CN101882584A - Heat-conducting insulating composite substrate and preparation method thereof - Google Patents
Heat-conducting insulating composite substrate and preparation method thereof Download PDFInfo
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- CN101882584A CN101882584A CN2009101364165A CN200910136416A CN101882584A CN 101882584 A CN101882584 A CN 101882584A CN 2009101364165 A CN2009101364165 A CN 2009101364165A CN 200910136416 A CN200910136416 A CN 200910136416A CN 101882584 A CN101882584 A CN 101882584A
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Abstract
The invention relates to a preparation method of a heat-conducting insulating composite substrate, which comprises the steps of: carrying out hydrolytic condensation reaction on at least one ceramic powder to obtain at least one modified ceramic powder, wherein the at least one modified ceramic powder comprises a plurality of modified powder particles, and the surface of each modified powder particle is grafted with an organic compound; mixing the at least one modified ceramic powder, a high molecular material and a curing agent to obtain an insulating material; extruding the insulating material to pass through a slit to form a plate shaped substrate; and respectively arranging a first film material and a second film material on two plate surfaces of the plate shaped substrate to from the heat-conducting insulating substrate, wherein the first film material and the second film material are selected from metal materials or release materials. Because of being made of rubber-like insulating materials with the characteristic of mutual transit network structure, the heat-conducting insulating substrate has the advantages of having high heat conduction, not generating the problem of solid and liquid demixing, being made in an extrusion mode, improving the preparation speed and the like.
Description
Technical field
The present invention relates to a kind of heat radiation substrate and its preparation method, particularly comprise and penetrate network configuration (inter-penetrating-network alternately; The heat radiation substrate and its preparation method of heat conductive insulating macromolecular material IPN).
Background technology
In recent years, because the power of the electronic component that uses on the circuit board in the electronic installation is more and more higher, the heat management problems that electronic component produces became very important.If the heat radiation of electronic component is bad, will make electronic component be in the condition of high temperature, temperature of electronic component is too high, not only significantly reduces the performance of electronic component, even influences its life-span and reliability.Therefore, electronic installation often uses heat conduction circuitry substrate preferably in when design, so that provide heat dissipation environment preferably for electronic component.
The making of the heat conduction circuitry substrate of prior art is that the paste resin that material mixing such as liquid-state epoxy resin, heat filling and curing agent form is coated on the metal base, be heated then to form colloidal state (B-stage), utilize hot pressing to be made into circuit board at last again; Perhaps, epoxy resin is coated on the glass fabric, add thermosetting colloidal state (B-stage) after, produce the glass fibre circuit board by heat pressing process again.
The technology of above-mentioned prior art need be used the paste resin of lower viscosity, yet low viscous paste resin can produce the phenomenon that solid and liquid layering take place because of the heat filling sedimentation, this phenomenon can cause mixes inequality, and then have influence on radiating efficiency, and described paste resin also has the problem that is difficult for storage.With the circuit board of glass fibre making, because the conductive coefficient low (being about 0.36W/mK) of glass fibre, so its heat-conducting effect is bad.In addition, the technology of above-mentioned prior art is all used coating process, and speed is slow, problem such as yield poorly yet coating process has.
In sum, the making of the heat conduction circuitry substrate of prior art is to utilize coating process, however coating process speed slow, yield poorly, and because of it need use low viscous paste resin, and the problem of solid and liquid layering easily takes place.In addition, because the conductive coefficient of glass fibre is low, therefore bad with the circuit board heat-conducting effect of glass fibre making.So, still need the heat conduction circuitry substrate of the high capacity of heat transmission of a kind of tool and the manufacture method of the heat conduction circuitry substrate of the high capacity of heat transmission of the energy described tool of high speed volume production at present.
Summary of the invention
The heat conductive insulating compound substrate and its preparation method that the invention provides a kind of heat conductive insulating substrate and be made with described heat conductive insulating substrate, the heat conductive insulating substrate is that present the insulating material of rubber-like (rubbery) to have the characteristic that penetrates network configuration alternately made, described insulating material tool high-termal conductivity, and the problem that solid and liquid layering do not take place, and can utilize the mode of extruding to make, so can improve its preparation speed.
First aspect present invention discloses a kind of preparation method of heat conductive insulating substrate, it comprises the following step: to the condensation reaction that is hydrolyzed of at least a ceramic powders, to obtain at least a modified ceramic powder, wherein each described at least a modified ceramic powder comprises a plurality of modified powder particles, and the surface grafting organic compound of each described modified powder particle; Described at least a modified ceramic powder, macromolecular material and curing agent are mixed, to obtain insulating material; Described insulating material is pressed through slit, to form plate-like substrate; And the first film material and the second film material are set respectively on two plate faces of described plate-like substrate, and form described heat conductive insulating substrate, the wherein said first film material and the second film material are selected from metal material or release material.
Second aspect present invention discloses a kind of preparation method of heat conductive insulating compound substrate, it comprises the following step: to the condensation reaction that is hydrolyzed of at least a ceramic powders, to obtain at least a modified ceramic powder, wherein each described at least a ceramic powders comprises a plurality of powder particles, and through behind the described hydrolysis-condensation reaction, the surface grafting organic compound of each described modified powder particle; Described at least a modified ceramic powder, macromolecular material and curing agent are mixed, to obtain insulating material; Described insulating material is pressed through slit, to form plate-like substrate; The metal material is set on a plate face of described plate-like substrate; The described plate-like substrate that cuts the described metal material of tool becomes the heat conductive insulating substrate; And under pressing-in temp, the described heat conductive insulating substrate of pressing multi-disc, and form described heat conductive insulating compound substrate.
