JP2006257208A - Adhesive, adhesive for connecting circuit, connecting body and semiconductor device - Google Patents
Adhesive, adhesive for connecting circuit, connecting body and semiconductor device Download PDFInfo
- Publication number
- JP2006257208A JP2006257208A JP2005074999A JP2005074999A JP2006257208A JP 2006257208 A JP2006257208 A JP 2006257208A JP 2005074999 A JP2005074999 A JP 2005074999A JP 2005074999 A JP2005074999 A JP 2005074999A JP 2006257208 A JP2006257208 A JP 2006257208A
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- Prior art keywords
- adhesive
- weight
- meth
- general formula
- parts
- 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.)
- Granted
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- 239000000853 adhesive Substances 0.000 title claims abstract description 82
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 77
- 239000004065 semiconductor Substances 0.000 title claims abstract description 31
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 11
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 9
- -1 acrylate compound Chemical class 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims 1
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical class [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 35
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920006287 phenoxy resin Polymers 0.000 description 3
- 239000013034 phenoxy resin Substances 0.000 description 3
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- ZVYSYCLZXICWLH-UHFFFAOYSA-N 1,3-dioxetan-2-one Chemical compound O=C1OCO1 ZVYSYCLZXICWLH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 2
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 1
- RPNDKNJEUSJAMT-UHFFFAOYSA-N (2,2,3,3-tetramethylpiperidin-1-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON1CCCC(C)(C)C1(C)C RPNDKNJEUSJAMT-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MVELOSYXCOVILT-UHFFFAOYSA-N (4-hydroxy-2-methylpentan-2-yl) 7,7-dimethyloctaneperoxoate Chemical compound CC(O)CC(C)(C)OOC(=O)CCCCCC(C)(C)C MVELOSYXCOVILT-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- JVNHNXXTIIQWBZ-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2,3-dimethylbutanenitrile Chemical compound CC(C)C(C)(C#N)N=NC(C)(C)C#N JVNHNXXTIIQWBZ-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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-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
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ZIDNXYVJSYJXPE-UHFFFAOYSA-N 2-methylbutan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)(C)C ZIDNXYVJSYJXPE-UHFFFAOYSA-N 0.000 description 1
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-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
- KPKMKACZPZUNDP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical class OP(O)(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O KPKMKACZPZUNDP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- HBWITNNIJDLPLS-UHFFFAOYSA-N 4-[1-[4-(dimethylamino)phenyl]ethenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(=C)C1=CC=C(N(C)C)C=C1 HBWITNNIJDLPLS-UHFFFAOYSA-N 0.000 description 1
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- YOQPKXIRWPWFIE-UHFFFAOYSA-N ctk4c8335 Chemical compound CC(=C)C(=O)OCCOP(=O)=O YOQPKXIRWPWFIE-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 150000004059 quinone derivatives Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920003002 synthetic resin 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
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
- H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01005—Boron [B]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01015—Phosphorus [P]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01019—Potassium [K]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01067—Holmium [Ho]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
- H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
- H01L2924/1901—Structure
- H01L2924/1904—Component type
- H01L2924/19042—Component type being an inductor
Landscapes
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Combinations Of Printed Boards (AREA)
- Wire Bonding (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、接着剤、回路接続用接着剤、接続体及び半導体装置に関する。 The present invention relates to an adhesive, an adhesive for circuit connection, a connection body, and a semiconductor device.
半導体素子及び液晶表示素子において、素子中の種々の部材を結合させる目的で従来から種々の接着剤が使用されている。接着剤に対する要求は、接着性をはじめとして、耐熱性、高温高湿状態における信頼性等多岐に渡る特性が要求されている。また、接着に使用される被着体は、プリント配線板やポリイミド等の有機基材をはじめ、銅、アルミニウム等の金属やＩＴＯ、Ｓｉ３Ｎ４、ＳｉＯ２等の多種多様な表面状態を有する基材が用いられ、各被着体にあわせた分子設計が必要である。
従来から、前記の半導体素子や液晶表示素子用の接着剤としては、高接着性でかつ高信頼性を示すエポキシ樹脂を用いた熱硬化性樹脂が用いられてきた（例えば、特許文献１参照）。樹脂の構成成分としては、エポキシ樹脂、エポキシ樹脂と反応性を有するフェノール樹脂等の硬化剤、エポキシ樹脂と硬化剤の反応を促進する熱潜在性触媒が一般に用いられている。熱潜在性触媒は硬化温度及び硬化速度を決定する重要な因子となっており、室温での貯蔵安定性と加熱時の硬化速度の観点から種々の化合物が用いられてきた。実際の工程での硬化条件は、１７０〜２５０℃の温度で１〜３時間硬化することにより、所望の接着を得ていた。しかしながら、最近の半導体素子の高集積化、液晶表示素子の高精細化に伴い、素子間及び配線間ピッチが狭小化し、硬化時の加熱によって、周辺部材に悪影響を及ぼす恐れが出てきた。さらに低コスト化のためには、スループットを向上させる必要性があり、より低温でかつ短時間での硬化、換言すれば低温速硬化での接着が要求されている。この低温速硬化を達成するためには、活性化エネルギーの低い熱潜在性触媒を使用する必要があるが、室温付近での貯蔵安定性を兼備することが非常に難しいことが知られている。
最近、アクリレート誘導体やメタアクリレート誘導体(以後(メタ)アクリレート誘導体と呼ぶ)等のラジカル重合性化合物とラジカル重合開始剤である過酸化物を併用した、ラジカル硬化型接着剤が注目されている。ラジカル硬化は、反応活性種であるラジカルが反応性に富むため、短時間硬化が可能である（例えば、特許文献２参照）。一方で、ラジカル硬化系の接着剤は、硬化時の硬化収縮が大きいために、エポキシ樹脂を用いた場合と比較して、接着強度に劣る。接着強度の改良方法として、エーテル結合によって柔軟性及び可とう性を付与したウレタンアクリレート化合物をラジカル重合性化合物として使用する方法が提案されている(特許文献３、４参照)。
In the semiconductor element and the liquid crystal display element, various adhesives are conventionally used for the purpose of bonding various members in the element. The adhesives are required to have various properties such as adhesiveness, heat resistance, reliability in a high temperature and high humidity state. Further, adherends used for bonding have various surface states such as printed wiring boards and organic base materials such as polyimide, metals such as copper and aluminum, ITO, Si 3 N 4 and SiO 2. A base material is used, and molecular design according to each adherend is required.
Conventionally, as the adhesive for the semiconductor element and the liquid crystal display element, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used (for example, see Patent Document 1). . As a constituent component of the resin, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst for promoting the reaction between the epoxy resin and the curing agent are generally used. The heat latent catalyst is an important factor for determining the curing temperature and the curing rate, and various compounds have been used from the viewpoint of storage stability at room temperature and curing rate during heating. The curing conditions in the actual process were that desired adhesion was obtained by curing at a temperature of 170 to 250 ° C. for 1 to 3 hours. However, with the recent high integration of semiconductor elements and high definition of liquid crystal display elements, the pitch between elements and wirings has become narrower, and there has been a risk of adversely affecting peripheral members due to heating during curing. In order to further reduce the cost, it is necessary to improve the throughput, and there is a demand for curing at a lower temperature and in a shorter time, in other words, adhesion at a lower temperature and faster curing. In order to achieve this low temperature rapid curing, it is necessary to use a thermal latent catalyst having a low activation energy, but it is known that it is very difficult to combine storage stability near room temperature.
Recently, radical curable adhesives using radically polymerizable compounds such as acrylate derivatives and methacrylate derivatives (hereinafter referred to as (meth) acrylate derivatives) and peroxides as radical polymerization initiators have attracted attention. Radical curing can be cured for a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Document 2). On the other hand, since radical curing type adhesive has large curing shrinkage at the time of curing, it is inferior in adhesive strength as compared with the case of using an epoxy resin. As a method for improving the adhesive strength, a method has been proposed in which a urethane acrylate compound imparted with flexibility and flexibility by an ether bond is used as a radical polymerizable compound (see Patent Documents 3 and 4).
