable. Furthermore, the melt is spouted from the tip of the crucible into an inert gas atmosphere. At the same time as the ejection, a high-speed airflow generated by adiabatically expanding compressed inert gas is ejected toward the melt to atomize it. Inert gas, as used herein, means a gas that does not react at all or reacts only very slowly with a melt of such composition. For example, nitrogen, helium, argon, hydrogen, and mixtures thereof are preferred. At this time, the oxygen contained in the gas is preferably 2% or less, more preferably 0.1% or less.

[0004] The pressure of the gas (just before expansion) is 5 kg/cm
2G or more is preferable, and 15kg/cm2G or more is more preferable. The velocity of the high-speed airflow is 50 at the point of collision with the melt.
The speed is preferably at least m/sec, more preferably at least 100 m/sec, and most preferably at least 300 m/sec. The mass velocity ratio of gas and melt (gas mass velocity/melt mass velocity) is 0.1
The number is preferably at least 1, and more preferably at least 1. Moreover, the cooling rate at this time is preferably 102°C/second to 109°C/second, most preferably 103°C/second to 107°C/second. AgxCuy used in the present invention (however, 0.001≦
x≦0.999, 0.001≦y≦0.999, x+y
= 1, atomic ratio), but when x is less than 0.001, sufficient oxidation resistance cannot be obtained, and when x exceeds 0.999, migration resistance is insufficient. When the copper alloy powder used in the present invention satisfies 0.001≦x≦0.4,
The silver concentration at the surface of the powder is higher than the average silver concentration, and there is a region near the surface where the silver concentration increases from the inside toward the surface, and the silver concentration at the surface is 2.5 times higher than the average silver concentration.
It is more than 1 times. Preferably, it is 3 times or more and 40 times or less, and more preferably 4 times or more and 15 times or less. The amount of silver x is
Preferably 0.005≦x≦0.3, more preferably 0.01≦
Preferably, x≦0.25.

[0005] The copper alloy powder of 0.001≦x≦0.4 used in the present invention has a surface silver concentration higher than the average silver concentration, but the mechanism by which silver, which has a low melting point, is concentrated on the surface is as follows.
As already disclosed by the present inventors (Application No. USP 395,531), it can be considered as follows. For example, fine metal droplets generated by collision with high-speed airflow gas are accompanied by the high-speed airflow and rapidly solidify while traveling at high speed. It is thought that during this solidification process, a liquid phase rich in silver with a low melting point is discharged to the surface and solidifies with a delay, forming a powder with concentrated silver on the surface. When using the water atomization method, a melt having the above composition is ejected from the tip of the crucible. At the same time as the ejection, pressurized water is ejected from the nozzle toward the melt ejected from the tip of the nozzle, collides with the melt having the composition, becomes fine particles, and rapidly solidifies. At this time, the ratio of mass velocity of water to mass velocity of melt is preferably 10 or more, more preferably 40 or more. Further, the speed of the water at the collision position of the water and the melt is preferably 80 m/sec or more, and more preferably 100 m/sec or more. The pressure when pressurized water is jetted from the nozzle tip is preferably 50 kg/cm2G or more, more preferably 100 kg/cm2G or more.

[0006] When the silver amount x exceeds 0.4, (0.4
<x≦0.999), it can be used especially when oxidation resistance at high temperatures is required. In this case, the migration resistance is high because the silver in the powder is alloyed with copper, and the concentration of silver on the surface is high, and silver is present even inside the particles. It is effective in preventing copper oxidation. The rapidly solidified powder produced by the water atomization method is often irregularly shaped, but in the present invention, it is mainly spherical particles. Here, the silver concentration means Ag/(Ag+Cu) (atomic ratio). The silver concentration on the surface and near the surface can be measured using XPS (X
Line photoelectron spectrometer; XSAM80 manufactured by KRATOS
0) was used. First, conductive carbon double-sided adhesive tape was attached to the sample stand, and the sample powder was gently adhered to completely cover the double-sided tape so as not to deform it. Measurement conditions for silver concentration; magnesium Kα ray (voltage 12
kv, current 10 mA), the photoelectron extraction angle was 90 degrees with respect to the sample surface, and the room pressure was 10-8 torr. Etching conditions: An argon ion gun was used at an accelerating voltage of 3 keV, an argon ion beam was incident on the sample surface at an angle of 45 degrees, and the room pressure was 10 -7 torr for 10 minutes.

To measure the silver concentration, measurement and etching were repeated five times, and the average value of the first two measurements was taken as the silver concentration on the surface. The average silver concentration was measured by dissolving the sample in concentrated nitric acid and using an ICP (inductively coupled plasma emission spectrometer). The copper alloy powder used in the present invention has an average particle size of 0.1 to 100 μm, but if it is less than 0.1 μm, contact resistance increases and conductivity is impaired. Also, 10
If it exceeds 0 μm, suitability for screen printing is poor. Preferably 0.1 to 50 μm, more preferably 0.1 to 50 μm.
It is 5 to 30 μm. The average particle size was measured using a laser diffraction particle size analyzer (SALD1100). As a measurement method, the powder was sufficiently dispersed in an ethylene glycol solution (powder concentration 1 to 20 x 10-3 g/cc) and measured five times. The average value of the volume cumulative average value measured five times was taken as the average particle diameter. The particle shape is preferably spherical, scaly, or a mixture thereof. When using scaly powder, a known method of mechanically flattening it can be used. For example, methods such as stamp milling and ball milling may be used. The copper alloy powder used in the present invention may contain Al, Zn, Sn, Pb, Si, Mn,
Bi, Mo, Cr, lr, Nb, Sb, B, P, Mg,
Li, C, Na, Ba, Ti, In, Au, Pd, Pt
, Rh, Ru, Zr, Hf, Y, La and other metals, semimetals, and compounds thereof may be added;
At the same time as the powder used in the present invention, Al, Zn, Sn, Pb
, Si, Mn, Bi, Mo, Cr, Ir, Nb, Sb,
B, P, Mg, Li, C, Na, Ba, Ti, In, A
u, Ag, Cu, Pd, Pt, Rh, Ru, Zr, Hf
, Y, La, etc., metalloids, and powders of compounds thereof may be mixed.

