JP4685145B2 - Method for manufacturing metal member assembly and metal member assembly - Google Patents

Description

The present invention relates to a method for producing a metal member assembly in which a plurality of metal members are joined by a sintered product of heat-sinterable metal particles, and a plurality of metal members are sintered from heat-sinterable metal particles. The present invention relates to a metal member joined body joined by an object.

A conductive / thermal conductive paste obtained by dispersing a metal powder such as silver, copper, or nickel in a liquid thermosetting resin composition is cured by heating to form a conductive / thermal conductive film. Therefore, formation of conductive circuits on printed circuit boards, formation of various electronic components such as resistors and capacitors, and electrodes of various display elements, formation of conductive films for electromagnetic wave shielding, capacitors, resistors, diodes, memories, arithmetic elements (CPU) and other chip components to substrates, formation of solar cell electrodes, especially formation of solar cell electrodes that cannot be processed at high temperatures due to the use of amorphous silicon semiconductors, multilayer ceramic capacitors, multilayer ceramic inductors It is used for forming external electrodes of chip-type ceramic electronic components such as multilayer ceramic actuators.

2. Description of the Related Art In recent years, chip components have increased in performance, and the amount of heat generated from the chip components has increased, and improvement in thermal conductivity as well as electrical conductivity is required. Therefore, it tries to improve electrical conductivity and thermal conductivity by increasing the content of metal particles as much as possible. However, when it does so, there exists a problem that the viscosity of a paste rises and workability | operativity falls remarkably.

In order to solve such a problem, the present inventors, when heated, the paste-like silver composition composed of silver powder and a volatile dispersion medium volatilizes the volatile dispersion medium and sinters the silver powder, An international application was made to find out that it was solid silver having extremely high electrical conductivity and thermal conductivity, and useful for joining metal members and forming conductive circuits (WO2006 / 126614, WO2007 / 034833).

However, the sintered product of heat-sinterable metal particles is a porous body having an irregular network structure in which a large number of metal particles are sintered and connected at a plurality of contact points, and a large number of pores and voids, In addition, since it has continuous pores and voids, there is a problem that the adhering liquid (for example, water) is easily sucked into the inside due to capillary action, and the sintered metal is corroded. They noticed.

WO2006 / 126614 WO2007 / 034833

As a result of intensive studies to solve the above problems, the present inventors have found that when the paste-like metal particle composition is used for joining between metal members, the metal particles are sufficiently heated and sintered to form the metal member. The present invention has been achieved by finding a method for producing a metal member joined body that is firmly joined and in which the sintered product does not suck liquid (for example, water).

An object of the present invention is to provide a method for manufacturing a metal member assembly in which a plurality of metal members are bonded together by a sintered product of heat-sinterable metal particles. The object of the present invention is to provide a method for manufacturing a metal member assembly in which a liquid does not inhale a liquid (for example, water). Further, a plurality of metal members are made of a sintered product of heat-sinterable metal particles. To provide a metal member joined body in which metal members are firmly joined and the sintered product does not absorb liquid (for example, water) in the joined metal member joined body. is there.

This purpose is
“[1] (A) Paste metal particle composition comprising (S) heat-sinterable metal particles having an average particle size of 0.1 μm or more and 50 μm or less and (B) a volatile dispersion medium (but does not contain a binder) and it is interposed between a plurality of metal members, by heating at 70 ° C. or higher 400 ° C. or less, to volatilize volatile dispersion medium, and the said metallic particles are generated allowed sintering, having a continuous pore Metal member joining, characterized in that a plurality of metal members are joined together by a porous sintered material, and thereafter a curable liquid resin composition is impregnated into the continuous pores of the sintered material and cured. Body manufacturing method.
[2] The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of these metals The method for producing a metal member bonded body according to [1], wherein the metal member bonded body is provided.
[3] The method for producing a metal member assembly according to [1], wherein the porosity of the porous sintered product is 5 to 50%.
[3-1] The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or each of these metals The method for producing a metal member assembly according to [1], which is an alloy, and the porosity of the porous sintered product is 5 to 50%.
[4] The method for producing a metal member assembly according to [1], wherein the curable liquid resin composition is thermosetting or room temperature curable.
[4-1] Manufacture of a metal member assembly according to [2], [3] or [3-1], wherein the curable liquid resin composition is thermosetting or room temperature curable Method. Is achieved.

This purpose is also
“[5] (A) Average particle diameter in paste metal particle composition (but not containing binder) in which a plurality of metal members are interposed between a plurality of metal members is 0.1 μm or more and 50 μm or less there heat sintering metal particles are produced by sintering, are joined by the porous sinter having a continuous pore, porous sinter, continuous pores in the cured resin is filled A metal member assembly, characterized by comprising:
[6] The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of each of these metals The metal member joined body according to [5], wherein
[7] The metal member assembly according to [5], wherein the porosity of the porous sintered product is 5 to 50%.
[7-1] The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or each of these metals The metal member joined body according to [5], which is an alloy and has a porosity of 5 to 50% of the porous sintered product
[8] The metal member assembly according to [5], wherein the curable resin is a cured product of a thermosetting liquid resin composition or a room temperature curable liquid resin composition.
[8-1] The cured resin is a cured product of a thermosetting liquid resin composition or a room temperature curable liquid resin composition, described in [6], [7] or [7-1] Metal member assembly.
[9] The metal member assembly according to [5], wherein the metal member is a metal substrate or an electronic component having a metal part.
[9-1] The metal member assembly according to [7-1] or [8-1], wherein the metal member is a metal substrate or an electronic component having a metal portion. Is achieved.

According to the method for manufacturing a metal member assembly of the present invention, the metal members are firmly bonded to each other by a sintered product of heat-sinterable metal particles, and the sintered product sucks liquid. No metal member assembly can be produced.

In the metal member joined body of the present invention, the metal members are firmly joined to each other by the heat-sintered product of the heat-sinterable metal particles (A), and the liquid in contact with the sintered product is sucked. There is nothing.

The method for producing a metal member assembly according to the present invention comprises a paste-like metal particle composition comprising (A) heat-sinterable metal particles having an average particle diameter of 0.1 μm or more and 50 μm or less and (B) a volatile dispersion medium. The porous sinter produced by interposing the product between a plurality of metal members, volatilizing the volatile dispersion medium by heating at 70 ° C. or more and 400 ° C. or less, and sintering the metal particles together A plurality of metal members are joined together, and then the curable liquid resin composition is impregnated into the sintered product and cured.