Compared to the technology of prior art, the outward appearance of described sheet heat conductive insulating composite material presents rubber-like (non-resin pulpous state (slurry)) thereby has the characteristic of convenient storage, processing.In addition, described heat conductive insulating composite material also can utilize the processing method that is generally used in thermoplastics to be processed, and improves its machinability thus.And the heat conductive insulating substrate is that present the insulating material of rubber-like (rubbery) to have the characteristic that penetrates network configuration alternately made, described insulating material tool high-termal conductivity, and the problem that solid and liquid layering do not take place, and can utilize the mode of extruding to make, so can improve its preparation speed.
Description of drawings
Fig. 1 shows preparation method's the schematic flow sheet of the heat conductive insulating substrate of one embodiment of the invention;
Fig. 2 A to Fig. 2 C shows the generalized section of the heat conductive insulating compound substrate of one embodiment of the invention; And
Fig. 3 shows the schematic diagram of the continous way device for injection moulding of one embodiment of the invention.
Embodiment
Fig. 1 shows preparation method's the schematic flow sheet of the heat conductive insulating compound substrate of one embodiment of the invention.One embodiment of the invention discloses the preparation method of heat conductive insulating compound substrate, described method comprises the following step: in step S11, to the condensation reaction that is hydrolyzed of at least a ceramic powders, to obtain at least a modified ceramic powder, wherein each described at least a modified ceramic powder comprises a plurality of modified powder particles, and the surface grafting organic compound of described modified powder particle.In one embodiment, described organic compound is an organosilicon, and described hydrolysis-condensation reaction is under sour environment, so that described organosilicon reacts described at least a ceramic powders; In another embodiment, described organic compound is an organic titanium, and described hydrolysis-condensation reaction is under sour environment, so that organic titanium reacts described at least a ceramic powders, and the sour environment in above-mentioned two embodiment, its pH-value is between PH 1 to PH 5.In step S12, described at least a modified ceramic powder is mixed with macromolecular material and curing agent (curingagent), to obtain insulating material, the conductive coefficient of wherein said insulating material is greater than 0.5W/mK.In step S13, described insulating material is pressed through slit, to form plate-like substrate, wherein said insulating material is pressed through described slit with the temperature between 50 ℃ to 150 ℃.
In step S14, on the two plate faces of described plate-like substrate, the first film material and the second film material are set respectively.The first film material and the second film material can comprise release material and metal material respectively.The combination of the first film material, plate-like substrate and the second film material (the first film material/plate-like substrate/second film material) can comprise release material/plate-like substrate/release material (that is preimpregnation substrate; Prepregsubstrate), metal material/plate-like substrate/release material (that is resin clad metal substrate; Resin coated metalsubstrate) and metal material/plate-like substrate/metal material (that is metal core substrate; Metal core substrate) various combination such as.In step S15, cut the plate-like substrate that the first film material and the second film material are set and become the heat conductive insulating substrate, the heat conductive insulating substrate can be overlapped into single sided board, double sided board, metal core core or MULTILAYER SUBSTRATE with other metal substrate or printed circuit board (PCB), under pressing-in temp, be pressed into the heat conductive insulating compound substrate, and described pressing-in temp can be between 80 ℃ to 220 ℃.In step S16, with forming technique, the described heat conductive insulating compound substrate of finishing pressing, wherein said forming technique comprise cut, shearing, die-cut, technology such as diamond is cut.
The composition of macromolecular material comprises thermoplastics (thermoplastic) and thermosetting epoxy resin (thermosetting epoxy), and the percent by volume that described thermosetting epoxy resin can account for described macromolecular material is between 70% to 97%.Described thermosetting epoxy resin can by described curing agent under curing temperature with its curing, wherein said curing temperature can be higher than 80 ℃.
Specific, the macromolecular material that the blending method of described insulating material at first will comprise described thermoplastics and described thermosetting epoxy resin mixes about 30 minutes to generate even colloid with 200 ℃ of heating.Mix to form even rubber-like material after again the ceramic powders after the modification being added described even colloid, again curing agent and accelerator are added described even rubber-like material under 80 ℃ of temperature, to form insulating material, wherein said even rubber-like material tool penetrates network configuration (inter-penetrating network) alternately, and because described thermoplastics and described thermosetting epoxy resin are to dissolve each other each other and be homogeneous phase (homogeneous), make described ceramic powders be dispersed evenly to described penetrating alternately in the network configuration thus, to reach best heat-conducting effect.Described ceramic powders is to be dispersed in the described macromolecular material, and the percent by volume that described ceramic powders accounts for described insulating material is between 40% to 70%.
Above-mentioned thermoplastics can be the super high molecular weight phenoxy resin, and the molecular weight of wherein said super high molecular weight phenoxy resin can be greater than 30000.Thermoplastics also can comprise hydroxyl-phenoxy resin ether macromolecular structure, and wherein said hydroxyl-phenoxy resin ether macromolecular structure can form through polymerization reaction via di-epoxide and difunctional material.Described thermoplastics can be reacted by modes such as liquid-state epoxy resin and bisphenol-A, liquid-state epoxy resin and divalent acid, liquid-state epoxy resin and amines respectively again and form.Above-mentioned thermosetting epoxy resin can comprise uncured liquid-state epoxy resin, polymeric epoxy resin, novolac epoxy resin or phenol methane resin.
