CN104885215B - Heat emission film and heat emission adhesive tape - Google Patents
Heat emission film and heat emission adhesive tape Download PDFInfo
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- CN104885215B CN104885215B CN201380068181.5A CN201380068181A CN104885215B CN 104885215 B CN104885215 B CN 104885215B CN 201380068181 A CN201380068181 A CN 201380068181A CN 104885215 B CN104885215 B CN 104885215B
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- heat emission
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
A kind of heat emission film, the heat emission film contains polyurethane series resin and heat conductive filler, and has more than 0.5W/m.K pyroconductivity, more than 0.85 heat emission rate, more than 5N/20mm tensile strength and 10 30 μm of thickness.
Description
Technical field
The present invention relates to heat emission film and heat emission adhesive tape.More specifically, the present invention relates to a kind of applicable
Put in the heat emission film and heat of the purposes that the part for it is expected to generate heat by electricity consumption from electrical equipment, electronic equipment etc. is radiated
Penetrating property adhesive tape.
Background technology
The part of electrical equipment, electronic equipment etc. is formed, is lifted with the lifting of its integrated level and running speed and increases consumption electric power
Add, its result causes caloric value to increase.Part self-temperature can be caused to rise if caloric value increase.Part temperature, which rises, to be made
Into parts error running or failure and he causes the life-span reduce, make user scald etc., it is desirable to can suppress the rising of temperature.
There is the technology for making heat sink and feature contacts known to the suppression means risen as temperature.By making heat sink and zero
Part contacts, and by heat transfer caused by part to heat sink, the temperature that its result can suppress part rises.
Heat sink uses the high material of pyroconductivity as metal.But the if difference of radiating plate temperature and outside air temperature
Small, then savings will not discharge in the heat of heat sink, and still put aside in heat sink.Therefore, suppression means are risen as temperature
Room for improvement also be present in heat sink.
Japanese Patent Publication No. No. 2807198 (patent documents 1) proposes the technology for the problem for solving above-mentioned heat sink.Patent text
In offering 1, propose using the thin slice formed by the big heat emission material of heat emission rate and by the big heat conductivity material of pyroconductivity
The layered product for the thin slice for expecting to be formed is as radiator.In patent document 1, cordierite, metatitanic acid can be enumerated as heat emission material
Aluminium, β-spodumene, ceramics, carbon black, carbon fiber etc., ferrite can be enumerated as thermally-conductive materials.In addition, in patent document 1,
Above-mentioned 2 kinds of thin slices are to maintain its shape by polysiloxanes plus sulphur body, and respective thickness is formed as 1mm.
[look-ahead technique document Prior Art]
Patent document 1：Japanese Patent Publication No. 2807198
The content of the invention
The temperature that the radiator of above-mentioned patent document 1 also can not fully suppress part rises, and wishes to more improve.Separately
Outside, because electrical equipment or electronic equipment require more thinning, therefore radiator also requires filming.Thus from the point of view of viewpoint, patent document 1
Radiator filming in scope can be used to have its limit at it.
In this way, a kind of heat emission film can be provided according to the present invention, it is characterised in that the heat emission film contains polyurethane
It is resin and heat conductive filler, and with more than 0.5W/mK pyroconductivity, more than 0.85 heat emission rate, 5N/20mm
Tensile strength above and 10-30 μm of thickness.
In addition, can provide a kind of heat emission adhesive tape according to the present invention, the heat emission adhesive tape has in thickness direction
There are above-mentioned heat emission film and adhering agent layer.
According to the present invention, it is possible to provide a kind of temperature that can more suppress to form the part of electrical equipment, electronic equipment etc. rises
Film heat emission film, and heat emission adhesive tape.
In addition, in possessing the following situation of any one, it is possible to provide can further suppress the thin of the temperature rising of part
The heat emission film of film, and heat emission adhesive tape.
(1) heat conductive filler be selected from aluminum oxide, titanium oxide, zirconium oxide, ferrite, silica, zinc oxide, magnesia,
More than a kind in aluminium carbide, carborundum, aluminium nitride, boron nitride, carbon black, graphite, carbon fiber and melamine cyanurate.
(2) heat conductive filler is selected from aluminum oxide, titanium oxide, zirconium oxide, ferrite, silica, zinc oxide, oxidation
Filler A in magnesium, aluminium carbide, carborundum, aluminium nitride, boron nitride and melamine cyanurate is fine with being selected from carbon black, graphite and carbon
The combination of filler B in dimension, or for selected from aluminum oxide, titanium oxide, zirconium oxide, ferrite, silica, zinc oxide, magnesia,
The filler D of filler C and melamine cyanurate in aluminium carbide, carborundum, aluminium nitride and boron nitride combination.
(3) relative to the polyurethane series resin of 100 parts by weight, the heat conductive filler containing 100-600 parts by weight.
(4) relative to the filler A of 100 parts by weight, the filler B containing 0.5-30 parts by weight, relative to filling out for 100 parts by weight
Expect C, the filler D containing 1-200 parts by weight.
(5) heat conductive filler is the filler and carbon in aluminum oxide, carborundum, aluminium nitride and melamine cyanurate
The combination of black filler, or the combination of the filler and the filler of melamine cyanurate for aluminum oxide.
(6) when the thickness of polyurethane series resin is 25 μm, there is more than 5N/20mm tensile strength.