The average particle diameter of the heat-sinterable metal particles (A) is 0.1 μm or more and 50 μm or less. This average particle diameter is an average particle diameter of primary particles obtained by a laser diffraction / scattering particle size distribution measurement method. When the average particle diameter exceeds 50 μm, the sinterability of the heat-sinterable metal particles is lowered, so that the average particle diameter is preferably small. For this reason, it is preferable that it is 20 micrometers or less, and it is especially preferable that it is 10 micrometers or less. However, the so-called nanoparticles having an average particle size of less than 0.1 μm have too high surface activity, so that the storage stability of the paste-like metal particle composition is lowered and the bonding strength at the time of heat sintering becomes non-uniform. The average particle size is 0.1 μm or more. That is, the average particle size range of the heat-sinterable metal particles (A) is preferably 0.1 to 10 μm.

The material of the heat-sinterable metal particles is solid at room temperature, and only needs to be easily sintered by heating. Gold, silver, copper, palladium, nickel, tin, aluminum, and alloys of these metals are exemplified. Furthermore, a metal compound is illustrated.
Among these materials, silver, copper, and nickel are preferable, silver, silver alloy, copper, and copper alloy are more preferable, and silver or copper is preferable in terms of heat-sinterability, thermal conductivity of the sintered product, and conductivity. Is particularly preferred. The silver particles may have a part of the surface or inside thereof that may be silver oxide or silver peroxide, and the entire surface may be silver oxide or silver peroxide. The copper particles may have copper oxide on the surface or part of the inside, or the entire surface may be copper oxide.

The heat-sinterable metal particles are usually made of a single material, but may be a mixture of particles made of a plurality of materials. Heat-sinterable metal particles are made of metal (for example, copper, nickel, or aluminum) particles whose surfaces are plated with the heat-sinterable metal (for example, silver), and the surface is made of the heat-sinterable metal (for example, silver). Plated resin (for example, epoxy resin, polyethersulfone resin) particles may be used.

The shape of the heat-sinterable metal particles is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, a spindle shape, a granular shape, a substantially cubic shape, a flake shape, and an indefinite shape. The shape is preferably spherical, granular or flaky from the viewpoint of storage stability. Preferred heat-sinterable metal particles are silver particles made by the reduction method and copper particles made by the reduction method.
Many methods for producing silver particles by the reduction method have been proposed. Usually, an aqueous solution of a reducing agent such as formalin is added to an aqueous solution of silver nitrate by adding an aqueous solution of sodium hydroxide to an aqueous solution of silver nitrate. It is produced by reducing silver to form a silver particle dispersion, filtering the dispersion, washing the filtration residue with water, and drying. In addition, a method for producing copper particles by a reduction method is usually prepared by bringing a copper sulfate aqueous solution and a hydrazine aqueous solution into contact reaction to reduce and precipitate copper powder, washing with pure water, and then drying (for example, JP Sho 59-11630).

The surface of the heat-sinterable metal particles (A) is preferably coated or treated with an organic substance to prevent aggregation of the heat-sinterable metal particles, and particularly preferably coated or treated with a water-repellent organic substance. . Examples of such water-repellent organic substances include high / intermediate fatty acids, high / intermediate fatty acid metal salts, high / intermediate fatty acid amides, high / intermediate fatty acid esters, and high / intermediate alkylamines. High and intermediate fatty acids are particularly preferred in terms of coating effect and treatment effect.

The higher fatty acid is a fatty acid having 15 or more carbon atoms, such as pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), 12-hydroxyoctadecanoic acid (12-hydroxystearic acid), eicosanoic acid ( Linear saturated fatty acids such as arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (serotic acid), octacosanoic acid (montanic acid); 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2- Examples are branched saturated fatty acids such as heptyldodecanoic acid and isostearic acid; unsaturated fatty acids such as palmitoleic acid, oleic acid, isooleic acid, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, gadrenic acid, erucic acid, and ceracoleic acid The

Intermediate fatty acids are fatty acids having 6 to 14 carbon atoms, such as hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, Linear saturated fatty acids such as dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid); isohexanoic acid, isoheptanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, 2-propylheptanoic acid, isodecanoic acid, Illustrative examples include branched saturated fatty acids such as isoundecanoic acid, 2-butyloctanoic acid, isododecanoic acid and isotridecanoic acid; and unsaturated fatty acids such as 10-undecenoic acid.

The coating amount of the organic matter varies depending on the particle size, specific surface area, shape, etc. of the metal particles, but is preferably 0.01 to 3% by weight, more preferably 0.1 to 2% by weight of the heat-sinterable metal particles (A). preferable. If the amount is too small, the heat-sinterable metal particles (A) tend to agglomerate and the storage stability is lowered.As a result, the bonding strength at the time of heat-sintering becomes uneven, and if too large, the heat-sinterable metal particles (A) This is because the heat sinterability of) decreases.

The coating amount of the organic substance can be measured by a usual method. For example, a method of measuring weight loss by heating above the boiling point of a water-repellent organic substance in nitrogen gas, heating sinterable metal particles (A) in an oxygen stream to heat sinterable metal particles (A) An example is a method of quantitatively analyzing the carbon in the organic matter adhering to carbon dioxide gas by infrared absorption spectroscopy.

The flaky heat-sinterable metal particles coated with an organic material can be produced, for example, by putting metal particles having a spherical shape and an organic material into a ball mill and hitting the metal particles with a ball (special feature). No. 40-6971 and JP-A 2000-234107 [0004]).
More specifically, ceramic heat-sinterable metal particles and water-repellent organic substances such as high / intermediate fatty acids, high / intermediate fatty acid metal salts, high / intermediate fatty acid esters, and high / intermediate fatty acid amides are used in ceramic balls. At the same time, it is put into a rotary drum device (for example, a ball mill), and the metal particles are beaten with a ball, whereby flaky heat-sinterable metal particles to which a water-repellent organic substance is adhered can be produced. In this case, repellent properties such as high / intermediate fatty acids, high / intermediate fatty acid metal salts (excluding alkali metal salts), high / intermediate fatty acid esters, high / intermediate fatty acid amides, and high / intermediate alkylamines for improving lubricity. The aqueous organic material adheres to the surface of the flaky heat-sinterable metal particles. The heat-sinterable metal particles (A) whose surfaces are coated with an organic material can also be produced by immersing the heat-sinterable metal particles in a solution of the organic material, and then taking out the metal particles and drying them.

