JP5425962B2 - Heat-sinterable silver particle production method, paste-like silver particle composition, solid silver production method, metal member joining method, printed wiring board production method, and electrical circuit connection bump production method - Google Patents

Description

The present invention relates to a method for producing heat-sinterable silver particles coated with a lower polyvalent carboxylic acid or derivative thereof; heat-sinterable silver particles coated with a lower polyvalent carboxylic acid or derivative thereof and a high dielectric constant A paste-like silver particle composition which is made of a volatile dispersion medium and becomes solid silver having excellent strength, electrical conductivity and thermal conductivity by sintering by heating; solid form from the paste-like silver particle composition A method for producing silver; a method for joining metal members using the paste-like silver particle composition; a method for producing a printed wiring board using the paste-like silver particle composition; and the paste-like silver particle composition The present invention relates to a method for manufacturing an electric circuit connecting bump using an object.

Conductive paste made by dispersing silver powder in thermosetting resin composition is cured by heating to form a conductive film, so that conductive circuit formation on printed circuit boards, resistors, capacitors, etc. Electrode formation of various electronic parts and display elements, formation of a conductive film for electromagnetic wave shielding, adhesion of chip parts such as capacitors, resistors, diodes, memories and arithmetic elements (CPUs) to substrates, solar cell electrodes, In particular, it is used for forming electrodes of solar cells that cannot be processed at high temperature using amorphous silicon semiconductors, forming external electrodes of chip-type ceramic electronic components such as multilayer ceramic capacitors, multilayer ceramic inductors, multilayer ceramic actuators, and the like.
In recent years, the amount of heat generated from chip parts has increased due to the high performance of chip parts, and it is required to improve the thermal conductivity as well as the electrical conductivity. When trying to improve the thermal conductivity, there is a problem that the viscosity of the paste increases and the workability is remarkably lowered.

In order to solve such a problem, the present inventors heated the paste-like silver particle composition composed of silver powder and a volatile dispersion medium, and the volatile dispersion medium volatilized and the silver powder was sintered. It became solid silver having extremely high electrical conductivity and thermal conductivity, and was found to be useful for joining metallic members and forming conductive circuits (Patent Document 1 and Patent Document 2).
However, the paste-like composition is sintered at a low temperature, for example, a temperature of 200 ° C. or less, and adhered to the base material due to heat resistance restrictions of electronic devices, electronic components, chip components, and the materials constituting them. Increasingly, it is required to have sex.
However, especially when sintered at a low temperature, the curability and adhesiveness are not sufficiently developed, and this is caused by the coating of silver particles such as higher fatty acids and higher fatty acid salts used for the purpose of preventing aggregation of silver particles. I noticed a problem with the drug. Therefore, a method for producing heat-sinterable silver particles that can be sintered at a low temperature by replacing these higher fatty acids and higher fatty acid salts with lower fatty acids or lower fatty acid salts, and the heat sintering A paste-like silver particle composition comprising conductive silver particles and a volatile dispersion medium, heating the paste-like silver particle composition, volatilizing the volatile dispersion medium and sintering the silver powder; It became solid silver having thermal conductivity, and was found to be useful for joining metal members and forming conductive circuits (Patent Document 3).
However, there is a problem that the adhesive strength is insufficient when the paste-like silver particle composition comprising the heat-sinterable silver particles and the volatile dispersion medium is used for joining metal members.

Since silver used in the paste-like silver particle composition is fine particles, the surface thereof is coated with an organic substance to prevent aggregation of the silver particles. In patent document 4, in order to prevent aggregation of silver powder, the silver powder coat | covered with the higher fatty acid is manufactured by making a higher fatty acid coexist in a silver powder production | generation process. Specifically, a reducing agent such as formalin and sodium hydroxide and a higher fatty acid such as stearic acid, oleic acid and palmitic acid are added to an aqueous silver nitrate solution and stirred, and then the silver powder coated with these higher fatty acids is separated. ing.
However, since the silver particles are coated with higher fatty acids that are difficult to remove by sintering at a low temperature, a paste-like silver particle composition comprising the silver particles and a volatile dispersion medium is used for joining metal members. In this case, there is a problem that the adhesive strength is insufficient.

In Patent Document 5, silver particles coated with a higher fatty acid salt are produced by making a higher fatty acid salt (eg, sodium oleate) coexist when reducing silver oxide to produce silver particles. Higher fatty acid salt-coated silver particles are flaked with a ball mill.
In Patent Document 6, a surfactant (eg, polyethylene glycol dioleate) and / or a higher fatty acid (eg, oleic acid, stearic acid, myristic acid) is added when the silver particles are flaked with a ball mill.
However, since the flaky silver particles are coated with higher fatty acids and / or higher fatty acid salts that are difficult to remove at low temperatures, the paste-like silver particle composition comprising the silver particles and a volatile dispersion medium is used as a metal member. When used for joining, there is a problem that the adhesive strength is insufficient.

Patent Document 7 states that “polyvalent carboxylic acid (eg, adipic acid, succinic acid, diglycolic acid, glutaric acid or maleic acid) is coated in an amount of 0.01% by mass to 0.5% by mass with respect to the material silver powder. Granular silver powder ”,“ Polyvalent carboxylic acid is added in an amount of 0.01% to 0.5% by mass with respect to the material silver powder in a state dissolved in a solvent, and the material silver powder to which the polyvalent carboxylic acid is added is pulverized and disintegrated. A method for producing granular silver powder, in which the polyvalent carboxylic acid is mixed with the material silver powder while being pulverized and pulverized by a crusher, and the solvent is removed to obtain granular silver powder "and" resin containing the granular silver powder " A “curable conductive paste” is disclosed. Only the silver powder produced by the wet reduction method is described as the material silver powder. However, if the surface of the silver powder produced in the manufacturing process by the wet reduction method is not immediately coated with a fatty acid, a large amount of silver powder having a large particle size is generated, and the resulting particle size distribution of the silver powder becomes unstable. There is a problem that the yield decreases. Furthermore, the above production method has a problem that it is difficult to produce silver powder having a small particle size. Moreover, when polyhydric carboxylic acid exceeds 0.5 mass%, there exists a problem which the electroconductivity of resin curable conductive paste falls. Further, the volume resistivity of the cured product of the resin curable conductive paste exceeds 1 × 10 ⁻⁵ Ω · cm, and there is a problem that the conductivity is low.

Patent Document 8 discloses an organic substance having an average primary particle diameter of 1 to 200 nm and having 8 or less carbon atoms (eg, an example) in order to make it possible to form a bonded body that exhibits practical bonding strength even in a nitrogen environment. , Hexanoic acid, heptanoic acid, adipic acid, sorbic acid, malonic acid), silver nanoparticles coated with a flux component (eg, oxydiacetic acid) having two or more carboxyl groups, and a dispersion medium are disclosed. ing. However, simply by adding a flux component having two or more carboxyl groups to the paste-like bonding material containing a solvent, an organic substance originally covering the surface of the silver nanoparticles is contained in the bonding material. Since it remains, there is a problem that bonding by sintering at a low temperature is not sufficient.

International Publication No. 2006/126614 International Publication No. 2007/034833 JP 2009-289745 A JP 54-121270 A JP 2001-49309 A JP 2003-55701 A JP 2011-140714 A JP 2011-240406 A

The inventors of the present invention have a silver paste that does not have the above problem, that is, a paste that sinters at a relatively low temperature and becomes solid silver excellent in adhesive strength, hardness, electrical conductivity, and thermal conductivity. As a result of diligent research to develop a silver particle composition, the fatty acid or derivative thereof of silver particles coated with a monovalent fatty acid or derivative thereof is converted into a lower polyvalent carboxylic acid having 2 to 4 carbon atoms. The inventors have found that substitution is effective and have completed the present invention.

The object of the present invention is to heat-sinterable silver particles that, when heated, are easily sintered at a relatively low temperature and become solid silver having excellent adhesion strength, hardness, electrical conductivity and thermal conductivity. A paste-like silver particle composition, which, when heated, easily sinters silver particles at a relatively low temperature to form solid silver having excellent adhesion strength, hardness, electrical conductivity and thermal conductivity; paste Of producing solid silver excellent in strength, electrical conductivity and thermal conductivity from a silver particle composition; using the paste-like silver particle composition to strengthen a metal member with good electrical and thermal conductivity A method of manufacturing a printed wiring board having a silver wiring having excellent adhesion, electrical conductivity, and thermal conductivity to a substrate; and an electric circuit connecting bump having excellent electrical conductivity and thermal conductivity It is in providing the method of manufacturing.

