WO2016116959A1 - Conductive resin composition and semiconductor device - Google Patents

Abstract

Provided is a conductive resin composition that has favorable conductivity, adhesion and workability and can be manufactured inexpensively. The conductive resin composition contains, as essential components, (A) silver-coated silica particles, (B) a thermosetting resin and (C) a curing agent. The conductive resin composition contains 35-90 mass% of the (A) silver-coated silica particles. Further, the (A) silver-coated silica particles are spherical particles having an aspect ratio of 1.0-1.2, a specific surface area of 0.3-5.0 m²/g, an accumulated volume particle size D₅₀ of 1-10 μm, a ratio D₅₀/D₁₀ of accumulated volume particle sizes D₁₀ and D₅₀ of 1.5-5.0 and a maximum particle size of at most 40 μm.

Description

Conductive resin composition and semiconductor device

The present invention relates to a conductive resin composition suitably used for bonding a semiconductor element to a support member and a semiconductor device using the same.

With the expansion of the advanced information society and the remarkable development of the electronics industry, the degree of integration of semiconductor elements used in semiconductor devices such as transistors, ICs, LSIs, and LEDs has increased. Improvement in reliability and the like is required. In addition, semiconductor devices are required to be smaller and have higher performance in order to improve convenience, portability, and the like, and components used for such devices are also required to be smaller and have higher performance. For example, in a semiconductor device, a conductive resin composition is used for adhesion between a support member and a semiconductor element. For such a conductive resin composition, in addition to basic characteristics such as conductivity, adhesion, and workability, weight reduction and cost reduction are required.

Generally, in a conductive resin composition, conductivity is expressed by filling silver powder as a conductive powder. However, since silver powder is expensive, it is preferable to refrain from use from the viewpoint of manufacturing cost. Moreover, since silver powder has a large specific gravity of 10.5, silver powder tends to settle in the conductive resin composition. For this reason, in recent years, the use of metal-coated powder in which the surface of particles made of a material other than silver is coated with a metal such as silver has been studied as a conductive powder. According to the metal-coated powder, since only the surface is coated with a metal such as silver, weight reduction and cost reduction can be achieved.

As a metal-coated powder, a metal component is added to a glass raw material, melted, and heat-treated in a reducing atmosphere to deposit a metal film on the surface (see, for example, Patent Document 1). . However, with such a metal-coated powder, the metal film tends to be non-uniform and the particle size tends to be uneven. Thereby, workability | operativity and electroconductivity of a conductive resin composition do not become favorable, and when a support member and a semiconductor element are adhere | attached, it is easy to generate | occur | produce an inclination in a semiconductor element.

Further, a metal-coated powder whose surface is coated with silver is known (see, for example, Patent Documents 2 and 3). However, this metal-coated powder is used for forming a conductive pattern and the conductive resin composition contains a large amount of an organic solvent. When such a conductive resin composition containing a large amount of organic solvent is used for bonding semiconductor elements, voids are generated and sufficient adhesion cannot be obtained.

Further, as a metal-coated powder, a flake-shaped powder whose surface is coated with silver and has a specific aspect ratio is known (for example, see Patent Document 4). However, in the case of flakes, it is difficult to cover the corners, and sufficient conductivity cannot be obtained. On the other hand, the coating can be made uniform by increasing the coating amount, but the specific gravity of the metal-coated powder tends to increase. When the specific gravity of the metal-coated powder increases, the mass of the conductive resin composition tends to increase, and the metal-coated powder tends to settle in the conductive resin composition. In the case of flakes, the coating is easily peeled off by an external factor such as a slight impact or stress, and sufficient conductivity and adhesiveness cannot be obtained. Furthermore, in the case of flakes, sufficient adhesion cannot be obtained because cracks at the time of breakage tend to extend.

Japanese Patent Laid-Open No. 51-053295 JP 2012-0779457 A Special table 2010-539650 gazette International Publication No. 2012/118061

The present invention has been made in response to such problems, and an object of the present invention is to provide a conductive resin composition that has good conductivity, adhesiveness, and workability and can be manufactured at low cost. Moreover, an object of this invention is to provide the semiconductor device excellent in the reliability which uses such a conductive resin composition.

The conductive resin composition of the present invention contains (A) silver-coated silica particles, (B) a thermosetting resin, and (C) a curing agent as essential components. (A) The silver-coated silica particles are contained in an amount of 35 to 90% by mass in the conductive resin composition. The silver-coated silica particles (A) have an aspect ratio of 1.0 to 1.2, a specific surface area of 0.3 to 5.0 m ² / g, a cumulative volume particle size D ₅₀ of 1 to 10 μm, diameter _{D 10,} the ratio of _{D 50 D 50 / D 10} of 1.5 to 5.0 and a maximum particle size of less spherical particles 40 [mu] m.

According to the present invention, it is possible to provide a conductive resin composition that has good conductivity, adhesion, and workability and can be manufactured at low cost. Moreover, according to the present invention, a semiconductor device having excellent reliability can be provided by bonding a semiconductor element using the conductive resin composition.

It is sectional drawing which shows the semiconductor device of one Embodiment.

Hereinafter, modes for carrying out the present invention will be described.
The conductive resin composition according to one embodiment of the present invention contains (A) silver-coated silica particles, (B) a thermosetting resin, and (C) a curing agent as essential components. Such a conductive resin composition is suitably used for bonding a semiconductor element to a support member.

The silver-coated silica particles (A) are obtained by coating the surfaces of the silica particles with silver, and are used for imparting conductivity to the conductive resin composition. The silver-coated silica particles have an aspect ratio of 1.0 to 1.2, a specific surface area of 0.3 to 5.0 m ² / g, a cumulative volume particle size D ₅₀ of 1 to 10 μm, a cumulative volume particle size D ₁₀ , D the ratio _D 50 _{/ D 10} of ₅₀ 1.5 to 5.0 and a maximum particle size of less spherical particles 40 [mu] m. In addition, a silver covering silica particle may be used individually by 1 type, and 2 or more types may be mixed and used for it. The specific surface area is measured by a gas adsorption method. Further, D ₁₀ , D ₅₀ , and the maximum particle size of the silver-coated silica particles are measured by a laser diffraction / scattering particle size distribution measurement method.

Silver-coated silica particles are spherical. The spherical shape is preferable because it is excellent in filling property, dispersibility, and stress relaxation property. The silver-coated silica particles may be hollow or porous as long as they are spherical as a whole, and may have a number of protrusions or irregularities on the surface.

Silver-coated silica particles have silica particles as a core material. The shape of the silica particles is preferably spherical. The spherical silica particles are produced, for example, by dropping silica melted in a melting furnace from the upper part and making it spheroidized during cooling. The silica particles may be subjected to a surface treatment before being coated with silver.

Examples of methods for coating the surface of the silica particles with silver include vapor deposition, sputtering, electroplating, displacement plating, and electroless plating. These methods can be performed in combination. Among these methods, the electroless plating method is preferable because the surface of the silica particles can be uniformly coated. As a specific coating method, for example, a method of activation by palladium, nickel plating, and then silver plating can be mentioned. According to such a method, the surface of the silica particles can be efficiently coated.

When the aspect ratio of the silver-coated silica particles is 1.0 to 1.2, the conductive resin composition can be highly filled with silver-coated silica particles, thereby reducing the volume resistivity. In addition, when the silver-coated silica particles have an aspect ratio of 1.0 to 1.2, workability is good because the increase in viscosity is suppressed even when the content of the silver-coated silica particles in the conductive resin composition is large. become. In addition, the aspect ratio in this specification is calculated | required by (the width | variety orthogonal to the largest long diameter / maximum long diameter of particle | grains).