The surface of the heat-sinterable metal particles (A) is only required to be covered with more than half of such high / intermediate fatty acids, but it is preferable that the surface is covered entirely. Thus, the heat-sinterable metal particles (A) whose metal surface is coated with a water-repellent organic substance exhibit water repellency.
The heat-sinterable metal particles (A) whose surfaces are coated with an organic material can also be produced by immersing the heat-sinterable metal particles in an organic material solution and then taking out and drying the metal particles.

The volatile dispersion medium (B) is blended in order to form powdery heat-sinterable metal particles into a paste. The paste form includes a cream form and a slurry form. In order to make the heat-sinterable metal particles sinterable during heating, or to make the paste-like metal particle composition usable as a bonding agent by heating, it must be volatile rather than non-volatile. is necessary. In particular, when the heat-sinterable metal particles (A) are silver particles or copper particles, if the dispersion medium is volatilized during sintering, the silver particles and copper particles are easily sintered and can be easily used as a bonding agent. Because. The boiling point of the volatile dispersion medium is preferably 60 ° C to 300 ° C. When the boiling point is less than 60 ° C., the solvent easily evaporates during the preparation of the paste-like metal particle composition, and when the boiling point is higher than 300 ° C., the volatile dispersion medium (B) remains even after heating. Because it might be.

Such a volatile dispersion medium (B) is composed of a volatile hydrocarbon compound composed of carbon atoms and hydrogen atoms, a volatile organic compound composed of carbon atoms, hydrogen atoms and oxygen atoms, carbon atoms, hydrogen atoms and nitrogen atoms. It is selected from volatile organic compounds, volatile organic compounds composed of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, a mixture of hydrophilic volatile organic compounds of the volatile organic compounds and water, and the like. These are all liquid at room temperature.
The water is preferably pure water, and its electric conductivity is preferably 100 μS / cm or less, more preferably 10 μS / cm or less. The pure water production method may be a normal method, and examples include an ion exchange method, a reverse osmosis method, and a distillation method.

Specifically, as volatile organic compounds composed of carbon atoms, hydrogen atoms and oxygen atoms, volatilization of ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, etc. Monohydric alcohol: ethylene glycol monomethyl ether (methyl cellosolve, methyl carbitol), ethylene glycol monoethyl ether (emethyl cellosolve, ethyl carbitol), ethylene glycol monopropyl ether (propyl cellosolve, propyl carbitol), ethylene glycol mono Ethers such as butyl ether (butyl cellosolve, butyl carbitol), propylene glycol monomethyl ether, methylmethoxybutanol Volatile monohydric alcohols having binding; benzyl alcohol, volatile aralkyl alcohols such as 2-phenylethyl alcohol, ethylene glycol, propylene glycol, volatile polyhydric aliphatic alcohols such as glycerin are exemplified.

Furthermore, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl-2-cyclohexene-1- ON), volatile aliphatic ketones such as dibutylketone (2,6-dimethyl-4-heptanone); ethyl acetate (ethyl acetate), butyl acetate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl octoate, decane Volatile aliphatic carboxylic acid esters such as methyl acid, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, 1,2-diacetoxyethane; tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol Volatile aliphatic ethers such as ethyl diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis (2-diethoxy) ethane, 1,2-bis (2-methoxyethoxy) ethane Illustrated. Other examples include ester ethers such as 2- (2-butoxyethoxy) ethane acetate and ether alcohols such as 2- (2-methoxyethoxy) ethanol.

Examples of volatile hydrocarbon compounds composed of carbon atoms and hydrogen atoms include volatile aliphatic hydrocarbons such as n-paraffin and isoparaffin; and volatile aromatic hydrocarbons such as toluene and xylene.

Examples of volatile organic compounds composed of carbon atoms, hydrogen atoms and nitrogen atoms include volatile alkyl nitriles such as acetonitrile and propionitrile.
Examples of volatile organic compounds composed of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms include volatile carboxylic acid amides such as acetamide and N, N-dimethylformamide. Other examples include low molecular weight volatile silicone oils and volatile organic modified silicone oils.

The blending amount of the volatile dispersion medium (B) is an amount sufficient to make the heat-sinterable metal particles (A) into a paste at room temperature. Depending on the particle size, surface area, shape, etc. of the heat-sinterable metal particles (A), and the type, viscosity, etc. of the volatile dispersion medium (B), the amount sufficient to make a paste varies, but the specific For example, it is 3 to 30 parts by weight per 100 parts by weight of the heat-sinterable metal particles (A).
Paste metal particle composition comprising (A) heat-sinterable metal particles having an average particle size of 0.1 μm or more and 50 μm or less and (B) a volatile dispersion medium used in the present invention (however, no binder is contained) the), unless contrary to the object of the present invention, the powder of the non-metallic non-heated sintered metal particles (a), metal compounds, metal complexes, contain small amounts or trace amounts of a stabilizer or coloring agents Also good.

In the paste-like metal particle composition used in the present invention, (A) heat-sinterable metal particles having an average particle size of greater than 0.1 μm and 50 μm or less and (B) a volatile dispersion medium are charged into a mixer. It can be easily produced by stirring and mixing until a uniform paste is obtained.

The paste-like metal particle composition used in the present invention is a mixture of heat-sinterable metal particles (A) and a volatile dispersion medium (B), and is paste-like at room temperature. The paste form includes a cream form and a slurry form. By making it into a paste, it can be discharged in a thin line from a cylinder or nozzle, and printing with a metal mask is easy. The thickness of the paste-like metal particle composition interposed between a plurality of metal members is not particularly limited as long as the necessary bonding strength is exhibited by heat sintering of the heat sinterable metal particles (A). . Usually, it is 5 μm or more and 1200 μm or less.

In the metal member used in the present invention, the applied paste-like metal particle composition volatilizes the volatile dispersion medium in the composition by heating, and the heat-sinterable metal particles (A) sinter. It is a to-be-joined body to join. Examples of the material of the metal member include gold, silver, copper, platinum, palladium, nickel, tin, aluminum, and alloys of these metals. Among these, copper, silver, gold, platinum, palladium, or an alloy of these metals is preferable in terms of conductivity and bondability. The metal member may be plated with the metal. Examples of the metal member include a lead frame, a printed circuit board, a semiconductor chip, and a heat sink, all or part of which is made of metal.