This purpose is
“[1] The average particle diameter (median diameter D50) is 0.01 μm to 20 μm, and the surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms or a derivative (a2) of the fatty acid (a1). and the derivative (a2) of the fatty acid silver particles (a1) or the fatty acid (a1), the derivative of the polyvalent carboxylic acid (b1) or the carboxylic acid of 2 to 4 carbon atoms (b1) (b2), complete In the differential thermal analysis chart for the substituted silver particles in the atmosphere, the heat-sinterable silver is substituted until the exothermic peak due to sintering of the silver particles before substitution disappears. Particle manufacturing method.
[1-1] The heat-sinterable silver particles according to [1], wherein the fatty acid (a1) derivative (a2) is a salt, ester or amide of the monovalent fatty acid (a1) Manufacturing method.
[1-1-1] The method for producing heat-sinterable silver particles according to [1-1], wherein the salt is a metal salt, an ammonium salt or an amine salt.
[1-2] The heating according to [1], wherein the derivative (b2) of the carboxylic acid (b1) is a nonmetallic salt, ester, amide or anhydride of the carboxylic acid (b1). A method for producing sinterable silver particles.
[1-2-1] The method for producing heat-sinterable silver particles according to [1-2], wherein the nonmetallic salt is an ammonium salt or an amine salt.
[2] The fatty acid (a1) of the silver particle whose surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms is converted to a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid. By substituting completely with the ammonium salt of (b1), in the differential thermal analysis chart in the atmosphere for the silver particles after substitution, substitution is performed until the exothermic peak due to sintering of the silver particles before substitution disappears. The method for producing heat-sinterable silver particles according to [1], which is characterized in that
[3] The alkali metal salt (a2) of the silver particles whose surface is coated with an alkali metal salt of a monovalent fatty acid having 5 to 24 carbon atoms (a2) is converted to a polyvalent carboxylic acid having 2 to 4 carbon atoms ( In the differential thermal analysis chart in the atmosphere for the silver particles after substitution by completely replacing by b1), the substitution is performed until the exothermic peak due to sintering of the silver particles before substitution disappears, The method for producing heat-sinterable silver particles according to [1].
[4] The method for producing heat-sinterable silver particles according to any one of [1] to [3], wherein the polyvalent carboxylic acid (b1) is a divalent aliphatic carboxylic acid.
[5] The method for producing heat-sinterable silver particles according to [1], wherein the shape of the silver particles is spherical, granular or flaky.
[5-1] The method for producing heat-sinterable silver particles according to any one of [2] to [4], wherein the silver particles are spherical, granular or flaky. Is achieved.

This purpose is
“[6] (A) Monovalent fatty acid (a1) having an average particle diameter (median diameter D50) of 0.01 to 20 μm and a surface of 5 to 24 carbon atoms or a derivative (a2) of said fatty acid (a1) The fatty acid (a1) or the derivative (a2) of the fatty acid (a1) of the silver particles coated with a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1) In the differential thermal analysis chart for the substituted silver particles in the atmosphere by complete substitution, the silver particles substituted until the exothermic peak due to sintering of the silver particles before substitution disappears, (B) A paste-like silver particle composition comprising a volatile dispersion medium having a dielectric constant of 20 to 90, wherein the volatile dispersion medium is volatilized by heating and the silver particles are sintered.
[6-1] The heat-sinterable silver particles according to [6], wherein the derivative (a2) of the fatty acid (a1) is a salt, ester or amide of the monovalent fatty acid (a1) Manufacturing method.
[6-1-1] The pasty silver particle composition according to [6-1], wherein the salt is a metal salt, an ammonium salt or an amine salt.
[6-2] The paste according to [6], wherein the derivative (b2) of the carboxylic acid (b1) is a nonmetallic salt, ester, amide or anhydride of the carboxylic acid (b1) -Like silver particle composition.
[6-2-1] The pasty silver particle composition according to [6-2], wherein the nonmetallic salt is an ammonium salt or an amine salt.
[7] The fatty acid (a1) of the silver particle whose surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms is converted to a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid. By substituting completely with the ammonium salt of (b1), in the differential thermal analysis chart in the atmosphere for the silver particles after substitution, substitution is performed until the exothermic peak due to sintering of the silver particles before substitution disappears. The pasty silver particle composition according to [6], which is characterized in that it is characterized.
[8] The alkali metal salt (a2) of the silver particles whose surface is coated with the alkali metal salt (a2) of a monovalent fatty acid having 5 to 24 carbon atoms is converted to a polyvalent carboxylic acid (2 to 4 carbon atoms). In the differential thermal analysis chart in the atmosphere for the silver particles after substitution by completely replacing by b1), the substitution is performed until the exothermic peak due to sintering of the silver particles before substitution disappears, The pasty silver particle composition according to [6].
[9] The pasty silver particle composition according to any one of [6] to [8], wherein the polyvalent carboxylic acid (b1) is a divalent aliphatic carboxylic acid.
[10] The pasty silver particle composition according to [6], wherein the silver particles are spherical, granular or flaky.
[10-1] The paste-like silver particle composition according to any one of [7] to [9], wherein the shape of the silver particles is spherical, granular or flaky. Is achieved.

This purpose is
“By heating the paste-like silver particle composition according to any one of [11] [6] to [9] at 70 ° C. or more and 300 ° C. or less, the volatile dispersion medium is volatilized to form the silver particles together. Sintered, the volume resistivity after sintering is 1 × 10 ⁻⁵ Ω · cm or less, and the thermal conductivity is 50 W / m · K or more, and the method for producing solid silver .
[11-1] By heating the paste-like silver particle composition according to [10] at 70 ° C. or more and 300 ° C. or less, the volatile dispersion medium is volatilized to sinter the silver particles, and sintering A method for producing solid silver, characterized in that the subsequent volume resistivity is 1 × 10 ⁻⁵ Ω · cm or less and the thermal conductivity is 50 W / m · K or more. Is achieved.

This purpose is
“[12] [6] to [9] The paste-like silver particle composition is interposed between a plurality of metal members, and is heated at 70 ° C. or more and 300 ° C. or less. The method for joining metal members is characterized in that the silver particles are volatilized and the silver particles are sintered to join together a plurality of metal members.
[12-1] The silver particle composition comprising the paste-like silver particle composition according to [10] interposed between a plurality of metal members, and volatilizing the volatile dispersion medium by heating at 70 ° C. or more and 300 ° C. or less. A method of joining metal members, comprising sintering metal members and joining a plurality of metal members together.
[13] The method for joining metal members according to [12], wherein the metal member is a metal substrate or a metal part of an electronic component. Is achieved.

This purpose is
“[14] The paste-like silver particle composition according to any one of [6] to [9] is applied onto a substrate coated with an adhesive and heated at 70 ° C. or more and 300 ° C. or less, A method for producing a printed wiring board, comprising: volatilizing a volatile dispersion medium and sintering the silver particles to form silver wiring on an adhesive.
[14-1] The volatile dispersion medium is volatilized by applying the paste-like silver particle composition according to [10] onto a substrate coated with an adhesive and heating at 70 ° C to 300 ° C. A method for producing a printed wiring board, comprising: sintering silver particles to form silver wiring on an adhesive. Is achieved.

This purpose is
“[15] The paste-like silver particle composition according to any one of [6] to [9] is applied in a dot shape to an electric circuit connecting pad on a semiconductor element or an electric circuit connecting electrode on a substrate. Then, by heating at 70 ° C. or more and 300 ° C. or less, the volatile dispersion medium is volatilized to sinter the silver particles to form silver bumps on the semiconductor element or the substrate, A method of manufacturing a bump for connecting an electric circuit.
[15-1] The paste-like silver particle composition according to [[10] is applied in the form of dots to an electric circuit connecting pad portion on a semiconductor element or an electric circuit connecting electrode portion on a substrate, and is 70 ° C. or higher. Bumps for electric circuit connection, characterized in that, by heating at 300 ° C. or less, the volatile dispersion medium is volatilized to sinter the silver particles to form silver bumps on a semiconductor element or substrate. Manufacturing method. Is achieved.

According to the method for producing heat-sinterable silver particles of the present invention, the silver particles (A) are sintered and bonded to each other by heating at a relatively low temperature, particularly by heating at 70 ° C. or more and 300 ° C. or less. It is possible to easily produce silver particles that are solid silver having excellent hardness, electrical conductivity, and thermal conductivity.
In the paste-like silver particle composition of the present invention, the volatile dispersion medium (B) is volatilized, and the silver particles (A) are sintered together by heating at 70 ° C. or more and 300 ° C. or less. And solid silver with excellent electrical and thermal conductivity.