When the specific surface area of the silver-coated silica particles is 0.3 to 5.0 m ² / g, the workability of the conductive resin composition is improved and the volume resistivity is also reduced. That is, when the specific surface area is 0.3 m ² / g or more, workability is improved. For example, even when dispensing with a syringe having a needle diameter of 0.3 mm, sag and stringing are suppressed, and workability is improved. When the specific surface area is 5.0 m ² / g or less, the viscosity and the thixotropy are lowered and the workability is improved. Moreover, when the specific surface area is 5.0 m ² / g or less, the specific gravity of the silver-coated silica particles can be reduced because the amount of silver covering the silica particles can be reduced, so that the silver-coated silica particles settle. Can be suppressed. In addition, when the specific surface area is 5.0 m ² / g or less, if the amount of silver is the same, the coating area becomes small, and thus the silver coating tends to be thick, thereby reducing the volume resistivity. The specific surface area is measured by a gas adsorption method.

When the D _{50 of the} silver-coated silica particles is 1 to 10 μm, the workability of the conductive resin composition is improved. That is, if the D ₅₀ is equal to or greater than 1 [mu] m, workability since the viscosity of the conductive resin composition is lowered is improved. If D ₅₀ is 10μm or less, for example, even when dispensed using a syringe needle diameter 0.3 mm, nozzle clogging is suppressed hardly poor coating occurs in the syringe tip, the workability becomes good.

When the ratio D ₅₀ / D _{10 of the} silver-coated silica particles is 1.5 to 5.0, the conductivity and adhesiveness of the conductive resin composition are improved. For example, when the ratio D ₅₀ / D ₁₀ is 5.0 or less, the area to be covered with silver is small because the proportion of fine powder is low. Thereby, it is easy to increase the thickness of the silver coating and to reduce the volume resistivity. In addition, when the ratio D ₅₀ / D ₁₀ is 5.0 or less, since the proportion of fine powder is low, the amount of the thermosetting resin used for coating the silver-coated silica particles is reduced, so that the support member and the conductive member are electrically conductive. The amount of the thermosetting resin at the interface with the conductive resin composition and at the interface between the semiconductor element and the conductive resin composition is increased, and the adhesiveness is improved.

When the maximum particle diameter of the silver-coated silica particles is 40 μm or less, the inclination of the semiconductor element when the semiconductor element and the support member are bonded is suppressed. For example, when the semiconductor element and the support member are bonded via the conductive resin composition, the thickness of the conductive resin composition between the semiconductor element and the support member is 10 to 30 μm. At this time, if silver-coated silica particles having a particle size exceeding 40 μm are present, the semiconductor element tends to tilt. When the maximum particle size of the silver-coated silica particles is 40 μm or less, nozzle clogging at the tip of the syringe is suppressed even when dispensing with a syringe having a needle diameter of 0.3 mm.

The specific gravity of the silver-coated silica particles is preferably 2.4 to 3.6. When the specific gravity is 2.4 to 3.6, the dispersibility and conductivity of the conductive resin composition are improved. That is, when the specific gravity is 2.4 or more, the silver coating on the silver-coated silica particles tends to have a sufficient thickness, and thereby the conductivity of the conductive resin composition tends to be good. When the specific gravity is 3.6 or less, precipitation of the silver-coated silica particles in the conductive resin composition is suppressed, and the silver-coated silica particles are uniformly dispersed. The specific gravity is more preferably 2.7 to 3.3.

The surface of the silver-coated silica particles is preferably coated with a silane coupling agent. When the surface of the silver-coated silica particles is coated with a silane coupling agent, the adhesion and compatibility between the silver-coated silica particles and the thermosetting resin is improved, and the adhesiveness of the conductive resin composition is improved. Become.

When the surface of the silver-coated silica particles is coated with a silane coupling agent, it is preferable to treat the surface of the silver-coated silica particles with a fatty acid or a fatty acid salt and then treat the outermost surface with a silane coupling agent. Thus, after processing with a fatty acid or a fatty acid salt, the adhesion and compatibility between the silver-coated silica particles and the thermosetting resin are improved by processing with a silane coupling agent. Good adhesion.

The method of coating with the silane coupling agent may be either a wet method or a dry method. For example, a method of adding a silane coupling agent to the plating solution when the surface of silica particles is coated with silver, a method of coating the surface of silver-coated silica particles with a silane coupling agent by a gas phase reaction, alcohol, petroleum solvent Examples include a method of immersing silver-coated silica particles in a solution obtained by adding a silane coupling agent to a solvent such as the above, a method of spraying the above solution onto silver-coated silica particles, and the like.

Examples of silane coupling agents include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyl Trimethoxysilane, bis ( Li) tetrasulfide, and the like. These silane coupling agents may be used alone or in a combination of two or more. From the viewpoint of compatibility and reactivity with thermosetting resins, particularly epoxy resins, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, Methyltrimethoxysilane and bis (triethoxysilylpropyl) tetrasulfide are preferred.

The surface of the silver-coated silica particles may be coated with a fatty acid or a fatty acid salt instead of coating with a silane coupling agent. When the surface of the silver-coated silica particles is coated with a fatty acid or a fatty acid salt, the dispersibility and compatibility of the silver-coated silica particles are improved, and aggregation of the silver-coated silica particles is suppressed. Thereby, the adhesiveness of a conductive resin composition becomes favorable.

As a method of coating with a fatty acid or a fatty acid salt, either a wet method or a dry method may be used. For example, a method of adding a fatty acid or a fatty acid salt to the plating solution when the surface of the silica particles is coated with silver, a method of coating the surface of the silver-coated silica particles with a fatty acid or a fatty acid salt by a gas phase reaction, alcohol, petroleum-based solvent Examples include a method of immersing silver-coated silica particles in a solution obtained by adding a fatty acid or a fatty acid salt to a solvent such as the above, and a method of spraying the above solution onto silver-coated silica particles.

Examples of fatty acids or fatty acid salts include lauric acid, myristic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, propionic acid, caprylic acid Acrylic acid, benzotriazole, and salts thereof. These fatty acids or fatty acid salts may be used alone or in a combination of two or more. Among these, it is preferable to use at least one selected from myristic acid, oleic acid, stearic acid, and palmitic acid from the viewpoint of compatibility with the thermosetting resin and workability of the conductive resin composition. In particular, myristic acid is preferably used from the viewpoint of compatibility with an epoxy resin.

The content of silver-coated silica particles is 35 to 90% by mass in the conductive resin composition. When the content of the silver-coated silica particles is 35 to 90% by mass, the conductivity, adhesion and workability of the conductive resin composition are improved. That is, when the content of the silver-coated silica particles is 35% by mass or more, the conductivity of the conductive resin composition is improved. Moreover, when content of a silver covering silica particle is 90 mass% or less, the adhesiveness and workability | operativity of a conductive resin composition become favorable, and the manufacturing cost of a conductive resin composition also falls. The content of silver-coated silica particles is preferably 40 to 80% by mass.

The conductive resin composition may contain a filler other than the silver-coated silica particles together with the silver-coated silica particles. As the filler other than the silver-coated silica particles, either conductive particles or non-conductive particles may be used.

Examples of the conductive particles contained in the conductive resin composition include silver particles, copper particles, nickel particles, aluminum particles, silver-coated copper particles, and nano silver particles. Among these, silver particles and nano silver particles are preferable from the viewpoints of conductivity and workability. In particular, nano silver particles are preferable because they improve adhesiveness at high temperatures.

The D ₅₀ of the silver particles is preferably 0.5 to 15 μm. The shape of the silver particles is preferably a flake shape or an indefinite shape. When D ₅₀ is 0.5 to 15 μm and the shape is flaky or irregular, it is preferable because the volume resistivity of the conductive resin composition decreases.

_{D 50} of the nanosilver particles is preferably 5 ~ 300 nm. Examples of the shape of the nano silver particles include flake shape, scale shape, dendritic shape, rod shape, wire shape, spherical shape, plate shape, and the like, and a spherical shape or a plate shape is preferable, and a plate shape is more preferable. In the case of a plate type, the effect of improving the adhesiveness at a high temperature is greater than that of a spherical shape. Moreover, in the case of a plate type, in addition to the effect of improving the adhesiveness at high temperature, there is also the effect of improving the adhesiveness at normal temperature. It is preferable that a coating layer made of an organic compound containing a functional group such as an amino group or a carboxyl group is provided on the surface of the nanosilver particle.