しかしながら、前記ウレタンアクリレートを使用した場合、分子内にエーテル結合を有しているため硬化後の弾性率やガラス転移温度等の接着剤物性が低下し、さらに吸水率上昇や耐加水分解性が低下する問題がある。このため、高温高湿条件(例えば８５℃／８５％ＲＨ)で長時間の暴露後も安定した性能が要求される半導体素子や液晶表示素子の接着剤に使用した場合、信頼性試験後に接着力や接続抵抗等の特性が悪化する。 However, when the urethane acrylate is used, since it has an ether bond in the molecule, the adhesive physical properties such as the elastic modulus after curing and the glass transition temperature are lowered, and further, the water absorption is increased and the hydrolysis resistance is lowered. There is a problem to do. For this reason, when used in adhesives for semiconductor elements and liquid crystal display elements that require stable performance even after prolonged exposure under high temperature and high humidity conditions (for example, 85 ° C./85% RH) And characteristics such as connection resistance deteriorate.
本発明は、ラジカル硬化系でありながら、高い接着強度を示し、かつ信頼性試験（例えば８５℃／８５%ＲＨ放置）後においても安定した性能を有し、さらに貯蔵安定性にも優れる接着剤、回路接続用接着剤、接続体及び半導体装置を提供するものである。 INDUSTRIAL APPLICABILITY The present invention is a radical curing system that exhibits high adhesive strength, has stable performance even after a reliability test (for example, left at 85 ° C./85% RH), and is excellent in storage stability. An adhesive for circuit connection, a connection body, and a semiconductor device are provided.
本発明は、［１］ （ａ）熱可塑性樹脂、（ｂ）下記一般式（Ｂ）及び／または（Ｃ）の構造を含み且つ分子中に２個以上の（メタ）アクリロイル基及び２個以上のウレタン結合を有するラジカル重合性物質、（ｃ）ラジカル重合開始剤を含む接着剤に関する。 The present invention provides [1] (a) a thermoplastic resin, (b) a structure containing the following general formula (B) and / or (C), and two or more (meth) acryloyl groups and two or more in the molecule: And (c) an adhesive containing a radical polymerization initiator.
また、本発明は、［２］ （ｂ）のラジカル重合性物質が下記一般式（Ａ）で表されるウレタン（メタ）アクリレート化合物である上記［１］に記載の接着剤に関する。
Moreover, this invention relates to the adhesive agent as described in said [1] whose radically polymerizable substance of [2] (b) is a urethane (meth) acrylate compound represented by the following general formula (A).
（一般式（Ａ）中、Ｒ1は、水素またはメチル基、Ｌは、１〜４０の整数を表す。また、Ｒ２は、一般式（Ｂ）及び／または（Ｃ）の構造であり、Ｍは１〜１０の整数、Ｎは１〜２０の整数であり繰り返し単位Ｌの中で任意の数を取る。）
また、本発明は、［３］ （ａ）熱可塑性樹脂１００重量部に対して、（ｂ）ラジカル重合性物質１０〜２５０重量部、（ｃ）ラジカル重合開始剤０.０５〜３０重量部を含有してなる上記［１］に記載の接着剤に関する。
また、本発明は、［４］ さらに、（ｄ）分子内に少なくとも一つ以上のリン酸基を有するビニル化合物を、熱可塑性樹脂１００重量部に対して０．１〜２０重量部含有してなる上記［１］ないし上記［３］のいずれかに記載の接着剤に関する。
また、本発明は、［５］ さらに、（ｅ）導電粒子を含有する上記［１］ないし上記［４］のいずれかに記載の接着剤に関する。
また、本発明は、［６］ 相対向する回路電極を有する基板間に上記［１］ないし上記［４］のいずれかに記載の接着剤を介在させ、相対向する回路電極を有する基板を加圧して加圧方向の電極間を電気的に接続する方法に用いる回路接続用接着剤に関する。
また、本発明は、［７］ 上記［６］に記載の回路接続用接着剤を用いて接続された接続体に関する。
また、本発明は、［８］ 半導体素子を上記［１］ないし上記［５］のいずれかに記載の接着剤を介して搭載用基板に搭載し電極間を電気的に接続した半導体装置に関する。
(In the general formula (A), R 1 is hydrogen or a methyl group, L represents an integer of 1 to 40, and R 2 is a structure of the general formula (B) and / or (C), M is an integer of 1 to 10, N is an integer of 1 to 20, and an arbitrary number is taken in the repeating unit L.)
The present invention also provides [3] (a) 10 to 250 parts by weight of a radically polymerizable substance and (c) 0.05 to 30 parts by weight of a radical polymerization initiator for 100 parts by weight of a thermoplastic resin. It is related with the adhesive agent as described in said [1] formed.
[4] The present invention further includes [4] 0.1 to 20 parts by weight of (d) a vinyl compound having at least one phosphate group in the molecule with respect to 100 parts by weight of the thermoplastic resin. The adhesive according to any one of [1] to [3].
The present invention also relates to [5] the adhesive according to any one of [1] to [4], further comprising (e) conductive particles.
The present invention also provides [6] an adhesive according to any one of [1] to [4] above interposed between substrates having circuit electrodes facing each other, and adding a substrate having circuit electrodes facing each other. The present invention relates to an adhesive for circuit connection used in a method of electrically connecting electrodes in a pressing direction by pressing.
Moreover, this invention relates to the connection body connected using the adhesive agent for circuit connection as described in [7] said [6].
The present invention also relates to [8] a semiconductor device in which a semiconductor element is mounted on a mounting substrate via the adhesive according to any one of [1] to [5] and the electrodes are electrically connected.
本発明によれば、ラジカル硬化系でありながら、高い接着強度を示し、かつ信頼性試験（例えば８５℃／８５%ＲＨ放置）後においても安定した性能を有し、さらに貯蔵安定性にも優れる接着剤、回路接続用接着剤、接続体及び半導体装置を提供することができる。 According to the present invention, although it is a radical curing system, it exhibits high adhesive strength, has stable performance even after a reliability test (for example, left at 85 ° C./85% RH), and is excellent in storage stability. An adhesive, an adhesive for circuit connection, a connection body, and a semiconductor device can be provided.
本発明において用いる（ａ）熱可塑性樹脂としては、特に制限無く公知のものを使用することができる。このような樹脂としては、ポリイミド、ポリアミド、フェノキシ樹脂類、ポリ（メタ）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類、ポリウレタンエステル類などを用いることができる。これらは単独あるいは２種類以上を混合して用いることができる。さらに、これらポリマ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、もしくはミクロ相分離が生じて白濁する状態であれば好適に用いることができる。上記ポリマの分子量は大きいほどフィルム形成性が容易に得られ、また接着剤としての流動性に影響する溶融粘度を広範囲に設定できる。分子量は特に制限を受けるものではないが、一般的な重量平均分子量としては５，０００〜１５０，０００が好ましく、１０，０００〜８０，０００が特に好ましい。この値が、５，０００未満ではフィルム形成性が劣る傾向があり、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。重量平均分子量は、GPC（ゲルパーミエーションクロマトグラフィー）で測定し標準ポリスチレン換算した値である。 As the (a) thermoplastic resin used in the present invention, known resins can be used without any particular limitation. As such a resin, polyimide, polyamide, phenoxy resins, poly (meth) acrylates, polyimides, polyurethanes, polyesters, polyvinyl butyrals, polyurethane esters, and the like can be used. These can be used alone or in admixture of two or more. Furthermore, these polymers may contain siloxane bonds and fluorine substituents. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy. The higher the molecular weight of the polymer, the easier it is to form a film, and the melt viscosity that affects the fluidity as an adhesive can be set over a wide range. The molecular weight is not particularly limited, but a general weight average molecular weight is preferably from 5,000 to 150,000, particularly preferably from 10,000 to 80,000. If this value is less than 5,000, the film formability tends to be inferior, and if it exceeds 150,000, the compatibility with other components tends to be poor. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and converted to standard polystyrene.
