JP5067101B2 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP5067101B2 JP5067101B2 JP2007259101A JP2007259101A JP5067101B2 JP 5067101 B2 JP5067101 B2 JP 5067101B2 JP 2007259101 A JP2007259101 A JP 2007259101A JP 2007259101 A JP2007259101 A JP 2007259101A JP 5067101 B2 JP5067101 B2 JP 5067101B2
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- JP
- Japan
- Prior art keywords
- adhesive composition
- mol
- diol
- molecular weight
- average molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims description 88
- 230000001070 adhesive effect Effects 0.000 title claims description 88
- 239000000203 mixture Substances 0.000 title claims description 61
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 31
- 150000002009 diols Chemical group 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 42
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- -1 peel strength Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000758 substrate Substances 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
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 description 6
- 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 5
- 229910019142 PO4 Inorganic materials 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
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 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 4
- 230000006866 deterioration Effects 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
- 239000007983 Tris buffer Substances 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 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
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 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
- 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer 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
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 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
- DCVWZWOEQMSMLR-UHFFFAOYSA-N silylperoxysilane Chemical compound [SiH3]OO[SiH3] DCVWZWOEQMSMLR-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 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
- 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
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-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
- IXWFFSPYFOEXQB-UHFFFAOYSA-N 1-[4-(4-decylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCCCCCCCCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IXWFFSPYFOEXQB-UHFFFAOYSA-N 0.000 description 1
- CTDLULCMHANDJK-UHFFFAOYSA-N 1-[4-[4-[1,1,1,3,3,3-hexafluoro-2-[4-[4-(3-methyl-2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]-3-methylpyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1C(C=C1)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(=CC=3)N3C(C(C)=CC3=O)=O)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 CTDLULCMHANDJK-UHFFFAOYSA-N 0.000 description 1
- PYTZZNUKESXWLN-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]-1,1,1,3,3,3-hexafluoropropan-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(F)(F)F)(C(F)(F)F)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O PYTZZNUKESXWLN-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
- YMMLZUQDXYPNOG-UHFFFAOYSA-N 2-methylpentan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CCCCCC(C)(C)C YMMLZUQDXYPNOG-UHFFFAOYSA-N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-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
- 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 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
- SMKMSUCZZOQDGA-UHFFFAOYSA-N 3-methyl-1-[4-(3-methyl-2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1C1=CC=C(N2C(C(C)=CC2=O)=O)C=C1 SMKMSUCZZOQDGA-UHFFFAOYSA-N 0.000 description 1
- ZYFIFFPWXKYFRR-UHFFFAOYSA-N 3-methyl-1-[4-[4-[1-[4-[4-(3-methyl-2,5-dioxopyrrol-1-yl)phenoxy]phenyl]decyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C(C)=CC2=O)=O)C=CC=1C(CCCCCCCCC)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=C(C)C1=O ZYFIFFPWXKYFRR-UHFFFAOYSA-N 0.000 description 1
- UMIADIZYYGHJBZ-UHFFFAOYSA-N 3-methyl-1-[4-[4-[2-[4-[4-(3-methyl-2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1C(C=C1)=CC=C1OC1=CC=C(C(C)(C)C=2C=CC(OC=3C=CC(=CC=3)N3C(C(C)=CC3=O)=O)=CC=2)C=C1 UMIADIZYYGHJBZ-UHFFFAOYSA-N 0.000 description 1
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-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
- 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
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 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
- FVSKBQVTQRMJAJ-UHFFFAOYSA-N C(C)(C)(C)C=C[Si](C=C)(C=C)OO[Si](C=C)(C=C)C=CC(C)(C)C Chemical compound C(C)(C)(C)C=C[Si](C=C)(C=C)OO[Si](C=C)(C=C)C=CC(C)(C)C FVSKBQVTQRMJAJ-UHFFFAOYSA-N 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
- 239000004902 Softening Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- UNKQAWPNGDCPTE-UHFFFAOYSA-N [2,5-dimethyl-5-(3-methylbenzoyl)peroxyhexan-2-yl] 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C=2C=C(C)C=CC=2)=C1 UNKQAWPNGDCPTE-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
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent 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
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-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
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 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
- 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 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
- 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
- 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 150000004979 silylperoxides Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- 239000011800 void material Substances 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 at least one potential-jump barrier or surface barrier, e.g. 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
Description
本発明は、接着剤組成物に関する。 The present invention relates to an adhesive composition.
半導体分野ではエポキシ樹脂などの有機材料が多く使われている。また、封止材の分野では、封止システムの９０％以上が樹脂封止システムに置き換わっている。封止材はエポキシ樹脂、硬化剤、各種添加剤、無機充填剤等によって構成される複合材料であり、エポキシ樹脂としてはクレゾールノボラック型エポキシ樹脂が多く使用されている。 Many organic materials such as epoxy resins are used in the semiconductor field. In the field of sealing materials, 90% or more of the sealing system is replaced with a resin sealing system. The sealing material is a composite material composed of an epoxy resin, a curing agent, various additives, an inorganic filler, and the like, and a cresol novolac type epoxy resin is often used as the epoxy resin.
しかし、クレゾールノボラック型エポキシ樹脂は、低吸水率、低弾性率といった特性において必ずしも満足する要求特性を有していないため、表面実装方式への対応が困難である。そのため、これに代わる新規高性能エポキシ樹脂が多く提案され実用化に至っている。 However, the cresol novolac type epoxy resin does not necessarily have the required characteristics satisfying the characteristics such as the low water absorption rate and the low elastic modulus, so that it is difficult to cope with the surface mounting method. For this reason, many new high performance epoxy resins have been proposed and put into practical use.
また、エポキシ樹脂などの有機材料は、ダイボンディング用導電性接着剤として、エポキシ樹脂に銀粉を混練した銀ペーストとして多く使用されている。しかし、半導体素子の配線基板への装着方法が表面実装法に移行するに従い、銀ペーストに対する耐はんだリフロー性向上の要求が強まっている。この問題を解決するために、硬化後のダイボンディング用接着層のボイド、ピール強度、吸水率、弾性率等の改善がなされている。 Also, organic materials such as epoxy resins are often used as silver pastes in which silver powder is kneaded with epoxy resin as a conductive adhesive for die bonding. However, as the mounting method of the semiconductor element to the wiring board shifts to the surface mounting method, there is an increasing demand for improving the solder reflow resistance with respect to the silver paste. In order to solve this problem, improvements have been made to the void, peel strength, water absorption, elastic modulus, etc. of the adhesive layer for die bonding after curing.
半導体実装分野では、低コスト化・高精細化に対応した新しい実装形態として、ＩＣチップを直接プリント基板やフレキシブル配線板に搭載するフリップチップ実装が注目されている。 In the semiconductor mounting field, flip chip mounting, in which an IC chip is directly mounted on a printed circuit board or a flexible wiring board, has attracted attention as a new mounting form corresponding to cost reduction and high definition.
フリップチップ実装方式としては、チップの端子にはんだバンプを設け、はんだ接続を行う方式や、導電性接着剤を介して電気的接続を行う方式が知られている。これらの方式では、接続するチップと基板との間の熱膨張係数差に基づくストレスが、各種環境に曝した場合に接続界面で発生し、接続信頼性が低下するという問題がある。 As the flip chip mounting method, there are known a method in which solder bumps are provided on the terminals of the chip to perform solder connection, and a method in which electrical connection is made through a conductive adhesive. In these methods, there is a problem that stress based on the difference in thermal expansion coefficient between the chip to be connected and the substrate is generated at the connection interface when exposed to various environments, and connection reliability is lowered.
このため、接続界面のストレスを緩和する目的で、一般にエポキシ樹脂系のアンダーフィル材をチップ／基板の間隙に注入する方式が検討されている。しかし、このアンダーフィル注入工程は、プロセスを煩雑化し、生産性、コストの面で不利になるという問題がある。このような問題を解決すべく、最近では異方導電性と封止機能とを有する異方導電性接着剤を用いたフリップチップ実装が、プロセス簡易性という観点から注目されている。 For this reason, a method of injecting an epoxy resin-based underfill material into the gap between the chip and the substrate has been studied for the purpose of alleviating the stress at the connection interface. However, this underfill injection process has a problem that the process becomes complicated and disadvantageous in terms of productivity and cost. In order to solve such problems, flip chip mounting using an anisotropic conductive adhesive having anisotropic conductivity and a sealing function has recently attracted attention from the viewpoint of process simplicity.
一方、近年、半導体、液晶ディスプレイ等の分野において、電子部品を固定したり回路接続を行うために各種の接着材料が使用されている。これらの用途では、回路の高密度化、高精細化が進み、接着性をはじめとして耐熱性、高温高湿環境下に長時間おかれた場合の接続信頼性などが要求される。 On the other hand, in recent years, various adhesive materials have been used in the fields of semiconductors, liquid crystal displays, and the like to fix electronic components and make circuit connections. In these applications, higher density and higher definition of the circuit are required, and heat resistance as well as adhesiveness, and connection reliability when placed in a high temperature and high humidity environment for a long time are required.
特に、液晶ディスプレイとＴＣＰとの接続、ＦＰＣとＴＣＰとの接続、及び、ＦＰＣとプリント配線板との接続には、回路接続材料として、接着剤中に導電粒子を分散させた異方導電性接着剤が使用されている。 Especially for the connection between liquid crystal display and TCP, the connection between FPC and TCP, and the connection between FPC and printed wiring board, anisotropic conductive adhesive with conductive particles dispersed in adhesive as circuit connection material The agent is being used.
また、最近では、半導体シリコンチップを基板に実装する場合でも、従来のワイヤーボンドではなく、半導体シリコンチップをフェイスダウンで基板に実装するいわゆるフリップチップ実装が行われており、ここでも異方導電性接着剤の適用が開始されている。 Recently, even when a semiconductor silicon chip is mounted on a substrate, so-called flip chip mounting in which the semiconductor silicon chip is mounted on the substrate face down is performed instead of the conventional wire bond. Adhesive application has begun.
