CN101144007B - Heat conduction paste - Google Patents
Heat conduction paste Download PDFInfo
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- CN101144007B CN101144007B CN2007101547148A CN200710154714A CN101144007B CN 101144007 B CN101144007 B CN 101144007B CN 2007101547148 A CN2007101547148 A CN 2007101547148A CN 200710154714 A CN200710154714 A CN 200710154714A CN 101144007 B CN101144007 B CN 101144007B
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- heat conduction
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- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- -1 Ethylene glycol bisthioglycolate (methylacrylic acid) ester Chemical class 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 10
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000004640 Melamine resin Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000012764 mineral filler Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- MGODLTYPPIBTRE-UHFFFAOYSA-N C(N)(O)=O.C(CCCCCN=C=O)N=C=O.C(C=C)(=O)O.C1(=CC=CC=C1)OCC1CO1 Chemical compound C(N)(O)=O.C(CCCCCN=C=O)N=C=O.C(C=C)(=O)O.C1(=CC=CC=C1)OCC1CO1 MGODLTYPPIBTRE-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 7
- 238000007650 screen-printing Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011231 conductive filler Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 230000014509 gene expression Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000012797 qualification Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical class CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WYCLKHIHQYPHIP-UHFFFAOYSA-I acetyl chloride;pentachloro-$l^{5}-stibane Chemical compound CC(Cl)=O.Cl[Sb](Cl)(Cl)(Cl)Cl WYCLKHIHQYPHIP-UHFFFAOYSA-I 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a thermal conductivity paste for screen printing with low viscosity, exothermicity, excellent storage stability and physical property of settability. The thermal conductivity paste is separated into A liquid containing acrylate resin and an epoxy resin hardener and B liquid containing epoxy resin and acrylate resin hardener. A thermally conductive filler is blended with one side or both sides of said A liquid and B liquid at a rate of 100 to 1000 weight section to total amount 100 weight section of said acrylate resin and an epoxy resin and the thermally conductive paste obtaining by mixing at a rate that a rate of a compounding ratio of said acrylate resin and an epoxy resin (however, weight %) is set to 10:90-90:10 before using said A liquid and B liquid.
Description
Technical field
The present invention relates to heat conduction paste (solidified nature thermally conductive resin composition), more particularly, relate to heat conduction paste as the insulating material of substrate.
Background technology
In recent years, along with the multifunction of electronics, the requirement of small-sized slimming, chip part, semi-conductive densification significantly develop, and it is more and more important to make the circuit substrate of installing be that high exothermicity has become.
As the circuit substrate of so high exothermicity, the method for having used heat-resistant glue to carry the heat release fin at heat generating components.So-called heat-resistant glue; Be meant high caking agent of having filled mineral filler in thermoset or thermoplastic resin; For example, open to disclose in the 2004-217861 communique the spy and be adhered to circuit substrate etc. with containing membranaceous heat-resistant glue that specific spherical alumina, silicone-modified polyamidoimide, thermosetting resin, thermo-setting elastomer form heat release fin (heat liberation board) with copper, aluminium etc.
But, in aforesaid method, contain solvent in order to make the caking agent film forming, when be filled into by obturation LZT, might produce space, cracking.
In addition, as additive method, used with metal sheet as core make substrate method (metal-cored), make method that through hole coating thickens, metal sheet pasted method on the substrate etc.
But, because the requirement that exothermic character further improves except the method for above-mentioned use metal, also requires to give exothermicity to insulating substrate itself.As the advantage of this method, the area that can enumerate through making the heat release part increases, thereby can improve exothermal effect.
As the existing method of the circuit substrate that makes high like this exothermicity, the most normally used is the method that adopts pressurization that the heat release sheet material is bonding.So-called heat release sheet material is the exothermic material of height having been filled the polymer processing slabbing of heat conductivity weighting agent, has the characteristic of easy utilization.For example special opening discloses the bonding film of heat conductivity that the adhesive composition by the high molecular weight resin that contains epoxy resin and solidifying agent thereof, setting, curing catalyst and mineral filler forms in the flat 10-183086 communique.