本発明において用いる（ｂ）一般式（Ｂ）及び／または（Ｃ）の構造を含み且つ分子中に２個以上の（メタ）アクリロイル基及び２個以上のウレタン結合を有するラジカル重合性物質は、耐熱性、流動性、接着性の観点から、一般式（Ｂ）、一般式(Ｃ)から選ばれる少なくとも一以上の構造によって構成されることが好ましく、さらに一般式（Ｂ）、一般式(Ｃ)を任意の割合で併用してもよい。 The radically polymerizable substance (b) used in the present invention has a structure of the general formula (B) and / or (C) and has two or more (meth) acryloyl groups and two or more urethane bonds in the molecule. From the viewpoints of heat resistance, fluidity, and adhesiveness, it is preferably constituted by at least one structure selected from general formula (B) and general formula (C), and further, general formula (B) and general formula (C ) May be used in any proportion.
（ｂ）のラジカル重合性物質として、下記一般式（Ａ）で表されるウレタン（メタ）アクリレート化合物であることが好ましく、一般式（Ａ）で示される構造を有するものであれば、特に制限なく公知のものを使用することが出来るが、耐熱性、流動性、接着性の観点から、一般式(Ａ)中のＲ２が一般式（Ｂ）、一般式(Ｃ)から選ばれる少なくとも一以上の構造によって構成されることが好ましく、さらに一般式（Ｂ）、一般式(Ｃ)を任意の割合で併用してもよい。ウレタン（メタ）アクリレート化合物は、ウレタンアクリレート化合物とウレタンメタアクリレート化合物を意味する。 The radically polymerizable substance (b) is preferably a urethane (meth) acrylate compound represented by the following general formula (A), and is particularly limited as long as it has a structure represented by the general formula (A). However, from the viewpoint of heat resistance, fluidity and adhesiveness, R 2 in the general formula (A) is at least one selected from the general formula (B) and the general formula (C). It is preferable to be constituted by the above structure, and the general formula (B) and the general formula (C) may be used in an arbitrary ratio. A urethane (meth) acrylate compound means a urethane acrylate compound and a urethane methacrylate compound.
（一般式（Ａ）中、Ｒ１は、水素またはメチル基を表す。Ｌは、１〜４０の整数を表す。また、Ｒ２は、一般式（Ｂ）及び／または（Ｃ）の構造であり、Ｍは１〜１０の整数、Ｎは１〜２０の整数であり繰り返し単位Ｌの中で任意の数を取る。） (In General Formula (A), R 1 represents hydrogen or a methyl group. L represents an integer of 1 to 40. R 2 has the structure of General Formula (B) and / or (C). Yes, M is an integer of 1 to 10, N is an integer of 1 to 20, and an arbitrary number is taken in the repeating unit L.)
前記（ｂ）のラジカル重合性物質としてウレタン(メタ)アクリレート化合物の繰り返し単位数Ｌとしては、１〜４０が好ましく、３〜２０がさらに好ましい。Ｌが４０を超える場合、架橋密度が低下し、接続信頼性が低下するおそれがある。 The number L of repeating units of the urethane (meth) acrylate compound as the radical polymerizable substance (b) is preferably 1 to 40, and more preferably 3 to 20. When L exceeds 40, a crosslinking density falls and there exists a possibility that connection reliability may fall.
前記（ｂ）のラジカル重合性物質としてウレタン(メタ)アクリレート化合物は、市販の標準ポリスチレンを使用して、ゲル浸透クロマトグラフィー(ＧＰＣ)測定によって分子量を測定することができる。本発明で用いるウレタン(メタ)アクリレート化合物の重量平均分子量（Ｍｗ）は、特に制限なく公知のものを使用することが出来るが、１，０００〜５０，０００が好ましく、５，０００〜３０，０００が特に好ましい。Ｍｗが１，０００未満では硬化収縮による接着力低下のおそれがあり、５０，０００を超えた場合では架橋密度が低下し、接続信頼性が低下するおそれがある。 The urethane (meth) acrylate compound as the radical polymerizable substance (b) can be measured for molecular weight by gel permeation chromatography (GPC) measurement using commercially available standard polystyrene. As the weight average molecular weight (Mw) of the urethane (meth) acrylate compound used in the present invention, known ones can be used without particular limitation, but 1,000 to 50,000 are preferable, and 5,000 to 30,000 are preferable. Is particularly preferred. If Mw is less than 1,000, the adhesive force may be reduced due to curing shrinkage, and if it exceeds 50,000, the crosslink density may be reduced and connection reliability may be reduced.
（ｂ）のラジカル重合性物質の添加量は、（ａ）熱可塑性樹脂１００重量部に対して、１０〜２５０重量部であり、好ましくは３０〜１５０重量部である。添加量が１０重量部未満の場合、硬化後の耐熱性低下が懸念され、また、２５０重量部以上の場合には、フィルムとして使用する場合にフィルム形成性が低下する恐れがある。 The amount of the radically polymerizable substance (b) added is 10 to 250 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the (a) thermoplastic resin. When the addition amount is less than 10 parts by weight, there is a concern about a decrease in heat resistance after curing, and when it is 250 parts by weight or more, there is a possibility that the film formability is lowered when used as a film.
本発明において用いる（ｃ）ラジカル重合開始剤としては、従来から知られている過酸化物やアゾ化合物等公知の化合物を用いることができるが、安定性、反応性、相溶性の観点から、１分間半減期温度が９０〜１７５℃で、かつ、分子量が１８０〜１,０００のパーオキシエステル誘導体が好ましい。
具体的には、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−エチルヘキサノエート、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、t−ヘキシルパーオキシ−２−エチルヘキサノエート、t−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシネオヘプタノエート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサヒドロテレフタレート、ｔ−アミルパーオキシ−３，５，５−トリメチルヘキサノエート、３−ヒドロキシ−１，１−ジメチルブチ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−２−エチルヘキサノエート、ｔ−アミルパーオキシネオデカノエート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、２，２’−アゾビス−２，４−ジメチルバレロニトリル、１，１’−アゾビス（１−アセトキシ−１−フェニルエタン）、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）、ジメチル−２，２’−アゾビスイソブチロニトリル、４，４’−アゾビス（４−シアノバレリン酸）、１，１’−アゾビス（１−シクロヘキサンカルボニトリル）、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−ブチルパーオキシマレイン酸、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシラウレート、２，５−ジメチル−２，５−ジ（３−メチルベンゾイルパーオキシ）ヘキサン、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、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシベンゾエート、ジブチルパーオキシトリメチルアジペート、ｔ−アミルパーオキシノルマルオクトエート、ｔ−アミルパーオキシイソノナノエート、ｔ−アミルパーオキシベンゾエート等が挙げられる。
これらの化合物は、単独で用いる他に、２種以上の化合物を混合して用いても良い。
As the radical polymerization initiator (c) used in the present invention, known compounds such as conventionally known peroxides and azo compounds can be used. From the viewpoint of stability, reactivity, and compatibility, 1 Peroxyester derivatives having a minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 are preferred.
Specifically, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t-hexylper Oxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl -2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneohepta Noate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t- Milperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate , T-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (1-acetoxy- 1-phenylethane), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4 '-Azobis (4-cyanovaleric acid), 1,1'-azobis (1-cyclohexanecarbonitrile), t-hexylperoxyisopropyl monocarbonate, -Butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy ) Hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutylperoxy Examples include trimethyl adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate and the like.
These compounds may be used alone or as a mixture of two or more compounds.
（ｃ）ラジカル重合開始剤の添加量は、（ａ）熱可塑性樹脂１００重量部に対して０．０５〜３０重量部であり、好ましくは０．１〜２０重量部である。添加量が０．０５重量部未満の場合、硬化不足が懸念され、また、３０重量部を超える場合には、放置安定性が低下する恐れがある。 (C) The addition amount of a radical polymerization initiator is 0.05-30 weight part with respect to 100 weight part of (a) thermoplastic resins, Preferably it is 0.1-20 weight part. When the addition amount is less than 0.05 parts by weight, there is a concern about insufficient curing, and when it exceeds 30 parts by weight, the standing stability may be lowered.
