KR20110003306A - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- KR20110003306A KR20110003306A KR1020100136474A KR20100136474A KR20110003306A KR 20110003306 A KR20110003306 A KR 20110003306A KR 1020100136474 A KR1020100136474 A KR 1020100136474A KR 20100136474 A KR20100136474 A KR 20100136474A KR 20110003306 A KR20110003306 A KR 20110003306A
- Authority
- KR
- South Korea
- Prior art keywords
- adhesive composition
- formula
- urethane resin
- adhesive
- resin
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 88
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 25
- 150000002009 diols Chemical group 0.000 claims abstract description 24
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 14
- 239000011521 glass Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 37
- -1 these Chemical class 0.000 description 23
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 229920006287 phenoxy resin Polymers 0.000 description 5
- 239000013034 phenoxy resin Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- DCVWZWOEQMSMLR-UHFFFAOYSA-N silylperoxysilane Chemical compound [SiH3]OO[SiH3] DCVWZWOEQMSMLR-UHFFFAOYSA-N 0.000 description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 4
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 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
- XTALUNJXILSOQT-UHFFFAOYSA-N 3,3-dimethyl-2h-biphenylene Chemical group C1=CC=C2C3=CCC(C)(C)C=C3C2=C1 XTALUNJXILSOQT-UHFFFAOYSA-N 0.000 description 2
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- YYJIYUNJTKCRHL-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC(=O)C=C YYJIYUNJTKCRHL-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- TUGAMVVIFZLKTI-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)peroxycarbonyl (3-methoxy-3-methylbutyl)peroxy carbonate Chemical compound COC(C)(C)CCOOOC(=O)OC(=O)OOOCCC(C)(C)OC TUGAMVVIFZLKTI-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- GKENVXBVOLNPDO-UHFFFAOYSA-N 1-[2,5-dimethyl-5-(3-methylphenyl)peroxyhexan-2-yl]peroxy-3-methylbenzene Chemical compound CC1=CC=CC(OOC(C)(C)CCC(C)(C)OOC=2C=C(C)C=CC=2)=C1 GKENVXBVOLNPDO-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NRVDNSHWNQZNDC-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)decane Chemical compound CCCCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C NRVDNSHWNQZNDC-UHFFFAOYSA-N 0.000 description 1
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- CHKCPIUYSMYEEW-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-ylperoxy)-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C1CCCCC1 CHKCPIUYSMYEEW-UHFFFAOYSA-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
- IEMBFTKNPXENSE-UHFFFAOYSA-N 2-(2-methylpentan-2-ylperoxy)propan-2-yl hydrogen carbonate Chemical compound CCCC(C)(C)OOC(C)(C)OC(O)=O IEMBFTKNPXENSE-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- MNOVHWSHIUHSAZ-UHFFFAOYSA-N 2-ethylhexoxyperoxycarbonyl 2-ethylhexylperoxy carbonate Chemical compound CCCCC(CC)COOOC(=O)OC(=O)OOOCC(CC)CCCC MNOVHWSHIUHSAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SEZLVNATVKZSQO-UHFFFAOYSA-N 3-methyl-1-[3-(3-methyl-2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1C1=CC=CC(N2C(C(C)=CC2=O)=O)=C1 SEZLVNATVKZSQO-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- CAMBAGZYTIDFBK-UHFFFAOYSA-N 3-tert-butylperoxy-2-methylpropan-1-ol Chemical compound CC(CO)COOC(C)(C)C CAMBAGZYTIDFBK-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- XWUNIDGEMNBBAQ-UHFFFAOYSA-N Bisphenol A ethoxylate diacrylate Chemical compound C=1C=C(OCCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCCOC(=O)C=C)C=C1 XWUNIDGEMNBBAQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XBCFXELSWDAYIW-UHFFFAOYSA-N [4-[2-[4-(prop-2-enoyloxymethoxy)phenyl]propan-2-yl]phenoxy]methyl prop-2-enoate Chemical compound C=1C=C(OCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCOC(=O)C=C)C=C1 XBCFXELSWDAYIW-UHFFFAOYSA-N 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JAHGTMJOPOCQIY-UHFFFAOYSA-N benzyl benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOCC1=CC=CC=C1 JAHGTMJOPOCQIY-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- UPDZRIPMRHNKPZ-UHFFFAOYSA-N carboxyoxy 4,4-dimethoxybutyl carbonate Chemical compound COC(OC)CCCOC(=O)OOC(O)=O UPDZRIPMRHNKPZ-UHFFFAOYSA-N 0.000 description 1
- BQGAYTNGDNRIJE-UHFFFAOYSA-N carboxyoxy ethoxymethoxy carbonate Chemical compound CCOCOOC(=O)OOC(=O)O BQGAYTNGDNRIJE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- LRIKRVKBBZQMPA-UHFFFAOYSA-N ethenylperoxysilane Chemical compound [SiH3]OOC=C LRIKRVKBBZQMPA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- XTXFUQOLBKQKJU-UHFFFAOYSA-N tert-butylperoxy(trimethyl)silane Chemical compound CC(C)(C)OO[Si](C)(C)C XTXFUQOLBKQKJU-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
Description
본 발명은 접착제 조성물에 관한 것이다.The present invention relates to an adhesive composition.
반도체 분야에서는 에폭시 수지 등의 유기 재료가 많이 사용되고 있다. 또한, 밀봉재 분야에서는 밀봉 시스템의 90 % 이상이 수지 밀봉 시스템으로 교체되고 있다. 밀봉재는 에폭시 수지, 경화제, 각종 첨가제, 무기 충전제 등에 의해서 구성되는 복합 재료이고, 에폭시 수지로서는 크레졸 노볼락형 에폭시 수지가 많이 사용되고 있다.In the semiconductor field, many organic materials, such as an epoxy resin, are used. Also, in the field of sealing materials, at least 90% of sealing systems are replaced with resin sealing systems. A sealing material is a composite material comprised by an epoxy resin, a hardening | curing agent, various additives, an inorganic filler, etc., and many cresol novolak-type epoxy resins are used as an epoxy resin.
그러나, 크레졸 노볼락형 에폭시 수지는 저흡수율, 저탄성률의 특성에 있어서 반드시 만족스러운 요구 특성을 가지고 있지 않기 때문에, 표면 실장 방식에 대한 대응이 곤란하다. 그 때문에, 이에 대신하는 신규 고성능 에폭시 수지가 많이 제안되어 실용화에 이르렀다.However, since the cresol novolac-type epoxy resin does not necessarily have satisfactory required characteristics in the properties of low water absorption and low elastic modulus, it is difficult to cope with the surface mounting method. For this reason, many new high-performance epoxy resins have been proposed instead and have been put into practical use.
또한, 에폭시 수지 등의 유기 재료는 다이 본딩용 도전성 접착제로서, 에폭시 수지에 은분을 혼련한 은 페이스트로서 많이 사용되었다. 그러나, 반도체 소자의 배선 기판에의 장착 방법이 표면 실장법으로 이행됨에 따라서, 은 페이스트에 대한 땜납 리플로우 내성 향상에 대한 요구가 강해지고 있다. 이 문제를 해결하기 위해서, 경화 후의 다이본딩용 접착층의 공극, 필 강도, 흡수율, 탄성률 등의 개선이 이루어졌다.Moreover, organic materials, such as an epoxy resin, were used a lot as a silver paste which knead | mixed silver powder with the epoxy resin as a conductive adhesive for die bonding. However, as the mounting method of the semiconductor element to the wiring board is shifted to the surface mounting method, there is a strong demand for improving solder reflow resistance to silver paste. In order to solve this problem, improvement of the space | gap, the peeling strength, water absorption rate, and the elasticity modulus of the adhesive bond layer for die bonding after hardening was made.
반도체 실장 분야에서는 저비용화ㆍ고정밀화에 대응한 새로운 실장 형태로서, IC 칩을 직접 인쇄 기판이나 연성 배선판에 탑재하는 플립 칩 실장이 주목받고 있다.In the field of semiconductor mounting, a flip chip mounting that mounts an IC chip directly on a printed board or a flexible wiring board has been attracting attention as a new mounting form corresponding to low cost and high precision.
플립 칩 실장 방식으로서는, 칩의 단자에 땜납 범프를 설치하여 땜납 접속을 행하는 방식이나, 도전성 접착제를 통해 전기적 접속을 행하는 방식이 알려져 있다. 이들 방식에서는, 접속시키는 칩과 기판 사이의 열팽창 계수차에 기초하는 스트레스가, 각종 환경에 노출된 경우에 접속 계면에서 발생하여 접속 신뢰성이 저하된다는 문제가 있다.As the flip chip mounting method, there are known a method in which solder bumps are attached to a terminal of a chip to perform solder connection, or a method in which electrical connection is performed through a conductive adhesive. In these systems, there is a problem that stress based on the thermal expansion coefficient difference between the chip to be connected and the substrate is generated at the connection interface when exposed to various environments, resulting in a decrease in connection reliability.
이 때문에, 접속 계면의 스트레스를 완화시킬 목적으로, 일반적으로 에폭시 수지계 언더 충전재를 칩/기판의 간극에 주입하는 방식이 검토되었다. 그러나, 이 언더 필 주입 공정은 공정을 번잡하게 하여 생산성, 비용면에서 불리해진다고 하는 문제가 있다. 이러한 문제를 해결하기 위해, 최근에는 이방 도전성과 밀봉 기능을 갖는 이방 도전성 접착제를 이용한 플립 칩 실장이, 공정 간이성이라는 관점에서 주목받고 있다.For this reason, in order to alleviate the stress of a connection interface, the system of inject | pouring an epoxy resin-type underfill filler into the clearance gap of a chip | substrate is generally examined. However, this underfill injection process has a problem that the process is complicated and disadvantageous in terms of productivity and cost. In order to solve such a problem, flip chip mounting using the anisotropically conductive adhesive which has anisotropic conductivity and a sealing function is attracting attention recently from a viewpoint of process simplicity.
한편 최근 반도체, 액정 디스플레이 등의 분야에서 전자 부품을 고정시키거나 회로 접속을 행기 위해서 각종 접착 재료가 사용되고 있다. 이들 용도에서는, 회로의 고밀도화, 고정밀화가 진행되어 접착성을 비롯하여 내열성, 고온 고습 환경하에서 장시간 둔 경우의 접속 신뢰성 등이 요구된다.In recent years, various adhesive materials have been used in the fields of semiconductors, liquid crystal displays and the like to fix electronic components or to make circuit connections. In these applications, the densification and high precision of a circuit advance, and adhesiveness, heat resistance, connection reliability in the case of leaving it in a high temperature, high humidity environment for a long time, etc. are calculated | required.
특히, 액정 디스플레이와 TCP와의 접속, FPC과 TCP와의 접속, 및, FPC과 인쇄 배선판과의 접속에는, 회로 접속 재료로서 접착제 중에 도전 입자를 분산시킨 이방 도전성 접착제가 사용되고 있다.In particular, the anisotropically conductive adhesive agent which disperse | distributed electroconductive particle in the adhesive agent is used for the connection of a liquid crystal display and TCP, the connection of FPC and TCP, and the connection of FPC and a printed wiring board.
또한, 최근에는 반도체 실리콘 칩을 기판에 실장하는 경우에도, 종래의 와이어 본드가 아니라, 반도체 실리콘 칩을 페이스 다운으로 기판에 실장하는 소위 플립 칩 실장이 행해지고 있고, 여기서도 이방 도전성 접착제의 적용이 개시되었다.Moreover, in recent years, also when mounting a semiconductor silicon chip on a board | substrate, what is called a flip-chip mounting which mounts a semiconductor silicon chip on a board | substrate at face down instead of the conventional wire bond, and application of the anisotropic conductive adhesive was also disclosed here. .
이방 도전성 접착제로서는, 상술한 바와 같이 에폭시 수지를 이용하는 것이 일반적이지만, 예를 들면 특허 문헌 1에 기재된, 분자의 양쪽 말단에 (메트)아크릴레이트기를 부가시킨 2관능 우레탄 아크릴레이트를 이용하는 것도 알려져 있다.As an anisotropic conductive adhesive, it is common to use an epoxy resin as mentioned above, but it is also known to use the bifunctional urethane acrylate which added the (meth) acrylate group to the both ends of the molecule | numerator as described in patent document 1, for example.
[특허 문헌 1] 일본 특허 공개 제2000-256641호 공보[Patent Document 1] Japanese Patent Application Laid-Open No. 2000-256641
그러나, 정밀 기기 분야에서는 회로의 고밀도화가 진행되어 왔고, 전극 폭 및 전극 간격이 매우 좁아졌다. 이 때문에, 종래의 에폭시 수지를 포함하는 이방 도전성 접착제를 이용하였을 때에는, 배선의 탈락, 박리, 위치 변동이 발생하거나 하여, 접속시키고자 하는 전극간의 전기적 접속이 불충분해지는 경우가 있는, 즉 접속 신뢰성이 낮다고 하는 문제가 있다.However, in the field of precision instruments, the densification of circuits has progressed, and the electrode width and electrode spacing have become very narrow. For this reason, when an anisotropically conductive adhesive containing a conventional epoxy resin is used, wires may fall off, peel off, or positional variation, resulting in insufficient electrical connection between the electrodes to be connected, i.e., connection reliability. There is a problem of being low.
또한, 특허 문헌 1에 기재된 2관능 우레탄 아크릴레이트를 이용하는 이방 도전성 접착제에 있어서는 다음과 같은 문제가 있다. 즉, 우레탄 아크릴레이트의 분자량이 작은 경우(예를 들면 수천 정도)에는 접착제의 접착성이 낮고, 우레탄 아크릴레이트의 분자량이 큰 경우에는, 고온 고습 환경하에서 장기간 두었을 때 접속 신뢰성이 저하된다고 하는 문제가 있다.Moreover, there exists the following problem in the anisotropic conductive adhesive which uses the bifunctional urethane acrylate of patent document 1. That is, when the molecular weight of the urethane acrylate is small (for example, thousands), the adhesiveness of the adhesive is low, and when the molecular weight of the urethane acrylate is large, the problem that connection reliability decreases when it is left in a high temperature and high humidity environment for a long time. There is.
본 발명은 상기 사정을 감안하여 이루어진 것이고, 접속되는 회로의 전극 폭 및 전극 간격이 매우 좁은 경우(예를 들면, 전극 폭이 25 ㎛ 이하이면서 전극 간격이 50 ㎛ 이하인 경우)에도, 충분한 접속 신뢰성 및 충분한 접착성을 얻을 수 있으면서 고온 고습 환경하에서 장기간 둔 경우에도 접속 신뢰성 및 접착성의 저하를 충분히 억제하는 것이 가능한 접착제 조성물을 제공하는 것을 목적으로 한다.The present invention has been made in view of the above circumstances, and even when the electrode width and the electrode interval of the circuit to be connected are very narrow (for example, when the electrode width is 25 µm or less and the electrode interval is 50 µm or less), sufficient connection reliability and It is an object of the present invention to provide an adhesive composition capable of sufficiently suppressing connection reliability and deterioration in adhesion even when sufficient adhesion is obtained for a long time in a high temperature, high humidity environment.
상기 목적을 달성하기 위해서, 본 발명은, (A) 측쇄에 (메트)아크릴레이트기를 가지고, 중량 평균 분자량이 10,000 내지 500,000인 우레탄 수지와, (B) 광 조사 또는 가열에 의해 유리 라디칼을 발생시키는 경화제를 함유하고, (A) 우레탄 수지가 하기 화학식 I로 표시되는 공중합체를 포함하는 접착제 조성물을 제공한다.In order to achieve the above object, the present invention provides a urethane resin having a (meth) acrylate group in the side chain (A) and having a weight average molecular weight of 10,000 to 500,000, and (B) generating free radicals by light irradiation or heating. It provides the adhesive composition containing a hardening | curing agent and (A) urethane resin containing the copolymer represented by following formula (I).
<화학식 I><Formula I>
[식 I 중, X는 디이소시아네이트 잔기를 나타내고, Y는 디올 잔기를 나타내고, n은 1 내지 100의 정수를 나타내며, 단, Y로 표시되는 디올 잔기 중 10 내지 90 몰%는 하기 화학식 II로 표시되는 구조를 갖는 기이면서 Y로 표시되는 디올 잔기 중 10 내지 90 몰%는 중량 평균 분자량 500 이상의 디올 잔기이다.][In Formula I, X represents a diisocyanate residue, Y represents a diol residue, n represents the integer of 1-100, provided that 10-90 mol% of the diol residue represented by Y is represented by following General formula II. 10-90 mol% of the diol residue represented by Y which is group which has a structure which becomes a weight average molecular weight 500 or more is a diol residue.]
<화학식 II><Formula II>
[식 II 중, Z는 2가의 유기기를 나타내고, R1 및 R2는 각각 독립적으로 수소 원자 또는 메틸기를 나타낸다.][In formula II, Z represents a divalent organic group, R <1> and R <2> respectively independently represents a hydrogen atom or a methyl group.]
본 발명의 접착제 조성물에 따르면, 상기 구성을 가짐으로써 접속되는 회로의 전극 폭 및 전극 간격이 매우 좁은 경우에도, 충분한 접속 신뢰성 및 충분한 접착성을 얻을 수 있으면서 고온 고습 환경하에서 장기간 둔 경우에도 접속 신뢰성 및 접착성의 저하를 충분히 억제하는 것이 가능하다. 이러한 효과가 얻어지는 이유가 반드시 분명하지는 않지만, (A) 성분이 특정 관능기에 의해 다관능화되어 있으면서 그의 중량 평균 분자량이 비교적 큰 것에서 적어도 기인하는 것으로 생각된다.According to the adhesive composition of this invention, even if the electrode width and electrode space | interval of the circuit connected by having the said structure are very narrow, sufficient connection reliability and sufficient adhesiveness can be obtained, and even if it is long-term in high temperature, high humidity environment, It is possible to sufficiently suppress the fall of adhesiveness. Although the reason why such an effect is acquired is not necessarily clear, it is thought that it originates at least because the weight average molecular weight of (A) component is polyfunctionalized by a specific functional group while it is comparatively large.
또한, 정밀 전자 기기의 분야에서는, 생산성 향상을 위해서 접속 시간의 단축화가 요구되었고, 이러한 요구를 만족시키기 위해서 저온 속경화성이 우수한 접착제가 강하게 요구되었다. 상기 구성을 갖는 본 발명의 접착제 조성물은 상기 효과뿐 아니라 이러한 저온 속경화성도 더욱 우수하다.Moreover, in the field of precision electronic devices, shortening of connection time was required for productivity improvement, and the adhesive which was excellent in low temperature fast hardenability was strongly requested | required in order to satisfy such a demand. The adhesive composition of the present invention having the above-mentioned composition is more excellent in such low temperature fast curing property as well as the above effects.
본 발명의 접착제 조성물은 (C) 열가소성 수지 및/또는 열가소성 엘라스토머를 더 함유하는 것이 바람직하다. 이에 의해, 접착제 조성물의 물성 및 접착성이 더욱 향상된다.It is preferable that the adhesive composition of this invention contains (C) thermoplastic resin and / or a thermoplastic elastomer further. Thereby, the physical property and adhesiveness of an adhesive composition further improve.
본 발명의 접착제 조성물은 (D) 라디칼 중합성 물질을 더 함유하는 것이 바람직하다. 이에 의해, 접착제 조성물의 접속 신뢰성이 더욱 향상된다.It is preferable that the adhesive composition of this invention contains (D) radically polymerizable substance further. Thereby, the connection reliability of an adhesive composition improves further.
본 발명의 접착제 조성물은 (E) 도전 입자를 더 함유하는 것이 바람직하다. 이에 의해, 접착제 조성물에 도전성 또는 이방 도전성을 부여할 수 있기 때문에, 이러한 접착제 조성물을, 회로 전극을 갖는 회로 부재끼리의 접속 용도 등으로, 보다 바람직하게 사용하는 것이 가능해진다.It is preferable that the adhesive composition of this invention contains (E) electroconductive particle further. Since electroconductivity or anisotropic electroconductivity can be provided to an adhesive composition by this, it becomes possible to use such adhesive composition more suitably for the connection use etc. of circuit members which have a circuit electrode.
본 발명의 접착제 조성물에 의하면, 접속되는 회로의 전극 폭 및 전극 간격이 매우 좁은 경우에도, 충분한 접속 신뢰성 및 충분한 접착성을 얻을 수 있으면서 고온 고습 환경하에서 장기간 둔 경우에도 접속 신뢰성 및 접착성의 저하를 충분히 억제하는 것이 가능하다. 또한, 본 발명의 접착제 조성물은 상기 효과에 더하여 우수한 저온 속경화성을 구비한다.According to the adhesive composition of this invention, even when the electrode width and electrode space | interval of a circuit to be connected are very narrow, sufficient connection reliability and sufficient adhesiveness can be obtained, and even if it is long-term in high temperature, high-humidity environment, sufficient connection reliability and adhesiveness fall. It is possible to suppress. Moreover, the adhesive composition of this invention is equipped with the outstanding low temperature quick hardening property in addition to the said effect.
바람직한 desirable 실시예의Example 설명 Explanation
이하, 경우에 따라서 도면을 참조하면서 본 발명의 바람직한 실시 형태에 대하여 상세하게 설명하지만, 본 발명이 이것으로 한정되는 것은 아니다. 또한, 본 명세서 중의 중량 평균 분자량은 겔 투과 크로마토그래피(이하, 「GPC」라 함)에 의해 측정되면서 표준 폴리스티렌의 검량선을 사용하여 환산된 것이다. 또한, 본 명세서 내의 「(메트)아크릴레이트」란, 아크릴레이트 또는 그에 대응하는 메타크릴레이트를 의미하고, 「(메트)아크릴산」이란, 아크릴산 또는 그것에 대응하는 메타크릴산을 의미한다.EMBODIMENT OF THE INVENTION Hereinafter, although preferred embodiment of this invention is described in detail, referring drawings, the present invention is not limited to this. In addition, the weight average molecular weight in this specification is converted using the calibration curve of standard polystyrene, measured by gel permeation chromatography (henceforth "GPC"). In addition, "(meth) acrylate" in this specification means an acrylate or methacrylate corresponding to it, and "(meth) acrylic acid" means acrylic acid or methacrylic acid corresponding to it.
본 발명의 접착제 조성물은 (A) 우레탄 수지 및 (B) 경화제를 함유한다.The adhesive composition of this invention contains (A) urethane resin and (B) hardening | curing agent.
이 중, (A) 우레탄 수지는 측쇄에 (메트)아크릴레이트기를 가지고, 중량 평균 분자량이 10,000 내지 500,000인 것이다. 이 우레탄 수지의 중량 평균 분자량이 10,000 미만인 경우에는 접착제 조성물의 접착성이 불충분해지고, 중량 평균 분자량이 500,000을 초과하는 경우에는 접착제 조성물의 취급이 곤란해진다. 또한, (A) 우레탄 수지의 중량 평균 분자량은 접착제 조성물의 접착성 및 취급성을 보다 향상시키는 관점에서 l5,000 내지 200,000인 것이 바람직하고, 20,000 내지 100,000인 것이 보다 바람직하다.Among these, (A) urethane resin has a (meth) acrylate group in a side chain, and a weight average molecular weight is 10,000-500,000. When the weight average molecular weight of this urethane resin is less than 10,000, the adhesiveness of an adhesive composition will become inadequate, and when a weight average molecular weight exceeds 500,000, handling of an adhesive composition will become difficult. Moreover, it is preferable that it is l5,000-200,000, and, as for the weight average molecular weight of (A) urethane resin, from a viewpoint of further improving adhesiveness and handleability of an adhesive composition, it is more preferable that it is 20,000-100,000.
또한, (A) 우레탄 수지는 하기 화학식 I로 표시되는 공중합체를 더 포함한다.In addition, the urethane resin (A) further includes a copolymer represented by the following general formula (I).
<화학식 I><Formula I>
여기서, 식 I 중, X는 디이소시아네이트 잔기를 나타내고, Y는 디올 잔기를 나타내고, n은 1 내지 100의 정수를 나타낸다.Here, in formula (I), X represents a diisocyanate residue, Y represents a diol residue, n represents the integer of 1-100.
또한, Y로 표시되는 디올 잔기 중 10 내지 90 몰%는 하기 화학식 II로 표시되는 구조를 갖는 기이고, 또한 Y로 표시되는 디올 잔기 중 10 내지 90 몰%는 중량 평균 분자량 500 이상의 디올의 잔기이다.In addition, 10-90 mol% of the diol residue represented by Y is group which has a structure represented by following formula (II), and 10-90 mol% of the diol residue represented by Y is residue of the diol of weight average molecular weight 500 or more. .
<화학식 II><Formula II>
여기서, 식 II 중, Z는 2가의 유기기를 나타내고, R1 및 R2는 각각 독립적으로 수소 원자 또는 메틸기를 나타낸다.Here, in Formula II, Z represents a divalent organic group, R <1> and R <2> respectively independently represents a hydrogen atom or a methyl group.
상술한 (A) 우레탄 수지는 디이소시아네이트 및 디올을 공중합시킴으로써 얻어진다. 공중합에 사용되는 디이소시아네이트로서는, 예를 들면 The urethane resin (A) mentioned above is obtained by copolymerizing diisocyanate and diol. As the diisocyanate used for copolymerization, for example
등을 들 수 있고, 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.These etc. are mentioned, These can be used individually by 1 type or in mixture of 2 or more types.
또한, 공중합에 사용되는 디올 중, 상기 화학식 II로 표시되는 구조를 갖는 기초로 대응하는 것으로서는, 예를 들면In addition, as a base which has a structure represented by the said Formula (II) among the diols used for copolymerization, it corresponds, for example
[식 중, R1 및 R2는 각각 독립적으로 수소 원자 또는 메틸기를 나타내고, m은 1 내지 10의 정수를 나타낸다.][Wherein R 1 and R 2 are Each independently represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.]
등의 (메트)아크릴레이트 변성 에폭시 화합물을 들 수 있다. 이들 (메트)아크릴레이트 변성 에폭시 화합물은, 예를 들면 2관능성 에폭시 화합물과 (메트)아크릴산을 반응시킴으로써 얻어지는 것이며, 예시한 것 외에도 각종 2관능성 에폭시 화합물로부터 얻어지는 (메트)아크릴레이트 변성 에폭시 화합물을 사용할 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.(Meth) acrylate modified epoxy compounds, such as these, are mentioned. These (meth) acrylate modified epoxy compounds are obtained by, for example, reacting a bifunctional epoxy compound with (meth) acrylic acid, and in addition to the examples, (meth) acrylate modified epoxy compounds obtained from various difunctional epoxy compounds. Can be used. These can be used individually by 1 type or in mixture of 2 or more types.
또한, 공중합에 사용되는 디올 중, 중량 평균 분자량 500 이상의 디올의 잔기초로 대응하는 것으로서는, 예를 들면In addition, as a thing corresponding to the residue second of the diol of a weight average molecular weight 500 or more among the diols used for copolymerization, for example,
등의 반복 단위를 갖는 중량 평균 분자량 500 이상의 디올을 들 수 있다. 이들 디올은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 또한, 이러한 디올의 중량 평균 분자량은 500 내지 5,000인 것이 바람직하고, 1,000 내지 2,000인 것이 보다 바람직하다.The weight average molecular weight 500 or more diol which has repeating units, such as these, is mentioned. These diols can be used individually by 1 type or in mixture of 2 or more types. Moreover, it is preferable that it is 500-5,000, and, as for the weight average molecular weight of such diol, it is more preferable that it is 1,000-2,000.
(A) 우레탄 수지는, 예를 들면 상술한 디이소시아네이트 및 디올을 50 내지 100 ℃에서 1 내지 10 시간 반응시킴으로써 얻어진다. 반응에는, 경우에 따라서 유기 주석 등의 일반적으로 우레탄 합성에 사용되는 촉매를 이용할 수도 있다. 또한, 원료 및/또는 생성물이 가용인 용매 중에서 반응을 행할 수도 있다. 또한, 경우에 따라서 1가 알코올, 옥심, 아민, 이소시아네이트 등을 더 첨가하여 반응시킴으로써 (A) 우레탄 수지의 말단을 수식할 수도 있다.The urethane resin (A) is obtained by, for example, reacting the above-described diisocyanate and diol at 50 to 100 ° C for 1 to 10 hours. In the reaction, a catalyst generally used for urethane synthesis, such as organotin, may be used for the reaction. The reaction may also be carried out in a solvent in which the raw materials and / or products are soluble. In addition, the terminal of the urethane resin (A) may be modified by further adding and reacting monohydric alcohol, oxime, amine, isocyanate, etc. as needed.
상술한 반응에 사용되는 디이소시아네이트와 디올의 조성비에 대하여, 디이소시아네이트 1.0 몰에 대하여 디올은 0.7 내지 1.3 몰인 것이 바람직하고, 0.9 내지 1.1 몰인 것이 보다 바람직하다. 또한, 디올 성분 중, 상술한 (메트)아크릴레이트 변성 에폭시 화합물은 10 내지 90 몰%인 것이 바람직하고, 30 내지 70 몰%인 것이 보다 바람직하다. 또한, 디올 성분 중, 상술한 중량 평균 분자량 500 이상의 디올은 10 내지 90 몰%인 것이 바람직하고, 30 내지 70 몰%인 것이 보다 바람직하다.It is preferable that it is 0.7-1.3 mol with respect to 1.0 mol of diisocyanate, and it is more preferable that it is 0.9-1.1 mol with respect to the composition ratio of the diisocyanate and diol used for the above-mentioned reaction. Moreover, it is preferable that it is 10-90 mol%, and, as for the above-mentioned (meth) acrylate modified epoxy compound, in a diol component, it is more preferable that it is 30-70 mol%. Moreover, it is preferable that it is 10-90 mol%, and, as for the diol mentioned above with a weight average molecular weight 500 or more in a diol component, it is more preferable that it is 30-70 mol%.
(B) 경화제는 광 조사 또는 가열에 의해 유리 라디칼을 발생시키는 것이다. 이러한 경화제로서는, 예를 들면 과산화물 및 아조 화합물 등을 들 수 있다. 이들 경화제는 목적하는 접속 온도, 접속 시간, 보존 안정성 등을 고려하여 적절하게 선택되지만, 고반응성과 보존 안정성의 관점에서 반감기 10 시간의 온도가 40 ℃ 이상이면서 반감기 1 분의 온도가 180 ℃ 이하인 유기 과산화물이 바람직하고, 반감기 10 시간의 온도가 50 ℃ 이상이면서 반감기 1 분의 온도가 170 ℃ 이하인 유기 과산화물이 특히 바람직하다.The curing agent (B) generates free radicals by light irradiation or heating. As such a hardening | curing agent, a peroxide, an azo compound, etc. are mentioned, for example. These curing agents are appropriately selected in consideration of the desired connection temperature, connection time, storage stability and the like. Peroxides are preferred, and organic peroxides having a half-life of 10 hours at 50 ° C or more and a half-life of 1 minute at 170 ° C or less are particularly preferred.
본 발명의 접착제 조성물에 있어서, (B) 경화제의 함유량은 접착제 조성물의 고형분 전량을 기준으로서 1 내지 20 질량%인 것이 바람직하고, 2 내지 15 질량%인 것이 보다 바람직하다. (B) 경화제의 함유량을 상기 범위 내로 함으로써, 접착제 조성물을 이용한 회로 부재끼리의 접속을 보다 단시간에 행할 수 있고, 예를 들면 160 ℃, 10 초간의 접속 조건에서 충분한 반응율을 얻을 수 있다.In the adhesive composition of this invention, it is preferable that it is 1-20 mass%, and, as for content of (B) hardening | curing agent based on solid content whole quantity of an adhesive composition, it is more preferable that it is 2-15 mass%. (B) By carrying out content of a hardening | curing agent in the said range, the connection of the circuit members using an adhesive composition can be performed in a short time more, for example, sufficient reaction rate can be obtained in connection conditions for 160 degreeC and 10 second.
본 발명에서 사용되는 유기 과산화물의 구체예로서는, 디아실퍼옥시드, 퍼옥시디카르보네이트, 퍼옥시에스테르, 퍼옥시케탈, 디알킬퍼옥시드, 히드로퍼옥시드, 실릴퍼옥시드 등을 들 수 있다. 이들 중에서 퍼옥시에스테르, 디알킬퍼옥시드, 히드로퍼옥시드 및 실릴퍼옥시드는, 개시제 중의 염소 이온이나 유기산이 5000 ppm 이하이고, 가열 분해 후에 발생하는 유기산이 적으며 회로 부재의 접속 단자의 부식을 억제할 수 있기 때문에 특히 바람직하다. Specific examples of the organic peroxide used in the present invention include diacyl peroxide, peroxydicarbonate, peroxy ester, peroxy ketal, dialkyl peroxide, hydroperoxide, silyl peroxide and the like. Among them, peroxyester, dialkyl peroxide, hydroperoxide and silyl peroxide have chlorine ions and organic acids in the initiator of 5000 ppm or less, less organic acids generated after thermal decomposition and suppress corrosion of the connection terminals of the circuit members. It is especially preferable because it can be done.
디아실퍼옥시드로서는, 예를 들면 이소부틸퍼옥시드, 2,4-디클로로벤조일퍼옥시드, 3,5,5-트리메틸헥사노일퍼옥시드, 옥타노일퍼옥시드, 라우로일퍼옥시드, 스테아로일퍼옥시드, 숙시닉퍼옥시드, 벤조일퍼옥시톨루엔, 벤조일퍼옥시드 등을 들 수 있다.Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide and stearoyl peroxane. Seed, succinic peroxide, benzoyl peroxy toluene, benzoyl peroxide, etc. are mentioned.
퍼옥시디카르보네이트로서는, 예를 들면 디-n-프로필퍼옥시디카르보네이트, 디이소프로필퍼옥시디카르보네이트, 비스(4-t-부틸시클로헥실)퍼옥시디카르보네이트, 디-2-에톡시메톡시퍼옥시디카르보네이트, 디(2-에틸헥실퍼옥시)디카르보네이트, 디메톡시부틸퍼옥시디카르보네이트, 디(3-메틸-3-메톡시부틸퍼옥시)디카르보네이트 등을 들 수 있다.As peroxy dicarbonate, di-n-propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, bis (4-t- butylcyclohexyl) peroxy dicarbonate, di-2-, for example Ethoxymethoxy peroxydicarbonate, di (2-ethylhexyl peroxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, and the like. Can be mentioned.
퍼옥시에스테르로서는, 예를 들면 쿠밀퍼옥시네오데카노에이트, 1,1,3,3-테트라메틸부틸퍼옥시네오데카노에이트, 1-시클로헥실-1-메틸에틸퍼옥시노에이트, t-헥실퍼옥시네오데카노에이트, t-부틸퍼옥시피발레이트, 1,1,3,3-테트라메틸부틸퍼옥시-2-에틸헥사노네이트, 2,5-디메틸-2,5-디(2-에틸헥사노일퍼옥시)헥산, 1-시클로헥실-1-메틸에틸퍼옥시-2-에틸헥사노네이트, t-헥실퍼옥시-2-에틸헥사노네이트, t-부틸퍼옥시-2-에틸헥사노네이트, t-부틸퍼옥시이소부틸레이트, 1,1-비스(t-부틸퍼옥시)시클로헥산, t-헥실퍼옥시이소프로필모노카르보네이트, t-부틸퍼옥시-3,5,5-트리메틸헥사노네이트, t-부틸퍼옥시라우레이트, 2,5-디메틸-2,5-디(m-톨루오일퍼옥시)헥산, t-부틸퍼옥시이소프로필모노카르보네이트, t-부틸퍼옥시-2-에틸헥실모노카르보네이트, t-헥실퍼옥시벤조에이트, t-부틸퍼옥시아세테이트 등을 들 수 있다.As peroxy ester, cumyl peroxy neodecanoate, 1,1,3,3- tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxynoate, t- Hexyl peroxy neodecanoate, t-butylperoxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2 -Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl Hexanonate, t-butylperoxy isobutylate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5, 5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluylperoxy) hexane, t-butylperoxyisopropylmonocarbonate, t- Butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxy benzo Sites, and the like t- butylperoxy acetate.
퍼옥시케탈로서는, 예를 들면 1,1-비스(t-헥실퍼옥시)-3,3,5-트리메틸시클로헥산, 1,1-비스(t-헥실퍼옥시)시클로헥산, 1,1-비스(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, 1,1-(t-부틸퍼옥시)시클로도데칸, 2,2-비스(t-부틸퍼옥시)데칸 등을 들 수 있다.As peroxy ketal, for example, 1,1-bis (t-hexyl peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) cyclohexane, 1,1- Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like Can be.
디알킬퍼옥시드로서는, 예를 들면 α,α'-비스(t-부틸퍼옥시)디이소프로필벤젠, 디쿠밀퍼옥시드, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산, t-부틸쿠밀퍼옥시드 등을 들 수 있다.As the dialkyl peroxide, for example, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexane, t-butyl cumyl peroxide, and the like.
히드로퍼옥시드로서는, 예를 들면 디이소프로필벤젠히드로퍼옥시드, 쿠멘히드로퍼옥시드 등을 들 수 있다.As hydroperoxide, diisopropyl benzene hydroperoxide, cumene hydroperoxide, etc. are mentioned, for example.
실릴퍼옥시드로서는, 예를 들면 t-부틸트리메틸실릴퍼옥시드, 비스(t-부틸)디메틸실릴퍼옥시드, t-부틸트리비닐실릴퍼옥시드, 비스(t-부틸)디비닐실릴퍼옥시드, 트리스(t-부틸) 비닐실릴퍼옥시드, t-부틸트리알릴실릴퍼옥시드, 비스(t-부틸)디알릴실릴퍼옥시드, 트리스(t-부틸)알릴실릴퍼옥시드 등을 들 수 있다.As a silyl peroxide, t-butyl trimethyl silyl peroxide, bis (t-butyl) dimethyl silyl peroxide, t-butyl trivinyl silyl peroxide, bis (t-butyl) divinyl silyl peroxide, tris (for example) t-butyl) vinylsilyl peroxide, t-butyltriallyl silyl peroxide, bis (t-butyl) diallyl silyl peroxide, tris (t-butyl) allyl silyl peroxide, etc. are mentioned.
또한, 접착제 조성물이 회로 접속 재료로서 사용되는 경우에는, 회로 부재의 접속 단자(회로 전극)의 부식을 억제하기 위해서, (B) 경화제 중에 함유되는 염소 이온이나 유기산은 5000 ppm 이하인 것이 바람직하고, 또한 가열 분해 후에 발생하는 유기산이 적은 것이 바람직하다. 또한, 제조된 회로 접속 재료의 안정성이 향상되기 때문에, 실온 상압하에서 24 시간의 개방 방치 후의 (B) 경화제의 질량 유지율은 20 질량%인 것이 바람직하다.In addition, when an adhesive composition is used as a circuit connection material, in order to suppress corrosion of the connection terminal (circuit electrode) of a circuit member, it is preferable that chlorine ion and organic acid contained in (B) hardening | curing agent are 5000 ppm or less, and also It is preferable that there are few organic acids which generate | occur | produce after thermal decomposition. Moreover, since the stability of the manufactured circuit connection material improves, it is preferable that the mass retention of the (B) hardening | curing agent after 24 hours of open standing under room temperature normal pressure is 20 mass%.
상술한 (B) 경화제는 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있고, 분해 촉진제, 억제제 등을 혼합하여 이용할 수도 있다. 또한, 이들 경화제를 폴리우레탄계, 폴리에스테르계의 고분자 물질 등으로 피복하여 마이크로 캡슐화한 것은, 가사 시간이 연장되기 때문에 바람직하다.The above-mentioned (B) hardening | curing agents can be used individually by 1 type or in mixture of 2 or more types, You can also mix and use a decomposition accelerator, an inhibitor, etc. Moreover, it is preferable to coat these hardening | curing agents with a polyurethane-type, polyester-type high molecular substance, etc., and to microencapsulate, since the pot life is extended.
본 발명의 접착제 조성물에서의 (A)폴리우레탄 수지와 (B) 경화제와의 함유비는 질량비로 (A):(B)=1:99 내지 99:1인 것이 바람직하고, 10:90 내지 90:10인 것이 보다 바람직하다.It is preferable that the content ratio of (A) polyurethane resin and (B) hardening | curing agent in the adhesive composition of this invention is (A) :( B) = 1: 99-99: 1 by mass ratio, and it is 10: 90-90 It is more preferable that it is: 10.
또한, 본 발명의 접착제 조성물에는, 접착제 조성물의 물성 및 접착성의 향상을 목적으로 하여 (C) 열가소성 수지 및/또는 열가소성 엘라스토머를 더 첨가할 수도 있다. Moreover, (C) thermoplastic resin and / or thermoplastic elastomer can also be added to the adhesive composition of this invention for the purpose of the improvement of the physical property and adhesiveness of an adhesive composition.
열가소성 수지로서는, 예를 들면 비스페놀 A형 페녹시 수지나 비스페놀 F형 페녹시 수지, 비스페놀 Aㆍ비스페놀 F 공중합형 페녹시 수지 등의 범용 페녹시 수지류, 폴리메타크릴레이트류, 폴리아크릴레이트류, 폴리이미드류, 폴리우레탄류, 폴리에스테르류, 폴리비닐부티랄 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Examples of the thermoplastic resins include general-purpose phenoxy resins such as bisphenol A-type phenoxy resins, bisphenol F-type phenoxy resins, and bisphenol A-bisphenol F copolymerized phenoxy resins, polymethacrylates, polyacrylates, Polyimide, polyurethane, polyester, polyvinyl butyral, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more type.
또한, 이들 열가소성 수지 중에는 실록산 결합이나 불소 치환기가 포함될 수도 있다. 이들은, 혼합하는 수지끼리 완전히 상용되거나 또는 마이크로 상분리가 생겨 백탁되는 상태이면 보다 바람직하게 사용할 수 있다. 상기 열가소성 수지의 분자량은 특별히 제한을 받지 않지만, 일반적인 평균 분자량으로서는 5,000 내지 150,000이 바람직하고, 10,000 내지 80,000이 보다 바람직하다. 이 값이, 5,000 미만이면 접착제 조성물의 물성이 저하되는 경향이 있고, 또한 150,000을 초과하면 다른 성분과의 상용성이 나빠지는 경향이 있다.In addition, these thermoplastic resins may contain a siloxane bond or a fluorine substituent. These resins can be used more preferably as long as they are completely compatible with each other or microphase separation occurs and becomes cloudy. Although the molecular weight of the said thermoplastic resin is not specifically limited, As a general average molecular weight, 5,000-150,000 are preferable and 10,000-80,000 are more preferable. When this value is less than 5,000, there exists a tendency for the physical property of an adhesive composition to fall, and when it exceeds 150,000, there exists a tendency for compatibility with other components to worsen.
열가소성 엘라스토머로서는, 예를 들면 SBS 및 그의 에폭시 변성체나, SEBS 및 그의 변성체 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.As a thermoplastic elastomer, SBS and its epoxy modified body, SEBS, its modified body, etc. are mentioned, for example. These can be used individually by 1 type or in combination of 2 or more type.
본 발명의 접착제 조성물에 있어서의 (C) 열가소성 수지 및/또는 열가소성 엘라스토머의 함유량은 (A) 폴리우레탄 수지 100 질량부에 대하여 20 내지 320 질량부로 하는 것이 바람직하다. 이 함유량이 20 질량부 미만 또는 320 질량부를 초과하는 경우에는, 접착제 조성물의 유동성이나 접착성이 저하되는 경향이 있다.It is preferable that content of the (C) thermoplastic resin and / or thermoplastic elastomer in the adhesive composition of this invention shall be 20-320 mass parts with respect to 100 mass parts of (A) polyurethane resin. When this content is less than 20 mass parts or more than 320 mass parts, there exists a tendency for the fluidity | liquidity and adhesiveness of an adhesive composition to fall.
또한, 본 발명의 접착제 조성물에는, 접착제 조성물의 접속 신뢰성의 향상을 목적으로 하여 (D) 라디칼 중합성 물질을 더 첨가할 수도 있다.Moreover, (D) radically polymerizable substance can also be added to the adhesive composition of this invention for the purpose of the improvement of the connection reliability of an adhesive composition.
(D) 라디칼 중합성 물질은 라디칼에 의해 중합시키는 관능기를 갖는 물질이고, 예를 들면 (메트)아크릴레이트 수지, 말레이미드 수지, 시트라콘이미드 수지, 나디이미드 수지 등의 수지를 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 이용할 수 있다. 또한, 이 라디칼 중합성 물질은 단량체, 올리고머 중 어느 상태에도 사용할 수 있고, 단량체와 올리고머를 혼합하여 이용할 수도 있다.(D) A radically polymerizable substance is a substance which has a functional group to superpose | polymerize with a radical, For example, resin, such as (meth) acrylate resin, maleimide resin, a citraconimide resin, a nadiimide resin, is mentioned. These can be used individually by 1 type or in mixture of 2 or more types. In addition, this radically polymerizable substance can be used also in any of a monomer and an oligomer, and can also mix and use a monomer and an oligomer.
(메트)아크릴레이트 수지는 (메트)아크릴레이트를 라디칼 중합시킴으로써 얻어지는 것이다. (메트)아크릴레이트로서는, 예를 들면 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, 에틸렌글리콜 디(메트)아크릴레이트, 디에틸렌글리콜 디(메트)아크릴레이트, 트리메틸올프로판 트리(메트)아크릴레이트, 테트라메틸렌글리콜 테트라(메트)아크릴레이트, 2-히드록시-1,3-디아크릴옥시프로판, 2,2-비스[4-(아크릴옥시메톡시)페닐]프로판, 2,2-비스[4-(아크릴옥시에톡시)페닐]프로판, 디시클로펜테닐(메트)아크릴레이트 트리시클로데카닐(메트)아크릴레이트, 트리스(아크릴옥시에틸)이소시아누레이트, 우레탄(메트)아크릴레이트, 이소시아누르산 에틸렌옥시드 변성 디아크릴레이트 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. 또한, 필요에 따라서 히드로퀴논, 메틸에테르히드로퀴논 등의 라디칼 중합 금지제를 경화성이 손상되지 않는 범위에서 사용할 수도 있다.(Meth) acrylate resin is obtained by radically polymerizing (meth) acrylate. As (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethylene glycol di (meth) acrylate, di Ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4 -(Acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, urethane (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more type. Moreover, radical polymerization inhibitors, such as hydroquinone and methyl ether hydroquinone, can also be used as needed in the range which does not impair sclerosis | hardenability.
말레이미드 수지는 분자 중에 말레이미드기를 1개 이상 가지는 것이며, 예를 들면 페닐말레이미드, 1-메틸-2,4-비스말레이미드벤젠, N,N'-m-페닐렌비스말레이미드, N,N'-p-페닐렌비스말레이미드, N,N'-4,4-비페닐렌비스말레이미드, N,N'-4,4-(3,3-디메틸비페닐렌)비스말레이미드, N,N'-4,4-(3,3-디메틸디페닐메탄)비스말레이미드, N,N-4,4-(3,3-디에틸디페닐메탄)비스말레이미드, N,N'-4,4-디페닐메탄비스말레이미드, N,N'-4,4-디페닐프로판비스말레이미드, N,N'-4,4-디페닐에테르비스말레이미드, N,N'-4,4-디페닐술폰비스말레이미드, 2,2-비스(4-(4-말레이미드페녹시)페닐)프로판, 2,2-비스(3-s-부틸-3,4-(4-말레이미드페녹시)페닐)프로판, 1,1-비스(4-(4-말레이미드페녹시)페닐)데칸, 4,4'-시클로헥실리덴-비스(1-(4-말레이미드페녹시)페녹시)-2-시클로헥실벤젠, 2,2-비스(4-(4-말레이미드페녹시)페닐)헥사플루오로프로판 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The maleimide resin has one or more maleimide groups in the molecule, for example, phenylmaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylenebismaleimide, N, N'-p-phenylenebismaleimide, N, N'-4,4-biphenylenebismaleimide, N, N'-4,4- (3,3-dimethylbiphenylene) bismaleimide, N, N'-4,4- (3,3-dimethyldiphenylmethane) bismaleimide, N, N-4,4- (3,3-diethyldiphenylmethane) bismaleimide, N, N ' -4,4-diphenylmethanebismaleimide, N, N'-4,4-diphenylpropanebismaleimide, N, N'-4,4-diphenyletherbismaleimide, N, N'-4 , 4-diphenylsulfonbismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-maleic Midphenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidephenoxy) phenyl) decane, 4,4'-cyclohexylidene-bis (1- (4-maleimidephenoxy) Phenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4-maleimidephenoxy) Phenyl) hexafluoro propane etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types.
시트라콘이미드 수지는 분자 중에 시트라콘이미드기를 1개 이상 가지는 시트라콘이미드 화합물을 중합시킨 것이다. 시트라콘이미드 화합물로서는, 예를 들면 페닐시트라콘이미드, 1-메틸-2,4-비스시트라콘이미드벤젠, N,N'-m-페닐렌비스시트라콘이미드, N,N'-p-페닐렌비스시트라콘이미드, N,N'-4,4-비페닐렌비스시트라콘이미드, N,N'-4,4-(3,3-디메틸비페닐렌)비스시트라콘이미드, N,N'-4,4-(3,3-디메틸디페닐메탄)비스시트라콘이미드, N,N'-4,4-(3,3-디에틸디페닐메탄)비스시트라콘이미드, N,N'-4,4-디페닐메탄비스시트라콘이미드, N,N'-4,4-디페닐프로판비스시트라콘이미드, N,N'-4,4-디페닐에테르비스시트라콘이미드, N,N'-4,4-디페닐술폰비스시트라콘이미드, 2,2-비스(4-(4-시트라콘이미드페녹시)페닐)프로판, 2,2-비스(3-s-부틸-3,4-(4-시트라콘이미드페녹시)페닐)프로판, 1,1-비스(4-(4-시트라콘이미드페녹시)페닐)데칸, 4,4'-시클로헥실리덴-비스(1-(4-시트라콘이미드페녹시)페녹시)-2-시클로헥실벤젠, 2,2-비스(4-(4-시트라콘이미드페녹시)페닐)헥사플루오로프로판 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The citraconimide resin is obtained by polymerizing a citraconimide compound having one or more citraconimide groups in a molecule. As a citraconimide compound, a phenyl cytraconimide, 1-methyl-2, 4-biscitraconimide benzene, N, N'-m-phenylene biscitraconimide, N, N ', for example -p-phenylenebiscitraconimide, N, N'-4,4-biphenylenebiscitraconimide, N, N'-4,4- (3,3-dimethylbiphenylene) bissheet Laconimide, N, N'-4,4- (3,3-dimethyldiphenylmethane) biscitraconimide, N, N'-4,4- (3,3-diethyldiphenylmethane) bis Citraconimide, N, N'-4,4-diphenylmethanebiscitraconimide, N, N'-4,4-diphenylpropanebiscitraconimide, N, N'-4,4- Diphenyletherbiscitraconimide, N, N'-4,4-diphenylsulfonbiscitraconimide, 2,2-bis (4- (4-citraconimidephenoxy) phenyl) propane, 2 , 2-bis (3-s-butyl-3,4- (4-citraconimidephenoxy) phenyl) propane, 1,1-bis (4- (4-citraconimidephenoxy) phenyl) decane , 4,4'-cyclohexylidene-bis (1- (4-citraconimidephenoxy) phenoxy) -2-cyclohexylbenne There may be mentioned 2,2-bis (4- (4-citraconimide) phenyl) hexafluoropropane. These can be used individually by 1 type or in mixture of 2 or more types.
나디이미드 수지는 분자 중에 나디이미드기를 1개 이상 가지는 나디이미드 화합물을 중합시킨 것이다. 나디이미드 화합물로서는, 예를 들면 페닐나디이미드, 1-메틸-2,4-비스나디이미드벤젠, N,N'-m-페닐렌비스나디이미드, N,N'-p-페닐렌비스나디이미드, N,N'-4,4-비페닐렌비스나디이미드, N,N'-4,4-(3,3-디메틸비페닐렌)비스나디이미드, N,N'-4,4-(3,3-디메틸디페닐메탄)비스나디이미드, N,N'-4,4-(3,3-디에틸디페닐메탄)비스나디이미드, N,N'-4,4-디페닐메탐비스나디이미드, N,N'-4,4-디페닐프로판비스나디이미드, N,N'-4,4-디페닐에테르비스나디이미드, N,N'-4,4-디페닐술폰비스나디이미드, 2,2-비스(4-(4-나디이미드페녹시)페닐)프로판, 2,2-비스(3-s-부틸-3,4-(4-나디이미드페녹시)페닐)프로판, 1,1-비스(4-(4-나디이미드페녹시)페닐)데칸, 4,4'-시클로헥실리덴-비스(1-(4-나디이미드페녹시)페녹시)-2-시클로헥실벤젠, 2,2-비스(4-(4-나디이미드페녹시)페닐)헥사플루오로프로판 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.Nadiimide resin superposes | polymerizes the nadiimide compound which has one or more nadiimide groups in a molecule | numerator. As a nadiimide compound, a phenyl namidide, 1-methyl- 2, 4- bis nadiiimide benzene, N, N'-m-phenylene bis nanimide, N, N'-p-phenylene bis naimide, for example , N, N'-4,4-biphenylenebisnamidimide, N, N'-4,4- (3,3-dimethylbiphenylene) bisnamidimide, N, N'-4,4- ( 3,3-dimethyldiphenylmethane) bisnamidimide, N, N'-4,4- (3,3-diethyldiphenylmethane) bisnamidimide, N, N'-4,4-diphenylmethambis Nadiimide, N, N'-4,4-diphenylpropanebisnamidide, N, N'-4,4-diphenyletherbisnamidimide, N, N'-4,4-diphenylsulfonbisnamidimide , 2,2-bis (4- (4-namidimidephenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-namidimidephenoxy) phenyl) propane, 1 , 1-bis (4- (4-namidimidephenoxy) phenyl) decane, 4,4'-cyclohexylidene-bis (1- (4-namidimidephenoxy) phenoxy) -2-cyclohexylbenzene And 2,2-bis (4- (4-nadiimidphenoxy) phenyl) hexafluoropropane. These can be used individually by 1 type or in mixture of 2 or more types.
상술한 수지를 (D) 라디칼 중합성 물질로서 이용한 경우, 그의 함유량은 접착제 조성물의 고형분 전량을 기준으로서 바람직하게는 10 내지 90 질량%이고, 보다 바람직하게는 30 내지 70 질량%이다.When using the above-mentioned resin as (D) radically polymerizable substance, its content becomes like this. Preferably it is 10-90 mass%, More preferably, it is 30-70 mass% based on solid content whole quantity of an adhesive composition.
또한, (D) 라디칼 중합성 물질로서는, 금속 등 무기물을 피착체로서 이용한 경우의 접착제 조성물의 접착성을 향상시키기 위해서, 상술한 라디칼 중합성 물질과 인산에스테르 구조를 갖는 라디칼 중합성 물질을 조합하여 이용하는 것이 바람직하다. 인산에스테르 구조를 갖는 라디칼 중합성 물질로서는, 예를 들면 무수 인산과 2-히드록시에틸(메트)아크릴레이트의 반응 생성물을 사용할 수 있다. 인산에스테르 구조를 갖는 라디칼 중합성 물질의 구체예로서는, 모노 (2-메타크릴로일옥시에틸)산포스페이트, 디(2-메타크릴로일옥시에틸)애시드포스페이트 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.Moreover, in order to improve the adhesiveness of the adhesive composition at the time of using inorganic substances, such as a metal, as a to-be-adhered body, as (D) radically polymerizable material, the radically polymerizable material which has the above-mentioned radically polymerizable substance and phosphate ester structure is combined, It is preferable to use. As a radically polymerizable substance which has a phosphate ester structure, the reaction product of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate can be used, for example. Specific examples of the radically polymerizable substance having a phosphate ester structure include mono (2-methacryloyloxyethyl) acid phosphate, di (2-methacryloyloxyethyl) acid phosphate, and the like. These can be used individually by 1 type or in mixture of 2 or more types.
인산에스테르 구조를 갖는 라디칼 중합성 물질을 (D) 라디칼 중합성 물질로서 이용한 경우, 그 함유량은 접착제 조성물의 고형분 전량을 기준으로 하여 바람직하게는 0.1 내지 10 질량%이고, 보다 바람직하게는 0.5 내지 5 질량%이다.When the radically polymerizable material having a phosphate ester structure is used as the (D) radically polymerizable material, the content thereof is preferably 0.1 to 10% by mass, more preferably 0.5 to 5, based on the total solid content of the adhesive composition. It is mass%.
본 발명의 접착제 조성물에는, 도전성 또는 이방 도전성을 부여하는 것을 목적으로 하여 (E) 도전 입자를 더 첨가할 수도 있다. 이 도전 입자로서는, 예를 들면 실리카, 삼산화이안티몬, 금, 은, 구리, 니켈, 알루미늄, 스테인레스, 카본, 세라믹, 또는 상기 금속, 비도전성 유리, 세라믹, 플라스틱 등을 핵으로 하고, 이 핵에 상기 금속이나 카본을 피복한 것을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.(E) Electroconductive particle can also be added to the adhesive composition of this invention for the purpose of providing electroconductivity or anisotropic electroconductivity. As the conductive particles, for example, silica, antimony trioxide, gold, silver, copper, nickel, aluminum, stainless steel, carbon, ceramic, or the metal, non-conductive glass, ceramic, plastic, and the like are used as nuclei. The thing which coat | covered metal and carbon is mentioned. These can be used individually by 1 type or in mixture of 2 or more types.
본 발명의 접착제 조성물에 있어서의 (E) 도전 입자의 함유량은 접착제 조성물의 고형분 전체 부피를 기준으로 하여 0.1 내지 50 부피%인 것이 바람직하다.It is preferable that content of (E) electroconductive particle in the adhesive composition of this invention is 0.1-50 volume% based on the solid content total volume of an adhesive composition.
접착제 조성물에는, 적절하게, 연화제, 촉진제, 노화 방지제, 착색제, 난연제, 커플링제, 충전재 등과 같은 첨가제를 더 첨가할 수도 있다.As the adhesive composition, additives such as a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a coupling agent, a filler, and the like may be further added as appropriate.
접착제 조성물은 상온에서 액상인 경우에는 페이스트형으로 사용할 수 있다. 실온에서 고체인 경우에는, 가열하여 사용하는 것 외에, 용제를 이용하여 페이스트화할 수도 있다. 사용할 수 있는 용제로서는, 상술한 성분과 반응성이 없으면서 충분한 용해성을 나타내는 것이면 특별히 제한은 받지 않지만, 상압에서의 비점이 50 내지 150 ℃인 것이 바람직하다. 비점이 50 ℃ 미만인 경우, 실온에서 방치하면 휘발될 우려가 있고, 개방계에서의 사용이 제한된다. 또한, 비점이 150 ℃를 초과하면, 용제를 휘발시키는 것이 어렵고, 접착 후의 신뢰성에 악영향을 미칠 우려가 있다.The adhesive composition may be used in paste form when it is liquid at room temperature. In the case of a solid at room temperature, in addition to heating, it can also paste into a solvent. The solvent that can be used is not particularly limited as long as it exhibits sufficient solubility without being reactive with the above-mentioned components, but the boiling point at normal pressure is preferably 50 to 150 ° C. If the boiling point is less than 50 ° C, there is a risk of volatilization when left at room temperature, the use of the open system is limited. Moreover, when a boiling point exceeds 150 degreeC, it is difficult to volatilize a solvent and it may have a bad influence on the reliability after adhesion.
접착제 조성물은 필름형으로 하여 이용할 수도 있다. 그 경우, 접착제 조성물에 필요에 따라서 용제 등을 첨가하거나 한 용액을, 불소 수지 필름, 폴리에틸렌테레프탈레이트 필름, 이형지 등의 박리성 기재 상에 도포하거나, 또는 부직포 등의 기재에 상기 용액을 함침시켜 박리성 기재 상에 배치하고, 용제 등을 제거하여 필름으로서 사용할 수 있다. 필름 형상으로 사용하면 취급성 등의 관점에서 한층 편리하다.An adhesive composition can also be used as a film form. In that case, the solution which added the solvent etc. to the adhesive composition as needed is apply | coated on peelable base materials, such as a fluororesin film, a polyethylene terephthalate film, a release paper, or the base material, such as a nonwoven fabric, is impregnated and peeled off. It can arrange | position on a base material, remove a solvent, etc., and can use as a film. When used in a film form, it is more convenient from the viewpoint of handling property.
본 발명의 접착제 조성물은 열팽창 계수가 다른 이종의 피착체의 접착제로서 사용할 수 있다. 구체적으로는 은 페이스트, 은 필름, 이방 도전 접착제 등으로 대표되는 회로 접속 재료, CSP용 엘라스토머, CSP용 언더 충전재, LOC 테이프, 다이 본딩용 접착제 등으로 대표되는 반도체 소자용 접착제로서 사용할 수 있다.The adhesive composition of the present invention can be used as an adhesive for heterogeneous adherends having different thermal expansion coefficients. Specifically, it can be used as an adhesive for semiconductor elements represented by a circuit connection material represented by a silver paste, a silver film, an anisotropic conductive adhesive, etc., an elastomer for CSP, an under filler for CSP, a LOC tape, an adhesive for die bonding, and the like.
<실시예><Examples>
이하, 실시예에 기초하여 본 발명을 보다 상세하게 설명하지만, 본 발명이 이것으로 한정되는 것은 아니다.EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this.
<우레탄 수지(PUA-1)의 합성><Synthesis of Urethane Resin (PUA-1)>
하기 화학식(a)로 표시되는 에틸렌글리콜 디글리시딜에테르의 메타크릴산 부가물(교에이샤 가가꾸 가부시끼가이샤 제조, 상품명 에폭시에스테르 40EM)(0.5 몰), 중량 평균 분자량 2000의 폴리(테트라메틸렌글리콜)(0.5 몰), 4,4'-디이소시아네이트디페닐메탄(0.425 몰), 2,4'-디이소시아네이트디페닐메탄(0.425 몰), 디라우릴산디부틸주석(0.5 밀리몰)을 메틸에틸케톤(MEK) 중 60 ℃에서 3 시간 반응시켜 우레탄 수지(PUA-1)의 MEK 용액을 얻었다. 얻어진 수지의 GPC를 측정한 결과, 폴리스티렌 환산으로 Mw(중량 평균 분자량)=65,000, Mn(수평균 분자량)=35,000이었다.Methacrylic acid adduct of ethylene glycol diglycidyl ether represented by the following general formula (a) (Kyosei Chemical Co., Ltd. make, brand name epoxy ester 40EM) (0.5 mol), poly (tetra) of the weight average molecular weight 2000 Methylene glycol) (0.5 mol), 4,4'- diisocyanate diphenylmethane (0.425 mol), 2,4'- diisocyanate diphenylmethane (0.425 mol), dibutyltin dilauryl acid (0.5 mmol) methylethyl It was made to react for 3 hours at 60 degreeC in ketone (MEK), and the MEK solution of urethane resin (PUA-1) was obtained. As a result of measuring GPC of obtained resin, it was Mw (weight average molecular weight) = 65,000 and Mn (number average molecular weight) = 35,000 in polystyrene conversion.
<우레탄 수지(PUA-2)의 합성><Synthesis of Urethane Resin (PUA-2)>
에틸렌글리콜 디글리시딜에테르의 메타크릴산 부가물 대신에 하기 화학식(b)로 표시되는 비스페놀 A 디글리시딜에테르의 메타크릴산 부가물(교에이샤 가가꾸 가부시끼가이샤 제조, 상품명 에폭시에스테르 3000M)(0.5 몰)를 이용한 것 외에는, PUA-1의 합성과 동일하게 하여 우레탄 수지(PUA-2)의 MEK 용액을 얻었다. 얻어진 수지의 GPC를 측정한 결과, 폴리스티렌 환산으로 Mw-60,000, Mn=34,000이었다.Methacrylic acid adduct of bisphenol A diglycidyl ether represented by the following general formula (b) instead of methacryl acid adduct of ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name epoxy ester A MEK solution of urethane resin (PUA-2) was obtained in the same manner as the synthesis of PUA-1, except that 3000 M) (0.5 mol) was used. As a result of measuring GPC of obtained resin, it was Mw-60,000 and Mn = 34,000 in polystyrene conversion.
<우레탄 수지(PUA-3)의 합성><Synthesis of Urethane Resin (PUA-3)>
중량 평균 분자량 2000의 폴리테트라메틸렌글리콜(0.5 몰) 대신에 중량 평균 분자량 2000의 폴리 헥사메틸렌카르보네이트디올(0.5 몰)을 이용한 것 외에는, PUA-1의 합성과 동일하게 하여 우레탄 수지(PUA-3)의 MEK 용액을 얻었다. 얻어진 수지의 GPC를 측정한 결과, 폴리스티렌 환산으로 Mw=64,000, Mn=33,000이었다.Polyurethane resin (PUA-) in the same manner as in the synthesis of PUA-1, except that polyhexamethylene carbonatediol (0.5 mol) having a weight average molecular weight of 2000 was used instead of polytetramethylene glycol (0.5 mol) having a weight average molecular weight of 2000. The MEK solution of 3) was obtained. As a result of measuring GPC of obtained resin, it was Mw = 64,000 and Mn = 33,000 in polystyrene conversion.
<우레탄 수지(PUA-4)의 합성><Synthesis of Urethane Resin (PUA-4)>
에틸렌글리콜 디글리시딜에테르의 메타크릴산 부가물의 물질량을 O.7 몰로, 중량 평균 분자량 2000의 폴리(테트라메틸렌글리콜)의 물질량을 0.3 몰로 변경한 것 외에는, 우레탄 수지(PUA-1)의 합성과 동일하게 하여 우레탄 수지(PUA-4)의 MEK 용액을 얻었다. 얻어진 수지의 GPC를 측정한 결과, 폴리스티렌 환산으로 Mw=52,000, Mn=24,000이었다.Synthesis of urethane resin (PUA-1) except changing the amount of substance of methacrylic acid adduct of ethylene glycol diglycidyl ether to 0.7 mol and the amount of poly (tetramethylene glycol) having a weight average molecular weight of 2000 to 0.3 mol In the same manner as in the above, a MEK solution of urethane resin (PUA-4) was obtained. As a result of measuring GPC of obtained resin, it was Mw = 52,000 and Mn = 24,000 in polystyrene conversion.
<비교용 우레탄 수지(PUA-5)의 합성><Synthesis of Comparative Urethane Resin (PUA-5)>
4,4'-디이소시아네이트디페닐메탄(0.5 몰), 2,4'-디이소시아네이트디페닐메탄(0.5 몰), 중량 평균 분자량 2000의 폴리(테트라메틸렌글리콜)(0.9 몰), 2-히드록시에틸메타크릴레이트(0.5 몰), 디라우릴산디부틸주석(0.5 밀리몰)을 메틸에틸케톤(MEK) 중, 60 ℃에서 3 시간 반응시켜, 양쪽 말단에 아크릴레이트가 부가된 비교용 우레탄 수지(PUA-5)의 MEK 용액을 얻었다. 얻어진 수지의 GPC를 측정한 결과, 폴리스티렌 환산으로 Mw=50,000, Mn=20,000이었다.4,4'- diisocyanate diphenylmethane (0.5 mol), 2,4'- diisocyanate diphenylmethane (0.5 mol), poly (tetramethylene glycol) (0.9 mol) with a weight average molecular weight of 2000, 2-hydroxy Ethyl methacrylate (0.5 mol) and dibutyltin dilauryl acid (0.5 mmol) were reacted in methyl ethyl ketone (MEK) at 60 ° C for 3 hours, and a comparative urethane resin in which acrylates were added at both ends (PUA- MEK solution of 5) was obtained. As a result of measuring GPC of obtained resin, it was Mw = 50,000 and Mn = 20,000 in polystyrene conversion.
<비교용 우레탄 수지(PUA-6)의 합성><Synthesis of Comparative Urethane Resin (PUA-6)>
4,4'-디이소시아네이트디페닐메탄(0.5 몰), 2,4'-디이소시아네이트디페닐메탄(0.5 몰), 중량 평균 분자량 2000의 폴리(테트라메틸렌글리콜)(0.7 몰), 2-히드록시에틸메타크릴레이트(0.8 몰), 디라우릴산디부틸주석(0.5 밀리몰)을 메틸에틸케톤(MEK) 중, 60 ℃에서 3 시간 반응시켜, 양쪽 말단에 아크릴레이트가 부가된 비교용 우레탄 수지(PUA-6)의 MEK 용액을 얻었다. 얻어진 수지의 GPC를 측정한 결과, 폴리스티렌 환산으로 Mw=9,000, Mn=5,000이었다.4,4'- diisocyanate diphenylmethane (0.5 mol), 2,4'- diisocyanate diphenylmethane (0.5 mol), poly (tetramethylene glycol) (0.7 mol) with a weight average molecular weight of 2000, 2-hydroxy Ethyl methacrylate (0.8 mole) and dibutyltin dilauryl acid (0.5 mmol) were reacted in methyl ethyl ketone (MEK) at 60 ° C. for 3 hours, and a comparative urethane resin in which acrylates were added at both ends (PUA- MEK solution of 6) was obtained. As a result of measuring GPC of obtained resin, it was Mw = 9,000 and Mn = 5,000 in polystyrene conversion.
<비교용 우레탄 수지(PUA-7)의 합성><Synthesis of Comparative Urethane Resin (PUA-7)>
에틸렌글리콜 디글리시딜에테르의 메타크릴산 부가물의 물질량을 1.0 몰로 하면서 중량 평균 분자량 2000의 폴리(테트라메틸렌글리콜)을 이용하지 않은 것 이외에는, 우레탄 수지(PUA-1)의 합성과 동일하게 하여 우레탄 수지(PUA-7)의 MEK 용액을 얻었다. 얻어진 수지의 GPC를 측정한 결과, 폴리스티렌 환산으로 Mw=50,000, Mn=22,000 였다.A urethane was prepared in the same manner as in the synthesis of urethane resin (PUA-1), except that poly (tetramethylene glycol) having a weight average molecular weight of 2000 was used while the amount of the methacrylic acid adduct of ethylene glycol diglycidyl ether was 1.0 mole. The MEK solution of resin (PUA-7) was obtained. As a result of measuring GPC of obtained resin, it was Mw = 50,000 and Mn = 22,000 in polystyrene conversion.
(실시예 1 내지 4)(Examples 1 to 4)
열가소성 수지로서 페녹시 수지(PKHC, 유니온 카바이드사 제조 상품명, 중량 평균 분자량 45,000)를, 라디칼 중합성 물질로서 이소시아누르산 EO 변성 디아크릴레이트(M215, 도아 고세이 가부시끼가이샤 제조 상품명) 및 2-(메트)아크릴옥시에틸포스페이트(라이트에스테르 P-2M, 교에이샤 가가꾸 가부시끼가이샤 제조 상품명)를, 우레탄 수지로서 상술한 PUA-1, PUA-2, PUA-3 및 PUA-4를, 경화제로서 t-헥실퍼옥시-2-에틸헥사노네이트의 50 질량% DOP(디옥틸프탈레이트) 용액(닛본 유시 가부시끼가이샤 제조, 상품명 퍼큐어 HO)을, 도전 입자로서 폴리스티렌을 핵으로 하는 입자의 표면에, 두께 0.20 ㎛의 금층을 설치한 평균 입경 4 ㎛, 비중 2.5의 도전 입자를 각각 준비하였다.Phenoxy resin (PKHC, Union Carbide brand name, weight average molecular weight 45,000) as a thermoplastic resin, Isocyanuric acid EO modified diacrylate (M215, Toagosei Co., Ltd. brand name) and 2- as a radically polymerizable substance PUA-1, PUA-2, PUA-3 and PUA-4 mentioned above as (urethane resin) the (meth) acryloxyethyl phosphate (light ester P-2M, Kyoeisha Chemical Co., Ltd. brand name) is a hardening | curing agent The surface of the particle | grains which make polystyrene as a nucleus the 50 mass% DOP (dioctyl phthalate) solution (The Nippon Yushi Chemical Co., Ltd. make, brand name Purcure HO) of t-hexyl peroxy-2-ethylhexanoate as an electroconductive particle , Conductive particles having an average particle diameter of 4 μm and a specific gravity of 2.5 having a gold layer of 0.20 μm in thickness were prepared, respectively.
PKHC 40 g을 메틸에틸케톤 60 g에 용해시켜 고형분 40 질량%의 용액으로 하였다. 이 열가소성, 우레탄 수지 및 경화제를 고형분에 대한 질량비가 표 1에 나타내는 바와 같이 배합하였다. 또한, 도전 입자를, 접착제 조성물의 고형분 전체 부피를 기준으로 하여 1.5 부피% 배합하여 분산시켜 접착제 조성물을 얻었다. 얻어진 접착제 조성물, 두께 80 ㎛의 불소 수지 필름 10 분의 열풍 건조에 의해서 건조시켜, 접착제 조성물로 이루어지는 접착제층의 두께가 15 ㎛의 필름형 접착제를 제조하였다. 40 g of PKHC was dissolved in 60 g of methyl ethyl ketone to obtain a solution of 40 mass% of solid content. This thermoplastic, urethane resin, and hardening | curing agent were mix | blended as mass ratio with respect to solid content is shown in Table 1. In addition, 1.5 vol% of the conductive particles were blended and dispersed based on the total solid content volume of the adhesive composition to obtain an adhesive composition. The obtained adhesive composition and 80-micrometer-thick fluororesin film were dried by hot air drying for 10 minutes, and the film adhesive of 15 micrometers of thickness of the adhesive bond layer which consists of an adhesive composition was manufactured.
(비교예 1 내지 3)(Comparative Examples 1 to 3)
우레탄 수지로서 PUA-5, PUA-6, PUA-7을 사용한 것 이외에는 실시예 1 내지 3과 동일하게 하여 필름형 접착제를 제조하였다.A film adhesive was produced in the same manner as in Examples 1 to 3 except that PUA-5, PUA-6, and PUA-7 were used as the urethane resin.
(회로 접속 구조체의 제조) (Manufacture of circuit connection structure)
상기에서 얻어진 필름형 접착제를, 라인 폭 25 ㎛, 피치 50 ㎛, 두께 18 ㎛의 구리 회로를 500개 갖는 연성 회로판(FPC)과, 두께 0.20 ㎛의 산화인듐주석(ITO)의 박층을 형성한 유리(두께 1.1 mm, 표면 저항 20 Ω/cm) 사이에 배치하고, 175 ℃, 3 MPa에서 15 초간의 가열 가압을 행하고, 폭 2 mm에 걸쳐 접속을 행하여 회로 접속 구조체를 제조하였다.The film adhesive obtained above was formed of a flexible circuit board (FPC) having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm, and a thin layer of indium tin oxide (ITO) having a thickness of 0.20 μm. It was arrange | positioned between (thickness 1.1mm and surface resistance 20 (ohm) / cm), heat pressurization for 15 second at 175 degreeC and 3 MPa, and it connected over 2mm width, and manufactured the circuit connection structure.
(접속 저항의 측정)(Measurement of connection resistance)
상기에서 얻어진 회로 접속 구조체의 인접 회로간의 저항값을, 접착 직후 및 85 ℃, 85 %RH의 고온 고습조 중에 120 시간 유지한 후에 멀티미터로 측정하였다. 저항값은 인접 회로간의 저항 150점의 평균값으로서 나타내었다. 얻어진 결과를 표 2에 나타낸다.The resistance value between adjacent circuits of the circuit connection structure obtained above was measured by the multimeter immediately after adhesion | attachment, and hold | maintained for 120 hours in 85 degreeC and the high temperature high humidity tank of 85% RH. The resistance value was shown as an average value of 150 points of resistance between adjacent circuits. The obtained results are shown in Table 2.
(접착 강도의 측정)(Measurement of Adhesive Strength)
상기에서 얻어진 회로 접속 구조체에 있어서의 회로 부재간의 접착 강도를, JIS-Z 0237에 준하여 90도 박리법으로 측정하였다. 여기서, 접착 강도의 측정 장치로서는 도요 볼드윈 가부시끼가이샤 제조 텐실 UTM-4를 이용하여 박리 속도 50 mm/분, 25 ℃에서 측정하였다. 또한, 접착 강도는 접착 직후 및 85 ℃, 85 %RH의 고온 고습조 중에 120 시간 유지한 후에 측정하였다. 얻어진 결과를 표 2에 나타낸다.The adhesive strength between the circuit members in the circuit connection structure obtained above was measured by the 90 degree peeling method according to JIS-Z 0237. Here, as a measuring apparatus of adhesive strength, it measured at the peeling speed of 50 mm / min and 25 degreeC using Tensil UTM-4 by Toyo Baldwin Co., Ltd .. In addition, adhesive strength was measured immediately after adhesion and after hold | maintaining for 120 hours in 85 degreeC and the high temperature, high humidity tank of 85% RH. The obtained results are shown in Table 2.
표 2에 나타낸 결과로부터 분명한 바와 같이, 실시예 1 내지 4의 필름형 접착제를 이용한 경우에는, 저온에서 그와 같이 단시간에 경화된 경우(175 ℃에서 15 초간)에도 접착 강도가 충분히 높은 것이 확인되었다. 이것은, 실시예 1 내지 4의 필름형 접착제에 의해 충분한 접착성이 얻어지는 것, 및 실시예 1 내지 4의 필름형 접착제는 상술한 우수한 저온 속경화성을 구비하는 것을 나타내었다.As apparent from the results shown in Table 2, in the case of using the film adhesives of Examples 1 to 4, it was confirmed that the adhesive strength was sufficiently high even when cured for such a short time at low temperature (15 seconds at 175 ° C). . This showed that sufficient adhesiveness is obtained by the film adhesives of Examples 1-4, and the film adhesive of Examples 1-4 is equipped with the outstanding low temperature fast hardenability mentioned above.
또한, 실시예 1 내지 4의 필름형 접착제를 이용한 경우에는, 회로 접속 구조체의 인접 회로간의 저항값이 충분히 낮으며, 회로 접속 구조체의 인접 회로 사이가 충분히 전기적 접속되어 있는 것이 확인되었다. 이것은, 실시예 1 내지 4의 필름형 접착제에 의해 충분한 접속 신뢰성이 얻어지는 것을 나타낸다.Moreover, when the film adhesives of Examples 1-4 were used, it was confirmed that the resistance value between the adjacent circuits of a circuit connection structure is low enough, and the electrical connection between adjacent circuits of a circuit connection structure is sufficiently. This shows that sufficient connection reliability is obtained by the film adhesive of Examples 1-4.
또한, 실시예 1 내지 4의 필름형 접착제를 이용한 경우에는, 접착 직후에서도 고온 고습 환경하에서 장기간 둔 후에도, 충분히 낮은 저항값 및 충분히 높은 접착 강도가 얻어지는 것이 확인되었다. 이것은, 실시예 1 내지 4의 필름형 접착제에 따르면, 고온 고습 환경하에서 장기간 둔 경우에도, 접속 신뢰성 및 접착성의 저하를 충분히 억제하는 것이 가능한 것을 나타낸다.Moreover, when the film adhesives of Examples 1-4 were used, even if it left for a long time in high temperature, high humidity environment immediately after adhesion | attachment, it was confirmed that sufficiently low resistance value and sufficiently high adhesive strength are obtained. This shows that according to the film adhesives of Examples 1-4, even if it is left in a high temperature, high humidity environment for a long time, the fall of connection reliability and adhesiveness can fully be suppressed.
이에 대하여, 비교예 1의 필름형 접착제를 이용한 경우에는, 고온 고습 환경하에서 장기간 둔 후의 저항값이 급격히 상승하는 것이 확인되었다. 이것은, 비교예 1의 필름형 접착제의 고온 고습 환경하에서 장기간 두었을 때 접속 신뢰성이 저하되는 것을 나타낸다. 또한, 비교예 2 및 3의 필름형 접착제를 이용한 경우에는, 접착성이 불충분한 것이 확인되었다.On the other hand, when the film adhesive of Comparative Example 1 was used, it was confirmed that the resistance value after a long time in a high temperature, high humidity environment rose rapidly. This shows that connection reliability falls when it puts in a high temperature, high humidity environment of the film adhesive of the comparative example 1 for a long time. Moreover, when the film adhesives of the comparative examples 2 and 3 were used, it was confirmed that adhesiveness is inadequate.
이상과 같이, 실시예 1 내지 4 및 비교예 1 내지 3으로부터, 본 발명의 접착제 조성물이 상술한 우수한 효과를 가지고, 회로 접속 또는 반도체 실장용 접착제에 바람직한 것은 분명하다.As mentioned above, it is clear from Examples 1-4 and Comparative Examples 1-3 that the adhesive composition of this invention has the outstanding effect mentioned above, and is preferable for the adhesive agent for circuit connection or a semiconductor mounting.
Claims (1)
(B) 광 조사 또는 가열에 의해 유리 라디칼을 발생시키는 경화제
를 함유하고,
상기 (A) 우레탄 수지가 하기 화학식 I로 표시되는 공중합체를 포함하는 것인 접착제 조성물.
<화학식 I>
[식 I 중, X는 디이소시아네이트 잔기를 나타내고, Y는 디올 잔기를 나타내고, n은 1 내지 100의 정수를 나타내며, 단, Y로 표시되는 디올 잔기 중 10 내지 90 몰%는 하기 화학식 II로 표시되는 구조를 갖는 기이면서 Y로 표시되는 디올 잔기 중 10 내지 90 몰%는 중량 평균 분자량 500 이상의 디올 잔기이다.]
<화학식 II>
[식 II 중, Z는 2가의 유기기를 나타내고, R1 및 R2는 각각 독립적으로 수소 원자 또는 메틸기를 나타낸다.](A) urethane resin which has a (meth) acrylate group in a side chain, and a weight average molecular weight is 10,000-500,000, and
(B) A curing agent that generates free radicals by light irradiation or heating
Containing,
Adhesive composition of the said (A) urethane resin containing the copolymer represented by following formula (I).
<Formula I>
[In Formula I, X represents a diisocyanate residue, Y represents a diol residue, n represents the integer of 1-100, provided that 10-90 mol% of the diol residue represented by Y is represented by following General formula II. 10 to 90 mol% of the diol residues represented by Y while being a group having a structure of
<Formula II>
[In formula II, Z represents a divalent organic group, R <1> and R <2> respectively independently represents a hydrogen atom or a methyl group.]
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