CN103192571A - Heat dissipation member, electronic element and battery - Google Patents
Heat dissipation member, electronic element and battery Download PDFInfo
- Publication number
- CN103192571A CN103192571A CN2012105674266A CN201210567426A CN103192571A CN 103192571 A CN103192571 A CN 103192571A CN 2012105674266 A CN2012105674266 A CN 2012105674266A CN 201210567426 A CN201210567426 A CN 201210567426A CN 103192571 A CN103192571 A CN 103192571A
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- CN
- China
- Prior art keywords
- heat release
- release member
- powder
- member according
- thermal conductivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- 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
- B32B2457/10—Batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
The present invention provides a heat dissipation member, an electronic element and a battery. The heat dissipation member has a bonding layer which is excellent in bonding strength between a metal layer and a graphitic layer and is thin, and includes a lamination body laminated with the metal layer and the graphitic layer through the bonding layer. And the bonding layer is formed by components including polyvinyl acetal resin.
Description
Technical field
The present invention relates to a kind of heat release member, electronic component and battery.
Background technology
The graphite flake (graphitesheet) of gained demonstrates excellent thermal conductivity by polymeric membrane is heat-treated, and therefore uses as heat carrier by (patent documentation 1).
In recent years therefore e-machine requires to use the more excellent heat carrier of exothermic character along with high performance, multifunction and caloric value increases in this machine.As this kind heat carrier, disclosed the method for using a kind of laminate, described laminate is by solid graphite flake and metallic plate then to be formed (patent documentation 2～patent documentation 5).
Use rubber-like elasticity solid or silicone-based thermal conductivity solid in described patent documentation 3, have been put down in writing as the method for solid; In described patent documentation 4, put down in writing the method for using the solid that contains electroconductive stuffings such as silver, gold, copper.And, in described patent documentation 5, put down in writing the method for using the acrylic acid series solid.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese patent laid-open 11-21117 communique
[patent documentation 2] Japan Patent spy opens the 2001-144237 communique
[patent documentation 3] Japanese patent laid-open 10-247708 communique
[patent documentation 4] Japan Patent spy opens the 2004-23066 communique
[patent documentation 5] Japan Patent spy opens the 2009-280433 communique
Summary of the invention
In existing heat carrier (laminate), there is the then situation of intensity difference of graphite flake and metallic plate.
And usually thermal conductivity is little to comprise the layer (following layer) of solid, and along with the thickness thickening of this layer, it is big that the thermal resistance of the lamination direction of described laminate becomes.Therefore, require the thin as far as possible following layer of used thickness.
Yet the following layer of putting down in writing in the described patent documentation is because the then intensity difference of graphite flake and metallic plate, therefore if do not make the thickness thickening of following layer, has that can't obtain can be in the situation of the heat carrier of use in the e-machine etc.Then particularly the thermal resistance of the lamination direction of laminate is big for the laminate of bed thickness, and exothermic character is poor.
Given this present invention plants the problem points person of forming, and its purpose is to provide the heat release member of the following layer of following excellent strength and thin thickness with metal level and graphite linings.
The present inventor has carried out with keen determination research in order to solve described problem, found that by following heat release member to solve described problem, thereby finish the present invention, and described heat release member comprises that lamination has the laminate of metal level and graphite linings via specific following layer.
[1] a kind of heat release member, it comprises the laminate that via following layer lamination has metal level and graphite linings, and this following layer is formed by the constituent that comprises the polyvinyl acetal resin.
[2] as [1] described heat release member, wherein, described constituent further comprises the thermal conductivity filler.
[3] as [1] or [2] described heat release member, wherein, described polyvinyl acetal resin comprises following construction unit A, construction unit B and construction unit C,
[changing 1]
Construction unit A
Among the construction unit A, R independently is hydrogen or alkyl [changing 2]
Construction unit B
[changing 3]
Construction unit C.
[4] as [3] described heat release member, wherein, described polyvinyl acetal resin further comprises following construction unit D,
[changing 4]
Construction unit D
Among the construction unit D, R
1Independent is that hydrogen or carbon number are 1～5 alkyl.
[5] as [3] or [4] described heat release member, wherein, the R among the described construction unit A is that hydrogen or carbon number are 1～3 alkyl.
[6] as each described heat release member in [1]～[5], wherein, the thermal conductivity of the lamination direction of the described laminate of described following layer is 0.05W/mK～50W/mK.
[7] as each described heat release member in [1]～[6], wherein, the thickness of described following layer is 0.05 μ m～10 μ m.
[8] as each described heat release member in [2]～[7], wherein, described following layer comprises for following layer 100vol% the thermal conductivity filler for 1vol%～80vol%.
[9] as each described heat release member in [2]～[8], wherein, described thermal conductivity filler comprises at least a kind of powder that is selected from the group that is made of metal powder, metal oxide powder, metal nitride powder and metal carbides powder.
[10] as [9] described heat release member, wherein, described thermal conductivity filler comprises at least a kind of powder that is selected from the group that is made of aluminum nitride powder, alumina powder, oxide powder and zinc, magnesia powder, carborundum powder, tungsten carbide powder, aluminium powder and copper powder.
[11] as [9] or [10] described heat release member, wherein, the average diameter of described thermal conductivity filler is 0.001 μ m～30 μ m.
[12] as each described heat release member in [2]～[8], wherein, described thermal conductivity filler is the filler that comprises material with carbon element.
[13] as [12] described heat release member, wherein, described thermal conductivity filler comprises at least a kind of powder that is selected from the group that is made of graphite powder, CNT and bortz powder.
[14] as each described heat release member in [1]～[13], wherein, the thermal conductivity of approximate vertical direction for the lamination direction of described laminate of described graphite linings is 250W/mK～2000W/mK.
[15] as each described heat release member in [1]～[14], wherein, the thickness of described graphite linings is 15 μ m～600 μ m.
[16] as each described heat release member in [1]～[15], wherein, described metal layer thickness is 0.01 times～100 times of thickness of described graphite linings.
[17] as each described heat release member in [1]～[16], wherein, described metal level is the layer that comprises by silver, copper, aluminium, nickel and contain at least a kind of metal of the group that the alloy of any at least a kind of metal of those metals constitutes.
[18] as each described heat release member in [1]～[17], wherein, described metal level is the layer that comprises by copper, aluminium and contain at least a kind of metal of the group that the alloy of any at least a kind of metal of those metals constitutes.
[19] as each described heat release member in [1]～[18], wherein, described heat release member comprises at least 2 metal levels, described metal level comprises by copper, aluminium and contains the metal more than a kind of the group that the alloy of any at least a kind of metal of those metals constitutes, and at least 2 of described metal level is different layers.
[20] as each described heat release member in [1]～[19], wherein, has resin bed in the outermost single or double of described heat release member.
[21] as [20] described heat release member, wherein, described resin bed comprises the filler that contains inorganic compound.
[22] as [20] or [21] described heat release member, wherein, described resin bed comprises: be selected from least a kind of resin of the group that is constituted by acrylic resin, epoxy resin, alkyd resins, amine ester resin and nitrocellulose, and at least a kind of compound that is selected from the group that is constituted by aluminium oxide, silica, cordierite, mullite, carborundum and magnesia.
[23] a kind of electronic component, it comprises as each described heat release member in [1]～[22].
[24] a kind of battery, it comprises as each described heat release member in [1]～[22].
[effect of invention]
The then high heat release member of intensity of thin thickness, metal level and the graphite linings of following layer can be provided by the present invention.
And, have excellent processability and/or the heat release member of bending but can provide by the present invention.
And then, but can provide the battery of lightweight, miniaturization or electronic component etc. by the present invention.
Description of drawings
Fig. 1 is the sectional skeleton diagram of an example that expression comprises the electronic component of heat release member of the present invention.
Fig. 2 is the skeleton diagram of an example that expression is provided with the graphite linings in hole.
Fig. 3 is the skeleton diagram of an example that expression is provided with the graphite linings of slit.
Fig. 4 is the sectional skeleton diagram of an example that expression comprises the electronic component of heat release member of the present invention.
Fig. 5 is the sectional skeleton diagram of an example of the expression LED illumination that comprises heat release member of the present invention.
The main element symbol description:
1: heat release member (laminate)
2: metal level
3: following layer
4,4 ', 4 ": graphite linings
5: following layer
6: metal level
7: heater
8: the hole
9: slit
10: the heat release member
11: heat conductive pad
12: dielectric film
The 13:LED body
14: electrode
15: metal wiring
The specific embodiment
The heat release member
Heat release member of the present invention comprises the laminate that via following layer lamination has metal level and graphite linings, and this following layer is formed by the constituent that comprises the polyvinyl acetal resin.
Lamination has metal level and graphite linings to described laminate via described following layer, therefore comprise this laminate heat release member of the present invention metal level and graphite linings follow the intensity height, and excellent in workability, but bending.
＜following layer 〉
Then there is no particular restriction as if being formed by the constituent that comprises the polyvinyl acetal resin for described following layer, also can be formed by following constituent, described constituent is except this resin, also can in the scope that does not undermine effect of the present invention, further comprise thermal conductivity filler, additive and solvent according to kind of metal level etc.
By using this kind following layer, can obtain the then excellent strength of metal level and graphite linings, but bending, the heat release member of toughness, flexibility, hear resistance and resistance to impact excellence.
[polyvinyl acetal resin]
There is no particular restriction for described polyvinyl acetal resin, from obtaining toughness, hear resistance and resistance to impact excellence, even thin thickness is also considered the aspects such as following layer of excellence with the connecting airtight property of metal level or graphite linings, preferably comprise the resin of following construction unit A, construction unit B and construction unit C.
[changing 5]
Construction unit A
Described construction unit A is the construction unit with acetal position, for example can form by the reaction of continuous polyvinyl alcohol chain element and aldehyde (R-CHO).
