CN102190900A - Thermal conductive sheet - Google Patents

Thermal conductive sheet Download PDF

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Publication number
CN102190900A
CN102190900A CN2011100345588A CN201110034558A CN102190900A CN 102190900 A CN102190900 A CN 102190900A CN 2011100345588 A CN2011100345588 A CN 2011100345588A CN 201110034558 A CN201110034558 A CN 201110034558A CN 102190900 A CN102190900 A CN 102190900A
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conductive sheet
heat conductive
epoxy
resins
boron nitride
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泉谷诚治
内山寿惠
福冈孝博
原和孝
平野仁嗣
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

A thermal conductive sheet contains a plate-like boron nitride particle, wherein the thermal conductivity in a direction perpendicular to the thickness direction of the thermal conductive sheet is 4 W/mK or more. The breakdown voltage of the thermal conductive sheet as measured in conformity with JIS C 2110 (2010) is 10 kV/mm or more.

Description

Heat conductive sheet
Technical field
The present invention relates to heat conductive sheet, specifically, relate to the heat conductive sheet that in power electronics (Power Electronics) technology, uses.
Background technology
In recent years, in hybrid device, high-brightness LED device, electromagnetic induction heater spare etc., adopt the Power Electronic Technique of electric power being changed, being controlled by semiconductor element.In Power Electronic Technique, big current conversion is become heat etc., thereby be disposed near the high thermal diffusivity (high thermal conductivity) of material require the semiconductor element.
The thermally-conductive sheet that has for example proposed to contain flaky boron nitride powder and acrylic copolymer resin is (for example with reference to TOHKEMY 2008-280496 communique.)。
In the thermally-conductive sheet of TOHKEMY 2008-280496 communique, the long axis direction of boron nitride powder (with the thick orthogonal direction of sheet of boron nitride powder) is orientated in the mode along the thickness direction of sheet material, has improved the thermal conductivity of the thickness direction of heat conductive sheet thus.
Summary of the invention
Yet,, need heat conductive sheet to have high thermal conductivity with the orthogonal orthogonal directions of thickness direction (face direction) sometimes according to purposes and purpose.Therefore at this moment, the long axis direction of the boron nitride powder of the thermally-conductive sheet of TOHKEMY 2008-280496 communique and face direction quadrature (intersection) have the inadequate shortcoming of thermal conductivity of described direction.
In addition, adopt, so heat conductive sheet also needs to have excellent anti-puncture of insulation (tracking index) owing to be used the Power Electronic Technique of high electric power.
The object of the present invention is to provide the excellent thermal conductivity of face direction, the heat conductive sheet that anti-puncture of insulation of while is also excellent.
Heat conductive sheet of the present invention, it is characterized in that, it contains flaky boron nitride particle, aforementioned heat conductive sheet and the thermal conductivity orthogonal direction of thickness direction are more than the 4W/mK, and breakdown voltage (dielectric breakdown voltage) aforementioned heat conductive sheet, that measure according to JIS C 2110 (version in 2010) is more than the 10kV/mm.
Heat conductive sheet of the present invention and excellent thermal conductivity orthogonal direction of thickness direction, anti-puncture of insulation is also excellent simultaneously.
Therefore, by the be covered electronic unit that uses in the Power Electronic Technique and/or when being used to their installation base plate is installed of heat conductive sheet of the present invention, can prevent the puncture of insulation of heat conductive sheet, can make the heat of electronic unit and/or installation base plate along the face directional divergence by described heat conductive sheet simultaneously.
Description of drawings
Fig. 1 is the stereographic map of an embodiment of heat conductive sheet of the present invention.
Fig. 2 is the process picture sheet that is used to illustrate the manufacture method of heat conductive sheet shown in Figure 1,
(a) illustrate mixture or laminated sheet carried out hot pressed operation,
(b) illustrate with the compacting sheet material (press sheet) be divided into a plurality of operations,
(c) illustrate and to cut apart the stacked operation of sheet material.
Fig. 3 is the stereographic map of the testing apparatus (before the resistance to bend(ing) test) of the type i of resistance to bend(ing) test.
Fig. 4 is the stereographic map of the testing apparatus (in the resistance to bend(ing) test) of the type i of resistance to bend(ing) test.
Embodiment
Heat conductive sheet of the present invention contains boron nitride particle.
Particularly, heat conductive sheet contains boron nitride (BN) particle as neccessary composition, and then, for example contain resinous principle.
Boron nitride particle forms sheet (or flakey), is disperseed with the form that is orientated along prescribed direction (aftermentioned) in heat conductive sheet.
The mean value of the longitudinal direction length of boron nitride particle (sheet with the maximum length orthogonal direction of thickness direction) for example is 1～100 μ m, is preferably 3～90 μ m.In addition, the mean value of the longitudinal direction length of boron nitride particle is more than the 5 μ m, is preferably more than the 10 μ m, more preferably more than the 20 μ m, especially be preferably more than the 30 μ m, most preferably be more than the 40 μ m, usually, for example be below the 100 μ m, be preferably below the 90 μ m.
In addition, the mean value of the thickness of boron nitride particle (the thickness direction length of sheet, be particulate horizontal direction length) for example is 0.01～20 μ m, is preferably 0.1～15 μ m.
In addition, the aspect ratio of boron nitride particle (longitudinal direction length/thickness) is 2～10000 for example, is preferably 10～5000.
And the median size of passing through light scattering determining of boron nitride particle for example is more than the 5 μ m, is preferably more than the 10 μ m, more preferably more than the 20 μ m, especially is preferably more than the 30 μ m, most preferably is more than the 40 μ m, is generally below the 100 μ m.
In addition, the median size by light scattering determining is the volume average particle size with dynamic light scattering formula particle size distribution device mensuration.
When the median size of passing through light scattering determining of boron nitride particle did not satisfy above-mentioned scope, heat conductive sheet can become fragile sometimes, and the property handled can reduce.
