CN102093713B - Heat dissipation composite material - Google Patents
Heat dissipation composite material Download PDFInfo
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- CN102093713B CN102093713B CN 200910254200 CN200910254200A CN102093713B CN 102093713 B CN102093713 B CN 102093713B CN 200910254200 CN200910254200 CN 200910254200 CN 200910254200 A CN200910254200 A CN 200910254200A CN 102093713 B CN102093713 B CN 102093713B
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Abstract
The invention provides a heat dissipation composite material and a preparation method thereof. Through the combination of core-shell filled particles with different particle diameters and different compositions, a polyimide film has high thermal conductivity as well as the electric property and flexibility of the polyimide film product.
Description
Technical field
The present invention relates to the heat-conducting type composite polyimide material, and be particularly related to composition, ratio and the size distribution of its nucleocapsid particle filled composite.
Background technology
Under the trend of and actionization slim towards light weight at electronic product, the structure of electronic product dress density is productive set more and more.The demand of adding function is also more and more higher, required driving electric power also up increases always, the heat that system produces is thereupon straight line rising also, how will become important key via good heat radiation to keep the stable running of electronic product system, polyimide resin is because having excellent thermotolerance, mechanical characteristics and electric characteristics, thereby often be used as the insulation layer of copper foil base plate materials, the heat dissipation problem that brings towards microminiaturization and high speed trend for the following electronic product of correspondence, if the resin insulating barrier in substrate is given the function of heat conduction, can provide good assembly radiating approach, to increase reliability and the life-span of assembly.
In EP 1672009 (A1), the boron nitride, silicon carbide, aluminium nitride, titanium oxide, calcium phosphide or the tantalum barium that have disclosed high heat conduction particle such as aluminum oxide, silicon oxide, boron nitride, alumina-coated are bonded to the structure of polyimide film, make polyimide have thermal conductive resin, high dielectric strength and high adhesion, but this patent does not disclose the heat conduction data of any polyimide film.In this patent, the high heat conduction particle up to 80 % by weight is disclosed, its particle diameter is between between the 50nm to 10000nm.
At US Pat.No.5, in 078,936, disclose the method that increases the thermal conductivity/electroconductibility of polyimide film with carbon black, but this patent only is confined to the application of electroconductibility.
At US Pat.No.6, in 001,440, disclose with centrifugal casting modulus method (centrifugal casting) and form the high heat conduction particle of gradient concentration in polyimide film, to improve its thermal conductivity.Those particles account for 10% to 30% of finished film gross weight, are the particles that is selected from boron nitride, silicon oxide, beryllium oxide or aluminium nitride.Yet this patent does not disclose the conduction values of polyimide film yet.
In JP 2004123867 (A), disclose with CNT (carbon nano-tube) promoting more than thermal conductivity to the 0.3 watts/meter .K of polyimide, wherein the consumption of CNT (carbon nano-tube) is up to 50% of the polyimide film gross weight.Yet aforesaid method need adopt a large amount of CNT (carbon nano-tube) and unfavorable volume production.
In JP 9137060 (A), disclose the thermal conductivity that improves polyimide film with boron nitride or aluminium nitride.Its median size is approximately between 0.1 micron to 10 microns, and the thermal conductivity of finished film is approximately between 0.2 watts/meter .K to 0.6 watts/meter .K.
Yet the expensive particle that aforesaid method adopts certainly will cause Cost Problems when volume production, and these patents are not discussed other critical nature such as flexibility and the dielectric radio of finished film.Add the polyimide film of a large amount of heat conduction particles, will have high rigidity and be difficult to practical application.In addition, when improving thermal conductivity with inorganic particulate, need consider that still finished film adds a large amount of inorganic particulates and can improve its dielectric radio and cause dissipation loss.Yet known technology is not systematized exposure or consideration the problems referred to above all.
The inorganic fill particle that known technology adopts can improve thermal conductivity, but also improves simultaneously many character that need not improve such as specific inductivity, dissipation loss and film hardness.So, even improve the thermal conductivity of finished film, but other deteriorated character will make the film can't practical application.Unfortunately, many commercially available heat conduction film formulation only consider that its thermal conductivity between 0.2 watts/meter .K to 0.5 watts/meter .K, but ignored deteriorated dielectric properties.
The heat conduction particle filled composite that most of known technology adopts is oxide compound or nitride, such as silicon oxide, aluminum oxide, titanium oxide, aluminium nitride or boron nitride, or the material of the high-k such as titanium carbide or silicon carbide and high dissipation loss.So, above-mentioned particle filled composite has not only improved the thermal conductivity of polyimide, has also improved other dielectric properties simultaneously.At present still can improve simultaneously the thermal conductivity of polyimide film without the known technology of being correlated with and reduce or keep its specific inductivity and dissipation loss.
Another problem is mechanical properties such as the flexibility that a certain proportion of inorganic fill particle must reduce polyimide.When the inorganic fill particle accumulation, the problems referred to above will more worsen even the embrittlement film product.
In addition, polyimide is different from the thermal expansivity between the inorganic fill particle, and this can make and produce microstress between the two.The phonon transmission of the microstress of uneven distribution in film in will blocking thin film, and can reduce thermal diffusion effect, reduce on the contrary the film thermal conductivity.In addition, above-mentioned microstress may make deformation of thin membrane, causes assembly displacement and the performance of deteriorated assembly.