Brief description of the drawings
Fig. 1 is the constructed profile of heat emission adhesive tape of the present invention.
Fig. 2 is the constructed profile of heat emission adhesive tape of the present invention.
Fig. 3 is the constructed profile of heat emission adhesive tape of the present invention.
Fig. 4 is the schematic illustration of the radiating effect experiment of embodiment.
Fig. 5 be the heat emission adhesive tape for representing embodiment 1 and comparative example 1 radiating effect experiment in, measurement temperature
The chart of rheological parameters' change with time.
Embodiment
(heat emission film)
Heat emission film refers to containing polyurethane series resin and heat conductive filler and with the film of 10-30 μm of thickness.Enter
One step, heat emission film have more than 0.5W/mK pyroconductivity, more than 0.85 heat emission rate and more than 5N/20mm
Tensile strength.
Heat emission film by the pyroconductivity with above range, heat emission rate, tensile strength and thickness, so as to
The temperature for suppressing part rises, and can realize filming can be used in scope.Here, scope can be used to refer to be affixed on part
When, film will not easily produce the usability for the degree for causing operation obstacle.
Pyroconductivity is preferably more than 0.5W/mK, more preferably more than 1.0W/mK.Heat emission rate is preferably 0.85
More than, more preferably more than 0.88.In the scope of these preferable pyroconductivities and heat emission rate, it is possible to provide can further press down
The film that the temperature of part processed rises.Pyroconductivity can be 0.5W/mK, 1.0W/mK, 1.5W/mK, 2.0W/mK,
2.5W/mK, 3.0W/mK etc. value.Heat emission rate can be 0.85,0.86,0.87,0.88,0.89,0.90,0.91,
0.92、0.95。
Tensile strength is preferably more than 5N/20mm, more preferably more than 10N/20mm.Thickness is preferably 10-30 μm, more excellent
Elect 10-25 μm as.In these preferable tensile strengths and the scope of thickness, it is possible to provide use is easier and thinner film.Draw
It can be 10N/20mm, 15N/20mm, 20N/20mm, 25N/20mm, 30N/20mm, 35N/20mm, 40N/20mm to stretch intensity.Film
Thickness can be 10 μm, 15 μm, 20 μm, 25 μm.
(a) polyurethane series resin
It can turn into the film shape of 30 μ m thicks as polyurethane series resin, as long as and film 5N/20mm can be assigned to pull up
The resin for stretching intensity is not particularly limited.In these polyurethane series resins, more preferably there is 5N/20mm in 25 μm of thickness
The resin of above tensile strength.In 30 μm and/or 25 μm of thickness, tensile strength can be 5N/20mm, 10N/20mm, 15N/
20mm、20N/20mm、25N/20mm、30N/20mm、35N/20mm、40N/20mm。
Polyurethane series resin, such as can enumerate：(1) poly-lactone polyol obtained by caprolactone ring-opening polymerisation and two isocyanic acids
Ester (such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate etc.)
By polymerizeing the caprolactone type polyurethane elastomer synthesized by addition reaction；(2) by dicarboxylic acids (such as adipic acid, phthalandione etc.) with
The dicarboxylic ester polyalcohol of glycol (such as polypropylene glycol), with diisocyanate by polymerizeing the dicarboxylic acids synthesized by addition reaction
Ester type polyurethane elastomer；(3) by the PPG of poly- tetramethylene glycol, PAG (such as polypropylene glycol) etc.,
With diisocyanate by polymerizeing the EU elastomer synthesized by addition reaction；And (4) polycarbonate polyol.It is poly-
Urethane system resin can be the mixture of these (1)~(4).
Polyurethane series resin can have the functional groups such as carboxyl, amido.Particularly by with carboxyl, heat conductivity can be lifted
The dispersiveness of filler.
Polyurethane elastomer is preferably with 10,000 to 200,000 weight average molecular weight.For the scope molecular weight when, can obtain
Easily use and the film of more film.
The commercially available product of polyurethane series resin can enumerate the DAIFERAMINE MAU series for coming from the industrial group that refines big day
The polyurethane bullets such as (model 5022,4308HV, 9022 etc.) or RESAMINE ME series (model ME-44ELP, ME-8105LP etc.)
The isocyanides such as CORONATE L-55E of elastomer precursor and Japanese polyurethane company, the Takenate D-160N of Mitsui Chemicals, Inc.
The elastomer of the reactant of acid esters system crosslinking agent reaction, kuraray companies KURAMIRON U1000 series (model 1180,
1190 etc.) or the elastomer of No. 9000 series (model 9180,9185 etc.) etc..
(b) heat conductive filler
As heat conductive filler, as long as pyroconductivity and more than 0.85 heat more than film 0.5W/mK can be assigned
The filler of emissivity is not particularly limited.Specifically, aluminum oxide, titanium oxide, zirconium oxide, ferrite, oxidation can be selected from
Silicon, zinc oxide, magnesia, aluminium carbide, carborundum, aluminium nitride, boron nitride, carbon black, graphite, carbon fiber and melamine cyanurate
In more than a kind.Pyroconductivity can be 0.5W/mK, 1.0W/mK, 1.5W/mK, 2.0W/mK, 2.5W/mK,
3.0W/mK etc. value.Heat emission rate can be 0.85,0.86,0.87,0.88,0.89,0.90,0.91,0.92,0.95.