R among the construction unit A independently is hydrogen or alkyl.If described R is bulky base (for example many alkyl of carbon number), then there is the tendency of the softening point reduction of polyvinyl acetal resin.And described R is the dissolubility height of polyvinyl acetal resin in solvent of bulky base, and chemical-resistant is poor but then.Therefore, described R preferably hydrogen or carbon number is 1～5 alkyl, considers that from the aspects such as toughness of the following layer of gained hydrogen more preferably or carbon number are 1～3 alkyl, and further more preferably hydrogen or propyl group consider that from aspects such as hear resistances special good is hydrogen.
[changing 6]
Construction unit B
[changing 7]
Construction unit C
From can acquisition and the aspects such as following layer of the then excellent strength of metal level or graphite linings consider that preferably described polyvinyl acetal resin also comprises following construction unit D except construction unit A～construction unit C.
[changing 8]
Construction unit D
Among the described construction unit D, R
1Independent is that hydrogen or carbon number are 1～5 alkyl, and preferably hydrogen or carbon number are 1～3 alkyl, more preferably hydrogen.
Total containing ratio of construction unit A in the described polyvinyl acetal resin, construction unit B, construction unit C and construction unit D preferably is 80mol%～100mol% for all construction units of this resin.As in the polyvinyl acetal resin other construction units that can comprise, can enumerate ethylene acetal chain element (R among the described construction unit A is the construction unit beyond the hydrogen or alkyl) beyond the construction unit A, following intermolecular acetal unit, and following hemiacetal unit etc.The containing ratio of the ethylene acetal chain element beyond the construction unit A is not enough 5mol% for all construction units of polyvinyl acetal resin preferably.
[changing 9]
Intermolecular acetal unit (R in the described intermolecular acetal unit and the R synonym among the described construction unit A)
[changing 10]
The hemiacetal unit
(the R synonym among the R in the described hemiacetal unit and the described construction unit A)
In described polyvinyl acetal resin, construction unit A～construction unit D can have systematicness and arrange (block copolymer, alternate copolymer etc.), also can randomly arrange (random copolymer), preferably randomly arranges.
As each construction unit in the described polyvinyl acetal resin, preferably for all construction units of this resin, the containing ratio of construction unit A is 49.9mol%～80mol%, the containing ratio of construction unit B is 0.1mol%～49.9mol%, the containing ratio of construction unit C is 0.1mol%～49.9mol%, and the containing ratio of construction unit D is 0mol%～49.9mol%.More preferably for all construction units of described polyvinyl acetal resin, the containing ratio of construction unit A is 49.9mol%～80mol%, the containing ratio of construction unit B is 1mol%～30mol%, the containing ratio of construction unit C is 1mol%～30mol%, and the containing ratio of construction unit D is 1mol%～30mol%.
Consider that from the aspects such as polyvinyl acetal resin that obtain chemical-resistant, pliability, mar proof and mechanical strength excellence preferably the containing ratio of construction unit A is more than the 49.9mol%.
If the containing ratio of described construction unit B is more than the 0.1mol%, then the dissolubility of polyvinyl acetal resin in solvent becomes good, and be therefore preferable.And, if the containing ratio of construction unit B is below the 49.9mol%, then the chemical-resistant of polyvinyl acetal resin, pliability, mar proof, and mechanical strength be difficult to reduce, therefore preferable.
From dissolubility or the following layer of gained and the aspect considerations such as then property of metal level or graphite linings of polyvinyl acetal resin in solvent, described construction unit C preferably containing ratio is below the 49.9mol%.And in the manufacturing of polyvinyl acetal resin, when the polyvinyl alcohol chain was carried out acetalation, construction unit B and construction unit C became equilibrium relation, and therefore preferably the containing ratio of construction unit C is more than the 0.1mol%.
From can acquisition and the aspects such as following layer of the then excellent strength of metal level or graphite linings consider that preferably the containing ratio of construction unit D is described scope.
The containing ratio of each of the construction unit A～construction unit C in the described polyvinyl acetal resin can be based on JIS K 6728 or JIS K 6729 and is measured.
The containing ratio of construction unit D in the described polyvinyl acetal resin can be measured by the method for the following stated.
In the 1mol/l sodium hydrate aqueous solution, the polyvinyl acetal resin was heated under 80 ℃ 2 hours.By this operation, addition sodium on carboxyl and can obtain to have-polymer of COONa.In this polymer, behind the NaOH of extraction surplus, dehydrate., make its carbonization and carry out atomic absorption analysis, obtain the addition amount of sodium and carry out quantitatively thereafter.
In addition, when the containing ratio of analytical structure unit B (vinyl acetate chain), construction unit D quantitatively is the vinyl acetate chain, therefore deduct the containing ratio of quantitative construction unit D from the containing ratio of the construction unit B that measures based on described JIS K 6728 or JIS K6729, the containing ratio of construction unit B is proofreaied and correct.
The weight average molecular weight of described polyvinyl acetal resin preferably 5000～300000, more preferably 10000～150000.If the operating weight mean molecule quantity is in the polyvinyl acetal resin of described scope, then can easily make the heat release member, obtain the heat release member of shaping processability or bending strength excellence, therefore preferable.
The weight average molecular weight of described polyvinyl acetal resin suits to select to get final product according to desired purpose, consider more preferably 10000～40000 from the aspects such as heat release member that can the temperature when making the heat release member suppress lowly, can obtain to have high thermal conductivity; Consider further more preferably 50000～150000 from obtaining the high aspects such as heat release member of heat resisting temperature.
The weight average molecular weight of polyvinyl acetal resin can be measured by the GPC method in the present invention.Concrete condition determination is as described below.
Detector: 830-RI (Japanese light splitting limited company make)
Baking oven: the western tail manufacturing NFL-700M of company
Separate tubing string: Shodex KF-805L * 2 piece
Pump: PU-980 (Japanese light splitting limited company make)
Temperature: 30 ℃
Carrier: oxolane
Standard specimen: polystyrene
The Ao Shihua viscosity of described polyvinyl acetal resin is 1mPas～100mPas preferably.If use the Ao Shihua viscosity to be in the polyvinyl acetal resin of described scope, then can easily make the heat release member, obtain the heat release member of tenacity excellent, therefore preferable.
The Ao Shihua viscosity can use polyvinyl acetal resin 5g is dissolved in the solution that forms among the dichloroethanes 100ml, measures in the 20 ℃ of following use Ao Shihua-Fen Sike of Canon viscosimeters (Ostwald-Cannon Fenske Viscometer).
As described polyvinyl acetal resin, particularly can enumerate polyvinyl butyral resin (polyvinyl butyral), polyvinyl formal (polyvinyl formal), polyethylene acetyl acetal and those derivative etc., from considering with the then property of graphite linings and the aspects such as hear resistance of following layer, preferably polyvinyl formal.
As described polyvinyl acetal resin, described resin can be used separately, also can and with different resins such as the order of the bond of construction unit more than 2 kinds or bond numbers.
Described polyvinyl acetal resin can synthesize and obtain, and also can be commercially available product.
There is no particular restriction to comprise the synthetic method of resin of described construction unit A, construction unit B and construction unit C, for example can enumerate the Japan Patent spy and open the method for putting down in writing in the 2009-298833 communique.And there is no particular restriction to comprise the synthetic method of resin of described construction unit A, construction unit B, construction unit C and construction unit D, for example can enumerate the Japan Patent spy and open the method for putting down in writing in the 2010-202862 communique.
Commercially available product as described polyvinyl acetal resin, polyvinyl formal can be enumerated Vinylec C, Vinylec K (manufacturing of prompt grace intelligence (JNC) limited company) etc., and polyvinyl butyral resin can be enumerated Denka Butyral 3000-K (manufacturing of electrochemical Industries, Inc) etc.
[thermal conductivity filler]
Described following layer makes the thermal conductivity of following layer improve by containing the thermal conductivity filler, described laminate is improved in the thermal conductivity of lamination direction.
Comprise the following layer of thermal conductivity filler by use, but the then heat release member of intensity height, excellent in workability bending of thin thickness, exothermic character and excellent in workability, metal level and the graphite linings of following layer can be provided.And, but the heat lightweight of fully removing spontaneous hot body and sending, the electronic component of miniaturization can be provided, even perhaps also can suppress for high-energy-density because the battery of the puzzlement that heating causes etc.
In addition, in the present invention, so-called " the lamination direction of laminate ", the lamination that for example refers to longitudinal direction that is laminate (heat release member) 1 in Fig. 1 has the direction of metal level 2, following layer 3, graphite linings 4.Particularly refer to from the direction of metal level 2 towards following layer 3, graphite linings 4, perhaps from the direction of graphite linings 4 towards following layer 3, metal level 2.
As described thermal conductivity filler, there is no particular restriction, can enumerate the filler of metals such as containing metal powder, metal oxide powder, metal nitride powder, metal hydroxides powder, metal oxynitrides powder and metal carbides powder or metallic compound, and comprise filler of material with carbon element etc.
As described metal powder, can enumerate metals such as comprising gold, silver, copper, aluminium, nickel and contain the powder etc. of the alloy of those metals.Described metal oxide powder can be enumerated alumina powder, oxide powder and zinc, magnesia powder, silica powder, silicate powder etc.Described metal nitride powder can be enumerated aluminum nitride powder, boron nitride powder, silicon nitride powder etc.Described metal hydroxides powder can be enumerated aluminium hydrate powder, magnesium hydroxide powder etc.Described metal oxynitrides can be enumerated aluminum oxynitride powder etc., and described metal carbides powder can be enumerated carborundum powder, tungsten carbide powder etc.
From thermal conductivity and obtain aspect such as easiness and consider, preferably aluminum nitride powder, alumina powder, oxide powder and zinc, magnesia powder, carborundum powder and tungsten carbide powder in those.
