CN114231230B - Adhesive capable of reducing stress and improving temperature resistance and preparation method thereof - Google Patents
Adhesive capable of reducing stress and improving temperature resistance and preparation method thereof Download PDFInfo
- Publication number
- CN114231230B CN114231230B CN202111669866.8A CN202111669866A CN114231230B CN 114231230 B CN114231230 B CN 114231230B CN 202111669866 A CN202111669866 A CN 202111669866A CN 114231230 B CN114231230 B CN 114231230B
- Authority
- CN
- China
- Prior art keywords
- adhesive
- temperature
- parts
- diamine
- stress
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 80
- 239000000853 adhesive Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 16
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 78
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- 239000003822 epoxy resin Substances 0.000 claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 150000004985 diamines Chemical class 0.000 claims description 29
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000001632 sodium acetate Substances 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- -1 zirconium aluminate Chemical class 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 150000001412 amines Chemical group 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 230000035882 stress Effects 0.000 description 76
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 9
- 208000019300 CLIPPERS Diseases 0.000 description 8
- 208000021930 chronic lymphocytic inflammation with pontine perivascular enhancement responsive to steroids Diseases 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000012536 packaging technology Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229920006259 thermoplastic polyimide Polymers 0.000 description 4
- 230000008901 benefit 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 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 3
- 150000003949 imides Chemical class 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009662 stress testing Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to an adhesive for reducing stress and improving temperature resistance and a preparation method thereof. Solves the problem that the adhesive used by the prior semiconductor device is difficult to realize low stress, high heat resistance and good electric conductivity at the same time. The adhesive is prepared from epoxy resin, bismaleimide resin containing a flexible structure, a curing agent, an accelerator, a coupling agent, conductive particles and an initiator; the preparation method comprises the following steps: 1. preparing bismaleimide resin containing a flexible structure; 2. weigh and mix.
Description
Technical Field
The invention relates to an adhesive and a preparation method thereof.
Background
With commercialization of silicon transistors in the 50 s of the 20 th century, electronic packaging technology has progressed rapidly. The performance of the initially packaged electronic components is dependent on the components themselves and is hardly affected by the packaging technology, but with the miniaturization, versatility and high frequency of modern electronic products, the original packaging technology and materials need to be continuously updated and iterated to exert the performance of the electronic devices to the maximum extent. Electronic packages have been relatively independent of their membership as post-electronic manufacturing processes, and various packaging technologies have been developed for different electronic products, such as quad flat package (Quad Flat Package, QFP), ball Grid Array (BGA), chip scale package (Chip Scale Package, CSP), flip Chip bonding (Flip Chip Bonding, FCB), multi-Chip Module (MCM), and three-dimensional packaging technologies.
The manufacturing process, the service performance and the application of the electronic package basically depend on various materials constituting the package, and the processability, the physical properties (such as resistivity, dielectric constant, thermal conductivity, thermal expansion coefficient and the like), the compatibility, the cost and the like of the materials need to be comprehensively considered. Among these, the role played by the encapsulation of the connection material is critical. The packaging connection material connects packaging structures of different levels and mainly plays roles of electric, mechanical connection, signal transmission and the like. The electronic adhesive is the most widely used packaging connection material, wherein the conductive adhesive is a packaging material which has adhesion and conductivity after being cured, and the main components of the electronic adhesive comprise polymer matrixes such as resin and the like, conductive inorganic fillers and the like. The curing process is simpler, and the production process of the electronic device is simplified; the required curing temperature is low, and the thermal deformation or damage of the device caused by the overhigh temperature in the packaging process is avoided; the higher line resolution is more suitable for fine lead pitch assembly, and is increasingly applied to the development requirements of integrated, high-density and miniaturized electronic devices.
In the practical use process of electronic devices, high reliability and stability are required to be ensured in a complex environment. The problem of residual stress generated by the conductive adhesive is very remarkable when the conductive adhesive is subjected to temperature change, the generation of stress often causes cracking, warping and even debonding of a glue layer, the larger the size of a device is, the larger the damage caused by the stress is, and the problem can be effectively solved by the low-stress conductive adhesive.
The current common low-stress conductive adhesive reduces stress by toughening and modifying a resin system, wherein the toughening method mainly comprises the steps of introducing modified resin and toughened rubber which account for about 5-30% of main resin and contain more fat units, however, the two modes can lower the heat resistance of the whole conductive adhesive, the glass transition temperature (Tg) is usually lower than 80 ℃, the modulus above Tg is relatively poor, and particularly, the device is subjected to high-temperature process treatment such as reflow soldering or is applied to a high-temperature environment, so that the debonding risk exists; and the addition of the toughening rubber affects the conductivity of the conductive adhesive to some extent. In addition, when the device is applied to an environment with a part of large high-low temperature span range (such as an aerospace vehicle), the bonding strength of the current low-stress conductive adhesive is greatly reduced after a plurality of temperature cycles, and the reliability is greatly reduced. Therefore, it is required to develop a modifier resin which can be blended with a main resin to reduce the curing stress and the temperature cycle stress of the system without losing the heat resistance, thereby obtaining a conductive adhesive capable of achieving both heat resistance and low stress.
Disclosure of Invention
The invention aims to solve the problem that the adhesive used by the traditional semiconductor device is difficult to realize low stress, high heat resistance and good electric conduction performance at the same time, and provides an adhesive for reducing stress and improving temperature resistance and a preparation method thereof.