In order to lift the efficiency of heat transfer and heat emission, heat conductive filler is preferably：Selected from aluminum oxide, titanium oxide, oxygen
Change zirconium, ferrite, silica, zinc oxide, magnesia, aluminium carbide, carborundum, aluminium nitride, boron nitride and melamine cyanurate
In filler A and filler B in carbon black, graphite and carbon fiber combination；Or for selected from aluminum oxide, titanium oxide, oxidation
Filler C and cyanuric acid in zirconium, ferrite, silica, zinc oxide, magnesia, aluminium carbide, carborundum, aluminium nitride and boron nitride
The filler D of melamine combination.
For example, filler A and filler B combination can be enumerated：Aluminum oxide/carbon black, titanium oxide/carbon black, zirconium oxide/carbon black, iron
Oxysome/carbon black, silica/carbon black, zinc oxide/carbon black, magnesia/carbon black, aluminium carbide/carbon black, silicon carbide/carbon are black, aluminium nitride/
Carbon black, boron nitride/carbon black and melamine cyanurate/carbon black；Aluminum oxide/graphite, titanium oxide/graphite, zirconium oxide/graphite, iron
Oxysome/graphite, silica/graphite, zinc oxide/graphite, magnesia/graphite, aluminium carbide/graphite, carborundum/graphite, aluminium nitride/
Graphite, boron nitride/graphite and melamine cyanurate/graphite；Aluminum oxide/carbon fiber, titanium oxide/carbon fiber, zirconium oxide/carbon are fine
Dimension, ferrite/carbon fiber, silica/carbon fiber, zinc oxide/carbon fiber, magnesia/carbon fiber, aluminium carbide/carbon fiber, carbonization
Silicon/carbon fiber, aluminium nitride/carbon fiber, boron nitride/carbon fiber and melamine cyanurate/carbon fiber.
Filler C and filler D combination can be enumerated：Aluminum oxide/melamine cyanurate, titanium oxide/melamine cyanurate,
Zirconium oxide/melamine cyanurate, ferrite/melamine cyanurate, silica/melamine cyanurate, zinc oxide/cyanogen urine
Sour melamine, magnesia/melamine cyanurate, aluminium carbide/melamine cyanurate, carborundum/melamine cyanurate,
Aluminium nitride/melamine cyanurate and boron nitride/melamine cyanurate.
The filler in aluminum oxide, carborundum, aluminium nitride and melamine cyanurate more preferably is combined as, with carbon black
Filler combination；Or the combination of the filler and the filler of melamine cyanurate for aluminum oxide.
In order to lift the efficiency of heat transfer, heat conductive filler preferably has small particle diameter.For example, particle diameter is preferably 20 μm
Hereinafter, more preferably less than 10 μm.From the viewpoint of operation easiness and acquirement easiness, the lower limit of particle diameter is preferably 0.1 μ
m.Particle diameter can be 0.1 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm.
Particle diameter can be determined by laser diffraction and scattering method.
(c) polyurethane series resin and heat conductive filler
The content ratio of polyurethane series resin and heat conductive filler, as long as pyroconductivity as defined in film can be assigned, heat is put
Penetrating property, tensile strength and thickness are not particularly limited.For example, relative to the polyurethane series resin of 100 parts by weight, preferably exist
The scope of 100-600 parts by weight contains heat conductive filler, more preferably contains heat conductivity in the scope of 200-500 parts by weight and fills out
Material.
Heat conductive filler using above-mentioned filler A and filler B combination when, relative to the filler A of 100 parts by weight, preferably
Filler B containing 0.5-30 parts by weight.Filler B content can be 0.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 weight
Part, 25 parts by weight, 30 parts by weight.In addition, using above-mentioned filler C and filler D combination when, relative to the filler of 100 parts by weight
C, preferably comprise the filler D of 1-200 parts by weight.Filler D content can be 1 parts by weight, 50 parts by weight, 100 parts by weight, 200
Parts by weight.
(d) other compositions
Film can contain other compositions in the range of without prejudice to effect of the present invention.Coloring can be enumerated as other compositions
Agent, antistatic additive, antioxidant etc..
(e) flat shape of heat emission film
Heat emission film is not particularly limited, and the flat shape of the requirement of the machine of heat emission can be needed according to.
(heat emission adhesive tape)
(a) adhering agent layer
Such as shown in Fig. 1 constructed profile, heat emission adhesive tape refers to there is above-mentioned heat emission in thickness direction
The adhesive tape of film 1, adhering agent layer.The thickness of adhering agent layer for example can be in 3-50 μm of scope.Adhering agent layer can be formed at heat and put
Penetrating property film is comprehensive, can also specific pattern and be partly formed.Thickness can be 3 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm.
Adhering agent layer is not particularly limited, the layer that known sticker can be used to be formed.Such as acrylic acid series can be enumerated and glued
Agent.
In acrylic acid series sticker, for example, can be used acrylic monomer is polymerize in the presence of any polymerization initiators and
Obtained sticker or commercially available sticker.
(a-1) acrylic monomer
In acrylic monomer, preferably contain (methyl) alkyl acrylate with the alkyl that carbon number is 1-10
As principal component (more than 50 weight %).In addition, (methyl) acrylate is methacrylate or acrylate.