Because of the characteristic of thermoplastics makes described heat-conducting insulation material can be via the thermoplastics process forming, again because of containing thermoset plastics, at high temperature be able to curing cross-linked, and the structure that formation thermoplastics and thermoset plastics penetrate alternately, this structure not only can have the thermoset plastics characteristic of high temperature resistant not modification, the characteristic that has tough non-fragile thermoplastics again, and can produce then powerful with metal electrode or substrate.
With reference to Fig. 2 A, on the two plate faces of heat conductive insulating substrate 11, a plate face can be provided with printed circuit board (PCB) 12, and another plate face can be provided with 1.0 to 1.5mm metal substrate 13, described iterative structure can utilize hot press under 200 ℃ with 25kg/cm
2The pressure pressing, form heat conductive insulating compound substrate 10, in one embodiment, metal substrate can be the aluminium substrate, making the compound substrate after the pressing is single-surface double-layer aluminium substrate.Printed circuit board (PCB) 12 can be the composition that has the metal material 14 of patterning at least one surface of heat conductive insulating substrate 11.With reference to Fig. 2 B, on the plate face of heat conductive insulating substrate 11, metal material 15 is set, in addition according to metal material 16 is set on the plate face, described metal material 15 heat conductive insulating substrates 11 metal materials 16, under 200 ℃ after 90 minutes hot pressing (and controlling its thickness, for example 0.5mm), promptly form thickness and be the heat conductive insulating compound substrate 10 of 0.2mm ' another form, i.e. single face metal substrate.11 of metal material 15, metal base 16 and heat conductive insulating substrates form that physics contacts and its conductive coefficient greater than 0.5W/mK.Described heat conductive insulating compound substrate 10 ' thickness less than 0.5mm and can be anti-greater than 1000 volts voltage.
With reference to Fig. 2 C, heat conductive insulating substrate 11 can be superimposed with multiple different metal material 15, carries out hot pressing again to form the metallic core substrat structure after being overlapped into metal material 15/ heat conductive insulating substrate 11/ metal material 15/ heat conductive insulating substrate 11/ metal material 15.
When carrying out above-mentioned hot pressing technique, described sheet heat conductive insulating composite material penetrates network configuration alternately because of tool, so the phenomenon of layering (separation) can not take place.The material of aforementioned many metal materials is selected from copper, aluminium, nickel, copper alloy, aluminium alloy, nickel alloy, corronil and aluminium copper.The outward appearance of described sheet heat conductive insulating composite material presents rubber-like (non-resin pulpous state (slurry)) thereby has the characteristic of convenient storage, processing.In addition, described heat conductive insulating composite material also can utilize the processing method that is generally used in thermoplastics to be processed, and improves its machinability thus.
In the macromolecular material that the present invention uses, described thermoplastics and described thermosetting epoxy resin are dissolve each other in fact each other (substantially mutually soluble)." dissolve each other in fact each other " and mean the solution that after described thermoplastics and the mixing of described thermosetting epoxy resin, forms tool single glass transition temperature (single glass transitiontemperature).Because described thermoplastics and described thermosetting epoxy resin are to dissolve each other each other, when the two mixes, described thermoplastics will be dissolved in the described thermosetting epoxy resin, make the glass transition temperature of described thermoplastics reduce substantially, and the normal softening temperature (normal softening temperature) that allows being blended in of the two to be lower than described thermoplastics take place down.Formed mixture (being described macromolecule component) is rubber-like (or solid-state) under room temperature, be easy to weigh and store.For example, even described thermosetting epoxy resin is a liquid-state epoxy resin, with formed mixture after described thermoplastics mixes, though itself non-liquid state can be made into alutaceous tough and tensile film (tough leathery film).Under 25 ℃, the coefficient of viscosity (about 10 that described mixture tool is quite high
5To 10
7Pool (poise)), this is to be avoided described macromolecule component to precipitate the key factor of (settling) or redistribution (redistribution).In addition, described mixture (about 40 ℃ to 100 ℃) under the temperature of generally mixing have the enough low coefficient of viscosity (under 60 ℃, about 10
4To 10
5Pool), feasible curing agent that adds and ceramic powders can be evenly distributed in the described mixture and react.Numerous examples of described mixture can be with reference to PCT patent publication No. WO92/08073 (on May 14th, 1992 is open) (in herein in the lump as a reference).
The curing temperature T of the curing agent in the heat conductive insulating macromolecular material of the present invention (curing agent)
SolidifyBe higher than 100 ℃, in order to solidify (promptly crosslinked (crosslink) or catalytic polymerization (catalyze polymerization)) described thermosetting epoxy resin.Described curing agent is to be higher than mixing temperature T
MixThe time described thermosetting epoxy resin solidified wherein said mixing temperature T fast
MixBe meant the temperature when described thermoplastics, described thermosetting epoxy resin and described curing agent mix, and described mixing temperature T
MixGenerally approximately from 25 ℃ to 100 ℃.Described curing agent is in described mixing temperature T
MixUnder when mixing, can't initial essence solidification process (substantial curing).Additive capacity in curing agent described in the present invention is to make described thermosetting epoxy resin in being higher than described mixing temperature T
MixIn time, be cured.Preferably, described curing agent can initial described essence solidification process in less than about 100 ℃ the time and is made described heat conductive insulating macromolecular material in remaining on essence its uncured state (substantially uncured) under 25 ℃ for half a year at least.