[0008] As the organic binder used in the present invention,
One or more types selected from thermosetting resins, thermoplastic resins, photocurable resins, electron beam curable resins, photodegradable resins, and electron beam decomposable resins, but as thermoplastic resins, thermoplastic acrylic Selected from resins, alkyd resins, vinyl chloride resins, urethane resins, polyester resins, vinyl chloride-vinyl acetate copolymers, vinyl acetate resins, ethylene-vinyl acetate copolymers, polycarbonate resins, styrene resins, etc. One or more types may be mentioned. In addition, thermosetting resins include epoxy resins, phenolic resins, amino resins, alkyd resins, polyurethane resins, polyester resins, thermosetting acrylic resins, polyimide resins, melamine alkyd resins, and modified resins thereof. One or more selected types are preferred.

[0009] Epoxy resins with a molecular weight of 380 to
8000 bisphenol A type epoxy resin, epoxyphenol novolac type resin, brominated bisphenol A type epoxy resin, alicyclic epoxy resin, linear epoxy resin, polyalkylene ether type epoxy resin, polyglycidyl epoxy resin - Ter type epoxy resin, diglycidyl ester type epoxy resin, dimer acid type diglycidyl ester type epoxy resin, epoxy acrylate resin, and their phenolic OH terminal modified epoxy resin, fatty acid modified epoxy resin, urethane Examples include modified epoxy resins. Further, a known reactive diluent can also be used if necessary. For example, diglycidyl ether, ethylene glycol diglycidyl ether, 1,3-butanediol diglycidyl ether, butadiene dioxide, diethylene glycol diglycidyl ether, vinylcyclohexane diepoxide, triglycidyl cyanurate, Examples include, but are not limited to, N-diglycidylamine and divinylbenzene diepoxide. Examples of phenolic resins include novolak-type phenolic resins, resol-type phenolic resins, alkylphenol-resol-type resins, xylene resin-modified resol-type resins, and rosin-modified phenolic resins. Can be mentioned. Among these, resol type and modified resol type resins are preferred. Examples of amino resins include methylated melamine resins,
Examples include butylated melamine resin, benzoguanamine resin, urea resin, and butylated urea resin. It is preferably used as a crosslinking agent for thermosetting acrylic resins, phenolic resins, and epoxy resins.

[0010] Examples of the polyimide resin include general polyimide, bismaleide resin, and addition type polyimide having an acetylene group at the end of the molecule. As a curing accelerator, organic polyamine, acid anhydride, dicyandiamide, benzoguanamine, biguanide,
Alkylphenyl biguanide, diphenyl biguanide,
Known curing agents such as Sanfukkahoso and amine compounds can be used. The acrylic resin has a functional group (-COOH) of 10 to 80 mg/g and a hydroxyl value (-O
H) 40 to 250 mg/g, especially 50 to 20 mg/g.
0 hydrogen group is preferable, and the acid value is preferably 20 to 75. Further, in order to improve water resistance, it is preferable to use an acrylic resin having a hydroxybutyl group. The molecular weight can be 2,400 or more, preferably 4,500 or more, and preferably 16,000 or less. The average molecular weight of the polyester resin or alkyd resin is preferably 4,000 or more, more preferably 7,000 or more.

[0011] As the polyurethane resin, urethane prepolymers that form urethane can be used, but preferably those mainly composed of blocked isocyanate prepolymers in which terminal active isocyanate groups are blocked with active hydrogen compounds. preferable. When using a thermosetting resin, heating methods include a box-type hot air convection furnace, a continuous hot-air furnace, a muffle-type heating furnace, a near-infrared furnace, a far-infrared furnace, a vapor phase heating furnace, etc. Any known method may be used. Furthermore, the temperature for drying or thermosetting is preferably a temperature that does not adversely affect the characteristics of the substrate, for example, preferably from room temperature to 300°C, and furthermore, from room temperature to 300°C.
50°C is preferred. In addition, the curing atmosphere is as follows:
It may be in air (oxygen concentration of about 20%), but it may also be in an atmosphere with low or no oxygen concentration. Examples of the photocurable resin include ultraviolet curable resins and visible light curable resins, with ultraviolet curable resins being preferred. When using an ultraviolet curable resin, it is preferable to use a photopolymerizable oligomer or a photopolymerizable monomer together with a photoinitiator and a photoinitiation aid.

[0012] Photopolymerizable oligomers are low molecular weight reactive molecules (several hundred to several thousand) with two or more acrylic or methacrylic groups added as functional groups to the backbone of polyester, epoxy, urethane, etc. Examples thereof include epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate. As the photopolymerizable monomer, an acryloyl group (C
H2=CHCO-) or methacryloyl group (CH
2C(CH3)CO-) per minute, monofunctional acrylate (meth) having one or more, polyfunctional acrylate having two or more, and other vinyl groups ( Those having CH2=CH-) are preferred. Examples of monofunctional acrylates include allyl acrylate, allyl methacrylate, benzyl acrylate (meth), isobonyl acrylate, cyclohexyl acrylate (meth), N,N- Examples include dimethylaminoethyl acrylate, glycidyl methacrylate, lauryl acrylate, polyethylene acrylate 90 methacrylate, and trifluoroethyl methacrylate. Examples of polyfunctional acrylates include 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol acrylate, and polyethylene glycol 400 diacrylate. , tripropylene glycol diacrylate, bisphenol A diethoxy diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, etc. . Examples of the reactive monomer having a vinyl group include styrene,
Monofunctional monomers such as vinyltoluene, vinyl acetate, and N-vinylpyrrolidone can be used.

The photoinitiator used together with the oligomer and monomer is preferably a substance that easily generates radicals by absorbing ultraviolet rays, and includes known photoinitiators such as acetophenone, thioxane, benzoin, and peroxide. can be used. For example, diethoxyacetophenone, 4-
Phenoxydichloroacetophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether
ter, benzyl dimethyl ketal, benzophenone, 4
-Phenylbenzophenone, acrylated benzophenone, thioxanthone, 2-ethyl anthraquinone, etc. In this case, preferred examples include polyester acrylate resin, epoxy acrylate resin, and polyurethane acrylate resin. The photoinitiation aid that can be used in the present invention is not activated by UV irradiation by itself, but when used together with a photoinitiator, the initiation reaction is accelerated more than the photoinitiator alone, making the curing reaction more efficient. Known photoinitiation aids such as aliphatic and aromatic amines can be used. For example, known photoinitiation aids such as triethanolamine, N-methyldiethanolamine, Michler's ketone, and 4,4-diethylaminophenone can be used.