In addition, the filler that contains metal or metallic compound in use is during as the situation of aforementioned thermal conductivity filler, preferably uses the filler that contains with the metal that constitutes described metal level metal of the same race.
Constitute local cell, the situation that metal level or filler are corroded as if using the filler that contains the metal different with the metal that constitutes described metal level or metallic compound as aforementioned thermal conductivity filler, then being present between metal level and the filler.
There is no particular restriction for the shape of the described filler that contains metal or metallic compound, can enumerate particle shape (comprising spherical, oval spherical), offset flat shape, column, needle-like (comprising square shape, dendroid) and indefinite shape etc.Those shapes can be used laser diffraction/diffuse transmission type particle size distribution analyzer or sweep electron microscope, and (scanning electronmicroscope SEM) confirms.
As the described filler that contains metal or metallic compound, preferably use aluminum nitride powder, alumina powder, and the oxide powder and zinc of needle-like (particularly square shape (tetrapot)).
With aluminium nitride Comparatively speaking, the thermal conductivity of zinc oxide is lower, but if use the oxide powder and zinc of square shape, then obtains exothermic character than the more excellent heat release member of situation that uses particle shape oxide powder and zinc.And, by the oxide powder and zinc that uses square shape, can be owing to deciding the generation that the anchor effect lowers the splitting of described metal level and graphite linings.
And, with aluminium nitride or zinc oxide Comparatively speaking, the thermal conductivity of aluminium oxide is low, but chemical stabilization, react owing to water or acid or is dissolved in water or the acid, so can obtain to have the heat release member of high-weatherability.
If use aluminum nitride powder as the described filler that contains metal or metallic compound, then can obtain the more excellent heat release member of exothermic character.
As long as the average diameter of the primary particle of the described filler that contains metal or metallic compound is the selections that suit such as the size of the heat release member that forms according to institute's desire, the thickness of following layer, aspects such as thermal conductivity on the lamination direction from described following layer in described laminate are considered, preferably 0.001 μ m～30 μ m, more preferably 0.01 μ m～20 μ m.The average diameter that contains the filler of metal or metallic compound can be used laser diffraction/diffuse transmission type particle size distribution analyzer or sweep electron microscope, and (scanning electronmicroscope SEM) waits and confirms.
In addition, what is called contains the average diameter of the filler of metal or metallic compound, when being emboliform situation, this filler refers to the diameter (when the spherical situation of ellipse, being the length of major axis) of particle, when being the situation of flat, this filler refers to the limit grown most, referring in the length of diameter of a circle (long axis of ellipse) or post the long side of person arbitrarily when this filler is the situation of column, is the length of pointer when this filler is the situation of needle-like.
The described filler that comprises material with carbon element can be enumerated graphite powder (native graphite, Delanium, exapnsion graphite, Ketjen black (Ketjen Black)), CNT, bortz powder, carbon fiber and fullerene etc., consider preferably graphite powder, CNT and bortz powder in those from aspects such as thermal conductivity excellences.
As long as the average diameter of the primary particle of the described filler that comprises material with carbon element is the selections that suit such as the size of the heat release member that forms according to institute's desire, the thickness of following layer, the aspects such as thermal conductivity on the lamination direction of described laminate from described following layer are considered, preferably 0.001 μ m～20 μ m, more preferably 0.002 μ m～10 μ m.The average diameter that comprises the filler of material with carbon element can be used laser diffraction/diffuse transmission type particle size distribution analyzer or sweep electron microscope, and (scanning electron microscope SEM) waits and confirms.
In addition, the average diameter of CNT or carbon fiber is the length of vial or fiber.
Described thermal conductivity filler can directly use average diameter or shape to be in commercially available product in the desired scope, also can use to commercially available product pulverize, classification, heating etc. make its average diameter or shape become the desired scope person of forming.
In addition, the average diameter of described thermal conductivity filler or shape can change in the manufacture process of heat release member of the present invention, but as long as the filler that allotment has described average diameter or shape in described constituent.
As described thermal conductivity filler, can directly use surface-treated commercially available products such as having carried out dispersion treatment, water-proofing treatment, also can use from this commercially available product and remove the surface conditioning agent person of forming.And, also can not use carrying out the surface-treated commercially available product to carry out surface treatment.
Particularly aluminium nitride and magnesia are easily because airborne moisture and therefore deterioration it is desirable to use carry out water-proofing treatment person.
As described thermal conductivity filler, can use above-mentioned filler separately, also can will also use more than 2 kinds.
As the allotment amount of described thermal conductivity filler, for following layer 100vol%, preferably 1vol%～80vol%, 2vol%～40vol% more preferably, further 2vol%～30vol% more preferably.
If in following layer, contain described thermal conductivity filler with described amount, then keep then property, and the raising of the thermal conductivity of following layer, therefore preferable.
If the allotment amount of described thermal conductivity filler is below the upper limit of described scope, then obtain the then high following layer of intensity to metal level or graphite linings; If the allotment amount of described thermal conductivity filler is more than the lower limit of described scope, then obtain the high following layer of thermal conductivity, therefore preferable.
[additive]
As described additive, then there is no particular restriction if do not undermine effect of the present invention, can enumerate thermosetting resins such as antioxidant, silane coupling agent, epoxy resin, curing agent, copper inhibitor, matal deactivator, antirust agent, tackifiers, age resister, defoamer, antistatic agent, weather resisting agent etc.
For example, preferably add as copper inhibitor or matal deactivator cited in the Japanese patent laid-open 5-48265 communique during situation of deterioration in the resin that forms following layer because with contacting of metal; In order to improve the connecting airtight property of thermal conductivity filler and polyvinyl acetal resin, preferably add silane coupling agent; For the hear resistance (glass transition temperature) that improves following layer, preferably add epoxy resin.
As described silane coupling agent, the preferably silane coupling agent (commodity are called S330, S510, S520, S530) made of JNC limited company etc.
Consider from the aspects such as connecting airtight property that can improve following layer and metal level, the addition of described silane coupling agent for total amount 100 weight portions of resin contained in the following layer, preferably 1 weight portion～10 weight portions.
Described epoxy resin is jER828, jER827, jER806, jER807, jER4004P, jER152, the jER154 of the manufacturing of Mitsubishi Chemical limited company preferably; Celloxide 2021P, Celloxide3000 that Daicel (DAICEL) limited company makes; The YH-434 that chemistry limited company of Nippon Steel makes; EPPN-201, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027, DPPN-503, DPPN-502H, DPPN-501H, NC6000 and EPPN-202 that Japan chemical drug limited company makes; The DD-503 that Ai Dike (ADEKA) limited company makes; The RicaresinW-100 that new Japanese physics and chemistry limited company makes etc.
Consider the addition of described epoxy resin preferably 1wt%～49wt% for the total amount 100wt% of resin contained in the following layer from the aspects such as glass transition temperature that improve following layer.
When adding described epoxy resin, preferably further add curing agent.Described curing agent preferably amine is that curing agent, phenol are that curing agent, phenol are that novolaks are that curing agent, imidazoles are curing agent etc.
The polyvinyl acetal resin of described formation following layer has been convenient to middle uses such as enamel-covered wire since previous, it is the resin that is difficult to Metal Contact deterioration or is difficult to make the metal deterioration, but under the many wet environments of high temperature, use in the situation etc. of heat release member, also can add copper inhibitor or matal deactivator.Described copper inhibitor is Mark ZS-27, the Mark CDA-16 of the manufacturing of Ai Dike limited company preferably; The SANKO-EPOCLEAN that three photochemistry Industries, Incs make; The IrganoxMD1024 that BASF (BASF) company makes etc.
Consider the addition of described copper inhibitor preferably 0.1 weight portion～3 weight portions for total amount 100 weight portions of resin contained in the following layer from the aspects such as resin deterioration of the part that can prevent following layer and Metal Contact.
[solvent]
As described solvent, if then there is no particular restriction for the described polyvinyl acetal resin of solubilized person, the solvent that preferably can disperse the thermal conductivity filler can be enumerated pure series solvents such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, second butanols, n-octyl alcohol, DAA, phenmethylol; Sai Lusu series solvents such as methyl Sai Lusu (cellosolve), ethyl Sai Lusu, butyl Sai Lusu; Ketone series solvents such as acetone, butanone, cyclohexanone, cyclopentanone, isophorone; N, N-dimethylacetylamide, N, dinethylformamide, 1-methyl-acid amides series solvents such as 2-Pyrrolizidine ketone; Ester such as methyl acetate, ethyl acetate series solvent; Ether such as dioxanes, oxolane series solvent; Chlorinated hydrocabon such as carrene, chloroform series solvent; Aromatic series such as toluene, pyridine series solvent; Dimethyl sulfoxide (DMSO); Acetic acid; Rosin spirit (terpineol); BC; Acetate of butyl carbitol etc.
Those solvents can use separately, also can be also with more than 2 kinds.
Consider from aspects such as the property easy to manufacture of heat release member and exothermic characters, preferably with the resin concentration in the constituent become preferably 3 quality %～30 quality %, more preferably 5 quality %～20 quality % amount and use described solvent.
[rerum natura of following layer etc.]
Described following layer is in the thermal conductivity of the lamination direction of described laminate preferably 0.05W/mK～50W/mK, more preferably 0.1W/mK～20W/mK.
Be in the described scope by the thermal conductivity that makes following layer, can obtain exothermicity, the then heat release member of property excellence.
If the thermal conductivity of following layer is below the upper limit of described scope, the adhesion height of described metal level and graphite linings then obtains the heat release member of mechanical strength and excellent in te pins of durability, so preferable.On the other hand, if the thermal conductivity of following layer is more than the lower limit of described scope, then obtain the heat release member of exothermicity excellence, therefore preferable.
Described following layer in the thermal conductivity of the lamination direction of laminate can according to or xenon quick by laser fast (laser flash/Xenon flash) thermal diffusivity determinator and gained thermal diffusivity, by differential scanning calorimetry device (differential scanningcalorimeter, DSC) and the specific heat of gained, by Archimedes' principle gained density etc. and calculate.
