CN102093713A - Heat dissipation composite material - Google Patents
Heat dissipation composite material Download PDFInfo
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- CN102093713A CN102093713A CN2009102542009A CN200910254200A CN102093713A CN 102093713 A CN102093713 A CN 102093713A CN 2009102542009 A CN2009102542009 A CN 2009102542009A CN 200910254200 A CN200910254200 A CN 200910254200A CN 102093713 A CN102093713 A CN 102093713A
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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 setization 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 produced is straight line rising thereupon also, how will become important key to keep the stable running of electronic product system via good heat radiation, polyimide resin is because of 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 is brought towards microminiaturization and high speed trend for the following electronic product of correspondence, the function of if can the resin insulating barrier in substrate giving heat conduction, can provide good assembly radiating approach, to increase the 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 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 die 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 the cost problem when volume production, and these patents are not discussed other critical nature such as the 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, need consider that still finished film adds a large amount of inorganic particulates and can improve its dielectric radio and cause dissipation loss with inorganic particulate.Yet all not systematized exposure of known technology or consideration the problems referred to above.
The inorganic particle filled composite that known technology adopted can improve thermal conductivity, but also improves many character that need not improve such as specific inductivity, dissipation loss and film hardness simultaneously.So, even improve the thermal conductivity of finished film, but the character of other deterioration 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 the dielectric properties of deterioration.
The heat conduction particle filled composite that most of known technology adopts is oxide compound or nitride, as silicon oxide, aluminum oxide, titanium oxide, aluminium nitride or boron nitride, or the material of 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.Still not having at present the known technology of being correlated with can improve the thermal conductivity of polyimide film simultaneously 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 particle filled composite must reduce polyimide.When inorganic particle filled composite was assembled, the problems referred to above will more worsen even the embrittlement film product.
In addition, polyimide is different with the thermal expansivity between the inorganic particle filled composite, 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 the film thermal conductivity on the contrary.In addition, above-mentioned microstress may make deformation of thin membrane, causes assembly displacement and the performance of deterioration assembly.
At last, surperficial potential energy catalyzed reaction (potential catalytic reaction) at high temperature may take place with polyimide or its precursor in inorganic particle filled composite surface.Particularly under the extra small situation of the particle diameter of particle filled composite as nano-scale, the 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 deterioration finished product character.
In sum, need the answer that a kind of new method provides the problems referred to above at present badly, with the high thermal conductivity of taking into account polyimide film simultaneously, high dielectric strength, low-k, low dissipation loss, and favorable mechanical flexibility.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 radiation matrix 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 difference of first and second nucleocapsid particle filled composite.
The embodiment of invention
The invention provides a kind of heat radiation matrix 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 i.e. fracture after the doubling 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 that repeats doubling and shakeout surpasses ten just fractures, 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 difference of two kinds of nucleocapsid particle filled composites.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, people such as CP Wang are published in Applied Physics Letters, 91 (14), 141904/1-3 (2007), JP 2007146068, people such as MX Gu are published in Journal ofApplied Physics, 100 (9) 94304/1-8 (2006), people such as Y Au are published in Physical Review B, 74 (15) 155317/1-10 (2006), people such as R Prasher are published in Applied Physics Letters, 89 (6) 63121/1-3 (2006), people such as M Hu are published in Chemical Physics Letters, 372 (5,6) 767-772 (2003), people such as T Zeng are published in Journal of Applied Physics, 93 (7) 4163-4168 (2003), people such as Y mamunye are published in European Polymer Journal, 38 (9) 1887-1897 (2002), people such as E Suvaci are published in Ceramic Engineering and ScienceProceedings, 21, in 79-86 periodicals such as (2000) or the patent.Yet above-mentioned known technology does not all disclose particle with nucleocapsid structure and is bonded to polyimide resin to improve its thermal conductivity and can take into account the solution of electrical character and flexibility simultaneously.
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 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 earlier at the deposition organic molecule with methods such as thermooxidizings.The environment of above-mentioned step of thermal oxidation is a general atmosphere, and temperature is between about 300 ℃ to 600 ℃, and the time was between 1 minute to 30 minutes.After the organic shell of deposition, promptly form the metallic core and the organic shell that coat by the oxidized metal.
The metal oxide of above-mentioned clad metal core and organic shell 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 influence 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 the deterioration polyimide film dielectric properties, but do not have known technology and mention or consider the problems referred to above.