異方導電性接着剤としては、上述のようにエポキシ樹脂を用いるものが一般的であるが、例えば特許文献１記載の、分子の両末端に（メタ）アクリレート基を付加させた２官能ウレタンアクリレートを用いるものも知られている。
しかしながら、精密機器分野では回路の高密度化が進んでおり、電極幅及び電極間隔が極めて狭くなっている。このため、従来のエポキシ樹脂を含む異方導電性接着剤を用いたときには、配線の脱落、はく離、位置ずれが生じる等して、接続しようとする電極間の電気的接続が不十分となる場合がある、すなわち接続信頼性が低いという問題がある。 However, in the precision instrument field, the density of circuits is increasing, and the electrode width and electrode interval are extremely narrow. For this reason, when an anisotropic conductive adhesive containing a conventional epoxy resin is used, the electrical connection between the electrodes to be connected may be insufficient due to wiring dropping, peeling, or misalignment. That is, there is a problem that connection reliability is low.
また、特許文献１記載の２官能ウレタンアクリレートを用いる異方導電性接着剤においては次のような問題がある。すなわち、ウレタンアクリレートの分子量が小さい場合（例えば数千程度）には接着剤の接着性が低く、ウレタンアクリレートの分子量が大きい場合には、高温高湿環境下に長期間おかれた際に接続信頼性が低下するという問題がある。 Further, the anisotropic conductive adhesive using the bifunctional urethane acrylate described in Patent Document 1 has the following problems. That is, when the molecular weight of urethane acrylate is small (for example, about several thousand), the adhesiveness of the adhesive is low, and when the molecular weight of urethane acrylate is large, the connection reliability is maintained when placed in a high temperature and high humidity environment for a long time. There is a problem that the performance is lowered.
本発明は上記事情に鑑みてなされたものであり、接続する回路の電極幅及び電極間隔が極めて狭い場合（例えば、電極幅が２５μｍ以下であり、かつ電極間隔が５０μｍ以下である場合）であっても、十分な接続信頼性及び十分な接着性を得ることができ、かつ高温高湿環境下に長期間おかれた場合でも接続信頼性及び接着性の低下を十分に抑制することが可能な接着剤組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a case where the electrode width and the electrode interval of a circuit to be connected are extremely narrow (for example, the electrode width is 25 μm or less and the electrode interval is 50 μm or less). However, it is possible to obtain sufficient connection reliability and sufficient adhesiveness, and sufficiently suppress deterioration in connection reliability and adhesiveness even when left in a high temperature and high humidity environment for a long period of time. An object is to provide an adhesive composition.
上記目的を達成するために、本発明は、（Ａ）側鎖に（メタ）アクリレート基を有し、重量平均分子量が１０，０００〜５００，０００であるウレタン樹脂と、（Ｂ）光照射又は加熱により遊離ラジカルを発生する硬化剤とを含有し、（Ａ）ウレタン樹脂が下記一般式（Ｉ）で表される共重合体を含む接着剤組成物を提供する。 In order to achieve the above object, the present invention provides (A) a urethane resin having a (meth) acrylate group in the side chain and a weight average molecular weight of 10,000 to 500,000, and (B) light irradiation or An adhesive composition comprising a curing agent that generates free radicals upon heating, and (A) a urethane resin containing a copolymer represented by the following general formula (I) is provided.
［式（Ｉ）中、Ｘはジイソシアネート残基を示し、Ｙはジオール残基を示し、ｎは１〜１００の整数を示す。ただし、Ｙで示されるジオール残基のうち１０〜９０ｍｏｌ％は下記一般式（ＩＩ）で表される構造を有する残基であり、かつＹで表されるジオール残基のうち１０〜９０ｍｏｌ％は重量平均分子量５００以上のジオールの残基である。］
[In formula (I), X represents a diisocyanate residue, Y represents a diol residue, and n represents an integer of 1 to 100. However, 10 to 90 mol% of diol residues represented by Y is a residue having a structure represented by the following general formula (II), and 10 to 90 mol% of diol residues represented by Y is It is a residue of a diol having a weight average molecular weight of 500 or more. ]
［式（ＩＩ）中、Ｚは２価の有機基を示し、Ｒ１及びＲ２は、それぞれ独立に水素原子又はメチル基を示す。］
[In Formula (II), Z represents a divalent organic group, and R 1 and R 2 each independently represent a hydrogen atom or a methyl group. ]
本発明の接着剤組成物によれば、上記構成を有することにより、接続する回路の電極幅及び電極間隔が極めて狭い場合であっても、十分な接続信頼性及び十分な接着性を得ることができ、かつ高温高湿環境下に長期間おかれた場合でも接続信頼性及び接着性の低下を十分に抑制することが可能である。このような効果が得られる理由は必ずしも明らかでないが、（Ａ）成分が特定の官能基により多官能化されており、且つその重量平均分子量が比較的大きいことに少なくとも起因するものと考えられる。 According to the adhesive composition of the present invention, by having the above configuration, sufficient connection reliability and sufficient adhesiveness can be obtained even when the electrode width and electrode interval of a circuit to be connected are extremely narrow. It is possible to sufficiently suppress the deterioration of connection reliability and adhesiveness even when left in a high temperature and high humidity environment for a long period of time. The reason why such an effect is obtained is not necessarily clear, but it is thought to be at least due to the fact that the component (A) is polyfunctionalized with a specific functional group and its weight average molecular weight is relatively large.
また、精密電子機器の分野では、生産性向上のために接続時間の短縮化が求められており、この要求を満たすために、低温速硬化性に優れた接着剤が強く求められている。上記構成を有する本発明の接着剤組成物は、上記効果に加えて、さらにこの低温速硬化性にも優れる。 In the field of precision electronic equipment, shortening of the connection time is required for improving productivity, and in order to satisfy this requirement, an adhesive excellent in low-temperature rapid curing is strongly demanded. In addition to the above effects, the adhesive composition of the present invention having the above configuration is further excellent in this low temperature fast curability.
本発明の接着剤組成物は、（Ｃ）熱可塑性樹脂及び／又は熱可塑性エラストマーをさらに含有することが好ましい。これにより、接着剤組成物の物性及び接着性がさらに向上する。 The adhesive composition of the present invention preferably further contains (C) a thermoplastic resin and / or a thermoplastic elastomer. Thereby, the physical property and adhesiveness of an adhesive composition further improve.
本発明の接着剤組成物は、（Ｄ）ラジカル重合性物質をさらに含有することが好ましい。これにより、接着剤組成物の接続信頼性がさらに向上する。 The adhesive composition of the present invention preferably further contains (D) a radical polymerizable substance. Thereby, the connection reliability of an adhesive composition further improves.
本発明の接着剤組成物は、（Ｅ）導電粒子をさらに含有することが好ましい。これにより、接着剤組成物に導電性又は異方導電性を付与することができるため、かかる接着剤組成物を、回路電極を有する回路部材同士の接続用途等に、より好適に使用することが可能となる。 The adhesive composition of the present invention preferably further contains (E) conductive particles. Thereby, since conductivity or anisotropic conductivity can be imparted to the adhesive composition, it is possible to more suitably use the adhesive composition for connection applications between circuit members having circuit electrodes. It becomes possible.
本発明の接着剤組成物によれば、接続する回路の電極幅及び電極間隔が極めて狭い場合であっても、十分な接続信頼性及び十分な接着性を得ることができ、かつ高温高湿環境下に長期間おかれた場合でも接続信頼性及び接着性の低下を十分に抑制することが可能である。さらに、本発明の接着剤組成物は、上記効果に加えて、優れた低温速硬化性を備える。 According to the adhesive composition of the present invention, sufficient connection reliability and sufficient adhesiveness can be obtained even when the electrode width and electrode interval of a circuit to be connected are extremely narrow, and a high-temperature and high-humidity environment. Even when it is left for a long time, it is possible to sufficiently suppress the deterioration of connection reliability and adhesiveness. Furthermore, the adhesive composition of the present invention has excellent low-temperature fast curability in addition to the above effects.
以下、場合により図面を参照しつつ本発明の好適な実施形態について詳細に説明するが、本発明はこれに限定されるものではない。なお、本明細書中、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（以下、「ＧＰＣ」という。）により測定され、かつ標準ポリスチレンの検量線を使用して換算されたものである。また、本明細書中、「（メタ）アクリレート」とは、アクリレート又はそれに対応するメタクリレートを意味し、「（メタ）アクリル酸」とは、アクリル酸又はそれに対応するメタクリル酸を意味する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings depending on cases, but the present invention is not limited thereto. In the present specification, the weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted using a standard polystyrene calibration curve. In the present specification, “(meth) acrylate” means acrylate or methacrylate corresponding thereto, and “(meth) acrylic acid” means acrylic acid or methacrylic acid corresponding thereto.
本発明の接着剤組成物は、（Ａ）ウレタン樹脂及び（Ｂ）硬化剤を含有する。 The adhesive composition of the present invention contains (A) a urethane resin and (B) a curing agent.
このうち、（Ａ）ウレタン樹脂は、側鎖に（メタ）アクリレート基を有し、重量平均分子量が１０，０００〜５００，０００であるものである。このウレタン樹脂の、重量平均分子量が１０，０００未満である場合には接着剤組成物の接着性が不十分になり、重量平均分子量が５００，０００を超える場合には接着剤組成物の取り扱いが困難になる。さらに、（Ａ）ウレタン樹脂の重量平均分子量は、接着剤組成物の接着性及び取り扱い性をより向上させる観点から、１５，０００〜２００，０００であることが好ましく、２０，０００〜１００，０００であることがより好ましい。 Among these, the (A) urethane resin has a (meth) acrylate group in the side chain and has a weight average molecular weight of 10,000 to 500,000. When the weight average molecular weight of this urethane resin is less than 10,000, the adhesiveness of the adhesive composition becomes insufficient, and when the weight average molecular weight exceeds 500,000, the adhesive composition is handled. It becomes difficult. Furthermore, the weight average molecular weight of the (A) urethane resin is preferably 15,000 to 200,000, more preferably 20,000 to 100,000, from the viewpoint of further improving the adhesiveness and handleability of the adhesive composition. It is more preferable that
さらにまた、（Ａ）ウレタン樹脂は下記一般式（Ｉ）で表される共重合体を含む。 Furthermore, (A) urethane resin contains the copolymer represented by the following general formula (I).
ここで、式（Ｉ）中、Ｘはジイソシアネート残基を示し、Ｙはジオール残基を示し、ｎは１〜１００の整数を示す。 Here, in formula (I), X represents a diisocyanate residue, Y represents a diol residue, and n represents an integer of 1 to 100.
さらに、Ｙで示されるジオール残基のうち１０〜９０ｍｏｌ％は下記一般式（ＩＩ）で表される構造を有する基であり、かつＹで示されるジオール残基のうち１０〜９０ｍｏｌ％は重量平均分子量５００以上のジオールの残基である。 Further, 10 to 90 mol% of the diol residues represented by Y is a group having a structure represented by the following general formula (II), and 10 to 90 mol% of the diol residues represented by Y is a weight average It is a residue of a diol having a molecular weight of 500 or more.
ここで、式（ＩＩ）中、Ｚは２価の有機基を示し、Ｒ１及びＲ２は、それぞれ独立に水素原子又はメチル基を示す。 Here, in formula (II), Z represents a divalent organic group, and R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
上述の（Ａ）ウレタン樹脂は、ジイソシアネート及びジオールを共重合させることにより得られる。共重合に用いられるジイソシアネートとしては、例えば、
等が挙げられ、これらは１種を単独で又は２種以上を混合して用いることができる。
The above-mentioned (A) urethane resin is obtained by copolymerizing diisocyanate and diol. As diisocyanate used for copolymerization, for example,
These may be used alone or in combination of two or more.
また、共重合に用いられるジオールのうち、上記一般式（ＩＩ）で表される構造を有する基に対応するものとしては、例えば、
［式中、Ｒ１及びＲ２は、それぞれ独立に水素原子又はメチル基を示し、ｍは１〜１０の整数を示す。］
等の（メタ）アクリレート変性エポキシ化合物が挙げられる。これらの（メタ）アクリレート変性エポキシ化合物は、例えば２官能性エポキシ化合物と（メタ）アクリル酸とを反応させることにより得られるものであり、例示したものの他にも種々の２官能性エポキシ化合物から得られる（メタ）アクリレート変性エポキシ化合物を用いることができる。これらは１種を単独で又は２種以上を混合して用いることができる。
Among the diols used for copolymerization, those corresponding to the group having the structure represented by the general formula (II) include, for example,
[Wherein, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and m represents an integer of 1 to 10. ]
And (meth) acrylate-modified epoxy compounds. These (meth) acrylate-modified epoxy compounds are obtained, for example, by reacting a bifunctional epoxy compound and (meth) acrylic acid, and obtained from various bifunctional epoxy compounds in addition to those exemplified. A (meth) acrylate-modified epoxy compound can be used. These can be used individually by 1 type or in mixture of 2 or more types.
さらに、共重合に用いられるジオールのうち、重量平均分子量５００以上のジオールの残基に対応するものとしては、例えば、
−（ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−Ｏ）−、
−（ＣＨ２−ＣＨ（ＣＨ３）−Ｏ）−、
−（ＣＨ２−ＣＨ２−Ｏ）−、
−（ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−Ｏ）−、
−（ＣＨ２−ＣＨ（ＣＨ３）−Ｏ）ａ−（ＣＨ２−ＣＨ２−Ｏ）ｂ− （ａ／ｂ＝９／１〜１／９ｍｏｌ％）、
−［ＣＯ−（ＣＨ２）４−ＣＯ−Ｏ−（ＣＨ２）２−Ｏ］−、
−［ＣＯ−（ＣＨ２）４−ＣＯ−Ｏ−（ＣＨ２）２−Ｏ−（ＣＨ２）２−Ｏ］−、
−［ＣＯ−（ＣＨ２）４−ＣＯ−Ｏ−ＣＨ２−ＣＨ（ＣＨ３）−Ｏ］−、
−［ＣＯ−（ＣＨ２）４−ＣＯ−Ｏ−（ＣＨ２）４−Ｏ］−、
−［ＣＯ−（ＣＨ２）４−ＣＯ−Ｏ−（ＣＨ２）６−Ｏ］−、
−［ＣＯ−（ＣＨ２）４−ＣＯ−Ｏ−ＣＨ２−Ｃ（ＣＨ３）２−ＣＨ２−Ｏ］−、
−［ＣＯ−（ＣＨ２）８−ＣＯ−Ｏ−（ＣＨ２）６−Ｏ］−、
−［ＣＯ−（ＣＨ２）５−Ｏ］−、
−［ＣＯ−Ｏ−（ＣＨ２）６−Ｏ］−、
−Ｒ３−（Ｓｉ（ＣＨ３）２−Ｏ）−Ｒ３− （Ｒ３は炭素数１〜１０の有機基）
等の繰り返し単位を有する重量平均分子量５００以上のジオールが挙げられる。これらのジオールは１種を単独で、又は２種以上を混合して用いることができる。また、このようなジオールの重量平均分子量は５００〜５，０００であることが好ましく、１，０００〜２，０００であることがより好ましい。
Furthermore, among the diols used for copolymerization, those corresponding to residues of diols having a weight average molecular weight of 500 or more include, for example:
- (CH 2 -CH 2 -CH 2 -CH 2 -O) -,
- (CH 2 -CH (CH 3 ) -O) -,
- (CH 2 -CH 2 -O) -,
- (CH 2 -CH 2 -CH 2 -CH 2 -O) -,
- (CH 2 -CH (CH 3 ) -O) a - (CH 2 -CH 2 -O) b - (a / b = 9 / 1~1 / 9mol%),
- [CO- (CH 2) 4 -CO-O- (CH 2) 2 -O] -,
- [CO- (CH 2) 4 -CO-O- (CH 2) 2 -O- (CH 2) 2 -O] -,
- [CO- (CH 2) 4 -CO-O-CH 2 -CH (CH 3) -O] -,
- [CO- (CH 2) 4 -CO-O- (CH 2) 4 -O] -,
- [CO- (CH 2) 4 -CO-O- (CH 2) 6 -O] -,
- [CO- (CH 2) 4 -CO-O-CH 2 -C (CH 3) 2 -CH 2 -O] -,
- [CO- (CH 2) 8 -CO-O- (CH 2) 6 -O] -,
- [CO- (CH 2) 5 -O] -,
- [CO-O- (CH 2 ) 6 -O] -,
—R 3 — (Si (CH 3 ) 2 —O) —R 3 — (R 3 is an organic group having 1 to 10 carbon atoms)
A diol having a weight average molecular weight of 500 or more having a repeating unit such as These diols can be used alone or in combination of two or more. Moreover, it is preferable that the weight average molecular weights of such a diol are 500-5,000, and it is more preferable that it is 1,000-2,000.
（Ａ）ウレタン樹脂は、例えば、上述のジイソシアネート及びジオールを５０〜１００℃で１〜１０時間反応させることにより得られる。反応には、場合により有機すず等の一般的にウレタン合成に使用される触媒を用いてもよい。また、原料及び／又は生成物が可溶な溶媒中で反応を行ってもよい。さらに、場合により、１価のアルコール、オキシム、アミン、イソシアネート等をさらに添加し反応させることにより、（Ａ）ウレタン樹脂の末端を修飾することもできる。 (A) A urethane resin is obtained by making the above-mentioned diisocyanate and diol react at 50-100 degreeC for 1 to 10 hours, for example. In the reaction, a catalyst generally used for urethane synthesis such as organic tin may be used in some cases. Moreover, you may react in the solvent in which a raw material and / or a product are soluble. Furthermore, the terminal of (A) urethane resin can also be modified by adding and reacting monohydric alcohol, oxime, amine, isocyanate, etc. depending on the case.
上述の反応に用いるジイソシアネートとジオールの組成比について、ジイソシアネート１．０ｍｏｌに対してジオールは０．７〜１．３ｍｏｌであることが好ましく、０．９〜１．１ｍｏｌであることがより好ましい。また、ジオール成分中、上述の（メタ）アクリレート変性エポキシ化合物は、１０〜９０ｍｏｌ％であることが好ましく、３０〜７０ｍｏｌ％であることがより好ましい。さらに、ジオール成分中、上述の重量平均分子量５００以上のジオールは、１０〜９０ｍｏｌ％であることが好ましく、３０〜７０ｍｏｌ％であることがより好ましい。 Regarding the composition ratio of the diisocyanate and the diol used in the above reaction, the diol is preferably 0.7 to 1.3 mol, more preferably 0.9 to 1.1 mol, relative to 1.0 mol of the diisocyanate. Moreover, it is preferable that it is 10-90 mol% in the above-mentioned (meth) acrylate modified epoxy compound in a diol component, and it is more preferable that it is 30-70 mol%. Furthermore, in the diol component, the diol having a weight average molecular weight of 500 or more is preferably 10 to 90 mol%, and more preferably 30 to 70 mol%.
（Ｂ）硬化剤は光照射又は加熱により遊離ラジカルを発生するものである。このような硬化剤としては、例えば、過酸化物及びアゾ化合物等が挙げられる。これらの硬化剤は、目的とする接続温度、接続時間、保存安定性等を考慮し適宜選択されるが、高反応性と保存安定性の点から、半減期１０時間の温度が、４０℃以上であり、かつ半減期１分の温度が１８０℃以下である有機過酸化物が好ましく、半減期１０時間の温度が、５０℃以上であり、かつ半減期１分の温度が１７０℃以下である有機過酸化物が特に好ましい。 (B) The curing agent generates free radicals by light irradiation or heating. Examples of such curing agents include peroxides and azo compounds. These curing agents are appropriately selected in consideration of the intended connection temperature, connection time, storage stability, etc. From the viewpoint of high reactivity and storage stability, the temperature of a half-life of 10 hours is 40 ° C. or higher. An organic peroxide having a half-life temperature of 1 minute or less is preferably 180 ° C. or less, a half-life time of 10 hours is 50 ° C. or more, and a half-life temperature of 1 minute is 170 ° C. or less Organic peroxides are particularly preferred.
本発明の接着剤組成物において、（Ｂ）硬化剤の含有量は、接着剤組成物の固形分全量を基準として、１〜２０質量％であることが好ましく、２〜１５質量％であることがより好ましい。（Ｂ）硬化剤の含有量を上記範囲内とすることにより、接着剤組成物を用いた回路部材同士の接続をより短時間で行うことができ、例えば、１６０℃、１０秒間の接続条件で十分な反応率を得ることができる。 In the adhesive composition of the present invention, the content of the (B) curing agent is preferably 1 to 20% by mass, and 2 to 15% by mass based on the total solid content of the adhesive composition. Is more preferable. (B) By making 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, for example on the connection conditions of 160 degreeC and 10 second. A sufficient reaction rate can be obtained.
本発明で使用される有機過酸化物の具体例としては、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル、パーオキシケタール、ジアルキルパーオキサイド、ハイドロパーオキサイド、シリルパーオキサイド等が挙げられる。これらの中で、パーオキシエステル、ジアルキルパーオキサイド、ハイドロパーオキサイド及びシリルパーオキサイドは、開始剤中の塩素イオンや有機酸が５０００ｐｐｍ以下であり、加熱分解後に発生する有機酸が少なく、回路部材の接続端子の腐食を抑えることができるため特に好ましい。 Specific examples of the organic peroxide used in the present invention include diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide, and the like. Among these, peroxyesters, dialkyl peroxides, hydroperoxides, and silyl peroxides contain 5000 ppm or less of chlorine ions and organic acids in the initiator, and less organic acids are generated after thermal decomposition. This is particularly preferable because corrosion of the connection terminal can be suppressed.
ジアシルパーオキサイドとしては、例えば、イソブチルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、スクシニックパーオキサイド、ベンゾイルパーオキシトルエン、ベンゾイルパーオキサイド等が挙げられる。 Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and succinic peroxide. , Benzoylperoxytoluene, benzoyl peroxide and the like.
パーオキシジカーボネートとしては、例えば、ジ−ｎ−プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ジ−２−エトキシメトキシパーオキシジカーボネート、ジ（２−エチルヘキシルパーオキシ）ジカーボネート、ジメトキシブチルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチルパーオキシ）ジカーボネート等が挙げられる。 Examples of peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, Examples include di (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, and the like.
パーオキシエステルとしては、例えば、クミルパーオキシネオデカノエート、１，１，３，３−テトラメチルブチルパーオキシネオデカノエート、１−シクロヘキシル−１−メチルエチルパーオキシノエデカノエート、ｔ−ヘキシルパーオキシネオデカノエート、ｔ−ブチルパーオキシピバレート、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノネート、２，５−ジメチル−２，５−ジ（２−エチルヘキサノイルパーオキシ）ヘキサン、１−シクロヘキシル−１−メチルエチルパーオキシ−２−エチルヘキサノネート、ｔ−ヘキシルパーオキシ−２−エチルヘキサノネート、ｔ−ブチルパーオキシ−２−エチルヘキサノネート、ｔ−ブチルパーオキシイソブチレート、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｔ−ヘキシルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノネート、ｔ−ブチルパーオキシラウレート、２，５−ジメチル−２，５−ジ（ｍ−トルオイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート、ｔ−ヘキシルパーオキシベンゾエート、ｔ−ブチルパーオキシアセテート等が挙げられる。 Examples of peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t -Hexylperoxyneodecanoate, t-butylperoxypivalate, 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-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane Sun, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanonate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m- Toluoyl peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate and the like.
パーオキシケタールとしては、例えば、１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−（ｔ−ブチルパーオキシ）シクロドデカン、２，２−ビス（ｔ−ブチルパーオキシ）デカン等が挙げられる。 Examples of peroxyketals include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis ( t-Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like.
ジアルキルパーオキサイドとしては、例えば、α，α’−ビス（ｔ−ブチルパーオキシ）ジイソプロピルベンゼン、ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ｔ−ブチルクミルパーオキサイド等が挙げられる。 Examples of the dialkyl peroxide include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t -Butyl cumyl peroxide etc. are mentioned.
ハイドロパーオキサイドとしては、例えば、ジイソプロピルベンゼンハイドロパーオキサイド、クメンハイドロパーオキサイド等が挙げられる。 Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
シリルパーオキサイドとしては、例えば、ｔ−ブチルトリメチルシリルパーオキサイド、ビス（ｔ−ブチル）ジメチルシリルパーオキサイド、ｔ−ブチルトリビニルシリルパーオキサイド、ビス（ｔ−ブチル）ジビニルシリルパーオキサイド、トリス（ｔ−ブチル）ビニルシリルパーオキサイド、ｔ−ブチルトリアリルシリルパーオキサイド、ビス（ｔ−ブチル）ジアリルシリルパーオキサイド、トリス（ｔ−ブチル）アリルシリルパーオキサイド等が挙げられる。 Examples of the silyl peroxide include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, tris (t- Examples include butyl) vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide, and tris (t-butyl) allylsilyl peroxide.
また、接着剤組成物が回路接続材料として使用される場合には、回路部材の接続端子（回路電極）の腐食を抑えるために、（Ｂ）硬化剤中に含有される塩素イオンや有機酸は５０００ｐｐｍ以下であることが好ましく、さらに、加熱分解後に発生する有機酸が少ないものが好ましい。また、作製した回路接続材料の安定性が向上することから、室温、常圧下で２４時間の開放放置後の（Ｂ）硬化剤の質量保持率は２０質量％であることが好ましい。 In addition, when the adhesive composition is used as a circuit connection material, in order to suppress corrosion of the connection terminals (circuit electrodes) of the circuit member, (B) chlorine ions and organic acids contained in the curing agent are It is preferably 5000 ppm or less, and more preferably less organic acid generated after thermal decomposition. Moreover, since the stability of the produced circuit connection material improves, it is preferable that the mass retention rate of the (B) hardening | curing agent after leaving open at room temperature and a normal pressure for 24 hours is 20 mass%.
上述の（Ｂ）硬化剤は、１種を単独で又は２種以上を混合して用いることができ、分解促進剤、抑制剤等を混合して用いてもよい。また、これらの硬化剤をポリウレタン系、ポリエステル系の高分子物質等で被覆してマイクロカプセル化したものは、可使時間が延長されるために好ましい。 The above-mentioned (B) curing agent can be used singly or in combination of two or more, and may be used by mixing a decomposition accelerator, an inhibitor and the like. In addition, those encapsulating these curing agents with polyurethane-based or polyester-based polymeric substances and the like and microencapsulated are preferable because the pot life is extended.
本発明の接着剤組成物における（Ａ）ポリウレタン樹脂と（Ｂ）硬化剤との含有比は、質量比で（Ａ）：（Ｂ）＝１：９９〜９９：１であることが好ましく、１０：９０〜９０：１０であることがより好ましい。 The content ratio of (A) polyurethane resin and (B) curing agent in the adhesive composition of the present invention is preferably (A) :( B) = 1: 99 to 99: 1 in terms of mass ratio. : More preferably, it is 90-90: 10.
また、本発明の接着剤組成物には、接着剤組成物の物性及び接着性の向上を目的として、（Ｃ）熱可塑性樹脂及び／又は熱可塑性エラストマーをさらに添加してもよい。 In addition, for the purpose of improving the physical properties and adhesiveness of the adhesive composition, (C) a thermoplastic resin and / or a thermoplastic elastomer may be further added to the adhesive composition of the present invention.
熱可塑性樹脂としては、例えば、ビスフェノールＡ型フェノキシ樹脂やビスフェノールＦ型フェノキシ樹脂、ビスフェノールＡ・ビスフェノールＦ共重合型フェノキシ樹脂等の汎用フェノキシ樹脂類、ポリメタクリレート類、ポリアクリレート類、ポリイミド類、ポリウレタン類、ポリエステル類、ポリビニルブチラール等が挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いることができる。 Examples of the thermoplastic resin include general-purpose phenoxy resins such as bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A / bisphenol F copolymer type phenoxy resin, polymethacrylates, polyacrylates, polyimides, and polyurethanes. , Polyesters, polyvinyl butyral, and the like. These can be used individually by 1 type or in combination of 2 or more types.
さらに、これら熱可塑性樹脂中にはシロキサン結合やフッ素置換基が含まれていても良い。これらは、混合する樹脂同士が完全に相溶するか、又はミクロ相分離が生じて白濁する状態であれば、より好適に用いることができる。上記熱可塑性樹脂の分子量は特に制限を受けるものではないが、一般的な平均分子量としては５，０００〜１５０，０００が好ましく、１０，０００〜８０，０００がより好ましい。この値が、５，０００未満では接着剤組成物の物性が低下する傾向があり、また１５０，０００を超えると他の成分との相溶性が悪くなる傾向がある。 Furthermore, these thermoplastic resins may contain siloxane bonds or fluorine substituents. These can be more suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and the liquid becomes cloudy. The molecular weight of the thermoplastic resin is not particularly limited, but a general average molecular weight is preferably 5,000 to 150,000, and more preferably 10,000 to 80,000. If this value is less than 5,000, the physical properties of the adhesive composition tend to decrease, and if it exceeds 150,000, the compatibility with other components tends to deteriorate.
熱可塑性エラストマーとしては、例えば、ＳＢＳ及びそのエポキシ変性体や、ＳＥＢＳ及びその変性体等が挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いることができる。 Examples of the thermoplastic elastomer include SBS and its epoxy-modified product, SEBS and its modified product, and the like. These can be used individually by 1 type or in combination of 2 or more types.
本発明の接着剤組成物における（Ｃ）熱可塑性樹脂及び／又は熱可塑性エラストマーの含有量は、（Ａ）ポリウレタン樹脂１００質量部に対して２０〜３２０質量部とすることが好ましい。この含有量が、２０質量部未満又は３２０質量部を超える場合は、接着剤組成物の流動性や接着性が低下する傾向がある。 The content of the (C) thermoplastic resin and / or thermoplastic elastomer in the adhesive composition of the present invention is preferably 20 to 320 parts by mass with respect to 100 parts by mass of the (A) polyurethane resin. When this content is less than 20 parts by mass or more than 320 parts by mass, the fluidity and adhesiveness of the adhesive composition tend to decrease.
さらに、本発明の接着剤組成物には、接着剤組成物の接続信頼性の向上を目的として、（Ｄ）ラジカル重合性物質をさらに添加してもよい。 Furthermore, you may further add (D) radically polymerizable substance to the adhesive composition of this invention for the purpose of the improvement of the connection reliability of an adhesive composition.
（Ｄ）ラジカル重合性物質は、ラジカルにより重合する官能基を有する物質であり、例えば、（メタ）アクリレート樹脂、マレイミド樹脂、シトラコンイミド樹脂、ナジイミド樹脂等の樹脂が挙げられる。これらは、１種を単独で又は２種以上を混合して用いることができる。また、このラジカル重合性物質は、モノマー、オリゴマーのいずれの状態でも使用することができ、モノマーとオリゴマーとを混合して用いてもよい。 (D) A radically polymerizable substance is a substance having a functional group that is polymerized by radicals, and examples thereof include resins such as (meth) acrylate resins, maleimide resins, citraconic imide resins, and nadiimide resins. These can be used individually by 1 type or in mixture of 2 or more types. Moreover, this radically polymerizable substance can be used in any state of a monomer and an oligomer, and a monomer and an oligomer may be mixed and used.
（メタ）アクリレート樹脂は、（メタ）アクリレートをラジカル重合させることで得られるものである。（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、エテレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチレングリコールテトラ（メタ）アクリレート、２−ヒドロキシ−１，３−ジアクリロキシプロパン、２，２−ビス［４−（アクリロキシメトキシ）フェニル］プロパン、２，２−ビス［４−（アクリロキシエトキシ）フェニル］プロパン、ジシクロペンテニル（メタ）アクリレートトリシクロデカニル（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、ウレタン（メタ）アクリテート、イソシアヌル酸エチレンオキシド変性ジアクリレート等が挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いることができる。また、必要に応じて、ハイドロキノン、メチルエーテルハイドロキノン等のラジカル重合禁止剤を硬化性が損なわれない範囲で使用してもよい。 The (meth) acrylate resin is obtained by radical polymerization of (meth) acrylate. Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, etherene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 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 DOO, and the like isocyanuric acid ethylene oxide modified diacrylate. These can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use radical polymerization inhibitors, such as hydroquinone and methyl ether hydroquinone, in the range by which sclerosis | hardenability is not impaired as needed.
マレイミド樹脂は、分子中にマレイミド基を少なくとも１個有しているものであり、例えば、フェニルマレイミド、１−メチル−２，４−ビスマレイミドベンゼン、Ｎ，Ｎ’−ｍ−フェニレンビスマレイミド、Ｎ，Ｎ’−ｐ−フェニレンビスマレイミド、Ｎ，Ｎ’−４，４−ビフェニレンビスマレイミド、Ｎ，Ｎ’−４，４−（３，３−ジメチルビフェニレン）ビスマレイミド、Ｎ，Ｎ’−４，４−（３，３−ジメチルジフェニルメタン）ビスマレイミド、Ｎ，Ｎ’−４，４−（３，３−ジエチルジフェニルメタン）ビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルプロパンビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルエーテルビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルスルホンビスマレイミド、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−ｓ−ブチル−３，４−（４−マレイミドフェノキシ）フェニル）プロパン、１，１−ビス（４−（４−マレイミドフェノキシ）フェニル）デカン、４，４’−シクロヘキシリデン−ビス（１−（４−マレイミドフェノキシ）フェノキシ）−２−シクロヘキシルベンゼン、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）ヘキサフルオロプロパン等が挙げられる。これらは、１種を単独で又は２種以上を混合して用いることができる。 The maleimide resin has at least one maleimide group in the molecule. For example, phenylmaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N , N′-p-phenylene bismaleimide, N, N′-4,4-biphenylene bismaleimide, 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-diphenylmethane bismaleimide, N, N ′ -4,4-diphenylpropane bismaleimide, N, N'-4,4-diphenyl ether bismaleimide, N, N'-4,4-diphenylsulfur Bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-maleimidophenoxy) phenyl) propane, 1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene-bis (1- (4-maleimidophenoxy) phenoxy) -2-cyclohexylbenzene, 2,2-bis (4 -(4-maleimidophenoxy) phenyl) hexafluoropropane and the like. These can be used individually by 1 type or in mixture of 2 or more types.
シトラコンイミド樹脂は、分子中にシトラコンイミド基を少なくとも１個有しているシトラコンイミド化合物を重合させたものである。シトラコンイミド化合物としては、例えば、フェニルシトラコンイミド、１−メチル−２，４−ビスシトラコンイミドベンゼン、Ｎ，Ｎ’−ｍ−フェニレンビスシトラコンイミド、Ｎ，Ｎ’−ｐ−フェニレンビスシトラコンイミド、Ｎ，Ｎ’−４，４−ビフェニレンビスシトラコンイミド、Ｎ，Ｎ’−４，４−（３，３−ジメチルビフェニレン）ビスシトラコンイミド、Ｎ，Ｎ’−４，４−（３，３−ジメチルジフェニルメタン）ビスシトラコンイミド、Ｎ，Ｎ’−４，４−（３，３−ジエチルジフェニルメタン）ビスシトラコンイミド、Ｎ，Ｎ’−４，４−ジフェニルメタンビスシトラコンイミド、Ｎ，Ｎ’−４，４−ジフェニルプロパンビスシトラコンイミド、Ｎ，Ｎ’−４，４−ジフェニルエーテルビスシトラコンイミド、Ｎ，Ｎ’−４，４−ジフェニルスルホンビスシトラコンイミド、２，２−ビス（４−（４−シトラコンイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−ｓ−ブチル−３，４−（４−シトラコンイミドフェノキシ）フェニル）プロパン、１，１−ビス（４−（４−シトラコンイミドフェノキシ）フェニル）デカン、４，４’−シクロヘキシリデン−ビス（１−（４−シトラコンイミドフェノキシ）フェノキシ）−２−シクロヘキシルベンゼン、２，２−ビス（４−（４−シトラコンイミドフェノキシ）フェニル）ヘキサフルオロプロパン等が挙げられる。これらは、１種を単独で又は２種以上を混合して用いることができる。 Citraconimide resin is obtained by polymerizing a citraconic imide compound having at least one citraconic imide group in the molecule. Examples of the citraconimide compound include phenyl citraconimide, 1-methyl-2,4-biscitraconimide benzene, N, N′-m-phenylene biscitraconimide, N, N′-p-phenylene biscitraconimide, N , N′-4,4-biphenylenebiscitraconimide, N, N′-4,4- (3,3-dimethylbiphenylene) biscitraconimide, N, N′-4,4- (3,3-dimethyldiphenylmethane ) Biscitraconimide, N, N′-4,4- (3,3-diethyldiphenylmethane) biscitraconimide, N, N′-4,4-diphenylmethane biscitraconimide, N, N′-4,4-diphenyl Propane biscitraconimide, N, N'-4,4-diphenyl ether biscitraconimide, N, N'- , 4-Diphenylsulfonebiscitraconimide, 2,2-bis (4- (4-citraconimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-citraconimidephenoxy) ) Phenyl) propane, 1,1-bis (4- (4-citraconimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene-bis (1- (4-citraconimidophenoxy) phenoxy) -2-cyclohexyl Examples include benzene, 2,2-bis (4- (4-citraconimidophenoxy) phenyl) hexafluoropropane, and the like. These can be used individually by 1 type or in mixture of 2 or more types.
ナジイミド樹脂は、分子中にナジイミド基を少なくとも１個有しているナジイミド化合物を重合したものである。ナジイミド化合物としては、例えば、フェニルナジイミド、１−メチル−２，４−ビスナジイミドベンゼン、Ｎ，Ｎ’−ｍ−フェニレンビスナジイミド、Ｎ，Ｎ’−ｐ−フェニレンビスナジイミド、Ｎ，Ｎ’−４，４−ビフェニレンビスナジイミド、Ｎ，Ｎ’−４，４−（３，３−ジメチルビフェニレン）ビスナジイミド、Ｎ，Ｎ’−４，４−（３，３−ジメチルジフェニルメタン）ビスナジイミド、Ｎ，Ｎ’−４，４−（３，３−ジエチルジフェニルメタン）ビスナジイミド、Ｎ，Ｎ’−４，４−ジフェニルメタンビスナジイミド、Ｎ，Ｎ’−４，４−ジフェニルプロパンビスナジイミド、Ｎ，Ｎ’−４，４−ジフェニルエーテルビスナジイミド、Ｎ，Ｎ’−４，４−ジフェニルスルホンビスナジイミド、２，２−ビス（４−（４−ナジイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−ｓ−ブチル−３，４−（４−ナジイミドフェノキシ）フェニル）プロパン、１，１−ビス（４−（４−ナジイミドフェノキシ）フェニル）デカン、４，４’−シクロヘキシリデン−ビス（１−（４−ナジイミドフェノキシ）フェノキシ）−２−シクロヘキシルベンゼン、２，２−ビス（４−（４−ナジイミドフェノキシ）フェニル）ヘキサフルオロプロパン等が挙げられる。これらは、１種を単独で又は２種以上を混合して用いることができる。 The nadiimide resin is obtained by polymerizing a nadiimide compound having at least one nadiimide group in the molecule. Examples of the nadiimide compound include phenyl nadiimide, 1-methyl-2,4-bisnadiimidebenzene, N, N′-m-phenylenebisnadiimide, N, N′-p-phenylenebisnadiimide, N, N′— 4,4-biphenylenebisnadiimide, N, N′-4,4- (3,3-dimethylbiphenylene) bisnadiimide, N, N′-4,4- (3,3-dimethyldiphenylmethane) bisnadiimide, N, N ′ -4,4- (3,3-diethyldiphenylmethane) bisnadiimide, N, N'-4,4-diphenylmethane bisnadiimide, N, N'-4,4-diphenylpropane bisnadiimide, N, N'-4,4 -Diphenyl ether bisnadiimide, N, N'-4,4-diphenylsulfone bisnadiimide, 2,2-bis (4- (4-nazii Dophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-3,4- (4-nadiimidophenoxy) phenyl) propane, 1,1-bis (4- (4-nadiimidophenoxy) phenyl ) Decane, 4,4′-cyclohexylidene-bis (1- (4-nadiimidophenoxy) phenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4-nadiimidophenoxy) phenyl) hexafluoro Examples include propane. These can be used individually by 1 type or in mixture of 2 or more types.
上述の樹脂を（Ｄ）ラジカル重合性物質として用いた場合、その含有量は、接着剤組成物の固形分全量を基準として、好ましくは１０〜９０質量％であり、より好ましくは３０〜７０質量％である。 When the above-mentioned resin is used as the radically polymerizable substance (D), the content thereof is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, based on the total solid content of the adhesive composition. %.
さらに、（Ｄ）ラジカル重合性物質としては、金属等無機物を被着体として用いた場合の接着剤組成物の接着性を向上させるために、上述のラジカル重合性物質と、リン酸エステル構造を有するラジカル重合性物質とを組み合わせて用いることが好ましい。リン酸エステル構造を有するラジカル重合性物質としては、例えば、無水リン酸と２−ヒドロキシエチル（メタ）アクリレートの反応生成物を用いることができる。リン酸エステル構造を有するラジカル重合性物質の具体例としては、モノ（２−メタクリロイルオキシエチル）アシッドホスフェート、ジ（２−メタクリロイルオキシエチル）アシッドホスフェート等が挙げられる。これらは、１種を単独で又は２種以上を混合して用いることができる。 Furthermore, as the radically polymerizable substance (D), in order to improve the adhesiveness of the adhesive composition when an inorganic substance such as a metal is used as an adherend, the radically polymerizable substance described above and a phosphate ester structure are used. It is preferable to use it in combination with the radically polymerizable substance it has. As a radically polymerizable substance having a phosphate ester structure, for example, a reaction product of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate can be used. Specific examples of the radical 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.
リン酸エステル構造を有するラジカル重合性物質を（Ｄ）ラジカル重合性物質として用いた場合、その含有量は、接着剤組成物の固形分全量を基準として、好ましくは０．１〜１０質量％であり、より好ましくは０．５〜５質量％である。 When the radical polymerizable substance having a phosphate ester structure is used as the radical polymerizable substance (D), the content is preferably 0.1 to 10% by mass based on the total solid content of the adhesive composition. Yes, more preferably 0.5 to 5% by mass.
本発明の接着剤組成物には、導電性又は異方導電性を付与することを目的として（Ｅ）導電粒子をさらに添加してもよい。この導電粒子としては、例えば、シリカ、三酸化二アンチモン、金、銀、銅、ニッケル、アルミニウム、ステンレス、カーボン、セラミック、又は上記金属、非導電性のガラス、セラッミク、プラスチック等を核としこの核に上記金属やカーボンを被覆したものが挙げられる。これらは、１種を単独で又は２種以上を混合して用いることができる。 (E) Conductive particles may be further added to the adhesive composition of the present invention for the purpose of imparting conductivity or anisotropic conductivity. Examples of the conductive particles include silica, antimony trioxide, gold, silver, copper, nickel, aluminum, stainless steel, carbon, ceramic, or the above metal, non-conductive glass, ceramic, plastic, etc. And those coated with the above metals and carbon. These can be used individually by 1 type or in mixture of 2 or more types.
本発明の接着剤組成物における（Ｅ）導電粒子の含有量は、接着剤組成物の固形分全体積を基準として０．１〜５０体積％であることが好ましい。 The content of the conductive particles (E) in the adhesive composition of the present invention is preferably 0.1 to 50% by volume based on the total solid content of the adhesive composition.
接着剤組成物には、適宜、軟化剤、促進剤、老化防止剤、着色剤、難燃剤、カップリング剤、フィラー等のような添加剤をさらに添加してもよい。 An additive such as a softening agent, an accelerator, an anti-aging agent, a colorant, a flame retardant, a coupling agent, and a filler may be further added to the adhesive composition as appropriate.
接着剤組成物は、常温で液状である場合にはペースト状で使用することができる。室温で固体の場合には、加熱して使用する他、溶剤を用いてペースト化してもよい。使用できる溶剤としては、上述の成分と反応性がなく、かつ十分な溶解性を示すものであれば、特に制限は受けないが、常圧での沸点が５０〜１５０℃であるものが好ましい。沸点が５０℃未満の場合、室温で放置すると揮発する恐れがあり、開放系での使用が制限される。また、沸点が１５０℃を超えると、溶剤を揮発させることが難しく、接着後の信頼性に悪影響を及ぼすおそれがある。 The adhesive composition can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, it may be heated and used, or may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it is not reactive with the above-described components and exhibits sufficient solubility, but a solvent having a boiling point of 50 to 150 ° C. at normal pressure is preferable. If the boiling point is less than 50 ° C., it may volatilize if left at room temperature, which limits the use in an open system. On the other hand, if the boiling point exceeds 150 ° C., it is difficult to volatilize the solvent, which may adversely affect the reliability after bonding.
接着剤組成物はフィルム状にして用いることもできる。その場合、接着剤組成物に必要により溶剤等を加えるなどした溶液を、フッ素樹脂フィルム、ポリエチレンテレフタレートフィルム、離形紙等の剥離性基材上に塗布し、あるいは不織布等の基材に上記溶液を含浸させて剥離性基材上に載置し、溶剤等を除去してフィルムとして使用することができる。フィルムの形状で使用すると取扱性等の点から一層便利である。 The adhesive composition can be used in the form of a film. In that case, a solution in which a solvent or the like is added to the adhesive composition as necessary is applied on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film or a release paper, or the above solution is applied to a substrate such as a nonwoven fabric. Can be impregnated and placed on a peelable substrate, and the solvent can be removed to use as a film. Use in the form of a film is more convenient from the viewpoint of handleability.
本発明の接着剤組成物は、熱膨張係数の異なる異種の被着体の接着剤として使用することができる。具体的には銀ペースト、銀フィルム、異方導電接着剤等に代表される回路接続材料、ＣＳＰ用エラストマー、ＣＳＰ用アンダーフィル材、ＬＯＣテープ、ダイボンディング用接着剤等に代表される半導体素子用接着剤として使用することができる。 The adhesive composition of the present invention can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, for semiconductor elements represented by silver paste, silver film, circuit connection materials represented by anisotropic conductive adhesive, CSP elastomer, CSP underfill material, LOC tape, die bonding adhesive, etc. Can be used as an adhesive.
以下、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
＜ウレタン樹脂（ＰＵＡ−１）の合成＞
下記化学式（ａ）で表されるエチレングリコールジグリシジルエーテルのメタクリル酸付加物（共栄社化学株式会社製、商品名エポキシエステル４０ＥＭ）（０．５ｍｏｌ）、重量平均分子量２０００のポリ（テトラメチレングリコール）（０．５ｍｏｌ）、４，４’−ジイソシアネートジフェニルメタン（０．４２５ｍｏｌ）、２，４’−ジイソシアネートジフェニルメタン（０．４２５ｍｏｌ）、ジラウリル酸ジブチルすず（０．５ｍｍｏｌ）をメチルエチルケトン（ＭＥＫ）中、６０℃で３時間反応させ、ウレタン樹脂（ＰＵＡ−１）のＭＥＫ溶液を得た。得られた樹脂のＧＰＣを測定したところ、ポリスチレン換算でＭｗ（重量平均分子量）＝６５，０００、Ｍｎ（数平均分子量）＝３５，０００であった。
<Synthesis of urethane resin (PUA-1)>
Methacrylic acid adduct of ethylene glycol diglycidyl ether represented by the following chemical formula (a) (trade name epoxy ester 40EM, manufactured by Kyoeisha Chemical Co., Ltd.) (0.5 mol), poly (tetramethylene glycol) having a weight average molecular weight of 2000 ( 0.5 mol), 4,4′-diisocyanate diphenylmethane (0.425 mol), 2,4′-diisocyanate diphenylmethane (0.425 mol), dibutyltin dilaurate (0.5 mmol) in methyl ethyl ketone (MEK) at 60 ° C. It was made to react for 3 hours and the MEK solution of urethane resin (PUA-1) was obtained. When GPC of the obtained resin was measured, it was Mw (weight average molecular weight) = 65,000 and Mn (number average molecular weight) = 35,000 in terms of polystyrene.
＜ウレタン樹脂（ＰＵＡ−２）の合成＞
エチレングリコールジグリシジルエーテルのメタクリル酸付加物の代わりに、下記化学式（ｂ）で表されるビスフェノールＡジグリシジエーテルのメタクリル酸付加物（共栄社化学株式会社製、商品名エポキシエステル３０００Ｍ）（０．５ｍｏｌ）を用いた他はＰＵＡ−１の合成と同様にして、ウレタン樹脂（ＰＵＡ−２）のＭＥＫ溶液を得た。得られた樹脂のＧＰＣを測定したところ、ポリスチレン換算で、Ｍｗ＝６０，０００、Ｍｎ＝３４，０００であった。
<Synthesis of urethane resin (PUA-2)>
Instead of methacrylic acid adduct of ethylene glycol diglycidyl ether, methacrylic acid adduct of bisphenol A diglycidyl ether represented by the following chemical formula (b) (trade name: Epoxy ester 3000M, manufactured by Kyoeisha Chemical Co., Ltd.) (0.5 mol) ) Was used in the same manner as in the synthesis of PUA-1, to obtain a MEK solution of urethane resin (PUA-2). When GPC of the obtained resin was measured, it was Mw = 60,000 and Mn = 34,000 in terms of polystyrene.
＜ウレタン樹脂（ＰＵＡ−３）の合成＞
重量平均分子量２０００のポリテトラメチレングリコール（０．５ｍｏｌ）の代わりに、重量平均分子量２０００のポリヘキサメチレンカーボネートジオール（０．５ｍｏｌ）を用いた他はＰＵＡ−１の合成と同様にして、ウレタン樹脂（ＰＵＡ−３）のＭＥＫ溶液を得た。得られた樹脂のＧＰＣを測定したところ、ポリスチレン換算で、Ｍｗ＝６４，０００、Ｍｎ＝３３，０００であった。
<Synthesis of urethane resin (PUA-3)>
A urethane resin was prepared in the same manner as in the synthesis of PUA-1, except that polyhexamethylene carbonate diol (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. A MEK solution of (PUA-3) was obtained. When GPC of the obtained resin was measured, it was Mw = 64,000 and Mn = 33,000 in terms of polystyrene.