The adhesive for reducing stress and improving temperature resistance is prepared from 100 parts by weight of epoxy resin, 10-30 parts by weight of bismaleimide resin containing a flexible structure, 10-100 parts by weight of curing agent, 1-5 parts by weight of accelerator, 0.05-0.2 part by weight of coupling agent, 400-800 parts by weight of conductive particles and 0.1-0.5 part by weight of initiator;
the monomer structural formula of the bismaleimide resin containing the flexible structure is as follows:
said R is 1 Is that
The preparation method of the adhesive for reducing stress and improving temperature resistance comprises the following steps:
1. preparation of bismaleimide resin containing Flexible Structure:
(1) mixing diamine, triethylamine and butanone, stirring and heating to 60-65 ℃, adding sodium acetate and dianhydride at 60-65 ℃ and stirring for 8-15 h, cooling to room temperature after the reaction is finished to obtain solution A, dissolving maleic anhydride in butanone to obtain maleic anhydride solution, adding maleic anhydride solution into solution A in batches, stirring for 2-4 h at normal temperature, then heating to 70-80 ℃ and heating to 70 DEG C ～ Reflux stirring for 3-5 h at 80 ℃, and cooling to room temperature after the reaction is finished to obtain a solution B;
the mol ratio of diamine to triethylamine is 1 (0.08-0.15); the mass ratio of the diamine to the sodium acetate is 1mol (0.1-0.2) g; the mol ratio of diamine to dianhydride is 1 (1.8-2.5); the mol ratio of diamine to maleic anhydride is 1 (1.8-2.1);
the structural formula of the diamine is H 2 N-R1-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the R1 is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a flexible structure;
2. weighing and mixing:
according to the mass portion, 100 portions of epoxy resin, 10 portions to 30 portions of bismaleimide resin containing flexible structure, 10 portions to 100 portions of curing agent, 1 portion to 5 portions of accelerator, 0.05 portion to 0.2 portion of coupling agent, 400 portions to 800 portions of conductive particles and 0.1 portion to 0.5 portion of initiator are weighed, firstly, the epoxy resin and the bismaleimide resin containing flexible structure are stirred for 15 minutes to 30 minutes at the temperature of 70 ℃ to 90 ℃, after cooling, the curing agent, the accelerator, the coupling agent, the conductive particles and the initiator are added, then the mixture is dispersed for 2 minutes to 10 minutes at the rotation speed of 500rpm to 2000rpm, and finally, the adhesive for reducing stress and improving temperature resistance is obtained for defoamation and filling.
The beneficial effects of the invention are as follows: the bismaleimide monomer containing the soft chain segment prepared by the invention. First, the molecular structure of the composite material contains an aromatic heterocyclic structure, so that the composite material has excellent heat resistance, and the glass transition temperature, the thermal decomposition temperature and the like of the whole composite material are effectively improved. And secondly, the structure of the bismaleimide resin has a flexible chain segment, and compared with the bismaleimide resin with a pure aromatic heterocyclic structure, the bismaleimide resin has slightly reduced heat resistance, but greatly reduces the curing stress of the whole system and the stress generated by high and low temperature change. In addition, the introduction of the siloxane chain links increases the bonding strength of the cured product to materials such as metal, silicon, glass and the like, and reduces the internal stress to a certain extent.
According to the invention, the epoxy resin system is adopted as a main body structure of the conductive adhesive, the bismaleimide resin is adopted as a modifier, and compared with the conductive adhesive of a pure epoxy resin system, the glass transition temperature and the thermal decomposition temperature are improved, meanwhile, the high modulus is kept above the glass transition temperature, and in addition, the effects of high adhesive strength and low stress are unexpectedly obtained, which are difficult to realize by other types of modifiers (such as cyanate, full-aromatic-structure bismaleimide, acrylic resin, rubber and thermoplastic polyimide).
The bismaleimide resin containing the flexible chain segment prepared by the invention can control the molecular weight and the main chain structure of the polymer by adjusting the types, the feeding proportion and the preparation process of diamine/dianhydride, so as to change the balance between the heat resistance and the residual stress of the conductive adhesive.
In the prior art, the evaluation of the residual stress of the conductive adhesive is carried out by only theoretical calculation or by deducing the stress of the conductive adhesive according to other test data, and the actual numerical value of the residual stress cannot be specifically quantified. In the literature reported so far, no direct investigation of conductive adhesives using residual stress testers has emerged. The invention uses the residual stress tester to effectively evaluate the stress generated by the conductive adhesive in various temperature environments. The residual stress tester is widely applied to the field of semiconductor manufacturing, a layer of material to be tested is covered on a substrate such as a silicon wafer by using methods such as coating, deposition and the like, the substrate is deformed due to the difference of physical numbers of the substrate and the material to be tested, and the tester measures the warping (curvature radius) of the substrate by an emission light source and calculates the stress, so that the magnitude of the stress is intuitively quantized. And the processes of curing, temperature circulation, thermal aging and the like of the conductive adhesive are simulated by the temperature rise and fall in the instrument, so that residual stress generated in different environments is obtained.
The conductive adhesive modified by the bismaleimide resin prepared by the invention has the following advantages:
(1) The heat resistance is high, and the 2% thermal decomposition temperature is more than or equal to 350 ℃;
(2) Has higher glass transition temperature: tg is more than or equal to 110 ℃;
(3) The adhesive property is good, the chip clipper strength is high at room temperature and high temperature, the room temperature clipper strength is more than 25MPa, and the clipper strength is more than or equal to 7.5MPa at 260 ℃;
(4) Has lower curing stress and stress generated under temperature cycle.
(5) Has better conductivity: the volume resistivity is less than or equal to 0.0007.
The invention relates to an adhesive for reducing stress and improving temperature resistance and a preparation method thereof.
Drawings
FIG. 1 shows the surface state of a conductive adhesive containing flexible bismaleimide resin prepared in example I after 500 cycles at-65 to 125 ℃ in a residual stress tester;
FIG. 2 is an infrared image of a flexible bismaleimide resin containing resin prepared in step one of the examples;
FIG. 3 is an infrared image of a flexible bismaleimide resin prepared in example three steps one.
