JP2018181605A - Sheet for joining metal member, method for joining metal member and metal member joint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet for joining a metal member for improving thermal impact resistance, a method for joining a metal member excellent in thermal impact resistance, and a metal member joint excellent in thermal impact resistance.SOLUTION: A sheet for joining a metal member has a solder particle paste layer, a conductive heating curable resin paste layer or a heating sinterable metal particle layer on both surfaces of a metal element wire fabric. A method for joining a metal member includes interposing the sheet for joining the metal member between a plurality of metal members, and heating the sheet to melt solder particles, and curing a conductive heating curable resin or sintering heating sinterable metal particles. A metal member joint has the sheet for joining the metal member interposed between a plurality of metal members, where the metal member is bonded a solder layer, a conductive curable resin layer or a metal particle sintering layer.SELECTED DRAWING: Figure 3

Description

The present invention relates to a metal member bonding sheet, a method of bonding metal members, and a metal member joined body.

The electrically conductive and thermally conductive paste obtained by dispersing metal powder such as silver, copper, and nickel in a liquid thermosetting epoxy resin composition is cured by heating to form an electrically conductive and thermally conductive film. Therefore, the formation of conductive circuits on printed circuit boards, the formation of electrodes of various electronic components such as resistors and capacitors and various display elements, the formation of conductive films for electromagnetic shielding, capacitors, resistors, diodes, memories, arithmetic elements Bonding chip components such as (CPU) to substrates, forming electrodes of solar cells, especially forming electrodes of solar cells that can not be processed at high temperature because amorphous silicon semiconductor is used, laminated ceramic capacitors, laminated ceramic inductors It is used to form external electrodes of chip-type ceramic electronic components such as laminated ceramic actuators. However, such a thermosetting epoxy resin composition has a problem of low electrical conductivity and thermal conductivity.

In recent years, with the advancement of the performance of chip components, the amount of heat generation from the chip components is increased, and it is required to improve not only the electrical conductivity but also the thermal conductivity. Therefore, if it is intended to improve the electrical conductivity and thermal conductivity by increasing the content of metal particles as much as possible, there is a problem that the viscosity of the paste is increased and the workability is significantly reduced. In addition, when a large amount of metal particles is contained, the cured product becomes brittle, and there is a problem that the cured epoxy resin that is the adhesive layer is easily broken in the thermal shock test.

Solder bonding with excellent electrical conductivity and thermal conductivity is also performed more than before, but in the thermal shock test, the solder alloy, which is the adhesive layer between the printed circuit board and the electronic component, may break or peel off. , The inventor noticed.

In order to solve such a problem, when the paste-like silver composition comprising silver powder and a volatile dispersion medium is heated, the volatile dispersion medium is volatilized and the silver powder is sintered, resulting in extremely high conductivity and heat. An international application was made as it was found to be solid silver having conductivity, and useful for joining metal members and forming a conductive circuit (Patent Document 1, Patent Document 2).

However, the sintered product of the 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 are obtained. In addition, since the porous body, which is a bonding layer between a plurality of metal members, has continuous pores and voids, there is a problem that the porous body is easily broken in the thermal shock test. I noticed.

After the international application, the thickness of the heat-sintered metal particles of the heat-sinterable metal particles between the metal members is a predetermined thickness, and the heat-sintered metal particles of the heat-sinterable metal particles remain between the metal members. And a method of manufacturing a metal member joined body in which a metal member is strongly joined by a heated and sintered product of metal particles and liquid or gas does not penetrate or pass through the sintered product, and the metal member joining. In order to provide a body, a patent application was filed and published as Japanese Patent Application Laid-Open No. 2011-236494 (Patent Document 3). However, the present inventors noticed a problem that a crack may occur in the bonding layer which is a heat sinter of heat sinterable metal particles which is a bonding layer between a lead frame and an electronic component in a thermal shock test. .

International Publication No. WO 2006/126614 International Publication No. 2007/034833 JP, 2011-236494, A

As a result of intensive studies to solve the above problems, the present inventors have found that solder particle paste layers, conductive thermosetting resin composition layers or heat sinterable metal particle composition layers are provided on both sides of a metal wire fabric. The sheet for bonding metal members is interposed between a plurality of metal members and heated to melt the solder particles, to harden the conductive heat-curable resin composition, or to heat-sinterable metal particles. When it is made to sinter, it is found that the metal member bonding sheet absorbs a thermal shock and can firmly bond a plurality of metal members while maintaining electric conductivity and thermal conductivity, according to the present invention. I reached.

An object of the present invention is to provide a metal member joining sheet useful for producing a metal member joined body excellent in thermal shock resistance. Another object of the present invention is to provide a method of joining metal members which can form a metal member assembly excellent in thermal shock resistance easily and reliably. Another object of the present invention is to provide a metal member assembly excellent in thermal shock resistance.

The purpose of this is
[1] A metal member bonding sheet having a solder particle paste layer, a conductive thermosetting resin paste layer, or a heat sinterable metal particle paste layer on both sides of a metal wire fabric.
[2] The metal wire is a wire having a cross-sectional diameter of 0.01 to 0.2 mm and made of gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing any of them [1 ] The sheet | seat for metal member joining as described in these.
[3] The metal member bonding sheet according to [1] or [2], wherein the metal wire fabric is a plain weave fabric comprising a bundle of 3 to 30 metal wires.

[4] A metal member bonding sheet having a solder particle paste layer, a conductive thermosetting resin paste layer or a heat sinterable metal particle paste layer on both sides of a metal wire fabric is interposed between a plurality of metal members. And heating the solder to melt the solder particles, curing the conductive thermosetting resin, or sintering the heat-sinterable metal particles.
[4-1] A method of joining metal members according to [4], wherein the plurality of metal members are two metal members
[5] The metal wire is a wire having a cross-sectional diameter of 0.01 to 0.2 mm and made of gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing any of these [4] The joining method of the metal members as described in-.
[6] The method for joining metal members according to [4] or [5], wherein the metal wire fabric is a plain weave fabric consisting of a bundle of 3 to 30 metal wires.
[7] The metal according to any one of [4] to [6], wherein the material of the metal member is gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. Method of joining members.

[8] A solder particle paste, a conductive thermosetting resin paste, or a heat sinterable metal particle paste is interposed between both surfaces of a metal wire fabric and a plurality of metal members, and heated to melt the solder particles. And bonding the conductive thermosetting resin or sintering the heat sinterable metal particles.
[8-1] The method for joining metal members according to [8], wherein the plurality of metal members are two metal members.
[9] The metal wire is a wire having a cross-sectional diameter of 0.01 to 0.2 mm and made of gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing any of these [8] ] Or the method of joining metal members according to [8-1].
[10] Joining of metal members according to [8] or [9], wherein the material of the metal members is gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. Method.