本発明において用いる（ｄ）分子内に少なくとも一つ以上のリン酸基を有するビニル化合物としては、特に制限なく公知のものを使用することができるが、下記一般式(１〜３)で示される化合物が好ましい。 As the vinyl compound having at least one phosphate group in the molecule (d) used in the present invention, known compounds can be used without any particular limitation, and are represented by the following general formulas (1 to 3). Compounds are preferred.
（一般式（１）中、Ｒ３は、アクリロイル基またはメタアクリロイル基、Ｒ４は水素またはメチル基、Ｗ、Ｘは独立に１〜８の整数を示す。）
(In general formula (1), R 3 is an acryloyl group or a methacryloyl group, R 4 is a hydrogen or methyl group, and W and X independently represent an integer of 1 to 8.)
具体的には、アシッドホスホオキシエチルメタクリレート、アシッドホスホオキシエチルアクリレート、アシッドホスホオキシプロピルメタクリレート、アシッドホスホオキシポリオキシエチレングリコールモノメタクリレート、アシッドホスホオキシポリオキシプロピレングリコールモノメタクリレート、２，２’-ジ（メタ）アクリロイロキシジエチルホスフェート、ＥＯ（エチレンオキサイド）変性リン酸ジメタクリレート、リン酸変性エポキシアクリレート等が挙げられる。 Specifically, acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2,2′-di ( Examples thereof include (meth) acryloyloxydiethyl phosphate, EO (ethylene oxide) -modified dimethacrylate phosphate, and phosphate-modified epoxy acrylate.
（ｄ）分子内に少なくとも一つ以上のリン酸基を有するビニル化合物の添加量は、（ａ）熱可塑性樹脂１００重量部に対して、０．１〜２０重量部であり、好ましくは０．５〜１０重量部である。添加量が０．１重量部未満の場合、高接着強度が得られにくく、また、２０重量部を超える場合には、硬化後の接着剤の物性低下が著しく、信頼性が低下する恐れがある。 (D) The addition amount of the vinyl compound having at least one phosphate group in the molecule is 0.1 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the thermoplastic resin (a). 5 to 10 parts by weight. When the addition amount is less than 0.1 parts by weight, it is difficult to obtain high adhesive strength, and when it exceeds 20 parts by weight, the physical properties of the adhesive after curing are remarkably deteriorated and the reliability may be lowered. .
本発明において用いる（ｅ）導電粒子としては、Ａｕ、Ａｇ、Ｎｉ、Ｃｕ、はんだ等の金属粒子やカーボン等が挙げられる。また、非導電性のガラス、セラミック、プラスチック等を核とし、この核に前記金属、金属粒子やカーボンを被覆したものでもよい。導電粒子が、プラスチックを核とし、この核に前記金属、金属粒子やカーボンを被覆したものや熱溶融金属粒子の場合、加熱加圧により変形性を有するので接続時に電極との接触面積が増加し電極の厚みばらつきを吸収するので信頼性が向上するので好ましい。またこれらの導電粒子の表面を、さらに高分子樹脂などで被覆した微粒子は、導電粒子の配合量を増加した場合の粒子同士の接触による短絡を抑制し、電極回路間の絶縁性が向上できることから、適宜これを単独あるいは導電粒子と混合して用いてもよい。 Examples of the conductive particles (e) used in the present invention include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, non-conductive glass, ceramic, plastic, or the like may be used as a core, and the core, metal particles, or carbon may be coated on the core. In the case where the conductive particles are made of plastic as a core and the core is coated with the metal, metal particles or carbon, or hot-melt metal particles, the contact area with the electrode during connection is increased because it is deformable by heating and pressing. It is preferable because reliability is improved because variations in electrode thickness are absorbed. In addition, the fine particles with the surface of these conductive particles coated with a polymer resin or the like can suppress short circuit due to contact between the particles when the amount of the conductive particles is increased, and can improve the insulation between the electrode circuits. These may be used alone or mixed with conductive particles as appropriate.
この導電粒子の平均粒径は、分散性、導電性の点から１〜１８μｍであることが好ましい。導電粒子の使用量は、特に制限は受けないが、接着剤組成物トータル１００体積に対して０．１〜３０体積％とすることが好ましく、０．１〜１０体積％とすることがより好ましい。この値が、０．１体積％未満であると導電性が劣る傾向があり、３０体積％を超えると回路の短絡が起こる傾向がある。なお、体積％は２３℃の硬化前の各成分の体積をもとに決定されるが、各成分の体積は、比重を利用して重量から体積に換算することができる。また、メスシリンダー等にその成分を溶解したり膨潤させたりせず、その成分をよくぬらす適当な溶媒（水、アルコール等）を入れたものに、その成分を投入し増加した体積をその体積として求めることもできる。 The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. The amount of the conductive particles used is not particularly limited, but is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% by volume with respect to 100 volumes of the total adhesive composition. . If this value is less than 0.1% by volume, the conductivity tends to be inferior, and if it exceeds 30% by volume, a short circuit tends to occur. In addition, although volume% is determined based on the volume of each component before 23 degreeC hardening, the volume of each component can be converted into a volume from a weight using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., but put in a suitable solvent (water, alcohol, etc.) that wets the component well. You can ask for it.
本発明の接着剤には、前記（ｂ）のラジカル重合性物質と併用して（ｂ）以外のラジカル重合性化合物を使用することができる。このようなラジカル重合性化合物としては、スチレン誘導体やマレイミド誘導体のように、ラジカルによって重合する化合物であれば、特に制限無く公知のものを使用することができる。 In the adhesive of the present invention, a radical polymerizable compound other than (b) can be used in combination with the radical polymerizable substance (b). As such a radically polymerizable compound, a known compound can be used without particular limitation as long as it is a compound that is polymerized by a radical, such as a styrene derivative or a maleimide derivative.
具体的には、エポキシ（メタ）アクリレートオリゴマー、ポリエーテル（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー等のオリゴマー、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、イソシアヌル酸変性２官能（メタ）アクリレート、イソシアヌル酸変性３官能（メタ）アクリレート等の多官能（メタ）アクリレート化合物が挙げられる。
また、流動性の調節を目的に、単官能(メタ)アクリレートを使用することもできる。例えば、ペンタエリスリトール（メタ）アクリレート、２−シアノエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、２−（２−エトキシエトキシ）エチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、イソボルニル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ−ラウリル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、２−フェノキシエチル（メタ）アクリレート、テトラヒドロフルフリール（メタ）アクリレート、２-（メタ）アクリロイロキシエチルホスフェート、Ｎ、Ｎ-ジメチルアミノエチル（メタ）アクリレート、Ｎ、Ｎ-ジメチルアミノエチル（メタ）アクリレート、Ｎ、Ｎ-ジメチルアミノプロピル（メタ）アクリレート、Ｎ、Ｎ-ジメチルアミノプロピル（メタ）アクリレート、（メタ）アクリロイルモルホリン等が挙げられる。
これらの化合物は単独で使用する以外に、必要に応じて複数の化合物を混合して用いてもよい。
Specifically, oligomers such as epoxy (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol Di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meta And polyfunctional (meth) acrylate compounds such as acrylate and isocyanuric acid-modified trifunctional (meth) acrylate.
Monofunctional (meth) acrylates can also be used for the purpose of adjusting fluidity. For example, pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, isobornyl (meta ) Acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N- Examples thereof include dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth) acryloylmorpholine, and the like.
In addition to using these compounds alone, a plurality of compounds may be mixed and used as necessary.