In the method for producing a metal member assembly of the present invention, a paste-like metal particle composition comprising (A) heat-sinterable metal particles having an average particle diameter of 0.1 μm or more and 50 μm or less and (B) a volatile dispersion medium. The porous sinter produced by interposing the product between a plurality of metal members, volatilizing the volatile dispersion medium by heating at 70 ° C. or more and 400 ° C. or less, and sintering the metal particles together A plurality of metal members are joined to each other, and then the curable liquid resin composition is impregnated into the sintered product and cured. The atmosphere gas at this time is not particularly limited as long as the sintering of the heat-sinterable metal particles is not inhibited, but the heat-sinterable metal particles and the metal member are easily oxidized such as copper or copper alloy. In this case, an inert gas such as nitrogen gas and a reducing gas containing hydrogen gas, which do not contain oxygen gas, are preferable. Of these, a reducing gas called a forming gas comprising 5 to 25% by volume of hydrogen gas and 95 to 75% by volume of nitrogen gas is particularly preferable.
When the heat-sinterable metal particles and the metal member are made of silver or a silver alloy, an oxidizing gas containing oxygen gas is preferable.
Note that the heat-sinterable metal particles (A) in the paste-like metal particle composition used for bonding and the surface metal of the metal member may be the same metal or metal alloy, and a metal that easily forms an alloy. Also good.

The paste-like metal particle composition used in the present invention volatilizes the volatile dispersion medium by heating. The paste-like metal particle composition used in the present invention is heated to a temperature equal to or higher than the sintering temperature of the heat-sinterable metal particles (A), whereby the volatile dispersion medium (B) is volatilized and the metal particles The metal members (A) are sintered to form a solid metal having excellent conductivity and thermal conductivity, and the metal members are joined to each other. Pressure or ultrasonic vibration may be applied during the heating of the paste-like metal particle composition.

At this time, the volatile dispersion medium (B) is volatilized, and then the heat-sinterable metal particles (A) may be sintered together, and with the volatilization of the volatile dispersion medium (B), the heat-sinterable metal particles ( A) may be sintered together. In particular, when the heat-sinterable metal particles (A) are silver particles, since silver has inherently high strength and extremely high electrical and thermal conductivity, the sintered product of silver particles also has high strength and extremely high. It has electrical conductivity and thermal conductivity. Also, when the heat-sinterable metal particles (A) are copper particles, copper inherently has extremely high electrical and thermal conductivity, so the sintered product of copper particles also has extremely high electrical and thermal conductivity. Have sex.

The heating temperature at this time may be a temperature at which the volatile dispersion medium (B) is volatilized and the heat-sinterable metal particles (A) can be sintered, and is usually 70 ° C. or higher, and more preferably 150 ° C. or higher. . However, if the temperature exceeds 400 ° C., the volatile dispersion medium may suddenly evaporate and the shape of the solid metal may be adversely affected. Therefore, the temperature must be 400 ° C. or less, more preferably 300 ° C. It is as follows.

In this way, the sintered product of the heat-sinterable metal particles between the metal members has many fine voids and voids, as shown in FIG. 1, and continuous voids, that is, pores. It has and is porous. The porosity is 5 to 50%. In addition, the normal measuring method can be utilized for the measuring method of the porosity. A cross section of the sintered body is photographed with an electron microscope, image analysis software is used to determine the area ratio between the metal part and the space part, and the photograph taken with the electron microscope is printed on homogeneous paper, etc. An example is a method in which a space portion is cut with scissors or the like to measure each weight, and the weight ratio is used as an area ratio.

As shown in FIG. 1, the shape and size of the pores are various. Since the gaps between the sinterable metal particles before sintering are mainly pores, they are usually 0.1-50 μm, but continuous pores can be much longer than 50 μm.

When the sintered product is porous, there is a problem that mechanical strength is difficult to be obtained, and when it comes into contact with a liquid such as water, there is a property that the liquid is taken into the sintered product by capillary action. If the liquid is water, the sintered product may be corroded and cause migration. Therefore, in the present invention, such pores are impregnated with a curable liquid resin composition and cured, so that the hardness and mechanical strength of the sintered product are improved. Moreover, since the cured product of the resin composition usually has adhesiveness to the metal member that has been in contact with the curing process, the bonding strength between the plurality of metal members by the sintered product is further improved. .
As a precaution, the situation in which the curable liquid resin composition penetrates into the porous sintered product has been clarified with reference to FIGS.

The curable liquid resin composition is not particularly limited as long as it easily penetrates into the pores and is easily cured. Curable liquid epoxy resin composition, curable liquid phenolic resin composition, curable liquid polyurethane resin composition, curable liquid alkyd resin composition, curable liquid polyester resin composition, curable liquid silicone resin composition, curable Examples thereof include a liquid polyamideimide resin composition and a curable liquid polyamic acid type polyimide resin composition. Among these, a curable liquid epoxy resin composition or a curable liquid polyimide resin composition is preferable from the viewpoint of improving adhesive strength, and a curable liquid epoxy resin is particularly preferable. The curing mechanism is preferably thermosetting or room temperature curable, and particularly preferably thermosetting. The curable liquid resin composition may be diluted with a solvent to improve the impregnation property of the heat-sinterable metal particles into the sintered product. The curable liquid resin composition may contain an inorganic or metal filler, a heat stabilizer, an antioxidant, a colorant and the like as long as the permeability to the pores and the curability are not inhibited.

The curable liquid epoxy resin composition is usually composed of a main agent such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, and alicyclic epoxy resin, and a curing agent such as amine, imidazole, and acid anhydride. If necessary, it further comprises additional components such as a curing accelerator, a monofunctional or polyfunctional reactive diluent.

When the above curable liquid resin composition is applied to all or a part of the outer peripheral portion of the sintered product of the heat-sinterable metal particles of the present invention, it is sucked into the pores in the sintered product by capillary action. . At this time, in order to promote inhalation, the pressure may be reduced after the sintered product is immersed in the curable liquid resin composition or after the curable liquid resin composition is applied to the outer periphery of the sintered product. Further, in order to improve the impregnation property by lowering the viscosity, the curable liquid resin composition may be heated to such an extent that the viscosity is not increased.