[11] Between a plurality of metal members, a metal member bonding sheet having a solder layer, a conductive cured resin layer, or a metal particle sintered layer is interposed on both sides of the metal wire fabric, and the metal members are solder A bonded metal member characterized in that it is bonded to a layer, a conductive cured resin layer or a sintered metal particle layer.
[11-1] The metal member joined body according to [11], wherein the plurality of metal members are two metal members.
[11-2] The metal wire is a wire having a cross-sectional diameter of 0.01 to 0.2 mm and made of gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these, The metal member joined body according to [11] or [11-1].
[12] The metal member joined body according to [11], [11-1] or [11-2], which is an electronic component having a metal part.
[12-1] The metal member assembly according to [12], wherein the material of the metal part is gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. Achieved by

The metal member bonding sheet of the present invention has a solder particle paste layer, a conductive thermosetting resin paste layer, or a heat sinterable metal particle paste layer on both sides of the metal wire fabric, so a plurality of metal members When it is interposed and heated, the solder particles melt, the conductive thermosetting resin hardens, or the heat sinterable metal particles sinter, and a metal member joined body excellent in thermal shock resistance is obtained. It is formed.

In the bonding method of the present invention, the metal member bonding sheet having the solder particle paste layer, the conductive thermosetting resin paste layer or the heat sinterable metal particle assembly paste layer on both sides of the metal wire fabric is a plurality of metals. A metal member excellent in thermal shock resistance, because it is interposed between members and heated to melt the solder particles, harden the conductive thermosetting resin, or sinter the heat sinterable metal particles. The joined body can be formed easily and reliably.
In the second bonding method of the present invention, a solder particle paste, a conductive heat curable resin paste or a heat sinterable metal particle paste is interposed between both surfaces of the metal wire fabric and a plurality of metal members, and heating is performed. To melt the solder particles, harden the conductive thermosetting resin, or sinter the heat-sinterable metal particles, so that a metal member assembly excellent in thermal shock resistance is easily and reliably formed. can do.

In the metal member joined body of the present invention, a metal member joining sheet having a solder layer, a conductive cured resin layer or a metal particle sintered layer on both sides of a metal wire fabric is interposed between a plurality of metal members. Since the metal member is bonded to the solder layer, the conductive cured resin layer or the metal particle sintered layer, it is excellent in thermal shock resistance.

FIG. 1 is a schematic plan view of a plain weave of a metal wire tin-plated on copper, which is used in Example 1. FIG. In FIG. 1, a thick line indicates a bundle of metal wires, and six wires constitute one bundle. Thin lines are lines for dividing one bundle into six strands. FIG. 2 is a plan view of a test sample for measuring shear adhesion strength in the example. FIG. 3 is a cross-sectional view taken along line XX in FIG. FIG. 4 is a schematic cross-sectional view immediately after applying the solder particle paste 5 prepared in Reference Example 1 to a thickness of 50 μm on both sides of the flat metal wire fabric 4 plated with tin in Example 1 in Example 1. . FIG. 5 is a schematic cross-sectional view in which the portion 2 in FIG. 3 is enlarged in the first embodiment. A portion of the solder particle paste 5 penetrates into the plain weave 4 to form a solder particle paste impregnated layer 6.

The metal member bonding sheet of the present invention is characterized in that a solder particle paste layer, a conductive thermosetting resin paste layer or a heat sinterable metal particle paste layer is provided on both sides of the metal wire fabric.
The metal wire fabric is cloth-like and sheet-like. Therefore, since it is flexible and easily deformed when a force is applied, it is excellent in the ability to follow a thermal shock, and the thermal stress can be relieved.

The weave of the woven fabric is exemplified by plain weave, twill weave and satin weave, but a plain weave which is easy to manufacture is preferable. Plain weave alternately weaves warp and weft, and the pattern is symmetrical, has mechanical strength and is resistant to friction.
In the twill weave, after the warp passes through the two wefts, it repeatedly passes under one nipping thread, and after the warp passes through the three weft threads, it passes under the one nipping thread. There are four folds that repeat passing through, and since the crossing portions of the yarns are oblique, they have stretchability and are more resistant to wrinkles.
Shishisu is made of five or more warp and weft yarns. It is characterized in that only warp yarns or weft yarns appear on the surface. It has the merit of being glossy and soft, but has the disadvantage of being weak to friction.
In addition, you may use the nonwoven fabric of a metal strand instead of these textiles. The non-woven fabric is an intertwined wire without weaving, has a porous structure, and has extremely high stress relaxation properties.

The metal wire is a thin wire of metal. In order for the metal member bonding sheet of the present invention to be excellent in flexibility, the cross-sectional diameter is preferably 0.01 to 0.2 mm, more preferably 0.03 to 0.12 mm, It is especially preferable that it is 0.05-0.10 mm. The cross-sectional shape of the metal wire is not limited, but is preferably a circle, an ellipse or a shape close to this which is easy to manufacture.

The material of the metal wire is preferably gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these.

When the metal wire fabric is a plain weave or twill fabric, it is preferable to weave them together as a bundle of 3 to 10 metal wires. By using the bundle, the stress relaxation property is improved. Plain fabrics and twill fabrics can be easily obtained by the existing methods. The thickness of the metal wire fabric is preferably 50 to 1000 μm. However, the thickness of the metal wire fabric is preferably five or more times the cross-sectional diameter of the metal wire.

The metal wire fabric used to manufacture the metal member bonding sheet of the present invention is easily deformed when it receives a thermal shock, and exhibits excellent stress relaxation properties, so that a solder paste may be contained therein. It is preferable that the conductive thermosetting resin paste or the heat sinterable metal particle paste hardly penetrates. For this reason, it is preferable that the area of the opening in the metal wire fabric is small, and the opening ratio indicating the ratio of the area of the opening in the metal member bonding sheet is preferably 5% or less, and 1% or less It is more preferable that The measurement method of an aperture ratio can utilize a normal measurement method. For example, the surface of the metal wire fabric is photographed, and the area of the opening is determined by image analysis software, or the photographed photograph is printed on a uniform paper etc. The method of dividing and measuring each mass and making the ratio into an area ratio is illustrated. It is preferable that the paper etc. in this case be of substantially uniform material and thickness.

Since the metal wire fabric does not have adhesiveness to the metal member as it is, in order to use it as a bonding material, it is necessary to have a material layer having adhesiveness on both sides thereof. In particular, a solder paste, a conductive heat-curable resin paste, or a heat-sinterable metal particle paste is preferable as a material having excellent adhesion to a metal member. As such a solder paste, a conductive heat-curable resin paste or a heat-sinterable metal particle paste, conventionally known ones can be used.