本発明の接着剤は、橋架け率の向上を目的として、前記（メタ）アクリロイル基を有する化合物の他に、アリル基、マレイミド基、ビニル基等の活性ラジカルによって重合する官能基を有する化合物を適宜添加してもよい。具体的には、Ｎ-ビニルイミダゾール、Ｎ-ビニルピリジン、Ｎ-ビニルピロリドン、Ｎ-ビニルホルムアミド、Ｎ-ビニルカプロラクタム、４，４’−ビニリデンビス（Ｎ，Ｎ−ジメチルアニリン）、Ｎ-ビニルアセトアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、アクリルアミド等が挙げられる。 The adhesive of the present invention comprises a compound having a functional group that is polymerized by an active radical such as an allyl group, a maleimide group, and a vinyl group in addition to the compound having the (meth) acryloyl group for the purpose of improving the crosslinking rate. You may add suitably. Specifically, N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N-dimethylaniline), N-vinylacetamide N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, acrylamide and the like.
本発明の接着剤には、硬化速度の制御や貯蔵安定性を付与するために、安定化剤を添加することできる。このような安定化剤としては、特に制限なく公知の化合物を使用することができるが、ベンゾキノンやハイドロキノン等のキノン誘導体、４−メトキシフェノールや４-ｔ-ブチルカテコール等のフェノール誘導体、２，２，６，６−テトラメチルピペリジン−１−オキシルや４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル等のアミノキシル誘導体、テトラメチルピペリジルメタクリレート等のヒンダードアミン誘導体が好ましい。 A stabilizer can be added to the adhesive of the present invention in order to control the curing rate and impart storage stability. As such a stabilizer, known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2,2 Preferred are aminoxyl derivatives such as 1,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate.
安定化剤の添加量は、（ａ）熱可塑性樹脂１００重量部に対して、０．０１〜３０重量部であり、好ましくは０．０５〜１０重量部である。添加量が０．０１重量部未満の場合、添加効果が著しく低下することが懸念され、また、３０重量部以上の場合には、他の成分との相溶性が低下する恐れがある。 The addition amount of the stabilizer is 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of (a) the thermoplastic resin. When the addition amount is less than 0.01 parts by weight, there is a concern that the addition effect is remarkably reduced, and when it is 30 parts by weight or more, the compatibility with other components may be reduced.
本発明の接着剤には、アルコキシシラン誘導体やシラザン誘導体に代表されるカップリング剤及び密着向上剤、レベリング剤などの接着助剤を適宜添加してもよい。具体的には、下記一般式（４）で示される化合物が好ましく、単独で用いる他に、２種以上の化合物を混合して用いても良い。 Adhesive aids such as coupling agents represented by alkoxysilane derivatives and silazane derivatives, adhesion improvers, and leveling agents may be appropriately added to the adhesive of the present invention. Specifically, a compound represented by the following general formula (4) is preferable, and two or more compounds may be mixed and used in addition to being used alone.
本発明の接着剤は、応力緩和及び接着性向上を目的に、ゴム成分を併用しても良い。具体的には、ポリイソプレン、ポリブタジエン、カルボキシル基末端ポリブタジエン、水酸基末端ポリブタジエン、１，２−ポリブタジエン、カルボキシル基末端１，２−ポリブタジエン、水酸基末端１，２−ポリブタジエン、アクリルゴム、スチレン-ブタジエンゴム、水酸基末端スチレン-ブタジエンゴム、アクリロニトリル−ブタジエンゴム、カルボキシル基、水酸基、（メタ）アクリロイル基またはモルホリン基をポリマ末端に含有するアクリロニトリル−ブタジエンゴム、カルボキシル化ニトリルゴム、水酸基末端ポリ（オキシプロピレン）、アルコキシシリル基末端ポリ（オキシプロピレン）、ポリ（オキシテトラメチレン）グリコール、ポリオレフィングリコール、ポリ−ε−カプロラクトン等が挙げられる。
上記ゴム成分としては、接着性向上の観点から、高極性基であるシアノ基、カルボキシル基を側鎖あるいは末端に含むゴム成分が好ましく、さらに流動性向上の観点から、液状ゴムがより好ましい。具体的には、液状アクリロニトリル−ブタジエンゴム、カルボキシル基、水酸基、（メタ）アクリロイル基またはモルホリン基をポリマ末端に含有する液状アクリロニトリル−ブタジエンゴム、液状カルボキシル化ニトリルゴムが挙げられ、極性基であるアクリロニトリル含有量が１０〜６０重量％が好ましい。
これらの化合物は単独で用いる他に、２種以上の化合物を混合して用いても良い。
In the adhesive of the present invention, a rubber component may be used in combination for the purpose of stress relaxation and adhesion improvement. Specifically, polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, Hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxy containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end Examples include silyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, and poly-ε-caprolactone.
As the rubber component, a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable from the viewpoint of improving adhesiveness, and liquid rubber is more preferable from the viewpoint of improving fluidity. Specific examples include liquid acrylonitrile-butadiene rubber, liquid acrylonitrile-butadiene rubber containing a carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer terminal, and liquid carboxylated nitrile rubber. Acrylonitrile which is a polar group The content is preferably 10 to 60% by weight.
These compounds may be used alone or in admixture of two or more compounds.
本発明の接着剤は、常温（２５℃）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（２５℃）で固体の場合には、加熱して使用する他、溶剤を使用してペースト化してもよい。使用できる溶剤としては、接着剤組成物及び添加剤と反応性がなく、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℃以下の場合、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℃以上だと、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恐れがある。 The adhesive of the present invention can be used in the form of a paste when it is liquid at room temperature (25 ° C.). In the case of a solid at room temperature (25 ° C.), in addition to heating, it may be pasted using a solvent. The solvent that can be used is not particularly limited as long as it is not reactive with the adhesive composition and additives, and exhibits sufficient solubility, but has a boiling point of 50 to 150 ° C. at normal pressure. Those are preferred. When the boiling point is 50 ° C. or lower, there is a risk of volatilization if left at room temperature, which limits the use in an open system. Moreover, when the boiling point is 150 ° C. or higher, it is difficult to volatilize the solvent, which may adversely affect the reliability after bonding.
本発明の接着剤はフィルム状にして用いることもできる。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前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 of the present invention can be used in the form of a film. A solution prepared by adding a solvent or the like to the adhesive composition as necessary is applied to a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or a substrate such as a nonwoven fabric is impregnated with the solution. Can be used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.
本発明の接着剤は、加熱及び加圧を併用して接着させることができる。加熱温度は、特に制限は受けないが、１００〜２５０℃の温度が好ましい。圧力は、被着体に損傷を与えない範囲であれば、特に制限は受けないが、一般的には０.１〜１０ＭＰａが好ましい。これらの加熱及び加圧は、０.５秒〜１２０秒間の範囲で行うことが好ましく、１４０〜２００℃、３ＭＰa、１０秒の加熱でも接着させることが可能である。 The adhesive of the present invention can be bonded by using heating and pressurization together. The heating temperature is not particularly limited, but a temperature of 100 to 250 ° C. is preferable. The pressure is not particularly limited as long as it does not damage the adherend, but is generally preferably 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds, and can be bonded by heating at 140 to 200 ° C., 3 MPa, and 10 seconds.
本発明の接着剤は、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、異方導電接着剤、銀ペースト、銀フィルム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テープ等に代表される半導体素子接着材料として使用することができる。 The adhesive of the present invention can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, silver film, etc., circuit connection material, CSP elastomer, CSP underfill material, LOC tape, etc. Can do.
以下に、本発明の接着剤及び導電粒子を使用して作製した異方導電フィルムと電極の接続の一例について説明する。接着剤または異方導電フィルムを、基板上の相対時する電極間に存在させ、加熱加圧することにより両電極の接触と基板間の接着を得、電極との接続を行える。すなわち、相対向する回路電極を有する基板間に接着剤（回路接続用接着剤）を介在させ、相対向する回路電極を有する基板を加圧して加圧方向の電極間を電気的に接続し、接続体を得る。電極を形成する基板としては、半導体、ガラス、セラミック等の無機質、ポリイミド、ポリカーボネート、ポリエステル、ポリエーテルスルホン等の有機物、ガラス／エポキシ等のこれら複合の各組み合わせが適用できる。 Below, an example of the connection of the anisotropic conductive film produced using the adhesive agent and electroconductive particle of this invention and an electrode is demonstrated. Adhesives or anisotropic conductive films are present between the electrodes on the substrate, and are heated and pressed to obtain contact between the electrodes and adhesion between the substrates, and connection to the electrodes can be performed. That is, an adhesive (circuit connection adhesive) is interposed between substrates having circuit electrodes facing each other, and a substrate having circuit electrodes facing each other is pressed to electrically connect the electrodes in the pressing direction. Get a connection. As the substrate for forming the electrodes, inorganic materials such as semiconductors, glass and ceramics, organic materials such as polyimide, polycarbonate, polyester and polyethersulfone, and combinations of these composites such as glass / epoxy can be applied.