At last, surperficial potential energy catalyzed reaction (potential catalytic reaction) at high temperature may occur with polyimide or its precursor in the inorganic fill particle surface.Particularly in the extra small situation such as nano-scale of the particle diameter of particle filled composite, surperficial potential energy and the defect distribution of particle filled composite will significantly improve, and this will make the precursor of polyimide produce outside the control when the high temperature cyclization and between the particle filled composite and the reaction outside the expection.Apparently, above-mentioned surperficial potential energy catalyzed reaction will deteriorated finished product character.
In sum, need at present the answer that a kind of new method provides the problems referred to above badly, with the high thermal conductivity of taking into account simultaneously polyimide film, high dielectric strength, low-k, low dissipation loss, and good mechanical flexure.In order to reach above-mentioned target, the invention provides the nucleocapsid particle filled composite that different compositions and different-grain diameter distribute.
Summary of the invention
The invention provides a kind of heat dissipation composite material, comprise the polyimide resin of 100 weight parts; 0.1 to the first nucleocapsid particle filled composite of 50 weight parts, its particle diameter is between between the 10nm to 100nm; And the second nucleocapsid particle filled composite of 1 to 60 weight part, its particle diameter is between between the 100nm to 2000nm.Wherein, the first nucleocapsid particle filled composite and the second nucleocapsid particle filled composite are dispersed in the polyimide resin; First and second nucleocapsid particle filled composite wherein has inorganic core and organic shell, and the composition of first and second nucleocapsid particle filled composite is different.
The embodiment of invention
The invention provides a kind of heat dissipation composite material, comprise the polyimide resin of 100 weight parts; 0.1 to the first nucleocapsid particle filled composite of 50 weight parts, its particle diameter is between between the 10nm to 100nm, and the second nucleocapsid particle filled composite of 1 to 60 weight part, its particle diameter is between between the 100nm to 2000nm.Can insert between the particle filled composite of greater particle size than the particle filled composite of small particle size, therefore can be scattered between the polyimide resin more uniformly.In other words, the degree of freedom of polyimide molecule is higher, can improve the flexibility of finished film.May improve magnetism each other when in addition, the particle diameter of particle filled composite increases.If the distribution of particle filled composite is narrow, between between the 50nm to 500nm, then the flexibility of film is poor such as only.
Above-mentioned flexibility is shakeout after being defined as direct doubling Kapton, repeats above-mentioned action to confirm the film flexibility.If doubling is afterwards i.e. fracture once, then this film flexibility is poor.If the number of times that repeats doubling and shakeout is less than ten i.e. fractures, then the flexibility of this film is medium.If the number of times more than ten that repeats doubling and shakeout time just fracture, then the flexibility of this film is good.
Above-mentioned two kinds of nucleocapsid particle filled composites all are dispersed in the polyimide resin, and all have inorganic core and organic shell.In addition, the composition of two kinds of nucleocapsid particle filled composites is different.For instance, two kinds of core-shell particles may have different cores and/or shell, should depend on the needs.
The preparation method of above-mentioned nucleocapsid particle filled composite can be published in MaterialsScience and Enginerring A with reference to people such as P.Rainder; The paper of A498 (1-2) .135-141 (2008), United States Patent (USP) discloses US Pub.No.20080087314 in early days, the people such as CP Wang are published in Applied Physics Letters, 91 (14), 141904/1-3 (2007), JP 2007146068, the people such as MX Gu are published in Journal ofApplied Physics, 100 (9) 94304/1-8 (2006), the people such as Y Au are published in Physical Review B, 74 (15) 155317/1-10 (2006), the people such as R Prasher are published in Applied Physics Letters, 89 (6) 63121/1-3 (2006), the people such as M Hu are published in Chemical Physics Letters, 372 (5,6) 767-772 (2003), the people such as T Zeng are published in Journal of Applied Physics, 93 (7) 4163-4168 (2003), the people such as Y mamunye are published in European Polymer Journal, 38 (9) 1887-1897 (2002), the people such as E Suvaci are published in Ceramic Engineering and ScienceProceedings, in the periodicals such as 21,79-86 (2000) or the patent.Yet the particle that above-mentioned known technology does not all disclose nucleocapsid structure is bonded to polyimide resin also can be taken into account electrical character and flexibility simultaneously to improve its thermal conductivity solution.
In one embodiment of the invention, the shell of above-mentioned nucleocapsid structure is low-molecular-weight organic molecule such as octadecanoic acid (stearic acid), 12-hydroxyl octadecanoic acid (12-hydroxystearic acid), octyl group ammonium chloride (octylammonium chloride), cetyl trimethylammonium bromide (cetyltrimethylammonium bromide), Dodecyl trimethyl ammonium chloride (dodecyltrimethylammoniuim chloride), polyoxyethylene sorbitol four oleic acid esters (polyoxyethylene soritan tetraoleate), polyoxyethylene groups tridecyl ether (polyoxyethylenetridecyl ether), 4,4 '-diaminodiphenyl oxide (4,4 '-oxydianiline), 4,4 '-(hexafluoroisopropyli,ene)-two (to benzo oxygen base) pentanoic (4,4 '-(hexafluoroisopropylidene) bis (p-phenylenoxy) dianiline), 4,4 '-(hexafluoroisopropyli,ene) Tetra hydro Phthalic anhydride (4,4 '-(hexafluoroisopropylidene) diphthalic anhydride), 4,4 '-(isopropylidene two phenoxy groups) Tetra hydro Phthalic anhydride (4,4 '-(isopropylidene-diphenoxy) bis (phthalic anhydride)), or their combination.Above-mentioned organic molecule has carboxyl, carbonyl, hydroxyl, amide group and/or inferior amide group, can make organic molecule and inorganic layer produce reaction, and be fixed on the surface of inorganic core.Not being fixed in organic molecule on the inorganic core can be used as stablizer and is mixed in the polyimide solution.Above-mentioned organic molecule is dissolved in the specific solvent, form metastable solution after, but deposit thickness between 1nm to 10nm, preferably between the organic shell between the 2nm to 10nm on the surface of inorganic particulate.Above-mentioned organic shell accounts for 0.1% to 20% of nucleocapsid structure gross weight; the high temperature synthetic environment of the precursor of polyimide such as dicarboxylic anhydride and diamide such as 350 ℃ under, can effectively protect the inorganic core surface to avoid producing surperficial potential energy catalyzed reaction (potential catalytic reaction).