For the higher problem of the high-k that solves above-mentioned part inorganic core, the present invention adopts blended nucleocapsid particle filled composite.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 high heat conduction, low-k, and characteristic such as high dielectric strength simultaneously concurrently, and a plurality of embodiment of the present invention has proved that above-mentioned conception is feasible.
Behind the nucleocapsid particle filled composite uniform mixing that above-mentioned two kinds of different-grain diameters distribute and difference is formed, add the precursor solution of polyimide.After violent high-speed stirring, carry out degasification, mold, drying and heating steps again, make the precursor cyclisation of polyimide form Kapton.Above-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 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,, can add another nucleocapsid particle filled composite of 5 to 70 weight parts again based on the polyimide of 100 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 with 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, do not give unnecessary details at this.
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,, then can reduce the mechanical properties such as the flexibility of polyimide film if nucleocapsid particle filled composite consumption is too high.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 radiation matrix 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 outer casing 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 is inorganic core and 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 the core-shell particles of 30 weight % be dispersed in the solution at the organic shell of the deposition ball-milling technology that zirconium oxide bead carried out 24 hours of in the step of inorganic core, arranging in pairs or groups.
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 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 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 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 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 with 300 ℃ to 600 ℃ high temperature under atmosphere, 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 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 weight %, and confirm deposition results by thermogravimetry.After above-mentioned deposition, can get silicon carbide and be inorganic core and 4 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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, but if the core-shell particles gross weight surpasses 60% of finished weight, then the mechanical properties of film is for crisp firmly.If will obtain the 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 above-mentioned finished film 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 above-mentioned finished film 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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, but if the core-shell particles gross weight surpasses 60% of finished weight, then the mechanical properties of film is for crisp firmly.If want preferable film flexibility, the core-shell particles gross weight of above-mentioned prescription is preferably less than 60% of finished film.
The thermal conductivity of above-mentioned finished film 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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 under core-shell particles content condition with higher, 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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 above-mentioned finished film 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 under core-shell particles content condition with higher, 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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 under core-shell particles content condition with higher, 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 above-mentioned finished film 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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 under core-shell particles content condition with higher, 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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
Get the single suspension of SS-1 of embodiment 1 and the precursor solution uniform mixing of polyimide, then with the violent high-speed stirring of said mixture two hours, after carrying out degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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 under core-shell particles content condition with higher.
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, with the precursor solution uniform mixing 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 degasification, mold, drying and heating steps (350 ℃) again, 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 above-mentioned finished film 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 | Difference |
1) DK (specific inductivity):
Medium coefficient under the dielectric medium coefficient/vacuum condition of D k=
=dielectric electrical capacity/with the vacuum is the electrical capacity of 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 after connecting power supply, and signal (hertzian wave) is promptly advanced in that copper is online, and the polarization that is subjected to electric field because of the atom in the substrate medium produces movement of electric charges, promptly so-called electric current.This current phenomena is very little and have more now near surface of conductors, 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 produce the required minimum voltage of electric 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 measure with the material of thickness L, then observed value will multiply by L, the value of gained is to be heat-conduction coefficient, remembers into k usually.
Metering facility: Hot-Disk 2400 types
Though the present invention discloses a plurality of better embodiment as above; but these embodiment are not in order to 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 (9)
- One kind the heat radiation matrix material, comprising: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; AndThe 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 difference of first and second nucleocapsid particle filled composite.
- 2. heat radiation matrix material as claimed in claim 1, wherein, this inorganic core is an oxide compound, is selected from silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, ferric oxide, cobalt oxide, cupric oxide or zinc oxide.
- 3. heat radiation matrix material as claimed in claim 1, wherein, this inorganic core is a nitride, is selected from silicon nitride, aluminium nitride or boron nitride.
- 4. heat radiation matrix material as claimed in claim 1, wherein, this inorganic core is a carbide, is selected from silicon carbide, titanium carbide or norbide.
- 5. heat radiation matrix material as claimed in claim 1, wherein, this inorganic core is a metal, is selected from aluminium, cobalt, nickel, titanium, silver, copper or iron.
- 6. heat radiation matrix material as claimed in claim 5, wherein, the surface of this inorganic core further comprises the oxide compound of corresponding core metal.
- 7. heat radiation matrix material as claimed in claim 1, 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.
- 8. heat radiation matrix 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 with this first and this second nucleocapsid particle filled composite different.
- 9. heat radiation matrix material as claimed in claim 1, it is applied to microelectronic product or photovoltaic.
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|---|---|---|---|
| CN 200910254200 CN102093713B (en) | 2009-12-10 | 2009-12-10 | Heat dissipation composite material |
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