According to the method for producing solid silver of the present invention, the volatile dispersion medium (B) is volatilized by heating at a relatively low temperature, and particularly the silver particles (A) are heated by heating at 70 ° C. or more and 300 ° C. or less. Can be sintered to produce solid silver having excellent adhesion strength, hardness, electrical conductivity and thermal conductivity.
According to the method for joining metal members of the present invention, the volatile dispersion medium (B) is volatilized and the silver particles (A) are heated by heating at a relatively low temperature, particularly by heating at 70 ° C. or more and 300 ° C. or less. Sinters, and a plurality of metal members can be firmly bonded with good electrical and thermal conductivity.

According to the method for producing a printed wiring board of the present invention, the volatile dispersion medium (B) is volatilized by heating at a relatively low temperature, in particular, by heating at 70 ° C. or more and 300 ° C. or less, and the silver particles (A) are made together. Can be sintered to produce a printed wiring board having silver wiring excellent in wear resistance, adhesion to the substrate, electrical conductivity and thermal conductivity. Further, a circuit board can be manufactured by mounting a chip or the like on the printed wiring board by the bonding method.

According to the method for manufacturing a bump for connecting an electric circuit of the present invention, a silver bump having excellent electrical conductivity and thermal conductivity can be efficiently and easily formed on a semiconductor element or a substrate.

2 is a differential thermal analysis (temperature increase rate: 10 ° C./min) chart in air for silver particles before substitution in Example 1. FIG. 3 is a differential thermal analysis (temperature increase rate: 10 ° C./min) chart in air for the silver particles after substitution in Example 1. FIG. It is a differential thermal analysis (temperature rising rate 10 degree-C / min) chart in the air | atmosphere about the silver particle before substitution in Example 6. FIG. 10 is a differential thermal analysis (temperature increase rate: 10 ° C./min) chart in air for the silver particles after substitution in Example 6. It is a top view of the test body A for adhesive strength measurement in an Example. The paste-like silver particle composition 2 is printed and applied on a silver substrate 1 with a metal mask, and after mounting the silver chip 3, it is heated to bond the silver substrate 1 and the silver chip 3 and measure the adhesive strength. . It is a side view of the XX line direction in FIG.

In the method for producing heat-sinterable silver particles of the present invention, the average particle diameter (median diameter D50) is 0.01 μm to 20 μm, and the surface is a monovalent fatty acid (a1) having 5 to 24 carbon atoms or the fatty acid ( The fatty acid (a1) of the silver particles coated with the derivative (a2) of a1) or the derivative (a2) of the fatty acid (a1) is converted to a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid. The derivative (b2) of (b1) is substituted until no exothermic peak due to sintering of the initial silver particles is detected in the differential thermal analysis. As a result of the substitution, heat-sinterable silver particles whose surface is coated with the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the polyvalent carboxylic acid (b1) are produced.

The paste-like silver particle composition of the present invention has (A) an average particle diameter (median diameter D50) of 0.01 μm to 20 μm and a surface of monovalent fatty acid (a1) having 5 to 24 carbon atoms or the fatty acid ( The fatty acid (a1) of the silver particles coated with the derivative (a2) of a1) or the derivative (a2) of the fatty acid (a1) is converted to a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid. (B1) derivative (b2), silver particles substituted until exothermic peaks due to sintering of initial silver particles are not detected in differential thermal analysis, and (B) volatile dispersion having a dielectric constant of 20 to 90 And a paste-like silver particle composition in which the volatile dispersion medium is volatilized by heating and the silver particles are sintered together.

The average particle diameter (median diameter D50) of 0.01 μm to 20 μm and the surface of the silver particles in the silver particles coated with the fatty acid (a1) having 5 to 24 carbon atoms or the fatty acid (a1) derivative (a2) Examples of the shape are spherical, needle-like, square-like, dendritic, fibrous, flake-like (single), granular, irregular shape, and teardrop-like (see JIS Z2500: 2000). Shape, grape shape, spindle shape, substantially cubic shape, hexagonal plate shape, columnar shape, rod shape, porous shape, lump shape, angled corner shape, round shape, etc., but in terms of manufacturability and procurement, it is spherical, It is preferable that it is granular and flaky.

The spherical shape referred to here is a shape that is almost a sphere (see JIS Z2500: 2000). The spherical shape is not necessarily required, and the ratio of the major axis (DL) to the minor axis (DS) of the particle (DL) / (DS) (sometimes referred to as spherical coefficient or sphericity) is 1.0 to 1. Those in the range of .2 are preferred.
Granular is not an irregular shape but a shape with almost equal dimensions (see JIS Z2500: 2000).
The flake shape (strip shape) is a plate-like shape (see JIS Z2500: 2000) and is also called a scale shape because it is a thin plate shape like a scale.

The aspect ratio of the flaky silver particles referred to here is a value of [average length of particles in the plane direction (μm)] / [average thickness of particles (μm)], and is in the range of 2 to 200. A thing is preferable and it is more preferable that it is the range of 5-50. In calculating the aspect ratio, the average length value in the planar direction is, for example, observed with a scanning electron microscope at a magnification of about 1000 to 10,000 times, and the length in the planar direction of 20 or more silver particles in the observed image. Can be obtained as an average value. In addition, the average thickness is obtained by, for example, manufacturing a sample in which flaky silver particles are hardened with a curable resin such as an epoxy resin, and observing the cross section of the sample with a scanning electron microscope at a magnification of about 5000 to 20000 times. Then, the thickness of 20 or more silver particles in the observed image can be measured and obtained as an average value. No matter the shape, the particle size distribution is not limited.

In the method for producing heat-sinterable silver particles of the present invention, the average particle size of the silver particles whose surface is coated with the fatty acid (a1) having 5 to 24 carbon atoms or the derivative (a2) of the fatty acid (a1) is In terms of sinterability, the thickness is 0.01 μm to 20 μm.
This average particle diameter is an average particle diameter (median diameter D50) of primary particles obtained by a laser diffraction / scattering particle size distribution measurement method. When the average particle diameter exceeds 20 μm, the sinterability between silver particles becomes low, and it is difficult to obtain excellent strength, electrical conductivity, thermal conductivity, and adhesion. Therefore, the average particle diameter is preferably 20 μm or less, and more preferably 10 μm or less. Moreover, since the surface activity of a silver particle is too strong and there exists a possibility that the storage stability of a paste-form silver particle composition may fall when it is less than 0.01 micrometer, it is preferable that it is 0.01 micrometer or more. The median diameter D50 is also referred to as a laser diffraction method 50% particle size (see Japanese Patent Application Laid-Open No. 2003-55701) or a volume cumulative particle size D50 (see Japanese Patent Application Laid-Open No. 2007-84860).

The laser diffraction / scattering particle size distribution measurement method is a method of irradiating a metal beam with a laser beam and measuring the intensity of the diffracted light or scattered light emitted in various directions depending on the size of the metal particle. This is a general-purpose measurement method for determining the particle size of particles. Many measuring devices are commercially available (for example, a laser diffraction particle size distribution measuring device SALD manufactured by Shimadzu Corporation, a laser diffraction scattering particle size distribution measuring device Microtrac manufactured by Nikkiso Co., Ltd.), and using these, the average particle size can be easily obtained. The diameter (median diameter D50) can be measured. In the case where the aggregation of the metal particles is strong, it is preferably measured after being dispersed in a primary particle state by a homogenizer.

The production method of the silver particles is not particularly limited, and examples thereof include a reduction method, a pulverization method, an electrolysis method, an atomization method, a heat treatment method, and a combination thereof, and examples thereof include polyvalent carboxylic acids having 2 to 4 carbon atoms (b1 In particular, the reduction method is preferable from the viewpoint of the substitution effect by the derivative (b2) of the carboxylic acid (b1).

The monovalent fatty acid (a1) having 5 to 24 carbon atoms previously coated on the surface of silver particles is pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (capryl). Acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (Stearic acid), 12-hydroxyoctadecanoic acid (12-hydroxyoleic acid), eicosanoic acid (arachinic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (serotic acid), octacosanoic acid (montan) Acid), etc .; 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptyl Branched saturated fatty acids such as ludodecanoic acid and isooleic acid; unsaturated fatty acids such as palmitoleic acid, oleic acid, isooleic acid, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, gadrenic acid, erucic acid, ceracoleic acid .

The fatty acid (a1) having 5 to 24 carbon atoms in the monovalent fatty acid (a1) having 5 to 24 carbon atoms or the derivative (a2) of the fatty acid (a1) previously coated on the surface of the silver particles is silver. Monovalent fatty acids having 5 to 16 carbon atoms are suitable when the average particle size of the particles is less than 0.1 μm, and monovalent fatty acids having 17 to 24 carbon atoms are suitable when the average particle size of the silver particles is 0.1 μm or more. It is.