There is no particular restriction for the thickness of described following layer, if have the thickness that described metal level and graphite linings are followed as far as possible, then in lowering aspect consideration such as thermal resistance, preferably thin as far as possible thickness, 0.05 μ m～10 μ m more preferably, further 0.1 μ m～7 μ m more preferably.
Owing to the following layer of heat release member of the present invention is formed by the constituent that comprises the polyvinyl acetal resin, even therefore the thickness of this following layer is that the following thickness of 1 μ m also can be followed metal level and graphite linings.
In addition, the thickness of so-called described following layer refers to metal level that the metal level that joins with the single face of 1 layer of following layer or graphite linings, the face opposite with the metal level of this following layer or face that graphite linings is joined join or the thickness between the graphite linings.Wherein, when the situation used as Fig. 2 or graphite linings shown in Figure 3, also refer to the thickness between metal level and/or the graphite linings, do not comprise the hole of this graphite linings or slit portion the thickness of the following layer that can fill.
And, in the described following layer the thermal conductivity filler that can comprise exist and thrust to the situation of graphite linings etc., even but when this situation, the thickness of following layer also refers to not consider to thrust to the metal level of the filler part of graphite linings and/or the thickness between the graphite linings.
＜metal level 〉
Described metal level is the lamination person in order to thermal capacity, mechanical strength and the processability etc. that improve the discharge member.
Described metal level preferably comprises the layer of the metal of excellent thermal conductivity, more preferably enumerate the layer of alloy that comprises gold, silver, copper, aluminium, nickel and contain those any at least a kind of metal, further more preferably enumerate the layer of alloy that comprises silver, copper, aluminium, nickel and contain those any at least a kind of metal, special good is to enumerate the layer that comprises the a kind of metal that is selected from the group that is made of following metal: copper, aluminium and contain the alloy of those any at least a kind of metal.
Described alloy can be the free position of solid solution, eutectic or intermetallic compound.
Described alloy particularly can be enumerated phosphor bronze, copper nickel, duralumin (duralumin) etc.
There is no particular restriction for described metal layer thickness, the suitable selection as long as consider the purposes, weight, thermal conductivity etc. of the discharge member of gained, preferably 0.01 of graphite linings times～100 times thickness, more preferably 0.1 times～10 times thickness.If metal layer thickness is in the described scope, then can obtain the heat release member of exothermic character, mechanical strength excellence.
＜graphite linings 〉
Described graphite linings has big thermal conductivity, and is light and be rich in flexibility.By using this kind graphite linings, can obtain the heat release member of exothermic character excellence, light weight.
Then there is no particular restriction if described graphite linings comprises the layer of graphite, for example can use that the producer also can use commercially available product by the Japan Patent spy opens the method for putting down in writing in clear 61-275117 communique and the Japanese patent laid-open 11-21117 communique.
As commercially available product, eGRAF SPREADERSHIELD SS-1500 (Ge Lafu science and technology international (GrafTECH International) is made), GRAPHINITY (manufacturing of Japanese Zhong Yuan (Kaneka) limited company), PGS graphite flake (manufacturing of limited company of Panasonic (Panasonic)) etc. can be enumerated by the electrographite thin slice of synthetic resin thin slice manufacturing, eGRAF SPREADERSHIELD SS-500 (GrafTECH International manufacturing) etc. can be enumerated by the natural graphite flake of native graphite manufacturing.
Described graphite linings is with respect to the lamination direction of described laminate and the thermal conductivity of the direction of approximate vertical preferably 250W/mK～2000W/mK, more preferably 500W/mK～2000W/mK.Be in described scope by the thermal conductivity that makes graphite linings, can obtain the heat release member of exothermicity, thermal uniformity excellence.
Described graphite linings with respect to the lamination direction of laminate and the thermal conductivity of the direction of approximate vertical can be respectively by laser fast or xenon Rapid Thermal diffusivity determinator, DSC and Archimedes' principle and measure thermal diffusivity, specific heat, density, by those being multiplied each other and measuring.
There is no particular restriction for the thickness of described graphite linings, in order to obtain the heat release member of exothermic character excellence, and preferably thick layer, 15 μ m～600 μ m more preferably, further 15 μ m～500 μ m more preferably, that special good is 20 μ m～300 μ m.
＜resin bed 〉
Heat release member of the present invention also can have resin bed in its outermost single or double for anti-oxidant or raising design.
If described resin bed comprise resin the layer then there is no particular restriction, this resin for example can enumerate as coating and widely used acrylic resin, epoxy resin, alkyd resins, amine ester resin, nitrocellulose it is desirable to have stable on heating resin in those.
As the commercially available product of the coating that comprises described resin, can enumerate heat-resisting paint (the heat-resisting paint OneTouch that this (OKITSUMO) limited company that rubs of figured woven silk material difficult to understand makes) etc.
Described resin bed also can comprise described thermal conductivity filler or the high filler of far infrared irradiation rate in order to give the heat release ability by the heat release component surface due to the far infrared irradiation.
As the high filler of described far infrared irradiation rate, there is no particular restriction, for example it is desirable to be selected from by mineral such as cordierite, mullites; Boron nitride, aluminum nitride and other nitride; Oxides such as silica, aluminium oxide, zinc oxide, magnesia; Carborundum; And at least a kind of filler of the group that constitutes of graphite.
The kind of employed resin in the described resin bed, the selection that suit gets final product according to the serviceability temperature of heat release member, method when forming resin bed or temperature.
And, as the kind of employed filler in the described resin bed, suit to select high filler and/or the high filler of far infrared irradiation rate of thermal conductivity to get final product according to the purposes of using the heat release member.
The formation of＜heat release member etc. 〉
Heat release member of the present invention is if comprise described laminate then there is no particular restriction, can be on the graphite linings of described laminate via described following layer mutual lamination the laminate of a plurality of metal levels and graphite linings is arranged or on the graphite linings of described laminate via described following layer in any order lamination the laminate of a plurality of metal levels and/or graphite linings is arranged.
When using the situation of a plurality of metal levels, graphite linings or following layer, those layers can be respectively same layer, also can be different layers, preferably use same layer.And, the thickness of those layers can be identical also can be different.
As the order of lamination, suit to select to get final product according to desired purposes, particularly consider desired exothermic character or design, corrosion resistance etc. and select to get final product.
As described lamination number, suit to select to get final product according to desired purposes, particularly consider the size of heat release member or exothermic character etc. and select to get final product.
Consider that from the aspects such as heat release member that obtain mechanical strength and excellent in workability preferably the outermost layer of heat release member of the present invention is metal level.
And, when using the situation of heat release member of the present invention with aspect shown in Figure 1, also can become big shape, for example sword mountain shape or snake abdomen shape by being made as surface area apart from the shape of the side of not joining with following layer of heater 7 layer (in Fig. 1 for metal level 6) farthest, and make the area increase that contacts with ambient atmos apart from the opposite face of the face that joins with following layer of heater 7 layer farthest.
Consider that from the aspect that exothermic character, mechanical strength, light weight and property easy to manufacture etc. are excellent heat release member of the present invention is as shown in Figure 1 laminate 1 preferably, its in regular turn lamination metal level 2, following layer 3, graphite linings 4, following layer 5 and metal level 6 are arranged.
In addition, when manufacturing comprises the situation of heat release member of laminate shown in Figure 11 that is in being situated between according to desired purposes, particularly desire manufacturing every the metal level of graphite linings 4 each other during the situation of the laminate that then intensity is high of (2 and 6), following layer 3 and following layer 5 also can directly join.As this kind example, can enumerate as shown in Figure 2 the graphite linings that is provided with hole 84 of use ' or the graphite linings that is provided with slit 94 as shown in Figure 3 " method.
As shape, quantity or the size of described hole or slit, consider from aspects such as the mechanical strength of heat release member and exothermic characters and suitable the selection gets final product.
When use is provided with the situation of graphite linings of hole or slit, for example with the situation that there is no this hole or slit Comparatively speaking, on metal level or graphite linings, form following layer than heavy back, temperature when setting applying than the highland, make following layer be formed into branch when adding thermo-compressed etc. by this and flow in hole or the slit, thus can be in the hole or slit portion fill this following layer and form composition.And, also can use dispenser (dispenser) etc. in advance and form on the metal level following layer with the part of the slit of graphite linings or hole butt than heavy back.
And, by using the littler graphite linings 4 of size than metal level 2 and metal level 6 (lengthwise of layer and grow crosswise), following layer 3 and following layer 5 are directly joined, but the high heat release member of manufacturing machine intensity.
Described resin bed is formed directly on metal level or the graphite linings, also can be formed on metal level or the graphite linings via described following layer.
In addition, during with situation that heater contacts, must adhere to heat conduction lubricating grease or bond plies band in heat release member of the present invention in this contact site, therefore preferably there is no described resin bed in this contact site.
The manufacture method of＜heat release member 〉
Heat release member of the present invention can be made by following mode: described constituent is coated the metallic plate of described formation metal level or form on the graphite cake of graphite linings, optionally carry out predrying after, mode with metallic plate and this constituent of graphite cake clamping is configured, and one side is exerted pressure and simultaneously heated.And when making described heat release member, the aspects such as heat release member that then intensity is high that obtain metal level and graphite linings certainly consider that preferably the both sides in metallic plate and graphite cake are coated with described constituent.
Before the described constituent of coating, consider from the aspects such as heat release member that then intensity is high that obtain metal level and graphite linings, metal level is preferably removed the oxide layer on surface in advance or cleaning by degreasing is carried out on the surface, and graphite linings preferably carries out easily then handling to the surface by oxygen electricity sizing device or strong acid treatment etc. in advance.