(methyl) alkyl acrylate with the alkyl that carbon number is 1-14, such as (methyl) acrylic acid first can be enumerated
Ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate,
(methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer,
(methyl) 2-EHA, the different nonyl ester of (methyl) acrylic acid, (methyl) dodecylacrylate etc..These (methyl)
Alkyl acrylate can be used only a kind, and two or more use also can be combined.In these (methyl) alkyl acrylates, preferably have
There is (methyl) alkyl acrylate for the alkyl that carbon number is 1-8, more preferably with the alkyl that carbon number is 1-4
(methyl) alkyl acrylate, more preferably (methyl) n-butyl acrylate, particularly preferably n-butyl acrylate.
Other acrylic monomers can enumerate acrylic acid, methacrylic acid, carboxyethyl acrylates etc. containing carboxyl
Monomer；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, (first
Base) monomer containing hydroxyl such as the own ester of acrylic acid 6- hydroxyls, acrylic acid (4- Hydroxymethyl-cyclo-hexyls)-methyl esters.It is these other
(methyl) acrylate can be used only a kind, and two or more use also can be combined.In (methyl) acrylate, preferably contain
Both the monomer of carboxyl and monomer containing hydroxyl.
Contain (methyl) alkyl acrylate with the alkyl that carbon number is 1-10 in acrylic monomer as master
Composition.Therefore, acrylic monomer can be without using other acrylic monomers, and only by (methyl) alkyl acrylate structure
Into.In addition, from the viewpoint of the adhesive composition of desired performance is readily available, other acrylic monomers preferably contain
Have less than 50 weight % and be more than 1 weight %, further preferably 5-30 weight %, further preferably 5-15 are weighed
Measure %.The content of acrylic monomer can be 1 weight %, 5 weight %, 10 weight %, 30 weight %, 40 weight %, 49 weights
Measure %.
Further, as needed, vinyl monomer can also be added in (methyl) acrylate.Vinyl monomer for example may be used
Enumerate itaconic acid, maleic acid, crotonic acid, maleic anhydride, itaconic anhydride, vinylacetate, N- vinylpyrrolidones, N- ethene first
Amide-type, styrene, N- vinyl caprolactams etc..These vinyl monomers can be used only a kind, and two or more use also can be combined.
(a-2) polymerization initiators
Arbitrarily used polymerization initiators, such as 2 can be enumerated, 2 '-azobis isobutyronitrile, 2, double (the 2- methyl-props of 2 '-azo
Amidine) disulphide, 2,2 '-azo double (4- methoxyl group -2,4- methyl pentane nitriles), 2,2 '-azo double (2,4- methyl pentane nitriles),
2,2 '-azo double (2- methylbutyronitriles), 1,1 '-azo double (hexamethylene -1- nitriles), double (the 2,4,4- trimethyls penta of 2,2 '-azo
Alkane), dimethyl -2,2 '-azo double (2 Methylpropionic acid ester), double [2- methyl-N- (phenyl methyl) the-the third amidines] two of 2,2 '-azo
Double [2- (3,4,5,6- tetrahydropyrimidine -2- bases) propane] dihydrochlorides of hydrochloride, 2,2 '-azo, double [2- (the 2- miaows of 2,2 '-azo
Oxazoline -2- bases) propane] etc. azo system polymerization initiators；The persulfate such as potassium peroxydisulfate, ammonium persulfate system polymerization initiators；Cross
BP, hydrogen peroxide, TBHP, di-tert-butyl hydrogen peroxide, t-butyl peroxybenzoate, peroxidating two
Double (the tert-butyl peroxide) -3,3,5- trimethyl-cyclohexanes of cumenyl, 1,1-, double (tert-butyl peroxide) rings 12 of 1,1-
The peroxide system polymerization initiators such as alkane, peroxidating 3,3,5- 3-methyl cyclohexanols acyl, tert-Butyl peroxypivalate；By persulfuric acid
Redox system polymerization initiators that salt is formed with sodium hydrogensulfite etc..These polymerization initiators can be used only a kind, also can group
Close two or more use.
Relative to the acrylic monomer of 100 parts by weight, polymerization initiators are preferably made with the scope of 0.005-1 parts by weight
With.By using polymerization initiators with the scope, the acrylic acid series sticker for improving adhesiveness can be formed.Further, it polymerize
The usage amount of initiator is more preferably the scope of 0.1-0.5 parts by weight.The usage amount of polymerization initiators can be 0.005 parts by weight,
0.01 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight.
(a-3) organic solvent
It can contain organic solvent from the viewpoint of the formation easiness of adhering agent layer.The organic solvent is not particularly limited,
The known organic solvent that can be used in adhesive composition can be enumerated.Such as the aliphatic hydrocarbons such as hexane, heptane can be enumerated；Tumer
The esters such as ester, ethyl acetate, propyl acetate；The fragrant family hydrocarbon such as toluene, dimethylbenzene, ethylo benzene.These organic solvents can only make
With a kind, two or more use also can be combined.
In addition, during using organic solvent, and preferably modulating its use ratio makes what acrylic acid series sticker formed to consolidate
Body component content is more than 10 weight %.Further, more preferably modulate use ratio and make solid component content for 20-50 weights
Measure %.