But, use the method for this heat release sheet material to exist for by the insufficient shortcoming of concavo-convex tracing ability of adhesives.Particularly the requirement of exothermic character in recent years is more and more stricter, therefore begins high filling ceramic particle, so the hardness rising, is difficult to follow concavo-convex tendency and has become more remarkable.In addition, the adhesive composition that above-mentioned spy opens flat 10-183086 communique contains high molecular weight resin, therefore has the insufficient problem of thermotolerance.
Fig. 1 is the schematic cross-section of the formation example of the expression substrate that used heat conduction paste, symbol 1 expression aluminium sheet, and 2 expression heat conduction pastes, 3 expression parts, 4 expressions are arranged on the figure on the parts.Shown in this figure (a), adopt print process coating heat conduction paste 2 with after the figure 4 of parts 3 is imbedded, process pressurization operation is with aluminium sheet 1 crimping.
Therefore, in print process or pressurization, require to have 4 flowabilities of imbedding of figure with parts 3 as shown in Figure 1, and, also require to have parts fixed adaptation for being used by inaccessible place and not containing solvent for heat conduction paste.
But, in order to give sufficient exothermicity, need to add a large amount of high thermal conductivity fillers, along with the increase of amount of filler, the viscosity of paste rises, and has the mobile problem that reduces.In addition, in paste, add fire retardant in order to give the substrate flame retardant resistance, the problem that this viscosity rises becomes more remarkable.For this problem, if through selecting epoxy resin to realize that viscosity reduces, and then produces the problem that rerum natura descends.
In addition,, required to prolong the storage period of heat conduction paste, promptly further improved storage stability along with the globalization at substrate manufacturing strong point.
Patent documentation 1: the spy opens flat 10-183086 communique
Patent documentation 2: the spy opens the 2004-217861 communique
Summary of the invention
The present invention proposes in order to address these problems, and its purpose is to provide not only exothermicity excellent, but and has a LV of silk screen printing, the heat conduction paste that the rerum natura of storage stability, cured article is also excellent.
Heat conduction paste of the present invention; In order to solve above-mentioned problem, contain: the compound that is selected from the formation acrylate resin with the reactive group shown in the formula (I) of vinylformic acid isopentyl ester, neopentylglycol diacrylate, Viscoat 295, two (TriMethylolPropane(TMP)) tetraacrylate, phenylglycidyl ether propenoate hexamethylene diisocyanate carbamate prepolymer, bisphenol A diglycidyl ether vinylformic acid affixture, ethylene glycol bisthioglycolate (methylacrylic acid) ester, glycol ether two (methylacrylic acid) ester, methylacrylic acid 2-hydroxyl-3-acryloxy propyl ester and triethylene glycol diacrylate; Make this compound solidified acrylate resin solidifying agent; Epoxy resin; Epoxy curing agent; Be selected from Al
2O
3, SiO
2, C, BN and AlN mineral filler,
In the formula (I), R representes H or alkyl,
Be separated into the A liquid and the B liquid that contains above-mentioned epoxy resin and aforesaid propylene acid ester resin solidifying agent of the compound that contains above-mentioned formation acrylate resin and above-mentioned epoxy curing agent; With respect to the compound of above-mentioned formation acrylate resin and total amount 100 weight parts of epoxy resin; Ratio with 100～1000 weight parts in side of A liquid and B liquid or two sides cooperates above-mentioned mineral filler, through before use with the cooperation ratio (weight %) of the compound of above-mentioned formation acrylate resin and epoxy resin reach 10: 90～90: 10 mixed A liquid and B liquid obtains.
As epoxy curing agent, can use to be selected from more than a kind or 2 kinds of phenols curing agent, imidazole curing agent and cationic solidifying agent.
In addition; As the acrylate resin solidifying agent, can use be selected from
type solidifying agent and more than a kind or 2 kinds of radical type solidifying agent.
In addition, as required, can in a side or two sides of A liquid and B liquid, cooperate the resin more than a kind or 2 kinds that is selected from Synolac, melamine resin and xylene resin with ratio less than 40 weight % in the resinous principle total amount of A liquid and B liquid.