As the method that described constituent is applied on metallic plate or the graphite cake, there is no particular restriction, preferably uses the wet type rubbing method that can be coated with constituent equably.In the wet type rubbing method, preferably when forming the situation of the thin following layer of thickness, can form the spin-coating method of the film of homogeneous easily.When paying attention to productive situation, preferably intaglio printing rubbing method, mould are coated with method, rod and are coated with method, counter being coated with (reverse coat) method, rolling method, slot coated method, spraying process, engagement rubbing method, anti-engagement rubbing method, airblade coating method, curtain and are coated with method, rod rubbing method etc.
It is described that predrying there is no particular restriction, can be by under room temperature, leaving standstill about 1 day～7 days and carry out, and preferably by heating plate or drying oven etc., in the heating of carrying out under the temperature about 80 ℃～120 ℃ about 1 minute～10 minutes.
And, described predryingly in atmosphere, get final product, but also can under inert gas environments such as nitrogen or rare gas, carry out, also can under decompression, carry out.Particularly when the situation of high drying of following short time of temperature, preferably under inert gas environment, carry out.
Described one side is exerted pressure, and there is no particular restriction for the method that simultaneously heats, and pressure is 0.1MPa～30MPa preferably, and preferably 200 ℃～250 ℃ of heating-up temperatures heat preferably 1 minute～1 hour pressing time.And, calorify in the atmosphere and get final product, also can under inert gas environments such as nitrogen or rare gas, carry out, also can under decompression, carry out.When particularly under high temperature, carrying out the situation of short time heating, preferably in carrying out under the inert gas environment or under the decompression.
The heat release member that has resin bed in outermost single or double also can be made by following mode: be coated with the coating that comprises resin in the outermost metal level of described heat release member or the single or double of graphite linings, optionally make its drying, make this coating sclerosis thereafter.And, also can make by following mode: be pre-formed resin-made membrane, be coated with described constituent in the outermost metal level of described heat release member or the single or double of graphite linings, optionally carry out predrying after, resin-made membrane is contacted with this coated face, optionally exert pressure, heat etc.
The purposes of heat release member
Heat release member of the present invention (laminate) comprises the then following layer of excellent strength, thin thickness of metal level and graphite linings.And, when in described following layer, comprising the situation of thermal conductivity filler, in the thermal conductivity height of approximate vertical direction for the lamination direction, even and whole thin thickness, also have exothermic character same with the thick heat liberation board of previous thickness or more than it.And, excellent in workability such as cut-out, boring, the demoulding, the bending but the adhesion of metal level and graphite linings is strong.Therefore, heat release member of the present invention can use in various uses, particularly can use aptly in electronic component or battery.
And, heat release member of the present invention also can suit as LCD or organic EL illumination in order to prevent the soaking plate of color spot.
As heat release member of the present invention in electronic component etc., make use-case, as Fig. 1 or use so that the mode that heat release member of the present invention (laminate) 1 and heater 7 in the electronic component join is configured as shown in Figure 4 and get final product.
Fig. 1 be expression with heat release member of the present invention (laminate) 1, generally perpendicularly be configured the sectional skeleton diagram of an example of the electronic component that forms with the face of the lamination direction of this laminate and heater 7.
By disposing heat release member 1 of the present invention as described above, can make heat to direction (transverse direction) diffusion of approximate vertical for the lamination direction of this heat release member (laminate), relax near the temperature of thermal source and rise.
And, Fig. 4 be expression so that heat release member 1 half-twist as shown in Figure 1, the sectional skeleton diagram of an example of the mode of joining with heater 7 and the electronic component that disposes.
By disposing heat release member 1 of the present invention as described above, can make heat to direction (longitudinal direction) diffusion of approximate vertical for the lamination direction of this heat release member (laminate), relax near the temperature of thermal source and rise.
In addition, when disposing the situation of heat release member of the present invention as shown in Figure 4, also can use heat release member (laminate) is cut off the person of forming in the lamination direction of this heat release member.When disposing the situation of heat release member of the present invention as shown in Figure 4, the heat heat release rapidly (for example moving to cooling device) that spontaneous hot body 7 is sent, the temperature that therefore can suppress heater 7 effectively rises.
＜electronic component 〉
Described electronic component for example can be enumerated (Application Specific Integrated Circuit such as employed application specific IC in image processing or TV, the audio frequency etc., ASIC) CPU (the CentralProcessing Unit of etc. wafer, PC, Smartphone etc., CPU), light-emittingdiode (Light Emitting Diode, LED) illumination etc.
[LED illumination]
With reference to Fig. 5 described LED illumination is illustrated.In addition, Fig. 5 is the sectional skeleton diagram of LED that mode that expression makes heat release member of the present invention contact with the back side of LED body to be situated between every heat conductive pad is configured one example of throwing light on.Particularly when using the very large LED of caloric value such as ultra-high brightness LED as the situation of described LED body, the use of the application's heat release member is effective.LED illumination in Fig. 5 comprises heat release member 10, heat conductive pad 11, dielectric film 12, LED body 13, electrode 14 and metal wiring 15.
The LED body 13 that converts electrical energy into luminous energy produces heat along with lighting, and this heat must be expelled to outside the LED body 13.This heat is conveyed to heat release member 10 of the present invention via heat conductive pad 11 from LED body 13, the heat release by this heat release member 10.
[battery]
Described battery can be recited in employed lithium rechargeable battery in automobile or the mobile phone etc., lithium-ion capacitor (Lithium ion capacitor), Ni-MH battery etc.
The module that described lithium-ion capacitor also can be a plurality of lithium-ion capacitors unit tandem or is formed by connecting side by side.
When this situation, the mode that heat release member of the present invention can join with the part of the outer surface of module integral body or be configured in the mode that covers module integral body, the mode that can also join with the part of the outer surface of each lithium-ion capacitor unit or be configured in the mode that covers each unit.
[example]
Below, use-case is described in detail the present invention.But the present invention is not limited to the content put down in writing in the following example.
Employed material is as described below in the example of the present invention.
＜following layer resin 〉
" PVF-C1 ": vinyl-formal resin, JNC limited company make, Vinylec C (trade name)
" PVF-C2 ": vinyl-formal resin, JNC limited company make, Vinylec C (trade name)
" PVF-K ": vinyl-formal resin, JNC limited company make, Vinylec K (trade name)
" PVB ": polyvinyl butyral resin, electrochemical Industries, Inc make, Denka Butyral 3000-K (trade name)
" epoxy ": epoxy resin, Mitsubishi Chemical limited company make, jER828 (trade name)
" terpenes-phenol ": terpene-phenol resin, Yasuhara Chemical Co., Ltd. (YASUHARA CHEMICAL CO., LTD.) manufacturing, YSPOLYSTER T160 (trade name)
" acrylic acid series ": acrylic acid series solid, emerging plastic cement limited company make, Acryl Dine B (trade name)
Record described " PVF-C1 ", " PVF-C2 " reach the structure transitivity of " PVF-K " in following table 1.
[table 1]
＜solvent 〉
1-methyl-2-Pyrrolizidine ketone: and the pure pharmaceutical worker's industry of light limited company makes and the light superfine
Cyclopentanone: and the pure pharmaceutical worker's industry of light limited company makes and the light one-level
＜thermal conductivity filler 〉
Oxide powder and zinc: safe and sound gram (AMTEC) limited company makes, Pana-TetraWZ-0511 (trade name, square shape, average diameter (length of pin): about 10 μ m)
Aluminum nitride powder: chemistry limited company in moral mountain makes, aluminium nitride H level (trade name, particle shape, average diameter (Al): 1 μ m)
Alumina powder: clear and electrician limited company makes, aluminium oxide (low sodium) AL-47-H (trade name, particle shape, average diameter: 2.1 μ m)
Nano-diamond powder: card ripple Dien (CARBODEON) is made, BLENDNUEVO (trade name, particle shape, average diameter: 0.004～0.006 μ m)
Aluminium powder: Ni La can (The Nilaco Corporation) makes, aluminium powder (particle shape, average diameter: 30 μ m)
＜graphite flake 〉
Graphite flake (electrographite): GrafTECH International manufacturing, SS-1500 (trade name), thickness are 25 μ the m, (thermal conductivity of the face direction of thin slice: 1500W/mK)
Graphite flake (electrographite): GrafTECH International manufacturing, SS-1500 (trade name), thickness are 40 μ the m, (thermal conductivity of the face direction of thin slice: 1500W/mK)
Graphite flake (native graphite): GrafTECH International manufacturing, SS-500 (trade name), thickness are 76 μ the m, (thermal conductivity of the face direction of thin slice: 500W/mK)
Graphite flake (electrographite) with the acrylic acid series sticker: Japanese Zhong Yuan (Kaneka) limited company makes, is provided with in the single face of GRAPHINITY (thickness is 25 μ m) thin slice of the layer (thickness is 12 μ m) that comprises the acrylic acid series sticker
Graphite flake (electrographite) with the silicone-based sticker: Kaneka limited company makes, is provided with in the single face of GRAPHINITY (thickness is 25 μ m) thin slice of the layer (thickness is 40 μ m) that comprises the silicone-based sticker
The PGS graphite flake: the manufacturing of limited company of Panasonic, EYG-S091203, thickness are 25 μ the m, (thermal conductivity of the face direction of thin slice: 1600W/mK)
＜metallic plate 〉
Copper coin: The Nilaco Corporation makes, thickness is 0.1mm
Copper coin: The Nilaco Corporation makes, thickness is 0.2mm
Copper coin: The Nilaco Corporation makes, thickness is 0.4mm
Copper Foil: The Nilaco Corporation makes, thickness is 0.03mm
Copper Foil: The Nilaco Corporation makes, thickness is 0.05mm
The printed substrate electrolytic copper foil: mining industry limited company of Mitsui Metal Co., Ltd. makes, thickness is 0.012mm
The printed substrate electrolytic copper foil: paper tinsel powder Industries, Inc of FUKUDA METAL makes, thickness is 0.018mm
Silver foil: The Nilaco Corporation makes, thickness is 0.03mm
Aluminium sheet: aluminium sheet, The Nilaco Corporation make, thickness is 0.1mm
Aluminium foil: The Nilaco Corporation makes, thickness is 0.03mm
Aluminium foil: aluminium foil limited company in the East Sea makes, thickness is 0.02mm
Corronil (copper-nickel alloy) paper tinsel: The Nilaco Corporation makes, thickness is 0.03mm
The phosphor bronze paper tinsel: The Nilaco Corporation makes, thickness is 0.03mm
＜resin bed resin 〉
" heat-resisting paint ": beautiful Si Mo difficult to understand limited company makes, heat-resisting paint OneTouch (trade name)
" epoxy ": epoxy resin, Mitsubishi Chemical limited company make, jER828 (trade name)
" clear lacquer (clear lacquer) ": clear lacquer, Northwest coating limited company make, SELVA 26 (trade name)
" PMMA ": methylmethacrylate polymer, three limited companies of plumage research institute make, MA-830-M50 (trade name)
＜resin bed filler 〉
The cordierite powder: ball must glaze limited company (Marusu Glaze Co., Ltd.) manufacturing, synthesis of dichroite SS-1000 (average grain diameter 1.7 μ m)
Alumina powder: clear and electrician limited company makes, aluminium oxide (low sodium) AL-47-H (trade name, particle shape, average diameter: 2.1 μ m)
Carborundum powder: carborundum, the Ao Ruiqi of Sigma (Sigma-Aldrich Japan K.K.) company make, 200 orders～450 orders
Magnesia powder: magnesia, Northeast chemistry limited company make, the deer superfine
The evaluation of＜thermal conductivity 〉
Obtain thermal diffusivity and the thermal conductivity of the direction perpendicular to the plate face (the lamination direction of laminate) of the heat release member of gained as described below.With the heat release member of gained in following example 1～example 13 and the comparative example 1～comparative example 3 cut out into the square of about 9.8mm dull and stereotyped, after will two-sidedly carrying out application with carbon spray (carbon spray) (DGF that Japanese marine tool Co., Ltd makes), be placed on the sample fixer of LFA-447 type xenon Rapid Thermal diffusivity determinator of anti-speeding (NETZSCH) company manufacturing.After this sample fixer becomes 25 ℃, this heat release member of laying is shone with the intensity of regulation with xenon lamp, mensuration changed from the time of the heat emission intensity of the face opposite with the light irradiation face of this heat release member, resolved by attached software, obtained thermal diffusivity therefrom.Condition determinations such as detector gain are made as automatically, as for parsing, in order to estimate the comprehensive hot rerum natura of heat release member, are made as 1 laminate and calculate.