Thus, the curable liquid resin composition impregnated in the sintered product is cured in the pores when allowed to stand at room temperature or heated to a temperature of 200 ° C. or lower. At this time, since the resin composition has adhesiveness, the resin composition adheres well to the sintered product and metal member of the heat-sinterable metal particles that have been in contact with the curing process. Further, the pores of the sintered product are filled with the cured product of the resin composition, and the interface between the sintered product and the metal member is filled with the cured product of the resin composition. Bonding strength such as mechanical strength such as thickness and shear bonding strength is improved. For this reason, when used for bonding between a plurality of metal members, the hardness and bonding strength are improved, so that the destruction of the sintered product due to thermal stress in the cooling cycle and the separation from the metal members are reduced, It has a feature that a strong bonding strength can be maintained.

In the paste-like metal particle composition used in the present invention, the volatile dispersion medium (B) is volatilized by heating, and the heat-sinterable metal particles (A) are sintered together. When used for joining a plurality of metal members, the heat-sintered material is a metal member that was in contact with the sintered material, for example, a gold-plated substrate, a silver substrate, a silver-plated metal substrate, a copper substrate, an aluminum substrate, or nickel-plated It adheres firmly to metal substrates such as substrates and tin-plated metal substrates, and adheres firmly to metal parts such as electrodes on electrically insulating substrates. Further, since the porous sinter is impregnated with the curable liquid resin composition and cured, it adheres more firmly. For this reason, the manufacturing method of the metal member assembly of the present invention is useful for manufacturing a metal member assembly such as an electronic component, an electronic device, an electrical component, and an electrical device having a metal substrate and a metal portion.

Such bonding includes bonding of chip parts such as capacitors and resistors and circuit boards, bonding of semiconductor chips such as diodes, memories, ICs, and CPUs to lead frames or circuit boards, and high-heat generation CPU chips and cooling plates. And the like.

In the metal member joined body of the present invention, a plurality of metal members are joined by a porous sintered product formed by sintering heat-sinterable metal particles, and the pores of the porous sintered product are joined. It is characterized by being filled with a cured resin.
Heat-sinterable metal particles having an average particle size of more than 0.1 μm and not more than 50 μm are heated and sintered between a plurality of metal members, and then the metal particles are porous by the curable liquid resin composition. The sintered product is impregnated and cured to block the pores, and mechanical strength such as hardness and adhesive strength of the sintered product are improved.

Metal parts, heat-sinterable metal particles, heat-sintering conditions, porous sintered products, pore shape and size, porosity, curable liquid resin composition, impregnation and curing thereof, metal parts It is as having demonstrated the manufacturing method of the conjugate | zygote. The thickness of the heat-sintered metal layer interposed between the plurality of metal members is not particularly limited as long as the necessary bond strength is exhibited. Usually, it is 3 μm or more and 1000 μm or less.

In the metal member assembly of the present invention, the heat-sinterable metal particles having an average particle size of greater than 0.1 μm and less than or equal to 50 μm are heat-sintered between the plurality of metal members, and the porous sintering is further performed. Since the pores of the object are filled with the cured resin, the metal member is more firmly bonded.
As such a joined body, a joined body of a chip component such as a capacitor or a resistor and a circuit board, a joined body of a semiconductor chip such as a diode, a memory, an IC, or a CPU and a lead frame or a circuit board, a high heat generating CPU chip, A joined body with a cooling plate is illustrated.

Examples and comparative examples of the present invention will be given. In the examples and comparative examples, “parts” means “parts by weight”. Hardness of porous sintered product of heat-sinterable metal particles (A) in paste-like metal particle composition, porosity thereof, heating of heat-sinterable metal particles (A) in paste-like metal particle composition Shear bond strength of metallic members joined by sintering, impregnation ratio of resin composition when porous sinter is impregnated with curable liquid resin composition and cured, to porous sintered product Porosity after impregnating and curing curable liquid resin composition, its hardness, metal after impregnating and curing curable liquid resin composition to porous sintered material between metal members The shear bond strength of the member and the shear bond strength after impregnating the porous sinter between the metal members with the curable liquid resin composition and curing and subjecting to a cold cycle were measured as follows. . In addition, the temperature in case there is no description in particular is 23 degreeC.

[Hardness of porous sintered product of heat-sinterable metal particles (A) in paste-like metal particle composition]
A 1 mm thick stainless steel mask having a 15 mm square opening was placed on the polytetrafluoroethylene resin plate, and the paste-like metal particle composition was applied by printing.

When the metal in the paste-like metal particle composition is silver, it is taken out by heating at 200 ° C. for 1 hour in a hot air circulating oven, and the heat-sinterable metal particles (A) in the paste-like metal particle composition (A) Was sintered.
When the metal in the paste-like metal particle composition is copper, this is put in a gas flow furnace at room temperature, the atmosphere gas is replaced with a mixed gas of 10% by volume of hydrogen gas and 90% by volume of nitrogen gas, and then the mixed gas is replaced. While flowing at a flow rate of 1 liter / min, the temperature is raised from room temperature to 250 ° C. at a heating rate of 1 ° C./second, held at 250 ° C. for 1 hour, and then cooled to room temperature to sinter the heat-sinterable silver particles (A). did.

The obtained porous sintered product was removed from the polytetrafluoroethylene resin plate to obtain a specimen for hardness measurement. The hardness of two specimens was measured according to JIS Z2244 (Vickers hardness test), and the average value was measured as hardness.

[Porosity of porous sintered product of heat-sinterable metal particles (A) in paste-like metal particle composition]
A 1 mm thick stainless steel mask having a 15 mm square opening was placed on the polytetrafluoroethylene resin plate, and the paste-like metal particle composition was applied by printing.

When the metal in the paste-like metal particle composition is silver, it is taken out by heating at 200 ° C. for 1 hour in a hot air circulating oven, and the heat-sinterable metal particles (A) in the paste-like metal particle composition (A) Was sintered.
When the metal in the paste-like metal particle composition is copper, this is put in a gas flow furnace at room temperature, the atmosphere gas is replaced with a mixed gas of 10% by volume of hydrogen gas and 90% by volume of nitrogen gas, and then the mixed gas is replaced. While flowing at a flow rate of 1 liter / min, the temperature is raised from room temperature to 250 ° C. at a heating rate of 1 ° C./second, held at 250 ° C. for 1 hour, and then cooled to room temperature to sinter the heat-sinterable silver particles (A). did.