The monovalent fatty acid (a1) derivative (a2) having 5 to 24 carbon atoms is preferably a salt of the monovalent fatty acid, and examples thereof include metal salts, ammonium salts, and amine salts. Other examples include esters of the monovalent fatty acids and amides of the monovalent fatty acids.
Examples of the metal salt of the monovalent fatty acid metal salt include alkali metal salts (for example, sodium salts and potassium salts), alkaline earth metal salts (for example, magnesium salts and calcium salts), aluminum salts, and transition metal salts. Alkali metal salts are preferred. Examples of amines of the monovalent fatty acid amine salts include primary alkyl amines (eg, ethylamine, propylamine), primary phenylamines, secondary alkylamines (eg, diethylamine), and tertiary alkylamines. These alkylamines preferably have 1 to 6 carbon atoms. Examples of the monovalent fatty acid esters include alkyl esters (for example, methyl esters and ethyl esters) and phenyl esters. The alkyl group of these alkyl esters preferably has 1 to 6 carbon atoms. Examples of the amide of the monovalent fatty acid amide include simple amide, N-alkylamide (for example, N-ethylamide), N, N′-dialkylamide (for example, N, N′-diethylamide), and N-phenylamide. . The alkyl group of these alkylamides preferably has 1 to 6 carbon atoms.

The polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms for substituting the monovalent fatty acid (a1) or the derivative (a2) of the fatty acid (a1) previously coated on the surface of the silver particle is a divalent carboxylic acid. Acids are preferred, followed by trivalent carboxylic acids. As such a carboxylic acid, a polyvalent aliphatic carboxylic acid is preferable, and a divalent aliphatic carboxylic acid is particularly preferable. Oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, and oxydiacetic acid (diglycolic acid) are preferred. Illustrated. Silver particles whose silver surface is coated with these polyvalent fatty acids (b1) usually show hydrophilicity.

The fatty acid (a1) or the derivative (a2) of the fatty acid (a1) of silver particles whose surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms or a derivative (a2) of the fatty acid (a1) The derivative (b2) of the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms for substitution is preferably a nonmetallic salt of the carboxylic acid in view of the substitution effect, and an ammonium salt or amine salt as the nonmetallic salt. Is exemplified.
Furthermore, the ester, amide, and anhydride of the carboxylic acid are exemplified. Examples of amines of the amine salts of the carboxylic acids include primary alkyl amines (eg, ethylamine, propylamine), primary phenylamines, secondary alkylamines (eg, diethylamine), and tertiary alkylamines. The alkyl group of these alkylamines preferably has 1 to 6 carbon atoms.

The fatty acid (a1) or the derivative (a2) of the fatty acid (a1) of silver particles whose surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms or a derivative (a2) of the fatty acid (a1) Substitution with polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or derivative (b2) of carboxylic acid (b1) until no exothermic peak due to sintering of initial silver particles is detected in differential thermal analysis By doing so, heat-sinterable silver particles are produced.

The substitution method is not particularly limited. For example, silver particles coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms or a derivative (a2) of the fatty acid (a1) are used. There is a method of dipping in a solution of the polyvalent carboxylic acid (b1) 4 or the derivative (b2) of the carboxylic acid (b1). At this time, the liquid may be stirred or shaken by a stirrer, a shaker, an ultrasonic vibrator, or the like.

In this case, when the polycarboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1) is solid at room temperature, it is dissolved in water or a lower alcohol, alcohol, ketone, It is preferable to use it by dissolving in an organic solvent such as ester or hydrocarbon. The mixing ratio of the polycarboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1) and water, a lower alcohol or an organic solvent is a polyvalent carboxylic acid having 2 to 24 carbon atoms. There is no particular limitation as long as the acid (b1) or the derivative (b2) of the carboxylic acid (b1) can be dissolved.

Although the temperature at the time of the said immersion is not specifically limited, In order to suppress aggregation of silver particles, it is preferable that it is below normal temperature. The dipping time may be a time sufficient to remove the monovalent fatty acid (a1) having 5 to 24 carbon atoms or the derivative (a2) of the fatty acid (a1) that has coated the surface of the silver particles. It is not limited. Next, the silver particles are separated by filtering the immersion liquid or the mixture.

The silver particles thus separated are coated on the surface with a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or a derivative (b2) of the carboxylic acid (b1). When the polyvalent carboxylic acid (b1) of 2 to 4 or the derivative (b2) of the carboxylic acid (b1) is attached, such excess can be removed to improve the stability of the silver particles. preferable. Further, the monovalent fatty acid (a1) having 5 to 24 carbon atoms or the derivative (a2) of the fatty acid (a1) previously coated on the surface of the silver particles may remain, and the low temperature of the silver particles may remain. These are also preferably removed in order to improve the sinterability.

For this purpose, it is preferable to wash the separated silver particles with water, a volatile organic solvent, or water and a volatile organic solvent. As an organic solvent for that purpose, acetone, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, dimethyl sulfone are used. Examples are xoxide and tetrahydrofuran. This is because these organic solvents have a low boiling point and high volatility, and therefore can be easily removed by air drying or drying under reduced pressure at room temperature. Further, when the silver particles are produced by a reduction method, there is an advantage that the organic reducing agent adhering to the silver particles is also removed.

The amount of the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1) covering the surface of the silver particle thus obtained depends on the sinterability of the silver particle. From the viewpoint of the strength, electrical conductivity, and thermal conductivity of the solid silver obtained by sintering, the solid silver content is preferably 0.01 to 5.0% by mass, and particularly 0.1 to 2.5% by mass. It is preferable that

The amount of the C2-C4 polycarboxylic acid (b1) or the derivative (b2) of the carboxylic acid (b1) covering the silver particles can be measured by a usual method. The silver particles coated with the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1) are heated to 500 ° C. in an air stream to adhere to the silver particles. An example is thermogravimetric analysis in which the weight loss is measured by removing the carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1) by oxidative decomposition, volatilization, or combustion. Is done. As another method, the silver particles are heated in an oxygen stream and are attached to the silver particles in the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1). An example is a method in which carbon is changed to carbon dioxide and quantitative analysis is performed by infrared absorption spectroscopy. In these cases, the total amount of the surface of the silver particles and the organic reducing agent in the silver particles is quantified, but the residual amount of the organic reducing agent is negligible and can be ignored.

Silver particles having a surface coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms or a derivative (a2) of the fatty acid (a1), a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid The silver particles coated with the derivative (b2) of the acid (b1) may have oxidized silver particle surfaces. However, if the ratio of silver oxide is high, a large amount of oxygen is generated during heating, which may cause voids in the solid silver produced by sintering. 50% or less of the entire surface of the particles is preferable, 20% or less is more preferable, and 2% or less is more preferable. Especially in use cases such as die-bonding agents that become semi-sealed with a relatively large bonding area due to large chip connection such as memory and CPU, the presence of silver oxide causes a decrease in adhesive strength due to void generation. 10% or less is preferable.

In addition, when the untreated silver particles are directly treated with the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1), the silver particles are aggregated. No silver particle powder coated with the polyvalent carboxylic acid (b1) 4 or the derivative (b2) of the carboxylic acid (b1) can be produced.

Since the silver particles coated with the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1) have high heat sinterability, it is necessary to obtain a pasty silver composition. It is better not to heat as much as possible.

The paste-like silver particle composition of the present invention has (A) an average particle diameter (median diameter D50) of 0.01 μm to 20 μm and a surface of monovalent fatty acid (a1) having 5 to 24 carbon atoms or the fatty acid ( The fatty acid (a1) of the silver particles coated with the derivative (a2) of a1) or the derivative (a2) of the fatty acid (a1) is converted to a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid. Silver particles substituted until the exothermic peak due to sintering of the initial silver particles is no longer detected in the differential thermal analysis by the derivative (b2) of (b1), and (B) a volatile dispersion medium having a dielectric constant of 20 to 90 The volatile dispersion medium is volatilized by heating and the silver particles are sintered together. This paste-like silver particle composition has a dielectric constant of 20 to 4 with silver particles (A) coated with a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or a derivative (b2) of the carboxylic acid (b1). It is a mixture with 90 volatile dispersion media (B), and powdery silver particles (A) are made into a paste by the action of the volatile dispersion media (B). By making a paste, it can be discharged in a thin line form from a cylinder or nozzle, and it can be easily applied with a metal mask, and can be easily applied to the shape of an electrode. The paste form includes a cream form and a slurry form.