Unlike spherical nano silver particles, plate-type nano silver particles are obtained by growing one metal crystal face greatly, and are flaky particles having a uniform thickness. As the plate-type nano silver particles, known ones can be used. In general, plate-type nano silver particles have a thickness of about several nanometers and a size on the order of microns. Examples of the shape of the plate-type nano silver particles include a triangular plate shape, a hexagonal plate shape, and a truncated triangular plate shape. It is preferable that the surface of the plate-type nano silver particle is widely covered with the [111] plane. The D ₅₀ of the plate-type nanosilver particles is preferably 0.3 to 15 μm.

The length of the long side in the plane direction of the plate-type nano silver particles is preferably 8 to 150 times, more preferably 10 to 50 times the thickness. In addition, the length of the short side in the plane direction of the plate-type nano silver particles is preferably 1 to 100 times, more preferably 3 to 50 times the thickness. When the length in the plane direction is within the above range, it is preferable because the plate-type nano silver particles are easily oriented in the horizontal direction, more contacts are formed, and the conductivity is improved. The plane direction means a direction perpendicular to the thickness direction.

Commercially available products can be used as the plate-type nano silver particles. Examples of such products include M612 (trade name, D ₅₀ : 6 to 12 μm, particle thickness: 60 to 100 nm, melting point: 250 ° C.), M27 (trade name, D ₅₀ : 2 to 7 μm) manufactured by Toxen Industries, Ltd. Particle thickness: 60 to 100 nm, melting point: 200 ° C., M13 (trade name, D ₅₀ : 1 to 3 μm, particle thickness: 40 to 60 nm, melting point: 200 ° C.), N300 (trade name, D ₅₀ : 0.3 to 0.6 μm, particle thickness: 50 nm or less, melting point: 150 ° C., manufactured by Mitsuboshi Belting Co., Ltd., MDot (trade name, D ₅₀ : 50 nm), Ag nano Powder-1 (specific surface area 15-20 mm ² / g, ≧ 95 wt) %), Ag nano Powder-2 (specific surface area 5 to 8 mm ² / g, ≧ 98 wt%), and the like.

In the case where conductive particles (excluding silver-coated silica particles) are contained, the content thereof is preferably 50% by mass or less and more preferably 30% by mass or less in the total of silver-coated silica particles and conductive particles. When the conductive particles are contained, the content is preferably 1% by mass or more and more preferably 5% by mass or more in the total of the silver-coated silica particles and the conductive particles from the viewpoint of obtaining a sufficient effect.

The nonconductive particles contained in the conductive resin composition may be either inorganic particles or organic particles.

Examples of the inorganic particles contained in the conductive resin composition include silica, fumed silica, alumina, boron nitride, titanium oxide, barium, talc, calcium carbonate, and aluminum hydroxide. Among these, silica or fumed silica is preferable from the viewpoint of workability and adhesiveness of the conductive resin composition. The D ₅₀ of silica is preferably 0.5 to 15 μm. The shape of silica is preferably spherical. The primary particle size D ₅₀ of fumed silica is preferably 5 to 300 nm. The shape of fumed silica is not particularly limited. When fumed silica is contained, it is preferable because workability is improved.

Examples of the organic particles contained in the conductive resin composition include resin particles such as silicone powder and a crosslinked polymer. Examples of the shape of the resin particles include a spherical shape and an indefinite shape, but a spherical shape is preferable from the viewpoint of dispersibility.

Silicone powder includes silicone rubber powder having a structure in which linear dimethylpolysiloxane is crosslinked, silicone resin powder that is a cured product of polyorganosilsesquioxane having a structure in which siloxane bonds are crosslinked in a three-dimensional network, silicone Examples thereof include a silicone composite powder in which the surface of rubber particles is coated with a silicone resin. Among these, silicone resin powder and silicone composite powder are preferable from the viewpoint of heat resistance and dispersibility.

Commercially available products can be used as the silicone powder. Examples of such materials include silicone composite powders (KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., silicone rubber powders (KMP-597, KMP). -598, KMP-594, X-52-875, etc.) and silicone resin powder (KMP-590, KMP-701, X-52-854, X-52-1621, etc.). These silicone powders may be used alone or in a combination of two or more.

Examples of the crosslinked polymer include divinylbenzene crosslinked polymer, methyl methacrylate resin (PMMA), ethyl methacrylate resin (PEMA), butyl methacrylate resin (PBMA), methyl methacrylate-ethyl methacrylate copolymer, and mixtures thereof. Etc. Among these, a divinylbenzene crosslinked polymer and a methyl methacrylate resin are preferable because of excellent heat resistance and stability.

The average particle diameter of the organic particles is preferably 0.5 to 40 μm. When the average particle diameter of the organic particles is 0.5 to 40 μm, the stress of the conductive resin composition is relaxed, and the reflow resistance, the thermal shock resistance, etc. are improved. The average particle size of the organic particles is more preferably 0.8 to 20 μm, further preferably 0.8 to 10 μm, and particularly preferably 0.8 to 5 μm.

In addition, the surface of the above-mentioned inorganic particles and organic particles can be used as conductive particles by coating a metal such as gold or silver.

When the non-conductive particles are contained, the content thereof is preferably 50% by mass or less and more preferably 30% by mass or less in the whole filler. Here, the filler means silver-coated silica particles, conductive particles, and non-conductive particles. Moreover, when it contains nonelectroconductive particle, the content is 1 mass% or more in the whole filler from a viewpoint of obtaining sufficient effect, and 3 mass% or more is more preferable.

(B) As a thermosetting resin of a component, what is used for an adhesive use etc. can be used conveniently. The thermosetting resin is preferably liquid at normal temperature (25 ° C.). Examples of the thermosetting resin include epoxy resins, phenol resins, unsaturated polyester resins, polyimide resins, silicone resins, polyurethane resins, xylene resins, butadiene resins, maleimide resins, cyanate resins, radical polymerizable acrylic resins, and the like. These thermosetting resins may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among these, it is preferable to contain at least one selected from an epoxy resin, an acrylic resin, and a maleimide resin.

As the epoxy resin, one having two or more glycidyl groups in one molecule can be used. Such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, ether or polyether type epoxy resin, ester or polyester epoxy resin, urethane type epoxy resin, polyfunctional Type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, hydrogenated epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, ethylene oxide modified bisphenol A type epoxy resin, propylene oxide modified bisphenol A type epoxy resin, glycidyl Modified polyptadiene resin, glycidyl modified triazine resin, silicone modified epoxy resin, aminophenol type epoxy resin, flexible epoxy resin, methacrylic modified epoxy resin, resin Lil modified epoxy resin, special modified epoxy resin, dicyclopentadiene type epoxy resin, side chain hydroxyl alkyl-modified epoxy resins, long-chain alkyl-modified epoxy resins, imide-modified epoxy resins, CTBN modified epoxy resins or the like. The epoxy resin is not limited to these.

The epoxy resin is preferably liquid at normal temperature. Note that an epoxy resin that is solid at room temperature can be used in a liquid state by diluting with a liquid epoxy resin, a reactive diluent, a solvent, or the like. Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, 1,6-hexanediol diglycidyl ether, 4,4′-isopropylidenedicyclohexanol diglycidyl ether, 1,4-cyclohexanedimethanol Diglycidyl ether, 1,4-butanediol diglycidyl ether, and a flexible epoxy resin are preferred. Among these, a flexible epoxy resin is preferable because good adhesive strength can be obtained.