The obtained porous sintered product was removed from the polyimide resin plate to obtain a test piece for measuring porosity.
The cross section of the obtained plate-like specimen was photographed with an electron microscope, and the ratio of space in the cross section was calculated using image analysis software (NIH Image manufactured by National Institute of Health, USA), and the ratio was calculated as follows. %.

[Shear bond strength of metal parts by heat sintering of heat-sinterable metal particles (A) in paste-like metal particle composition]
100 μm thick having four openings (2.5 mm × 2.5 mm) at a distance of 10 mm on a silver substrate (silver purity 99.99%) of width 25 mm × length 70 mm and thickness 1.0 mm The paste-like metal particle composition was printed and applied using a metal mask, and a silver chip (silver purity 99.99%) having a size of 2.5 mm × 2.5 mm × 0.5 mm was mounted thereon.

When the metal in the paste-like metal particle composition was silver, the silver substrate on which the silver chip was mounted was joined by heating at 200 ° C. for 1 hour in a hot air circulation oven.
When the metal in the paste-like metal particle composition is copper, the silver substrate on which the silver chip is mounted is placed in a gas flow furnace at room temperature, and the atmosphere gas is changed to a mixed gas of 10% by volume of hydrogen gas and 90% by volume of nitrogen gas. After the replacement, the mixed gas is flowed at a flow rate of 1 liter / min, the temperature is raised from room temperature to 250 ° C. at a temperature rising rate of 1 ° C./second, held at 250 ° C. for 1 hour, cooled to room temperature, and then heat-sinterable silver The silver substrate and the silver chip were joined by sintering the particles.

The obtained test body for bonding strength measurement was set on a test specimen mounting tool of an adhesive strength tester, and the side surface of the silver chip was pressed with a pressing bar of the adhesive strength tester at a pressing speed of 23 mm / min. The load when the part was subjected to shear fracture was defined as the adhesive strength (unit: MPa). The average value for the four specimens was the shear bond strength.

[Impregnation rate of the resin composition when the porous sintered material is impregnated with a curable liquid resin composition and cured]
A 1 mm thick stainless steel mask having a 15 mm square opening was placed on the polytetrafluoroethylene resin plate, and the paste-like metal particle composition was applied by printing. When the metal in the paste-like metal particle composition is silver, it is taken out by heating at 200 ° C. for 1 hour in a hot air circulating oven, and the heat-sinterable metal particles (A) in the paste-like metal particle composition (A) Was sintered.
When the metal in the paste-like metal particle composition is copper, this is put in a gas flow furnace at room temperature, the atmosphere gas is replaced with a mixed gas of 10% by volume of hydrogen gas and 90% by volume of nitrogen gas, and then the mixed gas is replaced. While flowing at a flow rate of 1 liter / min, the temperature is raised from room temperature to 250 ° C. at a heating rate of 1 ° C./second, held at 250 ° C. for 1 hour, and then cooled to room temperature to sinter the heat-sinterable silver particles (A). did.

The obtained porous sintered product was removed from the polytetrafluoroethylene resin plate and used as a specimen for impregnation amount measurement. After measuring the weight W1 of this sintered product, it was immersed in the thermosetting liquid epoxy resin composition prepared in the Reference Example, depressurized to 1 kPa, allowed to stand for 10 minutes, and then returned to normal pressure. The epoxy resin composition that was not impregnated in was wiped off and removed.

When the metal in the paste-like metal particle composition was silver, the sintered product was cured by heating at 150 ° C. for 1 hour in a hot air circulation oven, and then the weight W2 of the sintered product was measured.
When the metal in the paste-like metal particle composition is copper, the sintered product is put into a gas flow furnace at room temperature, and the atmosphere gas is replaced with a mixed gas of 10% by volume of hydrogen gas and 90% by volume of nitrogen gas. While flowing the mixed gas at a flow rate of 1 liter / min, the temperature was raised from room temperature to 150 ° C. at a heating rate of 1 ° C./second, held at 150 ° C. for 1 hour, cooled to room temperature, and then the weight W2 of the sintered product Was measured.

The impregnation rate of the epoxy resin composition was determined by the following calculation.
Impregnation rate of the resin composition (%) = {(W2−W1) / W1} × 100

[Hardness after porous sinter is impregnated with curable liquid resin composition and cured]
The specimen used for measuring the amount of impregnation of the resin composition when the porous sintered product is impregnated with a curable liquid resin composition and cured is based on JIS Z2244 (Vickers hardness test). The hardness was measured.

[Porosity after impregnating curable liquid resin composition into porous sintered product and curing]
Porosity after impregnating and hardening curable liquid resin composition to porous sintered product = [void of porous sintered product of heat-sinterable metal particles (A) in paste-like metal particle composition The porosity measured by [Ratio] − [Impregnation rate of the resin composition in the case where the porous sintered product is impregnated with the curable liquid resin composition and cured] is obtained by calculation.

[Shear bond strength of metal member after impregnating curable liquid resin composition into porous sintered material between metal members and curing]
100 μm thick having four openings (2.5 mm × 2.5 mm) at a distance of 10 mm on a silver substrate (silver purity 99.99%) of width 25 mm × length 70 mm and thickness 1.0 mm The paste-like metal particle composition was printed and applied using a metal mask, and a silver chip (silver purity 99.99%) having a size of 2.5 mm × 2.5 mm × 0.5 mm was mounted thereon.

When the metal in the paste-like metal particle composition was silver, the silver substrate on which the silver chip was mounted was joined by heating at 200 ° C. for 1 hour in a hot air circulation oven.
When the metal in the paste-like metal particle composition is copper, the silver substrate on which the silver chip is mounted is placed in a gas flow furnace at room temperature, and the atmosphere gas is changed to a mixed gas of 10% by volume of hydrogen gas and 90% by volume of nitrogen gas. After the replacement, the mixed gas is flowed at a flow rate of 1 liter / min, the temperature is raised from room temperature to 250 ° C. at a temperature rising rate of 1 ° C./second, held at 250 ° C. for 1 hour, cooled to room temperature, and then heat-sinterable silver The silver substrate and the silver chip were joined by sintering the particles.