The volatile dispersion medium having a dielectric constant of 20 to 90 is used for the volatile dispersion medium and the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the derivative (b2) of the carboxylic acid (b1). This is because when the coated silver particles are mixed to produce the paste-like silver particle composition of the present invention, the silver particles are easily dispersed and have an effect of preventing aggregation. More preferably, the volatile dispersion medium has a dielectric constant of 30 to 80. The dielectric constant is a value measured at room temperature.
The volatile dispersion medium is used instead of the non-volatile dispersion medium because the silver particles (A) are easily sintered when the dispersion medium volatilizes in advance when the silver particles (A) are sintered by heating. This is because the strength, electrical conductivity, and thermal conductivity of solid silver are likely to increase. The volatile dispersion medium does not alter the surface of the silver particles (A), and has a boiling point of 60 ° C. or higher and preferably 300 ° C. or lower. When the boiling point is less than 60 ° C., the solvent easily evaporates during the operation of preparing the paste-like silver particle composition, and when the boiling point is higher than 300 ° C., the volatile dispersion medium is obtained even after the silver particles (A) are sintered. This is because it may remain.

Such a volatile dispersion medium (B) has water, butanediol, glycerin, ethylene glycol, hexylene glycol and other alcohol solvents, dimethyl sulfoxide and other sulfur-containing solvents, dimethylformamide, dimethylacetamide, and ether bonds. Examples include amide solvents such as alkylamides, nitrile solvents such as acetonitrile, urea solvents such as tetramethylurea, and dimethyl sulfoxide and alkylamides having an ether bond are preferred. Two or more kinds of volatile dispersion media (B) may be used in combination, and if the dielectric constant of the combined volatile dispersion media (B) is in the range of 20 to 90, the dielectric constant is less than 20. A volatile dispersion medium or a volatile dispersion medium having a dielectric constant exceeding 90 may be used.

The compounding amount of the volatile dispersion medium (B) is a paste of silver particles (A) coated with a polycarboxylic acid (b1) having 2 to 4 carbon atoms or a derivative (b2) of the carboxylic acid (b1). A sufficient amount is sufficient, and as a guide, it is 5 to 20 parts by mass, preferably 6 to 14 parts by mass, per 100 parts by mass of the silver particles (A) that are heat-sinterable.

The paste-like silver particle composition of the present invention is a reduced silver, atomized silver, silver colloid, silver alloy, surface silver other than silver particles (A) that are heat-sinterable unless the effects of the present invention are not adversely affected. Coated powder, metal or non-metallic powder such as gold, copper, tin, solder alloy, metal compound or metal complex, silver particle or powder dispersibility improver (dispersant), thixotropic agent, stabilizer, You may contain additives, such as a coloring agent.

In the paste-like silver particle composition of the present invention, the volatile dispersion medium (B) is volatilized by heating, and the silver particles (A) that are heat-sinterable sinter together to give strength and electrical conductivity. It becomes solid silver excellent in thermal conductivity, and exhibits adhesiveness to the contacting substrate. At this time, the volatile dispersion medium (B) is volatilized, and then the silver particles (A) that are heat-sinterable may be sintered together, and the silver particles that are heat-sinterable together with the volatilization of the volatile dispersion medium. (A) may be sintered. Since silver inherently has high strength and extremely high electrical and thermal conductivity, the sintered product of the silver particles of the present invention also has high strength and extremely high electrical and thermal conductivity. The heating temperature at this time should just be the temperature which a volatile dispersion medium volatilizes and silver particle (A) can sinter, and is 70 degreeC or more normally. However, if the temperature exceeds 400 ° C., the volatile dispersion medium (B) may suddenly evaporate and adversely affect the shape of the solid silver. Therefore, the temperature must be 400 ° C. or less, preferably 220 ° C. It is below, More preferably, it is 180 degrees C or less, More preferably, it is 150 degrees C or less.

The electrical conductivity of solid silver formed by sintering silver particles (A) coated with a polycarboxylic acid (b1) having 2 to 4 carbon atoms or a derivative (b2) of the carboxylic acid (b1) is The volume resistivity is more preferably 1 × 10 ⁻⁵ Ω · cm or less, and the thermal conductivity is preferably 50 W / m · K or more. The shape of the solid silver formed by sintering the silver particles (A) that are heat-sinterable is not particularly limited, and is a sheet shape, a film shape, a tape shape, a linear shape, a disk shape, a block shape, a spot shape, An indefinite shape is illustrated.

When the paste-like silver particle composition of the present invention is heated at 70 ° C. or more and 300 ° C. or less, the volatile dispersion medium (B) is volatilized and the heat-sinterable silver particles (A) sinter, whereby the strength and Excellent electrical and thermal conductivity, metal parts that were in contact, such as gold substrate, gold-plated substrate, silver substrate, silver-plated metal substrate, copper substrate, palladium substrate, palladium-plated metal substrate, platinum substrate, platinum-plated metal Metallic substrates such as substrates, aluminum substrates, nickel-plated substrates, tin-plated metal substrates, or metal substrates, or solid silver having adhesion to metal parts such as electrodes on electrically insulating substrates. It is useful for joining electronic parts having parts, electronic devices, electrical parts, electrical devices and the like. Such bonding includes bonding of chip components such as capacitors and resistors and circuit boards; bonding of semiconductor chips such as diodes, transistors, memories, ICs, and CPUs to lead frames or circuit boards; cooling semiconductor chips having high heat generation and cooling. The joining with a board is illustrated.
The paste-like silver particle composition of the present invention is interposed between a plurality of metal members and heated at 70 ° C. or more and 300 ° C. or less to volatilize the volatile dispersion medium and sinter the silver particles. These metal members can be firmly bonded to each other.

Although washing | cleaning of the sintered compact of the silver particle (A) produced | generated by heating the paste-form silver particle composition of this invention is unnecessary, you may wash | clean with water or an organic solvent. In particular, when the volatile dispersion medium (B) is a hydrophilic solvent, it can be washed with water, and there is no problem of VOC generation as in the case of washing with an organic solvent such as alcohol. Since each component of the paste-like silver particle composition of the present invention has few impurities, it can be easily washed.

When the paste-like silver particle composition of the present invention is heated, the volatile dispersion medium (B) is volatilized, and the silver particles (A) that are heat-sinterable sinter together, resulting in high strength and extremely high electrical conductivity. And solid silver having thermal conductivity. Therefore, a curable adhesive such as an epoxy resin adhesive, a silicone resin adhesive, a printed wiring board coated with a polyimide resin adhesive, or a primer composition was applied, and then a curable adhesive was applied. By applying the paste-like silver particle composition to a printed wiring board and curing at 70 ° C. or more and 300 ° C. or less before the adhesive is cured, it is excellent in wear resistance and adhesion to the substrate. Silver wiring can be formed. Thus, a printed wiring board can be manufactured.
The method for applying the paste-like silver particle composition of the present invention is not particularly limited, and includes dispensing, printing (for example, screen printing), metal mask coating, spraying, brushing, and the like. Moreover, a circuit board can be manufactured by mounting a chip or the like on the printed wiring board.

The heating temperature may be a temperature at which the volatile dispersion medium (B) is volatilized and the silver particles (A) can be sintered, and is usually 70 ° C. or higher. However, if the temperature exceeds 300 ° C., the volatile dispersion medium (B) may suddenly evaporate and adversely affect the shape of the solid silver. Therefore, the temperature must be 300 ° C. or less, preferably 220 ° C. It is below, More preferably, it is 180 degrees C or less, More preferably, it is 150 degrees C or less.

When the paste-like silver particle composition of the present invention is heated, the volatile dispersion medium (B) is volatilized, and the silver particles (A) are sintered together, thereby having high strength, extremely high electrical conductivity, and thermal conductivity. It becomes solid silver. Accordingly, the volatile dispersion medium is volatilized by applying the paste-like silver particle composition in a dot shape to the electric circuit connecting pad part on the semiconductor element or the electric circuit connecting end part on the substrate and heating. The silver particles (A) can be sintered to form silver bumps on the semiconductor element or the substrate. Thus, a bump for connecting an electric circuit can be manufactured.

Here, examples of the semiconductor element include a diode, a transistor, a memory, and a CPU.
Examples of the method for applying the paste-like silver particle composition in the form of dots include dripping, dispensing, printing (for example, screen printing), and metal mask application.
The heating temperature may be a temperature at which the volatile dispersion medium (B) is volatilized and the silver particles (A) can be sintered, and is usually 70 ° C. or higher. However, if the temperature exceeds 300 ° C., the volatile dispersion medium (B) may suddenly evaporate and adversely affect the shape of the solid silver. Therefore, the temperature must be 300 ° C. or less, preferably 220 ° C. It is below, More preferably, it is 180 degrees C or less, More preferably, it is 150 degrees C or less.