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
（ウレタンアクリレート（ＵＡ-１）の合成）
攪拌機、温度計、冷却管及び空気ガス導入管を備えた反応容器に空気ガスを導入した後、２−ヒドロキシエチルアクリレート２３８重量部(２．０５モル)、数平均分子量８６０のポリ（ヘキサメチレンカーボネート）ジオール（アルドリッチ社製）８６０重量部（１モル）、１，４−シクロヘキサンジメタノール１４４重量部（１モル）、ハイドロキノンモノメチルエーテル０．１９重量部、ジブチルスズジラウレート１．９１重量部を仕込み、７０〜７５℃に加熱し、イソフォロンジイソシアネート６６６重量部（３モル）を３時間で均一に滴下し、反応させた。滴下完了後約１５時間反応を継続し、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、数平均分子量３，７００のウレタンアクリレート（ＵＡ-１）を得た。
(Synthesis of urethane acrylate (UA-1))
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate and poly (hexamethylene carbonate) having a number average molecular weight of 860 ) Diol (manufactured by Aldrich) 860 parts by weight (1 mol), 1,4-cyclohexanedimethanol 144 parts by weight (1 mole), hydroquinone monomethyl ether 0.19 parts by weight, dibutyltin dilaurate 1.91 parts by weight, The mixture was heated to ˜75 ° C., and 666 parts by weight (3 mol) of isophorone diisocyanate was uniformly dropped over 3 hours to be reacted. The reaction was continued for about 15 hours after the completion of the dropping, and the reaction was terminated by confirming that the isocyanate had disappeared by IR measurement, and urethane acrylate (UA-1) having a number average molecular weight of 3,700 was obtained.
（ウレタンアクリレート（ＵＡ-２）の合成）
攪拌機、温度計、冷却管及び空気ガス導入管を備えた反応容器に空気ガスを導入した後、２−ヒドロキシエチルアクリレート２３８重量部(２．０５モル)、数平均分子量２，０００のポリ（ヘキサメチレンカーボネート）ジオール（アルドリッチ社製）２０００重量部（１モル）、１，４−シクロヘキサンジメタノール１４４重量部（１モル）、ハイドロキノンモノメチルエーテル０．３０重量部、ジブチルスズジラウレート３．０５重量部を仕込み、７０〜７５℃に加熱し、イソフォロンジイソシアネート６６６重量部（３モル）を３時間で均一に滴下し、反応させた。滴下完了後約１８時間反応を継続し、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、数平均分子量５，４００のウレタンアクリレート（ＵＡ-２）を得た。
(Synthesis of urethane acrylate (UA-2))
After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and an air gas introduction pipe, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate and a poly (hexahexane) having a number average molecular weight of 2,000 Methylene carbonate) diol (manufactured by Aldrich) 2000 parts by weight (1 mole), 1,4-cyclohexanedimethanol 144 parts by weight (1 mole), hydroquinone monomethyl ether 0.30 parts by weight, dibutyltin dilaurate 3.05 parts by weight The mixture was heated to 70 to 75 ° C., and 666 parts by weight (3 mol) of isophorone diisocyanate was uniformly added dropwise over 3 hours to be reacted. The reaction was continued for about 18 hours after completion of the dropwise addition, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement. Thus, urethane acrylate (UA-2) having a number average molecular weight of 5,400 was obtained.
（ウレタンアクリレート（ＵＡ-３）の合成）
攪拌機、温度計、冷却管及び空気ガス導入管を備えた反応容器に空気ガスを導入した後、２−ヒドロキシエチルアクリレート２３８重量部(２．０５モル)、数平均分子量２，０００のポリ（ヘキサメチレンカーボネート）ジオール（アルドリッチ社製）４０００重量部（２モル）、ハイドロキノンモノメチルエーテル０．４９重量部、ジブチルスズジラウレート４．９０重量部を仕込み、７０〜７５℃に加熱し、イソフォロンジイソシアネート６６６重量部（３モル）を３時間で均一に滴下し、反応させた。滴下完了後約１５時間反応を継続し、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、数平均分子量６，８００のウレタンアクリレート（ＵＡ-３）を得た。
(Synthesis of urethane acrylate (UA-3))
After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and an air gas introduction pipe, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate and a poly (hexahexane) having a number average molecular weight of 2,000 Methylene carbonate) diol (manufactured by Aldrich) 4000 parts by weight (2 mol), hydroquinone monomethyl ether 0.49 parts by weight, dibutyltin dilaurate 4.90 parts by weight, heated to 70-75 ° C., isophorone diisocyanate 666 parts by weight (3 mol) was added dropwise in 3 hours and allowed to react. The reaction was continued for about 15 hours after completion of the dropwise addition, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, to obtain urethane acrylate (UA-3) having a number average molecular weight of 6,800.
（ウレタンアクリレート（ＵＡ-４）の合成）
攪拌機、温度計、冷却管及び空気ガス導入管を備えた反応容器に空気ガスを導入した後、２−ヒドロキシエチルアクリレート２３８重量部(２．０５モル)、数平均分子量９００のポリ（エチレングリコール）ジオール（アルドリッチ社製）１，８００重量部（２モル）、ハイドロキノンモノメチルエーテル０．２７重量部、ジブチルスズジラウレート２．７０重量部を仕込み、７０〜７５℃に加熱し、イソフォロンジイソシアネート６６６重量部（３モル）を３時間で均一に滴下し、反応させた。滴下完了後約１５時間反応を継続し、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、数平均分子量４，８００のウレタンアクリレート（ＵＡ-４）を得た。
(Synthesis of urethane acrylate (UA-4))
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate and poly (ethylene glycol) having a number average molecular weight of 900 Diol (manufactured by Aldrich) 1,800 parts by weight (2 moles), hydroquinone monomethyl ether 0.27 parts by weight, dibutyltin dilaurate 2.70 parts by weight were charged and heated to 70 to 75 ° C., and isophorone diisocyanate 666 parts by weight ( 3 mol) was added dropwise uniformly over 3 hours to allow reaction. The reaction was continued for about 15 hours after completion of the dropwise addition, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, and urethane acrylate (UA-4) having a number average molecular weight of 4,800 was obtained.
（ウレタンアクリレート（ＵＡ-５）の合成）
攪拌機、温度計、冷却管及び空気ガス導入管を備えた反応容器に空気ガスを導入した後、２−ヒドロキシエチルアクリレート２３８重量部(２．０５モル)、ハイドロキノンモノメチルエーテル０．１６重量部、ジブチルスズジラウレート１．５８重量部を仕込み、７０〜７５℃に加熱し、イソフォロンジイソシアネート４４４重量部（２モル）を３時間で均一に滴下し、反応させた。この反応液に、数平均分子量９００のポリ（エチレングリコール）ジオール（アルドリッチ社製）９００重量部（１モル）を３時間で均一に滴下し、反応させた。滴下完了後約１５時間反応を継続し、ＩＲ測定によりイソシアネートが消失したことを確認して反応を終了し、ウレタンアクリレート（ＵＡ-５）を得た。
(Synthesis of urethane acrylate (UA-5))
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate, 0.16 part by weight of hydroquinone monomethyl ether, dibutyltin 1.58 parts by weight of dilaurate was charged and heated to 70 to 75 ° C., and 444 parts by weight (2 mol) of isophorone diisocyanate was uniformly added dropwise over 3 hours to be reacted. To this reaction solution, 900 parts by weight (1 mol) of poly (ethylene glycol) diol (manufactured by Aldrich) having a number average molecular weight of 900 was uniformly dropped over 3 hours to be reacted. The reaction was continued for about 15 hours after completion of the dropwise addition, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, to obtain urethane acrylate (UA-5).