Except that the above, thermoplastics of the present invention also can be selected essence amorphous thermoplastic resin (essentiallyamorphous thermoplastic resin) for use, its definition please refer to " competition pool spirit (Saechtling) is for the international plastic process handbook (International plastic Handbook for the Technology; Engineer andUser) of engineer and user's use; second edition; 1987; Han Si publisher (Hanser Publishers), Munich (Munich) " the 1st page." crystallinity " that " essence is noncrystalline " means in the described resin (crystallinity) partly accounts for 15% at the most, preferably accounts for 10% at the most, accounts for 5% at the most especially, for example: account for 0 to 5% crystallinity.The noncrystalline thermoplastic resin of described essence is a high molecular weight polymers, at room temperature present hard shape (rigid) or rubber-like (rubbery), its described macromolecule component during in its uncured state (uncured state) in order to intensity (strength) and high viscosity character such as (high viscosity) to be provided.The noncrystalline thermoplastic resin of described essence shared percent by volume in described macromolecule component generally is between 10% to 75%, preferably between 15% to 60%, in particular between 25% to 45%.The noncrystalline thermoplastic resin of described essence can be selected from polysulfones (polysulfone), polyether sulfone (polyethersulfone), polystyrene (polystyrene), polyphenylene oxide (polyphenylene oxide), polyphenylene sulfide (polyphenylene sulfide), polyamide (polyamide), phenoxy resin (phenoxy resin), polyimides (polyimide), Polyetherimide (polyetherimide), Polyetherimide/silicone block copolymer (polyetherimide/silicone blockcopolymer), polyurethane (polyurethane), polyester (polyester), Merlon (polycarbonate), acrylic resin (acrylic resin) (for example: polymethyl methacrylate (polymethyl methacrylate), styrene (styrene)/acrylonitrile (Acrylonitrile) and styrene block copolymer (styrene block copolymer)).
Described in addition thermoplastics most preferably can comprise hydroxyl-phenoxy ethers (hydroxyl-phenoxyether) macromolecular structure.Described hydroxyl-phenoxy ethers is to be formed through polymerization reaction (polymerization) by the stoichiometric mixture (stoichiometric mixture) of di-epoxide (diepoxide) with difunctional material (difunctionalspecies).Described di-epoxide is that tool epoxide equivalent (epoxy equivalent weight) is approximately from 100 to 10000 epoxy resin.For example: bisphenol A diglycidyl ether (diglycidyl ether of bisphenol A), 4,4 '-sulphonyl biphenol diglycidyl ether (diglycidyl ether of 4,4 '-sulfonyldiphenol), 4,4 '-oxo biphenol diglycidyl ether (diglycidylether of 4,4 '-oxydiphenol), 4,4 '-dihydroxy benaophenonel diglycidyl ether (diglycidyl ether of4,4 '-dihydroxybenzophenone), hydroquinones diglycidyl ether (diglycidyl ether of hydroquinone) and 9,9-(4-hydroxy phenyl) fluorine diglycidyl ether (diglycidyl ether of 9,9-(4-hydroxyphenyl) fluorine).Described difunctional material is dihydric phenol (dihydric phenol), dicarboxylic acids (dicarboxylic acid), primary amine (primary amine), two mercaptan (dithiol), disulfonic acid amide (disulfonamide) or two secondary amine (bis-secondaryamine).Described dihydric phenol can be selected from 4,4 '-isopropylidene bis-phenol (4,4 '-isopropylidene bisphenol) (bisphenol-A (bisphenol A)), 4,4 '-the sulphonyl biphenol (4,4 '-sulfonyldiphenol), 4,4 '-oxo biphenol (4,4 '-oxydiphenol), 4,4 '-dihydroxy benaophenonel (4,4 '-dihydroxybenzophenone) or 9,9-(4-hydroxy phenyl) fluorenes (9,9-bis (4-hydroxyphenyl) fluorene).Described dicarboxylic acids can be selected from M-phthalic acid (isophthalic acid), terephthalic acid (TPA) (terephthalic acid), 4,4 '-biphenyl dicarboxylic acid (4,4 '-biphenylenedicarboxylic acid) or 2,6-naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid).Described pair of secondary amine can be selected from piperazine (piperazine), lupetazin (dimethylpiperazine) or 1, two (N-methylamino) ethane (1,2-bis (N-methylamino) ethane) of 2-.Described primary amine can be selected from 4-aminoanisole (4-methoxyaniline) or monoethanolamine (2-aminoethanol).Described two mercaptan can be 4,4 '-the dimercapto diphenyl ether (4,4 '-dimercaptodiphenyl ether).Described disulfonic acid amide (disulfonamide) can be selected from N, N '-dimethyl-1,3-benzene disulfonic acid amide (N, N '-dimethyl-1,3-benzenedisulfonamide) or N, N '-two (2-ethoxy)-4,4-biphenyl disulfonic acid amide (N, N '-bis (2-hydroxyethyl)-4,4-biphenyldisulfonamide).In addition, described difunctional material also comprise two kinds can with the mixture of the different functional groups (functionality) of epoxide group (epoxide group) reaction; For example; Salicylic acid (salicylic acid) and 4-hydroxybenzoic acid (4-hydroxybenzoicacid).