A curable liquid epoxy resin composition is applied around the sintered product of the heat-sinterable metal particles of the joined body, and left to stand for 30 minutes to impregnate the pores in the sintered product. When the metal in the paste-like metal particle composition is silver, the sintered product is cured by heating at 150 ° C. for 1 hour in a hot air circulating oven. .
When the metal in the paste-like metal particle composition is copper, the sintered product is put into a gas flow furnace at room temperature, and the atmosphere gas is replaced with a mixed gas of 10% by volume of hydrogen gas and 90% by volume of nitrogen gas. While flowing the mixed gas at a flow rate of 1 liter / min, the temperature was raised from room temperature to 150 ° C. at a heating rate of 1 ° C./second, held at 150 ° C. for 1 hour, and then cooled to room temperature and cured.

The test specimen for measuring the bonding strength thus obtained was set on a test specimen fixture of an adhesive strength tester, and the side surface of the silver chip was pressed at a pressing speed of 23 mm / min with a pressing bar of the adhesive strength tester, The bond strength (unit: MPa) was defined as the load when the joint was sheared and broken. The average value of the four pieces was taken as the shear bond strength.

[Shear bond strength after impregnating curable liquid resin composition into porous sintered material between metal members and curing and applying to cold cycle]
The test specimen for measuring the joint strength of a metal member was subjected to 1000 cycles in a thermal shock tester in which the test specimen was left at −40 ° C. for 30 minutes and left at + 125 ° C. for 30 minutes, and a silver joint strength test as a metal member. The adhesive strength was measured in the same manner as described above to obtain the shear adhesive strength.

[Reference Example 1]
[Preparation of thermosetting liquid epoxy resin composition]
In a mixer, bisphenol A type epoxy resin (trade name: ZX1059, viscosity 3 Pa · s, epoxy equivalent 160 g) manufactured by Tohto Kasei Co., Ltd., glycidyl ester of alkanoic acid having an average of 10 carbon atoms (viscosity: 0. 6 parts of 1 Pa · s, epoxy equivalent 250 g), 6 parts of monoglycidyl ether of alkyl alcohol having an average of 13 carbon atoms (viscosity 0.2 Pa · s, epoxy equivalent 280 g), polyoxypropylene diamine ( By uniformly mixing 33 parts of a viscosity of 0.2 Pa · s and an active hydrogen equivalent of 100 g) and 5 parts of 2,4,6-tri (dimethylaminomethyl) phenol (viscosity 0.3 Pa · s) as a curing accelerator. A thermosetting liquid epoxy resin composition having a viscosity of 3 Pa · s was prepared.

[Example 1]
Volatile in 100 parts of commercially available silver particles produced by the reduction method and coated with stearic acid on the surface (shape: granular, average particle size of primary particles: 1.1 μm, amount of stearic acid: 0.3 wt%) 8 parts of acetic acid 2- (2-butoxyethoxy) ethane (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1) is added as an aqueous dispersion medium, and a paste-like silver particle composition is prepared by uniformly mixing with a spatula did.

Heating in the paste-like silver particle composition using the paste-like silver particle composition as the paste-like metal particle composition and using the thermosetting liquid epoxy resin composition prepared in the reference example as the curable liquid resin composition Hardness of porous sintered product of sinterable silver particles (A), shear adhesion strength of metal parts joined by heat sintering of heat-sinterable silver particles (A) in paste-like silver particle composition When the porous sintered product is impregnated with the thermosetting liquid epoxy resin composition and cured, the amount of the resin composition impregnated, and the porous sintered product is impregnated with the thermosetting liquid epoxy resin composition. Hardness after being cured, its porosity, the shear adhesive strength of the metallic member after impregnating and curing the thermosetting liquid epoxy resin composition to the porous sintered product between the metallic members, And a thermosetting liquid epoxy resin composition to a porous sintered product between metal members. Soak the measurement of shear bond strength after being subjected to thermal cycling cured, results are summarized in Table 1. From the above results, it was found that this joining method is useful for firmly joining metal members together.
FIGS. 4 and 5 are enlarged cross-sectional photographs of the porous sintered product obtained by completely impregnating and curing the thermosetting liquid epoxy resin composition.

[Reference Example 2]
In FIG. 2 and FIG. 3, the cross-sectional enlarged photographs of the porous sintered product obtained by impregnating the thermosetting liquid epoxy resin composition partway and curing it in Example 1 are shown.

[Example 2]
By putting silver particles (shape: granular, average particle size of primary particles: 1.0 μm, no coating with organic matter) manufactured by a commercially available reduction method into a ball mill, and adding oleic acid, Flake-like silver particles having a surface coated with oleic acid (average particle size of primary particles: 3.0 μm, oleic acid amount: 0.3% by weight) were prepared.
A pasty silver particle composition was prepared under the same conditions as in Example 1 except that the flaky silver particles were used in place of the silver particles used in Example 1.

Using the above paste-like silver particle composition as the paste-like metal particle composition, and using the thermosetting liquid epoxy resin composition prepared in the reference example as the curable liquid resin composition,
Hardness of porous sintered product of heat-sinterable silver particles (A) in paste-like silver particle composition, bonding by heat-sintering of heat-sinterable silver particles (A) in paste-like silver particle composition Shear bond strength of the metal member made, impregnated amount of the resin composition when the porous sintered product is impregnated with a thermosetting liquid epoxy resin composition and cured to the porous sintered product After impregnating and curing the curable liquid epoxy resin composition, the porosity, the porosity, and the porous sintered material between the metal members after impregnating the thermosetting liquid epoxy resin composition and curing Measure the shear bond strength of metal members and the shear bond strength after the porous sintered product between metal members is impregnated with a thermosetting liquid epoxy resin composition and cured and subjected to a cold cycle. The results are summarized in Table 1. From the above results, it was found that this joining method is useful for firmly joining metal members together.

[Example 3]
Volatile in 100 parts of commercially available copper particles produced by the reduction method and coated with oleic acid on the surface (shape: granular, average particle size of primary particles: 1.0 μm, oleic acid amount: 0.7% by weight) Paste-like copper particle composition by adding 8 parts of 1,2-bis (2-methoxyethoxy) ethane (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1) as a porous dispersion medium and mixing uniformly using a spatula A product was prepared.