（実施例１〜３、比較例１〜２）
（ａ）熱可塑性樹脂として、フェノキシ樹脂及びウレタン樹脂を使用した。フェノキシ樹脂（ＰＫＨＣ、ユニオンカーバイト社製商品名、平均分子量４５，０００）４０ｇを、メチルエチルケトン６０ｇに溶解して、固形分４０重量％の溶液とした。また、ウレタン樹脂は、平均分子量２，０００のポリブチレンアジペートジオール４５０重量部と平均分子量２，０００のポリオキシテトラメチレングリコール４５０重量部、１，４−ブチレングリコール１００重量部をメチルエチルケトン４０００重量部中で均一に混合し、ジフェニルメタンジイソシアネート３９０重量部を加えて７０℃にて反応させて得られた重量平均分子量３５万のウレタン樹脂を使用した。ラジカル重合性化合物として、前記ウレタンアクリレート（ＵＡ-１〜ＵＡ-５）及び２-（メタ）アクリロイロキシエチルホスフェート（ライトエステルＰ-２Ｍ、共栄社株式会社製商品名）、ラジカル重合開始剤としてｔ-ヘキシルパーオキシ−２−エチルヘキサノエート（パーヘキシルＯ、日本油脂株式会社製商品名）を用いた。またポリスチレンを核とする粒子の表面に、厚み０．２μｍのニッケル層を設け、このニッケル層の外側に、厚み０．０２μｍの金層を設けた平均粒径４μｍ、比重２．５の導電粒子を作製した。
固形重量比で表１に示すように配合し、さらに導電粒子を１．５体積％配合分散させ、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接着剤層の厚みが１５μｍのフィルム状接着剤を得た。
(Examples 1-3, Comparative Examples 1-2)
(A) Phenoxy resin and urethane resin were used as the thermoplastic resin. 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) was dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by weight. The urethane resin contains 450 parts by weight of polybutylene adipate diol having an average molecular weight of 2,000, 450 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, and 100 parts by weight of 1,4-butylene glycol in 4000 parts by weight of methyl ethyl ketone. And a urethane resin having a weight average molecular weight of 350,000 obtained by adding 390 parts by weight of diphenylmethane diisocyanate and reacting at 70 ° C. was used. As the radical polymerizable compound, the urethane acrylate (UA-1 to UA-5) and 2- (meth) acryloyloxyethyl phosphate (light ester P-2M, trade name, manufactured by Kyoeisha Co., Ltd.), t as the radical polymerization initiator -Hexylperoxy-2-ethylhexanoate (Perhexyl O, a product name manufactured by NOF Corporation) was used. Conductive particles having an average particle size of 4 μm and a specific gravity of 2.5, in which a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.02 μm is provided outside the nickel layer. Was made.
It mix | blends as shown in Table 1 by solid weight ratio, Furthermore, 1.5 volume% of conductive particles are mix-dispersed, and it apply | coats to an 80-micrometer-thick fluororesin film using a coating device, 70 degreeC hot-air drying for 10 minutes As a result, a film adhesive having an adhesive layer thickness of 15 μm was obtained.
〔接着強度、接続抵抗の測定〕 上記製法によって得たフィルム状接着剤を用いて、ライン幅２５μｍ、ピッチ５０μｍ、厚み８μｍの銅回路を５００本有するフレキシブル回路板（ＦＰＣ）と、０．２μｍの酸化インジウム（ＩＴＯ）の薄層を形成したガラス（厚み１．１ｍｍ、表面抵抗２０Ω／□）とを、熱圧着装置（加熱方式：コンスタントヒート型、東レエンジニアリング株式会社製）を用いて１６０℃の温度で圧力３ＭＰａで１０秒間の加熱加圧を行って幅２ｍｍにわたり接続し、接続体を作製した。この接続体の隣接回路間の抵抗値を、接着直後と、８５℃、８５％ＲＨの高温高湿槽中に１６８時間保持した後にマルチメータで測定した。抵抗値は隣接回路間の抵抗３７点の平均で示した。 [Measurement of adhesive strength and connection resistance] 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 8 μm, and a 0.2 μm A glass (thickness 1.1 mm, surface resistance 20 Ω / □) on which a thin layer of indium oxide (ITO) is formed using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) A pressure was applied at a pressure of 3 MPa for 10 seconds, and a connection was made over a width of 2 mm. The resistance value between adjacent circuits of this connection body 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 168 hours. The resistance value was shown as an average of 37 resistances between adjacent circuits.
また、この接続体の接着強度をＪＩＳ−Ｚ０２３７に準じて９０度剥離法で測定し、評価した。ここで、接着強度の測定装置は東洋ボールドウィン株式会社製テンシロンＵＴＭ−４（剥離速度５０ｍｍ／ｍｉｎ、２５℃）を使用した。
以上のようにして行った接続体の接着強度、接続抵抗の測定の結果を表２に示した。
Moreover, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength.
Table 2 shows the results of measurement of the adhesive strength and connection resistance of the connection body performed as described above.
一般式（Ａ）で表されるウレタン（メタ）アクリレート化合物を有する実施例１〜３で得られた接着剤は、接着直後及び８５℃、８５％ＲＨの高温高湿槽中に１６８時間保持した後で、良好な接続抵抗及び接着強度を示し、良好な特性を示すことが分かった。一方、一般式（Ａ）で表されるウレタン（メタ）アクリレート化合物を有しない比較例１では、接着直後の接続抵抗値は良好なものの、８５℃、８５％ＲＨの高温高湿槽中に１６８時間保持した後(信頼性試験後)では接続抵抗値が上昇した。また、接着力についても、実施例１〜３と比較して接着直後の接着力が低く、さらに信頼性試験後の接着力低下が顕著であった。また、一般式（Ａ）で表されるウレタン（メタ）アクリレート化合物を有しない比較例２では、接続抵抗は良好なものの、接着直後、信頼性試験後とも低接着強度を示した。以上の結果から、本発明の特定構造のラジカル重合性物質を用いることで、良好な接続抵抗と接着力を両立できることが明らかになった。 The adhesives obtained in Examples 1 to 3 having the urethane (meth) acrylate compound represented by the general formula (A) were held immediately after bonding and in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 168 hours. Later, it was found that it showed good connection resistance and adhesive strength and good properties. On the other hand, in Comparative Example 1 which does not have the urethane (meth) acrylate compound represented by the general formula (A), although the connection resistance value immediately after bonding is good, it is 168 in a high-temperature and high-humidity tank at 85 ° C. and 85% RH. The connection resistance value increased after holding for a time (after the reliability test). Moreover, also about the adhesive force, compared with Examples 1-3, the adhesive force immediately after adhesion | attachment was low, and also the adhesive force fall after a reliability test was remarkable. Moreover, in Comparative Example 2 having no urethane (meth) acrylate compound represented by the general formula (A), although the connection resistance was good, the adhesive strength was low immediately after adhesion and after the reliability test. From the above results, it has been clarified that by using the radical polymerizable substance having a specific structure of the present invention, both good connection resistance and adhesive force can be achieved.
（実施例４）
実施例１で得られたフィルム状接着剤を、真空包装を施して、４０℃で３日間放置した後、実施例１と同様にＦＰＣとＩＴＯとを１６０℃、３ＭＰa、１０秒で加熱圧着を行った。以上のようにして行った接続体の接着強度、接続抵抗を測定したところ、接着強度は７２０Ｎ/ｍ、接続抵抗は１.６Ωを示し、放置安定性に優れることが分かった。
Example 4
The film adhesive obtained in Example 1 was vacuum-packed and allowed to stand at 40 ° C. for 3 days, and then FPC and ITO were thermocompression bonded at 160 ° C., 3 MPa, and 10 seconds as in Example 1. went. When the adhesion strength and connection resistance of the connection body as described above were measured, the adhesion strength was 720 N / m, the connection resistance was 1.6Ω, and it was found that the storage stability was excellent.