Thermoplastics in the heat conductive insulating macromolecular material of the present invention also can be selected from the product of product (reaction product), liquid-state epoxy resin and diacid (diacid) of liquid-state epoxy resin and bisphenol-A (bisphenol A), Bisphenol F (bisphenol F) or bisphenol S (bisphenol S) or the product of liquid-state epoxy resin and amine (amine).
Thermosetting epoxy resin in the heat conductive insulating macromolecular material of the present invention is except that the described material of table one, also can be selected from defined thermosetting resin (thermosettingresin) in " the international plastic process handbook (International plasticHandbook for the Technology; Engineer and User) that competition pool spirit (Saechtling) is used for engineer and user; second edition; 1987; Han Si publisher (HanserPublishers), Munich (Munich) " the 1st page and the 2nd page.Described thermosetting resin shared percent by volume in described macromolecule component generally is between 90% to 25%, preferably between 85% to 40%, in particular between 75% to 55%.And the noncrystalline thermoplastic resin of described essence in the described macromolecule component and the volume ratio of described thermosetting resin are approximately between 1: 9 to 3: 1.Described thermosetting resin preferably has the functional group's base greater than 2.Under room temperature, described thermosetting resin presents liquid or solid-state.If described thermosetting resin is under the condition that does not add thermoplastic resin and solidify, then described thermosetting resin will present hard shape (rigid) or rubber-like (rubbery).Preferred thermosetting resin is uncured epoxy resin (uncured epoxy resin), particularly is defined in the uncured liquid-state epoxy resin of ASTM D 1763.Epoxy resin about liquid state can be with reference to the narration of " being rolled up by the engineering material handbook the 2nd that U.S. material informatics meeting (ASM International) is published: engineering plastics (Volume 2of Engineered Materials Handbook, Engineering Plastics) " the 240th to 241 page.Relevant " epoxy resin " speech is meant tradition two poly epoxy resins (dimeric epoxy), oligomerization epoxy resin (oligomeric epoxy) or the polymeric epoxy resin (polymeric epoxy) that comprises at least two epoxy-functionals (epoxy functional group).The kind of described epoxy resin can be the product of bisphenol-A (bisphenol A) and epoxychloropropane (epichlorohydrin), the product (it is a kind of novolac resin (novolacresin)) of phenol (phenol) and formaldehyde (formaldehyde), epoxychloropropane (epichlorohydrin), cycloaliphatic (cycloaliphatic), peracid epoxy resin (peracidepoxy) and ethylene oxidic ester (glycidyl ester), the product of epoxychloropropane and para-aminophenol (p-amino phenol), the product of epoxychloropropane and glyoxal four phenol (glyoxal tetraphenol), novolac epoxy resin (novolac epoxy) or bisphenol A epoxide resin (bisphenol A epoxy).Obtainable epoxidised ester in the commercialization (epoxidic ester) preferably 3,4-7-oxa-bicyclo[4.1.0-formic acid 3,4-epoxycyclohexyl methyl ester (3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane-carboxylate) (for example: the ERL 4221 of associating carbide (Union Carbide) company or the CY-179 of Xi Ba-Gai Ji (Ciba Geigy) company) or adipic acid two (3,4-epoxycyclohexyl methyl) (bis (3,4-epoxycyclohexylmethyl) adipate) (for example: the ERL 4299 of associating carbide (Union Carbide) company) for ester.The diglycidyl ether of obtainable bisphenol-A in the commercialization (diglycidicether of bisphenol-A) (DGEBA) the love jail of optional Ba-Gai Ji westerly (Ciba Geigy) company reaches the Epon 825,828,826,830,834,836,1001,1004 or 1007 etc. of the DER 331 of (Araldite) 6010, Dow Chemical and shell chemical company (Shell Chemical Company).In addition, poly-epoxidation phenol formaldehyde (PF) phenolic aldehyde prepolymer (polyepoxidized phenol formaldehyde novolac prepolymer) can be selected from the DEN431 or 438 and the CY-281 of Xi Ba-Gai Ji (Ciba Geigy) company of Dow Chemical.The ENC 1285,1280 or 1299 of poly-epoxidation CF phenolic aldehyde prepolymer (polyepoxidized cersol formaldehyde novolac prepolymer) then optional Ba-Gai Ji westerly (Ciba Geigy) company.It (is with butane-1 that the love jail of the polyglycidyl ether of polyalcohol (Polyglycidyl ether of polyhydricalcohol) optional Ba-Gai Ji westerly (Ciba Geigy) company reaches (Araldite) RD-2,4-glycol (butane-1,4-diol) for basis) or be selected from the Epon 812 (being) of shell chemical company based on glycerine (glycerin).The diepoxide of suitable alkyl-cycloalkyl hydrocarbon (diepoxide of an alkylcycloalkyl hydrocarbon) is the dioxide (vinyl cyclohexane dioxide) of vinyl cyclohexane, for example: the ERL 4206 of associating carbide (Union Carbide) company.In addition, the diepoxide of suitable cycloalkyl ethers (diepoxide of a cycloalkyl ether) is two (2,3-diepoxy cyclopenta)-and ether (bis (2,3-diepoxycyclopentyl)-ether), for example: the ERL 0400 of associating carbide (UnionCarbide) company.In addition, obtainable flexible-epoxy in the commercialization (flexible epoxy resin) (for example: the DER 732 and 736 of Dow Chemical) comprises polyethylene glycol diepoxy (polyglycol diepoxy), the Epon 871 and 872 of shell chemical company) and the 2-glycidyl ester of bis-phenol (diglycidyl ester of a bisphenol) (for example:, wherein aromatic rings (aromatic ring) is (for example: Le Kusaimu (Lekutherm) X-80 of Mo Bei chemical company (Mobay Chemical company)) to connect by long aliphatic chain (long aliphatic chain) to the 2-glycidyl ester of linoleic acid dimer (diglycidyl ester of linoleic dimer acid).