As a method of forming a solder particle paste layer, a conductive thermosetting resin paste layer or a heat sinterable metal particle paste layer on both sides of a metal wire fabric, screen printing, stencil printing, dispense coating on the surface of a metal wire fabric There is. Under the present circumstances, since it is a paste form, although one part permeates and entraps into the clearance gap of metal wire fabric, it is preferable not to entrap the whole clearance gap. It is because the stress relaxation property of the metal member joining sheet is lowered if the whole of the gap is entered.

The solder particle paste for forming the solder particle paste layer on both sides of the metal wire fabric is composed of solder alloy particles and a flux, and any known one can be used. As such a solder alloy, for example, Sn-Pb-based (60 Sn / 40 Pb, 40 Sn / 60 Pb, etc.) where 60 Sn / 40 Pb means 60 mass% of Sn and 40 mass% of Pb. The same applies. Also, Sn-Ag-Pb system (5Sn / 1.5Ag / 93.5Pb etc.), Sn-Bi-Pb system (43Sn / 14Bi / 43Pb etc.), Sn-Sb-Pb system (27Sn / 3Sb / 70Pb etc.) And lead-containing alloy such as Sn-Bi-Ag-Pb (such as 57Sn / 3Bi / 2Ag / 38Pb). Furthermore, Sn-In (such as 48Sn / 52In, 58Sn / 42In), Sn-Bi (such as 43Sn / 57Bi, 60Sn / 40Bi), In-Ag (such as 97In / 3Ag), In-Bi (such as 95In) / 5Bi etc., Sn-Zn-based (91Sn / 9Zn etc.), Sn-Ag-based (96.5Sn / 3.5Ag, 90Sn / 10Ag etc.), Sn-Cu-based (99.3Sn / 0.7Cu, 97Sn /) 3Cu etc., Sn-Sb system (95Sn / 5Sb etc.), Sn-Au system (20Sn / 80Au etc.), Sn-Bi-Ag-Cu system (90Sn / 7.5Bi / 2Ag / 0.5Cu etc.), Sn -Ge system (99Sn / 1Ge etc.), Sn-Bi-Cu system (92Sn / 7.5Bi / 0.5Cu etc.), Sn-Cu-Sb-Ag system (97Sn / 2Cu 0.8Sb / 0.2Ag etc., Sn-Ag-Zn system (95.5Sn / 3.5Ag / 1Zn etc.), Sn-Ag-Cu system (95.5Sn / 3Ag / 0.5Cu etc.), Sn- Bi-Sb system (52 Sn / 45 Bi / 3 Sb, 85 Sn / 10 Bi / 5 Sb, etc.), Sn-Bi-Sb-Zn system (51 Sn / 45 Bi / 3 Sb / 1 Zn, 84 Sn / 10 Bi / 5 Sb / 1 Zn etc.), Sn-Bi- Cu-Zn system (88.2 Sn / 10Bi / 0.8Cu / 1Zn etc.), Sn-Ag-Sb system (89Sn / 4Ag / 7Sb, 98Sn / 1Ag / 1Sb etc.), Sn-Ag-Sb-Zn system (88Sn) / 4Ag / 7Sb / 1Zn, 97Sn / 1Ag / 1Sb / 1Zn etc., Sn-Ag-Cu-Zn system (91.2Sn / 2Ag / 0.8Cu / 6Zn, 89. Such as Sn / 2Ag / 0.9Cu / 8Zn), Sn-Zn-Bi-based (89Sn / 8Zn / 3Bi, like 86Sn / 8Zn / 6Bi) those lead-free systems, such as are exemplified.

The shape of the solder alloy particles is preferably spherical, granular or droplet-like, and more preferably spherical. The median diameter is 0.01 to 100 μm, and more preferably 0.1 to 50 μm.

The flux for solder particle paste usually contains a base resin, an activator, a thixotropic agent, and a solvent.
Examples of base resins include rosin or rosin derivatives and synthetic resins. In addition, gum rosin, tall rosin, wood rosin etc. are illustrated as rosin. Examples of rosin derivatives include thermally treated rosin, polymerized rosin, modified rosin (eg, acrylated rosin, hydrogenated rosin, formylated rosin, rosin ester, rosin modified maleic resin, rosin modified phenolic resin, rosin modified alkyd resin), low The softening point rosin is exemplified.
The amount that the base resin occupies in the flux is preferably 30 to 70% by mass.

As an activator, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, hexylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, triethanolamine, cyclohexylamine, methylcyclohexylamine Examples thereof include amines such as dimethylcyclohexylamine and diphenyl guanidine, and hydrochlorides or bromates of the amines. Further, acids such as succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid and the like carboxylic acids may also be mentioned. Also, tetrabromomethane, 1,1,2,2-tetrabromobutane, 1,2-dibromo-2-butene, 2,3-diboromo-1-propanol, 1,2-diboromo-2,3-butanediol And organic halides such as trans-2,3-diboromo-2-butene-1,4-diol and 2,2-bis (bromomethyl) -1,3-propanediol.
The amount that the activator occupies in the flux is preferably 1 to 10% by mass.

The thixotropic agent is an important component contained in the solder paste in order to suppress the flowability of the solder paste. For example, hydrogenated castor oil, hydrogenated castor oil, beeswax, carnauba wax, sorbitol, amide and the like can be mentioned. The amount of this type of thixotropic agent in the flux is preferably 0.5 to 10% by mass.

As the solvent, alcohols such as ethyl alcohol, isopropyl alcohol, ethyl cellosolve, butyl carbitol, α-terpineol, β-terpineol, hexylene glycol, butyl carbitol, benzyl alcohol, isopalmityl alcohol, isostearyl alcohol, lauryl alcohol , Carboxylic acid esters such as ethyl acetate, butyl acetate, diisobutyl adipate, diethyl phthalate, dibutyl phthalate, toluene, turpentine oil, hydrocarbons such as hexadecane, dodecyl benzene, kerosene, light oil, etc., tributyl phosphate, tricresyl phosphate, phosphorus Examples include phosphoric acid esters such as tripentyl acid. The solvent is blended in an amount sufficient to dissolve the base resin and the like.

The solder particle paste consists of solder alloy particles and a sufficient amount of flux to make it paste-like. The amount occupied by the solder alloy particles in the solder particle paste is preferably 70 to 95% by mass, and the amount occupied by the flux in the solder particle paste is preferably 5 to 30% by mass.

A conductive thermosetting resin paste for forming a conductive thermosetting resin paste layer on both sides of a metal wire fabric is made of a thermosetting resin and conductive metal particles, and is used as a diluent to make it paste-like. It may contain a volatile solvent. Moreover, it may be a paste-like thing by heating like a hot melt type.