＜ウレタン樹脂（ＰＵＡ−４）の合成＞
エチレングリコールジグリシジルエーテルのメタクリル酸付加物の物質量を０．７ｍｏｌに、重量平均分子量２０００のポリ（テトラメチレングリコール）の物質量を０．３ｍｏｌに変更した他は、ウレタン樹脂（ＰＵＡ−１）の合成と同様にして、ウレタン樹脂（ＰＵＡ−３）のＭＥＫ溶液を得た。得られた樹脂のＧＰＣを測定したところ、ポリスチレン換算でＭｗ＝５２，０００、Ｍｎ＝２４，０００であった。
<Synthesis of urethane resin (PUA-4)>
Urethane resin (PUA-1) except that the amount of methacrylic acid adduct of ethylene glycol diglycidyl ether was changed to 0.7 mol and the amount of poly (tetramethylene glycol) having a weight average molecular weight of 2000 was changed to 0.3 mol. In the same manner as in the above synthesis, an MEK solution of urethane resin (PUA-3) was obtained. When GPC of the obtained resin was measured, it was Mw = 52,000 and Mn = 24,000 in terms of polystyrene.
＜比較用ウレタン樹脂（ＰＵＡ−５）の合成＞
４，４’−ジイソシアネートジフェニルメタン（０．５ｍｏｌ）、２，４’−ジイソシアネートジフェニルメタン（０．５ｍｏｌ）、重量平均分子量２０００のポリ（テトラメチレングリコール）（０．９ｍｏｌ）、２−ヒドロキシエチルメタクリレート（０．５ｍｏｌ）、ジラウリル酸ジブチルすず（０．５ｍｍｏｌ）をメチルエチルケトン（ＭＥＫ）中、６０℃で３時間反応させ、両末端にアクリレートが付加した比較用ウレタン樹脂（ＰＵＡ−５）のＭＥＫ溶液を得た。得られた樹脂のＧＰＣを測定したところ、ポリスチレン換算でＭｗ＝５０，０００、Ｍｎ＝２０，０００であった。
<Synthesis of comparative urethane resin (PUA-5)>
4,4′-diisocyanate diphenylmethane (0.5 mol), 2,4′-diisocyanate diphenylmethane (0.5 mol), poly (tetramethylene glycol) having a weight average molecular weight of 2000 (0.9 mol), 2-hydroxyethyl methacrylate (0 0.5 mol) and dibutyltin dilaurate (0.5 mmol) were reacted in methyl ethyl ketone (MEK) at 60 ° C. for 3 hours to obtain a MEK solution of a urethane resin for comparison (PUA-5) in which acrylates were added to both ends. . When GPC of the obtained resin was measured, it was Mw = 50,000 and Mn = 20,000 in terms of polystyrene.
＜比較用ウレタン樹脂（ＰＵＡ−６）の合成＞
４，４’−ジイソシアネートジフェニルメタン（０．５ｍｏｌ）、２，４’−ジイソシアネートジフェニルメタン（０．５ｍｏｌ）、重量平均分子量２０００のポリ（テトラメチレングリコール）（０．７ｍｏｌ）、２−ヒドロキシエチルメタクリレート（０．８ｍｏｌ）、ジラウリル酸ジブチルすず（０．５ｍｍｏｌ）をメチルエチルケトン（ＭＥＫ）中、６０℃で３時間反応させ、両末端にアクリレートが付加した比較用ウレタン樹脂（ＰＵＡ−６）のＭＥＫ溶液を得た。得られた樹脂のＧＰＣを測定したところ、ポリスチレン換算でＭｗ＝９，０００、Ｍｎ＝５，０００であった。
<Synthesis of comparative urethane resin (PUA-6)>
4,4′-diisocyanate diphenylmethane (0.5 mol), 2,4′-diisocyanate diphenylmethane (0.5 mol), poly (tetramethylene glycol) (0.7 mol) having a weight average molecular weight of 2000, 2-hydroxyethyl methacrylate (0 .8 mol) and dibutyltin dilaurate (0.5 mmol) were reacted in methyl ethyl ketone (MEK) at 60 ° C. for 3 hours to obtain a MEK solution of a comparative urethane resin (PUA-6) in which acrylates were added to both ends. . When GPC of the obtained resin was measured, it was Mw = 9,000 and Mn = 5,000 in terms of polystyrene.
＜比較用ウレタン樹脂（ＰＵＡ−７）の合成＞
エチレングリコールジグリシジルエーテルのメタクリル酸付加物の物質量を１．０ｍｏｌとし、且つ重量平均分子量２０００のポリ（テトラメチレングリコール）を用いなかったこと以外は、ウレタン樹脂（ＰＵＡ−１）の合成と同様にして、ウレタン樹脂（ＰＵＡ−７）のＭＥＫ溶液を得た。得られた樹脂のＧＰＣを測定したところ、ポリスチレン換算でＭｗ＝５０，０００、Ｍｎ＝２２，０００であった。
<Synthesis of comparative urethane resin (PUA-7)>
Similar to the synthesis of urethane resin (PUA-1) except that the amount of the methacrylic acid adduct of ethylene glycol diglycidyl ether was 1.0 mol and poly (tetramethylene glycol) having a weight average molecular weight of 2000 was not used. Thus, a MEK solution of urethane resin (PUA-7) was obtained. When GPC of the obtained resin was measured, it was Mw = 50,000 and Mn = 22,000 in terms of polystyrene.
（実施例１〜４）
熱可塑性樹脂として、フェノキシ樹脂（ＰＫＨＣ、ユニオンカーバイド社製商品名、重量平均分子量４５，０００）を、ラジカル重合性物質として、イソシアヌル酸ＥＯ変性ジアクリレート（Ｍ２１５、東亜合成株式会社製商品名）、及び２−（メタ）アクリロキシエチルホスフェート（ライトエステルＰ−２Ｍ、共栄社化学株式会社製商品名）を、ウレタン樹脂として上述のＰＵＡ−１、ＰＵＡ−２、ＰＵＡ−３及びＰＵＡ−４を、硬化剤として、ｔ−ヘキシルパーオキシ−２−エチルヘキサノネートの５０質量％ＤＯＰ（ジオクチルフタレート）溶液（日本油脂株式開会社製、商品名パーキュアＨＯ）を、導電粒子として、ポリスチレンを核とする粒子の表面に、厚み０．２０μｍの金層を設けた平均粒子径４μｍ、比重２．５の導電粒子をそれぞれ準備した。
(Examples 1-4)
As a thermoplastic resin, phenoxy resin (PKHC, trade name made by Union Carbide, weight average molecular weight 45,000) is used as a radical polymerizable substance, and isocyanuric acid EO-modified diacrylate (M215, trade name made by Toa Gosei Co., Ltd.), And 2- (meth) acryloxyethyl phosphate (light ester P-2M, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) as a urethane resin, the above-mentioned PUA-1, PUA-2, PUA-3 and PUA-4 are cured. Particles with polystyrene as the core, using as conductive agent 50% by mass DOP (dioctyl phthalate) solution of t-hexylperoxy-2-ethylhexanonate (trade name Percure HO, manufactured by Nippon Oil & Fats Co., Ltd.) Conductive particles having an average particle diameter of 4 μm and a specific gravity of 2.5 provided with a 0.20 μm thick gold layer Prepared each.
ＰＫＨＣ４０ｇをメチルエチルケトン６０ｇに溶解して固形分４０質量％の溶液とした。この熱可塑性樹脂の溶液と上述のラジカル重合性物質、ウレタン樹脂及び硬化剤を、固形分についての質量比が表１に示すものとなるように配合した。さらに、導電粒子を、接着剤組成物の固形分全体積を基準として、１．５体積％配合し分散させて接着剤組成物を得た。得られた接着剤組成物を、厚み８０μｍのフッ素樹脂フィルムに、塗工装置を用いて塗布し、７０℃、１０分の熱風乾燥によって乾燥させ、接着剤組成物からなる接着剤層の厚みが１５μｍのフィルム状接着剤を作製した。 40 g of PKHC was dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by mass. This thermoplastic resin solution and the above-mentioned radical polymerizable substance, urethane resin and curing agent were blended so that the mass ratio with respect to the solid content would be as shown in Table 1. Further, the conductive particles were mixed and dispersed in an amount of 1.5% by volume based on the total solid volume of the adhesive composition to obtain an adhesive composition. The obtained adhesive composition was applied to a fluororesin film having a thickness of 80 μm using a coating apparatus, dried by hot air drying at 70 ° C. for 10 minutes, and the thickness of the adhesive layer made of the adhesive composition was A 15 μm film adhesive was prepared.
（比較例１〜３）
ウレタン樹脂としてＰＵＡ−５、ＰＵＡ−６、ＰＵＡ−７を用いたこと以外は実施例１〜３と同様にして、フィルム状接着剤を作製した。
(Comparative Examples 1-3)
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.
（回路接続構造体の作製）
上記で得られたフィルム状接着剤を、ライン幅２５μｍ、ピッチ５０μｍ、厚み１８μｍの銅回路を５００本有するフレキシブル回路板（ＦＰＣ）と、厚み０．２０μｍの酸化インジウムスズ（ＩＴＯ）の薄層を形成したガラス（厚み１．１ｍｍ、表面抵抗２０Ω／ｃｍ）との間に配置し、１７５℃、３ＭＰａで１５秒間の加熱加圧を行って幅２ｍｍにわたり接続を行い、回路接続構造体を作製した。
(Production of circuit connection structure)
The film-like adhesive obtained above is composed 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 placed between the formed glass (thickness 1.1 mm, surface resistance 20 Ω / cm), and heated and pressurized at 175 ° C. and 3 MPa for 15 seconds to make a connection over a width of 2 mm to produce a circuit connection structure. .
（接続抵抗の測定）
上記で得られた回路接続構造体の隣接回路間の抵抗値を、接着直後、及び、８５℃、８５％ＲＨの高温高湿槽中に１２０時間保持した後に、マルチメーターで測定した。抵抗値は隣接回路間の抵抗１５０点の平均値として示した。得られた結果を表２に示す。
(Measurement of connection resistance)
The resistance value between adjacent circuits of the circuit connection structure obtained above was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 120 hours. The resistance value is shown as an average value of 150 resistances between adjacent circuits. The obtained results are shown in Table 2.