In addition, above-mentioned thermosetting resin with a plurality of functional groups can be selected from the DEN 4875 of Dow Chemical, and (it is a solid phenolic resin type epoxy resin, solid epoxy novolac resin), (it is the four-functional group solid epoxy resin to the Epon 1031 of shell chemical company, tetrafunctional solid epoxy resin) and the love jail of Xi Ba-Gai Ji (Ciba Geigy) company reach (Araldite) MY 720 (N, N, N ', N '-four glycidyl group-4,4 '-methylene dianiline (N, N, N ', N '-tetraglycidyl-4,4 '-methylenebisbenzenamine)).In addition, difunctional epoxy resin (difunctional epoxy resin, it is a di-epoxide) HPT 1071 that can be selected from shell chemical company (is solid resin, N, N, N ', N '-four glycidyl group-a, a '-two (4-aminophenyl) is right-diisopropyl benzene (N, N, N ', N '-tetraglycidyl-a, a '-bis (4-aminophenyl) p-diisopropylbenzene)), the HPT 1079 (being solid-state bis-phenol-9-fluorenes diglycidyl ether (diglycidyl ether of bisphenol-9-fluorene)) or the love jail of Xi Ba-Gai Ji (CibaGeigy) company reach (Araldite) 0500/0510 (triglycidyl ether of para-aminophenol (triglycidyletherof para-aminophenol)).
Be used in described curing agent of the present invention and can be selected from isophthaloyl dihydrazide (isophthaloyl dihydrazide), benzophenone tetracarboxylic acid dianhydride (benzophenone tetracarboxylic dianhydride), diethyl toluene diamine (diethyltoluene diamine), 3,5-diformazan sulfenyl-2,4-toluenediamine (3,5-dimethylthio-2,4-toluenediamine), dicyandiamide (dicyandiamide, can take from Ke Ruozao (Curazol) 2PHZ of american cyanamide (American Cyanamid) company) or DDS (diamino-diphenyl sulfone (diaminodiphenyl sulfone), the Ka Erkule (Calcure) of desirable Ba-Gai Ji westerly (CibaGeigy) company).Described curing agent is also optional from being substituted dicyandiamide (substituteddicyandiamide, for example 2,6-xylyl biguanides (2,6-xylenyl biguanide), solid-state polyamide (solidpolyamide, for example: An Kemi (Ancamine) 2014AS that the HT-939 of Xi Ba-Gai Ji (Ciba Geigy) company or Pacific Ocean peace can (Pacific Anchor) company), solid-state aromatic amine (solid aromatic amine, for example: the HPT 1061 and 1062 of shell chemical company), solid-state acid anhydride curing agent (solid anhydride hardener, for example: pyromellitic dianhydride (pyromellitic dianhydride; PMDA)), phenolic resins curing agent (phenolic resin hardener, for example: poly-(para hydroxybenzene ethene) (poly (p-hydroxy styrene), imidazoles (imidazole), 2-phenyl-2,4-dihydroxy methylimidazole (2-phenyl-2,4-dihydroxymethylimidazole) with 2,4-diaminourea-6[2 '-methylimidazolyl (1)] ethyl-s-triazine isocyanate adduct (2,4-diamino-6[2 '-methylimidazolyl (1)] ethyl-s-triazine isocyanateadduct)), boron trifluoride (boron trifluoride) and amine complex (amine complex, for example: the peace that Pacific Ocean peace can (Pacific Anchor) company can (Anchor) 1222 and 1907) and trimethylolpropane tris acrylic acid ester (trimethylol propane triacrylate).
At described thermosetting epoxy resin, preferably curing agent is above-mentioned dicyandiamide (dicyandiamide), and can cooperate curing accelerator (curing accelerator) to use.Curing accelerator commonly used comprises urea (urea) or carbamide compound (urea compound).For example: 3-phenyl-1,1-dimethyl urea (3-phenyl-1,1-dimethylurea), 3-(4-chlorphenyl)-1,1-dimethyl urea (3-(4-chlorophenyl)-1,1-dimethyl urea), 3-(3, the 4-dichlorophenyl)-1, (3-(3 for the 1-dimethyl urea, 4-dichlorophenyl)-1,1-dimethyl urea), 3-(3-chloro-4-aminomethyl phenyl)-1,1-dimethyl urea (3-(3-chloro-4-methylphenyl)-1,1-dimethyl urea) and imidazoles (imidazole) (for example: 2-heptadecyl imidazoles (2-heptadecylimidazole), 1-cyano ethyl-2-phenylimidazole-trimellitate (1-cyanoethyl-2-phenylimidazole-trimellitate) or 2-[β-2 '-methylimidazolyl-(1 ') }]-ethyl-4,6-diaminourea-s-triazine (2-[.beta.-{2 '-methylimidazoyl-(1 ') }]-ethyl-4,6-diamino-s-triazine)).
If described thermosetting epoxy resin is carbamate (urethane), then described curing agent can use blocked isocyanate (blocked isocyanate) (for example: alkyl phenol blocked isocyanate (alkyl phenol blockedisocyanate), what it can take from Mo Bei company (Mobay Corporation) wears this Kemp (Desmocap) 11A) or phenol block type PIC addition product (phenol blocked polyisocyanate adduct) (for example: not Du (Mondur) S of Mo Bei company (MobayCorporation)).If described thermosetting epoxy resin is that mylar (unsaturatedpolyester resin) is closed in insatiable hunger, then described curing agent can use peroxide (peroxide) or other free radical catalyst (freeradical catalyst), for example: cumyl peroxide (dicumyl peroxide), 2,5-dimethyl-2,5-two (t-butylperoxy) hexane (2,5-dimethyl-2,5-di (t-butylperoxy) hexane), tert-butyl peroxide isopropylbenzene (t-butylcumyl peroxide) and 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3 (2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3).In addition, described insatiable hunger is closed mylar and can be utilized radiation exposure (irradiation, for example: irradiation of ultraviolet irradiation, high-power electron beam or γ radiation) crosslinked to produce.
Some thermosetting epoxy resin need not use curing agent promptly curable.For example: if described thermosetting epoxy resin is bismaleimides (bismaleimide, BMI), then described bismaleimides will produce crosslinked and co-curing agent (co-curing agent) down in high temperature, O for example, O '-diallyl bisphenol (O, O '-diallyl bisphenol A), can add together and make that the bismaleimides solidified is more tough and tensile.
Above-mentionedly utilize peroxide cross-linking agent (peroxide crosslinking agent), high-power electron beam or γ radiation preferably can add insatiable hunger and close crosslinking coagent (unsaturated crosslinking aid) to produce crosslinked resin, for example: cyamelide triallyl (triallyl isocyanurate, TAIC), triallyl cyanurate (triallyl cyanurate, TAC) or trimethylolpropane triacrylate (trimethylol propanetriacrylate, TMPTA).
Can comprise one or more ceramic powders in the insulating material, ceramic powders can be selected from the mixture of nitride, oxide or aforementioned nitride and aforesaid oxides.Described nitride can use zirconium nitride, boron nitride, aluminium nitride or silicon nitride.Described oxide can use aluminium oxide, magnesium oxide, zinc oxide, silicon dioxide or titanium dioxide.
Fig. 3 shows the schematic diagram of the continous way device for injection moulding 20 of one embodiment of the invention.Continous way device for injection moulding 20 comprises die head 23, pressing wheel device 24 and the cutting means 25 of feeding mechanism 21, feed mechanism 22, tool slit 32.Feeding mechanism 21 is to be used to provide the insulating material 26 of making usefulness.Feed mechanism 22 is pressed through the described slit 32 of described die head 23 with described insulating material 26, forms plate-like substrate 27 thus, and the temperature when wherein said insulating material 26 is pressed through described slit 32 can be between 50 ℃ to 150 ℃.Pressing wheel device 24 comprises steel wheel 28, and the first film material 29 and the second film material 30 rotate respectively on the described steel wheel 28.When plate-like substrate 27 during by described steel wheel 28, the described first film material 29 and the described second film material 30 are attached to two plate faces of plate-like substrate 27 respectively.Cutting means 25 is to be used for described plate-like substrate 27 is cut into heat conductive insulating substrate 31.
Technology contents of the present invention and technical characterstic disclose as above, yet the those skilled in the art still may be based on teaching of the present invention and announcement and done all replacement and modifications that does not deviate from spirit of the present invention.Therefore, protection scope of the present invention should be not limited to those disclosed embodiments, and should comprise various do not deviate from replacement of the present invention and modifications, and is covered by in above claims.
Claims (29)
1. the preparation method of a heat conductive insulating substrate comprises the following step:
To the condensation reaction that is hydrolyzed of at least a ceramic powders, to obtain at least a modified ceramic powder, wherein each described at least a modified ceramic powder comprises a plurality of modified powder particles, and the surface grafting organic compound of each described modified powder particle;
Described at least a modified ceramic powder, macromolecular material and curing agent are mixed, to obtain insulating material;
Described insulating material is pressed through slit, to form plate-like substrate; And
The first film material and the second film material are set respectively on two plate faces of described plate-like substrate, and form described heat conductive insulating substrate, wherein said first film material and the described second film material are selected from metal material or release material.
2. the preparation method of heat conductive insulating substrate according to claim 1, wherein said organic compound is an organosilicon, and described hydrolysis-condensation reaction is under sour environment, so that described organosilicon reacts described at least a ceramic powders.
3. the preparation method of heat conductive insulating substrate according to claim 1, wherein said organic compound is an organic titanium, and described hydrolysis-condensation reaction is under sour environment, so that organic titanium reacts described at least a ceramic powders.
4. according to the preparation method of claim 2 or 3 described heat conductive insulating substrates, the pH-value of wherein said sour environment is between PH 1 to PH 5.
5. the preparation method of heat conductive insulating substrate according to claim 1, the composition of wherein said macromolecular material comprises thermoplastics and thermosetting epoxy resin.
6. the preparation method of heat conductive insulating substrate according to claim 5, the percent by volume that wherein said thermosetting epoxy resin accounts for described macromolecular material is between 70% to 97%.
7. the preparation method of heat conductive insulating substrate according to claim 5, wherein said curing agent solidifies described macromolecular material with curing temperature, and described curing temperature is higher than 80 ℃.