Examples of the flexible epoxy resin include diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyoxyalkylene glycol and polytetramethylene ether glycol containing an alkylene group having 2 to 9 carbon atoms (preferably 2 to 4 carbon atoms), etc. A long chain polyol polyglycidyl ether, a copolymer of glycidyl (meth) acrylate and a radically polymerizable monomer such as ethylene, vinyl acetate or (meth) acrylic acid ester, a (co) polymer of a conjugated diene compound or its Epoxidized unsaturated carbon bond in partially hydrogenated (co) polymer, polyester resin having epoxy group, urethane modified epoxy or polycaprolactone modified epoxy resin with urethane bond or polycaprolactone bond introduced Dimer acid or dimer acid-modified epoxy resin obtained by introducing an epoxy group in the molecule of its derivatives, NBR, CTBN, polybutadiene, and a rubber-modified epoxy resin obtained by introducing a molecular epoxy group in a rubber component such as acrylic rubber.

As a flexible epoxy resin, the flexible epoxy resin represented by following formula (1) is preferable.

(In the formula, A is a divalent aliphatic hydrocarbon group having 6 to 14 carbon atoms, B is —CH ₂ — or —C (CH ₃ ) ₂ —, and Ar is an aliphatic hydrocarbon substituted or non-substituted group. A substituted phenylene group, and n is an integer of 1 to 10.)

A commercially available product can be used as the flexible epoxy resin represented by the formula (1). As such, YL7175-500 (epoxy equivalent 487) manufactured by Japan Epoxy Resin, YL7150-1000 (epoxy equivalent 1000), EP-4003S (epoxy equivalent 412) manufactured by DIC, which is a bisphenol A modified epoxy resin, EP-4000S (epoxy equivalent 260) and the like.

The acrylic resin is a compound having a (meth) acryloyl group in the molecule, and is cured by forming a three-dimensional network structure by the reaction of the (meth) acryloyl group. It is preferable that one or more (meth) acryloyl groups are contained in the molecule.

Acrylic resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,2-cyclohexanediol mono (meth) acrylate, 1,3-cyclohexanediol mono (meth) acrylate, 1,4-cyclohexanediol mono (meth) acrylate, 1,2-cyclohexane Dimethanol mono (meth) acrylate, 1,3-cyclohexanedimethanol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1,2-cyclohexanediethanol mono (Meth) acrylate, 1,3-cyclohexanediethanol mono (meth) acrylate, 1,4-cyclohexanediethanol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane mono (meth) acrylate , Having a hydroxyl group such as trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate (meth) Examples include acrylates and (meth) acrylates having a carboxy group obtained by reacting these (meth) acrylates having a hydroxyl group with a dicarboxylic acid or a derivative thereof. That. Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, And derivatives thereof.

Further, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) Acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl ( Acrylate), isobornyl (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) Acrylate, neopentyl glycol (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4-hexafluorobutyl ( (Meth) acrylate, perfluorooctyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butyl Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,10-decanediol di ( (Meth) acrylate, tetramethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyalkylene glycol mono (meth) acrylate, octoxypolyalkylene glycol mono (Meth) acrylate, Lauroxy polyalkylene glycol mono (meth) acrylate, Stearoxy polyalkylene glycol mono (meth) acrylate, Allyloxy polyalkylene glycol Mono (meth) acrylate, nonylphenoxypolyalkylene glycol mono (meth) acrylate, acryloylmorpholine, hydroxyethylacrylamide, N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, 1, 2-di (meth) acrylamide ethylene glycol, di (meth) acryloyloxymethyltricyclodecane, N- (meth) acryloyloxyethylmaleimide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meta ) Acryloxyethyl phthalimide, n-vinyl-2-pyrrolidone, styrene derivatives, α-methylstyrene derivatives, etc. can also be used.

Particularly preferred acrylic resins include polyethers, polyesters, polycarbonates, poly (meth) acrylates having a (meth) acrylic group, (meth) acrylates having a hydroxyl group, and hydroxyl groups having a molecular weight of 100 to 10,000. (Meth) acrylamide etc. are mentioned.

Here, the polyether skeleton is preferably one in which an organic group having 1 to 6 carbon atoms is repeated via an ether bond, and preferably does not contain an aromatic ring. A compound having a (meth) acrylic group in a polyether can be obtained by a reaction between a polyether polyol and (meth) acrylic acid or a derivative thereof.

As the polyester skeleton, those in which an organic group having 1 to 6 carbon atoms is repeated via an ester bond are preferable, and those having no aromatic ring are preferable. A compound having a (meth) acrylic group in polyester can be obtained by a reaction between a polyester polyol and (meth) acrylic acid or a derivative thereof.

The polycarbonate skeleton is preferably one in which an organic group having 1 to 6 carbon atoms is repeated via a carbonate bond, and preferably does not contain an aromatic ring. A compound having a (meth) acrylic group in polycarbonate can be obtained by a reaction between a polycarbonate polyol and (meth) acrylic acid or a derivative thereof.

As a poly (meth) acrylate skeleton, a copolymer of (meth) acrylic acid and (meth) acrylate, a (meth) acrylate having a hydroxyl group and a (meth) acrylate having no polar group such as a carboxyl group and a hydroxyl group; A copolymer of (meth) acrylate having a glycidyl group and a (meth) acrylate having no polar group is preferred.

Each of the above copolymers reacts with (meth) acrylate having a hydroxyl group having a hydroxyl group or (meth) acrylate having a glycidyl group, whereby (meth) acrylic acid having a hydroxyl group having no polar group and a derivative thereof By reacting, the glycidyl group can be obtained by reacting with (meth) acrylic acid having no polar group and its derivative.

And the compound which has a (meth) acryl group with poly (meth) acrylate can be obtained by reaction of poly (meth) acrylate polyol and (meth) acrylic acid or its derivative.

The (meth) acrylate or (meth) acrylamide having a hydroxyl group is a (meth) acrylate or (meth) acrylamide having one or more (meth) acryl groups in one molecule, and contains a hydroxyl group. To do.

The (meth) acrylate having a hydroxyl group can be obtained by a reaction between a polyol compound and a (meth) acrylic acid derivative. As this reaction, a known reaction can be used, and usually 0.5 to 5 moles of acrylic acid ester or acrylic acid is used with respect to the polyol compound.

(Meth) acrylamide having a hydroxyl group can be obtained by reaction of an amine compound having a hydroxyl group with (meth) acrylic acid and its derivatives. The method of producing (meth) acrylamides by reacting (meth) acrylic acid esters with amine compounds is based on the fact that the double bonds of (meth) acrylic acid esters are extremely reactive, so amines, cyclopentadiene, alcohols In general, the compound is previously added to the double bond as a protecting group, and after completion of the amidation, the product is heated to remove the protecting group to produce the target product.

Here, the hydroxyl group is an alcoholic group in which the hydrogen atom of the aliphatic hydrocarbon group is substituted, and the hydroxyl group content is preferably 1 to 50 in one molecule.

Examples of such an acrylic resin compound having a hydroxyl group include compounds represented by the following formulas (2) to (5).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent aliphatic hydrocarbon group having 1 to 100 carbon atoms or an aliphatic hydrocarbon group having a cyclic structure.)

(In the formula, R ¹ and R ² are the same as described above.)

(In the formula, R ¹ represents the same as above, and n represents an integer of 1 to 50.)

(Wherein R ¹ and n each represents the same as above)

The maleimide resin contains one or more maleimide groups in one molecule and is cured by forming a three-dimensional network structure by reacting the maleimide groups by heating. Examples of maleimide resins include N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2,2-bis [4- (4-maleimide). And bismaleimide resins such as phenoxy) phenyl] propane.

The maleimide resin is more preferably a compound obtained by the reaction of a dimer acid diamine and maleic anhydride, or a compound obtained by a reaction of a maleimidated amino acid such as maleimide acetic acid or maleimide caproic acid with a polyol.

As the maleimide resin, it is particularly preferable that the main chain connecting two maleimide groups has an aliphatic hydrocarbon group, and this main chain has a hydrocarbon group having 1 or more carbon atoms. Here, the hydrocarbon group may be any of linear, branched and cyclic forms, preferably having 6 or more carbon atoms, more preferably 12 or more carbon atoms, Is particularly preferably 24 or more. The hydrocarbon group is preferably directly bonded to the maleimide group.