In addition, the specific heat (measuring by the diamond DSC type input offset type differential scanning calorimetry device that Pa Jinaierma (PerkinElmer) limited company makes) of obtaining the heat release member and proportion are (by (the AlfaMirage Co. of Alpha's mirage limited company, Ltd.) the MD-300s type electronics densimeter of Zhi Zaoing and measure), obtain thermal conductivity by the formula of thermal conductivity=thermal diffusivity * specific heat * proportion.Thermal diffusivity and the thermal conductivity of the heat release member of gained in following example 1～example 13 and the comparative example 1～comparative example 3 are shown in Table 2.
When the situation of stack-up type heat release member, the heat conduction of the direction of approximate vertical is subjected to the domination of the ratio of the high layer of thermal conductivity for the lamination direction of laminate, therefore be not subjected to the big influence of preparation method of heat release member, and obtain the performance shown in design basically.On the contrary, the attenuating of the thermal resistance of the lamination direction of the laminate in the interface of each layer exists with ... the thermal resistance at interface of each layer and the thermal resistance of following layer largely, preferably with its attenuating.That is the thermal conductivity of the lamination direction of laminate is more high, we can say more that then metal level and graphite linings can follow, also be high performance heat release member well.
The evaluation of＜exothermic character 〉
The single face of the heat release member of gained in following example 14～example 37, the mode that becomes about 20 μ m with the thickness of filming spray heat-resisting paint (the heat-resisting paint OneTouch that beautiful Si Mo difficult to understand limited company makes), make its drying.Use two-sided tape (the thermal conductivity solid transfer printing adhesive tape No.9885 that 3M limited company in Sumitomo makes) that the side of the face of the not application heat-resisting paint of this heat release member and the transistor (2SD2013 that limited company of Toshiba makes) of T0220 encapsulation are fitted.In the transistorized back side that is fitted with the face of heat release member K thermocouple (ST-50 that physics and chemistry Industries, Inc makes) is installed, serviceability temperature data recorder (day GL220 that figure (GRAPHTEC) limited company makes), available PC record is transistorized to be fitted with the temperature of opposite sides of the face of heat release member.The transistor that this thermocouple is installed is statically placed in the thermostat central authorities that are set at 40 ℃, confirm transistorized temperature be 40 ℃ become fixing after, use the DC stabilization power supply that transistor is applied 1.0V, measure surface temperature change.Mensuration applies voltage after 1000 seconds or the transistorized temperature after 3000 seconds.Show the result in table 3 or the table 4.
Transistor is if applying identical wattage then produces fixing heat, and therefore the more high then temperature of exothermal effect of the heat release member of installing more reduces.That is transistorized temperature is more low, then more we can say the exothermal effect height of heat release member.
In addition, 9～comparative example 11 as a comparative example, and the copper coin that used thickness is respectively 0.2mm, 0.4mm and 0.05mm replaces described heat release member, similarly carry out in addition and measure applying voltage after 1000 seconds and the transistorized temperature after 3000 seconds.Show the result in the table 3.
＜then the evaluation of property 〉
The then intensity of the metal level of the heat release member of gained and graphite linings in 1～example 25 and the comparative example 1～comparative example 8 as an example because graphite linings has the characteristic of splitting (peeling off) in layer, therefore is difficult to the numerical value such as tension load when peeling off and obtains.Therefore by the metal of the heat release member of made in the example is partly peeled off, the state of visualization metal level inner surface and estimating.Be evaluated as ◎ during situation that graphite that the surperficial integral body of the metal level of peeling off is split covers, be evaluated as zero when only exposing the situation of a little metal level or following layer, be evaluated as △ when exposing the situation of metal level more than 1/4 or following layer, be not evaluated as when almost or fully having the residual situation of graphite *.Show the result in table 2 or the table 3.
[example 1]
In the there-necked flask of 200ml, put into 1-methyl-2-Pyrrolizidine ketone (NMP) 80g, lay the stirring vane of fluororesin system from top, make the stirring vane rotation by motor.According to the viscosity of solution and the timely adjustment rotating speed.Use the funnel of glass system and in this flask, drop into vinyl-formal resin (PVF-C1) 10g.After will being attached to PVF-C1 flushing on the funnel by the NMP of 20g, take out funnel, cover glass cover.The solution of gained one side in being set at 80 ℃ water-bath is stirred 4 hours one sides heat, PVF-C1 is dissolved among the NMP fully.Flask after stirring is taken out in water-bath, return to room temperature after, use dry funnel and drop into the 10g oxide powder and zinc as the thermal conductivity filler, stir a night, obtain solid (constituent) therefrom.
The mode that becomes 4 μ m with the thickness of the following layer of gained use spin coater (the 1H-D3 type that three large bamboo hats with a conical crown and broad brim (Mikasa) limited company makes) and with 1500 rev/mins with this solid coat size as 50mm * 50mm, thickness as after on the copper coin of 0.1mm, in being set on 80 ℃ the heating plate, carrying out 3 minutes predrying with 80 ℃, obtain with the copper coin of then filming.In addition, when coating solid on the copper coin, gather solid and be coated with in the mode of 2 times big particles of not being coated with drag and being precipitated.
Should be with the copper coin of then filming by 2 pieces, making the thickness that is cut to 50mm * 50mm in advance for the inboard clamping of then filming is the graphite flake (SS-1500) of 25 μ m, is statically placed on the hot plate of small-sized heating press (well unit makes the manual press of the small-sized heating of IMC-19EC type of manufacturing).One side is noted 2 pieces of copper coins and graphite flake are not departed from, and one side is carried out several pressurization repeatedly and reduced pressure, making by this then films outgas after, be forced into 6MPa., by heater hot plate be heated to 220 ℃, keep 30 minutes temperature and pressure thereafter.After through 30 minutes, under the state that keep-ups pressure, disconnect the power supply of heater, naturally cool to about 50 ℃.After cooling, release pressure and obtain the heat release member.In addition, the thickness of heat release member integral body is deducted the thickness of the thickness of 2 pieces of metallic plates and graphite flake and 1/2 thickness as following layer of the value of gained.Measure the thickness of heat release member by the digital type scale ID-C112CXB of three rich limited companies manufacturing.
[comparative example 1]
In example 1, the copper coin that is pasted with thermal conductivity solid transfer printing adhesive tape No.9882 (thickness is 50 μ m) that uses Sumitomo 3M limited company to make replaces with the copper coin of then filming, and similarly carries out with example 1 in addition and obtains the heat release member.
[example 2～example 11, example 13～example 15, example 17～example 24 and comparative example 4～comparative example 8]
In example 1, shown in table 2～table 3, change kind and the thickness of metallic plate and graphite flake like that, and use and shown in table 2～table 3, change the kind of resin, the kind (having or not) of thermal conductivity filler or the solid of content like that, shown in table 2～table 3, change the thickness of following layer like that, similarly carry out with example 1 in addition and obtain the heat release member.
In following table, the thickness of the heat release member that will measure from the digital type scale ID-C112CXB that makes by three rich limited companies deduct the thickness of the thickness of 2 pieces of metallic plates and graphite flake and the situation of the value less than 1 of gained, be recited as below the determination limit.