Using the paste copper particle composition as the paste metal particle composition, using the thermosetting liquid epoxy resin composition prepared in the reference example as the curable liquid resin composition,
Bonding by hardness of porous sintered product of heat-sinterable copper particles (A) in paste-like copper particle composition, heat-sintering of heat-sinterable copper particles (A) in paste-like copper particle composition Shear bond strength of the metal member made, impregnated amount of the resin composition when the porous sintered product is impregnated with a thermosetting liquid epoxy resin composition and cured to the porous sintered product After impregnating and curing the curable liquid epoxy resin composition, the porosity, the porosity, and the porous sintered material between the metal members after impregnating the thermosetting liquid epoxy resin composition and curing Measure the shear bond strength of metal members and the shear bond strength after the porous sintered product between metal members is impregnated with a thermosetting liquid epoxy resin composition and cured and subjected to a cold cycle. The results are summarized in Table 1. From the above results, it was found that this joining method is useful for firmly joining metal members together.

[Comparative Example 1]
In Example 1, heat-sinterable silver particles (A in the paste-like silver particle composition (A) were similarly used except that the thermosetting liquid epoxy resin composition prepared in the reference example was not used as the curable liquid resin composition. ) Of the porous sintered product, its porosity, the shear adhesive strength of the metal members joined by heat sintering of the heat-sinterable silver particles (A) in the paste-like silver particle composition, and Then, the porous sintered material between the metal members was impregnated with the thermosetting liquid epoxy resin composition, cured, and subjected to a cooling and heating cycle. Then, the shear bond strength was measured, and the results are summarized in Table 2. . From the above results, it was found that the bonding method using no curable liquid resin composition has low bonding strength between metal members. In addition, the cross-sectional part enlarged photograph of the said porous sintered compact was hung up as FIG.

[Comparative Example 2]
In Example 2, the heat-sinterable silver particles (A in the paste-like silver particle composition (A) were similarly used except that the thermosetting liquid epoxy resin composition prepared in the reference example was not used as the curable liquid resin composition. ) Of the porous sintered product, its porosity, the shear adhesive strength of the metal members joined by heat sintering of the heat-sinterable silver particles (A) in the paste-like silver particle composition, and Then, the porous sintered material between the metal members was impregnated with the thermosetting liquid epoxy resin composition, cured, and subjected to a cooling and heating cycle. Then, the shear bond strength was measured, and the results are summarized in Table 2. . From the above results, it was found that the bonding method using no curable liquid resin composition has low bonding strength between metal members.

[Comparative Example 3]
In Example 3, heat-sinterable copper particles (A in the paste-like copper particle composition (A) were similarly used except that the thermosetting liquid epoxy resin composition prepared in the reference example was not used as the curable liquid resin composition. ) Of the porous sintered product, the porosity thereof, the shear adhesive strength of the metal member joined by heat sintering of the heat-sinterable copper particles (A) in the paste-like copper particle composition, In addition, the porous adhesive sintered between the metal members was impregnated with the thermosetting liquid epoxy resin composition, cured, and subjected to a cooling and heating cycle. Then, the shear bond strength was measured, and the results are summarized in Table 2. It was. From the above results, it was found that the bonding method using no curable liquid resin composition has low bonding strength between metal members.

According to the metal member joining method of the present invention, the sintered material is firmly joined by the sintered product of heat-sinterable metal particles, and the porous pores of the sintered product are impregnated with the curable liquid resin composition. Since the metal members can be bonded to each other more firmly without impairing the conductivity, the metal member bonding method of the present invention includes a capacitor, a resistor, a diode, a memory, an arithmetic element (CPU). It is useful for joining chip components such as) to a substrate, joining a heat radiating member, and the like.
The metal member assembly of the present invention is useful for electronic components, electronic devices, electrical components, electrical devices, and the like.

2 is an enlarged cross-sectional view of a porous sintered product of Comparative Example 1. It is a cross-sectional enlarged photograph of the porous sintered compact (reference example 2) which impregnated the thermosetting liquid epoxy resin composition to the middle and was hardened. The dark part of the peripheral part is the permeation part, and the thin part of the central part is the non-penetration part. It is the elements on larger scale of FIG. It is a cross-sectional enlarged photograph of the porous sintered compact which was completely impregnated and hardened with the thermosetting liquid epoxy resin composition of the Example. It is the elements on larger scale of FIG. It is a top view of the test body A for shear bond strength measurement in an Example. The silver substrate 1 and the silver chip 3 are joined by solid silver or solid copper 2 which is a heat-sintered product of silver particles or copper particles. It is the XX sectional view taken on the line in FIG.

Explanation of symbols

A Test specimen for measuring shear bond strength 1 Silver substrate 2 Paste-like silver particle composition or paste-like copper particle composition (solid silver or solid copper after heat sintering)
3 Silver chip

Claims (9)

A paste-like metal particle composition (but not containing a binder) composed of (A) a heat-sinterable metal particle having an average particle diameter of 0.1 μm or more and 50 μm or less and (B) a volatile dispersion medium, It is interposed between the metal member, by heating at 70 ° C. or higher 400 ° C. or less, to volatilize volatile dispersion medium, and the said metallic particles are generated allowed sintered, porous sintered with continuous pores A method for producing a metal member assembly comprising: joining a plurality of metal members with an object, and then impregnating and curing the curable liquid resin composition in continuous pores of the sintered product. . The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of each of these metals The method for producing a metal member assembly according to claim 1, wherein The method for producing a metal member assembly according to claim 1, wherein the porosity of the porous sintered product is 5 to 50%. The method for producing a metal member assembly according to claim 1, wherein the curable liquid resin composition is thermosetting or room temperature curable. (A) The average particle diameter in the paste-like metal particle composition (however, containing no binder) in which a plurality of metal members are interposed between the plurality of metal members is 0.1 μm or more and 50 μm or less. sex metal particles produced by sintering, characterized in that are joined by a porous sintered product having a continuous pore, the porous sintered material, curing the resin in the continuous pores are filled A metal member assembly. The metal of the heat-sinterable metal particles is silver, silver alloy, copper or copper alloy, and the metal of the metal member is copper, silver, gold, platinum, palladium, or an alloy of each of these metals The metal member assembly according to claim 5, wherein the metal member assembly is characterized in that: The metal member assembly according to claim 5, wherein the porosity of the porous sintered product is 5 to 50%. The metal member assembly according to claim 5, wherein the curable resin is a cured product of a thermosetting liquid resin composition or a room temperature curable liquid resin composition. The metal member assembly according to claim 5, wherein the metal member is a metal substrate or an electronic component having a metal portion.