As the maleimide resin, a compound represented by the following formula (6) is also preferably used.

(In the formula, Q represents a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 6 or more carbon atoms, P is a divalent atom or an organic group, and A group containing at least one divalent atom or organic group selected from CO, COO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , S, S ₂ , SO, and SO ₂ And m represents an integer of 1 to 10.)

Here, examples of the divalent atom represented by P include O and S, and examples of the divalent organic group include CO, COO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , S ₂ , SO, SO _{2 and the} like, and organic groups containing at least one or more of these atoms or organic groups can be mentioned. Examples of the organic group including an atom or an organic group described above include those having a hydrocarbon group having 1 to 3 carbon atoms, a benzene ring, a cyclo ring, a urethane bond, etc. as a structure other than the above. Examples include groups represented by the following chemical formula.

Use of a bismaleimide resin having an aliphatic hydrocarbon group in the main chain is preferable because it provides a thermosetting resin composition for semiconductor adhesion that is excellent in heat resistance and good in heat bond strength after moisture absorption at low stress. .

Specific examples of such maleimide resins include BMI-1500 (manufactured by Designer Molecules, trade name, molecular weight: 1500), BMI-1700 (manufactured by Diginer Molecules, trade name, molecular weight: 1700). , Etc.

Furthermore, the maleimide resin is particularly preferably used in combination with an allylated epoxy resin which is a polymer of allylated bisphenol and epichlorohydrin, or an acrylic resin containing a hydroxy group.

Here, an allylated epoxy resin which is a polymer of allylated bisphenol and epichlorohydrin can be obtained, for example, as follows. First, the polyhydric phenol compound is dissolved in a solvent such as alcohols such as methanol, isopropanol and n-propanol, and ketones such as acetone and methyl ethyl ketone. Thereafter, a base such as sodium hydroxide or potassium hydroxide is used to react with an allyl halide such as allyl chloride or allyl bromide to obtain an allyl ether of a polyhydric phenol compound. As a catalyst to a mixture of an allylated polyphenol compound and an epihalohydrin, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added all at once or gradually, at 0.5 to 20 ° C. at 20 to 120 ° C. Let react for 10 hours. Thereby, an allylated epoxy resin can be obtained.

As the allylated epoxy resin, a compound represented by the following formula (7) is preferably used.

Wherein R ³ to R ¹⁰ are each independently a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group and a substituted or unsubstituted allyl group, at least one of which is substituted or unsubstituted X is a divalent atom or organic group selected from SO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, CO, and COO; k is 0 or 1.)

When maleimide resin and allylated epoxy resin are used in combination, the blending ratio is preferably 50/50 to 95/5, more preferably 65/35 to 90/10.

When maleimide resin and acrylic resin are used in combination, the blending ratio is preferably 5/95 to 95/5.

The conductive resin composition may contain a resin other than the thermosetting resin for the purpose of improving stress relaxation and adhesion. Examples of such resins include acrylic resins, polyester resins, polybutadiene resins, phenol resins, polyimide resins, silicone resins, polyurethane resins, xylene resins, and the like. These resins may be used alone or in combination of two or more. The content of the resin other than the thermosetting resin is preferably 50 parts by mass or less with respect to 100 parts by mass of the thermosetting resin.

The curing agent for the component (C) is not particularly limited as long as it cures the thermosetting resin, and one kind may be used alone, or two or more kinds may be mixed and used. Examples of the epoxy resin curing agent include dicyandiamide, phenol resin, amine compound, latent amine compound, cationic compound, acid anhydride, and special epoxy curing agent. Among these, it is preferable to contain at least one selected from dicyandiamide and a phenol resin from the viewpoints of curability and adhesiveness.

The content of the curing agent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin. In addition, it is preferable to adjust content of a hardening | curing agent according to the kind of thermosetting resin and a hardening | curing agent. For example, when the thermosetting resin is an epoxy resin and the curing agent is a phenol resin, the content of the phenol resin is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin. Is more preferable. When the thermosetting resin is an epoxy resin and the curing agent is dicyandiamide, the content of dicyandiamide is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin.

The conductive resin composition may contain a curing accelerator. A known curing accelerator can be used as the curing accelerator. For example, when the thermosetting resin is an epoxy resin, as a curing accelerator, an imidazole curing accelerator, an amine curing accelerator, a triphenylphosphine curing accelerator, a diazabicyclo curing accelerator, a urea curing accelerator, Examples thereof include a borate salt curing accelerator and a polyamide curing accelerator. These may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among these, it is preferable to use at least 1 sort (s) chosen from an imidazole series hardening accelerator and an amine type hardening accelerator from a viewpoint of sclerosis | hardenability and adhesiveness, and it is preferable to use an imidazole type hardening accelerator.

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2-phenyl-4-methylimidazole (2P4MZ ), 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like.

Examples of the amine curing accelerator include aliphatic amines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, menthanediamine, isophoronediamine. Alicyclic and heterocyclic amines such as 1,8-diazabicyclo (4.5.0) undecene-7, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, m-xylenediamine , Aromatic amines such as pyridine and picoline, epoxy compound-added polyamines, Michael-added polyamines, Mannich-added polyamines, thiourea-added polyamines, modified polyamines such as ketone-capped polyamines, Dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amineimide, boron trifluoride - piperidine complex, boron trifluoride - monoethylamine complexes. From the viewpoint of curability, the imidazole curing accelerators 2-phenyl-4-methylimidazole (2P4MZ), 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ), 2-phenyl-4-methyl-5-hydroxy Methylimidazole (2P4MHZ) is more preferred.

When the thermosetting resin is a cyanate resin, as a curing accelerator, an organic metal complex such as zinc octylate, tin octylate, cobalt naphthenate, zinc naphthenate, and acetylacetone iron, metal such as aluminum chloride, tin chloride, and zinc chloride Salts, amines such as triethylamine and dimethylbenzylamine are used. One of these curing accelerators may be used alone, or two or more thereof may be mixed and used.

When the curing accelerator is contained, the content varies depending on the type of the thermosetting resin, but is preferably 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermosetting resin. 0.0 part by mass is more preferable.

The conductive resin composition may further contain an adhesion assistant. Examples of the adhesion assistant include silane coupling agents. As an adhesion assistant, it is preferable to contain a compound represented by the following formula (8). By containing the compound represented by Formula (8) as an adhesion assistant, the adhesiveness and reflow resistance at high temperatures of the conductive resin composition are particularly improved.

(In the formula (8), R and R ′ are each independently an alkyl group having 1 to 4 carbon atoms, and A ′ is a divalent hydrocarbon group having 3 to 12 carbon atoms which may have an oxygen atom interposed therebetween. And n is an integer of 1 to 3.)

Examples of R and R ′ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and these may be the same or different. R is preferably a methyl group or an ethyl group. R ′ is preferably a methyl group.

Examples of the divalent hydrocarbon group for A ′ include a hydrocarbon group or a group having an ether bond (—O—) in which oxygen is interposed in the hydrocarbon group. When the carbon number of the divalent hydrocarbon group of A ′ is 3 or more, the adhesiveness, particularly the adhesiveness at high temperature and the adhesiveness at high temperature after moisture absorption are improved. When carbon number is 12 or less, a viscosity will become low and a dispersibility will become favorable. The number of carbon atoms is more preferably 5 to 12, and further preferably 7 to 12. As the hydrocarbon group, an alkylene group is preferable. As the group having an ether bond, —C ₆ H ₁₂ —O—CH ₂ —, —C ₈ H ₁₆ —O—CH ₂ —, —C ₁₀ H ₂₀ —O—CH ₂ — and the like are preferable. In the divalent hydrocarbon group for A ′, one or more hydrogen atoms may be substituted with a halogen atom such as a fluorine atom or a chlorine atom. n is preferably 2 or 3, and more preferably 3.