As such a conductive thermosetting resin paste, a conductive thermosetting epoxy resin paste, a conductive thermosetting liquid phenolic resin paste, a conductive thermosetting polyurethane resin paste, a conductive thermosetting alkyd resin paste Examples thereof include conductive heat curable liquid polyester resin paste, conductive heat curable liquid silicone resin paste, conductive heat curable liquid polyamideimide resin paste, conductive heat curable liquid polyamic acid type polyimide resin paste and the like. It is preferable that it is a conductive thermosetting epoxy resin paste in terms of adhesiveness and heat resistance.

Such conductive thermosetting epoxy resin is usually selected from main ingredients such as bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, amine, imidazole, acid anhydride, etc. It consists of a curing agent and, if necessary, further comprises an additional component such as a curing accelerator and a monofunctional or polyfunctional reactive diluent. From the viewpoint of heat resistance, bisphenol A epoxy resin, bisphenol F epoxy resin, and biphenyl epoxy resin are preferable.

Examples of the material of the conductive metal particles in the conductive thermosetting resin paste include silver, copper, nickel, indium, tin, aluminum, and alloys containing these metals. Among these materials, silver, a silver alloy, copper, and a copper alloy are preferable in terms of electrical conductivity and thermal conductivity, and silver is particularly preferable. The silver particles may have silver oxide or silver peroxide on the surface or inside, but the proportion is preferably 50% or less, more preferably 20% or less, and 5% or less Particularly preferred. The copper particles may have copper oxide on the surface or inside, but the proportion is preferably 50% or less, more preferably 20% or less, and particularly preferably 5% or less.

The conductive metal particles are usually made of a single material, but may be a mixture of particles of a plurality of materials. Conductive metal particles are metal (for example, copper, nickel, indium, tin, or aluminum) particles whose surface is plated with the conductive metal (for example, silver), and the surface is plated with the conductive metal (for example, silver) It may be a resin (eg, epoxy resin, polyether sulfone resin) particles.

The shape of the conductive metal particles is preferably spherical, granular, droplet-like or flake-like, more preferably spherical, granular-like, droplet-like. The median diameter is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm. Also, a plurality of conductive metal particles having different materials, shapes and particle sizes of conductive metal particles may be used in combination.

The conductive metal particles are preferably coated or treated on the surface with an organic substance to prevent aggregation of the conductive metal particles. Examples of such organic substances include fatty acids, fatty acid metal salts, fatty acid amides, fatty acid esters, polymer dispersants and alkylamines. Particularly in view of the covering effect and the treating effect, fatty acids having 6 or more carbon atoms are preferable. Moreover, it is preferable that the coating amount of organic substance is 0.1-5 mass parts in 100 mass parts of heat-sinterable metal particles.

The compounding amount of the conductive metal particles is such that the conductive thermosetting resin becomes paste-like at normal temperature. Although it changes with the kind of thermosetting resin, a viscosity, and the particle size of an electroconductive metal particle, a specific surface area, a shape etc., Specifically, for example, it is 40 ~ in 100 mass parts of conductive thermosetting resin pastes. 80 parts by mass.
The conductive thermosetting resin paste used in the present invention is a metal-based or non-metal-based powder other than the conductive metal particles, a metal compound, a metal complex, as long as the object of the present invention is not violated and the effect is not impaired. Minor to trace amounts of additives such as thixotropic agents, stabilizers, solvents, diluents, coloring agents and the like may be contained.

A heat sinterable metal particle paste for forming a heat sinterable metal particle composition layer on both sides of a metal wire fabric comprises a heat sinterable metal particle and a volatile dispersion medium, and is paste-like at normal temperature It is.

The median diameter of the heat sinterable metal particles is preferably 0.01 μm or more and 10 μm or less. When the median diameter exceeds 10 μm, the sinterability of the heat sinterable metal particles is lowered. However, if the median diameter is less than 0.01 μm, the surface activity of the heat sinterable metal particles is too strong, the storage stability of the heat sinterable metal particle paste decreases, and the bonding strength during heat sintering is not good. In order to become uniform, the median diameter is preferably 0.01 μm or more, and preferably 0.1 μm or more.
The median diameter is the particle size value at which the integrated value becomes 50% in the volume-based particle size distribution curve obtained by measuring the particle size distribution of particles on a volume basis by a laser diffraction type particle size distribution measuring apparatus. is there.

Examples of the material of the heat sinterable metal particles include gold, silver, copper, palladium, tin, and alloys containing these metals. Among these materials, silver, a silver alloy, copper, and a copper alloy are preferable, and silver is particularly preferable, in terms of heat sinterability, electrical conductivity and thermal conductivity of a sintered product. The silver particles may have silver oxide or silver peroxide on the surface or inside, but the proportion is preferably 50% or less, more preferably 20% or less, and 5% or less Particularly preferred. The copper particles may have copper oxide on the surface or inside, but the proportion is preferably 50% or less, more preferably 20% or less, and particularly preferably 5% or less.

The heat sinterable metal particles are usually made of a single material, but may be a mixture of particles of a plurality of materials. The heat sinterable metal particles are metal (e.g., copper, nickel, tin or aluminum) particles whose surface is plated with the heat sinterable metal (e.g. silver), the heat sinterable metal (e.g. silver) It may be resin (for example, epoxy resin, polyether sulfone resin) particles whose surface is plated.

The shape of the heat sinterable metal particle is not particularly limited as long as it has heat sinterability, and it is spherical, needle-like, horn-like, dendritic, fibrous, flake-like (granular), granular, irregularly shaped, tears A drop is exemplified (see JIS Z 2500: 2000). Furthermore, spheroid, spongy, vine-like, spindle-like, substantially cubic and the like are exemplified.
The shape thereof is preferably spherical, granular, teardrop-like and flake-like in view of easily forming a porous sinter.
The spherical shape referred to here is a shape almost similar to a spherical shape (see JIS Z2500: 2000). It is not necessary for the particle to be truly spherical, and the ratio (DL) / (DS) of the major axis (DL) to the minor axis (DS) of the particle (sometimes referred to as a spherical coefficient) is in the range of 1.0 to 1.2. The ones in are preferred.
Grains are not irregular shapes, but have round dimensions with almost equal dimensions in width, depth and height.
The teardrop shape is a rounded irregular shape as shown by the teardrop.
The flake shape (piece shape) is a shape like a thin plate, and is also referred to as a scaly shape because it is a thin plate shape like a bowl. The particle size distribution is not limited in any of the shapes.

Preferred heat sinterable metal particles are silver particles produced by a reduction method in terms of heat sinterability. Many methods for producing silver particles by the reduction method have been proposed. For example, an aqueous solution of sodium hydroxide is added to an aqueous solution of silver nitrate to prepare silver oxide, and oxidation is performed by adding an aqueous solution of a reducing agent such as formalin thereto. It is manufactured by reducing silver to obtain a silver particle dispersion, filtering the dispersion, washing the filtration residue with water and drying.