Heat conduction paste of the present invention is high exothermicity, under the situation of not using solvent, have can silk screen printing LV, excellent storage stability.The rerum natura of the cured article that makes its curing and obtain is also excellent.
Description of drawings
Fig. 1 is the schematic cross-section of the formation example of the expression substrate that used heat conduction paste, and the heat conduction paste that (a) has been illustrated on the parts that the surface formed figure coating (printing) (b) is illustrated in the state that is crimped with on (a) after aluminium sheet and the curing.
Nomenclature
1: aluminium sheet
2: heat conduction paste
3: parts
4: figure
Embodiment
Heat conduction paste of the present invention as stated, is separated into A liquid that contains the compound that constitutes acrylate resin and epoxy curing agent and the B liquid that contains epoxy resin and acrylate resin solidifying agent before the use.Through being separated into A liquid and B liquid, can make the solidifying agent that promotes each resin solidification when two liquid mix and resin isolation, therefore make the storage stability excellence that becomes.Two liquid mix the back because therefore the solidifying agent that exists each resin to use can promptly solidify.
The compound of the formation acrylate resin that contains in the A liquid; Be the compound that is selected from vinylformic acid isopentyl ester, neopentylglycol diacrylate, Viscoat 295, two (TriMethylolPropane(TMP)) tetraacrylate, phenylglycidyl ether propenoate hexamethylene diisocyanate carbamate prepolymer, bisphenol A diglycidyl ether vinylformic acid affixture, ethylene glycol bisthioglycolate (methylacrylic acid) ester, glycol ether two (methylacrylic acid) ester, methylacrylic acid 2-hydroxyl-3-acryloxy propyl ester and triethylene glycol diacrylate with reactive group of record in 1 or 2 the above molecular structural formulas (I), also can be with more than 2 kinds and use.
In the formula (I), R representes H or alkyl, does not have special qualification for the carbon number of alkyl, but is generally 1～3.
Among the present invention,, under the situation of not using solvent, can highly fill the heat conductivity filler, exothermicity is improved through using these compounds that constitutes acrylate resins, can realize simultaneously can silk screen printing LV.
In addition, contained epoxy resin in the B liquid can be the resin that intramolecularly has 1 above epoxy group(ing), also can be with more than 2 kinds and use.As concrete example, can enumerate bisphenol A type epoxy resin, brominated epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin, alicyclic epoxy resin, glycidyl amine type epoxy resin, Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, hetero ring type epoxy resin etc.
The cooperation ratio (weight %) of the compound of above-mentioned formation acrylate resin and epoxy resin, use the compound that constitutes acrylate resin: epoxy resin is represented, is 10: 90～90: 10, is preferably 20: 80～60: 40.The ratio of compound that constitutes acrylate resin is during less than 10 weight %, and viscosity changes and increases, if surpass 90 weight %, the rerum natura after the curing reduces.
In heat conduction paste of the present invention; In the compound of above-mentioned formation acrylate resin, epoxy resin, can distinguish blend use in Synolac, melamine resin and the xylene resin more than a kind or 2 kinds as modifier; The resin that these resins can suitably be selected to realize this purpose uses, and does not have special qualification.
These resins as modifier can add a side or two sides of A liquid and B liquid to.
Above-mentioned A liquid constitute in compound and/or the B pendular ring epoxy resins of acrylate resin in blend Synolac, melamine resin and the xylene resin more than a kind the time proportioning; Make compound and B pendular ring epoxy resins that A liquid constitutes acrylate resin with the gross weight of these resins in be more than the 60 weight %, more than the preferred 90 weight %.That is, as the ratio of the resin of properties-correcting agent blend with the gross weight of these resins in less than 40 weight %, preferably less than 10 weight %.
As the example of the epoxy curing agent that contains in the A liquid, can enumerate phenols curing agent, imidazole curing agent, cationic solidifying agent etc., can use a kind separately, also can use more than 2 kinds.
As the example of the acrylate resin solidifying agent (polymerization starter) that contains in the B liquid, can type of enumerating solidifying agent, radical type solidifying agent etc., these can use a kind separately, also can use more than 2 kinds.
As the example of phenols curing agent, can enumerate phenolic varnish type phenol, naphthol compound etc.
Example as imidazole curing agent; Can enumerate imidazoles, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-ethyl imidazol(e), 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 2-phenylimidazole, 2,4-diamino--6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine.
As the example of cationic solidifying agent, can enumerate boron trifluoride amine salt, antimony pentachloride-Acetyl Chloride 98Min. complex compound, have styroyl, allylic sulfonium salt.
As the example of class solidifying agent, can enumerate anisole diazonium hexafluorophosphate, diphenyl iodine hexafluorophosphate, triphenylsulfonium, Si Zheng Ding Ji Phosphonium tetraphenyl borate salts, Si Zheng Ding Ji Phosphonium-o, o-diethyl dithiophosphate etc.
As the example of radical type solidifying agent, can enumerate dicumyl peroxide, tert-butyl peroxide cumyl, t-butyl hydroperoxide, cumene hydroperoxide etc.
The usage quantity of solidifying agent is different because of kind, as index, measures 100 weight parts with respect to the epoxy resin and the total of the compound that constitutes acrylate resin, is about 1～40 weight part.If usage quantity is very few, generation is solidified bad,, might reduce by storage stability perhaps rerum natura reduction if too much.
Can also can in two sides, cooperate to cooperate the heat conductivity filler the arbitrary of above-mentioned A liquid and B liquid.The heat conductivity filler can use and be selected from Al
2O
3, SiO
2, among C, BN and the AlN more than a kind or 2 kinds.The particle diameter of filler is represented with median size, about preferred 0.1～50 μ m.
The use level of filler is different because of the kind of filler, measures 100 weight parts, preferred 100～1000 weight parts, more preferably 300～900 weight parts with respect to the epoxy resin and the total of the compound that constitutes acrylate resin usually.
Through kind and the amount of selecting above-mentioned heat conductivity filler, can access the cured article of the about 0.2～2.8W/mK of thermal conductivity.
In heat conduction paste of the present invention, can add the flame retardant resistance imparting agent as required.The kind of flame retardant resistance imparting agent does not have special qualification, can use so far as the general fire retardant of resin additive.As an example, can enumerate phosphate compounds such as triphenylphosphate, tricresyl phosphate (toluene) ester, tricresyl phosphate base diphenyl ester, chlorine compounds such as clorafin; Bromine compounds such as hexabromobenzene; Oxyhydroxide such as Marinco H, white lake, mineral-type fire retardants such as brometo de amonio, ANTIMONY TRIOXIDE SB 203 99.8 PCT, but consider environmental problem etc.; In above-mentioned, preferred oxyhydroxide class, Phosphorus or phosphoric acid based flame retardant.
The addition of flame retardant resistance imparting agent is also different because of kind, purpose, as index, with respect to resinous principle 100 weight parts, is 5～100 weight parts.
In resin combination, add the tendency that there is HVization usually in the flame retardant resistance imparting agent; But because heat conduction paste of the present invention adopts aforesaid formation; Therefore even under the situation of having added the flame retardant resistance imparting agent, also can under the situation of not using solvent, keep can silk screen printing LV.
And then, in heat conduction paste of the present invention, in the scope that does not break away from the object of the invention, can also add additives such as skimmer, thixotropic agent, pigment.
Heat conduction paste of the present invention, through above-mentioned each components matching of set amount, mixing are prepared A liquid and B liquid respectively, before using with two liquid cooperations, mixing so that the compound of epoxy resin and formation acrylate resin reaches the ratio of above-mentioned setting.
The paste employing silk screen printing that mixing obtains etc. is coated with, and makes it be solidified to form the substrate of desired shape.Condition of cure is different because of the resin that uses etc., as index, is being about 30～120 minutes under 150～200 ℃.
Embodiment
Embodiments of the invention below are shown, but the present invention does not receive the qualification of following examples.