The conductive resin composition can further contain, for example, a reactive diluent having reactivity with respect to ring-opening polymerization of an epoxy resin for the purpose of improving workability. Examples of the reactive diluent include n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, glycidyl methacrylate. T-butylphenyl glycidyl ether, diglycidyl ether, (poly) ethylene glycol glycidyl ether, butanediol glycidyl ether, trimethylolpropane triglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them. Of these, phenyl glycidyl ether and t-butylphenyl glycidyl ether are more preferred. The amount of the reactive diluent used is preferably in the range in which the viscosity of the conductive adhesive composition (measured with a 3 ° cone using an E-type viscometer) is in the range of 5 to 200 Pa · s.

The conductive resin composition may contain a diluent other than the above for the purpose of improving workability. As the diluent, solvents, (meth) acrylate compounds and the like can be used.

Examples of the solvent include diethylene glycol diethyl ether, n-butyl glycidyl ether, t-butylphenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, dioxane, hexane, methyl Cellosolve, cyclohexane, butyl cellosolve, butyl cellosolve acetate, butyl carbitol, butyl carbitol acetate, diethylene glycol dimethyl ether, diacetone alcohol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, and 1,3-dimethyl-2-imidazo Examples include lysinone.

These diluents may be used alone or in combination of two or more. These diluents are preferably added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the conductive resin composition.

The conductive resin composition can contain components other than the above components as long as not departing from the spirit of the present invention. Examples of such components include viscosity modifiers, antifoaming agents, colorants, flame retardants, and the like.

Examples of the viscosity modifier include cellosolve acetate, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, butyl carbitol acetate, propylene glycol phenyl ether, diethylene glycol dimethyl ether, diacetone alcohol and the like. One of these viscosity modifiers may be used alone, or two or more thereof may be mixed and used.

The conductive resin composition comprises, for example, high-speed mixing of (A) silver-coated silica particles, (B) a thermosetting resin, and (C) an essential component composed of a curing agent, and an optional component added as necessary. It can be manufactured by mixing uniformly using a machine, kneading using a disperse, kneader, three-roll, etc., and further defoaming.

The specific gravity of the conductive resin composition is preferably 1.0 to 3.0. When the specific gravity is 1.0 to 3.0, the conductivity and dispersibility of the conductive resin composition are improved. That is, when the specific gravity is 1.0 or more, the conductivity of the conductive resin composition is improved. When specific gravity becomes 3.0 or less, the dispersibility and workability | operativity of a conductive resin composition will become favorable, and the manufacturing cost of a conductive resin composition will also fall. The specific gravity of the conductive resin composition is more preferably 1.3 to 2.5.

The viscosity of the conductive resin composition is preferably 5 to 200 Pa · s. The viscosity is measured using an E-type viscometer (3 ° cone) at 25 ° C. and 0.5 rpm. When the viscosity is 5 to 200 Pa · s, the workability of the conductive resin composition is improved. That is, when the viscosity is 5 Pa · s or more, the occurrence of dripping or the like is suppressed. Moreover, when a viscosity is 200 Pa * s or less, dispensing becomes easy and workability | operativity becomes favorable. The viscosity of the conductive resin composition is more preferably 20 to 180 Pa · s.

The conductive resin composition of the embodiment is excellent in workability with little stringiness and dripping. In addition, the conductive resin composition of the embodiment is excellent in conductivity and adhesiveness in bonding the semiconductor element and the support member. Here, examples of the support member include a copper frame, a silver-plated copper frame, and a PPF frame. Furthermore, the conductive resin composition of the embodiment has a long pot life and suppresses the generation of voids.

The conductive resin composition of the embodiment has, for example, a viscosity of 5 to 200 Pa · s, a volume resistivity of the cured product of 1 × 10 ⁻¹ Ω · cm or less, an adhesive strength at 25 ° C. of 20 N or more, and 260 ° C. The adhesive strength is 6N or more. According to the conductive resin composition of the embodiment, the above characteristics can be obtained by containing (A) silver-coated silica particles, (B) a thermosetting resin, and (C) a curing agent as essential components. . In addition, the said characteristic is based on the test conditions in an Example.

Next, the semiconductor device of the present invention will be described.
FIG. 1 shows a semiconductor device according to an embodiment of the present invention.

The semiconductor device 1 has, for example, a semiconductor element 2, a conductive resin composition 3, a support member 4, a bonding wire 5, and a sealing resin composition 6. Here, the conductive resin composition 3 is composed of the conductive resin composition of the above-described embodiment. The support member 4 is composed of a lead frame. The semiconductor device 1 is excellent in reliability and productivity because the semiconductor element 2 and the support member 4 are bonded by the conductive resin composition 3 made of the conductive resin composition of the embodiment.

The semiconductor device 1 is manufactured as follows, for example. First, the semiconductor element 2 is laminated on the support member 4 with the conductive resin composition 3 interposed therebetween, and the conductive resin composition 3 is cured by heating so that the semiconductor element 2 and the support member 4 are connected to the conductive resin composition. 3. Adhere by 3. Further, the electrodes 2a of the semiconductor element 2 and the lead portions 4a of the support member 4 are wire-bonded by ultrasonic waves. Thereafter, these are sealed with a sealing resin composition 6.

Specific examples of the present invention will be described below.
The present invention is not limited to these examples.

<Production example of particle-1>
10 g of spherical silica particles having a D ₅₀ of 3.5 μm (trade name: US-5, manufactured by Tatsumori) are alkali degreased, acid neutralized and etched, washed with water, added to a palladium dichloride solution, stirred, palladium Adhering substrate particles were obtained.

The palladium-adhered substrate particles were stirred in 300 ml of deionized water for 3 minutes, and 1 g of metal nickel particle slurry (trade name: 2020SUS, manufactured by Mitsui Kinzoku Co., Ltd.) was added to obtain nickel particle-attached substrate particles.

The nickel particle-adhered substrate particles were diluted with 1000 ml of distilled water, added with 4 ml of a plating stabilizer, and stirred to obtain a substrate particle mixed solution. Thereafter, 150 ml of a mixed solution of 400 g / l of nickel sulfate, 100 g / l of sodium hypophosphite, 100 g / l of sodium citrate, and 6 ml of a plating stabilizer is gradually added to this base particle mixed solution while stirring. A nickel coating was formed on the material particles. The solution after plating was filtered, and the filtrate was washed with water and dried to obtain nickel-coated substrate particles.

Nickel-coated substrate particles in an electroless silver plating solution prepared by mixing and dissolving 30 g of succinimide and 4 g of citric acid in a mixed solution of 5 g of silver nitrate, 1200 ml of distilled water and 10 g of benzimidazole, and adding 10 g of glyoxylic acid Was introduced. The mixture was heated and stirred at 80 ° C. to perform electroless plating, then washed with water and dried with alcohol to obtain particles-1 which are spherical silver-coated silica particles.

Particle-1 has an aspect ratio of 1.01, a specific surface area of 1.5 m ² / g, D ₅₀ = 3.8 μm, a ratio D ₅₀ / D ₁₀ = 1.8, a maximum particle size of 19 μm, and a specific gravity of 2.8. The silver coating amount was 27.3 mass%.

<Production example of particle-2>
Using spherical silica particles having a D ₅₀ of 8.3 μm (trade name: US-10, manufactured by Tatsumori Co., Ltd.), electroless plating was performed in the same manner as for particles-1, and particles that were spherical silver-coated silica particles- 2 was obtained. Particle-2 has an aspect ratio of 1.04, a specific surface area of 0.5 m ² / g, D ₅₀ = 8.5 μm, a ratio D ₅₀ / D ₁₀ = 1.6, a maximum particle size of 32 μm, and a specific gravity of 3.1. The silver coating amount was 29.2% by mass.