Except the protection inorganic core, organic shell also has other advantage.For instance, the characteristic of organic shell and polyimide resin compatibility can make core-shell particles can not assemble (aggregation) and more uniform being scattered in the polyimide, can be used as the buffer layer between polyimide and the inorganic core, and then improve the flexibility of finished film, and reduce the thermal expansivity of Kapton by higher loading level.
In a preferred embodiment, the inorganic core in the nucleocapsid structure can be including but not limited to oxide compound such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, ferric oxide, cobalt oxide, cupric oxide or zinc oxide; Nitride such as silicon nitride, aluminium nitride or boron nitride; Carbide such as silicon carbide, titanium carbide or norbide.But above-mentioned organic molecule formation of deposits shell in the surface of above-mentioned inorganic core to form nucleocapsid structure.
Inorganic core of the present invention can be metallic element, including but not limited to high-thermal conductive metals such as aluminium, nickel, cobalt, iron, copper.In another embodiment, before above-mentioned metallic core surface, can further form the surface that zone of oxidation coats above-mentioned metallic core with methods such as thermooxidizings first at the deposition organic molecule.The environment of above-mentioned step of thermal oxidation is general atmosphere, and temperature is between about 300 ℃ to 600 ℃, and the time was between 1 minute to 30 minutes.After the deposition organic shell, namely form the metallic core and the organic shell that are coated by the oxidized metal.
Metal oxide and the organic shell of above-mentioned clad metal core belong to insulating material together, can improve the characteristic that is electrically insulated of polyimide film.Adopt thermal oxidation method to form metal oxide and can dwindle even eliminate between the two mechanical properties difference in the practice on metallic core surface.Be close to the metal oxide layer of metallic core and can avoid the conduction property of metallic core to affect the characteristic that is electrically insulated of polyimide, in the voltage breakdown that promotes finished film, still take into account its thermal conductivity.
Yet above-mentioned nucleocapsid particle filled composite still may make polyimide film raising specific inductivity and dissipation loss to a certain degree.This is because the specific inductivity of metal oxide or metal alloy is still higher, for instance, magnesian specific inductivity is 9.7, the specific inductivity of aluminum oxide is between 9 to 11.5, and the specific inductivity of titanium oxide is 110, and the specific inductivity of cupric oxide is 18.1, the specific inductivity of silicon carbide is 10.8, the specific inductivity of ferric oxide is 14.2, and the specific inductivity of titanium carbide is between 5.8-7.0, and the specific inductivity of aluminium nitride is 9.The inorganic core of above-mentioned high-k all can deteriorated polyimide film dielectric properties, but mention or consider the problems referred to above without known technology.
For the higher problem of the high-k that solves above-mentioned part inorganic core, the present invention adopts the nucleocapsid particle filled composite of mixing.In brief, the present invention adopts the nucleocapsid particle filled composite of low-k and low dissipation loss, the nucleocapsid particle filled composite of high heat conduction of above-mentioned high-k and high dissipation loss of arranging in pairs or groups.So, can make polyimide film have simultaneously high heat conduction, low-k, and the characteristic such as high dielectric strength concurrently, and a plurality of embodiment of the present invention has proved that above-mentioned conception is feasible.
After the even mixing of the nucleocapsid particle filled composite that above-mentioned two kinds of different-grain diameters distribute and difference forms, add the precursor solution of polyimide.After violent high-speed stirring, carry out again degasification, mold, drying and heating steps, make the precursor cyclisation of polyimide form Kapton.Mentioned solution can be including but not limited to NMP, DMAc, DMSO, hexane, toluene, heptane, octane or their combination.The selection standard of solvent can not produce the phenomenons such as co-precipitation when being the mixing different solutions, and can not produce reaction with polyimide and nucleocapsid particle filled composite.
In another embodiment of the present invention, take the polyimide of 100 weight parts as the basis, can add again another nucleocapsid particle filled composite of 5 to 70 weight parts.Above-mentioned nucleocapsid particle filled composite also is dispersed in the polyimide resin, and its particle diameter is between between the 2000nm to 10000nm.Another nucleocapsid particle filled composite has inorganic core and organic shell, and its composition is different from first and second nucleocapsid particle filled composite.The inorganic core of another particle filled composite and the kind of organic shell are selected to be similar to first and second above-mentioned nucleocapsid particle filled composite, are not repeated herein.