The heat sinterable metal particles are preferably coated or treated on the surface with an organic substance to prevent aggregation of the heat sinterable metal particles. Examples of such organic substances include fatty acids, fatty acid metal salts, fatty acid amides, fatty acid esters, polymer dispersants and alkylamines. Particularly in view of the covering effect and the treating effect, fatty acids having 6 or more carbon atoms are preferable. Moreover, it is preferable that the coating amount of organic substance is 0.1-5 mass parts in 100 mass parts of heat-sinterable metal particles.

The volatile dispersion medium in the heat-sinterable metal particle paste is blended to make the powder-like heat-sinterable metal particles into a paste. The boiling point of the volatile dispersion medium is preferably 60 ° C. to 300 ° C. at normal pressure.

Such volatile dispersion medium includes volatile hydrocarbon compounds consisting of carbon atoms and hydrogen atoms, volatile organic compounds consisting of carbon atoms, hydrogen atoms and oxygen atoms, volatile organic compounds consisting of carbon atoms, hydrogen atoms and nitrogen atoms It is selected from a compound, a volatile organic compound consisting of a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom, a mixture of a hydrophilic volatile organic compound of the volatile organic compounds and water, and the like. These are all liquid at normal temperature.

Specifically, volatile organic compounds comprising carbon atom, hydrogen atom and oxygen atom include volatiles such as ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and the like Monohydric alcohols; ethylene glycol monomethyl ether (methyl cellosolve, methyl carbitol), ethylene glycol monoethyl ether (ethyl 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, methyl methoxy butanol Volatile monohydric alcohols having a bond; volatile aralkyl alcohols such as benzyl alcohol and 2-phenylethyl alcohol; terpene alcohols such as terpineol; volatile polyhydric aliphatic alcohols such as ethylene glycol, propylene glycol and glycerin Ru.

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-one) Volatile aliphatic ketones such as dibutyl ketone (2,6-dimethyl-4-heptanone); ethyl acetate (ethyl acetate), butyl acetate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl octanoate, 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 diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis (2-diethoxy) ethane, 1,2-bis (2-methoxyethoxy) ethane, etc. It is illustrated. In addition, ester ethers such as acetic acid 2- (2-butoxyethoxy) ethane, and ether alcohols such as 2- (2-methoxyethoxy) ethanol are exemplified.

Examples of volatile hydrocarbon compounds comprising carbon atom and hydrogen atom include volatile aliphatic hydrocarbons such as n-paraffin and isoparaffin; terpene hydrocarbons such as limonene; volatile aromatic hydrocarbons such as toluene and xylene Ru.

Examples of volatile organic compounds consisting of carbon atom, hydrogen atom and nitrogen atom include volatile alkyl nitriles such as acetonitrile and propionitrile.
Examples of volatile organic compounds comprising carbon atom, hydrogen atom, oxygen atom and nitrogen atom include volatile carboxamides such as acetamide and N, N-dimethylformamide. In addition, low molecular weight volatile silicone oils and volatile organic modified silicone oils are exemplified.

The blending amount of the volatile dispersion medium is an amount sufficient to make the heat sinterable metal particles into a paste at normal temperature. Depending on the particle size, specific surface area, shape, etc. of the heat sinterable metal particles, and the kind of the volatile dispersion medium, viscosity, etc., the amount sufficient to form a paste varies, but specifically, for example, The amount is 3 to 30 parts by mass per 100 parts by mass of the heat sinterable metal particles.
The heat sinterable metal particle paste used in the present invention is a metal-based or non-metal powder, metal compound other than heat sinterable metal particles, as long as the effect of the present invention is not impaired. Minor to trace amounts of additives such as metal complexes, thixotropic agents, stabilizers and colorants may be contained.

The solder particle paste, the conductive heat-curable resin paste, and the heat-sinterable metal particle paste used in the bonding method of the present invention are paste-like at normal temperature. In addition, paste-like includes cream-like and slurry-like. By making it paste, metal printing application, stencil printing application, and application by a cylinder or a nozzle become easy.

In the sheet for bonding metal members according to the present invention, the thickness of the solder particle paste layer, the conductive thermosetting resin paste layer or the heat sinterable metal particle paste layer present on both sides of the metal wire fabric is a metal wire. The thickness is not particularly limited as long as the thickness is sufficient to adhere the fabric to the metal member, but preferably 20 μm to 1000 μm, and more preferably 50 μm to 500 μm.

The method of bonding metal members according to the present invention is for bonding metal members having the solder particle paste layer, the conductive thermosetting resin paste layer or the heat sinterable metal particle paste layer on both sides of the metal wire fabric described above. The sheet is interposed between a plurality of metal members and heated to melt the solder particles, to harden the conductive thermosetting resin, or to sinter the heat sinterable metal particles. .

According to a second bonding method of a metal member of the present invention, a solder particle paste, a conductive heat-curable resin paste or paste are interposed between both surfaces of a metal wire fabric and a plurality of metal members, and heating is performed. It is characterized in that the solder particles are melted, the conductive thermosetting resin is cured, or the heat sinterable metal particles are sintered.

The metal member used at that time is a bonded body to which the solder particles are melted, the conductive thermosetting resin is cured, or the heat-sinterable metal particles are sintered and adhered.
Examples of the material of the metal member include gold, silver, copper, platinum, palladium, nickel, tin, iron, and an alloy containing each of these metals. Among them, gold, silver, copper, nickel, tin or an alloy containing these is preferable in terms of conductivity and bondability.

The metal member may be plated in whole or in part with the metal, and in the present invention, one in which the metal is plated in whole or in part is also a metal member. As such a metal member, one obtained by plating the whole or a part of a ceramic member or a synthetic resin member with the metal is exemplified. Examples of the metal member include a lead frame formed entirely or partially of metal, a printed board, a semiconductor chip, a can for sealing a semiconductor chip, a case, a cap and a lid, and a heat sink.

In the method of bonding metal members according to the present invention, a heat sinterable metal particle paste present on both sides of a metal wire fabric, and a heat sinterability present between both surfaces of a metal wire fabric and a plurality of metal members When the metal particle paste is heated, the volatile dispersion medium is volatilized, and the heat-sinterable metal particles are sintered to form a porous sintered product. The porous sinter preferably has a porosity of 5% to 50% in area ratio.

