WO2013145961A1 - 硬化性放熱組成物 - Google Patents
硬化性放熱組成物 Download PDFInfo
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- WO2013145961A1 WO2013145961A1 PCT/JP2013/054334 JP2013054334W WO2013145961A1 WO 2013145961 A1 WO2013145961 A1 WO 2013145961A1 JP 2013054334 W JP2013054334 W JP 2013054334W WO 2013145961 A1 WO2013145961 A1 WO 2013145961A1
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- filler
- fracture strength
- compressive fracture
- resin
- heat
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- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L24/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/07802—Adhesive characteristics other than chemical not being an ohmic electrical conductor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12042—LASER
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
- H01L2924/191—Disposition
- H01L2924/19101—Disposition of discrete passive components
- H01L2924/19107—Disposition of discrete passive components off-chip wires
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
Definitions
- the present invention is a curable heat dissipation composition excellent in heat dissipation in the thickness direction used for heat transfer from a heat generating member such as an electronic or electrical component to a heat radiating member, an adhesive sheet using the composition, and
- the present invention relates to a heat-cured product obtained by curing the composition.
- an insulating adhesive or sheet that conducts heat from the heat generation target portion of the electronic component to the heat radiating member is used.
- a composition in which a thermosetting resin is filled with an inorganic high heat dissipation filler is used.
- the amount of heat generated from electronic devices and electronic components tends to increase, and further improvements in thermal conductivity are required for adhesives and sheets used in these devices. For that purpose, it is necessary to fill the resin with an inorganic high heat dissipation filler.
- Suitable fillers include spherical alumina (thermal conductivity 36 W / m ⁇ K), crystalline silica ( 12W / m ⁇ K).
- thermal conductivity of these fillers has a limit to high heat dissipation. Therefore, in recent years, agglomerated grains of hexagonal boron nitride (hereinafter sometimes abbreviated as hBN) have attracted attention as fillers that improve heat dissipation in the thickness direction.
- hBN hexagonal boron nitride
- the primary particle of hBN has a hexagonal network layer structure similar to graphite and a particle shape of scale, and the thermal conductivity in the plane direction is larger than the thermal conductivity in the thickness direction of the scale-like particle.
- the conductivity is about 20 times (60 to 80 W / m ⁇ K), and the thermal conductivity is anisotropic.
- the hBN agglomerated grains are those in which the primary particles are aggregated, and the thermal conductivity has an isotropic characteristic, and the heat dissipation in the thickness direction of the molded body containing the hBN can be greatly improved.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2003-60134
- Patent Document 2 Japanese Patent Application Laid-Open No. 2009-24126
- Patent Document 3 Japanese Patent Application Laid-Open No. 2011-6586
- Patent Document 1 uses a combination of hBN primary particles and hBN aggregated particles, but the thermal conductivity in the thickness direction is only obtained up to 3.8 W / m ⁇ K.
- Patent Document 2 proposes that the hBN aggregated grains having a hardness by a constant nanoindentation method of 500 MPa or more are used so that the hBN aggregated grains do not break at the time of molding. The thermal conductivity is only obtained up to 10 W / m ⁇ K.
- Patent Document 3 uses two types of hBN agglomerates with different agglomeration strengths, and the hBN agglomerates with a low agglomeration strength are deformed and collapsed during molding by pressing to achieve close packing, and the thickness direction thermal conductivity. Have suggestions to improve. However, in this proposal, it is necessary to perform press molding under conditions that do not break the hBN aggregates having high agglomeration strength, so pressure control is considered difficult.
- the present invention is excellent in heat dissipation in the thickness direction by having a high thermal conductivity and a low porosity, and has a large allowable width (margin) for pressure molding conditions, as well as an electronic component and an electrical component. It aims at providing the curable thermal radiation composition which can be used as an adhesive agent, and the adhesive sheet using the composition.
- the inventors of the present invention blend a filler (A) having a high compressive fracture strength and a filler (B) having a low compressive fracture strength into a thermosetting resin so as to have a constant compressive fracture strength ratio.
- a curable heat radiation composition having a high thermal conductivity in the thickness direction and a low porosity was obtained, and the present invention was completed.
- the filler (A) having a high compressive fracture strength is deformed or broken by the filler (A) having a high compressive fracture strength, and the filler (A) having a high compressive fracture strength.
- the present invention provides the following [1] to [11] curable heat radiation composition, [12] adhesive sheet, [13] to [14] adhesive sheet production method, and [15] to [16].
- a curable heat-dissipating composition having a strength ratio [compressive fracture strength of filler (A) having high compressive fracture strength / compressive fracture strength of filler (B) having low compressive fracture strength] of 5 to 1500.
- the filler (A) having a high compressive fracture strength and the filler (B) having a low compressive fracture strength have a total content of 50 to 95% by mass, or a filler (A) having a high compressive fracture strength and a compressive fracture strength.
- the total content of the filler (B) having a small size and the other inorganic filler is 50 to 95% by mass, and the mass ratio of the filler (A) having a high compressive fracture strength and the filler (B) having a low compressive fracture strength [( 7.
- thermosetting resin (C) has at least three reactive groups of at least one of an epoxy group and a (meth) acryloyl group in one molecule, and the molecular weight per reactive group is 200.
- the curable heat-dissipating composition according to item 8 above which comprises the first thermosetting resin (C-1) having a number average molecular weight of less than 1,000.
- the thermoplastic resin (D) contains at least one selected from a polyvinyl butyral resin and a polyester resin.
- the curable heat-dissipating resin composition according to any one of 1 to 11 above is applied to two support films, and a surface applied to the one support film and a surface applied to the other support film;
- a method for producing an adhesive sheet, comprising heating and pressurizing a laminate obtained by bonding together with a roll press.
- the void ratio is 5% or less obtained by heat-molding the curable heat-dissipating composition according to any one of 1 to 11 above in a temperature range of 70 to 200 ° C. and a pressure of 1 to 100 MPa, A heat radiation cured product having a thermal conductivity in the thickness direction of 10 W / m ⁇ K or more.
- a heat radiation cured product having a porosity of 5% or less and a thermal conductivity in the thickness direction of 10 W / m ⁇ K or more.
- the curable heat dissipation composition of the present invention has excellent heat dissipation in the thickness direction, a power semiconductor, a semiconductor element including an optical semiconductor, a semiconductor device, a circuit metal plate, a circuit comprising the metal plate, and a circuit board It can be used as an adhesive or sheet for fixing electrical components in the field of hybrid integrated circuits.
- the compressive fracture strength of the filler can be measured with a micro compression tester (eg, MCT-510) manufactured by Shimadzu Corporation. This tester measures the breaking strength by applying a test force to the filler particles fixed between the upper pressure terminal and the lower pressure plate at a constant rate of increase and measuring the amount of deformation of the filler at this time. can do.
- the compressive fracture strength can be calculated by the following equation (1) shown in JIS R 1639-5 (2007). In the formula, Cs represents strength (MPa), P represents test force (N), and d represents particle diameter (mm).
- the compression fracture strength ratio of the two types of fillers is preferably 5 to 1500, and more preferably 10 to 500.
- the filler having a small compressive fracture strength is destroyed too much to form an efficient heat transfer path route.
- the filler having a low compressive fracture strength cannot be deformed / destructed and the contact between the fillers becomes a point contact, making it difficult to form an efficient heat transfer path route.
- the preferred compressive fracture strength range of the filler (A) having a high compressive fracture strength is 100 to 1500 MPa, more preferably 150 to 800 MPa. If it exceeds 1500 MPa, there is a possibility of damaging a molding machine such as a press machine, and if it is less than 100 MPa, the filler having a low compressive fracture strength cannot be sufficiently deformed or broken, and sufficient heat dissipation can be obtained. Disappear.
- the preferred compressive fracture strength range of the filler (B) having a small compressive fracture strength is 1.0 to 20 MPa, more preferably 1.5 to 10 MPa.
- the filler (A) having a high compressive fracture strength does not cause sufficient deformation or fracture, and high heat dissipation due to the surface contact of the filler cannot be obtained.
- the pressure is less than 1.5 MPa, the filler (B) having a low compressive fracture strength is broken in the process of dispersing the filler in the resin, and all the fillers lie in the surface direction during pressing, and heat transfer in the target thickness direction is performed. Path route formation becomes difficult.
- the preferred average particle diameter range of the filler (A) having a high compressive fracture strength is 20 to 100 ⁇ m, preferably 40 to 80 ⁇ m. If the filler (B) is less than 20 ⁇ m and has a small compressive fracture strength, it cannot be efficiently deformed or broken. If it exceeds 100 ⁇ m, smoothness is lost when it is applied to a substrate.
- the preferred average particle diameter range of the filler (B) having a low compressive fracture strength is 10 to 120 ⁇ m, preferably 30 to 80 ⁇ m. If it is less than 10 ⁇ m, the filler (B) having a low compressive fracture strength cannot be efficiently deformed or broken. If it exceeds 120 ⁇ m, smoothness is lost when it is applied to a substrate.
- the ratio of the average particle diameter of the filler (A) having a high compressive fracture strength and the filler (B) having a low compressive fracture strength is preferably from 0.1 to 10, and more preferably from 0.5 to 2.7.
- the average particle diameter of the filler used in the present invention is a value obtained by measuring the particle size distribution by a laser diffraction / scattering method. Specifically, it can be measured by using a laser diffraction / scattering particle size distribution analyzer (LMS-2000e) manufactured by Seishin Corporation.
- LMS-2000e laser diffraction / scattering particle size distribution analyzer manufactured by Seishin Corporation.
- the average particle diameter indicates the diameter of a particle diameter having an integrated value of 50% with respect to a certain particle size distribution.
- the preferred total filler content in the curable heat-radiating composition excluding volatile components is 50 to 95% by mass, preferably 60 to 90% by mass. When it exceeds 95% by mass, the adhesiveness and strength are lowered. On the other hand, if it is less than 50% by mass, sufficient heat dissipation cannot be obtained.
- the preferable mass ratio [(A) / (B)] of the filler (A) having a large compressive fracture strength and the filler (B) having a small compressive fracture strength in the total amount of filler in the curable heat radiation composition of the present invention is 0.
- the range is from 1 to 10, preferably from 1 to 5. If it is less than 0.1, the deformation / breakage of the filler having a low compressive fracture strength does not occur sufficiently, and the heat dissipation is reduced. On the other hand, if it exceeds 10, the filler (B) having a small compressive fracture strength that should be filled with voids due to deformation / destruction is reduced, and the heat dissipation is reduced.
- examples of the filler (A) having a high compressive fracture strength include alumina, aluminum nitride, glass beads, fused silica, cubic boron nitride (cBN), etc., and particularly high thermal conductivity. (200 W / m ⁇ K) Aluminum nitride is preferred.
- the filler (A) having a high compressive fracture strength examples include aluminum nitride FAN-f50-J (average particle size 50 ⁇ m) and FAN-f30 (average particle size 30 ⁇ m) manufactured by Furukawa Denshi.
- FAN-f50-J average particle size 50 ⁇ m
- FAN-f30 average particle size 30 ⁇ m
- CB-A50S average particle size 50 ⁇ m
- CB-A30S average particle size 28 ⁇ m
- CB-A20S average particle size 21 ⁇ m
- AS-10 average particle size 39 ⁇ m
- AS-20 average particle size 22 ⁇ m
- AL-17-1 average particle size 60 ⁇ m
- AL-17-2 average particle size 60 ⁇ m
- AL-13-H average particle size 60 ⁇ m
- AL- 13-M average particle size 60 ⁇ m
- AL-13KT average particle size 97 ⁇ m
- J-320 As glass beads, J-320 (average particle size 50 ⁇ m) manufactured by Potters Ballotini Co., Ltd., GB301S ( Average particle size 50 ⁇ m), GB301SA-PN (average particle size 50 ⁇ m), GB301SB-PN (average particle size 50 ⁇ m), GB-301SC-PN (average particle size)
- fused silica examples include FB-20D (average particle size of 23 ⁇ m) and FB-950 (average particle size of 24 ⁇ m) manufactured by Denki Kagaku Kogyo Co., Ltd.
- fillers (B) having low compressive fracture strength include aggregated particles of metal oxides such as zinc oxide, iron oxide, titanium oxide, zirconium oxide, and silicon oxide, and metal hydroxides such as nickel hydroxide and yttrium hydroxide. Agglomerates of metals such as tantalum, aggregates of salts such as calcium carbonate and lithium manganate, and hexagonal boron nitride (hBN) agglomerates. Among these, hBN aggregates are preferable from the viewpoint that excellent heat dissipation can be obtained.
- thermosetting resin (C) used in the present invention is not particularly limited, and a known thermosetting resin can be used.
- thermosetting resins include epoxy resins, urethane resins, phenol resins, (meth) acryloyl group-containing resins, vinyl ester resins, silicone resins and the like.
- the thing containing an epoxy resin from an adhesive viewpoint with a base material is preferable.
- the notation of (meth) acryloyl means acryloyl, methacryloyl, or both.
- the notation of (meth) acryl also means acrylic, methacrylic, or both.
- the curable heat radiation composition of the present invention is used as a heat conductive resin sheet of a power semiconductor module as shown in FIGS. 1 to 5, not only the adhesion to a substrate but also heat resistance and voltage resistance. Therefore, it is necessary to select resin components that match those required characteristics.
- the first thermosetting resin (C-1) used as the thermosetting resin of the present invention has at least three reactive groups of epoxy group and (meth) acryloyl group in one molecule. And a resin having a molecular weight per reactive group of 80 or more and less than 200 and a number average molecular weight of 300 or more and less than 1000.
- the thermosetting resin (C-1) is blended for the purpose of increasing the crosslink density after curing of the curable heat radiation composition of the present invention and imparting heat resistance and voltage resistance to the cured product.
- the number of reactive groups in one molecule is less than 3, or the molecular weight per reactive group is 200 or more, the crosslinking density is lowered and the heat resistance is lowered.
- the number average molecular weight exceeds 1000, the fluidity of the resin composition decreases, and the withstand voltage decreases due to the occurrence of microcracks and the presence of voids due to the decrease in sheet moldability.
- the resin having an epoxy group of the thermosetting resin (C-1) examples include a glycidylamine type epoxy resin, a heterocyclic type epoxy resin, and a trifunctional or higher functional aromatic epoxy resin.
- Specific examples of the glycidylamine type epoxy resin include N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane (product name: Epototo YH-434L, Nippon Steel & Sumikin Chemical Co., Ltd.), N, N, N ′, N′-tetraglycidyl-1,3-benzenedi (methanamine) (product name: TETRAD-X, Mitsubishi Gas Chemical Co., Inc.), 4- (glycidyloxy) -N, N-diglycidylaniline, 3- (Glycidyloxy) -N, N-diglycidylaniline and the like, and specific examples of the heterocyclic epoxy resin include triglycidyl isocyanur
- an aromatic epoxy resin having a functionality or higher a tetrafunctional naphthalene type epoxy resin (product name: Epicron HP-4700) DIC Corporation), triphenylmethane type epoxy resin (product name: 1032H60, mention may be made of Mitsubishi Chemical Co., Ltd.) and the like.
- Examples of the resin having a (meth) acryloyl group include (meth) acrylic acid esters and heterocyclic (meth) acrylates of polyols having 3 or more hydroxyl groups per molecule.
- Specific examples of the (meth) acrylic acid ester of a polyol having 3 or more hydroxyl groups per molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Examples include pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
- heterocyclic (meth) acrylates include resins such as tris (2-acryloyloxyethyl) isosinurate and tris (2-methacryloyloxyethyl) isosinurate. Can be mentioned.
- the thermosetting resin (C-1) is contained in an amount of 25 to 60% by mass of the resin component, the desired performance can be exhibited. More preferably, it is 30 to 50% by mass. If it is less than 25% by mass, the heat resistance and withstand voltage characteristics deteriorate, and if it exceeds 60% by mass, the flexibility of the cured product decreases.
- thermosetting resin (C-2) The thermosetting resin (C-2) used in the present invention is blended for the purpose of controlling the fluidity of the curable heat radiation composition, the adhesiveness of the cured product, and the flexibility.
- a resin include epoxy resins other than the above (C-1) and resins having a (meth) acryloyl group. As described above, epoxy resins are particularly preferable from the viewpoint of adhesiveness.
- Epoxy resins corresponding to the thermosetting resin (C-2) include bifunctional glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, polyfunctional epoxy resins not included in the thermosetting resin (C-1), wires And aliphatic epoxy resins.
- Specific examples of the bifunctional glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenyl type epoxy resin, and glycidyl ester.
- Specific examples of the epoxy resin include hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester.
- polyfunctional epoxy resin not included in the thermosetting resin (C-1) include phenol novolac epoxy.
- glycidyl ether type epoxy resins such as resins, cresol novolac type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene aralkyl type epoxy resins, epoxidized polybutadiene, and linear aliphatic epoxy resins Linear aliphatic epoxy resins such as epoxidized soybean oil.
- the said epoxy resin can be used individually or in mixture of 2 or more types.
- examples of the resin having a (meth) acryloyl group include (meth) acrylic acid ester of a diol compound, (meth) acrylic acid ester of a caprolactone adduct of polyol, and the like.
- the (meth) acrylic acid ester of the diol compound examples include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc.
- (meth) acrylic of caprolactone adduct of polyol Specific examples of the acid ester include (meth) acrylic acid ester of pentaerythritol caprolactone, (meth) acrylic acid ester of dipentaerythritol caprolactone, and the like.
- thermosetting resins (C-1) and (C-2) when an epoxy resin is used for the thermosetting resins (C-1) and (C-2), a curing agent and a curing accelerator (curing catalyst) may be blended.
- the curing agent include alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and hymic anhydride; aliphatic acid anhydrides such as dodecenyl succinic anhydride; phthalic anhydride and trihydric anhydride.
- Aromatic acid anhydrides such as merit acid; 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2- (3-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, bis Bisphenols such as (4-hydroxyphenyl) methane (also known as bisphenol F) and bis (4-hydroxyphenyl) sulfone (also known as bisphenol S); phenol-formaldehyde resins, phenol-aralkyl resins, naphthol-aralkyl resins, phenol- Phenol such as dicyclopentadiene copolymer resin Resins; organic dihydrazides such as dicyandiamide and adipic acid dihydrazide, and examples of the curing catalyst include tris (dimethylaminomethyl) phenol; dimethylbenzylamine; 1,8-diazabicyclo (5,4,0) undecene and its Derivatives; imidazoles such as 2-methylimidazole, 2-ethyl
- an organic peroxide may be blended as a curing agent.
- organic peroxides include diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1,3 , 3-Tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, lauryl peroxide, 1,1-bis (t-butylperoxy) -3,3 Examples include 5-trimethylcyclohexanone, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butylcumyl peroxide, cumene hydroperoxide, and the like
- thermoplastic resin As the resin component used in the curable heat dissipation composition of the present invention, a thermoplastic resin (D) may be mentioned.
- the thermoplastic resin imparts appropriate flexibility to an uncured sheet or a cured sheet, and plays an important role as an improvement in workability during sheet handling and as a stress relaxation agent for a cured product.
- specific examples of such thermoplastic resins include polyvinyl butyral resins, polyester resins, phenoxy resins, and acrylic copolymers.
- polyvinyl butyral resins and polyester resins are preferred from the viewpoint of imparting flexibility. used.
- a preferable blending amount of these thermoplastic resins is 5 to 30% by mass, more preferably 10 to 25% by mass in the resin component. If it is less than 5% by mass, the flexibility is insufficient, and if it exceeds 30% by mass, the moldability is deteriorated.