（接着強度の測定）
上記で得られた回路接続構造体における回路部材間の接着強度を、ＪＩＳ−Ｚ０２３７に準じて９０度はく離法で測定した。ここで、接着強度の測定装置としては東洋ボールドウィン株式会社製テンシロンＵＴＭ−４を用い、はく離速度５０ｍｍ／ｍｉｎ、２５℃で測定した。なお、接着強度は、接着直後、及び、８５℃、８５％ＲＨの高温高湿槽中に１２０時間保持した後に測定した。得られた結果を表２に示す。
(Measurement of adhesive strength)
The adhesive strength between circuit members in the circuit connection structure obtained above was measured by a 90-degree peeling method in accordance with JIS-Z0237. Here, Tensilon UTM-4 manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength, and measurement was performed at a peeling speed of 50 mm / min and 25 ° C. The adhesive strength was measured immediately after bonding and after being kept in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 120 hours. The obtained results are shown in Table 2.
表２に示した結果から明らかなように、実施例１〜４のフィルム状接着剤を用いた場合には、低温でしかも短時間で硬化した場合（１７５℃で１５秒間）であっても接着強度が十分に高いことが確認された。これは、実施例１〜４のフィルム状接着剤により十分な接着性が得られること、及び実施例１〜４のフィルム状接着剤は上述の優れた低温速硬化性を備えることを示している。 As is apparent from the results shown in Table 2, when the film adhesives of Examples 1 to 4 were used, even when cured at a low temperature for a short time (175 ° C. for 15 seconds) It was confirmed that the strength was sufficiently high. This shows that sufficient adhesiveness is obtained by the film-like adhesives of Examples 1 to 4, and that the film-like adhesives of Examples 1 to 4 have the above-described excellent low-temperature fast curability. .
また、実施例１〜４のフィルム状接着剤を用いた場合には、回路接続構造体の隣接回路間の抵抗値が十分に低く、回路接続構造体の隣接回路間が十分に電気的接続されていることが確認された。これは、実施例１〜４のフィルム状接着剤により十分な接続信頼性が得られることを示している。 Moreover, when the film adhesives of Examples 1 to 4 are used, the resistance value between adjacent circuits of the circuit connection structure is sufficiently low, and the adjacent circuits of the circuit connection structure are sufficiently electrically connected. It was confirmed that This has shown that sufficient connection reliability is acquired with the film adhesive of Examples 1-4.
さらに、実施例１〜４のフィルム状接着剤を用いた場合には、接着直後でも高温高湿環境下に長期間おかれた後にも、十分に低い抵抗値、及び十分に高い接着強度が得られることが確認された。これは、実施例１〜４のフィルム状接着剤によれば、高温高湿環境下に長期間おかれた場合でも、接続信頼性及び接着性の低下を十分に抑制することが可能であることを示している。 Further, when the film adhesives of Examples 1 to 4 are used, a sufficiently low resistance value and a sufficiently high adhesive strength can be obtained immediately after bonding or after being placed in a high temperature and high humidity environment for a long period of time. It was confirmed that According to the film-like adhesives of Examples 1 to 4, it is possible to sufficiently suppress the deterioration of connection reliability and adhesiveness even when left in a high temperature and high humidity environment for a long time. Is shown.
これに対し、比較例１のフィルム状接着剤を用いた場合には、高温高湿環境下に長期間おかれた後の抵抗値が急激に上昇することが確認された。これは、比較例１のフィルム状接着剤の高温高湿環境下に長期間おかれた際に接続信頼性が低下することを示している。また、比較例２及び３のフィルム状接着剤を用いた場合には、接着性が不十分であることが確認された。 On the other hand, when the film adhesive of Comparative Example 1 was used, it was confirmed that the resistance value after standing for a long time in a high temperature and high humidity environment increased rapidly. This indicates that the connection reliability is lowered when the film-like adhesive of Comparative Example 1 is placed in a high temperature and high humidity environment for a long period of time. Moreover, when the film adhesives of Comparative Examples 2 and 3 were used, it was confirmed that the adhesiveness was insufficient.
以上のように、実施例１〜４及び比較例１〜３から、本発明の接着剤組成物が上述の優れた効果を有し、回路接続又は半導体実装用接着剤に好適であることは明らかである。 As described above, from Examples 1 to 4 and Comparative Examples 1 to 3, it is clear that the adhesive composition of the present invention has the above-described excellent effects and is suitable for an adhesive for circuit connection or semiconductor mounting. It is.
Claims (5)
（Ｂ）光照射又は加熱により遊離ラジカルを発生する硬化剤と、
を含有し、
前記（Ａ）ウレタン樹脂が下記一般式（Ｉ）で表される共重合体を含む接着剤組成物。
−（ＣＨ ２ −ＣＨ ２ −ＣＨ ２ −ＣＨ ２ −Ｏ）−、
−（ＣＨ ２ −ＣＨ（ＣＨ ３ ）−Ｏ）−、
−（ＣＨ ２ −ＣＨ ２ −Ｏ）−、
−（ＣＨ ２ −ＣＨ（ＣＨ ３ ）−Ｏ） ａ −（ＣＨ ２ −ＣＨ ２ −Ｏ） ｂ − （ａ／ｂ＝９／１〜１／９ｍｏｌ％）、
−［ＣＯ−（ＣＨ ２ ） ４ −ＣＯ−Ｏ−（ＣＨ ２ ） ２ −Ｏ］−、
−［ＣＯ−（ＣＨ ２ ） ４ −ＣＯ−Ｏ−（ＣＨ ２ ） ２ −Ｏ−（ＣＨ ２ ） ２ −Ｏ］−、
−［ＣＯ−（ＣＨ ２ ） ４ −ＣＯ−Ｏ−ＣＨ ２ −ＣＨ（ＣＨ ３ ）−Ｏ］−、
−［ＣＯ−（ＣＨ ２ ） ４ −ＣＯ−Ｏ−（ＣＨ ２ ） ４ −Ｏ］−、
−［ＣＯ−（ＣＨ ２ ） ４ −ＣＯ−Ｏ−（ＣＨ ２ ） ６ −Ｏ］−、
−［ＣＯ−（ＣＨ ２ ） ４ −ＣＯ−Ｏ−ＣＨ ２ −Ｃ（ＣＨ ３ ） ２ −ＣＨ ２ −Ｏ］−、
−［ＣＯ−（ＣＨ ２ ） ８ −ＣＯ−Ｏ−（ＣＨ ２ ） ６ −Ｏ］−、
−［ＣＯ−（ＣＨ ２ ） ５ −Ｏ］−、
−［ＣＯ−Ｏ−（ＣＨ ２ ） ６ −Ｏ］−、又は、
−Ｒ ３ −（Ｓｉ（ＣＨ ３ ） ２ −Ｏ）−Ｒ ３ − （Ｒ ３ は炭素数１〜１０の有機基）、
の繰り返し単位を有する重量平均分子量５００以上のジオールの残基である。］
(B) a curing agent that generates free radicals upon light irradiation or heating;
Containing
The adhesive composition in which the (A) urethane resin contains a copolymer represented by the following general formula (I).
- (CH 2 -CH 2 -CH 2 -CH 2 -O) -,
- (CH 2 -CH (CH 3 ) -O) -,
- (CH 2 -CH 2 -O) -,
- (CH 2 -CH (CH 3 ) -O) a - (CH 2 -CH 2 -O) b - (a / b = 9 / 1~1 / 9mol%),
- [CO- (CH 2) 4 -CO-O- (CH 2) 2 -O] -,
- [CO- (CH 2) 4 -CO-O- (CH 2) 2 -O- (CH 2) 2 -O] -,
- [CO- (CH 2) 4 -CO-O-CH 2 -CH (CH 3) -O] -,
- [CO- (CH 2) 4 -CO-O- (CH 2) 4 -O] -,
- [CO- (CH 2) 4 -CO-O- (CH 2) 6 -O] -,
- [CO- (CH 2) 4 -CO-O-CH 2 -C (CH 3) 2 -CH 2 -O] -,
- [CO- (CH 2) 8 -CO-O- (CH 2) 6 -O] -,
- [CO- (CH 2) 5 -O] -,
- [CO-O- (CH 2 ) 6 -O] -, or,
-R 3 - (Si (CH 3 ) 2 -O) -R 3 - (R 3 is an organic group having 1 to 10 carbon atoms),
And a diol residue having a weight average molecular weight of 500 or more. ]
−（ＣＨ-(CH ２2 −ＣＨ-CH ２2 −ＣＨ-CH ２2 −ＣＨ-CH ２2 −Ｏ）−、-O)-,
−（ＣＨ-(CH ２2 −ＣＨ（ＣＨ-CH (CH ３3 ）−Ｏ）−、又は、) -O)-or
−（ＣＨ-(CH ２2 −ＣＨ-CH ２2 −Ｏ）−、-O)-,
の繰り返し単位を有する重量平均分子量５００以上のジオールの残基である、請求項１〜４のいずれか一項に記載の接着剤組成物。The adhesive composition according to any one of claims 1 to 4, wherein the adhesive composition is a residue of a diol having a repeating unit having a weight average molecular weight of 500 or more.
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| JP2007259101A JP5067101B2 (en) | 2007-05-24 | 2007-10-02 | Adhesive composition |
| KR1020080048080A KR101081290B1 (en) | 2007-05-24 | 2008-05-23 | Adhesive composition |
| KR1020100136474A KR20110003306A (en) | 2007-05-24 | 2010-12-28 | Adhesive composition |
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| JP2007259101A JP5067101B2 (en) | 2007-05-24 | 2007-10-02 | Adhesive composition |
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| JP2011008904A (en) | 2009-05-29 | 2011-01-13 | Panasonic Corp | Optical device |
| JP5914024B2 (en) * | 2012-02-16 | 2016-05-11 | 日東電工株式会社 | Method for producing radiation-curable pressure-sensitive adhesive composition, radiation-curable pressure-sensitive adhesive composition obtained by the production method, and pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition |
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