The atmosphere at the time of joining includes oxygen gas when the material of metal wire fabric, heat-sinterable metal particles and metal members is a material easily oxidized like copper, copper alloy, tin or tin alloy. It is preferable to use an inert gas such as nitrogen gas or a reducing gas containing hydrogen gas. As a reducing gas, a forming gas composed of 5 to 25% by volume of hydrogen gas and 95 to 75% by volume of nitrogen gas is exemplified.
When the metal wire fabric, the heat sinterable metal particles and the metal member are made of silver or a silver alloy, an oxidizing gas containing oxygen gas, particularly air, is preferable. The metal particles in the heat sinterable metal particle paste used for bonding and the surface metal of the metal member may be a metal that easily forms an alloy.

The heating temperature at the time of joining operation may be as long as the solder particles are melted, the conductive thermosetting resin is cured, or the heat sinterable metal particles are sintered, and is usually 70 ° C. or more, 150 ° C. or more More preferable. However, if the temperature exceeds 380 ° C., the resin in the conductive thermosetting resin may be thermally decomposed. Therefore, the temperature is preferably 380 ° C. or less, and more preferably 300 ° C. or less.

In the metal member joined body of the present invention, a metal member joining sheet having a solder layer, a conductive cured resin layer or a metal particle sintered layer on both sides of a metal wire fabric is interposed between a plurality of metal members. The metal member is bonded to a solder layer, a conductive cured resin layer or a metal particle sintered layer.

Electronic parts having a metal part, for example, chip parts such as capacitors and resistors, semiconductor chips such as diodes, memories, ICs, IGBTs, and CPUs, high heat generation IGBT chips, as metal members in the metal member joined body of the present invention , CPU chip, lead frame, circuit board, and cooling plate are exemplified. Furthermore, an electronic device, an electrical component, and an electrical device having a metal part are exemplified.

The number of metal members is usually two, but may be three or more.
When two or more metal members are used, a metal member bonding sheet having a solder layer, a conductive cured resin layer, or a metal particle sintered layer on both sides of a metal wire fabric between two metal members Is sandwiched. When the plurality of metal members is three, a metal member bonding sheet having a solder layer, a conductive cured resin layer or a metal particle sintered layer on both surfaces of the metal wire fabric between three metal members. Is sandwiched.

In the metal member joined body of the present invention, for example, the electronic component having a metal part is a gold plated substrate, a silver substrate, a silver plated metal substrate, a copper substrate, an aluminum substrate, a nickel plated substrate, a tin plated metal substrate, a lead containing iron It is firmly bonded to a metal-based substrate such as a frame in a durable manner, and firmly bonded to a conductive metal portion such as an electrode on an electrically insulating substrate in a durable manner. In these metal member bonded bodies, a metal member bonding sheet having a solder layer, a conductive cured resin layer or a metal particle sintered layer on both sides of the metal wire fabric is held between a plurality of metal members. Because of that, it is excellent in thermal shock resistance.

Bonding of chip parts such as capacitors and resistors to circuit board, bonding of semiconductor chips such as diodes, memories, ICs, IGBTs and CPUs to lead frames or circuit boards, bonding of multiple metal members The junction between the IGBT chip, the CPU chip and the cooling plate is exemplified.

Examples of the present invention and comparative examples will be given. In Examples and Comparative Examples, the term "parts" means parts by mass.
The measurement items and the measurement method are as follows. The temperature at the time of measurement is 25 ° C. unless otherwise specified.

[Volume Resistivity and Thermal Conductivity of a Specimen Having a Solder Alloy Layer, a Conductive Hardened Epoxy Resin Layer, or a Silver Particle Sintered Layer Formed on Both Sides of a Metal Wire Fabric]
On both sides of a metal wire fabric with a length of 10 mm and a width of 500 mm and a thickness of 500 μm (a diameter of 0.08 mm, a circular cross-section, and a bundle of six metal wires tin-plated on copper or copper) Apply solder particle paste, heat sinterable epoxy resin paste or heat sinterable metal particle paste respectively by stencil printing, and heat the solder particle paste for 10 minutes at 230 ° C in a nitrogen stream in a reflow furnace. Then, solder alloy layers were formed on both sides of the metal wire fabric. In the conductive thermosetting epoxy resin paste and the heat sinterable silver particle paste, the conductive curing epoxy resin layer is applied to both sides of the metal wire fabric by heating at 230 ° C. for 1 hour in a nitrogen flow circulation oven. It formed. Similarly, silver particle sintered layers were formed on both sides of the metal wire fabric.

The thermal conductivity (unit: W / m · K) was measured by the laser flash method for the test body for thermal conductivity measurement thus produced.

Moreover, about the test body for volume resistivity measurement produced in this way, volume resistivity (unit; ohm * cm) was measured by the method according to JISK7194.

[Preparation of test specimen for bonding strength measurement (1) and shear bond strength before and after application of thermal shock]
50 μm thickness with four openings (2.5 mm × 2.5 mm) at 10 mm intervals on a 25 mm wide × 70 mm long, 1.0 mm thick gold-plated substrate 1 (gold purity 99.99%) Solder paste, conductive heat-curable epoxy resin paste or heat-sinterable silver particle paste is applied by printing using a metal mask, and a metal wire of 2.5 mm in length and width and 500 μm in thickness is formed thereon. Mount a woven fabric (a plain weave of a bundle with a diameter of 0.08 mm, a circular cross-section, and a copper wire or a bundle of six metal wires tin-plated with copper) and the thickness of 50 μm Solder particle paste, conductive heat curable epoxy resin paste or heat sinterable silver particle paste is applied, and silver chip 3 of 2.5 mm × 2.5 mm × 0.5 mm in size (silver purity 99.99) Equipped with%)
Next, in the solder particle paste, this is heated in a nitrogen stream at 230 ° C. for 10 minutes in a reflow furnace to bond the gold-plated substrate and the silver chip with a solder alloy, conductive heat curable epoxy resin paste and heat baked In the case of the conductive silver particle paste, the gold plating substrate and the silver chip were joined by heating at 230 ° C. for 1 hour in a nitrogen flow circulation type oven to cure the conductive epoxy resin or the sintered silver particles.

The test specimen for bonding strength measurement (1) thus obtained was used as a test specimen before applying a thermal shock. In addition, thermal shock is performed for 1000 cycles, in which the test specimen for bonding strength measurement (1) is allowed to stand for 30 minutes at -40 ° C. and 30 minutes at + 150 ° C. in one cycle with a thermal shock tester. It was set as the test body after addition.

The test body (1) is set to the test body fixture of the adhesion strength tester, and the side surface of the silver chip 3 is pressed by the pressing bar of the adhesion strength tester at a thickness of 23 mm / min. The adhesive strength (unit; MPa) was taken as the load at the time of shear failure. The average value of 4 pieces was taken as the shear adhesion strength.
In addition, the top view of the test body for shear bond strength measurement was shown in FIG. 2, and XX sectional drawing in this top view was shown in FIG.