<Production example of particle-3>
100 g of Particle-1 was blended in a mixed solution of 1.0% by mass of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403) and methanol, stirred, filtered, Drying was performed to obtain Particles-3, which are spherical silver-coated silica particles that have been treated with a silane coupling agent. Particle-3 has an aspect ratio of 1.01, a specific surface area of 1.5 m ² / g, D ₅₀ = 3.8 μm, a ratio D ₅₀ / D ₁₀ = 1.8, a maximum particle size of 24 μm, and a specific gravity of 2.8. The silver coating amount was 27.4% by mass.

<Production example of particle-4>
Put 100g of Particle-1 into a ball mill, add 2g of myristic acid and 200g of mineral spirit, add zirconia balls with a diameter of 2mm, and after 3 hours fatty acid coating treatment, filter and dry, and coat with fatty acid Particle-4, which was a spherical silver-coated silica particle, was obtained. Particle-4 has an aspect ratio of 1.01, a specific surface area of 1.5 m ² / g, D ₅₀ = 3.8 μm, a ratio D ₅₀ / D ₁₀ = 1.8, a maximum particle size of 23 μm, and a specific gravity of 2.8, The silver coating amount was 27.4% by mass.

<Production Example of Particle-5>
100 g of Particle-4 was blended in a solution in which 1.0% by mass of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403) and methanol were mixed, stirred, filtered, Drying was performed to obtain Particles-5, which are spherical silver-coated silica particles that have been treated with a silane coupling agent. Particle-5 has an aspect ratio of 1.01, a specific surface area of 1.5 m ² / g, D ₅₀ = 3.8 μm, a ratio D ₅₀ / D ₁₀ = 1.8, a maximum particle size of 22 μm, and a specific gravity of 2.8. The silver coating amount was 27.3 mass%.

<Production Example of Particle-6>
Electroless plating using spherical silica particles with a D ₅₀ of 1.0 μm (trade name: SO-E3, manufactured by Admatechs), followed by washing with water and substitution with alcohol in the same manner as for particles-1. Was dried to obtain particles-6 which are spherical silver-coated silica particles. Particle-6 has an aspect ratio of 1.03, a specific surface area of 6.0 m ² / g, D ₅₀ = 1.9 μm, a ratio D ₅₀ / D ₁₀ = 2.5, a maximum particle size of 18 μm, and a specific gravity of 2.6. The silver coating amount was 20.0% by mass.

<Production example of particle-7>
Particles that are spherical silver-coated silica particles are obtained by performing electroless plating using silica particles having a D ₅₀ of 8.0 μm in the same manner as the particles-1, washing with water, and drying the particles substituted with alcohol. 7 was obtained. Particle-7 has an aspect ratio of 1.29, a specific surface area of 2.2 m ² / g, D ₅₀ = 8.5 μm, a ratio D ₅₀ / D ₁₀ = 1.5, a maximum particle size of 72 μm, and a specific gravity of 4.9, The silver coating amount was 30.0% by mass.

<Production example of particle-8>
Using spherical silica particles having a D ₅₀ of 7.0 μm, electroless plating was performed in the same manner as for the particles-1 to obtain particles-8 which are silver-coated silica particles. Particle-8 has an aspect ratio of 1.01, a specific surface area of 1.1 m ² / g, D ₅₀ = 7.6 μm, a ratio D ₅₀ / D ₁₀ = 1.8, a maximum particle size of 46 μm, and a specific gravity of 2.8, The silver coating amount was 29.0% by mass.

<Production Example of Particle-9>
Using spherical silica particles having a D ₅₀ of 4.0 μm and a D ₁₀ of 0.68 μm, electroless plating was performed in the same manner as the particle-1 to obtain particles-9 which are spherical silver-coated silica particles. Particle-9 has an aspect ratio of 1.03, a specific surface area of 4.5 m ² / g, D ₅₀ = 4.3 μm, D ₁₀ = 0.71 μm, a ratio D ₅₀ / D ₁₀ = 6.1, a maximum particle size of 22 μm, The specific gravity was 3.0, and the silver coating amount was 30.5% by mass.

The aspect ratio was measured with a scanning electron microscope SSX-550 (manufactured by Shimadzu Corporation). The specific surface area was measured with a flow-type specific surface area measuring apparatus Flow Soap II 2300 (manufactured by Shimadzu Corporation). D ₅₀ , D ₁₀ and the maximum particle size were measured with a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.). The silver coating amount was calculated from the weight of the silver-coated silica particles and the weight of the silver-removed silica particles that were removed by dissolving silver with nitric acid. Table 1 summarizes the characteristics of particles-1 to 9.

<Examples 1 to 16, Comparative Examples 1 to 6>
Each component was sufficiently blended and mixed so as to have the compositions shown in Tables 2, 4, and 6, and then kneaded with three rolls to prepare a conductive resin composition. This conductive resin composition was defoamed with a self-revolving vacuum defoaming apparatus, and then various characteristics were evaluated. The results are shown in Tables 3, 5, and 7. In addition, the detail of each component used for preparation of a conductive resin composition is as follows.

Thermosetting resin: bisphenol A type epoxy resin (epoxy equivalent 185)
Thermosetting resin: flexible epoxy resin (Mitsubishi Chemical Co., Ltd., trade name: YL7175-500, epoxy equivalent: 487, formula (1))
・ Thermosetting resin: hydroxylethyl acrylamide (product name: HEAA)
-Thermosetting resin: Imide-expanded bismaleimide (manufactured by Designer Molecules, Inc., trade name: BMI-1500, number average molecular weight: 1500)
Thermosetting resin: Allylated bisphenol epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: RE-810NM, epoxy equivalent: 223, hydrolyzable chlorine: 150 ppm (1N KOH-ethanol, dioxane solvent, reflux 30 minutes))
・ Curing agent: Bisphenol F (Honshu Chemical Co., Ltd.)
Curing agent: Diciadiamide (DICY)
Polymerization initiator: Dicumyl peroxide (manufactured by NOF Corporation, trade name: Park Mill D, decomposition temperature in rapid heating test: 126 ° C.)
Curing accelerator: 2-phenyl-4-methyl-5-hydroxymethylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name: 2P4MHZ)
Adhesion aid: Glycidoxyoctyltrimethoxysilane (manufactured by Shin-Etsu Silicone, trade name: KBM-4803)
Diluent: t-butylphenyl glycidyl ether (Nippon Kayaku Co., Ltd., trade name: TGE-H)
・ Thixotropic agent: fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 200)
Filler (flaky silver-coated glass): flaky silver-coated glass (manufactured by Ecka, trade name: Ag / flaky glass 5/30, aspect ratio: 1.25, D ₅₀ : 6.0 μm, D ₅₀ / D ₁₀ (1.7, maximum particle size: 28 μm, specific gravity: 4.6, silver coating amount: 30% by mass)
Filler (flaky silver powder): flaky silver powder (made by Fukuda Metal Foil Industry Co., Ltd., trade name: AgC-221A, D ₅₀ : 6.6 μm, specific gravity: 10.5)
Filler (silica powder): fused silica (manufactured by Tatsumori Co., Ltd., trade name: US-5, D ₅₀ : 3.5 μm, specific gravity: 2.2)
Filler (nano silver particles): Plate type nano silver particles (manufactured by Toxen Industries, trade name: M13, D ₅₀ : 2 μm, thickness: 50 nm or less)
Filler (nano silver particles): spherical nano silver particles (manufactured by Mitsuboshi Belting, trade name: MDot, D ₅₀ : 50 nm)
Filler (resin particles): spherical resin particles (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KMP-600, D ₅₀ : 1 μm)

<Evaluation method>
(1) Viscosity Using an E-type viscometer (3 ° cone) manufactured by Toki Sangyo Co., Ltd., the viscosity was measured at 25 ° C. and 0.5 rpm.

(2) Thixotropic Using an E-type viscometer (3 ° cone) manufactured by Toki Sangyo Co., Ltd., measuring the viscosity under the conditions of 25 ° C. and 5.0 rpm, differing from the results of (1) The ratio of the viscosity measured by the number of revolutions was calculated as thixotropy (viscosity (0.5 rpm) / viscosity (5.0 rpm)).