In addition, in the heat release member of gained, by the section of this heat release member of sem observation, the result is that the thickness of following layer exists deviation according to the position, is about 0.3 μ m～0.5 μ m in example 9.
[example 12]
In example 1, use the such kind of thermal conductivity filler and solid of content of changing as shown in table 2, by the method same with example 1, it is that 50mm * 50mm, thickness are on the copper coin of 0.2mm that the mode that becomes 1 μ m with the thickness of following layer is coated size, by obtaining with the copper coin of then filming with the same method of example 1.
This had the copper coin of then filming, be that the mode that the graphite flake (SS-1500) of 25 μ m joins is configured then to film with thickness, be statically placed on the hot plate of small-sized heating press (well unit makes the manual press of the small-sized heating of IMC-19EC type of manufacturing).One side is noted copper coin and graphite flake are not departed from, and one side is carried out several pressurization and decompression repeatedly, making by this then films outgas after, pressurize, maintenance is 120 minutes under room temperature, 6MPa, obtains the heat release member by this.
In addition, the thickness of following layer is that the thickness of heat release member integral body deducts the thickness of the thickness of metallic plate and graphite flake and the value of gained.Measure the thickness of heat release member by the digital type scale ID-C112CXB of three rich limited companies manufacturing.
[comparative example 2 and comparative example 3]
In example 12, use the graphite flake of having the acrylic acid series sticker or the graphite flake of having the silicone-based sticker to replace solid and graphite flake (SS-1500) respectively, the copper coin put down in writing in the table 2 is configured in the mode that the sticker with described graphite flake with sticker joins, similarly carries out with example 12 in addition and obtain the heat release member.And, similarly carry out with example 12 and measure the thickness of following layer.
[example 16]
In example 1, such content that changes the thermal conductivity filler as shown in table 3 similarly carries out with example 1 in addition and modulates solid.
Become the mode of 1 μ m with the thickness of following layer, this solid is coated on the single face of the graphite flake that thickness is 25 μ m (SS-1500), in addition by being coated with the same method of example 1, carry out predryingly, obtain with the graphite flake of then filming by this.
This had the graphite flake of then filming, be that the mode that the graphite flake (SS-1500) of 25 μ m joins is configured then to film with thickness, be statically placed on the hot plate of small-sized heating press (well unit makes the manual press of the small-sized heating of IMC-19EC type of manufacturing).One side is noted 2 pieces of graphite flakes are not departed from, and one side is carried out several pressurization and decompression repeatedly, making the degassing of then filming by this after, pressurize, and maintenance 120 minutes under room temperature, 6MPa obtains the laminate that lamination has 2 pieces of graphite flakes by this.
In example 1, use the laminate of gained to replace graphite flake, similarly carry out with example 1 in addition and obtain the heat release member.That is acquisition has the heat release member of the structure of copper coin/following layer/graphite flake/following layer/graphite flake/following layer/copper coin.
In addition, will deduct the thickness of the thickness of 2 pieces of copper coins and 2 pieces of graphite flakes from the thickness of heat release member integral body and 1/3 thickness as following layer of the value of gained.Measure the thickness of heat release member by the digital type scale ID-C112CXB of three rich limited companies manufacturing.
[example 25]
In example 1, such content that changes the thermal conductivity filler as shown in table 3 similarly carries out with example 1 in addition and obtains solid.
By the method same with example 1, become the mode of 1 μ m with the thickness of the following layer of gained, it is on the aluminium foil of 0.03mm for 50mm * 50mm, thickness that this solid is coated size, and become the mode of 1 μ m with the thickness of the following layer of gained, it is on the Copper Foil of 0.03mm for 50mm * 50mm, thickness that this solid is coated size, carry out predryingly, obtain respectively by this with the aluminium foil of then filming and with the Copper Foil of then filming.
Have aluminium foil and the Copper Foil of then filming by this, making the thickness that is cut to 50mm * 50mm in advance for the inboard clamping of then filming is the graphite flake (SS-1500) of 25 μ m, by the method same with example 1, one side is noted aluminium foil, Copper Foil and graphite flake are not departed from, and one side is carried out and obtained the heat release member.
In addition, in the evaluation of exothermic character, (the heat-resisting paint OneTouch that beautiful Si Mo difficult to understand limited company makes) sprays on aluminium foil in the mode that the thickness of filming becomes about 20 μ m with heat-resisting paint, makes its drying.Except using this heat release member, estimate exothermic character with above-mentioned similarly carrying out.
[example 26]
In example 1, do not use the thermal conductivity filler, use cyclopentanone to replace NMP, similarly carry out with example 1 in addition and obtain solid.Use the solid of gained, the such kind of metal level and thickness of following layer of changing as shown in table 4 similarly carries out with example 1 in addition and obtains the heat release member.
In addition, after example 26, when the evaluation of exothermic character, be not coated with heat-resisting paint.
[example 27]
The solid of gained in the use-case 26, the such kind of metallic plate and thickness of following layer of changing as shown in table 4 similarly carries out with example 1 in addition and obtains laminate.
Single face in the laminate of gained, the mode that becomes about 30 μ m with the thickness of filming is sprayed heat-resisting paint (the heat-resisting paint OneTouch that beautiful Si Mo difficult to understand limited company makes), makes it dry and be attained at the heat release member that is formed with resin bed on the described laminate.Use two-sided tape (the thermal conductivity solid transfer printing adhesive tape No.9885 that 3M limited company in Sumitomo makes) that the face (metal level) of the face opposition side that is formed with resin bed of this heat release member and the transistor of T0220 encapsulation (2SD2013 that limited company of Toshiba makes) are fitted, in addition with the evaluation of described＜exothermic character〉similarly carry out and estimate exothermic character.
[example 28]
Similarly carry out with example 27 and obtain laminate.
In NMP 90g, be dissolved with in the solution that epoxy resin (jER828) 10g forms, adding is the cordierite of 10wt% for resinous principle, the deaeration mixer ARE-250 type that uses new basic (Thinky) limited company to make, carry out 5 minutes stirring with the rotating speed of 2000rpm after, carry out 5 minutes deaeration with the rotating speed of 2000rpm, obtain heat release coating by this.Use spin coater (the 1H-D3 type that Mikasa limited company makes), become the mode of 0.03mm with the thickness of the resin bed of gained, after this coating being coated on one of them Copper Foil of described laminate, carry out 30 minutes heating in being set on 120 ℃ the heating plate, be attained at the heat release member that is formed with resin bed on the described laminate by this.
In addition, adjust the thickness of resin bed by the rotating speed of the resin concentration in the adjustment coating and spin coater.
[example 29～example 36]
Similarly carry out with example 27 and obtain laminate.
Use the laminate of gained, the such kind of the resin that forms resin bed and kind of filler of changing as shown in table 4, in addition with implement 28 and similarly carry out and be attained at the heat release member that is formed with resin bed on the laminate.
[example 37]
The solid of gained in the use-case 26, the such kind of metallic plate and graphite flake and thickness of following layer of changing as shown in table 4 similarly carries out with example 1 in addition and obtains laminate.
Use the laminate of gained, the such kind of the resin that forms resin bed and kind of filler of changing as shown in table 4, in addition with implement 28 and similarly carry out and be attained at the heat release member that is formed with resin bed on the laminate.
[research of thermal conductivity filler]
If thermal diffusivity and thermal conductivity to the heat release member of example 1～example 5 compare, then as can be known: with the heat release member of the example 2 of not allocating the thermal conductivity filler in the following layer Comparatively speaking, allotment has the thermal conductivity of heat release member of thermal conductivity filler higher in following layer.
With aluminium nitride Comparatively speaking, about little 1 bit digital of the thermal conductivity of zinc oxide, but if example 1 and example 3 are compared, the situation of the situation of allotment zinc oxide and allotment aluminium nitride in following layer then, the thermal conductivity of the heat release member of gained there is no larger difference.And, with the length of the needle-like of zinc oxide part Comparatively speaking, the thin thickness of following layer.Think that its reason is: the part of the pin that extends to the lamination direction of heat release member (laminate) in the acicular crystal of zinc oxide is thrust to graphite linings, because this part and efficient is conducted heat to graphite linings from metal level well.
Even the Nano diamond addition is few, equal exothermicity when also demonstrating with the situation of using other fillers.Think that its reason is: adamantine thermal conductivity and other thermal conductivity fillers are Comparatively speaking very high.The output of Nano diamond is few, but can use when particularly making the situation of high performance heat liberation board on a small quantity.
[research of heat filling addition]
If example 1 and example 6～example 8 are compared, then as can be known: the allotment amount of thermal conductivity filler is more many, and then thermal conductivity more uprises.But if the too much filler of interpolation, then therefore the tendency of the then intensity reduction of existence and metal level and graphite linings it is desirable to take into account thermal conductivity and the addition of following intensity.
[research of the kind of resin]
If example 1 and comparative example 1 are compared, then the heat release member that the heat release member of gained carries out lamination in the example 1 with using commercially available thermal conductivity solid transfer printing adhesive tape Comparatively speaking, the thermal conductivity height of the lamination direction of heat release member (laminate).
And as for the heat release member of gained in example 12, comparative example 2 and the comparative example 3, any heat release member all has the above then intensity of graphite linings splitting.When using the polyvinyl acetal resin as the situation of the kind of the resin of following layer, even the thickness of attenuate following layer also can keep then intensity, so the thermal conductivity of the lamination direction of the heat release member (laminate) of gained is the highest when using the polyvinyl acetal resin as the situation of the kind of the resin of following layer.Therefore as can be known: by using the polyvinyl acetal resin, Comparatively speaking be high performance heat release member in the time of can making with the situation of using commercially available solid.
If example 2, example 9～example 11 are compared with comparative example 4～comparative example 8, then as can be known: if use the polyvinyl acetal resin as the kind of the resin of following layer, then the heat release member of gained shows good then property.