[embodiment]
Each composition shown in the table 1 is pressed the ratio shown in the table 1 (weight ratio) mix, prepare A liquid and B liquid respectively.Have, the details of each composition is described below again.
Constitute the compound of acrylate resin: methylacrylic acid 2-hydroxyl-3-acryloxy propyl ester (80 weight %), triethylene glycol diacrylate (20 weight %)
Epoxy resin: epoxy resin-4901E (Asahi Denka Kogyo K. K's system) (80 weight %), ED-529 (Asahi Denka Kogyo K. K's system) (20 weight %)
Synolac: EZ-3020-60-S (Dainippon Ink. & Chemicals Inc's system)
Melamine resin: L-121-60 (Dainippon Ink. & Chemicals Inc's system)
Xylene resin: ニ カ ノ one Le PR-1540 (Japanese ガ ス KCC system)
Silicon dioxide powder: FB-24 (Deuki Kagaku Kogyo Co., Ltd's system)
Phenols curing agent: タ マ ノ Le 758 (Arakawa Chemical Industries, Ltd.'s system)
Imidazole curing agent: 2-ethyl imidazol(e) (Shikoku Chem's system)
Class solidifying agent: Si Zheng Ding Ji Phosphonium tetraphenyl borate salts
Radical type solidifying agent: cumene hydroperoxide
For A liquid and B liquid, use BH type viscometer rotor No.7 (10rpm), measure initial stage viscosity (V respectively
0) and the viscosity (V of normal temperature placement after 14 days
14), viscosity velocity of variation (%) after the employing following formula is obtained 14 days.It is qualified that viscosity velocity of variation (%) is defined as in-20%～20% scope.
Viscosity velocity of variation (%) after 14 days=＜(V
14-V
0)/V
0＞* 100
Before using above-mentioned A liquid and B liquid are mixed and form heat conduction paste, it is coated on the copper coin, heated 60 minutes down and obtain cured article at 160 ℃.
Stick with paste and cured article for the exothermicity that obtains, to printing, have velocity of variation after tight generation, shearing resistance, humidity test and the oven test, viscosity velocity of variation and thermal conductivity to estimate.The result is shown in table 2.Test, measuring method are described below.
Printing is to use 120 order tPolyester Filament half tones that the groove of the Copper Foil of the thick 200 μ m that on the thick substrate of 1.6mm, are provided with, wide 1mm, long 10cm is printed, and investigates the fillibility of sticking with paste, and will stuck with paste to fill fully be designated as zero, will be stuck with paste completely filled be designated as *.
There is tight to produce and is after making it solidify 60 minutes under 160 ℃, the top layer is ground, observe, be judged to be the space for the space more than the 500 μ m with opticmicroscope.
Shearing resistance is according to JIS K6850, uses copper coin as test film, after solidifying 60 minutes under 160 ℃, measures.
Velocity of variation after humidity test velocity of variation and the oven test; The former measures shearing resistance to the test portion after in 85 ℃, 85% constant temperature and humidity cabinet, placing 1000 hours; The latter measures shearing resistance to the test portion of heating after 30 seconds in 260 ℃ baking oven, is obtained by following formula.It is qualified that velocity of variation (%) is defined as in-20%～20% scope.
Velocity of variation (%)=[＜(intensity after the test)-(early strength)＞/(early strength)] * 100
Viscosity velocity of variation (%) is to use BH type viscometer rotor No.7 (10rpm), measures initial stage viscosity (V
0) and the viscosity (V of normal temperature placement after 3 days
3), adopt following formula to obtain.It is qualified that velocity of variation (%) is defined as in-20%～20% scope.
Viscosity velocity of variation (%) after 3 days=＜(V
3-V
0)/V
0＞* 100
Thermal conductivity is under 160 ℃, making its cured article that has solidified 60 minutes adopt laser flash method to measure.
[comparative example]
Each composition shown in the table 3 is mixed to reach the ratio shown in the table 3 (weight ratio), and the preparation heat conduction paste is coated on it on copper coin, obtains cured article 160 ℃ of following heating 60 minutes.The details of each composition is same as the previously described embodiments.For paste that obtains and cured article, likewise velocity of variation and thermal conductivity after viscosity velocity of variation, printing, shearing resistance, humidity test and the oven test are estimated with the foregoing description.The result is shown in table 3.