Detailed Description
The first embodiment is as follows: the adhesive for reducing stress and improving temperature resistance of the embodiment is prepared from 100 parts by weight of epoxy resin, 10-30 parts by weight of bismaleimide resin containing a flexible structure, 10-100 parts by weight of curing agent, 1-5 parts by weight of accelerator, 0.05-0.2 part by weight of coupling agent, 400-800 parts by weight of conductive particles and 0.1-0.5 part by weight of initiator;
the monomer structural formula of the bismaleimide resin containing the flexible structure is as follows:
said R is 1 Is that
In the specific embodiment, if the excessive bismaleimide resin proportion is adopted, the curing degree of the whole system at a certain curing temperature is reduced, the bonding strength is reduced, the viscosity of the whole system is increased, and the original operation manufacturability is lost; whereas a too low bismaleimide resin ratio will not provide performance improvements in terms of bond strength and residual stress to the overall system.
The curing agent according to the present embodiment is preferably 20 to 50 parts by mass, more preferably 20 to 30 parts by mass.
The accelerator according to the present embodiment is preferably 1 to 3 parts by mass.
The coupling agent according to the present embodiment is preferably 0.1 to 0.15 parts by mass.
The conductive particles according to this embodiment are preferably 400 to 600 parts by mass.
The adhesive of the present embodiment is an adhesive material having thermal conductivity and electrical conductivity, and can be used to connect a semiconductor element to a support member. In detail, the conductive adhesive of the embodiment can bear the higher operating temperature of the power component for a long time, and compared with the traditional high-temperature resistant conductive adhesive, the conductive adhesive of the embodiment has smaller stress and is not easy to crack when undergoing rapid high-low temperature change, so that the possibility of falling off of the semiconductor component is reduced. Compared with other low-stress conductive adhesives, the conductive adhesive of the embodiment has better heat resistance.
The bismaleimide used in the present embodiment is a bismaleimide containing a flexible chain segment structure, and aims to reduce stress generated by curing stress and temperature change of a material by introducing the bismaleimide containing a flexible chain segment structure, and the contained siloxane chain segments also play a role in reducing stress, and by introducing the siloxane-containing structure into a semi-aromatic structure, the situation that a rigid chain segment cannot be stretched due to thermal shrinkage in a curing gel process is reduced by utilizing the length and the flexibility of the siloxane chain segments, and the bismaleimide containing a flexible chain segment has lower stress and residual stress values in the curing process and the circulating process through stress test.
Meanwhile, the bismaleimide resin structure also has an aromatic heterocyclic structure, after the bismaleimide resin structure is introduced, the glass transition temperature, the modulus at high temperature and the bonding strength at high temperature of the conductive adhesive are improved, and the defect of insufficient heat resistance of the traditional low-stress conductive adhesive is effectively overcome. Unexpectedly, the semi-aromatic long-chain structure bismaleimide containing a siloxane structure, after containing a polyimide structure and a long-chain siloxane, even though the modulus slightly decreases when the glass transition temperature is exceeded, has a high deformation amount (linear expansion coefficient) and a high elongation at a high temperature, so that the overall adhesive strength (calculated from modulus and elongation) still has a large value.
The bismaleimide resin can control the molecular weight and the main chain structure of the polymer by adjusting the types of raw materials, the feeding proportion and the preparation process, so as to balance the heat resistance and the low stress characteristic of the conductive adhesive.
The beneficial effects of this concrete implementation are: the bismaleimide monomer containing the flexible chain segment is prepared in the specific embodiment. First, the molecular structure of the composite material contains an aromatic heterocyclic structure, so that the composite material has excellent heat resistance, and the glass transition temperature, the thermal decomposition temperature and the like of the whole composite material are effectively improved. And secondly, the structure of the bismaleimide resin has a flexible chain segment, and compared with the bismaleimide resin with a pure aromatic heterocyclic structure, the bismaleimide resin has slightly reduced heat resistance, but greatly reduces the curing stress of the whole system and the stress generated by high and low temperature change. In addition, the introduction of the siloxane chain links increases the bonding strength of the cured product to materials such as metal, silicon, glass and the like, and reduces the internal stress to a certain extent.
In the specific embodiment, the epoxy resin system is adopted as a main structure of the conductive adhesive, the bismaleimide resin is adopted as a modifier, and compared with the conductive adhesive of a pure epoxy resin system, the glass transition temperature and the thermal decomposition temperature are improved, meanwhile, the better modulus is kept above the glass transition temperature, and in addition, the effects of high bonding strength and low stress are unexpectedly obtained, which are difficult to realize by other types of modifiers (such as cyanate, full-aromatic bismaleimide, acrylic resin, rubber and thermoplastic polyimide).
The bismaleimide resin containing the soft chain segment prepared by the specific embodiment changes the balance between the heat resistance and the residual stress of the conductive adhesive by controlling the molecular weight and the main chain structure of the polymer through adjusting the types, the feeding proportion and the preparation process of diamine/dianhydride.
In the prior art, the evaluation of the residual stress of the conductive adhesive is carried out by only theoretical calculation or by deducing the stress of the conductive adhesive according to other test data, and the actual numerical value of the residual stress cannot be specifically quantified. In the literature reported so far, no direct investigation of conductive adhesives using residual stress testers has emerged. The present embodiment uses a residual stress tester to effectively evaluate the stress generated by the conductive adhesive in various temperature environments. The residual stress tester is widely applied to the field of semiconductor manufacturing, a layer of material to be tested is covered on a substrate such as a silicon wafer by using methods such as coating, deposition and the like, the substrate is deformed due to the difference of physical numbers of the substrate and the material to be tested, and the tester measures the warping (curvature radius) of the substrate by an emission light source and calculates the stress, so that the magnitude of the stress is intuitively quantized. And the processes of curing, temperature circulation, thermal aging and the like of the conductive adhesive are simulated by the temperature rise and fall in the instrument, so that residual stress generated in different environments is obtained.