[0014] As a curing method, for example, the coated film is irradiated at room temperature or higher, preferably from 40 to 80°C, using an ultraviolet generator such as a mercury lamp as a light source. The light source may be any known device, but preferably 100 watts/cm or more. As for the irradiation time, several seconds to several tens of seconds is sufficient. As the electron beam curable resin, the photocurable resins (photopolymerizable oligomers, photopolymerizable monomers)
) can be used. When curing with electron beam,
Electrons accelerated by high voltage have a large amount of energy and have greater material permeability than light, so they have great curing ability and can be cured at room temperature. In addition, the oligomer, monomer
absorbs electron beams and generates ions and radicals,
In principle, photoinitiators and photoinitiation aids are not required. In the case of electron beam curing, any known method may be used. For example, if the coating film thickness is about 100 μm or less, an accelerating voltage of 150 kV or more is preferable, and a known method can be used. The copper alloy composition of the present invention contains 5 to 200 parts by weight of an organic binder per 100 parts by weight of copper alloy powder, but if the amount is less than 5 parts by weight, the conductive metal powder in the coating film may be There is not enough resin to keep it bonded, reducing conductivity and mechanical strength. Moreover, when it exceeds 200 parts by weight, the amount of conductive metal powder is insufficient and conductivity cannot be obtained. Preferably it is 5 to 100 parts by weight. Furthermore, 5 to 50 parts by weight is preferred.

When using the copper alloy composition of the present invention, a solvent may be used if necessary. The amount of solvent is preferably 0 to 100 parts by weight based on 100 parts by weight of the copper alloy powder and organic binder. The solvent that can be used in the present invention varies depending on the resin, but any known solvent may be used. For example, aromatics such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as butyl acetate and ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. -ter, ethylene glycol dimethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monoallyl ether, ethylene glycol dodecyl ether, ethylene glycol monoisobutyl ether -ter, ethylene glycol monoisopropyl ether and its acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether
diethylene glycol monoisobutyl ether,
Diethylene glycol dodecyl ether, diethylene glycol monohexyl ether and its acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol monomethyl ether, triethylene glycol dodecyl ether -ter, triethylene glycol mono-n-butyl ether and its acetate, triethylene glycol dimethyl ether and α
-Alcohols such as tenopenol, β-terpenol, isopropanol, butanol, phenols such as phenol and chlorphenol, dioxane, dimethylacetamide, dimethylformamide, N-methyl Preferably, it contains one or more selected from pyrrolidone and γ-lactone.

The copper alloy composition of the present invention comprises copper alloy powder 1
Additives capable of removing copper oxide are added to 0.00 parts by weight.
．． 01 to 50 parts by weight, and has the function of reducing copper oxide on the powder surface or eluting and removing copper oxide from the powder surface. That is, the conductive mechanism of the copper alloy composition of the present invention is that it has conductivity through powder-to-powder contact, and therefore the characteristics of the surface of each particle are important. The copper alloy powder used in the present invention has silver concentrated on the particle surface, but by removing or reducing the copper oxide present on the powder surface, sufficient silver contact is secured, and it can be used at high temperatures or high humidity. This shows long-term stability regarding the oxidation resistance of the particle surface. On the other hand, with pastes using known copper powder, even if the surface is treated with an oxide remover, the new contact is a copper-copper contact, so it is still possible to avoid exposure to high temperatures or high humidity over long periods of time. In this case, the surface is oxidized and the conductivity gradually deteriorates. Furthermore, when the additive of the present invention is added to a known paste using copper powder, the additive is instead adsorbed onto the silver surface, increasing particle contact resistance and impairing conductivity. The amount of additive used is 0.1
If the amount is less than 1 part by weight, sufficient conductivity cannot be obtained, and
If the amount exceeds 50 parts by weight, the additive will instead be adsorbed onto the particle surface, impairing the conductivity. Therefore, it is preferable to add the necessary amount to the amount of copper oxide present on the particle surface, and 1 to
It is preferably 50 parts by weight, and more preferably 1 to 30 parts by weight. The additives used in the present invention include fatty acids, dicarboxylic acids, oxycarboxylic acids and their metal salts, phenol compounds, metal chelate forming agents, higher aliphatic amines, organic titanium compounds, rosin, anthracene and their derivatives. One or more selected types may be mentioned.

Examples of fatty acids include saturated fatty acids (for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, heptadecylic acid, stearic acid) acid, nonadecanoic acid, arachidic acid, behenic acid, etc.) and unsaturated fatty acids (e.g., acrylic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassicic acid, sorbic acid, linoleic acid, arachidonic acid, stearyl acid, etc.) - acid, etc.) and their metal salts. At this time, in order to produce a coating film with high adhesion, metal salts of higher fatty acids or fatty acids having 13 or less carbon atoms and metal salts thereof are preferable. Dicarboxylic acids include aliphatic saturated dicarboxylic acids (for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and aliphatic unsaturated dicarboxylic acids (for example, (maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid, etc.) and their metal salts (e.g., copper, iron, magnesium, manganese, silver, etc.), and anhydrides. .

[0018] Examples of the oxycarboxylic acids include aliphatic oxycarboxylic acids (for example, glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, glyceric acid, tartronic acid, tartaric acid, citric acid, etc.) and aromatic oxycarboxylic acids. Carboxylic acids (e.g. salicylic acid, p-, m-oxybenzoic acid, mandelic acid, tropic acid, oxyphenylacetic acid, resorcinic acid, orceric acid, gentisic acid, protocatechuic acid, caffeic acid, umbelic acid, etc.) and their metal salts can be mentioned. Examples of metals include copper, manganese, silver, iron, magnesium, and cobalt. Preferably mandelic acid, citric acid, salicylic acid, resorcinic acid, p-,
m-oxybenzoic acid. Examples of phenolic compounds include monovalent, divalent, and trivalent phenols and their derivatives (e.g., phenol, cresol, 3,5-xylenol, carvacrol, thymol, naphthol, catechol, resorcinol, hydroquinone, methylhydroquinone, tert-butylhydroquinone, chlorohydroquinone, phenylhydroquinone, 1,2,4benzenetriol, pyrogallol, phloroglucin, etc.). Examples of metal chelate forming agents include amino alcohols (e.g., ethanolamine, diethanolamine, triethanolamine and their derivatives), amine compounds such as ethylenediamine, triethylenediamine, toluethylenetetramine, acetylacetone and Derivatives thereof (for example, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, etc.) can be mentioned.

The higher fatty acid amine is preferably one having 8 to 22 carbon atoms and is soluble in a solvent. For example, the saturated monoamine includes stearylamine, palmitylamine, behenylamine, cetylamine, octylamine, decylamine, Examples of unsaturated monoamines such as laurylamine include oleylamine, and examples of diamines include stearylamine propylene diamine and oleylpropylene diamine. As the organic titanium compound, R1-Ti-(R2)3 (wherein R1 has 1 to 4 carbon atoms,
Preferably, an alkoxy group having 1 to 3 carbon atoms, R2 is a carboxylic acid ester having 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms), such as isopropyl triisostearoyl titanate, isopropyl trioctano Examples include il titanate. Examples of anthracene and its derivatives include anthracenecarboxylic acid. Examples of the rosin include modified rosins such as partially hydrogenated rosin, fully hydrogenated rosin, esterified rosin, maleated rosin, disproportionated rosin, and polymerized rosin.

The amount of the additive is 0.00% of one or more selected from the above additives per 100 parts by weight of the copper alloy powder.
1 to 50 parts by weight is added, but if it is less than 0.1 part by weight, sufficient conductivity will not be obtained, and if it exceeds 50 parts by weight, bleeding from the coating will occur, resulting in poor conductivity. On the contrary, it gets worse. Preferably it is 1 to 50 parts by weight, more preferably 1 to 30 parts by weight. The copper alloy composition of the present invention provides a conductive paste with excellent conductivity and migration resistance. inhibitor, leveling agent,
It goes without saying that additives such as antifoaming agents, silane coupling agents, titanium coupling agents, aluminum coupling agents, etc. may be added. When using the copper alloy composition of the present invention, screen printing, spray method, brush, bar coating method, doctor blade method, flexure printing, microdispenser method, Known printing and coating methods such as a gravure printing method, an offset printing method, and a Ben-lighting method can be used. Among these, the screen printing method is preferred. When using a screen printing method, it is preferably 50 to 400 mesh, and more preferably 150 to 400 mesh, although it depends on the pattern. Among them, 200 mesh or more is preferable for printing fine lines.

[0021] The substrate on which the copper composition of the present invention is printed can be any known substrate, such as a glass epoxy resin substrate, a paper phenol resin substrate, a paper epoxy resin substrate, a polyimide substrate, or a polyester resin substrate. Substrates, BT resin substrates, polysulfone resin substrates, polyether sulfone resin substrates, polyetherimide resin substrates, hard and flexible substrates such as resin, polybutadiene resin substrates, glass polyimide resin substrates, alumina substrates, aluminum nitride substrates, etc. Can be applied to ceramic substrates, metal substrates such as aluminum and stainless steel. for example,
When used for flexible substrates made of polyimide, polyester, or the like, a copper composition using a binder containing a vinyl resin (eg, vinyl chloride-vinyl acetate copolymer, etc.), a saturated polyester, or a polyurethane resin as a main component is preferable. The copper alloy composition of the present invention can be used as an electromagnetic shield plate.
When used as a shield, it is preferable to print on the surface of a printed circuit board and shield it. We also sell word processors, computer equipment housings, card readers, measuring instruments, car phones, keyboards, medical equipment, musical instruments,
It can also be used by coating a plastic casing such as a CRT. In addition, when the copper alloy composition of the present invention is used as a conductive adhesive, for example, an adhesive for taking out lead wires from the electrodes of a crystal resonator, an adhesive between molded carbon and metal, an adhesive for liquid crystal Conductive adhesive between glass inside (LCD), adhesive to lead frame and substrate for elements such as IC, LSI, LED, SAW filter (especially for IC die bonding), CdS for photoconductive element It can be applied to adhesives for parts and potentiometer lead wires, circuit collectors, adhesives for materials that cannot be directly soldered, materials that cannot be exposed to high temperatures, etc.

[0022] Also, when used for through holes, through holes made by punching etc. on a printed wiring board can be used.
The copper composition described above is used in the hole by filling only the inner surface of the hole or filling the inside of the hole. In this case, it is preferable to use, for example, screen printing or flexure printing.
It is best to reduce the pressure somewhat from the back of the hole. The conductivity of the coating film made of the copper alloy composition of the present invention was measured using a four-terminal method. In addition, the migration test
A DC voltage of 10V was applied between the two films applied at an interval, and a 0.2ml water drop was further dropped between the films to measure the leakage current.The time during which the current value exceeded 100μA was determined as
tion time. Durability test: 60℃, 90℃
% humidity Change in conductivity after storage (humidity resistance test), and
A soldering heat resistance test (change in conductivity after immersion at 260° C. for 10 seconds) was conducted. The adhesion of the film was determined using a substrate test. electromagnetic wave sea
The waveguide characteristics can be measured using a spectrum analyzer using a waveguide.
, using a tracking generator, 100kHz
The shielding effect up to GHz was measured. Conductive properties for through holes are 1.5, 1, 0.5, 0.3m
Using screen printing (320 mesh) on a paper phenol resin substrate in which 30 mφ holes were lined up and opened, printing was carried out under reduced pressure so that the holes were completely filled. After printing, each composition was cured using a method appropriate to its composition. Further, if necessary, the cured product made of the composition of the present invention can be trimmed by laser or other methods. Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

[0023]

[Examples] Powder Preparation Examples Example 1 315.595 g of copper particles and 3.237 g of silver particles were melted in a graphite crucible using high frequency induction heating. The atmosphere is 9
It was carried out in a nitrogen atmosphere of 9.9% or more. After heating to 1720° C., the melt falling from the tip of the crucible was atomized with 99.9% or more nitrogen gas at a pressure of 15 k/G at a gas/liquid mass velocity ratio of 1. The linear velocity of the gas at the impact location was 80 m/sec. The obtained powder had an average particle size of 20 μm. When measured by XPS, the silver concentration on the surface was 0.0% lower than that on the surface.
05, 0.04, 0.03, 0.02, 0.01, the surface silver concentration is 0.045, and the average silver concentration is x
=0.006, y=0.994, and the silver concentration on the surface was 7.5 times the average silver concentration. Example 2 314.325 g of copper particles and 5.395 g of silver particles were melted under high frequency induction heating in the same manner as in Example 1. 16
After melting to 80°C, nitrogen gas (99°C) with a gas pressure of 20k/G
．． 7% or more) was atomized to the melt ejected from the nozzle tip at a gas/liquid mass velocity ratio of 1.5. The linear velocity of the gas at the collision position at this time was 120 m/sec. The obtained powder had an average particle size of 19 μm. The silver concentration on the surface is 0.07, 0.06, 0.05, 0.04, 0
．． 03, the surface silver concentration is 0.065, and the average silver concentration is x = 0.01, y = 0.99, and the surface silver concentration is 6.5 times the average silver concentration. Ta.

Example 3 285.75 g of copper particles and 53.95 g of silver particles were similarly melted in a graphite crucible. After melting to 1570° C., the melt was ejected from the tip of the crucible, and at the same time nitrogen gas (99.9% or more) at a pressure of 20 k/G was atomized at a gas/liquid mass velocity ratio of 2. At this time, the linear velocity of the gas at the collision position is 1
00 m/sec, and the average particle size of the obtained powder was 18 μm. Also, the silver concentration on the surface is 0.72, 0.
65, 0.55, 0.5, 0.48, the surface silver concentration is 0.685, and the average silver concentration is x=0.1, y
= 0.9, and the surface silver concentration is 6.8 of the average silver concentration.
It was 5 times more. Example 4 254 g of copper particles and 107.9 g of silver particles were similarly melted by high frequency induction heating. After heating to 1800℃, nitrogen gas (pressure 15k/G, 99.9% or more) is directed toward the melt that is spouted from the tip of the crucible into an inert atmosphere (nitrogen).
was atomized at a gas/liquid mass velocity ratio of 2. The linear velocity of the gas at the collision position at this time was 80 m/sec. The obtained powder had an average particle size of 20 μm. The silver concentration on the surface is 0.8, 0.75, 0.7, 0.65, 0.6 from the surface, the silver concentration on the surface is 0.775, and the average silver concentration is x = 0 .2, y=0.8, and the surface silver concentration was 3.85 times the average silver concentration.

Example 5 206.375 g of copper particles and 188.825 g of silver particles were similarly melted to 1500° C. by high frequency induction heating. Furthermore, the melt was spouted from the tip of the crucible into an inert atmosphere (nitrogen). Simultaneously with the ejection, nitrogen gas (with a gas pressure of 15k/G)
99.9% or more) to the melt at a gas/liquid mass velocity ratio of 2
It was atomized. The gas linear velocity at this time was 90 m/sec. The average particle size of the obtained powder was 18 μm. The silver concentrations on the surface are 0.88, 0.8, 0.75, 0.
7, 0.65, and the surface silver concentration was 0.84. Further, the average silver concentration was x=0.35, y=0.65, which was 2.4 times the average silver concentration. Example 6 127 g of copper particles and 323.7 g of silver particles were prepared in the same manner.
It melted to 00°C. The melt was ejected from the tip of the crucible into an inert gas atmosphere (nitrogen). At the same time as the ejection, the gas pressure is 3
Nitrogen gas (99.9% or more) of 0 k/G was atomized to the melt at a gas/liquid mass ratio of 0.7. The linear velocity of the gas at this time was 150 m/sec at the collision position, and the obtained powder had an average particle size of 16 μm. The average silver concentration of the obtained powder was x=0.6, y=0.4.

Example 7 63.5 g of copper particles and 431.6 g of silver particles were similarly melted to 1700° C. by high-frequency induction heating. The melt was ejected from the tip of the crucible into an inert atmosphere. Simultaneously with the ejection, the melt was atomized with nitrogen gas (99.9% or more) at a gas pressure of 40 k/G at a gas/liquid mass velocity ratio of 2.1. The gas linear velocity at this time was 160 m/sec. The average particle size of the obtained powder was 14 μm. Moreover, the average silver concentration was x=0.8 and y=0.2. Example 8 9.525 g of copper particles and 523.315 g of silver particles were similarly heated and melted to 1800° C. by high-frequency induction heating. The melt is ejected from the tip of the crucible, and at the same time the gas pressure is 50k/G.
of nitrogen gas (99.9% or more) was atomized to the melt at a gas/liquid mass velocity ratio of 2.3. The linear velocity of the gas at this time was 180 m/sec at the collision position. The obtained powder had an average particle size of 13 μm. The average silver concentration is x=0
．． 97, y=0.03. Paste example

00
27] Example 9 x=0.006, y=0.99 obtained in Example 1
Particles of 10 μm or less in powder No. 4 (average particle size 5 μm)

10g alkylated phenolic resin

3g linoleic acid copper salt

0.1g pyrocatechol

0.5g
Butyl carbitol

3 g were thoroughly mixed and coated on a glass epoxy resin substrate using hes screen printing (250 mesh). The coating film was cured by heating at 160° C. for 20 minutes. The volume resistivity of the resulting coating film was 1×10 −4 Ω·cm, and the migration time was 295 seconds, which was about the same as that of copper. Furthermore, when we conducted a temperature resistance test, (60℃
, 90%) The rate of change after 1000 hours was 20%. Also, the result of the second test was 100/100.

Example 10 Particles of 15 μm or less in the powder with x=0.01 and y=0.99 obtained in Example 2


10g fatty acid modified epoxy resin

2g methylated melamine

1
g maleic acid

0.5g lauric acid

0.05
g pyrocatechol

0.2g Butyl carbitol acetate
3 g were thoroughly mixed and screen printed on a glass epoxy substrate. Paint film 170
C. for 30 minutes in air. The volume resistivity of the obtained coating film was 1 x 10-4 Ωcm,
The migration test result was 295 seconds, which was about the same as copper. Further, as a result of the humidity resistance test, the rate of change after 1000 hours was within 20%. Gobanmoku test result 10
It was 0/100.

Example 11 Among the powders with x=0.1 and y=0.9 obtained in Example 3, the powder size is 15 μm or less


10g resol type phenolic resin

4g mandelic acid

0.7
g Triethanolamine

0.3g Butyl cellosolve

4 g were thoroughly mixed and coated on a glass epoxy resin substrate using screen printing. The coating film was heat cured in air at 150°C for 30 minutes. The volume resistivity of the obtained coating film was 8×10−
5Ω・cm, and as a result of the migration test, 29
As a result of the humidity resistance test, the rate of change was 10% even after being left for 1000 hours. Gobanmoku test result 100/1
It was 00.