[Preparation of test specimen for bonding strength measurement (2) and shear bond strength before and after application of thermal shock]
600 μm thick with four openings (2.5 mm × 2.5 mm) at 10 mm intervals on a 25 mm wide × 70 mm long, 1.0 mm thick gold-plated substrate 1 (gold purity 99.99%) Solder paste, conductive heat curable epoxy resin paste or heat sinterable silver particle paste are printed and applied using a metal mask, and the size is 2.5 mm × 2.5 mm × 0.5 mm. Silver chip 3 (silver purity 99.99%) was mounted.
Next, in the solder particle paste, this is heated in a nitrogen stream at 230 ° C. for 10 minutes in a reflow furnace to bond the gold-plated substrate and the silver chip with a solder alloy, conductive heat curable epoxy resin paste and heat baked In the case of a solid silver particle paste, heating is performed at 230 ° C. for 1 hour in a nitrogen flow circulation type oven to bond a gold plating substrate and a silver chip with a conductive epoxy resin cured product or a silver particle sintered product, and bonding strength A test specimen for measurement (2) was produced.

The test specimen for bonding strength measurement (2) thus obtained was used as a test specimen before applying a thermal shock. In addition, thermal shock is performed for 1000 cycles, in which the test specimen for bonding strength measurement (2) is allowed to stand for 30 minutes at -40 ° C. and 30 minutes at + 150 ° C. in one cycle with a thermal shock tester. It was set as the test body after addition.

The test body (2) is set in the test piece attachment of the bond strength tester, and the side of the silver chip 3 is pressed by the press bar of the bond strength tester at a thickness of 23 mm / min. The adhesive strength (unit: MPa) was taken as the load at the time of shear failure. The average value of 4 pieces was taken as the shear adhesion strength.

[Reference Example 1]
Sn-Ag-Cu alloy (solidus temperature: 218 ° C., liquidus temperature: 220 ° C.), 90 parts of solder alloy particles having a median diameter of 30 μm, and polymerized rosin as a base resin (trade name: aladim) A solder particle paste was prepared comprising 10 parts of a liquid flux containing cyclohexylamine hydrobromide (reagent) as an activator, dibenzylidene sorbitol derivative (reagent) as a thixotropic agent, and butyl carbitol (reagent) as a solvent. The viscosity of the solder particle paste was 200 Pa · s.

[Reference Example 2]
50 parts of silver particles (shape: granular, median diameter: 1.0 μm, oleic acid content: 0.3% by weight) manufactured by reduction method and coated with oleic acid on the surface, and bisphenol A epoxy resin (trade name) Conductive heat-curable composition comprising 37.5 parts of jER 828, 4.0 parts of monofunctional epoxy resin diluent (trade name: ED509S), and 8.5 parts of epoxy resin curing agent (trade name: PN-40) An epoxy resin paste was prepared. The viscosity of the conductive thermosetting epoxy resin paste was 100 Pa · s.

[Reference Example 3]
100 parts of silver particles (shape: granular, median diameter: 1.0 μm, amount of hexanoic acid: 0.3% by weight) manufactured by reduction method and coated with hexanoic acid on the surface, and octanediol (volatile dispersion medium) A heat sinterable silver particle paste consisting of 10 parts of a reagent) was prepared. The viscosity of the heat sinterable metal particle paste was 20 Pa · s.

Example 1

The solder particle paste prepared in Reference Example 1 has a thickness of 50 μm on both sides of a metal wire fabric plain weave with a bundle having a diameter of 0.08 mm and a cross section having a circular shape and having six metal wires plated with copper. To form a solder alloy layer on both sides of the metal wire fabric by heating at 230 ° C. for 10 minutes in a nitrogen stream in a reflow furnace, as a test body for thermal conductivity measurement and for volume resistivity measurement The test body was produced.
The thermal conductivity and the volume resistivity were measured for these test bodies, and the results are summarized in Table 1.

Using the metal wire fabric and the solder particle paste prepared in Reference Example 1, a test body (1) for bonding strength measurement was produced. The preparation conditions are as described in the preparation of the test specimen for bond strength measurement (1) and the shear bond strength before and after the application of thermal shock. The shear bond strengths before and after thermal shock were measured on these test bodies, and the results are summarized in Table 1.

According to the above results, according to the method for joining metal members using the metal member joining sheet having the solder layer on both sides of the metal wire fabric of the present invention, the metal members can be joined firmly. It turned out that it becomes a metal member joined body which is excellent in thermal shock resistance and does not lose thermal conductivity and electrical conductivity.

Example 2
Conductive thermosetting epoxy resin paste prepared in Reference Example 2 on both sides of a metal wire fabric plain woven with a bundle having a diameter of 0.08 mm and a cross section having a circular shape and six metal wires plated with copper. Is applied to a thickness of 50 μm, and heated for 1 hour at 230 ° C. in a nitrogen flow circulating oven to form a cured conductive epoxy resin layer on both sides of the metal wire fabric, thereby measuring thermal conductivity. Test specimens and test specimens for volume resistivity measurement were prepared.
The thermal conductivity and the volume resistivity were measured for these test bodies, and the results are summarized in Table 1.

Using the metal wire fabric and the conductive thermosetting epoxy resin paste prepared in Reference Example 2, etc., a test body (1) for bonding strength measurement was produced. The preparation conditions are as described in [Preparation of test specimen for bond strength measurement (1) and shear bond strength before and after application of thermal shock]. The shear bond strengths before and after thermal shock were measured on these test specimens, and the results are summarized in Table 1,

According to the above results, according to the method for joining metal members using the metal member joining sheet having the conductive cured epoxy resin layer on both sides of the metal wire fabric of the present invention, the metal members are firmly joined. It turned out that it becomes a metal member joined body which is excellent in thermal shock resistance and does not lose thermal conductivity and electric conductivity.

[Example 3]
The heat sinterable silver particle paste prepared in Reference Example 3 was thickened on both sides of a plain weave of a bundle of plain weave with a bundle having a diameter of 0.08 mm and a cross section having a circular shape and copper made of a metal wire. It is applied so as to be 50 μm thick and heated at 230 ° C. for 1 hour in a nitrogen flow circulation type oven to form a silver particle sintered material layer on both sides of the metal wire fabric, a test for thermal conductivity measurement Test specimens for measuring body and volume resistivity were prepared.
The thermal conductivity and the volume resistivity were measured for these test bodies, and the results are summarized in Table 1.

Using the metal wire fabric and the heat sinterable silver particle paste prepared in Reference Example 3, a test body (1) for bonding strength measurement was produced. The preparation conditions are as described in [Preparation of test specimen for bond strength measurement (1) and shear bond strength before and after application of thermal shock]. The shear bond strengths before and after thermal shock were measured on these test bodies, and the results are summarized in Table 1.