The bismaleimide resin modified conductive adhesive prepared by adopting the specific embodiment has the following advantages:
(1) The heat resistance is high, and the 2% thermal decomposition temperature is more than or equal to 350 ℃;
(2) Has higher glass transition temperature: tg is more than or equal to 110 ℃;
(3) The adhesive property is good, the chip clipper strength is high at room temperature and high temperature, the room temperature clipper strength is more than 25MPa, and the clipper strength is more than or equal to 7.5MPa at 260 ℃;
(4) Has lower curing stress and stress generated under temperature cycle.
(5) Has better conductivity: the volume resistivity is less than or equal to 0.0007.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the epoxy resin molecule has more than two glycidyl groups, and the softening point is 15-100 ℃. The other is the same as in the first embodiment.
The softening point of the epoxy resin in the specific embodiment is preferably 20-80 ℃; in the case of the epoxy resin mixture, the softening point of the epoxy resin mixture still needs to satisfy the above range.
The epoxy resin according to the present embodiment is one or a mixture of several of bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, ether or polyether type epoxy resin, ester or polyester epoxy resin, urethane type epoxy resin, multifunctional type epoxy resin, alicyclic type epoxy resin, aliphatic epoxy resin, hydrogenated type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, ethylene oxide modified bisphenol a type epoxy resin, propylene oxide modified bisphenol a type epoxy resin, glycidyl modified polybutadiene resin, glycidyl modified triazine resin, silicone modified epoxy resin, aminophenol type epoxy resin, flexible epoxy resin, methacrylic acid modified epoxy resin, acrylic acid modified epoxy resin, special modified epoxy resin, dicyclopentadiene type epoxy resin, side chain hydroxyalkyl modified epoxy resin, long chain alkyl modified epoxy resin, imide modified epoxy resin, and carboxyl terminated nitrile rubber (CTBN) modified epoxy resin. Bisphenol type epoxy resins such as bisphenol a type epoxy resins and bisphenol F type epoxy resins are preferable from the viewpoint of adhesion.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the curing agent is an amine curing agent, an anhydride curing agent or an imidazole curing agent. The other is the same as the first or second embodiment.
The curing agent according to the present embodiment may be aliphatic amine, aromatic amine, dicyandiamide, dihydrazide compound, acid anhydride, phenolic resin. The dihydrazide compound is carboxylic dihydrazide such as adipic dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide and parahydroxybenzoic acid dihydrazide; the anhydride is phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, dodecenyl succinic anhydride, reactants of maleic anhydride and polybutadiene, and copolymers of maleic anhydride and styrene. In view of thermal properties, amine-based curing agents are preferred.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the accelerator is imidazole-based curing accelerator, amine-based curing accelerator, triphenylphosphine-based curing accelerator, diazabicyclo-based curing accelerator, urea-based curing accelerator, borate-based curing accelerator or polyamide-based curing accelerator. The other embodiments are the same as those of the first to third embodiments.
The accelerator according to the present embodiment is preferably an imidazole-based curing accelerator or an amine-based curing accelerator, and more preferably an imidazole-based curing accelerator, from the viewpoints of curability and adhesiveness.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the coupling agent is a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent or a zirconium aluminate coupling agent. The other embodiments are the same as those of the first to fourth embodiments.
The preferred silane coupling agent in this embodiment is 3-glycidoxypropyl trimethoxysilane (CAS number: 2530-83-8), gamma-aminopropyl methyldimethoxy silane (CAS number: 3663-44-3), gamma-mercaptopropyl trimethoxysilane; 3-glycidoxypropyl trimethoxysilane is particularly preferred.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the conductive particles are silver powder, copper powder or nickel powder; the silver powder is flaky or spherical; the average particle diameter D of the conductive particles 50 Is 1-20 mu m. The other embodiments are the same as those of the first to fifth embodiments.
The conductive particles according to the present embodiment are preferably silver powder, and have an average particle diameter D 50 Preferably 3 μm to 10. Mu.m.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the initiator is dibenzoyl peroxide. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: the preparation method of the adhesive for reducing stress and improving temperature resistance in the embodiment comprises the following steps:
1. preparation of bismaleimide resin containing Flexible Structure:
(1) mixing diamine, triethylamine and butanone, stirring and heating to 60-65 ℃, adding sodium acetate and dianhydride at 60-65 ℃ and stirring for 8-15 h, cooling to room temperature after the reaction is finished to obtain solution A, dissolving maleic anhydride in butanone to obtain maleic anhydride solution, adding maleic anhydride solution into the solution A in batches, stirring for 2-4 h at normal temperature, and then heating to 70 DEG C ～ 80 ℃ at 70 DEG C ～ Reflux stirring for 3-5 h at 80 ℃, and cooling to room temperature after the reaction is finished to obtain a solution B;
the mol ratio of diamine to triethylamine is 1 (0.08-0.15); the mass ratio of the diamine to the sodium acetate is 1mol (0.1-0.2) g; the mol ratio of diamine to dianhydride is 1 (1.8-2.5); the mol ratio of diamine to maleic anhydride is 1 (1.8-2.1);
the structural formula of the diamine is H 2 N-R1-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the R1 is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a flexible structure;
2. weighing and mixing:
according to the mass portion, 100 portions of epoxy resin, 10 portions to 30 portions of bismaleimide resin containing flexible structure, 10 portions to 100 portions of curing agent, 1 portion to 5 portions of accelerator, 0.05 portion to 0.2 portion of coupling agent, 400 portions to 800 portions of conductive particles and 0.1 portion to 0.5 portion of initiator are weighed, firstly, the epoxy resin and the bismaleimide resin containing flexible structure are stirred for 15 minutes to 30 minutes at the temperature of 70 ℃ to 90 ℃, after cooling, the curing agent, the accelerator, the coupling agent, the conductive particles and the initiator are added, then the mixture is dispersed for 2 minutes to 10 minutes at the rotation speed of 500rpm to 2000rpm, and finally, the adhesive for reducing stress and improving temperature resistance is obtained for defoamation and filling.
