KR20020091224A - Rheology-Controlled Epoxy-Based Compositions - Google Patents
Rheology-Controlled Epoxy-Based Compositions Download PDFInfo
- Publication number
- KR20020091224A KR20020091224A KR1020027014071A KR20027014071A KR20020091224A KR 20020091224 A KR20020091224 A KR 20020091224A KR 1020027014071 A KR1020027014071 A KR 1020027014071A KR 20027014071 A KR20027014071 A KR 20027014071A KR 20020091224 A KR20020091224 A KR 20020091224A
- Authority
- KR
- South Korea
- Prior art keywords
- composition
- methylimidazole
- epoxy
- amount
- component
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 122
- 239000004593 Epoxy Substances 0.000 claims abstract description 51
- 239000004065 semiconductor Substances 0.000 claims abstract description 49
- 238000004377 microelectronic Methods 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims description 50
- 230000001070 adhesive effect Effects 0.000 claims description 50
- 239000000758 substrate Substances 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- -1 trialkoxysilyl isocyanurate derivatives Chemical class 0.000 claims description 17
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 239000000565 sealant Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000006254 rheological additive Substances 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004756 silanes Chemical class 0.000 claims description 5
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- NOQONXWBCSGVGF-UHFFFAOYSA-N 1,2,4-triphenylimidazole Chemical compound C=1C=CC=CC=1N1C=C(C=2C=CC=CC=2)N=C1C1=CC=CC=C1 NOQONXWBCSGVGF-UHFFFAOYSA-N 0.000 claims description 2
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 claims description 2
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 claims description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- XIOGJAPOAUEYJO-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical compound COC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 XIOGJAPOAUEYJO-UHFFFAOYSA-N 0.000 claims description 2
- OPHSKKPSEMOQLM-UHFFFAOYSA-N 2-(2-phenylethenyl)-1h-imidazole Chemical compound N=1C=CNC=1C=CC1=CC=CC=C1 OPHSKKPSEMOQLM-UHFFFAOYSA-N 0.000 claims description 2
- YAXVEVGFPVWPKA-UHFFFAOYSA-N 2-[2-(4-methoxyphenyl)ethenyl]-1h-imidazole Chemical compound C1=CC(OC)=CC=C1C=CC1=NC=CN1 YAXVEVGFPVWPKA-UHFFFAOYSA-N 0.000 claims description 2
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 claims description 2
- XUZOLVDRTWTQJB-UHFFFAOYSA-N 2-heptadec-1-enyl-5-methyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCC=CC1=NC(C)=CN1 XUZOLVDRTWTQJB-UHFFFAOYSA-N 0.000 claims description 2
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 claims description 2
- RFWOZDRUDBNGSY-UHFFFAOYSA-N 2-heptadecyl-5-methyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC(C)=CN1 RFWOZDRUDBNGSY-UHFFFAOYSA-N 0.000 claims description 2
- OMBXZTBWATXTMQ-UHFFFAOYSA-N 2-methyl-1-(1-phenyltridecyl)imidazole Chemical compound C1=CN=C(C)N1C(CCCCCCCCCCCC)C1=CC=CC=C1 OMBXZTBWATXTMQ-UHFFFAOYSA-N 0.000 claims description 2
- SIQHSJOKAUDDLN-UHFFFAOYSA-N 2-methyl-1-propylimidazole Chemical compound CCCN1C=CN=C1C SIQHSJOKAUDDLN-UHFFFAOYSA-N 0.000 claims description 2
- WBDSXISQIHMTGL-UHFFFAOYSA-N 2-methyl-4,5-diphenyl-1h-imidazole Chemical compound N1C(C)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 WBDSXISQIHMTGL-UHFFFAOYSA-N 0.000 claims description 2
- GSKPCWYORDSBPC-UHFFFAOYSA-N 2-naphthalen-2-yl-4,5-diphenyl-1h-imidazole Chemical compound C1=CC=CC=C1C1=C(C=2C=CC=CC=2)NC(C=2C=C3C=CC=CC3=CC=2)=N1 GSKPCWYORDSBPC-UHFFFAOYSA-N 0.000 claims description 2
- UPOLYUOBDJSLRC-UHFFFAOYSA-N 2-undec-1-enyl-1h-imidazole Chemical compound CCCCCCCCCC=CC1=NC=CN1 UPOLYUOBDJSLRC-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 2
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- YGOFNNAZFZYNIX-UHFFFAOYSA-N 3-N-phenylbenzene-1,2,3-triamine Chemical compound NC=1C(=C(C=CC1)NC1=CC=CC=C1)N YGOFNNAZFZYNIX-UHFFFAOYSA-N 0.000 claims description 2
- LTGRDWFVGBZDIR-UHFFFAOYSA-N 4-(4,5-diphenyl-1h-imidazol-2-yl)-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 LTGRDWFVGBZDIR-UHFFFAOYSA-N 0.000 claims description 2
- MJZYCDYAVCQQEQ-UHFFFAOYSA-N 5-tert-butyl-2-(4,5-diphenyl-1H-imidazol-2-yl)phenol Chemical compound OC1=CC(C(C)(C)C)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 MJZYCDYAVCQQEQ-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- IKZDMJSZEMDIMC-UHFFFAOYSA-N chembl389656 Chemical compound OC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 IKZDMJSZEMDIMC-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 230000013011 mating Effects 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- SEAZOECJMOZWTD-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethyl)silane Chemical compound CO[Si](OC)(OC)CC1CO1 SEAZOECJMOZWTD-UHFFFAOYSA-N 0.000 claims description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims 2
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 claims 1
- VPGCUZIHMJEVGN-UHFFFAOYSA-N 3-(4,5-diphenyl-1H-imidazol-2-yl)benzene-1,2-diol Chemical compound OC=1C(=C(C=CC=1)C=1NC(=C(N=1)C1=CC=CC=C1)C1=CC=CC=C1)O VPGCUZIHMJEVGN-UHFFFAOYSA-N 0.000 claims 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims 1
- 229910052582 BN Inorganic materials 0.000 claims 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 claims 1
- 125000002883 imidazolyl group Chemical group 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 16
- 239000000945 filler Substances 0.000 description 12
- 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 11
- 229920003319 Araldite® Polymers 0.000 description 8
- 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 8
- 239000000126 substance Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 4
- 229940106691 bisphenol a Drugs 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KFUSXMDYOPXKKT-VIFPVBQESA-N (2s)-2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OC[C@H]1OC1 KFUSXMDYOPXKKT-VIFPVBQESA-N 0.000 description 1
- 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
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- UPJQFPBIFZYRLB-UHFFFAOYSA-N 3-(4,5-diphenyl-1h-imidazol-2-yl)phenol Chemical compound OC1=CC=CC(C=2NC(=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 UPJQFPBIFZYRLB-UHFFFAOYSA-N 0.000 description 1
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 1
- 229940086681 4-aminobenzoate Drugs 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- 235000013175 Crataegus laevigata Nutrition 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SOOZEQGBHHIHEF-UHFFFAOYSA-N methyltetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21C SOOZEQGBHHIHEF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
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- 230000000930 thermomechanical effect Effects 0.000 description 1
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- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
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Abstract
본 발명은 인쇄 산업을 위한 잉크 젯 프린트헤드의 조립에서와 같은 코팅 용도에서 및 반도체 소자의 조립에서와 같은 마이크로전자 산업에서 사용하기에 특히 적합한 유동성 조절된 에폭시계 조성물에 관한 것이다.The present invention relates to a flow controlled epoxy based composition particularly suitable for use in coating applications such as in the assembly of ink jet printheads for the printing industry and in the microelectronics industry such as in the assembly of semiconductor devices.
Description
에폭시계 조성물은 잘 알려져 있다. 실제로, 에폭시계 조성물은 다양한 최종 용도에 이용가능하다.Epoxy-based compositions are well known. Indeed, epoxy-based compositions are available for a variety of end uses.
그러한 용도 중 하나인 잉크젯 프린트헤드의 조립에서 부품들은 광범위한 온도 변동을 겪게 된다. 대개, 플렉스 (flex) 회로가 먼저 배리어 필름을 통해 실리콘 기판에 부착된다. 이어서 플렉스 회로와 기판 두 부분이 모두 펜 (pen) 몸체에 부착된다. 플렉스 회로 부분을 펜 몸체에 부착시키기 위해, 인접한 구조체들을 승온으로 가열하여 펜 몸체 내의 구멍 주변의 홈에 도포된 접착제를 경화시켜, 플렉스 회로를 펜 몸체에 결합시킨다. 경화시킨 후, 펜을 실온으로 냉각시킨다. 어떤 경우에 도포된 접착제가 특히 경화 과정 동안 온도가 증가하기 시작함에 따라 홈에서 "흘러 (run)" 나올 수 있다. 이러한 사고가 일어나면, 접착제가 그를 통해 잉크 액적을 사출시키고자 의도되는 플렉스 회로의 노즐 내로 들어가 차단시키거나막는 (경화되면 결국 영구적임) 경향이 있다. 이러한 사고는 잉크의 종이로의 전달을 기껏해야 불량하게 만들고 종종 잉크가 노즐을 통해 전혀 유동하지 못하도록 할 수 있다 [예를 들어 미국 특허 제5,825,389호 (Cowger) 참조]. 상기 문제는 접착제의 유동성의 적절한 조정에 의해 해결될 수 있다.In one such application, the assembly of inkjet printheads, the components undergo extensive temperature fluctuations. Usually, a flex circuit is first attached to a silicon substrate through a barrier film. Subsequently, both the flex circuit and the substrate are attached to the pen body. To attach the flex circuit portion to the pen body, the adjacent structures are heated to elevated temperatures to cure the adhesive applied to the grooves around the holes in the pen body, thereby joining the flex circuit to the pen body. After curing, the pen is cooled to room temperature. In some cases, the applied adhesive may “run” out of the grooves, especially as the temperature begins to increase during the curing process. When this happens, the adhesive tends to enter, block or block (and eventually become permanent if cured) the nozzles of the flex circuit through which the ink droplets are intended to eject. This accident can lead to poor delivery of ink to paper and often prevent ink from flowing through the nozzle at all (see, eg, US Pat. No. 5,825,389 to Cowger). This problem can be solved by appropriate adjustment of the fluidity of the adhesive.