- a coupling agent can be added to the curable heat dissipation composition of the present invention for the purpose of improving the dispersibility of the inorganic filler in the resin component and the adhesion to the substrate.
- Examples of coupling agents include silane, titanate, and aluminum.
- a silane coupling agent can be preferably used, and preferred specific examples thereof include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethyl.
- the curable heat-radiating composition of the embodiment of the present invention can contain a solvent from the viewpoint of adjusting the viscosity of the composition.
- the solvent is not particularly limited, and a known solvent may be appropriately selected according to the type of thermosetting resin or inorganic filler. Examples of such solvents include toluene, xylene, cyclohexane, isophorone, tetrahydrofuran, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol.
- Examples include toluene and methyl ethyl ketone such as monomethyl ether, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, etc. , These alone Others may be used in combination of two or more.
- the blending amount of the solvent in the curable heat-radiating composition of the present invention is not particularly limited as long as kneading is possible, and generally, the sum of the resin and the inorganic filler in the curable heat-radiating composition. 30 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass.
- inorganic fillers can be blended in an amount that does not impede heat dissipation for the purpose of controlling characteristics other than heat dissipation.
- examples of such inorganic fillers include aluminum hydroxide for the purpose of imparting flame retardancy, fumed silica for the purpose of controlling the fluidity of the composition, and inorganic pigments such as titanium oxide for the purpose of coloring. it can.
- the method for producing the curable heat dissipation composition of the present embodiment is not particularly limited and can be performed according to a known method.
- the curable heat dissipation composition of this Embodiment can be manufactured as follows.
- a predetermined amount of curable resin and an amount of a curing agent or curing accelerator necessary for curing the curable resin are mixed.
- an inorganic filler specifically, a filler (A) having a high breaking strength and a filler (B) having a low breaking strength are added and premixed.
- a curable heat-radiating composition can be obtained by kneading the preliminary mixture using a planetary mixer or the like.
- what is necessary is just to add a coupling agent before a kneading
- the said curable thermal radiation composition can be apply
- a cured product having excellent heat dissipation can be obtained by curing the curable heat-radiating composition thus obtained or a sheet on a base material while applying pressure with a predetermined press pressure.
- an inorganic filler is highly filled in order to improve heat dissipation, voids are generated in the cured product, so that it is necessary to increase the pressing pressure in the pressing step.
- the filler (B) having a small breaking strength that has been deformed and broken enters the voids, and no voids are generated.
- the heat-radiating curable composition of the present invention has high heat dissipation.
- a preferable pressure range is 1 to 100 MPa, more preferably 2 to 50 MPa. When the pressure exceeds 100 MPa, the filler (A) having a high breaking strength is also destroyed. When the pressure is less than 1 MPa, the filler (B) having a low breaking strength is not sufficiently deformed or broken.
- a preferred temperature range is 70 to 200 ° C, more preferably 90 to 180 ° C. If the temperature is higher than 200 ° C, the resin component may be decomposed due to oxidation or the like.
- the fluidity of the composition is insufficient. Absent.
- the curable heat-radiating composition of the present invention is cured under such conditions, a low value of 5% or less is obtained as the porosity of the obtained cured product.
- curable heat radiation composition liquid a curable heat radiation composition (curable heat radiation composition liquid) dispersed and / or dissolved in an organic solvent is used in consideration of coating properties.
- the curable heat-dissipating composition liquid is applied to the support film using a coating device such as an applicator or a knife coater, and then heated to dry the organic solvent.
- a preferable drying temperature is 40 to 150 ° C, more preferably 50 to 120 ° C. If it is less than 40 degreeC, an organic solvent will remain
- the preferable film thickness after drying the solvent is 30 to 500 ⁇ m, more preferably 50 to 300 ⁇ m. If it is less than 30 ⁇ m, the flatness of the coating film is lost due to the influence of the particle size of the filler used, and if it exceeds 500 ⁇ m, the organic solvent remains and adversely affects the thermal conductivity and physical properties of the cured product.
- the method for producing the adhesive sheet is not particularly limited, but a laminate obtained by covering a part of or the entire coated surface of a sheet formed by applying a curable heat-dissipating composition liquid on a support film. Can be made into an adhesive sheet by a method of heating and pressing under the above-mentioned conditions.
- the curable heat dissipation composition liquid is applied to two support films, and is applied to the surface applied to the one support film and the other support film.
- the method of heating and pressurizing the laminated body obtained by bonding together the obtained surface on the said conditions is mentioned.
- the filler (B) having a low breaking strength is deformed / destroyed in the heating / pressurizing step, and the broken filler (B) having a low breaking strength is filled in the gap to give a high thermal conductivity. It is preferable to do so, and as a result, the electronic component can be bonded at a low pressure when mounted.
- the heating condition for the adhesive sheet in which the filler (B) having a low breaking strength is broken or deformed is preferably above the softening point of the resin component used, specifically 50 to 150 ° C., more preferably 70 to 120 ° C. It is. If the temperature is lower than 50 ° C., the resin is not softened, so that the filler (B) having a low fracture strength remains in the shape as it is, so that the thermal conductivity is deteriorated. If the temperature exceeds 150 ° C., the reaction of the curable resin component proceeds so much that it does not adhere when the electronic component is mounted.
- a preferable pressure condition is 1 to 100 MPa, more preferably 2 to 50 MPa.
- the shape of the filler (B) having a low breaking strength remains as it is, and the thermal conductivity is deteriorated.
- the pressure exceeds 100 MPa, the filler (B) having a low fracture strength is almost destroyed, and, for example, when hexagonal boron nitride aggregation is used, the flat primary particles of hexagonal boron nitride are oriented in the in-plane direction and have a thickness. The thermal conductivity in the direction decreases.
- a batch type press As a means for heating and pressurizing at the time of producing an adhesive sheet, a batch type press can be used, but in consideration of productivity, a roll press capable of continuous heating and pressurization may be mentioned as a preferable device. it can.
- a preferable line speed when using a roll press is 0.1 to 5 m / min, and more preferably 0.3 to 3 m / min. If it is less than 0.1 m / min, the productivity is poor, and if it exceeds 5 m / min, the fracture of the filler (B) having a small fracture strength is insufficient and the thermal conductivity in the thickness direction is lowered.
- the support film used in the production of the adhesive sheet can be selected depending on the purpose of use of the adhesive sheet.
- metal foil such as copper and aluminum, polypropylene, polycarbonate, polyethylene naphthalate, polyethylene terephthalate, polytetra
- polymer films such as fluoroethylene, polyphenylene sulfide, polyvinylidene fluoride, and polyimide.
- a film subjected to a release treatment may be used.
- the coating film used at the time of producing the laminated sheet of the present invention can be selected from those mentioned as the support film described above.
- the preferred thickness of the support film and coating film is 10 to 200 ⁇ m.
- a cured product having excellent heat dissipation can be obtained by placing the adhesive sheet thus obtained on a substrate and curing it while applying pressure with a predetermined press. Moreover, when bonding electronic components, after peeling off at least one of the support films, the electronic components can be bonded to the curable heat-dissipating resin surface, and then heated and pressurized to be cured. In the case of bonding electronic parts, the electronic parts are damaged when the pressure is too high. Therefore, it is necessary to set the pressure range so that the electronic parts can be bonded without being damaged. When the adhesive sheet of the present invention is used for bonding electronic parts, it is pressurized and heated under conditions where only bonding occurs.
- a preferable pressure range is 0.1 to 10 MPa, more preferably 0.5 to 8 MPa. If it is less than 0.1 MPa, it does not adhere, and if it exceeds 10 MPa, the electronic component may be broken.
- the temperature range is preferably 70 to 200 ° C, more preferably 90 to 180 ° C. If it is higher than 200 ° C., the resin component may be decomposed due to oxidation or the like, and if it is lower than 70 ° C., the fluidity of the composition is insufficient, so that it does not adhere.
- the thermal conductivity in the thickness direction of the cured product is measured in accordance with a method defined in JIS R 1611 (2010), a thermal diffusivity, specific heat, and thermal conductivity test method of fine ceramics by a laser flash method.
- a test piece having a thickness of 200 to 500 ⁇ m obtained by curing the curable heat radiation composition of the present invention is cut out as a test piece of about 10 mm ⁇ 10 mm, and a thermal conductivity measuring device LFA447 NanoFlash (manufactured by NETZSCH) was used to measure the thermal diffusivity at 25 ° C.
- the thermal conductivity was calculated from the specific heat and density determined by the DSC method according to the following formula (2).
- the curable heat dissipation composition of the present invention is a power semiconductor, a semiconductor element including an optical semiconductor, a semiconductor device, a circuit metal plate, and the metal plate as an adhesive having high heat dissipation, adhesiveness after curing, and long-term reliability. It can be used for fixing electrical parts such as circuits, circuit boards, and hybrid integrated circuits.
- FIG. 2 and FIG. 3 are schematic cross-sectional views of power modules corresponding to FIG. 4, FIG. 5 and FIG.
- the power semiconductor element (2) is placed on one side of the lead frame (1a), and the heat is applied to the opposite side of the lead frame (1a) where the power semiconductor element (2) is placed.
- a heat sink member (4) is provided through a cured body (3) of a conductive resin sheet.
- the power semiconductor element (2) is connected to the control semiconductor element (5) mounted on the lead frame (1b) by a metal wire (6), and the heat conductive resin sheet (3), the lead frame (1a, 1b)
- Power module components such as heat sink member (4), power semiconductor element (2), control semiconductor element (5), metal wire (6) are sealed with mold resin (7).
- the part of the frame (1a, 1b) connected to the external circuit and the surface of the heat sink member (4) facing the adhesive surface of the heat conductive resin sheet (3) are not covered with the mold resin (7). .
- the power module (20) of FIG. 2 has a structure in which the heat sink member (4) in the power module of FIG. 1 is buried in a cured body (3) of a heat conductive resin sheet.
- FIG. 3 shows a casing type power module (30), a heat sink member (14) made of an inorganic insulating plate, a circuit board (12) formed on the surface of the heat sink member (14), and a circuit board (12).
- the curable heat radiation composition of the present invention When the curable heat radiation composition of the present invention is used for the heat conductive resin sheet of the power module shown in FIGS. 1 to 3, a heat sink (4 in FIGS. 1 and 2) or a heat spreader (17 in FIG. 3)
- the curable heat radiation composition of the present invention is applied to a metal plate to have a desired thickness, solvent-dried, and optionally B-staged, and further necessary members are formed on a layer formed of the curable heat radiation composition. Adhere.
- the necessary members may be bonded.
- the curable heat-radiating composition of the present invention can also be suitably used as a high thermal conductive insulating sheet of the power module (40) having the structure shown in FIG.
- the metal heat spreader (24) is fixed on the metal foil (22) by the heat conductive resin sheet (23) according to the present invention, and the power semiconductor element (on the heat spreader (24)).
- 25, 26) is soldered (27), and the power semiconductor element (25, 26) is connected to the lead frame (21a, 21b) via the metal wire (28), and the heat spreader (24), power semiconductor Connection portions of the elements (25, 26), the metal wires (28), and the lead frames (21a, 21b) to the metal wires (28) have a structure sealed with a mold resin (29).
- the curable heat-radiating composition of the present invention When the curable heat-radiating composition of the present invention is used as the high thermal conductive insulating sheet (23) of the power module of FIG. 4, the curable heat-radiating composition of the present invention has a desired thickness on the metal foil (22). Then, the solvent is dried and optionally B-staged, and necessary members such as a heat spreader (24) are adhered to the layer formed of the curable heat radiation composition. Moreover, after bonding the curable heat-radiating composition formed into a sheet in advance to the metal foil and bonding it, a necessary member such as a heat spreader may be bonded.
- the curable heat-radiating composition of the present invention is applied to both the metal foil and the metal heat spreader so as to have a desired thickness. Solvent drying, in some cases B-stage, the surfaces of the curable heat-radiating composition layer of the metal foil and metal heat spreader are bonded and bonded together by heating and pressurizing between the surfaces on which the curable heat-dissipating composition layer is formed I do. Furthermore, you may adhere
- a metal having excellent thermal conductivity such as copper and aluminum is preferably used.
- the curable heat-dissipating composition of the present invention can also be suitably used as a high thermal conductive insulating resin adhesive sheet (38) of a double-sided cooling type semiconductor device as shown in FIG.
- 30 is a power conductor element
- 31 is solder
- 32 is a metal thermal conductive spacer
- 33a is a metal heat transfer plate
- 33b is a protruding terminal portion
- 34 is a control electrode terminal portion
- 35 is a refrigerant tube
- 36 is A bonding wire 37 is a mold resin.
- the metal heat transfer plate (33a) and the refrigerant tube (35) are joined to each other through a high heat conductive insulating resin adhesive sheet (cured body) (38) using the curable heat radiation composition of the present invention.
- the heat of 30) is efficiently conducted from the heat transfer plate (33a) to the refrigerant tube.
- Filler and its compressive fracture strength [Filler (A)] The following filler was used as the filler (A) having a high compressive fracture strength.
- CB-A50S spherical alumina with an average particle size of 50 ⁇ m manufactured by Showa Denko KK
- FAN-f50-J Aluminum nitride having an average particle diameter of 50 ⁇ m manufactured by Furukawa Denshi Co., Ltd.
- GB301S Glass beads having an average particle diameter of 50 ⁇ m manufactured by Potters Ballotini Co., Ltd.
- Hygielite HT-32I Aluminum hydroxide having an average particle size of 8 ⁇ m manufactured by Showa Denko K.K.
- filler (B) The following filler was used as the filler (B) having a low compressive fracture strength.
- UHP-2 hBN agglomerated particle classification manufactured by Showa Denko KK
- PTX-60S hBN aggregates made by Momentive Performance Materials having an average particle size of 60 ⁇ m
- PT-405 hBN aggregates made by Momentive Performance Materials having an average particle size of 40 ⁇ m
- TECO-20014545-B hBN aggregates made by Momentive Performance Materials having an average particle size of 63 ⁇ m.
- the compressive fracture strength of the filler was measured by the above-described method using a micro compression tester MCT-510 manufactured by Shimadzu Corporation. The results are shown in Table 1.
- Resin component [Thermosetting resin (C-1)] (1) Epoxy resin 1: tetrafunctional epoxy resin, number average molecular weight 420, epoxy equivalent 118 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: Epototo YH-434L, (2) Epoxy resin 2: 4-functional naphthalene type epoxy resin, number average molecular weight 560, epoxy group equivalent 166 g / eq, manufactured by DIC Corporation, product name: Epicron HP-4700, (3) Acrylic resin 1: Trifunctional acrylic resin, number average molecular weight 423, functional group equivalent 141 g / eq, manufactured by Hitachi Chemical Co., Ltd., product name: FANCLIL FA-731A.
- Epoxy resin 3 bisphenol A type epoxy resin, epoxy equivalent 190 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: Epototo YD-128, (2)
- Epoxy resin 4 bisphenol F type epoxy resin, epoxy equivalent 160 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: Epototo YDF-870GS, (3)
- Epoxy resin 6 polyfunctional epoxy resin, number average molecular weight 400, epoxy equivalent 250 g / eq, manufactured by DIC Corporation, product name: Epicron HP-7200L, (5)
- Acrylic resin 2 6-functional acrylic resin, number average molecular weight 1260, functional group equivalent 141 g / eq, manufactured by Nippon
- Thermoplastic resin (D) (1) Polyvinyl butyral resin: number average molecular weight 53,000, manufactured by Sekisui Chemical Co., Ltd., product name: ESREC SV-02, (2) Polyester resin: number average molecular weight 22,000, manufactured by Nippon Synthetic Chemical Co., Ltd., product name: SP182.
- Phenol resin polyfunctional phenol resin, number average molecular weight 470, hydroxyl group equivalent 108 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: SN-395
- Phenol resin Phenol novolac resin, Showa Denko K.K., product name: Shonor BRN-5834Y.
- Molded product evaluation method [Density (specific gravity)] The specific gravity of the moldings measured in all Examples and Comparative Examples was measured using an electronic balance (CP224S) and a specific gravity / density measurement kit (YDK01 / YDK01-OD / YDK01LP) manufactured by Sartorius Mechatronics Japan Co., Ltd. The mass of the molded body in the mass and the mass of the molded body in the water were measured, and the specific gravity was calculated using the following formula (3). Where ⁇ is the specific gravity of the solid, ⁇ (fl) is the density of the liquid, W (a) is the mass of the solid in the air, and W (fl) is the mass of the solid in the liquid. All use water.
- thermo conductivity A molded product with a thickness of 200 to 500 ⁇ m produced using a curable heat radiation composition is cut into 10 mm ⁇ 10 mm, and the thermal diffusivity at 25 ° C. is measured by using a thermal conductivity measuring device LFA447 NanoFlash (manufactured by NETZSCH). did. Furthermore, thermal conductivity was calculated from the specific heat and specific gravity obtained separately by the following formula (2).
- Example 1 Bisphenol A type epoxy resin (Product name: Epototo YD-128, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 17.6 parts by mass, boron nitride agglomerated particles (UHP-2, Showa Denko Co., Ltd.) as filler having low compressive fracture strength ) And 65.9 parts by weight of aluminum nitride (FAN-f50-J, manufactured by Furukawa Electronics Co., Ltd.) as a filler having high compressive fracture strength, and then a rotating / revolving mixer (Sinky Corporation) Manufactured and manufactured by Fotaro Kentaro) to obtain the desired curable heat-dissipating resin composition.
- boronitride agglomerated particles UHP-2, Showa Denko Co., Ltd.
- FAN-f50-J aluminum nitride
- FAN-f50-J manufactured by Furukawa Electronics Co., Ltd.
- This curable heat-dissipating resin composition was heat-molded at 130 ° C. for 30 minutes at a predetermined pressure (10 MPa) using a hot press to prepare a molded and cured plate that was cured into a sheet, and the thermal conductivity was measured.
- the thermal conductivity in the thickness direction was as high as 16.4 W / m ⁇ K.
- the porosity of the molded body was calculated by the above method, it was 0.20%.
- Examples 2-12 With the composition shown in Table 2, a curable heat-radiating composition and a molded cured plate were prepared in the same manner as in Example 1, the thermal conductivity was measured, and the porosity was calculated. The results are shown in Table 2.
- Comparative Examples 1 to 5 With the composition shown in Table 3, a curable heat-radiating composition and a molded cured plate were prepared in the same manner as in Example 1, the thermal conductivity was measured, and the porosity was calculated. The results are shown in Table 3.
- Example 13 Production of sheet (1) As described in Table 4, component (C-1) N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane (product name: YH-434L, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 35 parts by mass, (C-2) component bisphenol A type epoxy resin (product name: Epototo YD-128, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 10 parts by mass, thermoplastic resin component (D) polyvinyl butyral resin (product name: ESREC SV-02 Sekisui Chemical Co., Ltd.) 25 parts by mass, phenol novolac resin (product name Shonor BRN-3824Y Showa Denko KK) 10 parts by mass, multifunctional phenol resin (product name: SN-395 Nippon Steel & Sumikin Chemical Co., Ltd.) 20 parts by mass of the company) and 150 parts by mass of propylene glycol mono
- the curable heat-radiating composition thus prepared was applied to a PET film having a thickness of 75 ⁇ m with an automatic bar coater (PI-1210 manufactured by Tester Sangyo Co., Ltd.) so that the coating film after solvent drying had a thickness of about 150 ⁇ m.
- an automatic bar coater PI-1210 manufactured by Tester Sangyo Co., Ltd.
- the surfaces on which the heat curable composition of the sheet was formed were bonded together, and a table-top small roll press (manufactured by Tester Sangyo) was used, under conditions of a temperature of 90 ° C., a pressure of 10 MPa, and a roll speed of 0.3 m / min.
- a table-top small roll press manufactured by Tester Sangyo
- Example 14 Preparation of sheet (2) Using the curable heat-radiating composition having the same composition as in Example 13, an adhesive sheet was prepared in the following manner.
- the curable heat-dissipating composition was applied to a PET film having a thickness of 75 ⁇ m with an automatic bar coater (PI-1210 manufactured by Tester Sangyo Co., Ltd.) so that the coating film after solvent drying was about 300 ⁇ m, and normal pressure was 70 ° C. ⁇ 20 minutes.
- seat with which the coating film of the heat-radiation-curable composition was formed in PET film was obtained by drying a solvent by 70 degreeC * 20 minute vacuum drying.
- This sheet is covered with a PET film and heated and pressed three times under the conditions of a temperature of 90 ° C., a pressure of 10 MPa, and a roll speed of 0.3 m / min using a desktop small roll press (manufactured by Tester Sangyo).
- An adhesive sheet of Example 14 having a thickness of about 200 ⁇ m was obtained.
- Examples 15-22, Comparative Examples 6-12 Adhesive sheets of Examples 15 to 22 and Comparative Examples 6 to 12 having a thickness of about 200 ⁇ m were prepared in the same manner as in Example 13 with the formulations shown in Tables 4 and 5.
- Adhesive sheet evaluation test About each adhesive sheet produced in Examples 13 to 22 and Comparative Examples 6 to 12, dielectric breakdown voltage, glass transition temperature, workability, formability, flexibility, adhesiveness, withstand voltage, thermal conductivity and The porosity was measured. The results are summarized in Tables 4 and 5.
- the adhesive sheet produced by a predetermined method was cut into 50 mm ⁇ 50 mm, and the support film was peeled off. It was press-cured at a temperature of 180 ° C. and a pressure of 3 MPa while being sandwiched between 70 mm ⁇ 70 mm ⁇ 35 ⁇ m and 40 mm ⁇ 40 mm ⁇ 35 ⁇ m electrolytic copper foil. About the obtained single-sided copper clad sheet, it confirmed that the copper foil was embedded in the sheet
- the adhesive sheet prepared by a predetermined method was cut into 50 mm ⁇ 50 mm, and the support film was peeled off. It was press-cured at a temperature of 180 ° C. and a pressure of 3 MPa while being sandwiched between 70 mm ⁇ 70 mm ⁇ 35 ⁇ m electrolytic copper foils. From the obtained double-sided copper-clad sheet, the copper foil was peeled off from only one side to create a single-sided copper-clad sheet. This single-sided copper-clad sheet was wound around a ⁇ 100 mm cylinder with the copper foil on the outside, and the flexibility was judged by the presence or absence of breakage of the sheet. The case where the sheet was not damaged was judged as ⁇ , and the case where it was damaged was judged as x.
- the adhesive sheet produced by a predetermined method was cut into 100 mm ⁇ 30 mm, and the support film was peeled off. It was press-cured at a temperature of 180 ° C. and a pressure of 3 MPa while being sandwiched between 150 mm ⁇ 30 mm ⁇ 1 mm aluminum plate and 150 mm ⁇ 30 mm ⁇ 35 ⁇ m electrolytic copper foil. About the obtained single-sided copper-clad aluminum sheet pasting sheet, copper foil other than width 10mm of a center part was removed, and the test piece for 90 degreeC peeling strength was created.
- test piece was measured according to JIS-C6481, and when the peel strength was 0.5 kN / m or more, the adhesion was good, and when the peel strength was less than 0.5 kN / m, the adhesion was poor. It was determined as x.
- the adhesive sheet produced by a predetermined method was cut into 50 mm ⁇ 50 mm, and the support film was peeled off. It was press-cured at a temperature of 180 ° C. and a pressure of 3 MPa while being sandwiched between 70 mm ⁇ 70 mm ⁇ 35 ⁇ m electrolytic copper foils. From the obtained double-sided copper-clad sheet, the copper foils on both sides were peeled off to obtain a cured sheet alone. A dielectric breakdown voltage test was performed under the following conditions using five cured sheets alone. The case where the dielectric breakdown voltage was 5 kV or higher was 80% or higher was evaluated as “good”, and the case where the acceptable rate was less than 80% was determined as “Poor withstand voltage”.
- the adhesive sheet produced by a predetermined method was cut into 50 mm ⁇ 50 mm, and the support film was peeled off. It was press-cured at a temperature of 180 ° C. and a pressure of 3 MPa while being sandwiched between 70 mm ⁇ 70 mm ⁇ 35 ⁇ m electrolytic copper foils. From the obtained double-sided copper-clad sheet, the copper foils on both sides were peeled off to obtain a cured sheet alone. The cured sheet alone was cut to 10 mm ⁇ 10 mm, and then the thermal diffusivity at 25 ° C. was measured by using a thermal conductivity measuring device LFA447 NanoFlash (manufactured by NETZSCH). The thermal conductivity was calculated by the same method as the thermal conductivity of the molded body described above. [Porosity] The porosity of the cured adhesive sheet was measured by the same method as the porosity of the molded body.
- thermosetting resin and filler (A) having a high compressive fracture strength, particularly aluminum nitride and filler (B) having a low compressive fracture strength, particularly hBN aggregated particles are used in the thickness direction.
- a cured product having a high thermal conductivity was obtained.
- a sheet manufacturing process is performed by combining a thermosetting resin, a filler (A) having a high compressive fracture strength and a filler (B) having a low compressive fracture strength, particularly hBN aggregated particles. Even after passing through, it was possible to obtain a cured product having a high thermal conductivity in the thickness direction and at the same time maintaining a low porosity in the molded body.
- Example 13 The adhesive sheets of Examples 13 to 22 showed no problem in practical physical properties and good thermal conductivity.
- the thermal conductivity of Example 14 which did not go through the process of bonding the heat-dissipating resin layers with the same composition was better than that of Example 13.
- Comparative Example 6 is a composition in which the thermosetting resin (C-1) is blended in an amount of less than 25% by mass with respect to all resin components, and the glass transition temperature of the sheet is low and the heat resistance is poor.
- Comparative Example 7 in which a polyfunctional epoxy resin having a number average molecular weight of 1000 or more is blended instead of the thermosetting resin component (C-1), the glass transition temperature is high because the polyfunctional epoxy resin is blended. Sheet handling properties, formability, and voltage resistance were poor.
- Comparative Example 8 in which an epoxy resin having a low functional group density was blended instead of the thermosetting resin (C-1), the glass transition temperature was low and the heat resistance was poor.
- Comparative Example 9 in which an acrylic resin having a low functional group density was blended instead of the thermosetting resin (C-1) had a low glass transition temperature and poor heat resistance.
- Comparative Example 10 in which the thermoplastic resin (D) was not blended, the sheet could not be stably formed.
- Comparative Example 11 with a small amount of the thermoplastic resin (D) was inferior in sheet flexibility, adhesiveness, and withstand voltage.
- the comparative example 12 with a large blending amount of the thermoplastic resin (D) was inferior in heat resistance, moldability, and withstand voltage of the sheet.
- a combination of a thermosetting resin and a filler (A) having a high compressive fracture strength, especially aluminum nitride and a filler (B) having a low compressive fracture strength, especially hBN aggregated particles, has a high thermal conductivity in the thickness direction of the cured product. It can be set as a curable thermal radiation composition.
- the curable heat-dissipating resin composition of the present invention exhibits a high thermal conductivity with a relatively small filler content and is excellent in adhesion to a substrate. Therefore, a power semiconductor, a semiconductor element including an optical semiconductor, a semiconductor device, and a circuit
- the present invention is extremely useful in the field of metal plates, circuits made of the metal plates, circuit boards, hybrid integrated circuits, and the like.
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Abstract
Description
また、特許文献2では一定のナノインデンテーション法による硬度が500MPa以上のhBN凝集粒を使用することで、成形時にhBN凝集粒が破壊しないことを主旨とした提案をしているが、厚み方向の熱伝導率は10W/m・Kまでしか得られていない。
また、特許文献3は、凝集強度が異なる2種類のhBN凝集粒を用い、プレスによる成形加工時に凝集強度が小さいhBN凝集粒が変形、崩壊することにより最密充填を図り、厚み方向熱伝導率を改善する提案をしている。しかし、本提案では凝集強度が大きいhBN凝集粒を破壊しない条件でプレス成形する必要があるので、圧力制御が難しいと考えられる。
本発明の熱硬化性放熱組成物は、加圧成形時に、圧縮破壊強度が大きいフィラー(A)により圧縮破壊強度が小さいフィラー(B)が変形もしくは破壊され、圧縮破壊強度が大きいフィラー(A)と破壊・変形した圧縮破壊強度が小さいフィラー(B)の接触面積が大きくなるために、有効な伝熱パスルートが形成されて、厚み方向へのとりわけ高い熱伝導率が得られると推測される。さらに、このような配合によって空隙率が小さくなるので、実質的な放熱性が格段に向上すると推測される。
[1]異なる圧縮破壊強度をもつ2種のフィラー(ただし、前記2種のフィラーは同一物質である場合は除く。)と熱硬化性樹脂(C)を含み、前記2種のフィラーの圧縮破壊強度比[圧縮破壊強度が大きいフィラー(A)の圧縮破壊強度/圧縮破壊強度が小さいフィラー(B)の圧縮破壊強度]が5~1500であることを特徴とする硬化性放熱組成物。
[2] 圧縮破壊強度が大きいフィラー(A)の圧縮破壊強度が100~1500MPaであり、圧縮破壊強度が小さいフィラー(B)の圧縮破壊強度が1.0~20MPaである前項1記載の硬化性放熱組成物。
[3] 前記フィラー(A)が窒化アルミニウムまたはアルミナである前項2記載の硬化性放熱組成物。
[4] 前記フィラー(B)が六方晶窒化ホウ素凝集粒である前項2記載の硬化性放熱組成物。
[5] 前記2種のフィラー以外に他の無機フィラーを含む前項1記載の硬化性放熱組成物。
[6] 前記他の無機フィラーが、水酸化アルミニウム、ヒュームドシリカ、及び酸化チタンから選ばれる前項5記載の硬化性放熱組成物。
[7] 圧縮破壊強度が大きいフィラー(A)及び圧縮破壊強度が小さいフィラー(B)の総含有量が50~95質量%であるか、または圧縮破壊強度が大きいフィラー(A)、圧縮破壊強度が小さいフィラー(B)及び前記他の無機フィラーの総含有量が50~95質量%であり、かつ圧縮破壊強度が大きいフィラー(A)と圧縮破壊強度が小さいフィラー(B)の質量比率[(A)/(B)]が0.1~10の範囲である前項1~6のいずれかに記載の硬化性放熱組成物。
[8] さらに熱可塑性樹脂(D)を含み、前記熱硬化性樹脂(C)と前記熱可塑性樹脂(D)との合計100質量部に対して、熱硬化性樹脂(C)70~95質量部を含有する前項1記載の硬化性放熱組成物。
[9] 熱硬化性樹脂(C)が、エポキシ基及び(メタ)アクリロイル基の少なくとも1種類の反応性基を1分子中に3個以上有し、前記反応性基1個あたりの分子量が200未満であり、かつ数平均分子量が1000未満である第1の熱硬化性樹脂(C-1)を含有する前項8記載の硬化性放熱組成物。
[10] 前記熱可塑性樹脂(D)が、ポリビニルブチラール樹脂及びポリエステル樹脂から選択される少なくとも1種類を含有する前項8記載の硬化性放熱組成物。
[11] さらに溶剤を含有する前項1~10のいずれかに記載の硬化性放熱組成物。
[12] 前項1~11のいずれかに記載の硬化性放熱樹脂組成物からなる膜を支持膜と被覆膜との間に形成させた接着シート。
[13] 前項1~11のいずれかに記載の硬化性放熱樹脂組成物を支持膜に塗布し、前記の塗布された面の一部または全面に被覆膜を被せて得られる積層体を、ロールプレスで加熱及び加圧することを特徴とする接着シートの製造方法。
[14] 前項1~11のいずれかに記載の硬化性放熱樹脂組成物を2つの支持膜に塗布し、前記の一方の支持膜に塗布された面と他方の支持膜に塗布された面とを貼り合わせて得られる積層体を、ロールプレスで加熱及び加圧することを特徴とする接着シートの製造方法。
[15] 前項1~11のいずれかに記載の硬化性放熱組成物を70~200℃の温度範囲、かつ1~100MPaの圧力で加熱成形して得られる、空隙率が5%以下であり、厚み方向の熱伝導率が10W/m・K以上であることを特徴とする放熱硬化物。
[16] 前項13または14に記載の製造方法で得た接着シートに基材を載せた積層体を70~200℃の温度範囲、かつ0.1~10MPaの圧力で加熱成形して得られる、空隙率が5%以下であり、厚み方向の熱伝導率が10W/m・K以上であることを特徴とする放熱硬化物。
本発明の硬化性放熱組成物においては、圧縮破壊強度が異なる2種のフィラーを使用する。本発明において、フィラーの圧縮破壊強度は、(株)島津製作所の微小圧縮試験機(例えば、MCT-510)にて測定することができる。本試験機は、上部加圧端子と下部加圧板の間に固定されたフィラーの粒子に、一定の増加割合で試験力を与え、このときのフィラーの変形量を測定することにより、破壊強度を測定することができる。圧縮破壊強度はJIS R 1639-5(2007)に示されている下記式(1)により計算できる。
圧縮破壊強度が大きいフィラー(A)と圧縮破壊強度が小さいフィラー(B)の平均粒子径の比率は0.1~10が好ましく、0.5~2.7がより好ましい。
本発明の熱硬化性樹脂として使用される第1の熱硬化性樹脂(C-1)は、エポキシ基、(メタ)アクリロイル基の少なくとも1種類の反応性基を1分子中に3個以上有し、反応性基1個あたりの分子量が80以上200未満であり、かつ数平均分子量が300以上1000未満の樹脂である。熱硬化性樹脂(C-1)は、本発明の硬化性放熱組成物の硬化後の架橋密度を上げ、硬化物に耐熱性、耐電圧を付与する目的で配合される。1分子中に有する反応性基が3個未満、もしくは反応性基1個あたりの分子量が200以上の場合では、架橋密度が低下して耐熱性が低下する。また、数平均分子量が1000を超えると樹脂組成物の流動性が低下し、シート成形性の低下により微小クラックの発生やボイドの存在により耐電圧が低下する。
熱硬化性樹脂(C-1)は、樹脂成分のうち25~60質量%含有することで、目的の性能を発現することができる。より好ましくは30~50質量%である。25質量%未満では耐熱性、耐電圧特性が低下し、60質量%を超えると硬化物の柔軟性が低下する。
本発明に使用される熱硬化性樹脂(C-2)は硬化性放熱組成物の流動性や硬化物の接着性、柔軟性を制御する目的で配合される。そのようなものとしては、前記(C-1)以外のエポキシ樹脂や、(メタ)アクリロイル基を有する樹脂を例示することができ、前述したように接着性の観点よりエポキシ樹脂が特に好ましい。
さらに必要に応じて上記硬化性放熱組成物を基材に塗布、必要に応じて溶剤を乾燥してシート状に加工することもできる。
接着シートとする場合は、塗工性を考慮して、有機溶剤に分散及び/または溶解した硬化性放熱組成物(硬化性放熱組成物液)を用いる。硬化性放熱組成物液は、アプリケーター、ナイフコーター等の塗工装置を用い支持膜に塗布後、加熱して有機溶剤を乾燥する。好ましい乾燥温度は40~150℃であり、より好ましくは50~120℃である。40℃未満では有機溶剤が残存し、150℃を超えると、硬化性樹脂成分の反応が進みすぎる。溶剤乾燥後の好ましい膜厚の範囲は30~500μm、より好ましくは50~300μmである。30μm未満では使用するフィラーの粒子径の影響を受けて塗膜の平坦性が失われ、500μmを超えると有機溶剤が残存し、熱伝導率、硬化物物性に悪影響を与える。
接着シートとする場合は、加熱・加圧工程で破壊強度が小さいフィラー(B)を変形・破壊し、破壊された破壊強度が小さいフィラー(B)が隙間に充填されて高い熱伝導率を出すようにすることが好ましく、その結果電子部品の実装時に低圧力で接着できる。
本発明の接着シートを電子部品の接着に使用する場合においては、接着のみが起こる条件にて加圧・加熱する。好ましい圧力の範囲としては0.1~10MPa、より好ましくは0.5~8MPaである。0.1MPa未満では接着せず、10MPaを超えると、電子部品が壊れる可能性がある。温度範囲としては70~200℃が好ましく、より好ましくは90~180℃である。200℃より高ければ、樹脂成分が酸化等により分解の可能性があり、70℃より低ければ組成物の流動性が不足するため接着しない。
本発明の硬化性放熱組成物は、高放熱性と硬化後の接着性、長期信頼性を有する接着剤として、パワー半導体、光半導体を含む半導体素子、半導体装置、回路用金属板、前記金属板からなる回路、回路基板、混成集積回路などの電気部品の固定に使用することができる。
本発明の硬化性放熱組成物は、例えば特開平2005-232313号公報に記載されているパワーモジュールの熱伝導性樹脂シートに好適に使用することができる。
図1、図2及び図3は上記公開公報の図4、図5及び図7に対応するパワーモジュールの模式断面図である。
図3はケーシングタイプのパワーモジュール(30)であり、無機の絶縁板からなるヒートシンク部材(14)と、ヒートシンク部材(14)の表面に形成された回路基板(12)と、回路基板(12)に載置されたパワー半導体(13)と、ヒートシンク部材(14)の周縁部に接着されたケーシング(15)と、ケース内の回路基板(12)及びパワー半導体(13)などを封止するモールド樹脂(16)と、ヒートシンク部材(14)の回路基板(12)が設けられた面に対向する反対面に積層された熱伝導性樹脂シートの硬化体(11)と、熱伝導性樹脂シートの硬化体(11)を介してヒートシンク部材(14)に接合されたヒートスプレッダー(17)とからなる。
図4のパワーモジュール(40)では、金属箔(22)上に本発明による熱伝導性樹脂シート(23)により金属ヒートスプレッダー(24)を固定し、ヒートスプレッダー(24)上にパワー半導体素子(25,26)をはんだ(27)付けし、パワー半導体素子(25,26)は金属線(28)を介してリードフレーム(21a,21b)に接続されてなり、ヒートスプレッダー(24)、パワー半導体素子(25,26)、金属線(28)及びリードフレーム(21a,21b)の金属線(28)との接続部はモールド樹脂(29)により封止された構造を有する。
図4のパワーモジュールに使用するヒートスプレッダー、ヒートシンク、金属箔の材質としては銅、アルミニウム等の熱伝導性に優れた金属が好適に使用される。
[フィラー(A)]
圧縮破壊強度が大きいフィラー(A)として、下記のフィラーを使用した。
(1)CB-A50S:昭和電工(株)製の平均粒子径50μmの球状アルミナ、
(2)FAN-f50-J:古河電子(株)製の平均粒子径50μmの窒化アルミニウム、
(3)GB301S:ポッターズ・バロティーニ(株)製の平均粒子径50μmのガラスビーズ、
(4)ハイジライト HT-32I:昭和電工(株)製の平均粒子径8μmの水酸化アルミニウム。
圧縮破壊強度が小さいフィラー(B)として、下記のフィラーを使用した。
(1)UHP-2:昭和電工(株)製hBN凝集粒分級品、
(2)PTX-60S:平均粒径60μmのモメンティブ・パフォーマンス・マテリアルズ製hBN凝集粒、
(3)PT-405:平均粒径40μmのモメンティブ・パフォーマンス・マテリアルズ製hBN凝集粒、
(4)TECO-20091045-B:平均粒径63μmのモメンティブ・パフォーマンス・マテリアルズ製hBN凝集粒。
[熱硬化性樹脂(C-1)]
(1)エポキシ樹脂1:4官能型エポキシ樹脂、数平均分子量420、エポキシ当量118g/eq、新日鉄住金化学株式会社製、製品名:エポトートYH-434L、
(2)エポキシ樹脂2:4官能ナフタレン型エポキシ樹脂、数平均分子量560、エポキシ基当量166g/eq、DIC株式会社製、製品名:エピクロンHP-4700、
(3)アクリル樹脂1:3官能型アクリル樹脂、数平均分子量423、官能基当量141g/eq、日立化成工業株式会社製、製品名:ファンクリルFA-731A。
(1)エポキシ樹脂3:ビスフェノールA型エポキシ樹脂、エポキシ当量190g/eq、新日鉄住金化学株式会社製、製品名:エポトートYD-128、
(2)エポキシ樹脂4:ビスフェノールF型エポキシ樹脂、エポキシ当量 160g/eq 新日鉄住金化学株式会社製、製品名:エポトートYDF-870GS、
(3)エポキシ樹脂5:多官能型エポキシ樹脂、数平均分子量1280、エポキシ当量218g/eq、DIC株式会社製、製品名:エピクロンN-680、
(4)エポキシ樹脂6:多官能型エポキシ樹脂、数平均分子量400、エポキシ当量250g/eq DIC株式会社製、製品名:エピクロンHP-7200L、
(5)アクリル樹脂2:6官能型アクリル樹脂、数平均分子量1260、官能基等量141g/eq、日本化薬株式会社製、製品名:カヤラッドDPCA-60。
(1)ポリビニルブチラール樹脂:数平均分子量53,000、積水化学株式会社製、製品名:エスレックSV-02、
(2)ポリエステル樹脂:数平均分子量22,000、日本合成化学株式会社製、製品名:SP182。
(1)フェノール樹脂:多官能型フェノール樹脂、数平均分子量470、水酸基当量108g/eq、新日鉄住金化学株式会社製、製品名:SN-395、
(2)フェノール樹脂:フェノールノボラック樹脂、昭和電工株式会社、製品名:ショウノールBRN-5834Y。
(1)イミダゾール化合物:1-(シアノエチル)-2-ウンデシルイミダゾール、四国化成株式会社製、製品名:キュアゾールC11Z-CN、
(2)有機過酸化物:クメンハイドロパーオキサイド、日本油脂株式会社製、製品名:パークミルH-80。
[数平均分子量]
ゲル浸透クロマトグラフィーを用いて測定を行った。なお、測定には昭和電工社製Shodex GPC System-21(カラム KF-802,KF-803、KF-805)を用い、測定条件はカラム温度40℃、溶出液テトラヒドロフラン、溶出速度1ml/分。標準ポリスチレン換算分子量(Mw)で表示した。
[密度(比重)]
全ての実施例、及び比較例において測定された成形物の比重はザルトリウス・メカトロニクス・ジャパン(株)の電子天秤(CP224S)と比重/密度測定キット(YDK01/YDK01-OD/YDK01LP)を用いて空気中での成形体の質量と水中での成形体の質量を測定し、下記の式(3)を用いて比重を算出した。
硬化性放熱組成物を用いて作製した厚み200~500μmの成形物を10mm×10mmに切断し、熱伝導率測定装置 LFA447 NanoFlash(NETZSCH社製)を使用することで25℃における熱拡散率を測定した。さらに別途求めた比熱及び比重から下記の式(2)により熱伝導率を算出した。
成形体の空隙率に関しては実施例あるいは比較例に示される樹脂、及び各フィラーの質量%から成形体の理論比重を計算する。また、実際に成形した成形体の比重を式(3)により算出する。これらの数値を下記の式(4)を用いて空隙率を算出した。
ビスフェノールA型エポキシ樹脂(製品名:エポトートYD-128、新日鉄住金化学(株)製)17.6質量部、圧縮破壊強度が低いフィラーとして窒化ホウ素凝集粒(UHP-2,昭和電工(株)製)を66.5質量部、圧縮破壊強度が高いフィラーとして窒化アルミニウム(FAN-f50-J,古河電子(株)製)15.9質量部を配合したのち、自転・公転ミキサー((株)シンキー製,泡取り練太郎)を用いて混練りし、目的の硬化性放熱樹脂組成物を得た。この硬化性放熱樹脂組成物を、熱プレスを用いて所定(10MPa)の圧力で130℃で30分加熱成形し、シート状にして硬化させた成形硬化板を作製し、熱伝導率を測定したところ厚み方向の熱伝導率は16.4W/m・Kと高い値を示した。また、上記の方法により成形体の空隙率を計算したところ0.20%であった。
表2に示す組成で、実施例1と同様の方法にて硬化性放熱組成物及び成形硬化板を作製し、熱伝導率を測定し、空隙率を計算した。結果を表2に示す。
表3に示す組成で、実施例1と同様の方法にて硬化性放熱組成物及び成形硬化板を作製し、熱伝導率を測定し、空隙率を計算した。結果を表3に示す。
表4に記載した通り、(C-1)成分のN,N,N’,N’-テトラグリシジル-4,4’-ジアミノジフェニルメタン(製品名:YH-434L、新日鉄住金化学(株)製)35質量部、(C-2)成分のビスフェノールA型エポキシ樹脂(製品名:エポトートYD-128 新日鉄住金化学株式会社製)10質量部、熱可塑性樹脂成分(D)のポリビニルブチラール樹脂(製品名 エスレック SV-02 積水化学工業株式会社)25質量部、フェノールノボラック樹脂(製品名 ショウノール BRN-3824Y 昭和電工株式会社製)10質量部、多官能型フェノール樹脂(製品名:SN-395 新日鉄住金化学株式会社製)20質量部に溶剤としてプロピレングリコールモノメチルエーテル(和光純薬株式会社製)150質量部を加えて樹脂成分を溶解した。さらに硬化触媒として、1-(シアノエチル)-2-ウンデシルイミダゾール(製品名 キュアゾール C11Z-CN 四国化成工業株式会社)0.3質量部を加えた。調製した樹脂溶液に圧縮破壊強度が高いフィラー(A)として窒化アルミニウム(製品名:FAN-f50-J、古河電子株式会社製)309質量部、圧縮破壊強度が小さいフィラーとして窒化ホウ素凝集粒(製品名:TECO20091045-B,モメンティブ・パフォーマンス・マテリアルズ合同会社製)71質量部、溶剤としてプロピレングリコールモノメチルエーテル650質量部を配合し、自転公転ミキサー((株)シンキー製,泡取り練太郎)を用いて混練りし、実施例13の硬化性放熱組成物を得た。
このように調製した硬化性放熱組成物を厚み75μmのPETフィルムに溶剤乾燥後の塗膜が約150μmとなるように自動バーコーター(テスター産業(株)製PI-1210)で塗装し、常圧70℃×20分さらに70℃×20分間真空乾燥により溶剤を乾燥することによりPETフィルムに放熱硬化性組成物の塗膜が形成されたシートを得た。該シートの放熱硬化性組成物が形成された面同士を貼り合わせ、卓上小型ロールプレス(テスター産業製)を用い、温度90℃、加圧圧力 10MPa、ロール速度0.3m/分の条件で3回加熱・加圧することにより、厚み約200μmの実施例13の接着シートを得た。
実施例13と同じ配合の硬化性放熱組成物を用い、以下の方法にして接着シートを作製した。
硬化性放熱組成物を厚み75μmのPETフィルムに溶剤乾燥後の塗膜が約300μmとなるように自動バーコーター(テスター産業(株)製PI-1210)で塗装し、常圧70℃×20分さらに70℃×20分間真空乾燥により溶剤を乾燥することによりPETフィルムに放熱硬化性組成物の塗膜が形成されたシートを得た。このシートにPETフィルムを被覆し、卓上小型ロールプレス(テスター産業製)を用い、温度90℃、加圧圧力 10MPa、ロール速度0.3m/分の条件で3回加熱・加圧することにより、厚み約200μmの実施例14の接着シートを得た。
表4及び表5に示した配合で、実施例13と同様の方法にて厚さ約200μmの実施例15~22及び比較例6~12の接着シートを作製した。
実施例13~22及び比較例6~12で作製した各接着シートについて、下記の方法で絶縁破壊電圧、ガラス転移温度、作業性、成形性、柔軟性、接着性、耐電圧、熱伝導率及び空隙率を測定した。結果をまとめて表4及び5に示す。
周波数50Hzの交流電源を、毎分5kVの速度で5kVまで昇圧後、1分間保持、毎分5kVの速度で0kVまで降圧するサイクルを行う。サイクル中に1mA以上の通電が確認された時点で、絶縁破壊したと判断した。なお、試験には菊水電工業株式会社製 耐電圧/絶縁抵抗測定装置 TOS9201を用い、電極にはΦ25mm円柱/Φ75mm円柱形状の物を用いた。
所定の方法で作製した接着シートを20mm四方の型枠に25枚重ねた状態で20mm四方の型枠に入れ、温度180℃、圧力3MPaでプレス硬化した。得られた成形物はシートの面方向を試験片の高さになるように切削加工し高さ10mm、幅5mm四方の試験片を得た。この試験片についてTMA法でガラス転移温度を測定した。測定条件は、昇温速度毎分10K、荷重5gの条件である。測定装置としてエスアイアイ・ナノテクノロジー株式社製 EXSTAR TMA/SS7000を用いた。
所定の方法で作製した接着シートについて23℃に保管した後に、支持フィルムからの離形性、及び、硬化前シートの柔軟性について確認を行った。離形性は支持フィルムを剥がしたときにシートに破損の有無で判断した。柔軟性については、硬化前シートを支持フィルムがついた状態でΦ50mmの円柱に巻き付けてシートの破損の有無で判断した。破損しなかった場合を○、破損した場合を×と判定した。
所定の方法で作製した接着シートを50mm×50mmに切断し、支持フィルムを剥がした。70mm×70mm×35μmと40mm×40mm×35μmの電解銅箔に挟んだ状態で、温度180℃、圧力3MPaでプレス硬化した。得られた片面銅張シートについて、銅箔がシートに埋め込まれている事、埋め込まれた銅箔の周囲にクラックが発生していないことを確認した。クラックの有無は、絶縁破壊電圧試験を行い、1.0kV未満で通電が確認した物をクラックが発生していると判断した。クラックが発生しなかった場合を○、クラックが発生した場合を×と判定した。
所定の方法で作成した接着シートについて50mm×50mmに切断し、支持フィルムを剥がした。70mm×70mm×35μmの電解銅箔で挟んだ状態で、温度180℃、圧力3MPaでプレス硬化した。得られた両面銅張シートから、片方のみ銅箔を剥がし、片面銅張シートを作成した。この片面銅張シートについて銅箔を外側にした状態で、Φ100mmの円柱に巻き付けてシートの破損の有無で柔軟性を判断した。シートが破損しなかった場合を○、破損した場合を×と判定した。
所定の方法で作製した接着シートを100mm×30mmに切断し、支持フィルムを剥がした。150mm×30mm×1mmのアルミ板と150mm×30mm×35μmの電解銅箔に挟んだ状態で、温度180℃、圧力3MPaでプレス硬化した。得られた片面銅張アルミ板貼り付けシートについて、中心部分の幅10mm以外の銅箔を除去し、90℃剥離強度用試験片を作成した。この試験片についてJIS-C6481に準拠して測定し、0.5kN/m以上の剥離強度を有している場合を接着性良好で○とし、0.5kN/m未満の剥離強度では接着性不良で×と判定した。
所定の方法で作製した接着シートを50mm×50mmに切断し、支持フィルムを剥がした。70mm×70mm×35μmの電解銅箔で挟んだ状態で、温度180℃、圧力3MPaでプレス硬化した。得られた両面銅張シートから、両面の銅箔を剥がし、硬化シート単体を得た。この硬化シート単体5枚を用いて下記の条件で絶縁破壊電圧試験を行った。絶縁破壊電圧5kV以上の合格率が80%以上の場合を耐電圧良好として○、合格率80%未満の場合は耐電圧不良として×と判定した。
所定の方法で作製した接着シートについて50mm×50mmに切断し、支持フィルムを剥がした。70mm×70mm×35μmの電解銅箔で挟んだ状態で、温度180℃、圧力3MPaでプレス硬化した。得られた両面銅張シートから、両面の銅箔を剥がし、硬化シート単体を得た。この硬化シート単体について、10mm×10mmに切断した後に熱伝導率測定装置 LFA447 NanoFlash(NETZSCH社製)を使用することで25℃における熱拡散率を測定した。熱伝導率は前述した成型体の熱伝導率と同様の方法で算出した。
[空隙率]
成型体の空隙率と同じ方法にて、硬化した接着シートの空隙率を測定した。
さらに、表4及び表5の結果の通り、熱硬化性樹脂と圧縮破壊強度が大きいフィラー(A)と圧縮破壊強度が小さいフィラー(B)、とりわけhBN凝集粒を組み合わせることにより、シートの製造工程を経た後でも、厚み方向への熱伝導率が高く、同時に成形体内の空隙率が低い状態を維持した硬化物が得ることができた。また、実用物性も良好であった。
実施例13~22の接着シートは実用物性に問題は見られず、熱伝導率も良好であった。同じ組成で放熱樹脂層同士を貼り合わせ工程を経なかった実施例14は実施例13に比べて熱伝導率は良くなった。
1a,1b リードフレーム
2 パワー半導体
3 熱伝導性樹脂シート(硬化体)
4 ヒートシンク部材
5 制御用半導体素子
6 金属線
7 モールド樹脂
11 熱伝導性樹脂シートの硬化体
12 回路基板
13 パワー半導体
14 ヒートシンク部材
15 ケーシング
16 モールド樹脂
17 ヒートスプレッダー
21a,21b リードフレーム
22 金属箔
23 熱伝導性樹脂シート(高熱伝導絶縁シート)
24 金属ヒートスプレッダー
25,26 パワー半導体素子
27 はんだ
28 金属線
29 モールド樹脂
30 パワー半導体素子
31 はんだ
32 金属製熱伝導性スペーサー
33a 金属伝熱板
33b 突出端子部
34 制御電極端子部
35 冷媒チューブ
36 ボンディングワイヤ
37 モールド樹脂
38 高熱伝導性樹脂接着シート(硬化体)
Claims (16)
- 異なる圧縮破壊強度をもつ2種のフィラー(ただし、前記2種のフィラーは同一物質である場合は除く。)と熱硬化性樹脂(C)を含み、前記2種のフィラーの圧縮破壊強度比[圧縮破壊強度が大きいフィラー(A)の圧縮破壊強度/圧縮破壊強度が小さいフィラー(B)の圧縮破壊強度]が5~1500であることを特徴とする硬化性放熱組成物。
- 圧縮破壊強度が大きいフィラー(A)の圧縮破壊強度が100~1500MPaであり、圧縮破壊強度が小さいフィラー(B)の圧縮破壊強度が1.0~20MPaである請求項1記載の硬化性放熱組成物。
- 前記フィラー(A)が窒化アルミニウムまたはアルミナである請求項2記載の硬化性放熱組成物。
- 前記フィラー(B)が六方晶窒化ホウ素凝集粒である請求項2記載の硬化性放熱組成物。
- 前記2種のフィラー以外に他の無機フィラーを含む請求項1記載の硬化性放熱組成物。
- 前記他の無機フィラーが、水酸化アルミニウム、ヒュームドシリカ、及び酸化チタンから選ばれる請求項5記載の硬化性放熱組成物。
- 圧縮破壊強度が大きいフィラー(A)及び圧縮破壊強度が小さいフィラー(B)の総含有量が50~95質量%であるか、または圧縮破壊強度が大きいフィラー(A)、圧縮破壊強度が小さいフィラー(B)及び前記他の無機フィラーの総含有量が50~95質量%であり、かつ圧縮破壊強度が大きいフィラー(A)と圧縮破壊強度が小さいフィラー(B)の質量比率[(A)/(B)]が0.1~10の範囲である請求項1~6のいずれかに記載の硬化性放熱組成物。
- さらに熱可塑性樹脂(D)を含み、前記熱硬化性樹脂(C)と前記熱可塑性樹脂(D)との合計100質量部に対して、熱硬化性樹脂(C)70~95質量部を含有する請求項1記載の硬化性放熱組成物。
- 熱硬化性樹脂(C)が、エポキシ基及び(メタ)アクリロイル基の少なくとも1種類の反応性基を1分子中に3個以上有し、前記反応性基1個あたりの分子量が200未満であり、かつ数平均分子量が1000未満である第1の熱硬化性樹脂(C-1)を含有する請求項8記載の硬化性放熱組成物。
- 前記熱可塑性樹脂(D)が、ポリビニルブチラール樹脂及びポリエステル樹脂から選択される少なくとも1種類を含有する請求項8記載の硬化性放熱組成物。
- さらに溶剤を含有する請求項1~10のいずれかに記載の硬化性放熱組成物。
- 請求項1~11のいずれかに記載の硬化性放熱樹脂組成物からなる膜を支持膜と被覆膜との間に形成させた接着シート。
- 請求項1~11のいずれかに記載の硬化性放熱樹脂組成物を支持膜に塗布し、前記の塗布された面の一部または全面に被覆膜を被せて得られる積層体を、ロールプレスで加熱及び加圧することを特徴とする接着シートの製造方法。
- 請求項1~11のいずれかに記載の硬化性放熱樹脂組成物を2つの支持膜に塗布し、前記の一方の支持膜に塗布された面と他方の支持膜に塗布された面とを貼り合わせて得られる積層体を、ロールプレスで加熱及び加圧することを特徴とする接着シートの製造方法。
- 請求項1~11のいずれかに記載の硬化性放熱組成物を70~200℃の温度範囲、かつ1~100MPaの圧力で加熱成形して得られる、空隙率が5%以下であり、厚み方向の熱伝導率が10W/m・K以上であることを特徴とする放熱硬化物。
- 請求項13または14に記載の製造方法で得た接着シートに基材を載せた積層体を70~200℃の温度範囲、かつ0.1~10MPaの圧力で加熱成形して得られる、空隙率が5%以下であり、厚み方向の熱伝導率が10W/m・K以上であることを特徴とする放熱硬化物。
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CN104220533A (zh) | 2014-12-17 |
KR20140111302A (ko) | 2014-09-18 |
TWI577790B (zh) | 2017-04-11 |
JPWO2013145961A1 (ja) | 2015-12-10 |
US20170283645A1 (en) | 2017-10-05 |
TW201348424A (zh) | 2013-12-01 |
US10717896B2 (en) | 2020-07-21 |
JP6022546B2 (ja) | 2016-11-09 |
KR101625422B1 (ko) | 2016-05-30 |
CN104220533B (zh) | 2016-09-21 |
US20150037575A1 (en) | 2015-02-05 |
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