The adhesive according to the present embodiment is mixed by using a dispersing machine, a kneader, a three-roll machine, or the like, preferably by using a dispersing machine, and more preferably by using a planetary dispersing machine.
Detailed description nine: this embodiment differs from the eighth embodiment in that: the volume ratio of diamine to butanone in the step one (1) is 1mol (2.5-3.5) L; the volume ratio of the mol of the maleic acid to the butanone in the step one (1) is 1mol (0.5-2) L. The other is the same as in embodiment eight.
Detailed description ten: this embodiment differs from one of the eighth or ninth embodiments in that: washing and drying in the step (2) specifically comprises the steps of washing with 10-20% of sodium bicarbonate solution by mass percent, washing with deionized water as a washing liquid until the washing liquid is neutral, and finally vacuum drying for 10h at the temperature of 40-60 ℃. The others are the same as those of the eighth or ninth embodiment.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the preparation method of the adhesive for reducing stress and improving temperature resistance comprises the following steps:
1. preparation of bismaleimide resin containing Flexible Structure:
(1) mixing 1mol of diamine, 0.1mol of triethylamine and 3L of butanone, stirring and heating to 65 ℃, adding 0.15g of sodium acetate and 2mol of dianhydride at the temperature of 65 ℃ and stirring for 8 hours, cooling to room temperature after the reaction is finished to obtain a solution A, dissolving 2mol of maleic anhydride in 1L of butanone to obtain a maleic anhydride solution, adding the maleic anhydride solution into the solution A in portions, stirring for 4 hours at normal temperature, then heating to 80 ℃, refluxing and stirring for 5 hours at the temperature of 80 ℃, and cooling to room temperature after the reaction is finished to obtain a solution B;
the structural formula of the diamine is H 2 N-R1-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the R1 is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a flexible structure;
the monomer structural formula of the bismaleimide resin containing the flexible structure is as follows:
2. weighing and mixing:
weighing 70 parts of bisphenol A type epoxy resin, 30 parts of o-cresol type phenolic epoxy resin, 20 parts of bismaleimide resin containing flexible structure, 20 parts of 4, 4-diamino diphenyl sulfone, 1 part of 2-ethyl-4-methylimidazole, 0.1 part of 3-glycidoxypropyl trimethoxysilane, 500 parts of flake silver powder and 0.3 part of dibenzoyl peroxide according to parts by mass; firstly, stirring bisphenol A epoxy resin, o-cresol type phenolic epoxy resin and bismaleimide resin containing a flexible structure for 20min at the temperature of 80 ℃, cooling, adding 4, 4-diaminodiphenyl sulfone, 2-ethyl-4-methylimidazole, 3-glycidoxypropyl trimethoxy silane, flake silver powder and dibenzoyl peroxide, dispersing in a planetary disperser for 5min at the rotating speed of 1800rpm, and finally performing vacuum defoaming and filling to obtain a conductive adhesive containing flexible bismaleimide resin;
3-glycidoxypropyl trimethoxysilane with CAS number 2530-83-8.
The average particle diameter D of the conductive particles 50 Is 3 μm.
The washing and drying in the step (2) is specifically to wash with 10% sodium bicarbonate solution by mass percent, then wash with deionized water as a washing liquid until the washing liquid is neutral, and finally dry for 10 hours in vacuum under the condition of 60 ℃.
Embodiment two: the first difference between this embodiment and the first embodiment is that: preparing bismaleimide resin containing flexible structure in the first step:
(1) mixing 1mol of diamine, 0.1mol of triethylamine and 3L of butanone, stirring and heating to 65 ℃, adding 0.15g of sodium acetate and 2.1mol of dianhydride at the temperature of 65 ℃ and stirring for 8 hours, cooling to room temperature after the reaction is finished to obtain a solution A, dissolving 2mol of maleic anhydride in 1L of butanone to obtain a maleic anhydride solution, adding the maleic anhydride solution into the solution A in a divided manner, stirring for 4 hours at the room temperature, then heating to 75 ℃, refluxing and stirring for 4 hours at the temperature of 75 ℃, and cooling to the room temperature after the reaction is finished to obtain a solution B;
the structural formula of the diamine is H 2 N-R1-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the R1 is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain the bismaleimide resin containing the flexible structure.
The monomer structural formula of the bismaleimide resin containing the flexible structure is as follows:
the method comprises the steps of carrying out a first treatment on the surface of the The other is the same as in the first embodiment.
Embodiment III: the first difference between this embodiment and the first embodiment is that: preparing bismaleimide resin containing flexible structure in the first step:
(1) mixing 1mol of diamine, 0.1mol of triethylamine and 3L of butanone, stirring and heating to 65 ℃, adding 0.15g of sodium acetate and 2.3mol of dianhydride at the temperature of 65 ℃ and stirring for 8 hours, cooling to room temperature after the reaction is finished to obtain a solution A, dissolving 2mol of maleic anhydride in 1L of butanone to obtain a maleic anhydride solution, adding the maleic anhydride solution into the solution A in a divided manner, stirring for 4 hours at the room temperature, then heating to 75 ℃, refluxing and stirring for 5 hours at the temperature of 75 ℃, and cooling to the room temperature after the reaction is finished to obtain a solution B;
the structural formula of the diamine is H 2 N-R1-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the R1 is/>
The structural general formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a flexible structure;
the bismaleimide monomer in the bismaleimide resin containing the flexible structure is as follows:
. The other is the same as in the first embodiment.