유동성 조절은 점도를 증가시키기 위해 충전제의 첨가, 또는 유동을 향상시키기 위해 충전제의 제거 및(또는) 가소화제의 첨가에 의해 종종 수행된다. 겉보기에 단순한 문제이지만, 많은 접착제 조성물, 특히 에폭시계 접착제 조성물은 다른 이유 때문에 이미 충전제를 포함하고 있다. 예를 들어, 접착제 조성물에 열 전도성을 부여하기 위해 접착제 조성물에 몇몇 충전제가 첨가될 수 있다. 접착제를 놓고자 하는 기판들 사이에 열 팽창 계수 ("CTE")를 매치시키는 것을 돕기 위해 다른 충전제가 첨가될 수 있다. 또 다른 충전제는 항복점 (접착제 조성물의 3차원 구조)을 향상시키기 위해 첨가될 수 있다. 그와 같이, 유동성을 증진시키기 위해 추가의 충전제를 첨가하는 것은 신속한 분배를 허용하기에는 너무 많은 것으로 입증될 수 있어서 분배 공정을 저해할 수 있다. 잉크 젯 프린트헤드의 맥락에서, 점도를 증진시키기 위해 충전제를 첨가하면 그를 통해 또한 잉크가 유동하게 되는 노즐을 막거나 차단시킬 수도 있고, 이 경우 접착제의 약간의 위킹 (wicking)이 일어난다.Flow control is often performed by the addition of fillers to increase viscosity, or by the removal of fillers and / or by the addition of plasticizers to enhance flow. Although apparently a simple matter, many adhesive compositions, especially epoxy based adhesive compositions, already contain fillers for other reasons. For example, some fillers may be added to the adhesive composition to impart thermal conductivity to the adhesive composition. Other fillers may be added to help match the coefficient of thermal expansion (“CTE”) between the substrates on which the adhesive is to be placed. Another filler can be added to improve the yield point (three-dimensional structure of the adhesive composition). As such, adding additional fillers to enhance fluidity may prove too much to allow for rapid dispensing, which may inhibit the dispensing process. In the context of ink jet printheads, the addition of fillers to enhance viscosity may also block or block nozzles through which ink flows, in which case some wicking of the adhesive occurs.
유동을 향상시키기 위한 충전제의 제거는 열 전도성, CTE 매칭 및(또는) 항복점 향상을 저해할 수 있다. 유동을 향상시키기 위한 가소화제의 포함은 접착에 불리한 영향을 끼칠 수 있다.Removal of fillers to improve flow can hinder thermal conductivity, CTE matching, and / or yield point improvement. The inclusion of plasticizers to enhance flow can adversely affect adhesion.
따라서, 유동성을 조절할 수 있는 통상의 방식은 프린트헤드, 예를 들어 테이프 헤드 조립체의 프린트헤드 하우징에의 결합에서와 같이 특정 접착제가 맞추어져야하는 특정 용도에 적합하지 않을 수 있다. 따라서, 이러한 점에서 잉크 젯 프린트헤드의 사출 통로에 불리한 영향을 끼치지 않으면서 결합선을 달성할 수 있는 방식이 필요한 것이 명백하다.Thus, conventional ways of controlling fluidity may not be suitable for the particular application in which a particular adhesive is to be tailored, such as in the coupling of a printhead, eg, a tapehead assembly to a printhead housing. Therefore, it is clear in this respect that a way is needed to achieve a bond line without adversely affecting the injection passage of the ink jet printhead.
또한 에폭시계 조성물의 가장 광범위하게 사용되는 용도 중 하나는 아마도 마이크로전자 소자의 조립에서이다. 전자 산업에서의 진보로 특히 많은 작업처리량과 공정 효율에 대한 필요의 면에서 중대한 가공 파라미터인 에폭시계 조성물의 정밀한 침적이 가능하게 되었다. 상기 목적에서 많은 마이크로전자 용도를 위해 상기한 필요를 충족시키기 위해 접착제 제제의 유동을 조정하는 것이 요망된다.Also one of the most widely used applications of epoxy based compositions is probably in the assembly of microelectronic devices. Advances in the electronics industry have enabled the precise deposition of epoxy-based compositions, which are critical processing parameters, particularly in view of the need for high throughput and process efficiency. For this purpose it is desirable to adjust the flow of adhesive formulation to meet the above needs for many microelectronic applications.
예를 들어, 열 팽창 계수가 반도체 소자와 캐리어 기판의 계수 사이의 중간인 재료를 제공하기 위해 접착제 제제가 반도체 소자와 캐리어 기판 사이에 유동하도록 의도되는 하부충전 (underfill) 용도에서, 반도체 소자와 캐리어 기판 사이의 간극 내로 통과하도록 허용하는 적합한 유동성을 갖는 접착제 제제를 제공하는 것이 중요하다. 상기한 바와 같이, 가소화제를 첨가함으로써 유동을 향상시킬 수 있다. 그러나, 그러한 가소화제의 첨가는 대가 없이는 불가능하다. 즉, 그러한 가소화제의 포함은 형성된 접착제 결합의 강도를 약화시키는 것과 같이 경화된 접착제의 물성에 불리한 영향을 끼칠 수 있다.For example, in underfill applications where the adhesive formulation is intended to flow between the semiconductor device and the carrier substrate to provide a material whose coefficient of thermal expansion is intermediate between the coefficients of the semiconductor device and the carrier substrate. It is important to provide an adhesive formulation with suitable fluidity that allows passage into the gaps between the substrates. As mentioned above, the flow can be improved by adding a plasticizer. However, the addition of such plasticizers is impossible without cost. That is, the inclusion of such plasticizers can adversely affect the physical properties of the cured adhesive, such as weakening the strength of the adhesive bond formed.
전자 부품을 인쇄된 회로판에 결합시키기 위해 표면 탑재 (mount) 접착제가 사용되는 칩결합 용도와 같은 다른 마이크로전자 용도에서, 항복점을 향상시켜 일단 기판 상에 분배되면 접착제 조성물이 기판 상에서 훌륭하게 견디도록 하는 것이 요망된다.In other microelectronic applications, such as chip bonding applications where surface mount adhesives are used to bond electronic components to printed circuit boards, it is desirable to improve the yield point so that the adhesive composition withstands well on the substrate once dispensed on the substrate. It is requested.
상기한 바와 같이 접착제 조성물을 점조하게 하기 위해 충전제를 사용하는 것 이외에, 이들 조성물이 정의된 구조적 완전성을 갖도록 하는 것이 또한 바람직하다. 이를 달성하기 위한 한 방법은 요변성 (thixotropy) 부여제, 예를 들어 점토 또는 실리카의 첨가를 통해서이며, 이들 중 많은 것이 잘 알려져 있다. 실제로, Degussa에서는 많은 처리된 열분해 (fumed) 실리카를 상표명 AEROSIL로 시판하고 있으며, 에폭시 수지에 점조화 및 요변성 효과를 부여하기 위해 이들을 사용하는 것을 제안하였다 [또한 C.D. Wright and J.M. Muggee, "Epoxy Structural Adhesives" inStructural Adhesives: Chemistry and Technology, S.R. Hartshorn, ed., 113-79, 131 (1986) 참조].In addition to using fillers to viscosity the adhesive compositions as described above, it is also desirable to have these compositions have defined structural integrity. One way to achieve this is through the addition of thixotropy imparting agents, for example clay or silica, many of which are well known. Indeed, Degussa sells many treated fumed silicas under the trade name AEROSIL, and has suggested using them to impart viscosity and thixotropic effects to epoxy resins [see also CD Wright and JM Muggee, "Epoxy Structural Adhesives "in Structural Adhesives: Chemistry and Technology , SR Hartshorn, ed., 113-79, 131 (1986)].
Loctite Corporation에 의한 최근의 진보에서, 고체 유기산을 사용하여 에폭시계 조성물에서 시간 경과에 따른 향상된 항복점 유지와 점도 유지가 달성되었다 (국제 특허 출원 제PCT/IE99/00001호 참조).In recent advances by Loctite Corporation, improved yield point retention and viscosity retention over time have been achieved in epoxy-based compositions using solid organic acids (see International Patent Application PCT / IE99 / 00001).
표면 탑재 용도에서 정밀한 접착제 침적이 일어나지 않는 경우 {접착제 침적 기술 부정확성 때문 또는 특정 용도에 대한 부적절한 유동성으로 인한 접착제의 퍼짐 때문 또는 둘 모두 때문} 부품 탑재는 전혀 일어날 수 없고, 심지어 탑재가 일어나는 경우에도 탑재는 상업적으로 허용되는 방식으로 일어날 수 없다.No precise adhesive deposition in surface mount applications {due to adhesive deposition technology inaccuracy or due to the spread of adhesive due to inadequate fluidity for a particular application, or both} Part mounting cannot occur at all, even when mounting occurs Cannot occur in a commercially acceptable manner.
마이크로전자 소자를 조립하기 위해 사용된 캐리어 기판과 반도체 소자는 종종 액정 중합체, 폴리아미드 또는 실리콘 다이와 같은 결합시키기 힘든 (hard-to-bond) 재료로 구성되거나, 그러한 재료로 적층되거나 또는 그러한 재료를 포함한다. 그래서, 접착 촉진 물질을 첨가함으로써 상기한 기판에 대한 접착제 조성물의 접착을 향상시키거나 또는 접착제 제제를 분배하기에 앞서 활성화제 물질로 기판의 표면을 먼저 프라이밍하는 것이 요망되며, 전자가 후자에서 관찰되는 부가적인 가공 단계와 작업처리량의 감소 및 프라이밍 단계를 위한 빈번한 이용불가능한 공간의 면에서 바람직하다.Carrier substrates and semiconductor devices used to assemble microelectronic devices are often composed of, laminated to, or containing hard-to-bond materials such as liquid crystal polymers, polyamides, or silicon dies. do. Thus, it is desirable to improve the adhesion of the adhesive composition to the above substrates by adding an adhesion promoter material or to prime the surface of the substrate with the activator material first before dispensing the adhesive formulation, the former being observed in the latter. It is desirable in view of the frequently unavailable space for additional processing steps, reduced throughput and priming steps.
에폭시계 조성물에 또한 조성물의 유동성을 변형시킬 수 있어서 조성물이 추구되는 최종 용도에 적절한 유동성을 갖도록 하는 접착 촉진 물질을 제공하는 것이 바람직할 것이다.It would be desirable to provide an adhesion promoting material in an epoxy based composition that can also modify the flowability of the composition such that the composition has fluidity suitable for the end use for which it is sought.
<발명의 개요><Overview of invention>
본 발명은 조절된 유동성을 갖는 에폭시계 조성물을 제공한다. 대체로, 본 발명은 에폭시 성분, 유동성 조절제 및 경화제를 포함하는 조성물을 제공한다.The present invention provides an epoxy based composition having controlled fluidity. In general, the present invention provides a composition comprising an epoxy component, a flow control agent and a curing agent.
물론, 본 발명은 이들 에폭시계 조성물의 반응 생성물을 또한 제공한다.Of course, the present invention also provides reaction products of these epoxy based compositions.
또한, 본 발명은 상기한 에폭시계 조성물의 반응 생성물의 접착 강도를 손상시키지 않으면서 에폭시계 조성물의 점도를 조절하는 방법을 제공한다.The present invention also provides a method of controlling the viscosity of an epoxy composition without impairing the adhesive strength of the reaction product of the epoxy composition described above.
본 발명은 또한 상기한 에폭시계 조성물을 제조하는 방법, 및 잉크 젯 프린트헤드 또는 마이크로전자 반도체 소자의 조립에서 상기한 에폭시계 조성물을 사용하는 방법을 제공한다.The present invention also provides a method of preparing the epoxy composition described above, and a method of using the epoxy composition described above in the assembly of an ink jet printhead or a microelectronic semiconductor device.
본 발명은 이하의 도면을 참조하여 "발명의 상세한 설명"을 읽음으로써 보다 충분히 이해될 것이다.The invention will be more fully understood by reading "Detailed Description of the Invention" with reference to the following drawings.
본 발명은 인쇄 산업을 위한 잉크 젯 프린트헤드의 조립에서와 같은 코팅 용도에서 및 반도체 소자의 조립에서와 같은 마이크로전자 산업에서 사용하기에 특히 적합한 유동성 조절된 에폭시계 조성물에 관한 것이다.The present invention relates to a flow controlled epoxy based composition particularly suitable for use in coating applications such as in the assembly of ink jet printheads for the printing industry and in the microelectronics industry such as in the assembly of semiconductor devices.
도 1은 본 발명에 따른 에폭시 조성물을 사용하여 조립된 잉크 젯 프린트헤드의 입면도이다.1 is an elevation view of an ink jet printhead assembled using an epoxy composition according to the present invention.
도 2는 본 발명에 따른 에폭시 조성물이 하부충전 밀봉제로서 사용된 플립 (flip) 칩 조립체의 예를 보여주는 단면도이다.2 is a cross-sectional view showing an example of a flip chip assembly in which the epoxy composition according to the present invention is used as a bottom filling sealant.
도 3은 본 발명에 따른 에폭시 조성물을 사용하여 회로판에 탑재되는 반도체 소자의 예를 보여주는 단면도이다.3 is a cross-sectional view showing an example of a semiconductor device mounted on a circuit board using the epoxy composition according to the present invention.
도 4는 본 발명에 따른 에폭시 조성물이 하부충전 밀봉제로서 사용된 탑재된 구조체의 예를 보여주는 단면도이다.4 is a cross-sectional view showing an example of a mounted structure in which an epoxy composition according to the present invention is used as a bottom fill sealant.
본 발명은 조절된 유동성을 갖는 에폭시계 조성물을 제공한다. 대체로, 본 발명은 에폭시 성분, 유동성 조절제 및 경화제를 포함하는 조성물을 제공한다.The present invention provides an epoxy based composition having controlled fluidity. In general, the present invention provides a composition comprising an epoxy component, a flow control agent and a curing agent.
본 발명의 에폭시 수지 성분은 임의의 일반적인 에폭시 수지, 예를 들어 다관능성 에폭시 수지를 포함할 수 있다. 보통, 다관능성 에폭시 수지는 전체 에폭시 수지 성분의 약 15 중량% 내지 약 75 중량% 범위의 양으로 포함되어야 한다. 비스페놀-A형 에폭시 수지의 경우, 바람직하게는 그 양은 전체 에폭시 수지 성분의 약 35 내지 약 65 중량%, 예를 들어 약 40 내지 약 50 중량% 범위이어야 한다.The epoxy resin component of the present invention may include any common epoxy resin, for example polyfunctional epoxy resin. Usually, the multifunctional epoxy resin should be included in an amount ranging from about 15% to about 75% by weight of the total epoxy resin component. In the case of bisphenol-A type epoxy resins, the amount should preferably be in the range of about 35 to about 65 weight percent, such as about 40 to about 50 weight percent of the total epoxy resin component.
다관능성 에폭시 수지의 예로는 비스페놀-A형 에폭시 수지 (예를 들어 Nippon Kayaku (Japan)의 RE-310-S), 비스페놀-F형 에폭시 수지 (예를 들어 Nippon Kayaku의 RE-404-S), 페놀 노볼락형 에폭시 수지 및 크레솔 노볼락형 에폭시 수지(예를 들어 Ciba Specialty Chemicals (Hawthorne, New York)의 ARALDITE ECN 1871 또는 Nippon Kayaku의 XD10002-L)를 포함한다.Examples of polyfunctional epoxy resins include bisphenol-A type epoxy resins (e.g. RE-310-S from Nippon Kayaku (Japan)), bisphenol-F type epoxy resins (e.g. RE-404-S from Nippon Kayaku), Phenol novolak type epoxy resins and cresol novolak type epoxy resins (eg ARALDITE ECN 1871 from Ciba Specialty Chemicals (Hawthorne, New York) or XD10002-L from Nippon Kayaku).
다른 적합한 에폭시 수지는 방향족 아민 및 에피클로로히드린에 기초한 폴리에폭시 화합물, 예를 들어 N,N,N',N'-테트라글리시딜-4,4'-디아미노디페닐 메탄; N-디글리시딜-4-아미노페닐 글리시딜 에테르; 및 N,N,N',N'-테트라글리시딜-1,3-프로필렌 비스-4-아미노벤조에이트를 포함한다.Other suitable epoxy resins include polyepoxy compounds based on aromatic amines and epichlorohydrin, for example N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl methane; N-diglycidyl-4-aminophenyl glycidyl ether; And N, N, N ', N'-tetraglycidyl-1,3-propylene bis-4-aminobenzoate.
본 발명에서 사용하기에 적합한 에폭시 수지 중에는 또한 페놀릭 화합물의 폴리글리시딜 유도체, 예를 들어 Shell Chemical Co.로부터 상표명 EPON으로 입수가능한 것, 예를 들어 EPON 828, EPON 1001, EPON 1009 및 EPON 1031; Dow Chemical Co.의 DER 331, DER 332, DER 334 및 DER 542; 및 Nippon Kayaku의 BREN-S가 있다. 다른 적합한 에폭시 수지는 폴리올 등과 페놀-포름알데히드 노볼락의 폴리글리시딜 유도체 (이는 Dow Chemical로부터 상표명 DEN, 예를 들어 DEN 431, DEN 438 및 DEN 439로 상업적으로 입수가능하다)로부터 제조된 폴리에폭시드를 포함한다. 크레솔 유사체는 또한 Ciba Specialty Chemicals로부터 상표명 ARALDITE, 예를 들어 ARALDITE ECN 1235, ARALDITE ECN 1273 및 ARALDITE ECN 1299로 상업적으로 입수가능하다. SU-8은 Interez, Inc로부터 입수가능한 비스페놀-A형 에폭시 노볼락이다. 아민, 아미노알코올 및 폴리카르복실산의 폴리글리시딜 부가물이 또한 본 발명에서 유용하며, 그의 시판 수지는 F.I.C. Corporation의 GLYAMINE 135, GLYAMINE 125 및 GLYAMINE 115; Ciba Specialty Chemicals의 ARALDITE MY-720, ARALDITE 0500 및 ARALDITE 0510; 및 Sherwin-Williams Co.의 PGA-X 및 PGA-C를 포함한다.Among the epoxy resins suitable for use in the present invention are also polyglycidyl derivatives of phenolic compounds, such as those available under the trade name EPON from Shell Chemical Co., for example EPON 828, EPON 1001, EPON 1009 and EPON 1031. ; DER 331, DER 332, DER 334 and DER 542 from Dow Chemical Co .; And BREN-S from Nippon Kayaku. Other suitable epoxy resins are polyepoxys prepared from polyols and the like, polyglycidyl derivatives of phenol-formaldehyde novolac, which are commercially available from Dow Chemical under the trade names DEN, for example DEN 431, DEN 438 and DEN 439. De Cresol analogs are also commercially available from Ciba Specialty Chemicals under the trade names ARALDITE, for example ARALDITE ECN 1235, ARALDITE ECN 1273 and ARALDITE ECN 1299. SU-8 is a bisphenol-A type epoxy novolac available from Interez, Inc. Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in the present invention and commercially available resins thereof are described in F.I.C. GLYAMINE 135, GLYAMINE 125 and GLYAMINE 115 from Corporation; ARALDITE MY-720, ARALDITE 0500 and ARALDITE 0510 from Ciba Specialty Chemicals; And PGA-X and PGA-C by Sherwin-Williams Co.
물론 상이한 에폭시 수지들의 조합물도 또한 본 발명에서 사용하기에 바람직하다.Of course, combinations of different epoxy resins are also preferred for use in the present invention.
유동성 조절제는 약 0.01 내지 약 2 중량%, 예를 들어 약 0.1 내지 약 1 중량% 범위의 양으로 사용되어야 한다.Flow control agents should be used in amounts ranging from about 0.01 to about 2 weight percent, such as from about 0.1 to about 1 weight percent.
유동성 조절제는 실란, 예를 들어 에폭시 실란 [예, 글리시딜 트리메톡시실란 (OSI에서 상표명 A-187로 입수가능함)], 및 아미노 실란 [예, 감마-아미노 프로필 트리에톡시실란 (OSI에서 상표명 A-1100으로 입수가능함)]을 포함한다. 또한, 트리알콕시실릴 이소시아누레이트 유도체 (예, OSI의 Y-11597)를 또한 사용할 수 있다. 대개, 본 발명의 에폭시계 조성물에서 에폭시 실란을 사용하면 조성물에 요변성을 부여하는 경향이 있을 것이며, 본 발명의 에폭시계 조성물에서 아미노 실란을 사용하면 조성물에 향상된 유동성을 부여하는 경향이 있을 것이다. 이들 유동성 조절제는 또한 결합시키기 힘든 표면에의 접착을 촉진시킨다.Rheology modifiers include silanes such as epoxy silanes [eg, glycidyl trimethoxysilane (available under the trade name A-187 from OSI)], and amino silanes [eg, gamma-amino propyl triethoxysilane (from OSI Available under the trade name A-1100). In addition, trialkoxysilyl isocyanurate derivatives (eg Y-11597 of OSI) can also be used. Usually, the use of epoxy silanes in the epoxy-based compositions of the present invention will tend to impart thixotropy to the composition, and the use of amino silanes in the epoxy-based compositions of the present invention will tend to impart improved fluidity to the compositions. These rheology modifiers also promote adhesion to surfaces that are difficult to bond.
경화제는 본 발명의 조성물의 에폭시 수지 성분을 촉매 중합시킬 수 있다.The curing agent can catalytically polymerize the epoxy resin component of the composition of the present invention.
경화제는 전체 조성물의 약 1 내지 약 25 중량%, 예를 들어 약 5 내지 약 8 중량%, 바람직하게는 약 6 내지 약 6.5 중량%의 양으로 사용할 수 있다.The curing agent may be used in an amount of about 1 to about 25 weight percent of the total composition, for example about 5 to about 8 weight percent, preferably about 6 to about 6.5 weight percent.
본 발명에 사용하기에 바람직한 경화제는 질소 함유 화합물, 예를 들어 아민 화합물, 아미드 화합물, 이미다졸 화합물 및 이들의 조합물을 포함한다.Preferred curing agents for use in the present invention include nitrogen containing compounds such as amine compounds, amide compounds, imidazole compounds and combinations thereof.
아민 화합물의 예로는 지방족 폴리아민, 예를 들어 디에틸렌트리아민, 트리에틸렌테트라민 및 디에틸아미노프로필아민; 방향족 폴리아민, 예를 들어 m-크실렌디아민 및 디아미노디페닐아민; 및 지환족 폴리아민, 예를 들어 이소포론디아민 및 멘텐디아민을 포함한다.Examples of amine compounds include aliphatic polyamines such as diethylenetriamine, triethylenetetramine and diethylaminopropylamine; Aromatic polyamines such as m-xylenediamine and diaminodiphenylamine; And cycloaliphatic polyamines such as isophoronediamine and mentendiamine.
물론, 상기 아민 화합물들의 조합물도 또한 본 발명의 조성물에 사용하기에 바람직하다.Of course, combinations of these amine compounds are also preferred for use in the compositions of the present invention.
아미드 화합물의 예로는 시아노 관능화 아미드, 예를 들어 디시안디아미드를 포함한다.Examples of amide compounds include cyano functionalized amides such as dicyandiamide.
이미다졸 화합물은 이미다졸, 이소이미다졸 및 치환 이미다졸, 예를 들어 알킬-치환 이미다졸 [예, 2-메틸 이미다졸, 2-에틸-4-메틸이미다졸, 2,4-디메틸이미다졸, 부틸이미다졸, 2-헵타데세닐-4-메틸이미다졸, 2-메틸이미다졸, 2-운데세닐이미다졸, 1-비닐-2-메틸이미다졸, 2-운데실이미다졸, 2-헵타데실이미다졸, 2-에틸-4-메틸이미다졸, 1-벤질-2-메틸이미다졸, 1-프로필-2-메틸이미다졸, 1-시아노에틸-2-메틸이미다졸, 1-시아노에틸-2-에틸-4-메틸이미다졸, 1-시아노에틸-2-운데실이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-구안아미노에틸-2-메틸이미다졸 및 이미다졸과 트리멜리트산, 2-n-헵타데실-4-메틸이미다졸 등의 부가 생성물 (일반적으로 여기에서 각 알킬 치환체는 약 17개 이하의 탄소 원자, 바람직하게는 약 6개 이하의 탄소 원자를 포함한다)]과 아릴 치환 이미다졸 [예, 페닐이미다졸, 벤질이미다졸, 2-메틸-4,5-디페닐이미다졸, 2,3,5-트리페닐이미다졸, 2-스티릴이미다졸, 1-(도데실 벤질)-2-메틸이미다졸, 2-(2-히드록실-4-t-부틸페닐)-4,5-디페닐이미다졸, 2-(2-메톡시페닐)-4,5-디페닐이미다졸, 2-(3-히드록시페닐)-4,5-디페닐이미다졸, 2-(p-디메틸아미노페닐)-4,5-디페닐이미다졸, 2-(2-히드록시페닐)-4,5-디페닐이미다졸, 디(4,5-디페닐-2-이미다졸)-벤젠-1,4, 2-나프틸-4,5-디페닐이미다졸, 1-벤질-2-메틸이미다졸, 2-p-메톡시스티릴이미다졸 등 (일반적으로 여기에서 각 아릴 치환체는 약 10개 이하의 탄소 원자, 바람직하게는 약 8개 이하의 탄소 원자를 포함한다)]로부터 선택될 수 있다.Imidazole compounds are imidazoles, isimidazoles and substituted imidazoles, for example alkyl-substituted imidazoles [eg, 2-methyl imidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimida Sol, Butylimidazole, 2-heptadecenyl-4-methylimidazole, 2-methylimidazole, 2-undecenylimidazole, 1-vinyl-2-methylimidazole, 2-undecyl Imidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimida Sol, 1-guanaminoethyl-2-methylimidazole and adducts such as imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidazole (generally wherein each alkyl substituent is about 17 Up to 6 carbon atoms, preferably up to about 6 carbon atoms) and an aryl substitution Midazoles [eg, phenylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1 -(Dodecyl benzyl) -2-methylimidazole, 2- (2-hydroxyl-4-t-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl)- 4,5-diphenylimidazole, 2- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethylaminophenyl) -4,5-diphenylimidazole, 2- (2-hydroxyphenyl) -4,5-diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4, 2-naphthyl-4,5- Diphenylimidazole, 1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole, etc. (In general, each aryl substituent is about 10 carbon atoms or less, preferably about Including up to eight carbon atoms).
시판 이미다졸 화합물의 예로는 Air Products (Allentown, Pennsylvania)의 상표명 CUREZOL 1B2MZ; Synthron, Inc. (Morganton, North Carolina)의 상표명 ACTIRON NXJ-60; 및 Borregaard Synthesis의 상표명 CURAMID CN을 포함한다.Examples of commercially available imidazole compounds include the trade name CUREZOL 1B2MZ under Air Products (Allentown, Pennsylvania); Synthron, Inc. Trade name ACTIRON NXJ-60 from Morganton, North Carolina; And the trade name CURAMID CN of Borregaard Synthesis.
물론, 상기 이미다졸 화합물들의 조합물도 또한 본 발명의 조성물에 사용하기에 바람직하다.Of course, combinations of such imidazole compounds are also preferred for use in the compositions of the present invention.
무기 충전제 성분이 본 발명의 조성물에 사용되는 경우, 충전제는 열 전도성, CTE 매칭 및(또는) 항복점 향상을 제공하기 위한 목적으로 사용된다. 이들 충전제는 강화 실리카, 예를 들어 용융 또는 열분해 실리카로부터 선택될 수 있고, 이들은 그들의 표면의 화학성을 변경시키도록 처리되거나 처리되지 않을 수 있다.When inorganic filler components are used in the compositions of the present invention, fillers are used for the purpose of providing thermal conductivity, CTE matching and / or yield point improvement. These fillers may be selected from reinforced silica, for example fused or pyrolytic silica, which may or may not be treated to alter the chemical properties of their surfaces.
상기한 처리된 열분해 실리카의 예로는 폴리디메틸실록산 처리된 실리카와 헥사메틸디실라잔 처리된 실리카를 포함한다. 상기한 처리된 실리카는 예를 들어 Cabot Corporation에서 상표명 CAB-O-SIL ND-TS으로 및 Degussa Corporation에서 상표명 AEROSIL, 예를 들어 AEROSIL R805로 상업적으로 입수가능하다.Examples of the treated pyrolytic silica described above include polydimethylsiloxane treated silica and hexamethyldisilazane treated silica. The treated silicas described above are commercially available, for example under the tradename CAB-O-SIL ND-TS from Cabot Corporation and under the trade name AEROSIL, for example AEROSIL R805 from Degussa Corporation.
비처리 실리카 중에서 비정질 및 함수 실리카가 사용될 수 있다. 예를 들어, 시판 비정질 실리카는 일차 입자의 평균 입도가 약 7 ㎚인 AEROSIL 300, 일차 입자의 평균 입도가 약 12 ㎚인 AEROSIL 200, 일차 입자의 평균 입도가 약 16 ㎚인AEROSIL 130을 포함하고; 시판 함수 실리카는 평균 입도가 4.5 ㎚인 NIPSIL E150, 평균 입도가 2.0 ㎚인 NIPSIL E200A 및 평균 입도가 1.0 ㎚인 NIPSIL E220A (Japan Silica Kogya Inc. 제품)를 포함한다.Among the untreated silicas, amorphous and hydrous silica can be used. For example, commercially available amorphous silica includes AEROSIL 300 having an average particle size of about 7 nm of primary particles, AEROSIL 200 having an average particle size of about 12 nm of primary particles, and AEROSIL 130 having an average particle size of about 16 nm of primary particles; Commercially available hydrous silica includes NIPSIL E150 with an average particle size of 4.5 nm, NIPSIL E200A with an average particle size of 2.0 nm and NIPSIL E220A (product of Japan Silica Kogya Inc.) with an average particle size of 1.0 nm.
바람직한 것은 또한 이온 농도가 낮고 입도가 비교적 작은 (예, 약 2 미크론 정도) 것, 예를 들어 Admatechs (Japan)에서 상표명 SO-E5로 입수가능한 실리카가 있다. 다른 바람직한 것은 비정질 침강 실리카인 ZEOTHIX 95 (J.M. Huber Corporation로부터 상업적으로 입수가능함)를 포함한다.Preference is also given to those having a low ion concentration and relatively small particle sizes (eg on the order of about 2 microns), for example silica available under the trade name SO-E5 from Admatechs (Japan). Other preferred include ZEOTHIX 95 (commercially available from J.M. Huber Corporation), amorphous precipitated silica.
무기 충전제 성분으로서 사용하기 위한 또 다른 바람직한 재료는 산화알루미늄, 질화규소, 질화알루미늄 및 실리카 코팅된 질화알루미늄으로 구성되거나 또는 이들을 함유하는 것이다.Another preferred material for use as the inorganic filler component is that consists of or contains aluminum oxide, silicon nitride, aluminum nitride and silica coated aluminum nitride.
무기 충전제 성분은 본 발명의 조성물에서 조성물의 5 내지 40 중량% 범위, 예를 들어 약 20-28 중량%, 바람직하게는 약 24 중량%의 양으로 사용되어야 한다.The inorganic filler component should be used in the composition of the present invention in an amount ranging from 5 to 40% by weight of the composition, for example about 20-28% by weight, preferably about 24% by weight.
유동성 조절된 에폭시계 조성물은 무수물 성분을 추가로 포함할 수 있다. 무수물의 예로는 모노- 및 폴리-무수물, 예를 들어 헥사히드로프탈산 무수물 ("HHPA")과 메틸 헥사히드로프탈산 무수물 ("MHHPA") (Lindau Chemicals, Inc. (Columbia, South Carolina)로부터 입수가능함, 단독으로 또는 조합물로서 사용되며, 조합물은 상표명 LINDRIDE 62C으로 입수가능함), 5-(2,5-디옥소테트라히드로)-3-메틸-3-시클로헥센-1,2-디카르복실산 무수물 (ChrisKev Co. (Leewood, Kansas)로부터 상표명 B-4400로 입수가능함) 및 나드산 메틸 무수물을 포함한다.The flow controlled epoxy based composition may further comprise an anhydride component. Examples of anhydrides are available from mono- and poly-anhydrides such as hexahydrophthalic anhydride ("HHPA") and methyl hexahydrophthalic anhydride ("MHHPA") (Lindau Chemicals, Inc. (Columbia, South Carolina), Used alone or in combination, the combination available under the trade name LINDRIDE 62C), 5- (2,5-dioxotetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydrides (available under the trade name B-4400 from ChrisKev Co. (Leewood, Kansas)) and methyl anhydride anhydride.
사용될 때 경화제는 에폭시 수지 성분의 중량을 기준으로 약 3 내지 약 100중량%의 양으로 존재할 수 있으며, 물론 선택된 양은 무수물의 종류와 본질 및 경화제가 사용되는지 여부에 또한 의존한다.When used, the curing agent may be present in an amount of about 3 to about 100 weight percent based on the weight of the epoxy resin component, of course the amount selected also depends on the type and nature of the anhydride and whether the curing agent is used.
본 발명의 다른 측면에서, 에폭시계 조성물의 유동성을 조절하는 방법을 제공한다. 상기 방법은 상기 목적으로 사용된 종래의 첨가제 때문에 보통 관찰되는 상기한 조성물의 반응 생성물의 접착 강도를 손상시키지 않으면서 유동성 조절을 허용한다. 상기 방법은 에폭시계 조성물에 조성물의 점도를 바람직한 양으로 조정하기에 충분한 양의 유동성 조절제를 첨가하는 것을 포함한다.In another aspect of the invention, a method of controlling the flowability of an epoxy based composition is provided. The method allows for fluidity control without compromising the adhesive strength of the reaction products of the above-mentioned compositions which are usually observed because of the conventional additives used for this purpose. The method includes adding to the epoxy-based composition an amount of a flow control agent sufficient to adjust the viscosity of the composition to the desired amount.
본 발명의 추가의 측면에서, 상기한 에폭시계 조성물을 제조하는 방법을 제공한다. 상기 방법은 에폭시 수지 성분, 유동성 조절제 및 경화제와 임의로 무기 충전제 성분을 혼합하는 것을 포함한다.In a further aspect of the invention, there is provided a method of making the epoxy-based composition described above. The method comprises mixing an epoxy resin component, a rheology control agent and a curing agent and optionally an inorganic filler component.
본 발명의 또 다른 추가의 측면에서, 잉크 젯 프린트헤드 또는 마이크로전자 반도체 소자의 조립에서 상기한 에폭시계 조성물을 사용하는 방법을 제공한다. 상기 방법은 기판 상에 충분한 양의 경화성 1액형 에폭시 수지 조성물을 전체적으로 분배하는 단계, 기판 상에 분배된 에폭시 수지 조성물 위에 전자 부품, 플렉스 회로 또는 펜 몸체를 배치시키는 단계, 전자 부품, 플렉스 회로 또는 펜 몸체를 각각 기판과 메이팅시켜 조립체를 형성하는 단계, 조립체를 경화성 1액형 에폭시 수지 조성물의 경화를 수행하기에 바람직한 조건에 노출시키는 단계를 포함한다.In yet a further aspect of the present invention, there is provided a method of using the epoxy-based composition as described above in the assembly of an ink jet printhead or a microelectronic semiconductor device. The method comprises distributing a sufficient amount of curable one-part epoxy resin composition on a substrate, placing an electronic component, a flex circuit, or a pen body over the epoxy resin composition dispensed on the substrate, an electronic component, a flex circuit, or a pen. Mating the bodies with a substrate, respectively, to form an assembly; exposing the assembly to conditions desirable to effect curing of the curable one-part epoxy resin composition.
일반적으로, 보다 큰 정도의 유동이 요망되는 하부충전 밀봉제와 같은 용도에 대해, 본 발명의 에폭시계 조성물은 회로판과 반도체 소자 사이의 공간 (예, 10 내지 200 ㎛의) 내로 통과하는 그의 능력을 향상시키도록 무기 충전제 성분의 존재량에 의존하여 25℃의 온도에서 점도가 500 내지 70,000 cps 범위, 예를 들어 800 내지 3,000 cps에 도달하도록 각종 성분의 종류와 양을 선택함으로써 제조될 수 있다. 접착제가 홈이 파인 표면 주변과 주위에 신속한 퍼짐을 허용하기에 적절한 유동성을 가져야 하는 경우, 접착제는 25℃의 온도에서 점도가 5 secs-1에서 약 35,000 cps 내지 약 70,000 cps 범위이고, 20 secs-1에서 약 24,000 cps 내지 약 40,000 cps 범위이어야 한다. 추가로, 표면 탑재 접착제의 항복점은 약 30 Pa 내지 약 70 Pa 범위이어야 한다.In general, for applications such as underfill sealants where a greater degree of flow is desired, the epoxy-based compositions of the present invention exhibit their ability to pass into the space between the circuit board and the semiconductor device (eg, 10-200 μm). Depending on the amount of inorganic filler component present to improve, it can be prepared by selecting the type and amount of various components such that the viscosity reaches a range of 500-70,000 cps, for example 800-3,000 cps, at a temperature of 25 ° C. If the adhesive is to have adequate fluidity to permit fine grooves around the surface and rapid spread around, the adhesive has a viscosity at a temperature of 25 ℃ from about 35,000 cps to about 70,000 cps range at 5 secs -1, 20 secs - 1 to about 24,000 cps to about 40,000 cps. In addition, the yield point of the surface mount adhesive should range from about 30 Pa to about 70 Pa.
상업적인 용도를 도면을 참조하여 설명한다. 예를 들어, 도 1은 통상의 잉크젯 에지-공급 펜 (10)의 프린트헤드 구역을 도시한다. 펜은 펜 몸체 (12), 실리콘 기판 (14) 및 플렉스 회로 (16)을 포함한다. 잉크는 잉크 공급물과 유체 소통 상태에 있는 잉크 채널을 통해 잉크 챔버로 전달된다. 잉크 공급물은 예를 들어 펜의 저장기 부분에 담겨 있을 수 있다. 작동 동안, 잉크는 채널 (18)에서 프린트헤드 노즐 (20)으로 유동한다. 노즐은 실리콘 기판 (14)와 플렉스 회로 (16)에 의해 한정된다. 따라서, 노즐이 발사되면, 잉크는 프린트헤드 노즐 (20)을 통해 인쇄 매체 시트로 사출된다.Commercial use will be described with reference to the drawings. For example, FIG. 1 shows the printhead area of a conventional inkjet edge-feed pen 10. The pen includes a pen body 12, a silicon substrate 14, and a flex circuit 16. Ink is delivered to the ink chamber through an ink channel in fluid communication with the ink feed. The ink feed may be contained, for example, in the reservoir portion of the pen. During operation, ink flows from the channel 18 to the printhead nozzle 20. The nozzle is defined by the silicon substrate 14 and the flex circuit 16. Thus, when the nozzle is fired, ink is injected through the printhead nozzle 20 into the print media sheet.
잉크젯 프린트헤드의 제작 동안, 플렉스 회로 (16)은 접착제를 사용하여 실리콘 기판 (14)에 부착된다. 이어서 플렉스 회로/기판 조립체는 접착제를 사용하여 펜 몸체 (12)에 부착된다. 펜 몸체 (12), 기판 (14) 및 플렉스 회로 (16)을 가열하여 접착제를 경화시킨다. 일단 접착제가 경화되면, 펜 몸체 (12), 기판 (14)및 플렉스 회로 (16)은 접착 지점에서 서로에 대해 고정된다.During fabrication of the inkjet printhead, the flex circuit 16 is attached to the silicon substrate 14 using an adhesive. The flex circuit / substrate assembly is then attached to the pen body 12 using an adhesive. The pen body 12, the substrate 14 and the flex circuit 16 are heated to cure the adhesive. Once the adhesive has cured, the pen body 12, substrate 14 and flex circuit 16 are secured to each other at the point of adhesion.
제작 동안 접착제가 채널 (18) 및(또는) 프린트헤드 노즐 (20) 안과 주변에 위킹되는 경우에, 접착제는 비경화 또는 경화 상태에서 그 안과 주변에 묻히게 될 수 있다. 이러한 사고는 프린트헤드로부터 잉크가 새로 발사되는 것을 방해하고, 기껏해야 잉크를 수용하는 기판 상으로 방출되는 잉크의 해상도를 불량하게 한다. 그래서, 접착제 조성물을 도포에 적절한 유동성을 갖도록 맞춤으로써 상기한 사고에 대한 가능성을 제거하지는 못하더라도 상당히 감소시킬 수 있다.If the adhesive is wicked in and around the channel 18 and / or printhead nozzle 20 during fabrication, the adhesive may be buried in and around the uncured or cured state. This accident prevents fresh ink from the printhead and, at best, degrades the resolution of ink released onto the substrate containing the ink. Thus, by tailoring the adhesive composition to have adequate fluidity for application, it can be significantly reduced, although this does not eliminate the possibility of such an incident.
도 2를 참조하면 본 발명의 에폭시 조성물이 도포되어 경화되는 FC 조립체를 보여준다.2 shows an FC assembly to which the epoxy composition of the present invention is applied and cured.
FC 조립체 (24)는 반도체 칩 (노출 (bare) 칩) (22)를 회로판 (21)에 접속시키고 열경화성 수지 조성물 (23)으로 그 사이의 공간을 적합하게 밀봉함으로써 형성된다.The FC assembly 24 is formed by connecting the semiconductor chip (bare chip) 22 to the circuit board 21 and suitably sealing the space therebetween with the thermosetting resin composition 23.
보다 구체적으로, 예를 들어, SBB 기술을 이용하는 FC 반도체 소자의 조립에서, 반도체 칩 (22)는 반도체 칩 (22) 상에 층을 형성하기 위해 전도성 접착제 페이스트 (예를 들어 금속 충전된 에폭시)를 갖는 기판 위로 통과될 수 있다. 상기 층은 보통 인쇄 기전에 의해 형성된다. 전도성 접착제 페이스트는 캐리어 기판 또는 반도체 칩 상에 도포될 수 있다. 그러한 한 가지 방법은 국제 특허 출원 공개 제PCT/FR95/00898호에 청구되고 기재된 스텐실을 사용하는 것이다. 별법으로, 상기 접속은 또한 등방성 전도성 접착제에 의해 만들어질 수 있다 (국제 특허 출원 공개 제PCT/US97/13677호 참조).More specifically, for example, in the assembly of an FC semiconductor device using SBB technology, the semiconductor chip 22 may be coated with a conductive adhesive paste (eg metal filled epoxy) to form a layer on the semiconductor chip 22. Can be passed over the substrate. The layer is usually formed by a printing mechanism. The conductive adhesive paste may be applied onto a carrier substrate or semiconductor chip. One such method is to use a stencil as claimed and described in International Patent Application Publication No. PCT / FR95 / 00898. Alternatively, the connection can also be made by an isotropic conductive adhesive (see International Patent Application Publication No. PCT / US97 / 13677).
그 후, 반도체 칩 (22)를 캐리어 기판 (21) 위에, 반도체 칩 (22)가 이제 전도성 접착제 페이스트 또는 땜납 (27 및 28)의 패턴화된 층으로 코팅된 회로판 (21) 상의 전극들 (25 및 26)과 일직선이 되는 방식으로 배치시킨다. 전도성 접착제 페이스트는 보통 가열 경화 기전이 사용될 수 있지만 다양한 방법으로 경화시킬 수 있다.Thereafter, the semiconductor chip 22 is placed on the carrier substrate 21, and the electrodes 25 on the circuit board 21 are now coated with a conductive adhesive paste or a patterned layer of solders 27 and 28. And 26). Conductive adhesive pastes can usually be cured in a variety of ways, although heat curing mechanisms may be used.
신뢰성을 향상시키기 위해, 반도체 칩 (22)와 회로판 (21) 사이의 공간을 본 발명의 범위 내에 있는 바와 같이 하부충전 밀봉 조성물 (23)으로 밀봉시킨다. 본 발명의 에폭시계 조성물은 반도체 칩과 회로판 사이의 공간 내로 통과하여 신속하게 유동하거나, 또는 적어도 가열 또는 사용 조건 하에 점도 감소를 보여 신속한 통과와 유동을 허용한다.In order to improve the reliability, the space between the semiconductor chip 22 and the circuit board 21 is sealed with the lower filling sealing composition 23 as is within the scope of the present invention. Epoxy-based compositions of the present invention pass rapidly into the space between the semiconductor chip and the circuit board, or show a decrease in viscosity under at least heating or use conditions to allow rapid passage and flow.
조성물의 겔 타임은 종종 약 150℃의 온도에서 명시된 시간 (예를 들어 15초 또는 1 또는 2분)으로 맞추어진다. 그러한 경우, 본 발명의 조성물은 약 6시간의 기간 후 점도 증가를 보이지 않거나 또는 실질적으로 보이지 않아야 한다. 그러한 겔 타임에서, 조성물은 회로판과 반도체 소자 사이의 공간 (예 10 내지 200 ㎛의) 내로 비교적 빠르게 통과하여, 도포에 덜 효과적으로 만드는 조성물에서의 점도 증가가 관찰되지 않으면서 보다 많은 수의 조립체들이 충전되도록 허용한다.The gel time of the composition is often set to the specified time (eg 15 seconds or 1 or 2 minutes) at a temperature of about 150 ° C. In such cases, the compositions of the present invention should show no or substantially no increase in viscosity after a period of about 6 hours. At such a gel time, the composition passes relatively quickly into the space between the circuit board and the semiconductor device (Examples 10-200 μm), filling a larger number of assemblies without increasing the viscosity in the composition making it less effective for application. Allow it.
사용시에, 본 발명의 에폭시 수지 조성물은 임의의 통상적인 양식으로 기판에 도포될 수 있다. 적합한 도포 방식은 시린지 분배, 핀-전달 (pin-transfer), 스크린 인쇄 및 다른 통상의 접착제 분배 장치를 통하는 것을 포함한다.In use, the epoxy resin composition of the present invention may be applied to a substrate in any conventional manner. Suitable modes of application include via syringe dispensing, pin-transfer, screen printing and other conventional adhesive dispensing devices.
도포되는 조성물의 양은 회로판과 반도체 칩 사이의 공간을 거의 완전히 충전시키도록 적합하게 조정되어야 하며, 그 양은 물론 용도에 따라 다를 수 있다. 이어서 열경화성 수지 조성물은 열을 인가하여 열 경화시킨다. 이러한 가열의 초기 단계 동안, 열경화성 수지 조성물은 상당한 점도 감소를 보이고 따라서 유동성을 증가시켜, 캐리어 기판과 반도체 칩 사이의 공간 내로 보다 쉽게 통과한다. 더욱이, 캐리어 기판을 예열함으로써, 열경화성 수지 조성물은 캐리어 기판과 반도체 칩 사이의 전체 공간 내로 충분히 통과할 수 있다. 열경화성 수지 조성물의 경화된 생성물은 상기 공간을 완전히 충전시킬 것이다.The amount of the composition to be applied should be suitably adjusted to almost completely fill the space between the circuit board and the semiconductor chip, and the amount may of course vary depending on the application. Subsequently, the thermosetting resin composition is thermally cured by applying heat. During this initial stage of heating, the thermosetting resin composition shows a significant decrease in viscosity and thus increases fluidity, making it easier to pass into the space between the carrier substrate and the semiconductor chip. Furthermore, by preheating the carrier substrate, the thermosetting resin composition can sufficiently pass into the entire space between the carrier substrate and the semiconductor chip. The cured product of the thermosetting resin composition will completely fill the space.
반도체 칩은 보통 환경 침식을 최소화하기 위해 폴리이미드계, 폴리-벤조시클로부탄계 또는 질화규소계 재료로 코팅할 수 있다.Semiconductor chips can usually be coated with polyimide, poly-benzocyclobutane or silicon nitride materials to minimize environmental erosion.
캐리어 기판은 Al2O3, SiN3및 뮬라이트 (Al2O3-SiO2)의 세라믹 기판; 내열 수지, 예를 들어 폴리이미드의 기판 또는 테이프; 유리 강화 에폭시; 또한 회로판으로서 일반적으로 사용되는 ABS 및 페놀릭 기판 등으로부터 제작될 수 있다. 캐리어 기판에 대한 반도체 칩의 임의의 전기 접속, 예를 들어 고온 용융 땜납 또는 전기 (또는 이방성) 전도성 접착제 등에 의한 접속을 사용할 수 있다. 접속을 용이하게 하기 위해, 특히 SBB 기술에서, 전극은 전선 결합 범프 (wire bond bumps)로서 형성될 수 있다.The carrier substrate may be a ceramic substrate of Al 2 O 3 , SiN 3 and mullite (Al 2 O 3 —SiO 2 ); Heat resistant resins such as substrates or tapes of polyimide; Glass reinforced epoxy; It can also be fabricated from ABS and phenolic substrates commonly used as circuit boards. Any electrical connection of the semiconductor chip to the carrier substrate may be used, for example a connection by hot melt solder or an electrically (or anisotropic) conductive adhesive or the like. To facilitate the connection, in particular in SBB technology, the electrodes can be formed as wire bond bumps.
반도체 칩을 캐리어 기판에 전기 접속시킨 후, 생성된 구조체에 대해 보통 연속상태 (continuity) 시험 등을 한다. 상기 시험에 통과시킨 후, 반도체 칩을 후술하는 바와 같이 열경화성 수지 조성물을 사용하여 그곳에 고정시킬 수 있다.이러한 방식으로, 실패하는 경우에 열경화성 수지 조성물을 사용하여 캐리어 기판에 고정시키기 전에 반도체 칩을 제거할 수 있다.After the semiconductor chip is electrically connected to the carrier substrate, the resulting structure is usually subjected to a continuity test or the like. After passing the test, the semiconductor chip can be fixed there using a thermosetting resin composition as described below. In this manner, in the event of failure, the semiconductor chip is removed before fixing to the carrier substrate using the thermosetting resin composition. can do.
표면 탑재 접착제 도포에서 및 도 3을 참조하면, 본 발명의 범위 내의 에폭시 조성물 (34)가 회로판 (31) 상의 땜납 랜드들 (33) 사이에 배치되어 있는 탑재된 구조체 (또는 칩 스케일 (scale) 패키지)가 도시되어 있다. 반도체 칩 (32)는 에폭시 조성물 (34)가 분배된 회로판 (31)의 위치 위에 놓이고, 그 후 회로판과 반도체 칩이 메이팅된다. 도 3은 회로판 (31) 상에 분배된 에폭시 조성물 (34)를 보여주며; 몇몇 경우 조성물을 대신 반도체 칩 (32) 상에 도포하거나, 또는 조성물을 회로판 (31)과 반도체 칩 (32) 둘 모두의 위에 도포하는 것이 바람직할 수 있다. 이어서 조성물을 상기한 바와 같이 경화시킨다.In surface mount adhesive application and referring to FIG. 3, a mounted structure (or chip scale package) in which an epoxy composition 34 within the scope of the present invention is disposed between solder lands 33 on a circuit board 31. ) Is shown. The semiconductor chip 32 is placed on the position of the circuit board 31 in which the epoxy composition 34 is distributed, and then the circuit board and the semiconductor chip are mated. 3 shows the epoxy composition 34 dispensed onto the circuit board 31; In some cases it may be desirable to apply the composition onto the semiconductor chip 32 instead, or to apply the composition onto both the circuit board 31 and the semiconductor chip 32. The composition is then cured as described above.
도 4의 배열에서, 반도체 소자 (또는 칩 스케일 패키지) (40)은 반도체 칩 (42)를 캐리어 기판 (41)에 전기 접속시키고 그들 사이의 공간을 본 발명에 따른 바와 같은 하부충전 밀봉제 (43)으로 밀봉시킴으로써 상기한 바와 같이 형성된 것이다. 상기 반도체 소자 (40)은 표면 탑재 접착제 (46)을 사용하여 회로판 (45)의 예정된 위치에서 탑재되고, 전극들 (48 및 49)는 땜납과 같은 적합한 접속 수단에 의해 전기 접속된다. 신뢰성을 향상시키기 위해, 반도체 소자 (40)과 회로판 (45) 사이의 공간을 또한 본 발명에 따른 바와 같이 하부충전 밀봉제로 밀봉시킨다.In the arrangement of FIG. 4, the semiconductor element (or chip scale package) 40 electrically connects the semiconductor chip 42 to the carrier substrate 41 and fills the space therebetween with the lower charge sealant 43 as according to the invention. It is formed as mentioned above by sealing with). The semiconductor element 40 is mounted at a predetermined position of the circuit board 45 using the surface mount adhesive 46, and the electrodes 48 and 49 are electrically connected by suitable connecting means such as solder. In order to improve the reliability, the space between the semiconductor element 40 and the circuit board 45 is also sealed with a bottom charge sealant as in accordance with the present invention.
본 발명의 조성물은 보통 약 120 내지 약 200℃ 범위의 온도로 약 0.5분 내지 약 2시간의 기간 동안 가열함으로써 경화시킬 수 있다. 그러나, 일반적으로 조성물을 도포한 후, 약 1분의 초기 경화 시간이 조성물을 경화시키기 시작하고, 약165℃에서 약 5 내지 약 15분 후 완전한 경화가 관찰된다. 따라서, 본 발명의 조성물은 비교적 중정도의 온도와 단시간의 경화 조건에서 사용될 수 있고 따라서 매우 우수한 생산성을 달성할 수 있다.The composition of the present invention can be cured by heating for a period of about 0.5 minutes to about 2 hours, usually at a temperature in the range from about 120 to about 200 ° C. Generally, however, after application of the composition, an initial cure time of about 1 minute begins to cure the composition, and complete cure is observed after about 5 to about 15 minutes at about 165 ° C. Thus, the compositions of the present invention can be used at relatively moderate temperatures and short curing conditions and thus achieve very good productivity.
본 발명의 조성물의 경화된 반응 생성물은 뛰어난 접착력, 내열성과 전기 특성, 및 본 발명에서 사용되는 용도를 위해 만족스러운 기계적 특성, 예를 들어 플렉스-균열 내성, 화학내성, 내습성 등을 나타낸다.The cured reaction product of the composition of the present invention exhibits excellent adhesion, heat and electrical properties, and satisfactory mechanical properties, such as flex-crack resistance, chemical resistance, moisture resistance, etc., for use in the present invention.
본 발명은 하기 실시예를 참조하여 보다 쉽게 이해될 것이다.The invention will be more readily understood with reference to the following examples.
이들 실시예에서, 본 발명에 따른 에폭시계 조성물을 제조하여 성능에 대해 평가하였다.In these examples, epoxy-based compositions according to the invention were prepared and evaluated for performance.
에폭시계 조성물Epoxy composition
본 발명에 따른 에폭시계 조성물은 하기 성분들을 나열된 순서로 개방 용기 내에서 실온에서 약 10분의 기간 동안 함께 혼합함으로써 제조하였다:Epoxy-based compositions according to the invention were prepared by mixing the following components together in a listed order in an open container for a period of about 10 minutes at room temperature:
1. 50 중량%의 비스페놀-A형 에폭시 수지 (Nippon Kayaku로부터 상표명 RE-310-S로 입수가능함) 및 15 중량%의 크레솔 노볼락형 에폭시 수지 (Nippon Kayaku로부터 상표명 XD-10002-L로 입수가능함)를 포함하는 에폭시 수지 성분;1. 50 wt% bisphenol-A type epoxy resin (available under the trade name RE-310-S from Nippon Kayaku) and 15 wt% cresol novolac type epoxy resin (available under the trade name XD-10002-L from Nippon Kayaku) Epoxy resin components;
2. 0.5 중량%의 에폭시 실란 (OSI로부터 상표명 A-187로 입수가능함)을 포함하는 유동성 조절제;2. rheology control agent comprising 0.5% by weight of epoxy silane (available under the trade name A-187 from OSI);
3. 6.5 중량%의 이미다졸 (Borregaard로부터 상표명 CURAMID CN으로 입수가능함)을 포함하는 경화제; 및3. curing agent comprising 6.5 weight percent imidazole (available under the trade name CURAMID CN from Borregaard); And
4. 15 중량%의 비정질 침강 실리카 (J.M. Huber Corporation으로부터 상표명 ZEOTHIX 95로 입수가능함) 및 9 중량%의 실리카 (Admatechs로부터 상표명 SO-E5로 입수가능함)를 포함하는 무기 충전제 성분.4. An inorganic filler component comprising 15% by weight of amorphous precipitated silica (available under the trade name ZEOTHIX 95 from J.M. Huber Corporation) and 9% by weight silica (available under the trade name SO-E5 from Admatechs).
상기 제제는 또한 4 중량%의 희석제 (o-크레실 글리시딜 에테르, CVC로부터 상표명 GE-10으로 입수가능함)를 포함하였다.The formulation also contained 4% by weight of diluent (o-cresyl glycidyl ether, available under the trade name GE-10 from CVC).
하기 성분들을 하기 표 1에 열거된 양으로 갖는 3가지 다른 제제들 (샘플 번호 2-4)를 제조하였다.Three different formulations (Sample Nos. 2-4) were prepared having the following ingredients in the amounts listed in Table 1 below.
조성물은 형성시에 사용되지만 (하기 참조), 이들은 점도 증가를 겪지 않으면서 약 -40℃의 온도에서 약 3개월 이하 내지 약 6개월과 같은 장기간 동안 보관될 수 있다.The compositions are used at the time of formation (see below), but they can be stored for a prolonged period of time, such as up to about 3 months to about 6 months at a temperature of about -40 ° C without experiencing an increase in viscosity.
형성 후, 조성물을 비반응성 플라스틱으로 제조된 10 ㎖ 시린지에 옮겨담았다.After formation, the composition was transferred to a 10 ml syringe made of non-reactive plastic.
물성Properties
조성물은 비경화 상태 및 경화 상태 모두에서 목적하는 필요를 위해 특정 제제를 선택하는데 있어서 최종 사용자에게 중요하고 유용한 파라미터가 되는 각종 특성을 갖는다.The composition has a variety of properties that make it an important and useful parameter for the end user in selecting a particular formulation for the desired needs in both the uncured and cured states.
예를 들어, 비경화 상태에서는 점도와 항복점이 중요하고; 경화 상태에 도달하면 경화 스케쥴이 중요하다.For example, in the uncured state, viscosity and yield point are important; The hardening schedule is important once the hardening state is reached.
점도를 이용하여 최종 사용자는 제작 공정, 예를 들어 회로 조립체 작동 동안 접착제가 도포될 수 있는 속도를 결정할 수 있다. Haacke 점도계를 사용하여 통상의 기술을 이용하여 측정할 수 있다.The viscosity can be used by the end user to determine the rate at which the adhesive can be applied during fabrication processes, such as circuit assembly operation. Measurements can be made using conventional techniques using a Haacke viscometer.
항복점 (또는 항복 스트레스)은 일반적으로 물질을 유동시키기 위해 필요한 최소의 스트레스로서 생각될 수 있다.The yield point (or yield stress) can generally be thought of as the minimum stress needed to flow the material.
경화 스케쥴은 명시된 시간 내에 특정 온도에서 경화의 개시가 일어나기 위해 필요한 시간을 나타낸다. 이는 표 2를 참조하여 보다 상세히 알 수 있다.The curing schedule represents the time required for the onset of curing to occur at a particular temperature within the specified time. This can be seen in more detail with reference to Table 2.
경화 상태에서, 조성물의 예정된 최종 용도에 따라 각종 특성들이 유용하다.In the cured state, various properties are useful depending on the intended end use of the composition.
예를 들어, 접착은 경화된 조성물에 의해 형성된 결합의 강도에 대한 정보를 제공한다. 시차 주사 열량계 (DSC)에 의해 또는 열 기계적 분석 (TMA)에 의해 측정되는 유리 전이 온도 (Tg)는 경화된 반응 생성물 (또는 네트워크)의 경도와 강도, 및 온도 변화에 대한 그의 행동에 대한 정보를 제공하며 -- 즉, 보다 높은 Tg는 승온을 보다 잘 견딜 수 있는 재료를 제공할 것이다.For example, adhesion provides information about the strength of the bond formed by the cured composition. The glass transition temperature (Tg), measured by differential scanning calorimetry (DSC) or by thermo mechanical analysis (TMA), provides information about the hardness and strength of the cured reaction product (or network) and its behavior with respect to temperature changes. Ie higher Tg will provide a material that is more resistant to elevated temperatures.
본 발명은 이와 같이 설명되지만, 당업계의 통상의 기술자에게 변경과 변형이 존재하며 본 발명의 범위 내에 있는 것으로 의도되고, 본 발명의 취지와 범위는 청구의 범위에 의해 정의된다는 것은 명백할 것이다.While the invention has been described as such, it will be apparent to those skilled in the art that changes and modifications exist and are intended to be within the scope of the invention, and the spirit and scope of the invention is defined by the claims.
Claims (17)
Applications Claiming Priority (3)
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US19874400P | 2000-04-21 | 2000-04-21 | |
US60/198,744 | 2000-04-21 | ||
PCT/US2001/011727 WO2001083607A1 (en) | 2000-04-21 | 2001-04-23 | Rheology-controlled epoxy-based compositions |
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KR20020091224A true KR20020091224A (en) | 2002-12-05 |
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KR1020027014071A KR20020091224A (en) | 2000-04-21 | 2001-04-23 | Rheology-Controlled Epoxy-Based Compositions |
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EP (1) | EP1282660A4 (en) |
JP (1) | JP2003531941A (en) |
KR (1) | KR20020091224A (en) |
AU (1) | AU2001253351A1 (en) |
WO (1) | WO2001083607A1 (en) |
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US6943058B2 (en) * | 2003-03-18 | 2005-09-13 | Delphi Technologies, Inc. | No-flow underfill process and material therefor |
JP5114111B2 (en) * | 2006-09-07 | 2013-01-09 | 日東シンコー株式会社 | Resin composition, heat conductive sheet, high heat conductive adhesive sheet with metal foil, and high heat conductive adhesive sheet with metal plate |
SG10201602081SA (en) | 2011-05-31 | 2016-04-28 | Mitsubishi Gas Chemical Co | Resin composition, prepreg, and laminate |
JP5958799B2 (en) * | 2012-03-08 | 2016-08-02 | パナソニックIpマネジメント株式会社 | Liquid epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
SG11201503925QA (en) * | 2012-11-28 | 2015-06-29 | Mitsubishi Gas Chemical Co | Resin composition, prepreg, laminate, metallic foil clad laminate, and printed circuit board |
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US3532653A (en) * | 1969-02-27 | 1970-10-06 | United States Steel Corp | Epoxy adhesive compositions containing amine hardener and tertiar y amine catalyst |
US3849187A (en) * | 1970-03-08 | 1974-11-19 | Dexter Corp | Encapsulant compositions for semiconductors |
US4248920A (en) * | 1978-04-26 | 1981-02-03 | Tokyo Shibaura Denki Kabushiki Kaisha | Resin-sealed semiconductor device |
US5476884A (en) * | 1989-02-20 | 1995-12-19 | Toray Industries, Inc. | Semiconductor device-encapsulating epoxy resin composition containing secondary amino functional coupling agents |
US5013383A (en) * | 1989-07-11 | 1991-05-07 | Hewlett-Packard Company | Epoxy adhesive for use with thermal ink-jet printers |
US5346743A (en) * | 1992-03-13 | 1994-09-13 | Kabushiki Kaisha Toshiba | Resin encapsulation type semiconductor device |
TW357180B (en) * | 1994-07-19 | 1999-05-01 | Sumitomo Chemical Co | An epoxy resin composition and semiconductor device sealed with the above epoxy resin composition |
JP3576684B2 (en) * | 1995-03-03 | 2004-10-13 | キヤノン株式会社 | Ink jet head and ink jet device |
JP3435250B2 (en) * | 1995-03-20 | 2003-08-11 | コニシ株式会社 | Adhesive composition |
US5908881A (en) * | 1996-11-29 | 1999-06-01 | Sumitomo Bakelite Company Limited | Heat-conductive paste |
US6180696B1 (en) * | 1997-02-19 | 2001-01-30 | Georgia Tech Research Corporation | No-flow underfill of epoxy resin, anhydride, fluxing agent and surfactant |
JP3851441B2 (en) * | 1998-04-23 | 2006-11-29 | 日東電工株式会社 | Epoxy resin composition for optical semiconductor element sealing and optical semiconductor device |
JP2002540235A (en) * | 1999-03-23 | 2002-11-26 | ロックタイト コーポレーション | Reprocessable thermosetting resin composition |
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2001
- 2001-04-23 WO PCT/US2001/011727 patent/WO2001083607A1/en not_active Application Discontinuation
- 2001-04-23 EP EP01926841A patent/EP1282660A4/en not_active Withdrawn
- 2001-04-23 JP JP2001580224A patent/JP2003531941A/en active Pending
- 2001-04-23 AU AU2001253351A patent/AU2001253351A1/en not_active Abandoned
- 2001-04-23 KR KR1020027014071A patent/KR20020091224A/en not_active Application Discontinuation
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JP2003531941A (en) | 2003-10-28 |
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