In addition, the volume density of boron nitride particle (JIS K 5101, apparent density) for example is 0.3～1.5g/cm 3, be preferably 0.5～1.0g/cm 3
In addition, the boron nitride particle processed goods that can use the commercially available prod or its processing is obtained.Commercially available prod as boron nitride particle, for example can list " PT " series that MomentivePerformance Materials Japan LLC makes (for example " PT-110 " etc.), clear and " SHOBN UHP " series that electrician company makes (for example " SHOBN UHP-1 " etc.) etc.
Resinous principle promptly, is used to disperse the dispersion medium (matrix) of boron nitride particle for disperseing the material of boron nitride particle, for example can list thermosetting resin composition, the thermoplastic resin resinous principle that becomes to grade.
As the thermosetting resin composition, for example can list Resins, epoxy, Thermocurable polyimide, resol, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, thermosetting polyurethane resin etc.
As the thermoplastic resin composition, for example can list polyolefine (polyethylene for example, polypropylene, ethylene-propylene copolymer etc.), acrylic resin (for example polymethylmethacrylate etc.), polyvinyl acetate (PVA), ethylene-vinyl acetate copolymer, polyvinyl chloride, polystyrene, polyacrylonitrile, polymeric amide, polycarbonate, polyacetal, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polysulfones, polyethersulfone, polyether-ether-ketone, polyene propyl group sulfone (polyallyl sulfone), thermoplastic polyimide, TPU(Thermoplastic polyurethanes), PABM, polyamidoimide, polyetherimide, bismaleimide-triazine resin, polymethylpentene, fluoride resin, liquid crystalline polymers, alkene-vinyl alcohol copolymer, ionomer, polyarylester, acrylonitrile ethylene styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitritrile-styrene resin etc.
These resinous principles may be used singly or in combin two or more.
In the thermosetting resin composition, preferably enumerate Resins, epoxy.
Resins, epoxy be at normal temperatures liquid, semi-solid state and solid-state in arbitrary form.
Particularly, as Resins, epoxy, for example can list bisphenol-type epoxy resin (bisphenol A type epoxy resin for example, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin, dimer acid modified bisphenol-type epoxy resin etc.), phenolic varnish (novolac) type Resins, epoxy (phenol novolak type epoxy resin for example, the cresols phenolic resin varnish type epoxy resin, biphenyl type epoxy resin etc.), naphthalene type Resins, epoxy, fluorenes type Resins, epoxy (for example two aryl fluorenes type Resins, epoxy etc.), fragrant family Resins, epoxy such as triphenyl methane type Resins, epoxy (for example trihydroxybenzene methylmethane type Resins, epoxy etc.), tri epoxy propyl isocyanurate (triglycidyl group isocyanuric acid ester) for example, glycolylurea Resins, epoxy etc. contains azo-cycle Resins, epoxy, aliphatics type Resins, epoxy for example, for example alicyclic type Resins, epoxy (for example dicyclo type Resins, epoxy etc.), for example Racemic glycidol ether type epoxy, for example glycidyl amine type epoxy resin etc.
These Resins, epoxy may be used singly or in combin two or more.
Preferably enumerate the combination of liquid Resins, epoxy and solid-state Resins, epoxy, further preferably enumerate the combination of the fragrant family Resins, epoxy and the solid-state fragrant family Resins, epoxy of liquid state.As such combination, particularly, can list the bisphenol-type epoxy resin of combination, liquid state of liquid bisphenol-type epoxy resin and solid-state triphenyl methane type Resins, epoxy and the combination of solid-state bisphenol-type epoxy resin.
In addition,, preferably enumerate the semi-solid Resins, epoxy of independent use, further preferably enumerate the semi-solid fragrant family Resins, epoxy of independent use as Resins, epoxy.As such Resins, epoxy, more specifically, can enumerate semi-solid fluorenes type Resins, epoxy.
If be combination, the semi-solid Resins, epoxy of liquid Resins, epoxy and solid-state Resins, epoxy, then can improve the difference of altitude tracing ability (aftermentioned) of heat conductive sheet.
In addition, the epoxy equivalent (weight) of Resins, epoxy is 100～1000g/eqiv. for example, is preferably 160～700g/eqiv., and softening temperature (ring and ball method) for example is (to be specially 20～80 ℃) below 80 ℃, is preferably below 70 ℃ and (is specially 25～70 ℃).
In addition, the melt viscosity of Resins, epoxy under 80 ℃ is 10～20000mPas for example, is preferably 50～15000mPas.When the Resins, epoxy that is used in combination more than 2 kinds, will be set in the above-mentioned scope as their melt viscosity of mixture.
In addition, under being used in combination normal temperature under solid-state Resins, epoxy and the normal temperature during for liquid Resins, epoxy, be used in combination softening temperature for example for less than 45 ℃, be preferably the 1st Resins, epoxy below 35 ℃ and softening temperature and for example be more than 45 ℃, be preferably the 2nd Resins, epoxy more than 55 ℃.Thus, the kinematic viscosity (according to JIS K 7233, aftermentioned) of resinous principle (mixture) can be set in the scope of expectation, in addition, can improve the difference of altitude tracing ability of heat conductive sheet.
In addition, for example can make and contain solidifying agent in the Resins, epoxy and curing catalyst is prepared into composition epoxy resin.
Solidifying agent for example can list imidazolium compounds, amine compound, anhydride compound, amide compound, hydrazide compound, imidazolinium compounds etc. for making the potentiality solidifying agent (epoxy curing agent) of epoxy resin cure by heating.In addition, except above-mentioned, also can list phenolic compound, urea compounds, polythioether compound etc.
As imidazolium compounds, for example can list 2-phenylimidazole, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole etc.