Embodiment four: the first difference between this embodiment and the first embodiment is that: preparing bismaleimide resin containing flexible structure in the first step:
(1) mixing 1mol of diamine, 0.1mol of triethylamine and 3L of butanone, stirring and heating to 65 ℃, adding 0.15g of sodium acetate and 2.3mol of dianhydride at the temperature of 65 ℃ and stirring for 8 hours, cooling to room temperature after the reaction is finished to obtain a solution A, dissolving 2mol of maleic anhydride in 1L of butanone to obtain a maleic anhydride solution, adding the maleic anhydride solution into the solution A in a divided manner, stirring for 4 hours at the room temperature, then heating to 75 ℃, refluxing and stirring for 5 hours at the temperature of 75 ℃, and cooling to the room temperature after the reaction is finished to obtain a solution B;
the structural formula of the diamine is H 2 N-R1-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the R1 is
The structural general formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a flexible structure;
the bismaleimide monomer in the bismaleimide resin containing the flexible structure is as follows:
. The other is the same as in the first embodiment.
Fifth embodiment: the first difference between this embodiment and the first embodiment is that: and step two, the mass part of the bismaleimide resin containing the flexible structure is 10 parts. The other is the same as in the first embodiment.
Example six: the first difference between this embodiment and the first embodiment is that: the mass part of the bismaleimide resin containing the flexible structure in the second step is 30 parts. The other is the same as in the first embodiment.
Comparative example one: the first difference between this comparative example and the example is: weighing 85 parts of bisphenol A epoxy resin, 35 parts of o-cresol type phenolic epoxy resin, 20 parts of 4, 4-diaminodiphenyl sulfone, 1 part of 2-ethyl-4-methylimidazole, 0.1 part of 3-glycidoxypropyl trimethoxy silane and 500 parts of flake silver powder according to parts by weight; firstly, bisphenol A epoxy resin and o-cresol type phenolic epoxy resin are stirred for 20min at the temperature of 80 ℃, after cooling, 4-diaminodiphenyl sulfone, 2-ethyl-4-methylimidazole, 3-glycidoxypropyl trimethoxy silane and flake silver powder are added, then the mixture is dispersed in a planetary disperser for 5min at the rotating speed of 1800rpm, and finally, the conductive adhesive is obtained after vacuum defoamation and filling. The other is the same as in the first embodiment.
Comparative example two: the first difference between this comparative example and the example is: the mass part of the bismaleimide resin containing the flexible structure in the second step is 50 parts. The other is the same as in the first embodiment.
Comparative example three: the first difference between this comparative example and the example is: in the second step, 20 parts of bismaleimide resin containing a flexible structure is replaced by 20 parts of N, N '-4,4' -diphenylmethane bismaleimide resin; in the second step, the mass part of dibenzoyl peroxide is 0.2 part. The other is the same as in the first embodiment.
Comparative example four: the first difference between this comparative example and the example is: in the second step, 20 parts of bismaleimide resin containing a flexible structure is replaced by 20 parts of 4,4' -diaminodiphenyl methane epoxy resin; in the second step, the addition of dibenzoyl peroxide is omitted. The other is the same as in the first embodiment.
Comparative example five: the first difference between this comparative example and the example is: in the second step, 20 parts of bismaleimide resin containing a flexible structure is replaced by 20 parts of 4,4' -diaminodiphenyl methane epoxy resin and 8 parts of liquid nitrile rubber; in the second step, the addition of dibenzoyl peroxide is omitted. The other is the same as in the first embodiment.
Comparative example six: the first difference between this comparative example and the example is: step two, replacing 20 parts of bismaleimide resin containing the flexible structure with 20 parts of phenoxy resin; in the second step, the addition of dibenzoyl peroxide is omitted. The other is the same as in the first embodiment.
Comparative example seven: the first difference between this comparative example and the example is: step two, replacing 20 parts of bismaleimide resin containing the flexible structure with 20 parts of thermoplastic polyimide resin; step two, omitting the addition of dibenzoyl peroxide; in the second step, stirring is carried out for 20min at the temperature of 90 ℃. The other is the same as in the first embodiment.
The thermoplastic polyimide resin is commercially available (Saint base 1010-1000).
The conductive adhesives prepared in examples one to six and comparative examples one to seven were subjected to thermal weight loss, chip shear strength, thermal expansion coefficient, glass transition temperature (Tg), storage modulus, cure shrinkage, residual stress and volume resistivity test, and detailed evaluation methods were as follows:
a. weight loss on heat: the cured samples were tested using a thermogravimetric analyzer (american TA instruments TGA Q50). Rate of temperature rise: 10 ℃/min; test atmosphere: air. Wherein T is d2 At a thermal decomposition temperature of 2%, T d5 Is 5% thermal decomposition temperature. The curing process comprises the following steps: heating at 150deg.C for 30min, and heating at 200deg.C for 30min.
b. Chip clipper strength: bonding a 2mm multiplied by 2mm silicon wafer on a silicon substrate by using a conductive adhesive, and curing the following conditions: the sample was subjected to compression shear test using a chip push-pull tester (Nordsondage 3800) at a temperature of 150deg.C for 30min, then at a temperature of 200deg.C for 30min at shear rates of 100 μm/s at 25deg.C and 260 deg.C, respectively. Temperature cycling conditions: and (3) placing the cured sample in a temperature circulation test box, wherein the heating rate is 30 ℃/min, and the cooling rate is 30 ℃/min.
c. Coefficient of thermal expansion: the cured samples were tested using a thermo-mechanical analyzer (american TA instruments TMA Q400). Rate of temperature rise: 5 ℃/min. The curing process is as follows: heating at 150deg.C for 30min, and heating at 200deg.C for 30min. Wherein alpha is 1 Is 25 to T g And (a) the coefficient of thermal expansion, alpha 2 Is T g A thermal expansion coefficient of +20 ℃ to 260 ℃.
d. Glass transition temperature (Tg), storage modulus: the cured samples were tested using a dynamic thermo-mechanical analyzer (TA instruments DMAQ800 in the united states). Rate of temperature rise: 5 ℃/min. The curing process comprises the following steps: heating at 150deg.C for 30min, and heating at 200deg.C for 30min.
e. Cure shrinkage: (post-cure sample density-pre-cure sample density)/post-cure sample density × 100%. The curing process comprises the following steps: heating at 150deg.C for 30min, and heating at 200deg.C for 30min.