Since the pasty silver particle composition of the present invention contains a volatile dispersion medium (B), it is preferably stored in a sealed container. When used after long-term storage, it is preferable to use the container after shaking or stirring the container. Refrigerated storage may be performed for the purpose of improving storage stability, and the storage temperature is 10 ° C. or less, but it is preferably a temperature at which the volatile dispersion medium (B) does not solidify in the sealed container. When a syringe is used for the sealed container, a small amount can be discharged using a dispenser.

Examples and comparative examples of the present invention will be given. In Examples and Comparative Examples, “parts” means “parts by mass”. Aspect ratio of flaky silver particles, differential thermal analysis (DTA) in air for silver particles before and after substitution, coating agent on surface of silver particles after substitution {polyvalent carboxylic acid having 2 to 4 carbon atoms (b1) or the amount of the carboxylic acid (b1) derivative (b2)}, the hardness, adhesion strength, and volume resistivity of solid silver produced by heating and sintering the paste-like silver particle composition The thermal conductivity was measured at 25 ° C. by the following method.

[Aspect ratio of flaky silver particles]
The flaky silver particles are observed with a scanning electron microscope at a magnification of 5000 times, the major axis and minor axis in the planar direction of 20 silver particles in the observed image are measured, and the average value is obtained as a plane average grain. The average value of the thickness of the flaky silver particles was measured to obtain the average thickness. Then, the aspect ratio was calculated by [plane average particle diameter (μm)] / [average thickness (μm)].

[Differential thermal analysis (DTA) in air for silver particles before and after substitution]
Using a differential thermothermal gravimetric simultaneous measurement apparatus (DTG-60AH type, manufactured by Shimadzu Corporation), the silver particles before and after substitution in the atmosphere are heated from room temperature (about 25 ° C.) to 400 at a temperature rising rate of 10 ° C./min. The temperature was raised to ° C. and a DTA curve was taken.

[Amount of coating on silver surface after substitution]
Using a differential thermothermal gravimetric simultaneous measurement apparatus (DTG-60AH type, manufactured by Shimadzu Corporation), the silver particles before and after substitution in the atmosphere are heated from room temperature (about 25 ° C.) to 400 at a temperature rising rate of 10 ° C./min. The temperature was raised to ° C., and the weight loss rate from the initial stage was calculated as the coating amount.

[Hardness]
A paste-like silver particle composition was applied on a polytetrafluoroethylene resin plate having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm, using a 500 μm-thick metal mask having an opening of a width of 10 mm and a length of 10 mm. Then, it was heated in a forced circulation oven at 180 ° C. for 2 hours to form film-like silver. The hardness of the film-like silver was measured by a method according to JIS Z 2244.

[Adhesive strength]
On a silver substrate (silver purity 99.99%) 1 having a width of 25 mm, a length of 70 mm, and a thickness of 1.0 mm, four openings having a width of 2.5 mm and a length of 2.5 mm are provided at an interval of 10 mm. A paste-like silver particle composition is applied using a metal mask having a thickness of 100 μm, and a silver chip (silver purity 99.99%) 3 having a width of 2.5 mm × a length of 2.5 mm × a thickness of 0.5 mm is formed thereon. After mounting, they were joined by heating in a forced circulation oven at 180 ° C. for 2 hours. The side surface of the silver chip 3 having a width of 2.5 mm, a length of 2.5 mm, and a thickness of 0.5 mm of the test specimen for measuring the adhesive strength thus obtained was pressed at a pressing speed of 23 mm / min by an adhesive strength tester. The bond strength was determined by the load when the joint was sheared. In addition, four said test bodies were measured and let the average value be adhesive strength.

[Volume resistivity]
A paste-like silver particle composition was applied on a polytetrafluoroethylene resin plate having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm, using a 500 μm-thick metal mask having an opening of a width of 10 mm and a length of 10 mm. Then, it was heated in a forced circulation oven at 180 ° C. for 2 hours to form film-like silver. The volume resistivity (unit: Ω · cm) of the film-like silver was measured by a method according to JIS K 7194.

[Thermal conductivity]
A paste-like silver particle composition is applied onto a polytetrafluoroethylene resin plate having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm using a 2 mm thick metal mask having an opening of a width of 10 mm and a length of 10 mm. Then, it was heated in a forced circulation oven at 180 ° C. for 2 hours to obtain plate-like silver. The plate-shaped silver was measured for thermal conductivity (unit: W / mK) by a laser flash method using a thermal constant measuring device.

[Reference example]
The method for producing silver particles (A) in which the monovalent fatty acid (a1) having 5 to 24 carbon atoms covering the surface is substituted with the polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms is as follows. It is as follows.
In a beaker, 100 parts of silver particles coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms and a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms {if liquid at 25 ° C. It was. In the case of solid at 25 ° C., 100 parts of ethanol (reagent manufactured by Kanto Chemical Co., Ltd. used as a 30% by mass solution) was added, and stirred at 25 ° C. for 5 hours using a magnetic stirrer. Let stand for 10 minutes to remove as much of the supernatant (polycarboxylic acid (b1) having 2 to 4 carbon atoms or ethanol solution thereof) as possible, and then add 100 parts of ethanol (a reagent manufactured by Kanto Chemical Co., Inc.) Then, the mixture was similarly stirred at 25 ° C. for 10 minutes using a magnetic stirrer. In the same manner, the supernatant was removed as much as possible, then acetone was added again to wash the silver particles in the same manner. After repeating this three times, the silver particles were taken out and air-dried at 25 ° C. for 16 hours.

[Example 1]
In the production method of the reference example, flaky silver particles (average particle diameter is 2 μm, aspect ratio is produced by a commercially available reduction method and the surface is coated with oleic acid which is a monounsaturated fatty acid having 18 carbon atoms. The ratio (average particle size / average thickness) is 20, the amount of organic substances (note: the total amount of oleic acid and a small amount of organic reducing agent is 0.6% by mass), and the number of carbon atoms is 3. Silver particles obtained by substituting malonic acid for the oleic acid (18 carbon atoms) covering the surface of the silver particles using malonic acid (a reagent manufactured by Kanto Chemical Co., Inc.) which is a divalent carboxylic acid. )

In order to confirm that oleic acid was replaced with malonic acid, a differential thermal analysis was performed in the atmosphere on the silver particles before and after substitution, and the analysis results are shown in FIG. 1 before substitution and in FIG. 2 after substitution. showed that. According to FIG. 1, the exothermic peak due to sintering of silver particles before substitution is 242.7 ° C. (the peak at 234.5 ° C. is the peak due to thermal decomposition of oleic acid). According to FIG. 2, the exothermic peak due to sintering of the silver particles (A) after substitution is 205.0 ° C., and the exothermic peak (242.7 ° C.) due to sintering of the silver particles before substitution is not detected. I understood. Therefore, it was confirmed that oleic acid was replaced with malonic acid. Moreover, the amount of the coating agent on the surface of the silver particles (A) after substitution was 0.2% by mass.

Paste silver is added to 50 parts of the silver particles (A) by adding 3.5 parts of dimethyl sulfoxide having a dielectric constant of 49 (a reagent manufactured by Kanto Chemical Co., Ltd.) and mixing with a spatula until uniform. A particle composition was prepared. This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 1. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Example 2]
In Example 1, paste-like silver particle composition was used in the same manner as in Example 1 except that succinic acid (a reagent manufactured by Kanto Chemical Co., Inc.), which is a divalent carboxylic acid having 4 carbon atoms, was used instead of malonic acid. A product was prepared.

In order to confirm that oleic acid was replaced with succinic acid, a differential thermal analysis in air was performed on the silver particles before and after substitution in the same manner as in Example 1. In the silver particles (A) after substitution, it was found that no exothermic peak was detected due to sintering of the silver particles before substitution. Therefore, it was confirmed that oleic acid was replaced with succinic acid. Moreover, the amount of the coating agent on the surface of the silver particles (A) after substitution was 0.2% by mass.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 1. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Example 3]
In Example 1, a pasty silver particle composition was prepared in the same manner as in Example 1 except that acetonitrile (a reagent manufactured by Kanto Chemical Co., Inc.) having a dielectric constant of 37 was used instead of dimethyl sulfoxide.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 1. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Example 4]
A paste-like silver particle composition was prepared in the same manner as in Example 1 except that distilled water having a dielectric constant of 80 (a reagent manufactured by Kanto Chemical Co., Inc.) was used instead of dimethyl sulfoxide.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 1. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Example 5]
In Example 1, instead of malonic acid, ammonium oxalate (a reagent manufactured by Kanto Chemical Co., Inc.) which is an oxalate salt of a divalent carboxylic acid having 2 carbon atoms was used in the same manner as in Example 1. Thus, a pasty silver particle composition was prepared.

In order to confirm that oleic acid was replaced with ammonium oxalate, a differential thermal analysis in air was performed on the silver particles before and after substitution in the same manner as in Example 1. In the silver particles (A) after substitution, it was found that no exothermic peak was detected due to sintering of the silver particles before substitution. Therefore, it was confirmed that oleic acid was replaced with oxalic acid. Further, the amount of the coating agent on the silver surface after substitution was 0.1% by mass.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 2. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Example 6]
In the production method of the reference example, substantially spherical silver particles (of primary particles obtained by laser diffraction method) that are produced by a commercially available reduction method and whose surfaces are coated with hexanoic acid, which is a monovalent saturated fatty acid having 6 carbon atoms. The average particle size (median diameter D50) is 0.02 μm, the amount of organic substances (note: the total amount of hexanoic acid and a small amount of organic reducing agent is 3% by mass), 2 for 3 carbon atoms Silver particles (A) in which hexanoic acid (6 carbon atoms) covering the surface of silver particles is replaced with malonic acid using malonic acid (a reagent manufactured by Kanto Chemical Co., Inc.), which is a valent carboxylic acid Obtained.

In order to confirm that hexanoic acid was replaced with malonic acid, differential thermal analysis was performed in air for the silver particles before and after substitution, and the analysis results are shown in FIG. 3 before substitution and in FIG. 4 after substitution. showed that. According to FIG. 3, the exothermic peak due to sintering of the silver particles before substitution is 252.7 ° C. (the peak at 145.2 ° C. is a peak due to thermal decomposition of hexanoic acid). According to FIG. 4, the exothermic peak due to sintering of the silver particles (A) after substitution is 194.7 ° C. (the peak at 137.5 ° C. is the peak due to thermal decomposition of malonic acid), and silver before substitution It was found that no exothermic peak (252.7 ° C.) due to particle sintering was detected. Therefore, it was confirmed that hexanoic acid was replaced with malonic acid. Moreover, the amount of the coating agent on the surface of the silver particles (A) after substitution was 1.5% by mass.

Paste silver particle composition was prepared by adding 12 parts of dimethyl sulfoxide (reagent manufactured by Kanto Chemical Co., Inc.) having a dielectric constant of 49 to 50 parts of the silver particles (A) and mixing with a spatula until uniform. A product was prepared. This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 2. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Example 7]
In Example 1, instead of flaky silver particles produced by a commercially available reduction method and coated with oleic acid, which is a monounsaturated fatty acid having 18 carbon atoms, the surface is produced by a commercially available reduction method. A paste-like silver particle composition was prepared in the same manner as in Example 1 except that flaky silver particles whose surface was coated with stearic acid, which is a monovalent saturated fatty acid having 18 carbon atoms, were used.

In order to confirm that stearic acid was substituted with malonic acid, as in Example 1, differential thermal analysis in air was performed on the silver particles before and after substitution. In the silver particles (A) after substitution, it was found that no exothermic peak was detected due to sintering of the silver particles before substitution. Therefore, it was confirmed that stearic acid was replaced with malonic acid. Further, the amount of the coating agent on the surface of the silver particles (A) after the substitution was 0.3% by mass.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 2. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Example 8]
In Example 7, instead of flaky silver particles produced by a commercially available reduction method and coated with oleic acid, which is a monounsaturated fatty acid having 18 carbon atoms, the surface is produced by a commercially available reduction method. A paste-like silver particle composition was prepared in the same manner as in Example 1 except that flaky silver particles coated with a potassium salt of oleic acid, which is a monovalent saturated fatty acid having 18 carbon atoms, were used.

In order to confirm that potassium oleate was replaced with malonic acid, as in Example 1, differential thermal analysis in air was performed on the silver particles before and after substitution. In the silver particles (A) after substitution, it was found that no exothermic peak was detected due to sintering of the silver particles before substitution. Therefore, it was confirmed that potassium oleate was replaced with malonic acid. Further, the amount of the coating agent on the surface of the silver particles (A) after the substitution was 0.3% by mass.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 2. The film-like silver used for the hardness measurement had sufficient hardness to be solid. From the above results, this paste-like silver particle composition is useful for producing solid solid silver, useful for joining metal members firmly with good electrical conductivity and thermal conductivity, Useful for forming silver wiring with excellent wear resistance, adhesion to substrates, electrical and thermal conductivity, and useful for forming silver bumps on semiconductor devices or substrates all right.

[Comparative Example 1]
In Example 1, flaky silver particles produced by a commercially available reduction method without using the production method of the reference example and coated with oleic acid, which is a monounsaturated fatty acid having 18 carbon atoms, were used as they were. A pasty silver particle composition was prepared in the same manner as in Example 1 except that it was used.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 3. Hardness, adhesive strength, volume resistivity, and thermal conductivity were all insufficient.

[Comparative Example 2]
The paste-like silver particle composition was the same as in Example 1 except that adipic acid (a reagent manufactured by Kanto Chemical Co., Inc.), which is a divalent carboxylic acid having 6 carbon atoms, was used instead of malonic acid. A product was prepared.

In order to confirm that oleic acid was substituted with adipic acid, as in Example 1, differential thermal analysis in air was performed on the silver particles before and after substitution. In the silver particles after substitution, it was found that no exothermic peak due to sintering of the silver particles before substitution was detected. Therefore, it was confirmed that oleic acid was substituted with adipic acid. Further, the amount of the coating agent on the silver surface after the substitution was 0.3% by mass.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 3. Hardness, adhesive strength, volume resistivity, and thermal conductivity were all insufficient.

[Comparative Example 3]
In Example 1, flaky silver particles produced by a commercially available reduction method without using the production method of the reference example and coated on the surface with oleic acid, which is a monovalent fatty acid having 18 carbon atoms, were added to the number of carbon atoms. In the same manner as in Example 1, except that malonic acid (a reagent manufactured by Kanto Chemical Co., Inc.), which is a divalent carboxylic acid 3, was added in an amount of 0.5% by mass with respect to silver particles, A particle composition was prepared.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 3. Hardness, adhesive strength, volume resistivity, and thermal conductivity were all insufficient.

[Comparative Example 4]
A paste-like silver particle composition was prepared in the same manner as in Example 1 except that cyclohexanol (reagent manufactured by Kanto Chemical Co., Inc.) having a dielectric constant of 15 was used instead of dimethyl sulfoxide. Silver particles in which oleic acid was substituted with malonic acid were slightly agglomerated due to a decrease in dispersibility in cyclohexanol.
This paste-like silver particle composition was found to sag and flow when applied with a metal mask. With respect to this paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 3. Hardness, adhesive strength, volume resistivity, and thermal conductivity were all insufficient.

[Comparative Example 5]
In Example 6, the substantially spherical silver particles produced by a commercially available reduction method and coated with hexanoic acid, which is a monovalent fatty acid having 6 carbon atoms, were used as they were without using the production method of the reference example. A paste-like silver particle composition was prepared in the same manner as in Example 6 except that.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to the paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 4. Hardness, adhesive strength, volume resistivity, and thermal conductivity were all insufficient.

[Comparative Example 6]
In Example 6, a paste-like silver particle composition was used in the same manner as in Example 6 except that butanoic acid (a reagent manufactured by Kanto Chemical Co., Inc.), which is a monovalent carboxylic acid having 4 carbon atoms, was used instead of malonic acid. A product was prepared.

In order to confirm that hexanoic acid was replaced with butanoic acid, as in Example 1, differential thermal analysis in air was performed on the silver particles before and after substitution. In the silver particles after substitution, it was found that no exothermic peak due to sintering of the silver particles before substitution was detected. Therefore, it was confirmed that hexanoic acid was replaced with butanoic acid. Further, the amount of the coating agent on the surface of the silver particles after substitution was 1.2% by mass.

In this paste-like silver particle composition, silver particles were aggregated, and sagging and flow occurred when applied with a metal mask, and could not be applied in a good shape. For this reason, it was not possible to measure the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver that is a heat-sintered product of the paste-like silver particle composition.

[Comparative Example 7]
In Comparative Example 1, instead of using the production method of Reference Example, instead of flaky silver particles produced by a commercially available reduction method and having a surface coated with oleic acid which is a monounsaturated fatty acid having 18 carbon atoms In addition, paste-like silver was produced in the same manner as in Comparative Example 1 except that flaky silver particles produced by a commercially available reduction method and having a surface coated with stearic acid which is a monovalent saturated fatty acid having 18 carbon atoms were used as they were. A particle composition was prepared.