(a-4) other compositions
In order to lift the shape stability of adhering agent layer, acrylic acid series sticker can have cross-linked structure.Handed over to assign
It is coupled structure, such as the acrylic acid series sticker relative to 100 parts by weight, isocyanic acid can be used with the scope of 0.01-10 parts by weight
Ester system crosslinking agent, aluminium chelate compound system crosslinking agent.The usage amount of the crosslinking agent can be 0.01 parts by weight, 0.1 parts by weight, 1.0 weights
Measure part, 5.0 parts by weight, 10 parts by weight.
In addition, in order to lift the heat conductivity of adhering agent layer, acrylic acid series sticker can contain heat conductive filler.This is filled out
Any one of the heat conductive filler enumerated in the explanation of above-mentioned heat emission film can be used in material.Relative to 100 parts by weight
Acrylic acid series sticker, heat conductive filler can be used in the scope of 50-500 parts by weight.The usage amount of heat conductive filler can
For 50 parts by weight, 100 parts by weight, 200 parts by weight, 350 parts by weight, 500 parts by weight.
(b) thin slice containing thermally-conductive materials
For the heat conductivity of elevator belt, heat emission adhesive tape can enter one between heat emission film and adhering agent layer
Step is with the thin slice containing the thermally-conductive materials in copper, aluminium and graphite.As its specific composition, can enumerate such as Fig. 2 institutes
That shows is directly close contact in thin slice 3 composition of heat emission film 1, or as shown in Figure 3 by adhering agent layer 4 that thin slice 3 is close
It is connected to the composition of heat emission film 1.
Such as when can individually keep flake-like shape with thermally-conductive materials such as copper foils, the thin slice can be used directly.In addition,
, can be by being mixed to flake with resinoid bond during using thermally-conductive materials such as particle shapes.
The thickness of thin slice is not particularly limited in the range of heat conductivity is not hindered, such as can be 10-5000 μm.
(purposes of heat emission film and heat emission adhesive tape)
As long as being desirable to make caused heat radiate to the purposes of outside, then heat emission film and heat emission adhesive tape can
It is used in any purposes.Such as the electrical equipment such as motor, illumination can be enumerated；The radiating purposes of the electronic equipments such as LSI, IC, resistance.By
Can be made full use of in the film and band of the present invention as film, therefore, the obvious filming in recent years of being particularly suitable for use in it is portable
The display such as phone or liquid crystal and organic EL.
Embodiment
Embodiment used below further illustrates the present invention, but the present invention is not limited to following examples.In addition, heat is put
The pyroconductivity of penetrating property film, the determination method of heat emission rate and tensile strength, the radiating effect test method of heat emission adhesive tape
Embodiment it is as follows.
(pyroconductivity)
The measure of pyroconductivity determines device GH-1 using ULVAC science and engineering company system steady state methods pyroconductivity and carried out.Will
Heat emission film is clamped with the aluminium sheet of 50mm diameters, and clamping thing is arranged at into measure device, is determined according to ASTM E1530
Pyroconductivity.
(heat emission rate)
The measure of heat emission rate is carried out using capital of a country Electronics Industry Company heating dose-rate meter D＆S AERD.By heat emission
Film is cut into wide and a length of 60mm size, obtains determination sample.After heat emission rate meter is corrected with standard sample, sample will be determined
Product are arranged at heat emission rate meter and determine heat emission rate.
(tensile strength)
Heat emission film is cut into wide 20mm, length 100mm size, obtains determination sample whereby.So that sample will be determined
The mode that Shimadzu Seisakusho Ltd. company system AUTOGRAPH AGS-H are fixed on the both sides of product is set, and is divided with draw speed 300mm/
Clock stretches determination sample.Power during determination sample rupture is determined, income value is tensile strength (N/20mm).
(radiating effect experiment)
At the following center of copper foil (wide and length be 150mm) of 70 μ m-thicks, set using sticker of the thickness for 10 μm
Put heater (output 10W, wide 25mm, length 50mm).Thermocouple is set in heater center, and thermocouple is placed in heat-insulated
After on material, heater is heated with constant output (10W).Determine the temperature after heating 15 minutes.On the basis of gained temperature
Temperature.
Then, on above-mentioned copper foil by heat emission adhesive tape be bonded after, with fiducial temperature determine identical method and
Determine the temperature after heating 15 minutes.The schematic diagram of setting situation when representing to determine in Fig. 4 (a) and Fig. 4 (b).Fig. 4 (a)
It is that top view, Fig. 4 (b) are side views.In figure, a represents heat emission adhesive tape, b represents copper foil, c represents heater, d is represented
Thermocouple, e represent heat-barrier material.
Fiducial temperature is subtracted by measurement temperature, and radiating effect is assessed using income value.When reduction calculated value is less than -10 DEG C then
Radiating effect is big and is evaluated as zero, then radiating effect deficiency and be evaluated as during higher than -10 DEG C ×.
Embodiment 1
(heat emission film)
In polyurethane resin precursor, (refine big day industrial group DAIFERAMINE MAU-5022, the weight of solid constituent 35
Measure %, weight average molecular weight 6-7 ten thousand) in 286 parts by weight, addition isocyanates system crosslinking agent (Japanese polyurethane company system
CORONATE L-55E, the weight % of solid constituent 55) 57 parts by weight, aluminum oxide (Showa electrician company system AL-47H, 2 μm of particle diameter)
400 parts by weight and carbon black (peaceful chemical company CB4873) 12 parts by weight simultaneously stir.Put after stirring by deaeration to obtain heat
Penetrating property film manufacture constituent.
Gained constituent is coated on stripping film with specific thicknesses.By gained film after 100 DEG C are dried 2 minutes,
40 DEG C of maturations 3 days, obtain the heat emission film that thickness is 25 μm.
(heat emission adhesive tape)
By the parts by weight of n-butyl acrylate 91, the parts by weight of acrylic acid 8, the parts by weight of 2-hydroxyethyl methacrylate 1, azo
0.2 parts by weight of double isobutyronitriles (AIBN, polymerization initiators), solvent (ethyl acetate：Toluene=9：1 (weight ratio)) 150 parts by weight
Mixing.Gained mixture is reacted 5 hours in nitrogen stream with 85 DEG C, obtains the weight % of solid constituent 40, viscosity 7000mP.s
Acrylic acid series sticker.
In the parts by weight of aforesaid propylene acid system sticker 100, addition isocyanates system crosslinking agent (Japanese polyurethane company system
CORONATE L-55E) 1 parts by weight and aluminum oxide (Showa electrician company system AL-47H) 120 parts by weight and stir.Lead to after stirring
Cross deaeration and obtain adhering agent layer manufacture constituent.
Gained constituent is coated on stripping film with specific thicknesses.Gained film is dry 2 minutes at 100 DEG C, thus
Form the adhering agent layer that thickness is 25 μm.Adhering agent layer is transferred to heat emission film, with 40 DEG C of maturations 3 days, thus obtains heat
Radioactivity adhesive tape.
Embodiment 2
In addition to the manufacture of heat emission film is set into 200 parts by weight with constituent institute salic addition, with
The same way of embodiment 1 and obtain heat emission adhesive tape.
Embodiment 3
In addition to the manufacture of heat emission film is set into 500 parts by weight with constituent institute salic addition, with
The same way of embodiment 1 and obtain heat emission adhesive tape.
Embodiment 4
Except the manufacture of heat emission film is set into 180 parts by weight with constituent institute salic addition, and add cyanogen
Uric acid melamine (Nissan Chemical Industries company system MC-6000,2 μm of particle diameter) 80 parts by weight substitution carbon black beyond, with implementation
The same way of example 1 and obtain heat emission adhesive tape.
Embodiment 5
Except addition melamine cyanurate (Nissan Chemical Industries company system MC-6000,2 μm of particle diameter) 170 parts by weight
Substitute beyond the aluminum oxide contained by heat emission film manufacture constituent, obtain heat emission in the same manner as in example 1
Adhesive tape.
Embodiment 6
Substitute heat emission film manufacture group except addition aluminium nitride (tokuyama company system H grade, 1 μm of particle diameter)
Into beyond the aluminum oxide contained by thing, heat emission adhesive tape is obtained in the same manner as in example 1.
Embodiment 7
The manufacture of heat emission film is substituted to use except addition carborundum (the electric refining company H3000 of SHIN-ETSU HANTOTAI, 4 μm of particle diameter)
Beyond aluminum oxide contained by constituent, heat emission adhesive tape is obtained in the same manner as in example 1.
Embodiment 8
By polyurethane series thermoplastic resin (kuraray company system KURAMIRON U1190, the weight of solid constituent 100
Amount %) 131 parts by weight are dissolved in the N of 131 parts by weight, N '-dimethyl formamide in 60 DEG C.Aluminum oxide is added in resulting solution
12 parts by weight are simultaneously for (Showa electrician company system AL-47H, 2 μm of particle diameter) 400 parts by weight and carbon black (peaceful chemical company CB4873)
Stirring.Heat emission film manufacture constituent is obtained by deaeration after stirring.
Gained constituent is coated on stripping film with specific thicknesses.By gained film after 150 DEG C are dried 3 minutes, with
40 DEG C of maturations 3 days, thus obtain the heat emission film that thickness is 25 μm.
In addition to using above-mentioned film, heat emission adhesive tape is obtained in the same manner as in example 1.
Embodiment 9
Except using kuraray company system KURAMIRON U9185 (the weight % of solid constituent 100) as polyurethane series heat
Beyond moldable resin, heat emission adhesive tape is obtained in a manner of same as Example 8.
Comparative example 1
Except not in heat emission film manufacture constituent add aluminum oxide in addition to, in the same manner as in example 1 and
Obtain heat emission adhesive tape.
Comparative example 2
In addition to the manufacture of heat emission film is set into 700 parts by weight with constituent institute salic addition, with
The same way of embodiment 1 and heat emission film to be manufactured, but can not film forming be film.
Comparative example 3
In addition to adding carbon black not in heat emission film manufacture constituent, obtain in the same manner as in example 1
To heat emission adhesive tape.
Comparative example 4
Except with not adding aluminum oxide and carbon black in constituent, and adding melamine cyanurate in the manufacture of heat emission film
Beyond (Nissan Chemical Industries company system MC-6000,2 μm of particle diameter) 150 parts by weight, heat is obtained in the same manner as in example 1
Radioactivity adhesive tape.
Comparative example 5
Except with not adding aluminum oxide and carbon black in constituent, and adding aluminium (aluminium company of Japan in the manufacture of heat emission film
11-0018 processed) beyond 200 parts by weight, heat emission adhesive tape is obtained in the same manner as in example 1.
Comparative example 6
In epoxy system resin, (aurification company system YP-50EK35, the weight % of solid constituent 35, Weight-average molecular are lived by Nippon Steel
Ten thousand) amount about 7 in 286 parts by weight, adds aluminum oxide (Showa electrician company system AL-47H, 2 μm of particle diameter) 200 parts by weight and carbon black
(peaceful chemical company CB4873) 12 parts by weight simultaneously stir.It is made up of after stirring deaeration to obtain the manufacture of heat emission film
Thing.
In addition to using above-mentioned film manufacture constituent, heat emission film is obtained in the same manner as in example 1.Institute
Film without being sufficiently tensile intensity.
Comparative example 7
In addition to the salic addition of heat emission film manufacture constituent institute is 400 parts by weight, with compared with
The same way of example 6 and heat emission film to be manufactured, but can not film forming be film.
Comparative example 8
In acrylic resin (DIC company system ACRYDIC A-804, the weight % of solid constituent 50) 200 parts by weight, add
Add isocyanates system crosslinking agent (Japanese polyurethane company system CORONATE L-55E, the weight % of solid constituent 55) 2 parts by weight, oxygen
Change aluminium (Showa electrician company system AL-47H, 2 μm of particle diameter) 200 parts by weight and carbon black (peaceful chemical company CB4873) 12 weight
Part is simultaneously stirred.After stirring, heat emission film manufacture constituent is obtained by deaeration.
In addition to using above-mentioned film manufacture constituent, heat emission film is obtained in the same manner as in example 1.Institute
Film without being sufficiently tensile intensity.
Comparative example 9
In addition to the manufacture of heat emission film is set into 400 parts by weight with constituent institute salic addition, with
The same way of comparative example 8 and heat emission film to be manufactured, but can not film forming be film.
Comparative example 10
By Polyester thermoplastic resin, (Mitsubishi Rayon company system ER-1082, the weight % of solid constituent 100, divide equally again
Ten thousand) 100 parts by weight of son amount about 3, the ethyl acetate of 100 parts by weight is dissolved in 50 DEG C.It is (clear that aluminum oxide is added in resulting solution
With electrician company system AL-47H, 2 μm of particle diameter) 200 parts by weight and carbon black (peaceful chemical company CB4873) 12 parts by weight and stir
Mix.Heat emission film manufacture constituent is obtained by deaeration after stirring.
Gained constituent is coated on stripping film with specific thicknesses.By gained film after 100 DEG C are dried 3 minutes, in
40 DEG C of maturations 3 days, thus obtain the heat emission film that thickness is 25 μm.Gained film, which does not have, is sufficiently tensile intensity.
Comparative example 11
In addition to the manufacture of heat emission film is set into 400 parts by weight with constituent institute salic addition, with
The same way of comparative example 10 and heat emission film to be manufactured, but can not film forming be film.
The various result of the tests of gained heat emission film and heat emission adhesive tape, use material category and usage amount equal
It is shown in table 1.
Table 1
UA, UB and UC are polyurethane series resin；EP is epoxy system resin；Ac is acrylic resin；
PE is polyester based resin；CB is carbon black；MC is melamine cyanurate
Fig. 5 is the warp for representing embodiment 1 and heat emission adhesive tape measurement temperature in radiating effect experiment of comparative example 1
Shi Bianhua chart.The chart of the heat emission adhesive tape without heat emission film is represented in Fig. 5 in the lump.
The pyroconductivity, more than 0.85 heat emission rate, 5N/ that can confirm there is more than 0.5W/mK by table 1 and Fig. 5
More than 20mm tensile strength and its radiating effect of the heat emission film of the embodiment of 10-30 μm of thickness are higher.
Description of reference numerals
1：Heat emission film
2、4：Adhering agent layer
3：Thermally-conductive materials (thin slice)
a：Heat emission adhesive tape
b：Copper foil
c：Heater
d：Thermocouple
e：Heat-barrier material
Claims (7)
- A kind of 1. heat emission film, it is characterised in that the heat emission film contains polyurethane series resin and heat conductive filler, and Pyroconductivity with more than 0.5W/mK, more than 0.85 heat emission rate, more than 5N/20mm tensile strength and 10-30 μm Thickness,The heat conductive filler is selected from aluminum oxide, titanium oxide, zirconium oxide, ferrite, silica, zinc oxide, magnesia, carbon Change filler A in aluminium, carborundum, aluminium nitride, boron nitride and melamine cyanurate with carbon black, graphite and carbon fiber Filler B combination；Or for selected from aluminum oxide, titanium oxide, zirconium oxide, ferrite, silica, zinc oxide, magnesia, carbonization The filler D of filler C and melamine cyanurate in aluminium, carborundum, aluminium nitride and boron nitride combination；Relative to the polyurethane series resin of 100 parts by weight, the heat conductive filler containing 100-600 parts by weight；The assay method of the tensile strength is：Heat emission film is cut into wide 20mm, length 100mm size, surveyed Random sample product, set in a manner of the both sides of determination sample to be fixed on to Shimadzu Seisakusho Ltd. company system AUTOGRAPH AGS-H, and with Draw speed 300mm/ minutes stretch determination sample, power when measure determination sample ruptures.
- 2. heat emission film according to claim 1, wherein, relative to the filler A of 100 parts by weight, contain 0.5- The filler B of 30 parts by weight, relative to the filler C of 100 parts by weight, the filler D containing 1-200 parts by weight.
- 3. heat emission film according to claim 1, wherein, the heat conductive filler be selected from aluminum oxide, carborundum, The combination of the filler of filler and carbon black in aluminium nitride and melamine cyanurate；Or the filler for aluminum oxide and cyanuric acid three The combination of the filler of poly cyanamid.
- 4. heat emission film according to claim 1, wherein, when the thickness of the polyurethane series resin is 25 μm, have More than 5N/20mm tensile strength.
- 5. a kind of heat emission adhesive tape, the heat emission adhesive tape has the heat emission described in claim 1 in thickness direction Property film and adhering agent layer.
- 6. heat emission adhesive tape according to claim 5, wherein, between the heat emission film and adhering agent layer, Further there is the thin slice containing the thermally-conductive materials in copper, aluminium and graphite.
- 7. heat emission adhesive tape according to claim 6, wherein, in the heat emission film and contain heat conductivity material Between the thin slice of material, further with adhering agent layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-030074 | 2013-02-19 | ||
| JP2013030074A JP5372270B1 (en) | 2013-02-19 | 2013-02-19 | Thermal radiation film and thermal radiation adhesive tape |
| PCT/JP2013/084312 WO2014129077A1 (en) | 2013-02-19 | 2013-12-20 | Heat radiating film and heat radiating adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104885215A CN104885215A (en) | 2015-09-02 |
| CN104885215B true CN104885215B (en) | 2017-12-15 |
Family
ID=49954913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380068181.5A Expired - Fee Related CN104885215B (en) | 2013-02-19 | 2013-12-20 | Heat emission film and heat emission adhesive tape |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5372270B1 (en) |
| KR (1) | KR102165850B1 (en) |
| CN (1) | CN104885215B (en) |
| TW (1) | TWI608071B (en) |
| WO (1) | WO2014129077A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6314797B2 (en) * | 2013-11-15 | 2018-04-25 | 信越化学工業株式会社 | Thermally conductive composite sheet |
| CN106536609B (en) | 2014-07-07 | 2022-04-29 | 霍尼韦尔国际公司 | Thermal interface material with ion scavenger |
| JP6566554B2 (en) * | 2014-08-20 | 2019-08-28 | 昭和電工株式会社 | LAMINATED SHEET AND METHOD FOR PRODUCING LAMINATED SHEET |
| JP6470004B2 (en) * | 2014-09-29 | 2019-02-13 | 日立オートモティブシステムズ株式会社 | In-vehicle control device |
| CN107250317A (en) | 2014-12-05 | 2017-10-13 | 霍尼韦尔国际公司 | High-performance thermal interfacial material with low thermal resistance |
| KR20170096050A (en) * | 2015-01-29 | 2017-08-23 | 쇼와 덴코 가부시키가이샤 | COF type semiconductor package and liquid crystal display device |
| US10312177B2 (en) | 2015-11-17 | 2019-06-04 | Honeywell International Inc. | Thermal interface materials including a coloring agent |
| BR112018067991A2 (en) | 2016-03-08 | 2019-01-15 | Honeywell Int Inc | thermal interface material, and electronic component |
| KR101722069B1 (en) | 2016-06-17 | 2017-03-31 | 주식회사 이노폴이 | Thermoconductive thin layer sheet and preparation method thereof |
| US10501671B2 (en) | 2016-07-26 | 2019-12-10 | Honeywell International Inc. | Gel-type thermal interface material |
| CN110234707B (en) * | 2017-03-17 | 2021-10-08 | 株式会社Lg化学 | Thermoplastic polyurethane film and method for producing same |
| WO2018174498A1 (en) * | 2017-03-20 | 2018-09-27 | 주식회사 엘지화학 | Method for manufacturing thermoplastic polyurethane film and thermoplastic polyurethane film manufactured thereby |
| CN107046738B (en) * | 2017-04-06 | 2021-01-05 | 昆明纳太科技有限公司 | Resistance heating element and manufacturing method thereof |
| US11041103B2 (en) | 2017-09-08 | 2021-06-22 | Honeywell International Inc. | Silicone-free thermal gel |
| US10428256B2 (en) | 2017-10-23 | 2019-10-01 | Honeywell International Inc. | Releasable thermal gel |
| US11072706B2 (en) | 2018-02-15 | 2021-07-27 | Honeywell International Inc. | Gel-type thermal interface material |
| KR20200031350A (en) * | 2018-09-14 | 2020-03-24 | 주식회사 엘지화학 | Manufacturing method for polyurethane film and polyurethane film manufactured by the same |
| US11373921B2 (en) | 2019-04-23 | 2022-06-28 | Honeywell International Inc. | Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing |
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- 2013-12-20 WO PCT/JP2013/084312 patent/WO2014129077A1/en active Application Filing
- 2013-12-20 KR KR1020157020034A patent/KR102165850B1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2014129077A1 (en) | 2014-08-28 |
| TWI608071B (en) | 2017-12-11 |
| TW201435039A (en) | 2014-09-16 |
| CN104885215A (en) | 2015-09-02 |
| KR20150119850A (en) | 2015-10-26 |
| KR102165850B1 (en) | 2020-10-14 |
| JP5372270B1 (en) | 2013-12-18 |
| JP2014160718A (en) | 2014-09-04 |
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