f. Residual stress test: spin-coating conductive adhesive on a 4-inch wafer, placing the wafer with a sample thickness of about 10 μm into a residual stress tester (TOHO FLX 2320-S) for testing; curing and residual stress testing are carried out in a residual stress tester, and curing conditions are as follows: heating to 150 ℃ at a heating rate of 10 ℃/min, heating to 30min at a temperature of 150 ℃, then heating to 200 ℃ at a heating rate of 10 ℃/min, heating to 30min at a temperature of 200 ℃, and finally cooling to room temperature at a cooling rate of 5 ℃/min. After curing, temperature cycle residual stress and heat aging residual stress are tested in a residual stress tester, and test conditions are as follows: the temperature rising rate is 30 ℃/min, and the temperature reducing rate is 30 ℃/min. Test atmosphere: air.
g. Volume resistivity test: volume resistivity testing was performed on cured samples using a microohm meter (daily RM 3545) according to GJB548B-2005 method 5011. The curing process is as follows: heating at 150deg.C for 30min, and heating at 200deg.C for 30min.
TABLE 1
TABLE 2
TABLE 3 Table 3
/>
TABLE 4 Table 4
Examples one to six are compared to comparative examples one to seven:
1. has better thermal stability, thermal decomposition temperature, T g Is generally higher. The bismaleimide structure disclosed by the invention can improve the thermal stability of the conductive adhesive.
2. Chip clipper strength is generally higher, especially after high and low temperature cycles and high temperature aging, the strength remains significantly higher than the latter. The bismaleimide structure disclosed by the invention can improve the bonding strength of the conductive adhesive.
3. The curing stress is lower, and the whole is lower than 7.5MPa; the cyclic stress of the conductive adhesive in the examples at different temperature intervals is substantially lower than that of the comparative examples; the stress after long-time high-temperature aging is low. The bismaleimide structure disclosed by the invention can obviously reduce the residual stress of a system.
In addition, in comparative example II, since the bismaleimide resin (A1) was excessively added in a part to cause incomplete curing, the thermal properties thereof were poor, but after a plurality of heat cycles and heat aging treatments, the degree of curing was increased to some extent, and the thermal properties were improved.
FIG. 1 shows the surface state of a conductive adhesive containing flexible bismaleimide resin prepared in example I after 500 cycles at-65 to 125 ℃ in a residual stress tester; the graph shows that the surface of the sample is smoother and has no obvious fluctuation, and the conductive adhesive containing the flexible bismaleimide resin in the embodiment can effectively reduce the stress generated with the substrate when the conductive adhesive is aged at high and low temperatures.
FIG. 2 is an infrared image of a flexible bismaleimide resin containing resin prepared in step one of the examples; as can be seen from the figure, 1703cm -1 Near the imide ring, a carbonyl stretching vibration absorption peak appears, 1360cm -1 、1173cm -1 C-N-C asymmetric and symmetric telescopic vibration absorption peak appears nearby, 3469cm -1 The nearby weak peak is the generalized frequency peak of carbonyl, and in addition, 1258cm -1 、818cm -1 Silane characteristic peak appears nearby, 1363cm -1 C-F characteristic peaks appear nearby. The appearance of these characteristic peaks surface synthesized a bismaleimide monomer.
FIG. 3 is an infrared plot of a flexible bismaleimide resin containing resin prepared in step one of the examples; from the figure, 1704cm -1 Near the imide ring, a carbonyl stretching vibration absorption peak appears, 1360cm -1 、1172cm -1 C-N-C asymmetric and symmetric telescopic vibration absorption peak appears nearby, 3466cm -1 The nearby weak peak is the generalized frequency peak of carbonyl, and 1260cm -1 、816cm -1 The characteristic peak of silane appears nearby, 1404cm -1 The o=s=o characteristic peak appears nearby. The appearance of these characteristic peaks surface synthesized a bismaleimide monomer.
Examples one to six can be used as high temperature resistant low stress conductive adhesives.
Claims (7)
1. The adhesive for reducing stress and improving temperature resistance is characterized by being prepared from 100 parts of epoxy resin, 20-30 parts of bismaleimide resin containing a flexible structure, 10-100 parts of curing agent, 1-5 parts of accelerator, 0.05-0.2 part of coupling agent, 400-800 parts of conductive particles and 0.1-0.5 part of initiator according to parts by weight;
the bismaleimide resin containing the flexible structure is prepared by the following steps:
(1) mixing diamine, triethylamine and butanone, stirring and heating to 60-65 ℃, adding sodium acetate and dianhydride at 60-65 ℃ and stirring for 8-15 h, cooling to room temperature after the reaction is finished to obtain solution A, dissolving maleic anhydride in butanone to obtain maleic anhydride solution, adding maleic anhydride solution into the solution A in batches, stirring for 2-4 h at normal temperature, and then heating to 70 DEG C ～ 80 ℃ at 70 DEG C ～ Reflux stirring for 3-5 h at 80 ℃, and cooling to room temperature after the reaction is finished to obtain a solution B;
the mol ratio of diamine to triethylamine is 1 (0.08-0.15); the mass ratio of the diamine to the sodium acetate is 1mol (0.1-0.2) g; the mol ratio of diamine to dianhydride is 1 (1.8-2.5); the mol ratio of diamine to maleic anhydride is 1 (1.8-2.1);
the structural formula of the diamine is H 2 N-R1-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the R1 is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain the bismaleimide resin containing the flexible structure.
2. The adhesive for reducing stress and improving temperature resistance according to claim 1, wherein the epoxy resin has two or more glycidyl groups in a molecule, and the softening point is 15 ℃ to 100 ℃.
3. The adhesive for reducing stress and improving temperature resistance according to claim 1, wherein the curing agent is an amine curing agent, an acid anhydride curing agent or an imidazole curing agent.