（実施例５）
半導体チップ（３×１０ｍｍ，高さ０．５ｍｍ，主面の４辺周囲にバンプとよばれる１００μｍ角、高さ２０μｍの突起した金電極が存在）のバンプ配置と対応した接続端子を有する厚み１ｍｍのガラスエポキシ基板（回路は銅箔で厚み１８μｍ）から作製した半導体搭載用基板を用意した。半導体搭載用基板の回路表面には、ニッケル／金めっきを施した。半導体チップの突起電極と半導体搭載用基板とを上記実施例３のフィルム状接着剤を用いて次のようにして接続した。半導体搭載用基板の回路面にフィルム状接着材を８０℃、１ＭＰａ、３秒で仮圧着し、剥離性フッ素樹脂フィルムを剥離後、半導体チップの突起電極と半導体搭載用基板との位置合せを行い、１８０℃、１０ｋｇｆ／チップの温度及び圧力により２０秒間加熱圧着した。
これによって、フィルム状接着剤を介して半導体チップの突起電極と半導体搭載用基板の回路とを電気的に接続すると同時に半導体チップと半導体搭載用基板の電極はフィルム状接着剤の硬化によって、この接続状態を保持した。このようにして得た半導体チップと半導体搭載用基板を接続した半導体装置を（−５５℃、３０分）／（１２５℃、３０分）の条件で繰り返す冷熱サイクル試験に曝した。この冷熱サイクル試験１，０００回後の半導体チップの突起電極と基板回路の接続抵抗を測定したところ接続抵抗の上昇がなく、良好な接続信頼性を示した。
(Example 5)
Thickness 1mm with connecting terminals corresponding to bump arrangement of semiconductor chip (3x10mm, height 0.5mm, 100μm square called bumps around the four sides of the main surface, and 20μm high protruding gold electrodes) The board | substrate for semiconductor mounting produced from the glass epoxy board | substrate (The circuit is copper foil and thickness is 18 micrometers) was prepared. The circuit surface of the semiconductor mounting substrate was subjected to nickel / gold plating. The protruding electrode of the semiconductor chip and the semiconductor mounting substrate were connected as follows using the film adhesive of Example 3 above. A film adhesive is temporarily bonded to the circuit surface of the semiconductor mounting substrate at 80 ° C., 1 MPa for 3 seconds, and after peeling the peelable fluororesin film, the semiconductor chip protruding electrode and the semiconductor mounting substrate are aligned. The thermocompression bonding was carried out for 20 seconds at a temperature and pressure of 180 kg, 10 kgf / chip.
As a result, the protruding electrode of the semiconductor chip and the circuit of the semiconductor mounting substrate are electrically connected via the film adhesive, and at the same time, the connection of the semiconductor chip and the electrode of the semiconductor mounting substrate by the curing of the film adhesive. Retained state. The semiconductor device obtained by connecting the semiconductor chip thus obtained and the semiconductor mounting substrate was subjected to a repeated thermal cycle test under the condition of (−55 ° C., 30 minutes) / (125 ° C., 30 minutes). When the connection resistance between the protruding electrode of the semiconductor chip and the substrate circuit after 1,000 times of the thermal cycle test was measured, there was no increase in the connection resistance, and good connection reliability was shown.
本発明によれば、ラジカル硬化系でありながら、高い接着強度を示し、かつ信頼性試験（例えば８５℃／８５%ＲＨ放置）後においても安定した性能を有し、さらに貯蔵安定性にも優れる接着剤を提供することができる。
According to the present invention, although it is a radical curing system, it exhibits high adhesive strength, has stable performance even after a reliability test (for example, left at 85 ° C./85% RH), and is excellent in storage stability. An adhesive can be provided.
Claims (8)
（一般式（Ａ）中、Ｒ1は、水素またはメチル基、Ｌは、１〜４０の整数を表す。また、Ｒ２は、一般式（Ｂ）及び／または（Ｃ）の構造であり、Ｍは１〜１０の整数、Ｎは１〜２０の整数であり繰り返し単位Ｌの中で任意の数を取る。） The adhesive according to claim 1, wherein the radical polymerizable substance (b) is a urethane (meth) acrylate compound represented by the following general formula (A).
(In the general formula (A), R 1 represents hydrogen or a methyl group, L represents an integer of 1 to 40, and R 2 has the structure of the general formula (B) and / or (C), M is an integer of 1 to 10, N is an integer of 1 to 20, and an arbitrary number is taken in the repeating unit L.)
A semiconductor device in which a semiconductor element is mounted on a mounting substrate via the adhesive according to any one of claims 1 to 5 and the electrodes are electrically connected.
Priority Applications (24)
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| JP2005074999A JP4760070B2 (en) | 2005-03-16 | 2005-03-16 | Adhesive, adhesive for circuit connection, connector and semiconductor device |
| EP11160369A EP2357215A1 (en) | 2005-03-16 | 2006-03-15 | Use of an adhesive composition, a circuit connecting material, a process for the production of a circuit member connection structure and a semiconductor device |
| KR1020117006895A KR101140095B1 (en) | 2005-03-16 | 2006-03-15 | Connection Structure of Circuit Member and Circuit Connection Member |
| US11/908,897 US8518303B2 (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| CN201210279658.1A CN102796486B (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| PCT/JP2006/305092 WO2006098352A1 (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| KR1020107019373A KR101081671B1 (en) | 2005-03-16 | 2006-03-15 | Adhesive Composition, Circuit Connecting Material, Connection Structure of Circuit Member, and Semiconductor Device |
| CN201110222705.4A CN102382613B (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| CN2006800081746A CN101142292B (en) | 2005-03-16 | 2006-03-15 | Adhesive, adhesive for connecting circuit, connecting body and semiconductor device |
| CN201210284584.0A CN102807836B (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| CN2011102233002A CN102391822A (en) | 2005-03-16 | 2006-03-15 | Adhesive, adhesive for connecting circuit, connecting body and semiconductor device |
| EP06729113A EP1860170A4 (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| CN201210279675.5A CN102796487B (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| KR1020077023601A KR101013277B1 (en) | 2005-03-16 | 2006-03-15 | Adhesive Composition, Circuit Connecting Material, Connection Structure of Circuit Member, and Semiconductor Device |
| CN2011102205106A CN102277123B (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| CN2012102796789A CN102786908B (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| CN2011102224874A CN102355793A (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| KR1020117006893A KR101140062B1 (en) | 2005-03-16 | 2006-03-15 | Adhesive Composition, Circuit Connecting Material, Connection Structure of Circuit Member, and Semiconductor Device |
| KR1020117006892A KR101140122B1 (en) | 2005-03-16 | 2006-03-15 | Film-like Adhesive, Connection Structure of Circuit Member and Semiconductor Device |
| CN201110222529.4A CN102277124B (en) | 2005-03-16 | 2006-03-15 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| TW100103469A TWI383028B (en) | 2005-03-16 | 2006-03-16 | An adhesive composition, a circuit connection material, a connection structure of a circuit member, and a semiconductor device |
| TW100121031A TW201202374A (en) | 2005-03-16 | 2006-03-16 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| TW095109011A TW200704738A (en) | 2005-03-16 | 2006-03-16 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
| US13/494,474 US8696942B2 (en) | 2005-03-16 | 2012-06-12 | Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007046189A1 (en) * | 2005-10-18 | 2007-04-26 | Hitachi Chemical Company, Ltd. | Adhesive composition, circuit connecting material, connection structure of circuit connenctor, and semiconductor devices |
| WO2007046190A1 (en) * | 2005-10-18 | 2007-04-26 | Hitachi Chemical Company, Ltd. | Adhesive composition, circuit connecting material, connection structure of circuit connectors, and semiconductor devices |
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| WO2008152998A1 (en) * | 2007-06-12 | 2008-12-18 | Sony Chemical & Information Device Corporation | Adhesive composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101142292B (en) | 2012-09-26 |
| JP4760070B2 (en) | 2011-08-31 |
| CN101142292A (en) | 2008-03-12 |
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