8. the preparation method of heat conductive insulating substrate according to claim 5, wherein said thermoplastics is the super high molecular weight phenoxy resin.
9. the preparation method of heat conductive insulating substrate according to claim 8, the molecular weight of wherein said super high molecular weight phenoxy resin is greater than 30000.
10. the preparation method of heat conductive insulating substrate according to claim 5, wherein said thermosetting epoxy resin is uncured liquid-state epoxy resin, polymeric epoxy resin, novolac epoxy resin or phenol methane resin.
11. the preparation method of heat conductive insulating substrate according to claim 5, wherein said thermoplastics and described thermosetting epoxy resin are homogeneous phase.
12. the preparation method of heat conductive insulating substrate according to claim 5, wherein said thermoplastics is to comprise hydroxyl-phenoxy resin ether macromolecular structure.
13. the preparation method of heat conductive insulating substrate according to claim 12, wherein said hydroxyl-phenoxy resin ether macromolecular structure is to be formed through polymerization reaction by di-epoxide and difunctional material.
14. the preparation method of heat conductive insulating substrate according to claim 5, wherein said thermoplastics is to be formed by liquid-state epoxy resin and bisphenol-a reaction.
15. the preparation method of heat conductive insulating substrate according to claim 5, wherein said thermoplastics is to be formed by liquid-state epoxy resin and divalent acid reaction.
16. the preparation method of heat conductive insulating substrate according to claim 5, wherein said thermoplastics is to be formed by liquid-state epoxy resin and amine reaction.
17. the preparation method of heat conductive insulating substrate according to claim 1, the percent by volume that wherein said at least a ceramic powders accounts for described insulating material is between 40% to 70%.
18. the preparation method of heat conductive insulating substrate according to claim 1, wherein said at least a ceramic powders is the mixture of nitride, oxide or described oxide and described nitride.
19. the preparation method of heat conductive insulating substrate according to claim 18, wherein said nitride is selected from the group that zirconium nitride, boron nitride, aluminium nitride and silicon nitride are formed.
20. the preparation method of heat conductive insulating substrate according to claim 18, wherein said oxide is selected from the group that aluminium oxide, magnesium oxide, zinc oxide, silicon dioxide and titanium dioxide are formed.
21. the preparation method of heat conductive insulating substrate according to claim 1, the step that wherein described insulating material is pressed through slit comprises the following step:
Feed mechanism is pressed through the described slit of die head with the described insulating material that feeding mechanism provided, to form described plate-like substrate.
22. the preparation method of heat conductive insulating substrate according to claim 1, the temperature when wherein described insulating material being pressed through described slit is between 50 ℃ to 150 ℃.
23. the preparation method of heat conductive insulating substrate according to claim 1 wherein is provided with the first film material and the second film material step on two plate faces of described plate-like substrate respectively, comprises the following step:
Utilize pressing wheel device that described first film material and the described second film material are pressed on the described plate face of described plate-like substrate.
24. the preparation method of heat conductive insulating substrate according to claim 1, the material of wherein said metal material is selected from copper, aluminium, nickel, copper alloy, aluminium alloy, nickel alloy, corronil and aluminium copper.
25. the preparation method of a heat conductive insulating compound substrate comprises the following step:
To the condensation reaction that is hydrolyzed of at least a ceramic powders, to obtain at least a modified ceramic powder, wherein each described at least a modified ceramic powder comprises a plurality of modified powder particles, and the surface grafting organic compound of each described modified powder particle;
Described at least a modified ceramic powder, macromolecular material and curing agent are mixed, to obtain insulating material;
Described insulating material is pressed through slit, to form plate-like substrate;
Metal material or release material are set on the plate face of described plate-like substrate;
The described plate-like substrate that cuts described metal material of tool or release material becomes the heat conductive insulating substrate; And
Under pressing-in temp, the described heat conductive insulating substrate of pressing multi-disc, and form described heat conductive insulating compound substrate.
26. the preparation method of heat conductive insulating compound substrate according to claim 25, wherein said pressing-in temp is between 80 ℃ to 220 ℃.
27. the preparation method of heat conductive insulating compound substrate according to claim 25, wherein said heat conductive insulating compound substrate comprises structures such as single sided board, double sided board, single-surface double-layer plate, metal core core, multi-layer sheet.
28. the preparation method of heat conductive insulating compound substrate according to claim 25, it more comprises the following step:
With forming technique, the described multi-disc heat conductive insulating substrate after the finishing pressing.
29. the preparation method of heat conductive insulating compound substrate according to claim 28, wherein said forming technique comprise cut, shearing, die-cut, technology such as diamond is cut.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220533A (en) * | 2012-03-30 | 2014-12-17 | 昭和电工株式会社 | Curable heat radiation composition |
| CN108470958A (en) * | 2018-03-27 | 2018-08-31 | 华霆（合肥）动力技术有限公司 | Thermal insulation layer preparation method, cooling line and battery modules |
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2009
- 2009-05-06 CN CN2009101364165A patent/CN101882584A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220533A (en) * | 2012-03-30 | 2014-12-17 | 昭和电工株式会社 | Curable heat radiation composition |
| CN104220533B (en) * | 2012-03-30 | 2016-09-21 | 昭和电工株式会社 | Curable Heat dissipation composition |
| CN108470958A (en) * | 2018-03-27 | 2018-08-31 | 华霆（合肥）动力技术有限公司 | Thermal insulation layer preparation method, cooling line and battery modules |
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