As amine compound, can list for example aliphatic polyamines such as quadrol, propylene diamine, diethylenetriamine, Triethylenetetramine (TETA), for example aromatic polyamines such as mphenylenediamine, diaminodiphenyl-methane, diaminodiphenylsulfone(DDS) etc.
As anhydride compound, for example can list Tetra hydro Phthalic anhydride (phthalicanhydride), maleic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, methyl carbic anhydride (methyl nadicanhydride), pyromellitic acid acid anhydride, dodecenylsuccinic anhydride, dichlorosuccinic acid acid anhydride, benzophenone tetracarboxylic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride (chlorendic anhydride) etc.
As amide compound, for example can list Dyhard RU 100, polymeric amide etc.
As hydrazide compound, for example can list adipic dihydrazide etc.
As imidazolinium compounds, for example can list Methylimidazole quinoline, 2-ethyl-4-methylimidazole quinoline, ethyl imidazol(e) quinoline, isopropylimdazole quinoline, 2,4-methylimidazole quinoline, benzylimidazoline, undecyl imidazole quinoline, heptadecyl tetrahydroglyoxaline, 2-phenyl-4-methylimidazole quinoline etc.
These solidifying agent may be used singly or in combin two or more.
As solidifying agent, preferably enumerate imidazolium compounds.
As curing catalyst, can list for example triethylenediamine, three-2,4, tertiary amine compounds such as 6-dimethylaminomethyl phenol, for example triphenylphosphine, tetraphenyl boric acid tetraphenylphosphoniphenolate, O, phosphorus compounds such as O-diethyldithiophosphoric acid four-Zheng Ding Ji Phosphonium, for example quarternary ammonium salt compound, for example organometalate compound, for example their derivative etc.These curing catalysts may be used singly or in combin two or more.
With respect to 100 mass parts Resins, epoxy, the cooperation ratio of the solidifying agent in the composition epoxy resin is 0.5～50 mass parts for example, is preferably 1～10 mass parts, and the cooperation ratio of curing catalyst is 0.1～10 mass parts for example, is preferably 0.2～5 mass parts.
Above-mentioned solidifying agent and/or curing catalyst can be prepared into the solvent solution and/or the solvent dispersions that form with dissolution with solvents and/or dispersion and use as required.
As solvent, can list for example ketone such as acetone, methylethylketone, ester class such as vinyl acetic monomer for example, N for example, organic solvents such as amidess such as dinethylformamide etc.In addition, as solvent, also can list for example water, for example water solvents such as alcohols such as methyl alcohol, ethanol, propyl alcohol, Virahol.As solvent, be preferably organic solvent, further preferably enumerate ketone, amides.
In the thermoplastic resin composition, preferably enumerate polyolefine.
As polyolefine, preferably list polyethylene, ethylene-propylene copolymer.
As polyethylene, for example can list new LDPE (film grade), high density polyethylene(HDPE) etc.
As ethylene-propylene copolymer, for example can enumerate random copolymers, segmented copolymer or the graft copolymer etc. of ethene and propylene.
These polyolefine may be used singly or in combin two or more.
In addition, polyolefinic weight-average molecular weight and/or number-average molecular weight for example are 1000～10000.
In addition, polyolefine may be used singly or in combin multiple.
In addition, passing through of resinous principle according to the kinematic viscosity of JIS K 7233 (air bubble viscosimeter method) test (temperature: 25 ℃ ± 0.5 ℃, solvent: diethylene glycol monobutyl ether, resinous principle (solids component) concentration: 40 quality %) kinematic viscosity of measuring for example is 0.22 * 10 -4～2.00 * 10 -4m 2/ s is preferably 0.3 * 10 -4～1.9 * 10 -4m 2/ s, more preferably 0.4 * 10 -4～1.8 * 10 -4m 2/ s.In addition, above-mentioned kinematic viscosity for example can be set at 0.22 * 10 -4～1.00 * 10 -4m 2/ s is preferably 0.3 * 10 -4～0.9 * 10 -4m 2/ s, more preferably 0.4 * 10 -4～0.8 * 10 -4m 2/ s.
When the kinematic viscosity of resinous principle exceeds above-mentioned scope, can't give flexibility and the difference of altitude tracing ability (aftermentioned) of heat conductive sheet sometimes with excellence.On the other hand, when the kinematic viscosity of resinous principle does not satisfy above-mentioned scope, boron nitride particle is orientated along prescribed direction.
In addition, in the kinematic viscosity test of foundation JIS K 7233 (air bubble viscosimeter method), the lift velocity of the bubble of resinous principle sample is compared with the lift velocity of the bubble of standard model (kinematic viscosity is known), the kinematic viscosity of standard model that will be consistent with its lift velocity is judged to be the kinematic viscosity of resinous principle, measures the kinematic viscosity of resinous principle thus.
And, in heat conductive sheet, boron nitride particle based on containing of volume reference proportional (solids component, be the percentage by volume of boron nitride particle) with respect to the cumulative volume of resinous principle and boron nitride particle for example be more than the 35 volume %, be preferably more than the 60 volume %, be preferably more than the 65 volume %, usually, for example be below the 95 volume %, be preferably below the 90 volume %.
Boron nitride particle based on the above-mentioned scope of containing of volume reference of proportional discontented foot the time, boron nitride particle is orientated along prescribed direction in heat conductive sheet.On the other hand, proportional when exceeding above-mentioned scope at boron nitride particle based on containing of volume reference, heat conductive sheet can become fragile sometimes, the property handled and difference of altitude tracing ability can reduce.
In addition, total amount (solids component total amount) 100 mass parts with respect to each composition (boron nitride particle and resinous principle) that forms heat conductive sheet, the cooperation ratio based on quality criteria of boron nitride particle for example is 40～95 mass parts, be preferably 65～90 mass parts, total amount 100 mass parts with respect to each composition that forms heat conductive sheet, the cooperation ratio based on quality criteria of resinous principle is 5～60 mass parts for example, is preferably 10～35 mass parts.In addition, with respect to 100 mass parts resinous principles, the cooperation ratio based on quality criteria of boron nitride particle is 60～1900 mass parts for example, is preferably 185～900 mass parts.
In addition, when being used in combination 2 kinds of Resins, epoxy (the 1st Resins, epoxy and the 2nd Resins, epoxy), the mass ratio of the 1st Resins, epoxy and the 2nd Resins, epoxy (quality of the quality of the 1st Resins, epoxy/the 2nd Resins, epoxy) can wait suitably according to the softening temperature of each Resins, epoxy (the 1st Resins, epoxy and the 2nd Resins, epoxy) and set, be 1/99～99/1 for example, be preferably 10/90～90/10.
In addition, in resinous principle, except above-mentioned each composition (polymkeric substance), for example also comprise polymer precursor (for example comprising the low-molecular weight polymer of oligopolymer etc.) and/or monomer.
Fig. 1 is the stereographic map of an embodiment of heat conductive sheet of the present invention, and Fig. 2 is the process picture sheet that is used to illustrate the manufacture method of heat conductive sheet shown in Figure 1.
Then, see figures.1.and.2 the method for an embodiment making heat conductive sheet of the present invention is described.
In the method, at first above-mentioned each composition is cooperated with above-mentioned proportioning example, and mix, prepare mixture thus.
In mixing, for each composition is mixed effectively, for example solvent can be cooperated with above-mentioned each composition, perhaps for example can make resinous principle (being preferably the thermoplastic resin composition) fusion by heating.
As solvent, can enumerate and above-mentioned same organic solvent.In addition, when above-mentioned solidifying agent and/or curing catalyst are prepared to solvent solution and/or solvent dispersions, can in mixing, not append solvent, directly with the solvent of solvent solution and/or solvent dispersions as the mixed solvent that mixes.Perhaps, also can in mixing, further append solvent as mixed solvent.
When using solvent to mix, mix the back except that desolvating.
For removing of solvent, for example at room temperature placed 1～48 hour, or for example 40～100 ℃ of down heating 0.5～3 hour, perhaps for example under the reduced atmosphere of 0.001～50kPa, 20～60 ℃ of heating 0.5～3 hour down.
By heating when making the resinous principle fusion, Heating temperature for example be near the softening temperature of resinous principle or above its temperature, particularly, is 40～150 ℃, is preferably 70～140 ℃.
Then, this method is carried out hot pressing to the gained mixture.
Particularly, shown in Fig. 2 (a), for example obtain suppressing sheet material 1A by carrying out hot pressing as required across 4 pairs of mixtures of 2 mould release films (mold release film).Hot pressed condition is: temperature is 50～150 ℃ for example, is preferably 60～140 ℃ that pressure is 1～100MPa for example, is preferably 5～50MPa that the time is 0.1～100 minute for example, is preferably 1～30 minute.
Further preferably mixture is carried out vacuum hotpressing.The vacuum tightness of vacuum hotpressing is 1～100Pa for example, is preferably 5～50Pa, and temperature, pressure and time are with above-mentioned hot pressed identical.
Hot pressed temperature, pressure and/or time can't be adjusted into the porosity P (aftermentioned) of heat conductive sheet 1 value of expectation outside above-mentioned scope the time sometimes.
The thickness of the compacting sheet material 1A that obtains by hot pressing for example is 50～1000 μ m, is preferably 100～800 μ m.
Then, in the method, shown in Fig. 2 (b), will suppress sheet material 1A and be divided into a plurality of (for example 4), obtain cutting apart sheet material 1B (segmentation process).In the cutting apart of compacting sheet material 1A, along the thickness direction of compacting sheet material 1A it is cut, it is a plurality of to make that it is broken into along the thickness direction projection time.In addition, compacting sheet material 1A becomes the mode of identical shape to cut along the thickness direction projection time so that respectively cut apart sheet material 1B.
Then, in the method, shown in Fig. 2 (c), it is stacked along thickness direction respectively to cut apart sheet material 1B, obtains laminated sheet 1C (stacked operation).
After this, in the method, shown in Fig. 2 (a), laminated sheet 1C is carried out hot pressing (being preferably vacuum hotpressing) (hot pressing process).Hot pressed condition is identical with the hot pressed condition of said mixture.
The thickness of laminated sheet 1C after the hot pressing for example is below the 1mm, to be preferably below the 0.8mm, usually, for example is more than the 0.05mm, to be preferably more than the 0.1mm.
After this, in order in heat conductive sheet 1, to make boron nitride particle 2 in resinous principle 3, implement above-mentioned segmentation process (Fig. 2 (b)), stacked operation (Fig. 2 (c)) and these a series of operations of hot pressing process (Fig. 2 (a)) repeatedly along the prescribed direction orientation effectively.The number of occurrence is not particularly limited, can suitably set according to the occupied state of boron nitride particle, and be 1～10 time for example, be preferably 2～7 times.
In addition, in above-mentioned hot pressing process (Fig. 2 (a)), for example can wait mixture and laminated sheet 1C are rolled by a plurality of stacks.
Thus, can obtain heat conductive sheet 1.
The thickness of gained heat conductive sheet 1 for example is below the 1mm, to be preferably below the 0.8mm, usually, for example is more than the 0.05mm, to be preferably more than the 0.1mm.
In addition, boron nitride particle in the heat conductive sheet 1 based on containing of volume reference proportional (solids component, be the percentage by volume of boron nitride particle) with respect to the cumulative volume of resinous principle and boron nitride particle as mentioned above, for example being that 35 volume % are above (is preferably more than the 60 volume %, more preferably more than the 75 volume %), be generally 95 volume % following (it is following to be preferably 90 volume %).
When the above-mentioned scope of containing of boron nitride particle of proportional discontented foot, boron nitride particle 2 is orientated in heat conductive sheet 1 along prescribed direction.
In addition, when resinous principle 3 is the thermosetting resin composition, for example under its uncured state, implements above-mentioned segmentation process (Fig. 2 (b)), stacked operation (Fig. 2 (c)) and these a series of operations of hot pressing process (Fig. 2 (a)) repeatedly and directly obtain the heat conductive sheet 1 of its uncured state.
In addition, behind the heat conductive sheet 1 lining aftermentioned electronic unit of its uncured state and/or installation base plate, make its thermofixation.
When heat conductive sheet 1 thermofixation that makes its uncured state, can use above-mentioned hot pressing or drying machine.The preferred drying machine that uses.The condition of described thermofixation is: Heating temperature is 60～250 ℃ for example, is preferably 80～200 ℃, is 10～200 minutes for example, is preferably 60～150 minutes heat-up time.
Then, in the heat conductive sheet 1 that obtains like this, shown in Fig. 1 and local enlarged diagram thereof, the longitudinal direction LD of boron nitride particle 2 intersects the face direction SD orientation of (quadrature) along heat conductive sheet 1 with thickness direction TD.
In addition, the arithmetical av (the orientation angles α with respect to heat conductive sheet 1 of boron nitride particle 2) of the face direction SD angulation of the longitudinal direction LD of boron nitride particle 2 and heat conductive sheet 1 for example is below 25 degree, be preferably below 20 degree, be generally more than 0 degree.
In addition, following the calculating of orientation angles α with respect to heat conductive sheet 1 of boron nitride particle 2: utilize cross section polishing instrument (CP) that heat conductive sheet 1 is carried out cutting processing along thickness direction, for the cross section that occurs thus, take pictures with the multiplying power in the visual field that can observe 200 above boron nitride particles 2 with scanning electron microscope (SEM), obtain by gained SEM photo boron nitride particle 2 longitudinal direction LD, with respect to the inclined angle alpha of the face direction SD (with the orthogonal direction of thickness direction TD) of heat conductive sheet 1, calculate its mean value.
Thus, the thermal conductivity of the face direction SD of heat conductive sheet 1 is more than the 4W/mK, is preferably more than the 5W/mK, more preferably more than the 10W/mK, more preferably more than the 15W/mK, especially is preferably more than the 25W/mK, is generally below the 200W/mK.
In addition, when resinous principle 3 was the thermosetting resin composition, the thermal conductivity of the face direction SD of heat conductive sheet 1 was basic identical before and after thermofixation.
When the thermal conductivity of the face direction SD of heat conductive sheet 1 did not satisfy above-mentioned scope, the thermal conductivity of face direction SD was insufficient, therefore can't be used for the heat radiation purposes of the thermal conductivity of this direction SD of needs sometimes.
In addition, measure the thermal conductivity of the face direction SD of heat conductive sheet 1 by the pulse heating method.Use xenon flash lamp analyser (xenon flashanalyser) " LFA-447 type " (manufacturing of NETZSCH company) in the pulse heating method.
In addition, the thermal conductivity of the thickness direction TD of heat conductive sheet 1 is 0.5～15W/mK for example, is preferably 1～10W/mK.
In addition, the thermal conductivity of the thickness direction TD of heat conductive sheet 1 can be measured by pulse heating method, laser flash (laser flash) method or TWA method.Use and above-mentioned same instrument in the pulse heating method, use " TC-9000 " (ULVAC-RIKO, Inc. makes) in the laser flash method, use " ai-Phase mobile " (ai-Phase Co., Ltd. makes) in the TWA method.
Thus, the thermal conductivity of the face direction SD of heat conductive sheet 1 for example is more than 1.5 with the ratio of the thermal conductivity of the thickness direction TD of heat conductive sheet 1 (thermal conductivity of the thermal conductivity of face direction SD/thickness direction TD), be preferably more than 3, more preferably more than 4, be generally below 20.
In addition, not shown among Fig. 1 in heat conductive sheet 1, for example be formed with hole (gap).
The ratio of the hole of heat conductive sheet 1, be porosity P can be by containing of boron nitride particle 2 proportional (volume reference), also have boron nitride particle 2 and temperature, pressure and/or the time of the hot pressing (Fig. 2 (a)) of the mixture of resinous principle 3 to adjust, particularly, can be by temperature, pressure and/or the time set of above-mentioned hot pressing (Fig. 2 (a)) be adjusted in above-mentioned scope.
Porosity P in the heat conductive sheet 1 for example is below the 30 volume %, is preferably below the 10 volume %.
Above-mentioned porosity P for example can be as the mensuration of getting off: at first, utilize cross section polishing instrument (CP) that heat conductive sheet 1 is carried out cutting processing along thickness direction, the cross section that occurs thus with 200 times of observations with scanning electron microscope (SEM), obtain image, by the gained image, carry out binary conversion treatment to the hole part with except that the part it, then calculate the hole part area ratio long-pending, measure thus with respect to thermally-conductive sheet 1 global sections.
In addition, in heat conductive sheet 1, the porosity P2 after the curing, is preferably below 50% below 100% with respect to the porosity P1 before solidifying.
In the mensuration of porosity P (P1), when resinous principle 3 is the thermosetting resin composition, use the preceding heat conductive sheet 1 of thermofixation.
The porosity P of heat conductive sheet 1 can improve the difference of altitude tracing ability (aftermentioned) of heat conductive sheet 1 in above-mentioned scope the time.
In addition, breakdown voltage heat conductive sheet 1, that measure according to JIS C 2110 (version in 2010) is more than the 10kV/mm.When the breakdown voltage of heat conductive sheet 1 does not satisfy 10kV/mm, can't guarantee excellent anti-puncture of insulation (tracking index).
In addition, above-mentioned breakdown voltage is measured according to the record of JIS C 2110-2 (version in 2010) " 2 ones of the test method-Di of the intensity of solid electrically insulating material-puncture of insulation: based on the test that applies volts DS ".Specifically, be that short period of time (the boosting rapidly) test of 1000V/s is measured and made heat conductive sheet 1 voltage of puncture of insulation take place as breakdown voltage by the rate of rise.
In addition, the breakdown voltage of heat conductive sheet 1 is preferably more than the 15kV/mm, is generally below the 100kV/mm.
When resinous principle 3 was the thermosetting resin composition, the breakdown voltage of heat conductive sheet 1 was basic identical before and after the thermofixation of heat conductive sheet 1.
In addition, heat conductive sheet 1 is in the resistance to bend(ing) test of the round shape axle method of foundation JIS K 5600-5-1, and when estimating under following test conditions, preferred view is less than fracture.
Test conditions
Testing apparatus: type i
Axle: diameter 10mm
Angle of bend: more than 90 degree
The thickness of heat conductive sheet 1: 0.3mm
In addition, Fig. 3 and Fig. 4 illustrate the stereographic map of the testing apparatus of type i, below, the testing apparatus of type i is described.
In Fig. 3 and Fig. 4, the testing apparatus 10 of type i comprises: first flat board 11; Second flat board 12, itself and first flat board 11 dispose side by side; And axle (turning axle) 13, it relatively rotates and is provided with in order to make first dull and stereotyped 11 and second flat board 12.
First flat board 11 forms the essentially rectangular tabular.In addition, an end of first flat board 11 (movable end) is provided with stop part 14.Stop part 14 is formed on the surface of first flat board 11 in the mode of extending along an end of first flat board 11.
Second flat board 12 is tabular in the form of a substantially rectangular, is to dispose in its one side mode adjacent with one side (one side of the other end (base end part) of a side opposite with an end that is provided with stop part 14) of first flat board 11.
Axle 13 is to form in the mode of extending along first dull and stereotyped 11 and second dull and stereotyped 12 one side adjacent one another are.
As shown in Figure 3, before beginning resistance to bend(ing) test, make the surface of first flat board 11 of testing apparatus 10 of the type I and the surface of second flat board 12 be in same plane.
And, when implementing the resistance to bend(ing) test, heat conductive sheet 1 is positioned on the surface of the surface of first flat board 11 and second flat board 12.In addition, heat conductive sheet 1 is on one side with the mode mounting of stop part 14 butts with it.
Then, as shown in Figure 4, first dull and stereotyped 11 and second flat board 12 is relatively rotated.Specifically, making the movable end of first flat board 11 and the movable end of second flat board 12 is that predetermined angular is rotated at the center with axle 13.In detail, make and first dull and stereotyped 11 be close with the surface of the movable end of second flat board 12 with first dull and stereotyped 11 with second flat board 12 (relative to) mode rotate.
Thus, heat conductive sheet 1 is a center curvature with axle 13 in the rotation of following first dull and stereotyped 11 and second flat board 12.
Further preferably, heat conductive sheet 1 is in above-mentioned test conditions, even angle of bend being set at 180 when spending, also do not observe fracture.
In addition, when resinous principle 3 is the thermosetting resin composition, be the heat conductive sheet 1 (heat conductive sheet before the thermofixation 1 promptly) of semicure (B scalariform attitude) for heat conductive sheet 1 in pliability test.
When observing heat conductive sheet 1 in the test of resistance to bend(ing) under above-mentioned angle of bend fracture being arranged, can't give the flexibility of heat conductive sheet 1 sometimes with excellence.
In addition, this heat conductive sheet 1 when estimating, does not for example observe fracture under following test conditions in the three point bending test of foundation JIS K 7171 (2008).
Test conditions
Test film: size 20mm * 15mm
Length of support is from 5mm
Trial speed: 20mm/min (speed that presses down of pressure head)
Angle of bend: 120 degree
Evaluation method: the fractures such as crackle of the central part of test film has or not when testing under above-mentioned test conditions with visual observation.
In addition, in three point bending test, when resinous principle 3 is the thermosetting resin composition, use the preceding heat conductive sheet 1 of thermofixation.
Therefore, from above-mentioned three point bending test, not observing fracture, the difference of altitude tracing ability excellence of this heat conductive sheet 1.In addition, the difference of altitude tracing ability be meant heat conductive sheet 1 is arranged at difference of altitude object is set the time, can follow the characteristic that this difference of altitude is carried out driving fit.
In addition, for heat conductive sheet 1, for example can adhere to marks such as literal, mark.That is the mark tack excellence of heat conductive sheet 1.The mark tack is meant and can makes above-mentioned mark be attached to the characteristic of heat conductive sheet 1 securely.
Particularly, mark can wait by printing or mint-mark and adhere to (coating, photographic fixing or set) in heat conductive sheet 1.
As printing, for example can list ink jet printing, letterpress, intaglio printing, laser printing etc.
In addition, when coming typographic(al) mark, for example can be provided for improving the black photographic fixing layer of the fixation performance of mark on the surface (printing side) of heat conductive sheet 1 by ink jet printing, letterpress or intaglio printing.
In addition, when coming typographic(al) mark, for example can be provided for improving the toner fixing layer of the fixation performance of mark on the surface (printing side) of heat conductive sheet 1 by laser printing.
As mint-mark, for example can list laser beam marking, impression etc.
And, the excellent thermal conductivity of the face direction SD of above-mentioned heat conductive sheet 1, anti-puncture of insulation (tracking index) is also excellent simultaneously.
Therefore, with the heat conductive sheet 1 lining electronic unit that Power Electronic Technique adopted and/or when their installation base plate is installed, can prevent the puncture of insulation of heat conductive sheet 1, by described heat conductive sheet 1 heat of electronic unit and/or installation base plate be dispersed along face direction SD simultaneously.
As electronic unit, for example can list IC (unicircuit) chip (the especially narrow electrode terminal part of width in the IC chip), thyristor (rectifier), electric motor (motor) parts, umformer, transmission of electricity parts, electrical condenser, coil, resistor, photodiode etc.
In addition, above-mentioned electronic unit is installed on the surface (face) of installation base plate, in described installation base plate, is spaced from each other distance ground configuration electronic unit along face direction (the face direction of installation base plate).
In addition, the deterioration that the heat conductive sheet 1 of above-mentioned electronic unit and/or installation base plate can also prevent that the high frequency noise that produced by electronic unit and/or installation base plate etc. from causing that is used to be covered.
Embodiment
Embodiment is shown below further specifies the present invention, but the present invention is not subjected to the qualification of embodiment fully.
Embodiment 1
Cooperate 13.42g PT-110 (trade(brand)name, flaky boron nitride particle, median size (light scattering method) 45 μ m, Momentive Performance Materials JapanLLC makes), 1.0g JER828 (trade(brand)name, bisphenol A type epoxy resin, the 1st Resins, epoxy, liquid, epoxy equivalent (weight) 184～194g/eqiv., softening temperature (ring and ball method) is less than 25 ℃, melt viscosity (80 ℃) 70mPas, Japan Epoxy Resins Co., Ltd. make) and 2.0g EPPN-501HY (trade(brand)name, triphenyl methane type Resins, epoxy, the 2nd Resins, epoxy, solid-state, epoxy equivalent (weight) 163～175g/eqiv., 57～63 ℃ of softening temperatures (ring and ball method), Japan's chemical drug corporate system is made) and 3g (solids component 0.15g) solidifying agent (Curezol 2P4MHZ-PW (trade(brand)name, the four countries company that changes into makes) 5 quality % methylethylketone dispersion liquids) (with respect to Resins, epoxy, being the total amount of JER828 and EPPN-501HY, is 5 quality %) and stir, placed for 1 evening down in room temperature (23 ℃), make methylethylketone (dispersion agent of solidifying agent) volatilization, prepare semi-solid mixture.
In addition, in above-mentioned cooperation, boron nitride particle is 70 volume % with respect to the percentage by volume (volume %) of the cumulative volume of the solids component except that solidifying agent (solids component of boron nitride particle and Resins, epoxy promptly).
Then, clamp the gained mixture with 2 mould release films that organosilicon was handled, under 80 ℃, the atmosphere (vacuum atmosphere) of 10Pa, (20MPa) carries out 2 minutes hot pressing to them with 5 tons loads, obtains the compacting sheet material (with reference to Fig. 2 (a)) of thickness 0.3mm thus with the heating under vacuum press.
After this, cutting gained compacting sheet material, it is a plurality of that it is divided into along the thickness direction projection of compacting sheet material the time, obtains cutting apart sheet material (with reference to Fig. 2 (b)) thus, then, cuts apart sheet material and obtain laminated sheet (with reference to Fig. 2 (c)) along thickness direction is stacked.
Then, use with above-mentioned same heating under vacuum press with above-mentioned same condition under the gained laminated sheet is carried out hot pressing (with reference to Fig. 2 (a)).
Then, with above-mentioned cutting, stacked and these a series of operations (with reference to Fig. 2) of hot pressing 4 times repeatedly, obtain the heat conductive sheet (its uncured state) of thickness 0.3mm.
After this, the gained heat conductive sheet is dropped into drying machine, heated 120 minutes down, make its thermofixation thus at 150 ℃.
Embodiment 2～9 and 11～16
According to the prescription of table 1～table 3 with create conditions and carry out similarly to Example 1 processing, obtain heat conductive sheet.
Embodiment 10
Prescription according to table 2 cooperates each composition (boron nitride particle and polyethylene) and stirring, prepares mixture thus.That is, when stirring each composition, be heated to 130 ℃ and make the polyethylene fusion.
Then, clamp the gained mixture with 2 mould release films that organosilicon was handled, under 120 ℃, the atmosphere (vacuum atmosphere) of 10Pa, (4MPa) carries out 2 minutes hot pressing to them with 1 ton load, obtains the compacting sheet material (with reference to Fig. 2 (a)) of thickness 0.3mm thus with the heating under vacuum press.
After this, cutting gained compacting sheet material, it is a plurality of that it is divided into along the thickness direction projection of compacting sheet material the time, obtains cutting apart sheet material (with reference to Fig. 2 (b)) thus, then, cuts apart sheet material and obtain laminated sheet (with reference to Fig. 2 (c)) along thickness direction is stacked.
Then, use with above-mentioned same heating under vacuum press with above-mentioned same condition under the gained laminated sheet is carried out hot pressing (with reference to Fig. 2 (a)).
Then, with above-mentioned cutting, stacked and these a series of operations (with reference to Fig. 2) of hot pressing 4 times repeatedly, obtain the heat conductive sheet of thickness 0.3mm.
Estimate
1. thermal conductivity
The heat conductive sheet that is obtained by embodiment 1～16 is carried out The determination of thermal conductivity.
That is, measure the thermal conductivity of face direction (SD) by the pulse heating method of using xenon flash lamp analyser " LFA-447 type " (manufacturing of NETZSCH company).
It the results are shown in table 1～table 3.
2. dielectric breakdown test (JIS C 2110 (version in 2010))
The heat conductive sheet that is obtained by embodiment 1～16 is carried out the mensuration of breakdown voltage according to JIS C 2110 (version in 2010).
Promptly, breakdown voltage is, is that breakdown voltage is measured in short period of time (the boosting rapidly) test of 1000V/s according to the record of JIS C 2110-2 (version in 2010) " 2 ones of the test method-Di of the intensity of solid electrically insulating material-puncture of insulation: based on the test that applies volts DS ", by the rate of rise.
It the results are shown in table 1～table 3.
3. porosity (P)
Measure the porosity (P1) of the heat conductive sheet before the thermofixation of embodiment 1～16 by following measuring method.
The measurement method of porosity method: at first, utilize cross section polishing instrument (CP) that heat conductive sheet is carried out cutting processing along thickness direction, the cross section with scanning electron microscope (SEM) occurs thus with 200 times of observations obtains image.After this,, carry out binary conversion treatment, then calculate the hole part area ratio long-pending with respect to the thermally-conductive sheet global sections to the hole part with except that the part it by the gained image.
It the results are shown in table 1～table 3.
4. difference of altitude tracing ability (three point bending test)
For the heat conductive sheet before the thermofixation of embodiment 1～16,, thereby estimate the difference of altitude tracing ability according to following metewand according to the three point bending test under the following test conditions of JIS K7171 (2008) enforcement.It the results are shown in table 1～table 3.
Test conditions
Test film: size 20mm * 15mm
Length of support is from 5mm
Trial speed: 20mm/min (speed that presses down of pressure head)
Angle of bend: 120 degree
Metewand
◎: do not observe fracture fully.
Zero: do not observe fracture substantially.
*: obviously observe fracture.
5. typographic(al) mark identity (typographic(al) mark tack: based on ink jet printing or sharp The mark tack of light printing)
Carry out ink jet printing and laser printing comes typographic(al) mark by heat conductive sheet, and observe described mark embodiment 1～16.
Its result, any one of the heat conductive sheet of embodiment 1～16 all can recognize well based on the two mark of ink jet printing and laser printing, can confirm that the typographic(al) mark tack is good.
Table 1
Figure BSA00000431042100221
g * A: fit quality
[volume %] * B: with respect to the percentage of the cumulative volume of thermally-conductive sheet (except that solidifying agent)
[volume %] * C: with respect to the percentage of the cumulative volume of thermally-conductive sheet
Number of times * D: the hot pressed number of times of laminated sheet
Table 2
Figure BSA00000431042100231
g * A: fit quality
[volume %] * B: with respect to the percentage of the cumulative volume of thermally-conductive sheet (except that solidifying agent)
[volume %] * C: with respect to the percentage of the cumulative volume of thermally-conductive sheet
Number of times * D: the hot pressed number of times of laminated sheet
Table 3
Figure BSA00000431042100241
g * A: fit quality
[volume %] * B: with respect to the percentage of the cumulative volume of thermally-conductive sheet (except that solidifying agent)
[volume %] * C: with respect to the percentage of the cumulative volume of thermally-conductive sheet
Number of times * D: the hot pressed number of times of laminated sheet
Numerical value in each composition in table 1～table 3 is represented the g number when not specifying.
In addition, in boron nitride particle one hurdle of table 1～table 3, top numerical value is the fit quality (g) of boron nitride particle, intermediary numerical value is boron nitride particle percentage by volume (volume %) with respect to the cumulative volume of the solids component except that solidifying agent (promptly, boron nitride particle and Resins, epoxy or poly solids component) in heat conductive sheet, and following numerical value is the percentage by volume (volume %) of boron nitride particle with respect to the cumulative volume of the solids component (solids component of boron nitride particle and Resins, epoxy and solidifying agent promptly) of heat conductive sheet.
In addition, for the composition of band ※ mark in each composition of table 1～table 3, its detailed content of record below.
PT-110 ※ 1: trade(brand)name, flaky boron nitride particle, median size (light scattering method) 45 μ m, Momentive Performance Materials Japan LLC makes.
UHP-1 ※ 2: trade(brand)name: SHOBN UHP-1, flaky boron nitride particle, median size (light scattering method) 9 μ m, clear and electrician company makes.
Resins, epoxy A ※ 3: OGSOL EG (trade(brand)name), two aryl fluorenes type Resins, epoxy, semi-solid state, epoxy equivalent (weight) 294g/eqiv., 47 ℃ of softening temperatures (ring and ball method), melt viscosity (80 ℃) 1360mPas, Osaka Gas Chemicals Co., Ltd. makes.
Resins, epoxy B ※ 4: JER828 (trade(brand)name), bisphenol A type epoxy resin, liquid state, epoxy equivalent (weight) 184～194g/eqiv., softening temperature (ring and ball method) be less than 25 ℃, melt viscosity (80 ℃) 70mPas, Japan Epoxy Resins Co., Ltd. makes.
Resins, epoxy C ※ 5: JER1002 (trade(brand)name), bisphenol A type epoxy resin, solid-state, epoxy equivalent (weight) 600～700g/eqiv., 78 ℃ of softening temperatures (ring and ball method), melt viscosity (80 ℃) 10000mPas above (measuring more than the boundary), Japan EpoxyResins Co., Ltd. makes.
Resins, epoxy D ※ 6: EPPN-501HY (trade(brand)name), triphenyl methane type Resins, epoxy, solid-state, epoxy equivalent (weight) 163～175g/eqiv., 57～63 ℃ of softening temperatures (ring and ball method), Japanese chemical drug corporate system is made.
Solidifying agent ※ 7: the 5 quality % methyl ethyl ketone solutions of Curezol 2PZ (trade(brand)name, four countries change into company and make).
Solidifying agent ※ 8: the 5 quality % methylethylketone dispersion liquids of Curezol 2P4MHZ-PW (trade(brand)name, four countries change into company and make).
Polyethylene ※ 9: new LDPE (film grade), weight-average molecular weight (Mw) 4000, number-average molecular weight (Mn) 1700, Aldrich company makes.
In addition, above-mentioned explanation provides as illustrative embodiment of the present invention, and it only is an example, should not explain limitedly.Present technique field personnel understand that variation of the present invention also is included in the claim scope.

Claims (1)

1. a heat conductive sheet is characterized in that, it contains flaky boron nitride particle,
Described heat conductive sheet and the thermal conductivity orthogonal direction of thickness direction are more than the 4W/mK,
The breakdown voltage that JIS C 2110 described heat conductive sheet, foundation version in 2010 measures is more than the 10kV/mm.
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Application publication date: 20110921