In a preferred embodiment, the gross weight of nucleocapsid particle filled composite preferably between finished film 10% to 60% between.If the consumption of nucleocapsid particle filled composite very little, then can't effectively promote the thermal conductivity of polyimide film.But relatively, if nucleocapsid particle filled composite consumption is too high, then can reduce mechanical properties such as the flexibility of polyimide film.Those skilled in the art can be under the prerequisite that does not exceed category of the present invention, adjust between above-mentioned two kinds of core-shell particles weight when kind and further be applied to microelectronic product or photovoltaic reaching the heat dissipation composite material of best effect.
For above and other objects of the present invention, feature and advantage can be become apparent, hereinafter the spy enumerates several embodiment and cooperates appended diagram, is described in detail below.
[embodiment]
Embodiment 1
Get the 60g particle diameter between the silicon oxide between the 10nm to 30nm (Nissonchemical/DMAc-ST), insert the N,N-DIMETHYLACETAMIDE (hereinafter to be referred as DMAc) of the octadecanoic acid that is dissolved with 0.06g to 12g and the mixed solvent (v/v=70: 30) of toluene, make octadecanoic acid be deposited on silicon oxide surface, and confirm deposition results by thermogravimetry.After above-mentioned deposition, can get silicon oxide and be inorganic core and octadecanoic acid is the core-shell particles (being called for short SS-1) of organic shell.When the octadecanoic acid of the silicon oxide of 60g collocation 12g, its organic shell thickness of the nucleocapsid structure of formation is between between the 2nm to 2.5nm.
The present invention can adopt above-mentioned condition, only octadecanoic acid is replaced into 4,4 '-(hexafluoroisopropyli,ene)-two (to benzo oxygen base) pentanoic, to form silicon oxide as inorganic core 4,4 '-(hexafluoroisopropyli,ene)-two (to benzo oxygen base) pentanoic is the core-shell particles (being called for short SS-2) of organic shell.
No matter be SS-1 or SS-2, all can at the deposition organic shell ball-milling technology that zirconium oxide bead carried out 24 hours of in the step of inorganic core, arranging in pairs or groups, the core-shell particles of 30 % by weight be dispersed in the solution.
Embodiment 2
Get the 45g particle diameter between the (Japanese light metal/LS-110F) of the aluminum oxide between the 200nm to 1000nm, insert the DMAc of the cetyl trimethylammonium bromide that is dissolved with 0.045g to 9g and the mixed solvent of heptane (v/v=60: 40), the collocation zirconium oxide bead carries out 24 hours ball-milling technology, make cetyl trimethylammonium bromide be deposited on alumina surface, form the suspension that solid content is about 30 % by weight, and confirm deposition results by thermogravimetry.After above-mentioned deposition, can get aluminum oxide and be inorganic core and cetyl trimethylammonium bromide is the core-shell particles (being called for short AS-1) of organic shell, and the weight ratio of inorganic core and organic shell is about between 100: 1 to 100: 1.5.
Embodiment 3
Get the 65g particle diameter between the zinc oxide between the 300nm to 2000nm (Lu Chang chemical industry/U.S.'s legal system), insert and be dissolved with 4 of 0.65g to 3.25g, 4 '-the N-methyl pyrrolidone (hereinafter to be referred as NMP) of (hexafluoroisopropyli,ene) Tetra hydro Phthalic anhydride and the mixed solvent (v/v=70: 30) of heptane, the collocation zirconium oxide bead carries out 24 hours ball-milling technology, make 4,4 '-(hexafluoroisopropyli,ene) Tetra hydro Phthalic anhydride is deposited on zinc oxide surface, form the suspension that solid content is about 30 % by weight, and confirm deposition results by thermogravimetry.After above-mentioned deposition, can get zinc oxide and be inorganic core and 4,4 '-(hexafluoroisopropyli,ene) Tetra hydro Phthalic anhydride is the core-shell particles (being called for short ZS-1) of organic shell, and the weight ratio of inorganic core and organic shell is about between 100: 1 to 100: 1.5.
Embodiment 4
Get the 45g particle diameter between the (industry in the Asia/CR-EL) of the titanium oxide between the 300nm to 1000nm, insert the dimethyl sulfoxide (DMSO) (hereinafter to be referred as DMSO) of the 12-hydroxyl octadecanoic acid that is dissolved with 0.045g to 2.25g and the mixed solvent (v/v=60: 40) of octane, the collocation zirconium oxide bead carries out 24 hours ball milling processing procedure, make 12-hydroxyl octadecanoic acid be deposited on titania surface, form the suspension that solid content is about 30 % by weight, and confirm deposition results by thermogravimetry.After above-mentioned deposition, can get titanium oxide and be inorganic core and 12-hydroxyl octadecanoic acid is the core-shell particles (being called for short TS-1) of organic shell, and the weight ratio of inorganic core and organic shell is about between 100: 1 to 100: 1.5.
Embodiment 5
Get the 65g particle diameter between the aluminium powder between the 2000nm to 10000nm (prosperous pottery/sphericalaluminum powder), carry out 1 to 30 minute oxidizing process under atmosphere with 300 ℃ to 600 ℃ high temperature, the aluminium powder surface is already oxidised as can be known by appearance change (transferring white to).At this moment, the surface of aluminium core coated aluminum oxide layer.