The polyvinyl acetal resin is with respect to the then property excellence of metal level and graphite linings, but so attenuate following layer.Particularly as can be known: even when forming the situation of thinner following layer in using PVF-C2, the thermal conductivity of heat release member rise (example 9) also tremendously.
In addition, when using acrylic acid series solid or epoxy resin to form the situation of material as following layer, if the thickness of this following layer is 1 μ m, then can not follow metal level and graphite linings fully.
And, shown in example 25, when heat release member of the present invention comprises the situation of the metal level more than 2 layers, also can optionally use different metal levels.This kind heat release member for example also can use the aluminium lamination that is difficult to get rusty in opposite face, and obtain to take into account exothermic character and the heat release member that is difficult to get rusty by in using the good copper layer of thermal conductivity with contacted of heater.The exothermic character of this heat release member demonstrates only to be used Copper Foil as the exothermic character of the heat release member (example 19) of metallic plate and only uses aluminium foil as the characteristic of the centre of the exothermic character of the heat release member (example 20) of metallic plate.
[research of metal level]
In table 2, if example 15 and comparative example 9 are compared, then as can be known: even when not allocating the situation of thermal conductivity filler in following layer, Comparatively speaking exothermicity is also good for the copper coin thick with the 0.2mm of the roughly the same thickness of heat release member.And, if example 14 and comparative example 10 are compared, then as can be known: by allotment thermal conductivity filler in following layer, with the thick copper coin of 0.4mm of the thickness of 2 times of the thickness that is about the heat release member Comparatively speaking, it is good that the exothermicity of the heat release member of gained becomes.Therefore as can be known:, by using heat release member of the present invention, can obtain to have identical or its above exothermicity, and weight and thickness are half high-performance heat release member of copper.
[research of resin bed]
Heat release member of the present invention can be by comprise the thermal conductivity good filler identical with the user of institute in the following layer in the most surperficial setting, the high fillers of far infrared irradiation rate such as cordierite, mullite, silica, or the both sides' of those fillers heat release resin bed, further make the heat release ability.
In table 4, as can be known: with the heat release member of not resinous layer Comparatively speaking, the heat release member that contains resin bed can make transistorized temperature further reduce, that is the heat release ability improves.In addition we know: with contain by the heat release member of the formed resin bed of heat-resisting paint Comparatively speaking, the heat release ability of heat release member that contains the resin bed of fillers such as comprising cordierite, aluminium oxide, carborundum, magnesium further improves.
Claims (25)
1. heat release member, it comprises the laminate that via following layer lamination has metal level and graphite linings, and this following layer is formed by the constituent that comprises the polyvinyl acetal resin.
2. heat release member according to claim 1, wherein, described constituent further comprises the thermal conductivity filler.
3. heat release member according to claim 1, wherein, described polyvinyl acetal resin comprises following construction unit A, construction unit B and construction unit C,
[changing 1]
Among the construction unit A, R independently is hydrogen or alkyl
[changing 2]
[changing 3]
Construction unit C.
4. heat release member according to claim 3, wherein, described polyvinyl acetal resin further comprises following construction unit D,
[changing 4]
Among the construction unit D, R
1Independent is that hydrogen or carbon number are 1～5 alkyl.
5. heat release member according to claim 3, wherein, the R among the described construction unit A is that hydrogen or carbon number are 1～3 alkyl.
6. heat release member according to claim 4, wherein, the R among the described construction unit A is that hydrogen or carbon number are 1～3 alkyl.
7. heat release member according to claim 1, wherein, the thermal conductivity of the lamination direction of the described laminate of described following layer is 0.05W/mK～50W/mK.
8. heat release member according to claim 1, wherein, the thickness of described following layer is 0.05 μ m～10 μ m.
9. heat release member according to claim 2, wherein, described following layer comprises for following layer 100vol% the thermal conductivity filler for 1vol%～80vol%.
10. heat release member according to claim 2, wherein, described thermal conductivity filler comprises at least a kind of powder that is selected from the group that is made of metal powder, metal oxide powder, metal nitride powder and metal carbides powder.
11. heat release member according to claim 10, wherein, described thermal conductivity filler comprises at least a kind of powder that is selected from the group that is made of aluminum nitride powder, alumina powder, oxide powder and zinc, magnesia powder, carborundum powder, tungsten carbide powder, aluminium powder and copper powder.
12. heat release member according to claim 10, wherein, the average diameter of described thermal conductivity filler is 0.001 μ m～30 μ m.
13. heat release member according to claim 2, wherein, described thermal conductivity filler is the filler that comprises material with carbon element.
14. heat release member according to claim 13, wherein, described thermal conductivity filler comprises at least a kind of powder that is selected from the group that is made of graphite powder, CNT and bortz powder.
15. heat release member according to claim 1, wherein, the thermal conductivity of approximate vertical direction for the lamination direction of described laminate of described graphite linings is 250W/mK～2000W/mK.
16. heat release member according to claim 1, wherein, the thickness of described graphite linings is 15 μ m～600 μ m.
17. heat release member according to claim 1, wherein, described metal layer thickness is 0.01 times～100 times of thickness of described graphite linings.
18. heat release member according to claim 1, wherein, described metal level is the layer that comprises by silver, copper, aluminium, nickel and contain at least a kind of metal of the group that the alloy of any at least a kind of metal of those metals constitutes.
19. heat release member according to claim 1, wherein, described metal level is the layer that comprises by copper, aluminium and contain at least a kind of metal of the group that the alloy of any at least a kind of metal of those metals constitutes.
20. heat release member according to claim 1, wherein, described heat release member comprises at least 2 metal levels, and described metal level comprises copper, aluminium and contains the metal more than a kind of the group that the alloy of any at least a kind of metal of those metals constitutes,
At least 2 of described metal level is different layers.
21. heat release member according to claim 1 wherein, has resin bed in the outermost single or double of described heat release member.
22. heat release member according to claim 21, wherein, described resin bed comprises the filler that contains inorganic compound.
23. heat release member according to claim 21, wherein, described resin bed comprises: be selected from least a kind of resin of the group that is constituted by acrylic resin, epoxy resin, alkyd resins, amine ester resin and nitrocellulose, and at least a kind of compound that is selected from the group that is constituted by aluminium oxide, silica, cordierite, mullite, carborundum and magnesia.
24. an electronic component, it comprises heat release member as claimed in claim 1.
25. a battery, it comprises heat release member as claimed in claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-000241 | 2012-01-04 | ||
| JP2012000241A JP2012136022A (en) | 2012-01-04 | 2012-01-04 | Heat dissipating member, electronic device and battery |
| JP2012102712A JP6136104B2 (en) | 2012-01-04 | 2012-04-27 | Heat dissipation member, electronic device and battery |
| JP2012-102712 | 2012-04-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103192571A true CN103192571A (en) | 2013-07-10 |
| CN103192571B CN103192571B (en) | 2017-08-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210567426.6A Expired - Fee Related CN103192571B (en) | 2012-01-04 | 2012-12-24 | Heat release component, electronic component and battery |
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| KR (1) | KR102075337B1 (en) |
| CN (1) | CN103192571B (en) |
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| CN104302148A (en) * | 2013-07-18 | 2015-01-21 | 苏州沛德导热材料有限公司 | Heat conduction and radiation device |
| CN105744718A (en) * | 2014-12-11 | 2016-07-06 | 深南电路有限公司 | Heat dissipation PCB and processing method thereof |
| CN105765713A (en) * | 2013-11-12 | 2016-07-13 | 捷恩智株式会社 | Heat sink |
| CN107078108A (en) * | 2014-11-05 | 2017-08-18 | 捷恩智株式会社 | Heat exchange sheet, electronic installation |
| CN107666818A (en) * | 2016-07-27 | 2018-02-06 | Ｊｘ金属株式会社 | Works, printed circuit board (PCB), electronic equipment and the heat transmission metal material of attached heat transmission metal material |
| CN108933548A (en) * | 2017-05-22 | 2018-12-04 | 株式会社东芝 | Generating element, electricity generation module, power generator and electricity generation system |
| CN110023079A (en) * | 2017-01-31 | 2019-07-16 | 松下知识产权经营株式会社 | Graphite composite film and its manufacturing method |
| CN110072958A (en) * | 2016-12-15 | 2019-07-30 | 捷恩智株式会社 | Transfer sheet |
| CN110253987A (en) * | 2019-05-07 | 2019-09-20 | 重庆全营紧固件有限公司 | It is a kind of for thermally conductive new material |
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Cited By (12)
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| CN104302148A (en) * | 2013-07-18 | 2015-01-21 | 苏州沛德导热材料有限公司 | Heat conduction and radiation device |
| CN105765713A (en) * | 2013-11-12 | 2016-07-13 | 捷恩智株式会社 | Heat sink |
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| CN110072958A (en) * | 2016-12-15 | 2019-07-30 | 捷恩智株式会社 | Transfer sheet |
| CN110023079A (en) * | 2017-01-31 | 2019-07-16 | 松下知识产权经营株式会社 | Graphite composite film and its manufacturing method |
| CN110023079B (en) * | 2017-01-31 | 2022-03-01 | 松下知识产权经营株式会社 | Graphite composite film and method for producing same |
| CN108933548A (en) * | 2017-05-22 | 2018-12-04 | 株式会社东芝 | Generating element, electricity generation module, power generator and electricity generation system |
| CN108933548B (en) * | 2017-05-22 | 2020-06-19 | 株式会社东芝 | Power generation element, power generation module, power generation device, and power generation system |
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| CN110253987A (en) * | 2019-05-07 | 2019-09-20 | 重庆全营紧固件有限公司 | It is a kind of for thermally conductive new material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103192571B (en) | 2017-08-18 |
| KR102075337B1 (en) | 2020-02-10 |
| KR20130080418A (en) | 2013-07-12 |
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