(3) Precipitation The syringe was filled with 10 g of the conductive resin composition, and placed in a 25 ° C. incubator so that the syringe was vertical. After 24 hours, the conductive resin composition was taken out from the upper and lower portions of the syringe, and the ash content was measured. The sedimentation property was calculated from the following formula. If the sedimentation property is greater than 1.5%, it can be determined that the sedimentation is likely to occur.
Sedimentability [%] = (Syringe lower ash−Syringe upper ash) / Syringe upper ash × 100

(4) Adhesive strength The conductive resin composition was applied on a silver-plated copper frame to a thickness of 20 μm, and a 2 mm × 2 mm silicon chip was mounted thereon and cured at 175 ° C. for 1 hour. Thereafter, the die shear strength during heating at 25 ° C. and 260 ° C. was measured using a die shear strength measuring device.

(5) Volume resistivity The conductive resin composition was printed on a glass plate so that the thickness after curing was 40 μm and the width was 5 mm, cured at 150 ° C. for 1 hour, and then measured with a digital multimeter. .

(6) Workability A syringe is filled with 10 g of a conductive resin composition, and a shot master manufactured by Musashi Engineering Co., Ltd. is used. Temperature 25 ° C., humidity 35% RH, needle diameter φ = 0.3 mm, discharge pressure 7. A dispensing test was performed on a silicon wafer substrate under the conditions of 85 N (0.8 kgf) and a gap of 100 μm. In the dispense test, the number of shots was set to 100, and the number of shots (number of defects) in which corner collapse due to stringing, syringe clogging, and dripping occurred was measured. And workability | operativity was computed by the following formula. When workability is greater than 10%, it can be determined that workability is poor.
Workability [%] = number of defects / 100 × 100

(7) Reflow resistance A conductive resin composition is applied to a thickness of 20 μm on a silver-plated copper frame, and a 4 mm × 4 mm silicon chip is mounted thereon and cured at 150 ° C. for 1 hour. I let you. Thereafter, an epoxy sealing material (trade name: KE-G3000D) manufactured by Kyocera Chemical Co., Ltd. was used to form a package according to the following [molding conditions]. The package was subjected to a moisture absorption treatment at 85 ° C. and a relative humidity of 85% for 168 hours, and then an IR reflow treatment (260 ° C., 10 seconds). About the package after a process, the presence or absence of generation | occurrence | production of a crack, peeling, etc. was observed using the ultrasonic microscope. For 10 samples, the number of cracks, peeling, etc. (number of defective products) was measured, and the reflow resistance was calculated by the following formula. If the reflow resistance is greater than 30%, it can be determined that the reflow resistance is poor.
Reflow resistance [%] = number of defective products / total number of samples × 100

(8) Thermal shock resistance A conductive resin composition is applied to a thickness of 20 μm on a silver-plated copper frame, and a 4 mm × 4 mm silicon chip is mounted thereon and cured at 150 ° C. for 1 hour. I let you. Thereafter, a package was molded under the following [molding conditions] using an epoxy sealing material (trade name: KE-G3000D) manufactured by Kyocera Chemical Co., Ltd. This package was subjected to a cold cycle treatment (the operation of raising the temperature from −55 ° C. to 150 ° C. and cooling to −55 ° C. as one cycle, which was 1000 cycles). About the package after a process, the presence or absence of generation | occurrence | production of a crack, peeling, etc. was observed using the ultrasonic microscope. About 10 samples, the number (number of defective products) in which cracks, peeling, etc. occurred was measured, and the thermal shock resistance was calculated by the following formula. If the thermal shock resistance is greater than 30%, it can be determined that the thermal shock resistance is poor.
Thermal shock resistance [%] = number of defective products / total number of measurements × 100

[Molding condition]
Package: 80pQFP (14mm x 14mm x 1.6mm thickness)
Chip: Silicon chip Lead frame: Copper Molding of sealing material: 175 ° C., 3 minutes Post mold cure: 175 ° C., 8 hours

(9) Comprehensive evaluation Comprehensive evaluation was performed based on each evaluation. Judgment criteria are as follows.
“A”: satisfying all of the following conditions.
Viscosity 5 to 200 Pa · s
Thixotropic 2.0-7.0
Specific gravity 1.0-3.0
Sedimentation 1.5% or less Adhesive strength (25 ° C.) 20 N or more Adhesive strength (260 ° C.) 6 N or more Volume resistivity 1 × 10 ⁻¹ Ω · cm or less Workability 10% or less Reflow resistance 30% or less Thermal shock resistance 30 % Or less “AA”: satisfying all the conditions of “A” and further satisfying all of the following conditions.
Adhesive strength (25 ° C.) 120 N or higher Adhesive strength (260 ° C.) 22 N or higher “B”: A material that does not satisfy any of the conditions of “A”.

DESCRIPTION OF SYMBOLS 1 ... Semiconductor device, 2 ... Semiconductor element, 2a ... Electrode, 3 ... Conductive resin composition, 4 ... Support member 4a ... Lead part, 5 ... Bonding wire, 6 ... Resin composition for sealing.

Claims (12)

1. (A) A silver-coated silica particle, (B) a thermosetting resin, and (C) a conductive resin composition containing a curing agent as essential components, wherein (A) the silver-coated silica particles are the conductive resin The composition contains 35 to 90% by mass, has an aspect ratio of 1.0 to 1.2, a specific surface area by gas adsorption method of 0.3 to 5.0 m ² / g, and a laser diffraction scattering type particle size distribution measuring method. cumulative volume particle diameter _{D 50} according to the 1 ~ 10 [mu] m, the ratio _D 50 _{/ D 10} of 1.5 to 5.0 cumulative volume particle diameter _{D 10, D 50,} and the maximum particle size is less spherical particles 40μm A conductive resin composition characterized by the above.
2. The conductive resin composition according to claim 1, wherein the specific gravity of the (A) silver-coated silica particles is 2.4 to 3.6.
3. The conductive resin composition according to claim 1 or 2, wherein the surface of the (A) silver-coated silica particles is coated with a silane coupling agent.
4. The conductive resin composition according to claim 1 or 2, wherein the surface of the (A) silver-coated silica particles is coated with a fatty acid or a fatty acid salt.
5. 3. The conductive resin composition according to claim 1 or 2, wherein the surface of the (A) silver-coated silica particles is coated with myristic acid.
6. 6. The conductive resin composition according to claim 1, wherein the specific gravity is 1.0 to 3.0 and the viscosity at 25 ° C. is 5 to 200 Pa · s.
7. The conductive resin composition according to any one of claims 1 to 6, further comprising nano silver particles.
8. The conductive resin composition according to any one of claims 1 to 7, wherein the (B) thermosetting resin contains an epoxy resin.
9. The conductive resin composition according to any one of claims 1 to 8, wherein the (B) thermosetting resin contains a flexible epoxy resin represented by the following formula (1).
   

   

   (In the formula, A is a divalent aliphatic hydrocarbon group having 6 to 14 carbon atoms, B is —CH ₂ — or —C (CH ₃ ) ₂ —, and Ar is an aliphatic hydrocarbon substituted or non-substituted group. A substituted phenylene group, and n is an integer of 1 to 10.)
10. Furthermore, the compound represented by following formula (2) is contained as an adhesion assistant, The conductive resin composition of any one of Claim 1 thru | or 9 characterized by the above-mentioned.
    

    

    (Wherein R and R ′ are each independently a hydrocarbon group having 1 to 4 carbon atoms, A ′ is a divalent hydrocarbon group having 3 to 12 carbon atoms which may have an oxygen atom interposed therebetween, n is an integer of 1 to 3.)
11. The conductive resin composition according to any one of claims 1 to 10, further comprising resin particles.
12. A support member;
    A semiconductor element bonded to the support member with the conductive resin composition according to any one of claims 1 to 11,
    A semiconductor device comprising:

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