Table 3
Heat conduction paste of the present invention can be used in the for example insulating material of the circuit substrate of various electronicss.
Claims (5)
1. heat conduction paste is characterized in that,
Contain: be selected from the vinylformic acid isopentyl ester; Neopentylglycol diacrylate; Viscoat 295; Two (TriMethylolPropane(TMP)) tetraacrylate; Phenylglycidyl ether propenoate hexamethylene diisocyanate carbamate prepolymer; Bisphenol A diglycidyl ether vinylformic acid affixture; Ethylene glycol bisthioglycolate (methylacrylic acid) ester; Glycol ether two (methylacrylic acid) ester; The compound of the formation acrylate resin with the reactive group shown in the formula (I) of methylacrylic acid 2-hydroxyl-3-acryloxy propyl ester and triethylene glycol diacrylate; Make this compound solidified acrylate resin solidifying agent; Epoxy resin; Epoxy curing agent; Be selected from Al
2O
3, SiO
2, C, BN and AlN mineral filler,
In the formula (I), R representes H or alkyl,
Be separated into the A liquid and the B liquid that contains above-mentioned epoxy resin and aforesaid propylene acid ester resin solidifying agent of the compound that contains above-mentioned formation acrylate resin and above-mentioned epoxy curing agent,
With respect to the compound of above-mentioned formation acrylate resin and total amount 100 weight parts of epoxy resin, the ratio with 100～1000 weight parts in side of above-mentioned A liquid and B liquid or two sides cooperates above-mentioned mineral filler,
With the compound of above-mentioned formation acrylate resin and the cooperation ratio of epoxy resin, in weight %, reach 10: 90～90: 10 the above-mentioned A liquid of mixed and B liquid and obtain through before use,
Measure 100 weight parts with respect to the epoxy resin and the total of the compound that constitutes acrylate resin, the usage quantity of solidifying agent is 1～40 weight part.
2. the described heat conduction paste of claim 1, it is characterized in that: above-mentioned epoxy curing agent is to be selected from more than a kind or 2 kinds of phenols curing agent, imidazole curing agent and cationic solidifying agent.
3. claim 1 or 2 described heat conduction pastes is characterized in that: aforesaid propylene acid ester resin solidifying agent is be selected from
type solidifying agent and more than a kind or 2 kinds of radical type solidifying agent.
4. claim 1 or 2 described heat conduction pastes; It is characterized in that: in a side or two sides of A liquid and B liquid, be combined with the resin more than a kind or 2 kinds that is selected from Synolac, melamine resin and xylene resin with ratio less than 40 weight % in the resinous principle total amount of above-mentioned A liquid and B liquid.