According to the above results, according to the method for joining metal members using the metal member joining sheet having the silver particle sintered layer on both sides of the metal wire fabric of the present invention, the metal members are firmly joined. It turned out that it becomes a metal member joined body which is excellent in thermal shock resistance and does not lose thermal conductivity and electric conductivity.

Comparative Example 1
The solder particle paste prepared in Reference Example 1 is print-coated on a fluorine resin plate so as to be 10 mm long, 10 mm wide, and 600 μm thick, and heated in a nitrogen stream at 230 ° C. for 10 minutes in a reflow furnace. The test body for thermal conductivity measurement and the test body for volume resistivity measurement which consist only of solder alloy were produced.
The thermal conductivity and the volume resistivity were measured for these test bodies, and the results are summarized in Table 2.

Using the solder particle paste prepared in Reference Example 1, a test sample (2) for bonding strength measurement in which the thickness of the solder alloy is 600 μm was produced. The preparation conditions are as described in [Preparation of test specimen for bond strength measurement (2) and shear bond strength before and after application of thermal shock]. The shear bond strength before and after thermal shock was measured on this test body, and the results are summarized in Table 2.

From the above results, it was found that the method of joining metal members using the metal member joining sheet having the solder alloy layer on both sides of the metal wire fabric results in a metal member joined body having poor thermal shock resistance. .

Comparative Example 2
The conductive thermosetting epoxy resin paste prepared in Reference Example 2 is print-coated on a plate made of a fluorine resin so as to be 10 mm long, 10 mm wide, and 600 μm thick, in a nitrogen flow circulation oven at 230 ° C. A test body for thermal conductivity measurement and a test body for volume resistivity measurement consisting only of the conductive epoxy resin cured product were produced by heating for 1 hour.
The thermal conductivity and the volume resistivity were measured for these test bodies, and the results are summarized in Table 2.

Using the conductive thermosetting epoxy resin paste prepared in Reference Example 2, a test sample for bonding strength measurement (2) having a thickness of the conductive epoxy resin cured product of 600 μm was produced. The preparation conditions are as described in [Preparation of test specimen for bond strength measurement (2) and shear bond strength before and after application of thermal shock]. The shear bond strength before and after thermal shock was measured on this test body, and the results are summarized in Table 2.

According to the above results, the method of joining metal members which does not use the metal member joining sheet having the conductive cured epoxy resin layer on both sides of the metal wire fabric is a metal member joined body having poor thermal shock resistance. I understand.

Comparative Example 3
The heat sinterable silver particle paste prepared in Reference Example 3 is print-coated on a plate made of a fluorine resin so as to be 10 mm long, 10 mm wide, and 600 μm thick, and heated at 230 ° C. in a nitrogen flow circulation oven. The sample was heated for time to prepare a test body for measuring the thermal conductivity and a test body for measuring the volume resistivity which consisted only of the silver particle sinter.
The thermal conductivity and the volume resistivity were measured for these test bodies, and the results are summarized in Table 2.

Using the heat sinterable silver particle paste prepared in Reference Example 3, a test sample for bonding strength measurement (2) in which the thickness of the silver particle sintered product is 600 μm was produced. The preparation conditions are as described in [Preparation of test specimen for bond strength measurement (2) and shear bond strength before and after application of thermal shock]. The shear bond strength before and after thermal shock was measured on this test body, and the results are summarized in Table 2.

According to the above results, the method of joining metal members that does not use a metal member joining sheet having a silver particle sintered layer on both sides of a metal wire fabric can result in a metal member joined body having poor thermal shock resistance. all right.

The metal member bonding sheet of the present invention is useful for producing a metal member joined body excellent in thermal shock resistance.
The method of joining metal members using the metal wire fabric of the present invention is useful for producing a metal member assembly excellent in thermal shock resistance.
The metal member joined body of the present invention is a joined body of a chip component such as a capacitor and a resistor and a circuit board, a joined body of a semiconductor chip and a lead frame or a circuit board such as a diode, memory, IC, IGBT, and CPU, high. It is useful as a heat generating IGBT, a junction of a CPU chip and a cooling plate, and the like. The metal member assembly of the present invention is useful for manufacturing electronic devices, electrical devices and the like.

A Test specimen for measuring shear adhesive strength 1 Gold-plated substrate 2 Sheet for bonding metal members 3 Silver chip 4 Flat metal wire fabric 5 Solder particle paste 6 Solder particle paste impregnated layer

Claims (13)

A sheet for bonding metal members, comprising a solder particle paste layer, a conductive thermosetting resin paste layer or a heat sinterable metal particle paste layer on both sides of a metal wire fabric. The metal wire according to claim 1, wherein the metal wire has a cross-sectional diameter of 0.01 to 0.2 mm and is made of gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. , Metal member joining sheet. The sheet | seat for metal member joining of Claim 2 which is a plain weave fabric which consists of a bundle | flux of a 3-30 metal wire. A metal member bonding sheet having a solder particle paste layer, a conductive thermosetting resin paste layer, or a heat sinterable metal particle paste layer on both sides of a metal wire fabric is interposed between a plurality of metal members and heated And melting the solder particles, curing the conductive thermosetting resin paste, or sintering the heat sinterable metal particles. The metal wire according to claim 4, wherein the metal wire has a cross-sectional diameter of 0.01 to 0.2 mm and is made of gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. Method of joining metal members. The method of bonding metal members according to claim 4 or 5, wherein the metal wire fabric is a plain fabric comprising a bundle of 3 to 30 metal wires. The metal member according to any one of claims 4 to 6, wherein the material of the metal member is gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. Bonding method. A solder particle paste, a conductive thermosetting resin paste, or a heat sinterable metal particle paste is interposed between both surfaces of the metal wire fabric and a plurality of metal members, and heated to melt the solder particles by heating. Method of bonding metal members, characterized in that the heat curable resin is cured or the heat sinterable metal particles are sintered. The metal wire according to claim 8, wherein the metal wire has a cross-sectional diameter of 0.01 to 0.2 mm and is made of gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. Method of joining metal members. The method of joining metal members according to claim 8 or 9, wherein the metal wire fabric is a plain fabric comprising a bundle of 3 to 30 metal wires. The metal member according to any one of claims 8 to 10, wherein the material of the metal member is gold, silver, copper, platinum, palladium, nickel, tin, iron or an alloy containing these. Bonding method. Between a plurality of metal members, a metal member bonding sheet having a solder layer, a conductive cured resin layer or a metal particle sintered layer is interposed on both sides of a metal wire fabric, and the metal members are a solder layer, a conductive layer Metal bonded body characterized in that it is bonded to a metallic cured resin layer or a metal particle sintered layer. The metal member joined body according to claim 11, wherein the metal member is an electronic component having a metal portion.

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