The aluminium powder particle that above-mentioned surface is coated with aluminum oxide is inserted the DMAc of the cetyl trimethylammonium bromide that is dissolved with 0.065g to 3.25g and the mixed solvent of heptane (v/v=60: 40), the collocation zirconium oxide bead carries out 24 hours ball-milling technology, make cetyl trimethylammonium bromide be deposited on the surface of aluminum oxide, form the suspension that solid content is about 30 % by weight, and confirm deposition results by thermogravimetry.After above-mentioned deposition, the aluminium that can get surface-coated aluminum oxide is that inorganic core and cetyl trimethylammonium bromide are the core-shell particles (being called for short AAS-1) of organic shell, and the weight ratio of inorganic core and organic shell is about between 100: 1 to 100: 1.5.
Embodiment 6
Get the 65g particle diameter between the nickel powder between the 2000nm to 10000nm (her agate science and technology/reduction kenel), carry out 1 to 30 minute oxidizing process under atmosphere with 300 ℃ to 600 ℃ high temperature, the nickel powder surface is already oxidised as can be known by appearance change (transferring deep green to).This moment, the surface of nickel core coated nickel oxide layer.
The nickel particles that above-mentioned surface is coated with nickel oxide is inserted the DMAc of the cetyl trimethylammonium bromide that is dissolved with 0.065g to 3.25g and the mixed solvent of heptane (v/v=70: 30), the collocation zirconium oxide bead carries out 24 hours ball milling processing procedure, make cetyl trimethylammonium bromide be deposited on the surface of nickel oxide, form the suspension that solid content is about 30 % by weight, and confirm deposition results by thermogravimetry.After above-mentioned deposition, the nickel that can get surperficial coating nickel oxide is that inorganic core and cetyl trimethylammonium bromide are the core-shell particles (being called for short NNS-1) of organic shell, and the weight ratio of inorganic core and organic shell is about between 100: 1 to 100: 1.5.
Embodiment 7
Get the 32g particle diameter between the silicon carbide between the 300nm to 1500nm (thick strong/C-8), insert and be dissolved with 4 of 0.32g to 1.6g, 4 '-NMP of diaminodiphenyl oxide and the mixed solvent of octane (v/v=60: 40), the collocation zirconium oxide bead carries out 24 hours ball-milling technology, make 4,4 '-diaminodiphenyl oxide is deposited on silicon carbide, forms the suspension that solid content is about 30 % by weight, and confirm deposition results by thermogravimetry.After above-mentioned deposition, can get silicon carbide and be inorganic core and 4，4′-diaminodipohenyl ether is the core-shell particles (being called for short SC-1) of organic shell, and the weight ratio of inorganic core and organic shell is about between 100: 1.5 to 100: 3.
Embodiment 8
Get the SS-1 suspension of embodiment 1 and the AS-1 suspension of embodiment 2, evenly mix with the precursor solution of polyimide, wherein the weight ratio of SS-1 and AS-1 is about 30: 70.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form the Kapton of thickness between 25 microns to 37 microns, its SS-1 and AS-1 account for 10% to 80% of finished product gross weight, decide on the initial formula ratio.The above-mentioned film that contains the core-shell particles of different ratios all has smooth-flat-surface, if but the core-shell particles gross weight surpasses 60% of finished weight, and then the mechanical properties of film is for firmly crisp.If obtain good film flexibility, the core-shell particles gross weight of above-mentioned prescription is preferably less than 60% of finished film.
The thermal conductivity of said film finished product is between 0.5 watts/meter .K to 2.8 watts/meter .K, and specific inductivity is between 3.7 to 4.8, and dissipation loss is between 0.0085 to 0.037, and dielectric strength is between between the 3.7kV to 5.3kV.
Above-mentioned finished product character has reached the acceptable level of industrial application, but in order further to promote its mechanical properties such as flexibility, its core-shell particles gross weight is preferably less than 60% of finished film.
Get the said film finished product and carry out the measurement of thermal stretch machinery character, measure temperature between room temperature to 250 ℃, its thermal expansivity (being called for short CTE) is between between the 19.8ppm to 16.7ppm.
Embodiment 9
Get the SS-1 suspension of embodiment 1 and the TS-1 suspension of embodiment 4, evenly mix with the precursor solution of polyimide, wherein the weight ratio of SS-1 and TS-1 is about 40: 60.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its SS-1 and TS-1 account for 20% to 80% of finished product gross weight, decide on the initial formula ratio.The above-mentioned film that contains the core-shell particles of different ratios all has smooth-flat-surface, if but the core-shell particles gross weight surpasses 60% of finished weight, and then the mechanical properties of film is for firmly crisp.If film flexibility that will be better, the core-shell particles gross weight of above-mentioned prescription is preferably less than 60% of finished film.
The thermal conductivity of said film finished product is between 0.4 watts/meter .K to 4.5 watts/meter .K, and specific inductivity is between 3.7 to 8.8, and dissipation loss is between 0.0165 to 0.047, and dielectric strength is between between the 3.7kV to 6.3kV.
Above-mentioned finished product character has reached the acceptable level of industrial application, but in order further to promote its mechanical properties such as flexibility, its core-shell particles gross weight is preferably less than 60% of finished film.
Embodiment 10
Get the SS-1 suspension of embodiment 1 and the ZS-1 suspension of embodiment 3, evenly mix with the precursor solution of polyimide, wherein the weight ratio of SS-1 and ZS-1 is about 50: 50.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its SS-1 and ZS-1 account for 10% to 70% of finished product gross weight, decide on the initial formula ratio.
The thermal conductivity of said film finished product is between 0.3 watts/meter .K to 2.6 watts/meter .K, and specific inductivity is between 4.0 to 7.5, and dissipation loss is between 0.0185 to 0.056, and dielectric strength is between between the 3.9kV to 6.3kV.Yet compare with embodiment 9, the finished film of embodiment 10 has higher dissipation loss in the higher situation of core-shell particles content, should come from the person's character of ZS-1.
Above-mentioned finished product character has reached the acceptable level of industrial application, but in order further to promote its mechanical properties such as flexibility, its core-shell particles gross weight is preferably less than 50% of finished film.
Embodiment 11
Get the AS-1 suspension of embodiment 2 and the SC-1 suspension of embodiment 7, evenly mix with the precursor solution of polyimide, wherein the weight ratio of AS-1 and SC-1 is about 50: 50.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its AS-1 and SC-1 account for 10% to 70% of finished product gross weight, decide on the initial formula ratio.
When core-shell particles account for the finished product gross weight 20% to 70% the time, the thermal conductivity of said film finished product is between 0.4 watts/meter .K to 10.6 watts/meter .K.When core-shell particles account for the finished product gross weight 10% to 70% the time, the specific inductivity of said film finished product is between 4.0 to 7.5, dissipation loss is between 0.0085 to 0.056, and dielectric strength is between between the 2.8kV to 5.3kV.Yet compare with embodiment 9, the finished product of embodiment 11 has higher dissipation loss in the higher situation of core-shell particles content, should come from the person's character of AS-1 and SC-1.
In order to make finished film have good flexibility, low-k, to reach low dissipation loss, its core-shell particles gross weight is preferably less than 50% of finished film.Compare with embodiment 9-10, the size distribution of the core-shell particles of embodiment 11 is narrower, may therefore cause the flexibility of finished film relatively poor.
Embodiment 12
Get the SS-1 suspension of embodiment 1 and the AAS-1 suspension of embodiment 5, evenly mix with the precursor solution of polyimide, wherein the weight ratio of SS-1 and AAS-1 is about 50: 50.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its SS-1 and AAS-1 account for 10% to 70% of finished product gross weight, decide on the initial formula ratio.
The thermal conductivity of said film finished product is between 0.3 watts/meter .K to 4.8 watts/meter .K, and specific inductivity is between 4.0 to 6.5, and dissipation loss is between 0.0085 to 0.0256, and dielectric strength is between between the 4.9kV to 6.3kV.Yet this finished film has higher dissipation loss in the higher situation of core-shell particles content, should come from the person's character of AAS-1.
In order to make finished film have good flexibility, its core-shell particles gross weight is preferably less than 50% of finished film.
Get the said film finished product and carry out thermal expansivity and measure, measure temperature between room temperature to 250 ℃, its thermal expansivity (being called for short CTE) is between between the 18.8ppm to 16.7ppm.By experimental result as can be known, when the consumption of core-shell particles increased, the thermal expansivity of finished film also decreased.
Embodiment 13
Get the SS-1 suspension of embodiment 1 and the NNS-1 suspension of embodiment 6, evenly mix with the precursor solution of polyimide, wherein the weight ratio of SS-1 and NNS-1 is about 50: 50.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its SS-1 and NNS-1 account for 20% to 80% of finished product gross weight, decide on the initial formula ratio.
The thermal conductivity of said film finished product is between 0.5 watts/meter .K to 5.6 watts/meter .K, and specific inductivity is between 4.0 to 7.5, and dissipation loss is between 0.0065 to 0.0156, and dielectric strength is between between the 4.9kV to 7.3kV.Yet this finished film has higher dissipation loss in the higher situation of core-shell particles content, should come from the person's character of NNS-1.
In order to make finished film have good flexibility, its core-shell particles gross weight is preferably less than 60% of finished film.
Embodiment 14
Get AS-1 suspension, and the SC-1 suspension of embodiment 7 of SS-1 suspension, the embodiment 3 of embodiment 1, evenly mix with the precursor solution of polyimide, wherein SS-1, AS-1, be about 30: 50: 20 with the weight ratio of SC-1.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its SS-1, AS-1, with SC-1 account for 20% to 80% of finished product gross weight, decide on the initial formula ratio.
The thermal conductivity of said film finished product is between 0.5 watts/meter .K to 4.6 watts/meter .K, and specific inductivity is between 4.3 to 6.5, and dissipation loss is between 0.0285 to 0.026, and dielectric strength is between between the 3.9kV to 6.3kV.In order to make finished film have good flexibility, its core-shell particles gross weight is preferably less than 65% of finished film.
Embodiment 15
Get ZS-1 suspension, and the AAS-1 suspension of embodiment 5 of SS-1 suspension, the embodiment 3 of embodiment 1, evenly mix with the precursor solution of polyimide, wherein SS-1, ZS-1, be about 20: 50: 30 with the weight ratio of AAS-1.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its SS-1, ZS-1, with AAS-1 account for 20% to 80% of finished product gross weight, decide on the initial formula ratio.
The thermal conductivity of said film finished product is between 0.5 watts/meter .K to 7.6 watts/meter .K, and specific inductivity is between 4.5 to 6.5, and dissipation loss is between 0.0085 to 0.046, and dielectric strength is between between the 3.5kV to 6.7kV.In order to make finished film have good flexibility, its core-shell particles gross weight is preferably less than 60% of finished film.
Comparative example 1
The single suspension of getting the SS-1 of embodiment 1 evenly mixes with the precursor solution of polyimide, then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its SS-1 accounts for 20% to 60% of finished product gross weight, decides on the initial formula ratio.
The thermal conductivity of said film finished product is between 0.5 watts/meter .K to 1.5 watts/meter .K, and specific inductivity is between 3.8 to 4.7, and dissipation loss is between 0.0095 to 0.028, and dielectric strength is between between the 3.6kV to 4.8kV.Yet this finished film has higher dissipation loss in the higher situation of core-shell particles content.
In order to make finished film have good flexibility, its core-shell particles gross weight is preferably less than 60% of finished film.
Comparative example 2
Get the AAS-1 suspension of embodiment 5 and the NNS-1 suspension of embodiment 6, evenly mix with the precursor solution of polyimide, wherein the weight ratio of ASS-1 and NNS-1 is about 50: 50.Then with the violent high-speed stirring of said mixture two hours, after carrying out again degasification, mold, drying and heating steps (350 ℃), make the precursor cyclisation of polyimide form Kapton, its ASS-1 and NNS-1 account for 20% to 60% of finished product gross weight, decide on the initial formula ratio.
The thermal conductivity of said film finished product is between 0.5 watts/meter .K to 5.8 watts/meter .K, specific inductivity is between 4.2 to 7.8, dissipation loss is between 0.018 to 0.078, and dielectric strength is between between the 2.5kV to 3.8kV, and made Kapton is bad through the flexibility test result.
| Ex8 | Ex9 | Ex10 | Ex11 | Ex12 | |
| Weighting material (Filler) kind | SS-1：30％ AS-1：70％ | SS-1：40％ TS-1：60％ | SS-1：50％ ZS-1：50％ | AS-1：50％ SC-1：50％ | SS-1：50％ AAS-1：50％ |
| Weighting material (Filler) filling ratio | ≤60wt％ | ≤60wt％ | ≤50wt％ | ≤50wt％ | ≤60wt％ |
| K (thermal conductivity) 4) W/M*K | 0.5～2.8 | 0.4～4.5 | 0.3～2.6 | 0.4～10.6 | 0.3～4.8 |
| DK 1) | 3.7～4.8 | 3.7～8.8 | 4.0～7.5 | 4.0～7.5 | 4.0～6.5 |
| Df 2) | 0.0085～0.037 | 0.0165～0.047 | 0.0185～0.056 | 0.0085～0.056 | 0.0085～0.0256 |
| Disintegration voltage 3) (KV) | 3.7～5.3 | 3.7～6.3 | 3.9～6.3 | 2.8～5.3 | 4.9～6.3 |
| Flexibility | Good | Good | Good | Good | In～good |
| Ex13 | Ex14 | Ex15 | Comparative example 1 | Comparative example 2 | |
| Weighting material (Filler) kind | SS-1：50％ NNS-1：50％ | SS-1：30％ AS-1：50％ SC-1：20％ | SS-1：20％ ZS-1：50％ AAS-1：30％ | SS-1：100％ | AAS-1：50％ NNS-1：50％ |
| Weighting material (Filler) filling ratio | ≤60wt％ | ≤65wt％ | ≤60wt％ | ≤60wt％ | ≤60wt％ |
| K (thermal conductivity) W/M*K | 0.5～5.6 | 0.5～4.6 | 0.5～7.6 | 0.5～1.5 | 0.5～5.8 |
| DK | 4.0～7.5 | 4.3～6.5 | 4.5～6.5 | 3.8～4.7 | 4.2～7.8 |
| Df | 0.0065～ 0.0156 | 0.0028～ 0.026 | 0.0085～ 0.046 | 0.0095～ 0.028 | 0.018～ 0.078 |
| Disintegration voltage (KV) | 4.9～7.3 | 3.9～6.3 | 3.5～6.7 | 3.6～4.8 | 2.5～3.8 |
| Flexibility | In～good | Good | In～good | In～good | Poor |
1) DK (specific inductivity):
Medium coefficient under the dielectric medium coefficient/vacuum condition of D k=
The electrical capacity of=dielectric electrical capacity/take vacuum as medium
C＝εA/d C
0＝ε
0A/d
C/C
0=ε/ε
0=Dk (specific inductivity)
A: electrode area d: thickness of sample
ε
0＝8.85×10-12
ε＝(C×D)÷(0.0885×A)
A＝πr
2
C: electric capacity
D: thickness of sample (cm)
A: electrode area
Metering facility: multifrequency L.C.R survey meter, HP42754 instrument
2) Df (dissipation loss):
Circuit substrate is behind plugged, and signal (hertzian wave) is namely advanced online at copper, because the atom in the substrate medium is subject to the movement that the polarization of electric field produces electric charge, i.e. so-called electric current.This current phenomena is very little and have more now surface near conductor, and very shallow decays to zero soon, and this phenomenon is the loss (dissipation) of energy.
Metering facility: multifrequency L.C.R survey meter, HP42754 instrument
3) disintegration voltage:
Medium can afford the high-voltage of a certain numerical value and the ability of unlikely collapse.Or a kind of nonconducting isolator become conductor and the required minimum voltage of generation current.
Metering facility: withstands voltage tester model 730-1
4) K (thermal conductivity):
Heat-conduction coefficient (Thermal Conductivity): under the unit temperature difference, the heat of unit time by the unit surface unit distance, the heat-conduction coefficient that is called this material, if the material with thickness L is measured, then observed value will multiply by L, the value of gained is to be heat-conduction coefficient, usually remembers into k.
Metering facility: Hot-Disk 2400 types
Although the present invention discloses a plurality of better embodiment as above; but these embodiment limit the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; can do a little change and retouching, so protection scope of the present invention should be as the criterion with the scope that appending claims was defined.
Claims (3)
1. heat dissipation composite material comprises:
The polyimide resin of 100 weight parts;
0.1 to the first nucleocapsid particle filled composite of 50 weight parts, its particle diameter is between the 10nm to 100nm; And
The second nucleocapsid particle filled composite of 1 to 60 weight part, its particle diameter is between the 100nm to 2000nm;
Wherein, this first nucleocapsid particle filled composite and this second nucleocapsid particle filled composite are dispersed in this polyimide resin;
First and second nucleocapsid particle filled composite of wherein this has inorganic core and organic shell, and the composition of first and second nucleocapsid particle filled composite is different,
Wherein, this inorganic core is oxide compound, is selected from silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, ferric oxide, cobalt oxide, cupric oxide or zinc oxide; Nitride is selected from silicon nitride, aluminium nitride or boron nitride; Carbide is selected from silicon carbide, titanium carbide or norbide; Or metal, be selected from aluminium, cobalt, nickel, titanium, silver, copper or iron, and the metallic surface comprises the oxide compound of corresponding core metal;
Wherein, this organic shell is selected from octadecanoic acid, 12-hydroxyl octadecanoic acid, octyl group ammonium chloride, cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride, polyoxyethylene sorbitol four oleic acid esters, polyoxyethylene groups tridecyl ether, 4,4 '-diaminodiphenyl oxide, 4,4 '-(hexafluoroisopropyli,ene)-two (to benzo oxygen base) pentanoic, 4,4 '-(hexafluoroisopropyli,ene) Tetra hydro Phthalic anhydride, 4,4 '-(isopropylidene two phenoxy groups) Tetra hydro Phthalic anhydride or their combination.
2. heat dissipation composite material as claimed in claim 1, further comprise the 3rd nucleocapsid particle filled composite 5 to 70 weight parts that are dispersed in the polyimide resin, its particle diameter is between the 2000nm to 10000nm, wherein, the 3rd nucleocapsid particle filled composite has inorganic core and organic shell, and its form from this first and this second nucleocapsid particle filled composite different.
3. heat dissipation composite material as claimed in claim 1, it is applied to microelectronic product or photovoltaic.
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| CN103367828B (en) * | 2012-03-29 | 2015-11-25 | 深圳市西盟特电子有限公司 | A kind of from radiating element and preparation method thereof |
| CN103367829B (en) * | 2012-03-29 | 2015-07-01 | 深圳市西盟特电子有限公司 | Self-cooling device and preparation method thereof |
| CN103194062B (en) * | 2013-03-29 | 2015-05-27 | 株洲时代电气绝缘有限责任公司 | Polyimide film and preparation method thereof |
| CN103923330A (en) * | 2014-04-30 | 2014-07-16 | 山东中天华德科技发展有限公司 | Method for preparing high-thermal conductivity polyimide/magnesium oxide composite film |
| CN105219068B (en) * | 2014-05-30 | 2017-12-29 | 杜邦公司 | Heat-conduction electric insulation composition comprising hud typed filler |
| DE102014107909A1 (en) * | 2014-06-05 | 2015-12-17 | Infineon Technologies Ag | Printed circuit boards and process for their manufacture |
| KR101774041B1 (en) | 2014-09-17 | 2017-09-01 | 주식회사 엘지화학 | Composition for forming conductive pattern and resin structure having conductive pattern thereon |
| CN107400360A (en) * | 2017-06-28 | 2017-11-28 | 徐昌霞 | A kind of microelectronic device polyimides/aluminium nitride hybridized film and preparation method thereof |
| CN107916090B (en) * | 2017-11-03 | 2020-07-28 | 浙江福斯特新材料研究院有限公司 | Low-modulus high-bonding-capacity thermoplastic polyimide composition and application and preparation method thereof |
| CN109576528B (en) * | 2018-12-21 | 2020-09-18 | 华北电力大学（保定） | Copper-based composite material with SiC-CDCs @ TiC as reinforcing phase and preparation method thereof |
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| JP2004189938A (en) * | 2002-12-12 | 2004-07-08 | Nippon Sheet Glass Co Ltd | Conductive molded resin part |
| JP2005171206A (en) * | 2003-12-15 | 2005-06-30 | Toyota Motor Corp | Powdery mixture for blending with resin, and resin composition |
| CN1865350A (en) * | 2005-05-16 | 2006-11-22 | 北京航空航天大学 | Organic-inorganic hybridized nano composite material resisting atomic oxygen denudation and its preparation method |
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| JP2004189938A (en) * | 2002-12-12 | 2004-07-08 | Nippon Sheet Glass Co Ltd | Conductive molded resin part |
| JP2005171206A (en) * | 2003-12-15 | 2005-06-30 | Toyota Motor Corp | Powdery mixture for blending with resin, and resin composition |
| CN1865350A (en) * | 2005-05-16 | 2006-11-22 | 北京航空航天大学 | Organic-inorganic hybridized nano composite material resisting atomic oxygen denudation and its preparation method |
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