5. the described heat conduction paste of claim 3; It is characterized in that: in a side or two sides of A liquid and B liquid, be combined with the resin more than a kind or 2 kinds that is selected from Synolac, melamine resin and xylene resin with ratio less than 40 weight % in the resinous principle total amount of above-mentioned A liquid and B liquid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006248357 | 2006-09-13 | ||
| JP2006248357A JP4351239B2 (en) | 2006-09-13 | 2006-09-13 | Thermal conductive paste |
| JP2006-248357 | 2006-09-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101144007A CN101144007A (en) | 2008-03-19 |
| CN101144007B true CN101144007B (en) | 2012-11-14 |
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ID=39206747
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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|---|---|
| JP (1) | JP4351239B2 (en) |
| KR (1) | KR101369047B1 (en) |
| CN (1) | CN101144007B (en) |
| HK (1) | HK1117865A1 (en) |
| TW (1) | TWI475080B (en) |
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| KR20100109791A (en) | 2009-04-01 | 2010-10-11 | 주식회사 동진쎄미켐 | Paste composition used for forming an electrode or wiring which is curable at a low temperature |
| KR101410058B1 (en) * | 2011-12-16 | 2014-06-23 | 주식회사 유니코정밀화학 | Environment friendly heat-dissipating resin composition having excellent heat-dissipating property and steel sheet using the same |
| KR101294672B1 (en) * | 2012-03-30 | 2013-08-09 | 엘지전자 주식회사 | Thermal interface material and manufacturing method for thereof |
| JP7414822B2 (en) * | 2019-01-22 | 2024-01-16 | 長江存儲科技有限責任公司 | Integrated circuit packaging structure and manufacturing method thereof |
| CN116606528B (en) * | 2023-07-18 | 2023-09-29 | 成都上泰科技有限公司 | Toughening modified epoxy resin high polymer for wide bandgap semiconductor packaging and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1398918A (en) * | 2001-07-19 | 2003-02-26 | 山荣化学株式会社 | Thermosetting resin composition |
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| JP3792327B2 (en) * | 1996-12-24 | 2006-07-05 | 日立化成工業株式会社 | Thermally conductive adhesive composition and thermally conductive adhesive film using the composition |
| JP2001181482A (en) * | 1999-12-27 | 2001-07-03 | Hitachi Chem Co Ltd | Resin paste composition and semi-conductor device using the same |
| JP2002012738A (en) * | 2000-06-28 | 2002-01-15 | Hitachi Chem Co Ltd | Resin paste composition and semiconductor device made therewith |
| EP1328590B1 (en) * | 2000-10-11 | 2011-08-03 | Chemetall GmbH | Method for pretreating and/or coating metallic surfaces with a paint-like coating prior to forming and use of substrates coated in this way |
| JP4752109B2 (en) * | 2000-12-12 | 2011-08-17 | 日立化成工業株式会社 | Resin paste composition and semiconductor device using the same |
| EP1245627B1 (en) * | 2001-03-30 | 2007-07-04 | Degussa GmbH | Organic silicon nano-microhybrid system or micro-hybrid system containing compositions for scratch and abrasion resistant coatings |
| JP2004168907A (en) * | 2002-11-20 | 2004-06-17 | Sumitomo Bakelite Co Ltd | Die attach paste and semiconductor device |
| JP2004168922A (en) * | 2002-11-21 | 2004-06-17 | Sumitomo Bakelite Co Ltd | Die attach paste and semiconductor device |
| JP2004217861A (en) * | 2003-01-17 | 2004-08-05 | Hitachi Chem Co Ltd | Heat-resistant adhesive, laminate using this adhesive, heat sink with adhesive, and metal foil with adhesive |
| JP4635423B2 (en) * | 2003-09-11 | 2011-02-23 | 住友ベークライト株式会社 | Resin paste for semiconductor and semiconductor device |
| JP4213616B2 (en) * | 2004-03-31 | 2009-01-21 | 大日本印刷株式会社 | Base film for liquid crystal panel, functional film for liquid crystal panel, method for producing functional film, and apparatus for producing functional film |
| JP4534716B2 (en) * | 2004-10-26 | 2010-09-01 | 日立化成工業株式会社 | Circuit connection material, circuit terminal connection structure and connection method |
| JP4639766B2 (en) * | 2004-11-16 | 2011-02-23 | 横浜ゴム株式会社 | Two-component room temperature curable epoxy resin composition and metal adhesive composition |
-
2006
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-
2007
- 2007-08-10 TW TW096129651A patent/TWI475080B/en not_active IP Right Cessation
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|---|---|---|---|---|
| CN1398918A (en) * | 2001-07-19 | 2003-02-26 | 山荣化学株式会社 | Thermosetting resin composition |
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| Publication number | Publication date |
|---|---|
| KR101369047B1 (en) | 2014-02-28 |
| HK1117865A1 (en) | 2009-01-23 |
| CN101144007A (en) | 2008-03-19 |
| TW200817481A (en) | 2008-04-16 |
| JP2008069238A (en) | 2008-03-27 |
| JP4351239B2 (en) | 2009-10-28 |
| TWI475080B (en) | 2015-03-01 |
| KR20080024444A (en) | 2008-03-18 |
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