Example 12 Among the powders with x=0.1 and y=0.9 obtained in Example 3, the powder size is 15 μm or less.


10g thermoplastic acrylic resin

5g Isopropyl triisostearoyl titanate
0.1g MEK


4 g were mixed well and applied to a paper phenolic resin substrate by spray coating. After coating, it was dried in air at 40°C for 2 days. The volume resistivity after drying was 9×10 −5 Ω·cm, and the migration time was 290 seconds, which was almost the same as that of copper. Further, as a result of a humidity resistance test, the rate of change after standing for 1000 hours was within 5%. Also, the result of the first exam is 100.
/100. Example 13 Among the powders with x = 0.1 and y = 0.9 obtained in Example 3, the powder is 15 μm or less


10g addition type polyimide

3.1g oleylamine

0.6
g pyrocatechol

0.3g n-methylpyrrolidone

2g triethylene glycol butyl ether
2 g were thoroughly mixed and applied onto an aluminum substrate. 200 coats of paint
C. for 15 minutes in air. The volume resistivity after curing was 1.5×10 −4 Ω·cm, the migration time was 290 seconds, and the rate of change was within 6% as a result of a humidity resistance test. Also, the result of the second test was 100/100.

A coating film of 10 cm x 10 cm x 50 μm was similarly prepared on a glass epoxy resin substrate. 100kHz after being left at 60℃ and 90% humidity for 1000 hours
When we measured the shielding characteristics from to 1GHz, we found that 3
A high shielding effect of 50 dB was obtained at 00 MHz. Example 14 Among the powders with x = 0.2 and y = 0.9 obtained in Example 4, the powder is 15 μm or less


10g novolac type phenolic resin

2g fatty acid modified epoxy resin
2g mandelic acid

0.01g pyrocatechol

0.05g titanium coupling agent
0.01g
Ethyl acetate

2g ethyl cellosolve

3 g were thoroughly mixed and applied onto a glass epoxy resin substrate. The coating film was heat cured in air at 155°C for 20 minutes. The volume resistivity of the cured coating film was 6×10 −5 Ω·cm, and the migration time was 285 seconds. Further, as a result of a humidity resistance test, the rate of change after standing for 1000 hours was within 1%. Also, the result of the second test was 100/100.

Example 15 Among the powders with x=0.2 and y=0.8 obtained in Example 4, the powder size is 15 μm or less.


10g epoxy modified polyimide resin

2g pyrogallol

1
g Diethanolamine

1g silane coupling agent

0.01g Butyl carbitol

2 g were thoroughly mixed and screen printed onto a glass epoxy resin substrate. The coating film was heat cured in air at 230°C for 15 minutes. The volume resistivity of the obtained coating film was 8×
10-5Ω・cm, and the migration time is 2
As a result of the humidity resistance test for 85 seconds, the rate of change after 1000 hours was within 1%. Also, the result of the first exam is 100/
It was 100. In addition, the composition prepared in the same manner was prepared using paper phenolic resin substrates with holes of 1, 0.5, and 0.3 mmφ.
The composition was printed into the through-holes using screen printing (250 mesh) under a vacuum of 700 mHg. Furthermore, it was heat-cured at 230° C. for 10 minutes. The cured product completely fills the holes, has high conductivity, and has zero conductivity on the front and back of the board.
．． The resistance value was 0.01Ω.

Example 16 Among the powders with x=0.2 and y=0.8 obtained in Example 4, powders with a diameter of 20 μm or less


10g Bis A type epoxy resin

6g resol type phenolic resin
1g
Methylhydroquinone

3g Butyl cellosolve acetate

4 g was sufficiently mixed and screen printed as a circuit to connect the resistor onto a glass epoxy resin substrate on which a carbon resistor had already been printed. The coating film was cured by heating at 160°C for 15 minutes. The volume resistivity of the cured film was 9×10 −5 Ω·cm, and no change was observed in the carbon resistor. The same composition was similarly applied for migration measurement to produce a cured film. As a result, the migration time was 285 seconds, and the humidity resistance test showed that the rate of change after being left for 1000 hours was within 2%. Also, the result of the second test was 100/100.

Example 17 Among the powders with x=0.35 and y=0.65 obtained in Example 5, the powder size is 10 μm or less.


10g OH-terminated modified epoxy resin

1g butylated melamine resin
2g
hydroquinone

0.2g ethanolamine

0.1g Butyl carbitol acetate
3g
were thoroughly mixed and screen printed onto an alumina substrate. The coating film was cured by heating at 180± for 30 minutes. The volume resistivity of the obtained cured film was 2 x 10-4 Ωcm,
The reaction time was 260 seconds. Furthermore, the rate of change after the humidity resistance test was within 1%. Also, the result of the second test was 100/100. Example 18 Powder of 10 μm or less among the powders with x = 0.35 and y = 0.65 obtained in Example 5


10g liquid epoxy resin

3g Trietano
Ruamine
0.1g
Methylhydroquinone

0.1 g was thoroughly mixed and applied onto a glass polyimide resin substrate. The coating film was cured by heating at 140° C. for 30 minutes. The volume resistivity of the cured film is 2×10-4Ω・cm
, the migration time was 260 seconds. Furthermore, as a result of the humidity resistance test, the rate of change after 1000 hours was 4%.
It was within Also, the result of the first exam is 100/10.
It was 0.

Example 19 Among the powders with x=0.35 and y=0.65 obtained in Example 5, the powder size is 10 μm or less.


10g epoxy acrylate

2g Valmitic acid copper salt
0.5g
phenol

1g Butyl cellosolve

2 g were thoroughly mixed in a kneader and applied onto a polyimide resin substrate. The coating film was cured with an electron beam. At this time, 2
Heated at 00°C for 1 minute. The volume resistivity of the resulting coating film was 1 x 10-4 Ωcm, and the migration time was 2
As a result of a 60 second humidity test, the rate of change after standing for 1000 hours was within 5%. Also, the results of the first exam
It was 00/100. Example 20 Among the powders with x = 0.6 and y = 0.4 obtained in Example 6, powders with a size of 10 μm or less


10g epoxy acrylate

2g photoinitiator

0
．． 1g pyrocatechol

0.1g organic titanate

0.1g
M.E.K.

Mix 1g thoroughly,
It was applied onto a polysulfone resin substrate and cured with ultraviolet light. At the same time, the mixture was heated at 200° C. for 5 minutes. The volume resistivity of the resulting coating film was 8×10 −5 Ω·cm, and the migration time was 230 seconds. Further, as a result of a humidity resistance test, the rate of change after being left for 1000 hours was within 1%. Also, the result of the second test was 100/100.

Example 21 Among the powders with x=0.8 and y=0.2 obtained in Example 7, powders with a size of 10 μm or less


10g thermoplastic acrylic resin

4g sebacic acid


0.1g ethyl cellosolve

4 g were thoroughly mixed and applied onto a polyester resin flexible substrate. Paint film 7
It was heated and dried at 0°C for 2 days. The volume resistivity of the coating film after drying is 6 x 10-5 Ω・cm, and the migration time is 1
It was 80 seconds. Furthermore, as a result of the humidity test, 1000
The rate of change after standing for a period of time was within 1%. Also, the result of the second test was 100/100. Example 22 Among the powders with x = 0.98 and y = 0.02 obtained in Example 8, powders with a size of 10 μm or less


10g resol type phenolic resin

3g rosin

0.
1g L-ascorbic acid

0.1g stearylamine

0.1g Butyl carbitol

3 g were thoroughly mixed and screen printed onto a polyimide resin substrate. After coating, the film was cured by heating in helium at 150°C for 20 minutes. Volume resistivity is 5×10-5Ω
・cm, migration time was 50 seconds. Furthermore, as a result of the humidity resistance test, the rate of change after 1000 hours was
It was within 2%. Also, the result of the first exam is 100/
It was 100.

Example 23 Among the powders with x=0.01 and y=0.99 obtained in Example 2, powders with a size of 10 μm or less


10g commercially available polyester resin

10 parts by weight Commercially available alkyd resin

5 parts by weight methylated melamine resin
10 parts by weight Butyl cellosolve

20 parts by weight toluene

5 parts by weight
citric acid

0.7g stearylamine

0.5g titanium coupling agent
0
．． 01g pyrocatechol

0.9 g was thoroughly mixed and screen printed onto a glass polyimide resin substrate. The coating film was cured by heating at 150° C. for 20 minutes in nitrogen. The volume resistivity of the cured film was 1×10 −4 Ω·cm. My Gray
As a result of the compression test, it was 250 seconds. Further, as a result of the humidity resistance test, the rate of change after 1000 hours was within 10%. The base test result was 100/100.

Example 24 Among the powders with x=0.2 and y=0.8 obtained in Example 4, powders with a diameter of 15 μm or less


10g liquid epoxy resin

2g triethanolamine
0.5
g was thoroughly mixed and used as an adhesive for die bonding of IC. It was heated and cured in nitrogen at 150°C for 10 minutes. The obtained cured film had high adhesiveness and no peeling was observed. Further, in the same manner, two sheets of Nesa glass used for liquid crystal were bonded together using the adhesive of the above composition. All conductive contacts after heat curing were good. Example 25 Among the powders with x = 0.2 and y = 0.8 obtained in Example 4, powders with a size of 10 μm or less


10g resol type phenolic resin

2g triethanolamine
0.3g Butyl carbitol

2 g were sufficiently mixed, screen printed as electrodes on both ends of a carbon resistor that had already been printed and hardened on a polyimide resin substrate, and then heated and hardened in nitrogen. When the cured film was measured, it was confirmed that sufficient ohmic contact was obtained.

[0039]

[Comparative example] Powder production comparative example Comparative example 1 Copper particles 317.46825g, silver particles 0.05395g
was melted to 1700°C by high frequency induction heating in a graphite crucible. The melt was spouted into an inert atmosphere (nitrogen) through a nozzle attached to the tip of the crucible. At the same time as blowing out, gas pressure 2
0 k/G nitrogen (99.9% or more) was atomized to the melt at a gas/liquid mass velocity ratio of 2. The gas linear velocity at this time was 100 m/sec. The average particle size of the obtained powder was 19 μm. The average silver concentration at this time is x=0
．． 0001, y=0.9999. Comparative Example 2 0.03175 g of copper particles and 539.446 g of silver particles were similarly melted to 1720° C. by high-frequency induction heating. While spouting the melt, nitrogen gas (9
9.9% or more) to the melt, gas/liquid mass velocity ratio 2
It was atomized. The gas linear velocity at this time was 110 m/
It was seconds. The average particle size of the obtained powder was 18 μm. The average silver concentration is x=0.9999, y=0.00
It was 01.

Comparative Example 3 285.75 g of copper particles and 53.95 g of silver particles were similarly melted to 1600°C. At the same time as the melt was ejected, a gas pressure of 20 k/G (mixed gas of 10% oxygen and 90% nitrogen) was atomized at a gas/liquid mass velocity ratio of 2. The gas linear velocity at this time was 110 m/sec. When the surface silver concentration of the obtained powder was measured, it was found that 0.08
, 0.09, 0.1, 0.11, 0.13, the silver concentration on the surface is lower, the silver concentration on the surface is 0.085, and the average silver concentration is x = 0.1, y = 0 .9, and the surface silver concentration was 0.85 times the average silver concentration. Paste Comparative Example Comparative Example 4 x=0.0001, y=0.9 produced in Example 1
Powder of 10μm or less among 999 powders

10
g Thermoplastic acrylic resin

3g linoleic acid copper salt

0.01g ME
K

Mix 3g thoroughly and add paper phenol.
spray applied onto the resin substrate. The coating film was dried by heating at 50° C. for 1 day. The volume resistivity of the coating film after drying is 2×10
It was as high as -3Ω·cm. Also, the results of the first exam
00/100, but as a result of the humidity test, it was 1000
The rate of change after standing for a period of time was as large as 300%. In addition, the composition obtained at the same time was placed on a paper phenol substrate.
, 0.5, 0.3mmφ hole screen printing (2
50 mesh) at 700 mmHg under reduced pressure.
I printed while pulling the back side of the card. The resistance value between the front and back surfaces of the obtained cured substrate was as high as 3Ω.

Comparative Example 5 x=0.9999, y=0.0 produced in Comparative Example 2
Powder of 10μm or less among 001 powders

10
g Bis A type epoxy resin

0.1g Butyl carbitol

2 g were thoroughly mixed and applied onto a glass epoxy resin substrate. The volume resistivity of the coating film is 5 x 10-5 Ωcm, and the humidity resistance test shows that the rate of change is 10% even after being left for 1000 hours.
The second test was also 100/100, but the migration time was short at 15 seconds, making it easy to migrate. Comparative Example 6 Among the powders with x=0.01 and y=0.99 produced in Example 2, the powder is 10 μm or less


10g resol type phenolic resin

30g ethyl cellosolve

20g were mixed and screen printed onto a glass epoxy resin substrate. The coating film was cured by heating at 150° C. for 30 minutes. The volume resistivity of the obtained cured film was as high as 1×10 −2 Ω·cm. Further, as a result of the humidity resistance test, the rate of change after being left for 1000 hours was as large as 200%. , First exam 100/
It was 100. In addition, a composition obtained in the same manner as 1
A coating film of 0 cm x 10 cm x 50 μm was applied onto a glass epoxy resin substrate and cured by heating. Cured film at 60℃, 9
0% humidity left for 1000 hours, 100kHz to 1GH
When the shielding up to z was measured, it showed only a low shielding effect of 10 dB.

Comparative Example 7 Among the powders x=0.1 and y=0.9 obtained in Comparative Example 3, the powder size is 10 μm or less.


10g fatty acid modified epoxy resin

0.1g pyrocatechol

0.2 g was mixed and screen printed onto a glass epoxy resin substrate. The coating film was cured by heating at 140° C. for 30 minutes. The volume resistivity of the cured film was as high as 2×10 −2 Ω·cm. Also,
As a result of humidity resistance test, the rate of change after being left for 1000 hours was 25
It was as large as 0%. In addition, the film was easy to peel off (coarse eye test 3/100). Comparative Example 8 Among the powders with x=0.01 and y=0.99 produced in Comparative Example 2, the powder is 15 μm or less


10g methylated melamine

0.1g pyrocatechol

0.1
g Ethyl cellosolve

2g were mixed and screen printed onto a glass epoxy resin substrate. Paint film at 150℃, 3
It was cured by heating in air for 0 minutes. The volume resistivity of the cured film is
As high as 1×10-2Ω・cm. The film also peeled off immediately (fine test 10/100). As a result of the humidity test, 100
The rate of change after standing for 0 hours was as high as 180%.

Comparative Example 9 Among the powders prepared in Comparative Example 2 with x=0.01 and y=0.99, 10 g of powder with a diameter of 15 μm or less was added to resol type phenolic resin.

2g triethanolamine

20g Butyl carbitol acetate
The composition dispersed in 2 g was similarly screen printed onto a glass epoxy resin substrate. The coating film was cured by heating at 160° C. for 20 minutes. The volume resistivity of the obtained cured film is 2×10
It was as high as -2Ω·cm. In addition, as a result of the humidity test, 1
The rate of change after standing for 000 hours was as large as 200%. Also, the result of the second test was 30/100, which was poor. Comparative Example 10 Copper powder plated with 90 wt% silver, average particle size 10 μm
powder 10g resol type phenolic resin
2
g Triethanolamine

0.8g Butyl cellosolve

2g were mixed and screen printed onto a glass epoxy resin substrate. 1
It was cured by heating at 50°C for 20 minutes. The volume resistivity of the cured film was 3×10 −3 Ω·cm, but the migration test results showed that it took only 15 seconds.

[0044]

Effects of the Invention As explained above, the present invention provides a copper alloy composition that has excellent conductivity, excellent oxidation resistance, and excellent migration resistance, and which paste, conductive adhesive, paste for conductive circuits,
It has excellent properties as a conductive paste for electrodes and a paste for through holes.

Claims (14)

[Claims] [Claim 1] General formula AgxCuy (where 0
．． 001≦x≦0.999, 0.001≦y≦0.99
9, x+y=1, atomic ratio) copper alloy powder 100
5 to 200 parts by weight of an organic binder, and 0.01 to 100 parts by weight of an additive capable of removing copper oxide. Claim 2: Copper alloy powder represented by the general formula AgxCuy is 0.001≦x≦0.4, 0.6≦y≦0.99
9 (atomic ratio), the silver concentration on the surface of the copper alloy powder particles is higher than the average silver concentration, and there is a region near the surface where the silver concentration increases from the inside toward the surface. Item 1. Copper alloy composition according to item 1. 3. The copper alloy composition according to claim 2, wherein the silver concentration on the surface of the copper alloy powder particles is 2.1 times or more the average silver concentration. [Claim 4] The average particle size of the particles of the copper alloy powder is 0.1.
4. The copper alloy composition according to claim 1, wherein the copper alloy composition has a diameter of 100 microns. 5. The copper alloy composition according to claim 1, wherein the copper alloy powder is produced using an atomization method. [Claim 6] The organic binder is one or more selected from thermosetting resins, thermoplastic resins, electron beam curable resins, photocurable resins, electron beam decomposable resins, and photodegradable resins. The copper alloy composition according to any one of claims 1 to 5, characterized in that: 7. Additives capable of removing copper oxides include fatty acids and their metal salts, dicarboxylic acids, oxycarboxylic acids, phenols, metal chelate forming agents, higher aliphatic amines,
7. The copper alloy composition according to claim 1, comprising one or more selected from organic titanate compounds, rosin, anthracene, and derivatives thereof. 8. The copper alloy composition according to any one of claims 1 to 7 can be used for glass epoxy resin substrates, paper phenol resin substrates, paper epoxy resin substrates, polyester resin substrates,
Polysulfone resin substrate, polyetherimide resin substrate, polyimide resin substrate, BT resin resin substrate, polyether
Telsulfone resin substrate, glass polyimide resin substrate,
Polybutadiene resin substrate, polyphenylene ether resin substrate, polyphenylene sulfide resin substrate, fluororesin substrate, alumina substrate, aluminum nitride substrate, aluminum substrate,
Molded products printed on one or more types of hard substrates such as stainless steel substrates, enamel substrates, or flexible substrates. 9. A screen printing paste comprising the copper alloy composition according to any one of claims 1 to 7. 10. A paste for electromagnetic shielding comprising the copper alloy composition according to any one of claims 1 to 7. 11. A conductive circuit paste comprising the copper alloy composition according to claim 1. 12. A conductive adhesive comprising the copper alloy composition according to claim 1. 13. An electrode paste comprising the copper alloy composition according to claim 1. 14. A paste for through-holes comprising the copper alloy composition according to any one of claims 1 to 7.