This paste-like silver particle composition could be applied in a good shape without sagging or flowing during application with a metal mask. With respect to the paste-like silver particle composition, the hardness, adhesion strength, volume resistivity, and thermal conductivity of solid silver as a heat-sintered product were measured, and the results are summarized in Table 4. Hardness, adhesive strength, volume resistivity, and thermal conductivity were all insufficient.

[Example 9]
On an FRP (glass fiber reinforced epoxy resin) plate having a thickness of 1.2 mm, an epoxy resin adhesive (product name SW2214, manufactured by Sumitomo 3M Limited) having a thickness of 50 μm and an opening having a width of 1 mm × length of 50 mm is used. The paste-like silver particle composition of Example 1 was printed and applied in the same manner as described above, overlaid on the applied epoxy resin adhesive using a metal mask. The FRP plate was heated in a forced circulation oven at 150 ° C. for 2 hours to cure the epoxy resin adhesive and sinter silver particles.
When the volume resistivity in the length direction of a silver wiring circuit having a width of 1 mm, a length of 50 mm and a thickness of 50 μm on this printed wiring board was measured, it was 9 × 10 ⁻⁶ Ω · cm, which was practically sufficient conductivity. Had.

[Comparative Example 8]
In Example 9, an epoxy resin having a width of 1 mm, a length of 50 mm, and a thickness of 50 μm was similarly used except that the paste-like silver particle composition of Comparative Example 2 was used instead of the paste-like silver particle composition of Example 1. A wiring circuit was produced. As in Example 4, when the volume resistivity in the length direction was measured for an epoxy resin wiring circuit having a width of 1 mm, a length of 50 mm, and a thickness of 50 μm, it was 3 × 10 ⁻⁵ Ω · cm or more, and the conductivity was Was low.

[Example 10]
A copper wiring circuit (width 1 mm, length 50 mm, thickness 30 μm) formed on a 1.2 mm thick FRP plate (glass fiber reinforced epoxy resin) is gold-plated on both ends of the electric circuit 1 mm in length. The paste-like silver particle composition of Example 1 was printed and applied in the form of dots using a metal mask having an opening having a width of 1 mm and a thickness of 100 μm. The FRP plate was heated in a forced circulation oven at 150 ° C. for 2 hours to sinter the silver particles, thereby producing electric circuit connecting bumps.
When the electric resistance between the electric circuit connecting bumps formed at both ends of the electric circuit was measured, it was less than 0.05Ω, and the electric conductivity was sufficiently practical.

The heat-sinterable silver particles produced by the production method of the present invention are useful as a main raw material for a paste-like silver particle composition.
The paste-like silver particle composition of the present invention is useful for producing solid silver and joining metal members.
The solid silver production method and metal member joining method of the present invention include formation of electrodes for various electronic components such as resistors and capacitors and various display elements, formation of conductive films for electromagnetic wave shielding, capacitors, resistors, and diodes. Bonding chip parts such as memory and arithmetic elements (CPU) to substrates, forming electrodes for solar cells, forming external electrodes for chip-type ceramic electronic parts such as multilayer ceramic capacitors, multilayer ceramic inductors and multilayer ceramic actuators, printing This is useful for forming a conductive circuit on a circuit board.
The method for producing a wiring board of the present invention is useful for efficiently producing a printed wiring board having silver wiring.
The method for producing a bump for connecting an electric circuit of the present invention is useful for efficiently producing a silver bump on a semiconductor element or a substrate.

A Test specimen for measuring adhesive strength 1 Silver substrate 2 Pasty silver particle composition (solid silver after heating and sintering)
3 Silver chip

Claims (15)

Silver particles having an average particle diameter (median diameter D50) of 0.01 μm to 20 μm and a surface coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms or a derivative (a2) of the fatty acid (a1) Completely replacing the fatty acid (a1) or the derivative (a2) of the fatty acid (a1) with a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or a derivative (b2) of the carboxylic acid (b1) The method for producing heat-sinterable silver particles is characterized in that, in the differential thermal analysis chart in the atmosphere for the silver particles after substitution , substitution is performed until the exothermic peak due to sintering of the silver particles before substitution disappears . The fatty acid (a1) of the silver particles whose surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms is converted to a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid (b1). the ammonium salts, by completely replacing, in differential thermal analysis chart in the atmosphere for the silver particles after substitution, characterized by replacing up to exothermic peak due to sintering of the silver particles before substitution is lost The manufacturing method of the heat-sinterable silver particle of Claim 1. The alkali metal salt (a2) of the silver particle whose surface is coated with the alkali metal salt (a2) of a monovalent fatty acid having 5 to 24 carbon atoms is converted with a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms. , by completely replacing, in differential thermal analysis chart in the atmosphere for the silver particles after substitution, characterized by replacing up to exothermic peak due to sintering of the silver particles before substitution is lost, according to claim 1 The manufacturing method of the heat-sinterable silver particle as described in any one of. The method for producing heat-sinterable silver particles according to any one of claims 1 to 3, wherein the polyvalent carboxylic acid (b1) is a divalent aliphatic carboxylic acid. The method for producing heat-sinterable silver particles according to claim 1, wherein the shape of the silver particles is spherical, granular or flaky. (A) The average particle diameter (median diameter D50) is 0.01 μm to 20 μm, and the surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms or a derivative (a2) of the fatty acid (a1). the derivative (a2) of the fatty acid (a1) or the fatty acid of the silver particles (a1), the derivative of the polyvalent carboxylic acid having 2 to 4 carbon atoms (b1) or the carboxylic acid (b1) (b2), complete In the differential thermal analysis chart in the atmosphere for the silver particles after substitution, silver particles substituted until the exothermic peak due to sintering of the silver particles before substitution disappears, and (B) the dielectric constant is 20 A paste-like silver particle composition comprising: ˜90 volatile dispersion medium, wherein the volatile dispersion medium is volatilized by heating and the silver particles are sintered together. The fatty acid (a1) of the silver particles whose surface is coated with a monovalent fatty acid (a1) having 5 to 24 carbon atoms is converted to a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms or the carboxylic acid (b1). the ammonium salts, by completely replacing, in differential thermal analysis chart in the atmosphere for the silver particles after substitution, characterized by replacing up to exothermic peak due to sintering of the silver particles before substitution is lost The paste-like silver particle composition according to claim 6. The alkali metal salt (a2) of the silver particle whose surface is coated with the alkali metal salt (a2) of a monovalent fatty acid having 5 to 24 carbon atoms is converted with a polyvalent carboxylic acid (b1) having 2 to 4 carbon atoms. , by completely replacing, in differential thermal analysis chart in the atmosphere for the silver particles after substitution, characterized by replacing up to exothermic peak due to sintering of the silver particles before substitution is lost, according to claim 6 The paste-like silver particle composition described in 1. The paste-like silver particle composition according to any one of claims 6 to 8, wherein the polyvalent carboxylic acid (b1) is a divalent aliphatic carboxylic acid. The paste-like silver particle composition according to claim 6, wherein the shape of the silver particles is spherical, granular or flaky. The paste-like silver particle composition according to any one of claims 6 to 9 is heated at 70 ° C to 300 ° C to volatilize the volatile dispersion medium and sinter the silver particles. And a volume resistivity after sintering is 1 × 10 ⁻⁵ Ω · cm or less and a thermal conductivity is 50 W / m · K or more. The paste-like silver particle composition according to any one of claims 6 to 9 is interposed between a plurality of metal members, and the volatile dispersion medium is volatilized by heating at 70 ° C to 300 ° C. And joining the plurality of metal members to each other by sintering the silver particles. The metal member joining method according to claim 12, wherein the metal member is a metal substrate or a metal portion of an electronic component. The volatile property is obtained by applying the paste-like silver particle composition according to any one of claims 6 to 9 on a substrate coated with an adhesive and heating at 70 ° C to 300 ° C. A method for producing a printed wiring board, wherein a silver wiring is formed on an adhesive by volatilizing a dispersion medium and sintering the silver particles. The paste-like silver particle composition according to any one of claims 6 to 9 is applied in a dot shape to an electric circuit connecting pad portion on a semiconductor element or an electric circuit connecting electrode portion on a substrate, An electrical circuit characterized by heating at 70 ° C. or more and 300 ° C. or less to volatilize the volatile dispersion medium and sinter the silver particles to form a silver bump on a semiconductor element or substrate. A method for manufacturing bumps for connection.

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