4. The adhesive for reducing stress and improving temperature resistance according to claim 1, wherein the accelerator is an imidazole-based accelerator, an amine-based accelerator, a triphenylphosphine-based accelerator, a diazabicyclo-based accelerator, a urea-based accelerator, a borate-based accelerator or a polyamide-based accelerator.
5. The adhesive for reducing stress and improving temperature resistance according to claim 1, wherein the coupling agent is a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent or a zirconium aluminate coupling agent.
6. The adhesive for reducing stress and improving temperature resistance according to claim 1, wherein the conductive particles are silver powder, copper powder or nickel powder; the silver powder is flaky or spherical; the average particle diameter D of the conductive particles 50 Is 1-20 mu m.
7. The adhesive of claim 1 wherein said initiator is dibenzoyl peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111669866.8A CN114231230B (en) | 2021-12-30 | 2021-12-30 | Adhesive capable of reducing stress and improving temperature resistance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111669866.8A CN114231230B (en) | 2021-12-30 | 2021-12-30 | Adhesive capable of reducing stress and improving temperature resistance and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114231230A CN114231230A (en) | 2022-03-25 |
| CN114231230B true CN114231230B (en) | 2023-10-20 |
Family
ID=80745268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111669866.8A Active CN114231230B (en) | 2021-12-30 | 2021-12-30 | Adhesive capable of reducing stress and improving temperature resistance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114231230B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117659916A (en) * | 2023-12-07 | 2024-03-08 | 杭州之江有机硅化工有限公司 | Conductive adhesive and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04366126A (en) * | 1991-06-13 | 1992-12-18 | Toshiba Chem Corp | Thermosetting resin composition |
| JP2002128996A (en) * | 2000-10-27 | 2002-05-09 | Toshiba Chem Corp | Heat-resistant epoxy resin composition |
| CN101037528A (en) * | 2007-04-26 | 2007-09-19 | 华东理工大学 | Heat-resistant bismaleimide/epoxy resin and preparation method thereof |
| CN103074021A (en) * | 2011-10-25 | 2013-05-01 | 上海本诺电子材料有限公司 | Organosilicon bimaleimide-epoxy conductive adhesive for LED |
| CN107406606A (en) * | 2015-03-23 | 2017-11-28 | 拓自达电线株式会社 | The manufacture method of resin impregnated thing, composite and copper clad layers stack |
| CN113736401A (en) * | 2021-09-06 | 2021-12-03 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance single-component adhesive and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8637611B2 (en) * | 2008-08-13 | 2014-01-28 | Designer Molecules, Inc. | Amide-extended crosslinking compounds and methods for use thereof |
-
2021
- 2021-12-30 CN CN202111669866.8A patent/CN114231230B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04366126A (en) * | 1991-06-13 | 1992-12-18 | Toshiba Chem Corp | Thermosetting resin composition |
| JP2002128996A (en) * | 2000-10-27 | 2002-05-09 | Toshiba Chem Corp | Heat-resistant epoxy resin composition |
| CN101037528A (en) * | 2007-04-26 | 2007-09-19 | 华东理工大学 | Heat-resistant bismaleimide/epoxy resin and preparation method thereof |
| CN103074021A (en) * | 2011-10-25 | 2013-05-01 | 上海本诺电子材料有限公司 | Organosilicon bimaleimide-epoxy conductive adhesive for LED |
| CN107406606A (en) * | 2015-03-23 | 2017-11-28 | 拓自达电线株式会社 | The manufacture method of resin impregnated thing, composite and copper clad layers stack |
| CN113736401A (en) * | 2021-09-06 | 2021-12-03 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance single-component adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114231230A (en) | 2022-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6170904B2 (en) | Epoxy resin composition for semiconductor encapsulation, semiconductor device using the same, and semiconductor manufacturing method | |
| US6548175B2 (en) | Epoxy-siloxanes based electrically conductive adhesives for semiconductor assembly and process for use thereof | |
| CN109439254B (en) | High-reliability filling adhesive capable of being repaired | |
| CN114231230B (en) | Adhesive capable of reducing stress and improving temperature resistance and preparation method thereof | |
| US10077385B2 (en) | Resin composition and electronic component | |
| US5912316A (en) | Flexible interpenetrating networks formed by epoxy-cyanate ester compositions via a polyamide | |
| KR100941315B1 (en) | Thermosetting adhesive composition and adhesive film using thereof | |
| CN115232589A (en) | High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof | |
| JP2001288244A (en) | Thermosetting resin composition, production method thereof, and product produced by using the same | |
| CN1880322A (en) | Epoxy compound comprising silicone grease and their application and preparation process | |
| CN117487489A (en) | Underfill with high stretching rate, preparation method thereof and chip packaging structure | |
| CN112662011A (en) | Modification method of silicon dioxide, silicon dioxide filler and epoxy resin composite material | |
| JPH0790239A (en) | Electrically conductive resin paste | |
| JP3384472B2 (en) | Conductive resin paste | |
| CN116751531A (en) | Heat-conducting insulating adhesive film and preparation method and application thereof | |
| US6846550B2 (en) | Adhesive film for underfill and semiconductor device using the same | |
| CN110591292B (en) | Underfill adhesive with high surface insulation resistance and preparation method thereof | |
| CN114196361B (en) | Adhesive with high temperature, high adhesive strength and low viscosity and preparation method thereof | |
| JPH07179833A (en) | Conductive resin paste | |
| JPH0484444A (en) | Conductive paste | |
| JPH0790238A (en) | Electrically conductive resin paste | |
| JP7351437B2 (en) | Conductive resin compositions for die attach materials, high thermal conductivity materials, and semiconductor devices | |
| WO2019127387A1 (en) | Resin composition, prepreg, laminate, and metal foil clad laminate | |
| US11961629B1 (en) | Antioxidant conductive thermal paste and method of manufacturing the same | |
| Liu et al. | Demonstration of flexible encapsulation in assembly industry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |