JP2012214586A - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- JP2012214586A JP2012214586A JP2011079951A JP2011079951A JP2012214586A JP 2012214586 A JP2012214586 A JP 2012214586A JP 2011079951 A JP2011079951 A JP 2011079951A JP 2011079951 A JP2011079951 A JP 2011079951A JP 2012214586 A JP2012214586 A JP 2012214586A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive composition
- sheet
- adhesive sheet
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000002086 nanomaterial Substances 0.000 claims abstract description 40
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 33
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 164
- 239000007787 solid Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 description 33
- 229920000647 polyepoxide Polymers 0.000 description 33
- 239000010410 layer Substances 0.000 description 31
- 239000002041 carbon nanotube Substances 0.000 description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 description 20
- 239000010408 film Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 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 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- -1 polymethylene Polymers 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012510 hollow fiber Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 230000005611 electricity 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
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- VHNJXLWRTQNIPD-UHFFFAOYSA-N 3-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(O)CCOC(=O)C(C)=C VHNJXLWRTQNIPD-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 241001050985 Disco Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- BWPYBAJTDILQPY-UHFFFAOYSA-N Methoxyphenone Chemical compound C1=C(C)C(OC)=CC=C1C(=O)C1=CC=CC(C)=C1 BWPYBAJTDILQPY-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 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 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- OPECTNGATDYLSS-UHFFFAOYSA-N naphthalene-2-sulfonyl chloride Chemical compound C1=CC=CC2=CC(S(=O)(=O)Cl)=CC=C21 OPECTNGATDYLSS-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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Abstract
Description
本発明は、粘着剤組成物及び粘着シートに関し、詳しくは半導体ウエハ加工などに用いられる帯電防止性または導電性ならびに再剥離性を有する粘着剤組成物及び粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet, and more particularly to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having antistatic properties or conductivity and removability, which are used for semiconductor wafer processing and the like.
従来から、電気部品、電子部品、半導体部品を生産する際に、ダイシングなどの処理工程において部品の固定や、回路などの保護を目的として粘着シートが使用されている。このような粘着シートとしては、基材フィルムに再剥離性のアクリル系粘着剤層が設けられた粘着シートや、貼付後の処理工程においては強い剥離抵抗性があるが、剥離時には小さい力で剥離可能なエネルギー線架橋型再剥離性粘着剤層が設けられた粘着シートなどがある。 Conventionally, when producing electrical parts, electronic parts, and semiconductor parts, pressure-sensitive adhesive sheets have been used for the purpose of fixing parts and protecting circuits in processing steps such as dicing. As such a pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet in which a releasable acrylic pressure-sensitive adhesive layer is provided on a base film, or a strong peeling resistance in a treatment process after sticking, is peeled off with a small force at the time of peeling. There is a pressure sensitive adhesive sheet provided with a possible energy ray crosslinkable removable pressure sensitive adhesive layer.
これらの粘着シートは、所定の処理工程が終了すると剥離されるが、このとき部品と粘着シートとの間に剥離帯電と呼ばれる静電気が発生する。この静電気による被着体への悪影響（例えば、回路の破壊）を抑えるため、基材フィルムの背面側を帯電防止処理した粘着シートや、粘着剤層へ帯電防止剤を添加混合した粘着シート、基材フィルムと粘着剤層との間に帯電防止中間層を設けた粘着シートが使用されている。 These pressure-sensitive adhesive sheets are peeled off when a predetermined processing step is completed. At this time, static electricity called peeling charging is generated between the component and the pressure-sensitive adhesive sheet. In order to suppress this adverse effect on the adherend due to static electricity (for example, circuit destruction), a pressure-sensitive adhesive sheet having an antistatic treatment on the back side of the base film, a pressure-sensitive adhesive sheet in which an antistatic agent is added to the pressure-sensitive adhesive layer, A pressure-sensitive adhesive sheet in which an antistatic intermediate layer is provided between the material film and the pressure-sensitive adhesive layer is used.
ところが、回路を形成する部品の基板がセラミックやガラスなどの絶縁材料である場合には、静電気の発生量が大きく、減衰に時間がかかる。このような場合には、前記粘着シートを用いても帯電防止性の効果が十分でなく、回路が破壊されてしまう可能性が大きかった。このため、上記部品の生産工程においては、例えば、イオナイザーなどの静電気除去装置をさらに使用して周囲環境における静電気の発生を抑えている。 However, when the substrate of the component forming the circuit is an insulating material such as ceramic or glass, the amount of static electricity generated is large and it takes time to attenuate. In such a case, even if the pressure-sensitive adhesive sheet is used, the effect of antistatic property is not sufficient, and there is a high possibility that the circuit is destroyed. For this reason, in the production process of the parts, for example, a static eliminating device such as an ionizer is further used to suppress the generation of static electricity in the surrounding environment.
しかしながら、上記の対策では十分な帯電防止効果が得られず、生産性が低く、また保護性も十分でないという問題があった。また、粘着シートの剥離帯電の防止には、基材フィルム側ではなく、粘着剤側に処理するのが効果的と考えられている。従来の帯電防止粘着剤としては、銅粉、銀粉、ニッケル粉、アルミニウム粉などの金属粉などの導電性物質を粘着剤中に分散させたものが多用されている。しかし、かかる帯電防止粘着剤において、優れた導電性を得るために、導電性物質粒子相互の接触が密になるように導電性物質を多量に含有させると粘着力が低下してしまう。一方、粘着力を高めるために導電性物質の含有量を低減させると、上記各接触が不十分となって、導電性が低下するという二律背反の問題があった。 However, the above countermeasures have a problem that a sufficient antistatic effect cannot be obtained, productivity is low, and protection is not sufficient. In addition, it is considered effective to treat the pressure-sensitive adhesive sheet not on the base film side but on the pressure-sensitive adhesive side in order to prevent peeling charging. As a conventional antistatic pressure-sensitive adhesive, a material in which a conductive material such as copper powder, silver powder, nickel powder, aluminum powder or the like is dispersed in a pressure-sensitive adhesive is widely used. However, in such an antistatic pressure-sensitive adhesive, in order to obtain excellent conductivity, if a large amount of conductive material is contained so that the contact between the conductive material particles is intimate, the adhesive strength is reduced. On the other hand, when the content of the conductive material is reduced in order to increase the adhesive strength, there is a trade-off problem that the above contacts become insufficient and the conductivity is lowered.
導電性を向上するため、カーボンナノチューブ及びカーボンマイクロコイルの何れか一方又は双方を粘着剤中に混合させた導電性粘着剤を、金属蒸着織布に塗布した粘着シートが提案されている（特許文献１参照）。しかしながら、特許文献１に記載されている粘着シートは、支持体層が金属蒸着織布であり用途が限定され、その導電性粘着剤は、汎用粘着シートに支持体として使用される樹脂フィルム材料への適応がなされておらず、支持体として樹脂フィルムを用いると、導電性が十分に発揮されない可能性がある。また、カーボンナノチューブは強い凝集性を示すので、カーボンナノチューブを単独で樹脂に混合させても、均一な分散が維持されず、性能が十分に発揮されない問題があった。 In order to improve conductivity, a pressure-sensitive adhesive sheet has been proposed in which a conductive pressure-sensitive adhesive in which one or both of carbon nanotubes and carbon microcoils are mixed in a pressure-sensitive adhesive is applied to a metal-deposited woven fabric (Patent Document). 1). However, the pressure-sensitive adhesive sheet described in Patent Document 1 has a support layer that is a metal-deposited woven fabric, and its use is limited. The conductive pressure-sensitive adhesive can be used as a resin film material used as a support for a general-purpose pressure-sensitive adhesive sheet. If the resin film is used as the support, there is a possibility that the conductivity is not sufficiently exhibited. In addition, since carbon nanotubes exhibit strong cohesiveness, there is a problem that even if carbon nanotubes are mixed with a resin alone, uniform dispersion is not maintained and performance is not sufficiently exhibited.
また、特許文献２には、導電性ポリマーとカーボンナノチューブとを含む導電層を設けた表面保護フィルムが開示されている。しかし、導電層に粘着性を付与することは記載がなく、粘着シートに関する教示はない。特許文献３には、親水性ポリマーを配合することで帯電防止性が付与された帯電防止性粘着フィルムが開示されている。しかし、この粘着フィルムは、親水性ポリマーを含有するため、水に触れるような状況、たとえば水を噴霧しつつウエハのダイシングを行うような半導体加工プロセス等では、使用することができない。 Patent Document 2 discloses a surface protective film provided with a conductive layer containing a conductive polymer and carbon nanotubes. However, there is no description of imparting adhesiveness to the conductive layer, and there is no teaching regarding the adhesive sheet. Patent Document 3 discloses an antistatic pressure-sensitive adhesive film provided with antistatic properties by blending a hydrophilic polymer. However, since this adhesive film contains a hydrophilic polymer, it cannot be used in a situation where it comes into contact with water, for example, in a semiconductor processing process where wafer dicing is performed while spraying water.
また、上記したように、カーボンナノ材料は強い凝集性を示すので、均一な分散が維持されず、性能が十分に発揮されない問題がある。この問題を解消するため、特許文献４、５では、分散剤を併用してカーボンナノ材料を粘着剤中に分散させる方法も提案されている。しかし、分散剤はイオン性のものが多く、半導体加工プロセスに使用されると半導体を汚染するおそれがある。また、分散剤の分子量が大きくなるほど、粘着剤との相溶性が悪化する傾向があり、粘着物性を不安定化しやすいという問題があった。 In addition, as described above, since the carbon nanomaterial exhibits strong cohesiveness, there is a problem that uniform dispersion is not maintained and performance is not sufficiently exhibited. In order to solve this problem, Patent Documents 4 and 5 also propose a method in which a carbon nanomaterial is dispersed in an adhesive using a dispersant. However, many dispersants are ionic and may contaminate the semiconductor when used in a semiconductor processing process. In addition, as the molecular weight of the dispersant increases, the compatibility with the pressure-sensitive adhesive tends to deteriorate, and the physical properties of the pressure-sensitive adhesive tend to be unstable.
なお、特許文献６には、ダイシングシートの粘着剤層に遊離のエポキシ基含有化合物を配合することで、粘着剤層とウエハ（チップ）との過度の密着が防止され、チップのピックアップ不良が低減されることが教示されている。しかし、特許文献６においては、前述したような剥離帯電にともなう諸問題については認識されていない。 In Patent Document 6, by adding a free epoxy group-containing compound to the adhesive layer of the dicing sheet, excessive adhesion between the adhesive layer and the wafer (chip) is prevented, and chip pickup defects are reduced. It is taught that However, Patent Document 6 does not recognize the problems associated with the peeling charging as described above.
本発明は、上記従来技術の状況に鑑みてなされたものであり、優れた帯電防止性または導電性ならびに再剥離性を有する粘着剤組成物、及び粘着シートを提供することを目的とする。さらに、エネルギー線を照射して硬化する場合に、その硬化後も優れた帯電防止性または導電性ならびに再剥離性を有する粘着剤組成物、及び粘着シートを提供することを目的とする。 The present invention has been made in view of the above-described state of the art, and an object thereof is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having excellent antistatic properties, electrical conductivity, and removability. Furthermore, when it hardens | cures by irradiating an energy ray, it aims at providing the adhesive composition and the adhesive sheet which have the antistatic property or electroconductivity and re-peelability which were excellent after the hardening.
本発明者らは、上記課題を解決するために鋭意検討したところ、エポキシ基含有化合物をカーボンナノ材料の分散剤として使用することを着想するに至った。エポキシ基含有化合物は、一般に粘着剤として使用されるアクリル重合体との相溶性に優れ、またダイシングシートの粘着剤層に配合した場合には、被着体との過度の密着を防止するという作用も期待される。したがって、エポキシ基含有化合物がカーボンナノ材料の分散剤として使用できる場合には、上述の諸問題を一挙に解消できる可能性がある。本発明は、このような着想に基づいて完成されるに至った。 The present inventors diligently studied to solve the above-mentioned problems, and came up with the idea of using an epoxy group-containing compound as a dispersant for the carbon nanomaterial. Epoxy group-containing compounds are generally compatible with acrylic polymers that are generally used as pressure-sensitive adhesives, and, when blended in the pressure-sensitive adhesive layer of a dicing sheet, prevent excessive adhesion to the adherend. Is also expected. Therefore, when the epoxy group-containing compound can be used as a dispersant for the carbon nanomaterial, the above-described problems may be solved at once. The present invention has been completed based on such an idea.
上記のような着想に基づいて完成された本発明は、下記の事項を要旨として含む。
（１）粘着剤中に、カーボンナノ材料およびエポキシ基含有化合物が含有されてなる粘着剤組成物。
（２）エポキシ基含有化合物の２３℃のおける粘度が７０００〜１８０００ｍＰａ・ｓである（１）に記載の粘着剤組成物。
（３）カーボンナノ材料の平均外周径が１〜１０００ｎｍ、平均長さが０．０１〜１００μｍである（１）または（２）に記載の粘着剤組成物。
（４）粘着剤が、エネルギー線重合性基を有する化合物を含む（１）〜（３）のいずれかに記載の粘着剤組成物。
（５）さらに、光重合開始剤を含む（４）に記載の粘着剤組成物。
（６）カーボンナノ材料を粘着剤組成物の固形分中０．０１〜２０質量％含有している（１）〜（５）のいずれかに記載の粘着剤組成物。
（７）基材シートの片面又は両面に、（１）〜（６）のいずれかに記載の粘着剤組成物からなる粘着剤層が設けられている粘着シート。
（８）粘着シートが半導体ウエハ加工に用いられるものである（７）に記載の粘着シート。
（９）半導体ウエハ加工が、半導体ウエハをダイシングして半導体チップを得る工程および得られた半導体チップをピックアップする工程を含む（８）に記載の粘着シート。
The present invention completed based on the above idea includes the following matters as a gist.
(1) A pressure-sensitive adhesive composition comprising a carbon nanomaterial and an epoxy group-containing compound in a pressure-sensitive adhesive.
(2) The pressure-sensitive adhesive composition according to (1), wherein the viscosity at 23 ° C. of the epoxy group-containing compound is 7000 to 18000 mPa · s.
(3) The pressure-sensitive adhesive composition according to (1) or (2), wherein the carbon nanomaterial has an average outer diameter of 1 to 1000 nm and an average length of 0.01 to 100 μm.
(4) The pressure-sensitive adhesive composition according to any one of (1) to (3), wherein the pressure-sensitive adhesive contains a compound having an energy beam polymerizable group.
(5) The pressure-sensitive adhesive composition according to (4), further comprising a photopolymerization initiator.
(6) The pressure-sensitive adhesive composition according to any one of (1) to (5), containing 0.01 to 20% by mass of a carbon nanomaterial in the solid content of the pressure-sensitive adhesive composition.
(7) The adhesive sheet in which the adhesive layer which consists of an adhesive composition in any one of (1)-(6) is provided in the single side | surface or both surfaces of a base material sheet.
(8) The adhesive sheet according to (7), wherein the adhesive sheet is used for semiconductor wafer processing.
(9) The adhesive sheet according to (8), wherein the semiconductor wafer processing includes a step of dicing the semiconductor wafer to obtain a semiconductor chip and a step of picking up the obtained semiconductor chip.
本発明の粘着剤組成物は、導電材であるカーボンナノ材料の分散性が高く、優れた帯電防止性または導電性を有し、また、エネルギー線を照射して硬化する場合にも、その硬化後も優れた帯電防止性または導電性を有する。さらに、本発明の粘着剤組成物にはエポキシ基含有化合物が含まれるため、半導体ウエハ等の被着体に貼付された場合であっても、エポキシ基含有化合物の作用により、被着体と粘着剤層との過度の密着が防止され、優れた再剥離性を示す。すなわち、加工対象であるウエハの裏面と粘着剤層との相互作用が小さくなり、ウエハ裏面と粘着剤層とが過度に接着せず、ダイシング工程後のチップのピックアップ工程におけるピックアップ不良を低減することができ、半導体チップの製造を効率よく行うことができる。 The pressure-sensitive adhesive composition of the present invention has high dispersibility of the carbon nanomaterial that is a conductive material, has excellent antistatic properties or conductivity, and also cures when irradiated with energy rays. Later, it has excellent antistatic properties or electrical conductivity. Further, since the pressure-sensitive adhesive composition of the present invention contains an epoxy group-containing compound, even when it is attached to an adherend such as a semiconductor wafer, it adheres to the adherend by the action of the epoxy group-containing compound. Excessive adhesion with the agent layer is prevented, and excellent removability is exhibited. That is, the interaction between the back surface of the wafer to be processed and the pressure-sensitive adhesive layer is reduced, the back surface of the wafer and the pressure-sensitive adhesive layer are not excessively bonded, and pickup defects in the chip pick-up process after the dicing process are reduced. The semiconductor chip can be manufactured efficiently.
本発明の粘着剤組成物には、粘着剤と、カーボンナノ材料と、エポキシ基含有化合物が含有されており、粘着剤中に、カーボンナノ材料が均一に分散されている。ここで、均一に分散とは、粘着剤組成物及びそれを用いて形成された粘着剤層において、目視でカーボンナノ材料が凝集することなく、分散している状態をいう。カーボンナノ材料が均一に分散していると、良好な帯電防止性又は導電性を発揮する。ここで、帯電防止性を有するとは、表面抵抗率が１０１３Ω／□未満であることをいい、導電性を有するとは、表面抵抗率が１０８Ω／□未満であることをいう。なお、粘着剤組成物がエネルギー線重合性基を有する化合物を含む場合、粘着剤組成物の硬化前及び／又は硬化後の表面抵抗率が前記の範囲であれば帯電防止性又は導電性を有するものとする。 The pressure-sensitive adhesive composition of the present invention contains a pressure-sensitive adhesive, a carbon nanomaterial, and an epoxy group-containing compound, and the carbon nanomaterial is uniformly dispersed in the pressure-sensitive adhesive. Here, “uniformly dispersed” refers to a state in which the carbon nanomaterial is dispersed without visual aggregation in the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition. When the carbon nanomaterial is uniformly dispersed, good antistatic property or conductivity is exhibited. Here, having antistatic properties means that the surface resistivity is less than 10 13 Ω / □, and having conductivity means that the surface resistivity is less than 10 8 Ω / □. When the pressure-sensitive adhesive composition contains a compound having an energy ray polymerizable group, the pressure-sensitive adhesive composition has antistatic properties or electrical conductivity as long as the surface resistivity before and / or after curing is within the above range. Shall.
粘着剤は、特に限定はされないが、カーボンナノ材料の分散性向上の観点から、有機溶剤可溶性粘着剤であることが好ましい。このような粘着剤としては、例えば、天然ゴム系粘着剤、合成ゴム系粘着剤、アクリル樹脂系粘着剤、ポリビニルエーテル樹脂系粘着剤、ウレタン樹脂系粘着剤、シリコーン樹脂系粘着剤などが挙げられる。 The pressure-sensitive adhesive is not particularly limited, but is preferably an organic solvent-soluble pressure-sensitive adhesive from the viewpoint of improving the dispersibility of the carbon nanomaterial. Examples of such adhesives include natural rubber adhesives, synthetic rubber adhesives, acrylic resin adhesives, polyvinyl ether resin adhesives, urethane resin adhesives, silicone resin adhesives, and the like. .
アクリル樹脂系粘着剤の具体例は、（メタ）アクリル酸エステル共重合体を主剤とする。（メタ）アクリル酸エステル共重合体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸−２−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチルなどの（メタ）アクリル酸アルキルエステルの１種以上の単量体と、必要に応じて、アクリル酸−２−ヒドロキシエチル、アクリル酸−２−ヒドロキシプロピル、アクリル酸−３−ヒドロキシプロピル、アクリル酸−３−ヒドロキシブチル、アクリル酸−４−ヒドロキシブチル、メタクリル酸−２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシプロピル、メタクリル酸−３−ヒドロキシプロピル、メタクリル酸−３−ヒドロキシブチル、メタクリル酸−４−ヒドロキシブチルなどの水酸基含有（メタ）アクリル酸アルキルエステル；アクリル酸、メタクリル酸などの（メタ）アクリル酸；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル；アクリロニトリル、メタクリロニトリルなどのシアノ基含有化合物；アクリルアミドなどのアミド基含有化合物；スチレン、ビニルピリジンなどの芳香族化合物などの共重合性単量体の１種以上の単量体の共重合体などが挙げられる。 A specific example of the acrylic resin-based pressure-sensitive adhesive is mainly composed of a (meth) acrylic acid ester copolymer. Examples of (meth) acrylic acid ester copolymers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. One or more monomers of (meth) acrylic acid alkyl ester such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, acrylic acid -3-hydroxybutyl, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, methacrylic acid-4 -Hydroxybutyl etc. Hydroxyl group-containing (meth) acrylic acid alkyl ester; (meth) acrylic acid such as acrylic acid and methacrylic acid; vinyl ester such as vinyl acetate and vinyl propionate; cyano group-containing compound such as acrylonitrile and methacrylonitrile; amide such as acrylamide Group-containing compounds: Copolymers of one or more monomers of copolymerizable monomers such as aromatic compounds such as styrene and vinylpyridine.
（メタ）アクリル酸エステル共重合体における（メタ）アクリル酸エステルに由来する単位の含有割合は、５０〜９８質量％が好ましく、６０〜９５質量％がより好ましく、７０〜９３質量％がさらに好ましい。（メタ）アクリル酸エステル共重合体の重量平均分子量は、３０万〜２５０万が好ましく、４０万〜１５０万がより好ましく、４５万〜１００万が特に好ましい。なお、本明細書において、重量平均分子量とは、ゲルパーミエーションクロマトグラフィー法により測定した標準ポリスチレン換算の値である。 The content ratio of the units derived from the (meth) acrylic acid ester in the (meth) acrylic acid ester copolymer is preferably 50 to 98% by mass, more preferably 60 to 95% by mass, and further preferably 70 to 93% by mass. . The weight average molecular weight of the (meth) acrylic acid ester copolymer is preferably 300,000 to 2,500,000, more preferably 400,000 to 1,500,000, particularly preferably 450,000 to 1,000,000. In the present specification, the weight average molecular weight is a value in terms of standard polystyrene measured by gel permeation chromatography.
これらの粘着剤は、１種単独でまたは２種以上を組み合わせて用いることができる。これらの粘着剤のうち、アクリル樹脂系粘着剤が好ましく用いられる。特に、アクリル系共重合体を、ポリイソシアナート系架橋剤、アジリジン系架橋剤、キレート系架橋剤などの架橋剤の１種以上で架橋させて得られるアクリル樹脂系粘着剤が好ましい。 These pressure-sensitive adhesives can be used alone or in combination of two or more. Of these pressure-sensitive adhesives, acrylic resin-based pressure-sensitive adhesives are preferably used. In particular, an acrylic resin-based pressure-sensitive adhesive obtained by crosslinking an acrylic copolymer with one or more of a crosslinking agent such as a polyisocyanate-based crosslinking agent, an aziridine-based crosslinking agent, or a chelate-based crosslinking agent is preferable.
ポリイソシアナート系架橋剤としては、トリレンジイソシアナート（ＴＤＩ）、ヘキサメチレンジイソシアナート（ＨＭＤＩ）、イソホロンジイソシアナート（ＩＰＤＩ）、キシリレンジイソシアナート（ＸＤＩ）、水素化トリレンジイソシアナート、ジフェニルメタンジイソシアナート及びその水添体、ポリメチレンポリフェニルポリイソシアナート、ナフチレン−１，５−ジイソシアナート、ポリイソシアナートプレポリマー、ポリメチロールプロパン変性ＴＤＩなどが挙げられる。 Polyisocyanate-based crosslinking agents include tolylene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated tolylene diisocyanate, diphenylmethane Examples thereof include diisocyanates and hydrogenated products thereof, polymethylene polyphenyl polyisocyanates, naphthylene-1,5-diisocyanates, polyisocyanate prepolymers, and polymethylolpropane-modified TDI.
架橋剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。架橋剤の使用量は、アクリル系共重合体１００質量部に対して、０．０１〜２０質量部が好ましい。 A crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. As for the usage-amount of a crosslinking agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of acrylic copolymers.
カーボンナノ材料は、種々の形状のものが用いられる。具体例としては、例えば、カーボンナノコイル、単層又は多層のカーボンナノチューブなどが挙げられる。カーボンナノコイルの形状は、円筒状の中空の繊維状のものであってもよいし、中空でない繊維状のものであってもよい。その末端形状は必ずしも円筒状である必要はなく、例えば円錐状など変形していても差し支えない。さらに、その末端は、閉じた構造であってもよいし、開いた構造であってもよい。また、カーボンナノチューブの形状は、一般に円筒状の中空の繊維状のものであるが、その末端形状は必ずしも円筒状である必要はなく、例えば円錐状など変形していても差し支えない。さらに、カーボンナノチューブの末端は、閉じた構造であってもよいし、開いた構造であってもよい。カーボンナノチューブの市販品としては、イルジン・ナノテクノロジー社製の商品名「ＣＶＤ−ＭＷＮＴ ＣＭ−９５」、昭和電工社製の商品名「ＶＧＣＦ」、「ＶＧＣＦ−Ｘ」、「ＶＧＣＦ−Ｈ」、Ｎａｎｏｃｙｌ社製、商品名「Ｎａｎｏｃｙｌ ＮＣ−７０００」などが好ましく挙げられる。カーボンナノ材料の含有量は、粘着剤組成物の固形分中０．０１〜２０質量％が好ましく、０．０５〜１０質量％がより好ましい。 Carbon nanomaterials having various shapes are used. Specific examples include carbon nanocoils, single-walled or multi-walled carbon nanotubes, and the like. The shape of the carbon nanocoil may be a cylindrical hollow fiber shape or a non-hollow fiber shape. The end shape does not necessarily have to be cylindrical, and may be deformed, for example, conical. Furthermore, the end may be a closed structure or an open structure. The shape of the carbon nanotube is generally a hollow cylindrical fiber shape, but the end shape does not necessarily need to be cylindrical, and may be deformed, for example, conical. Furthermore, the end of the carbon nanotube may be a closed structure or an open structure. Commercially available carbon nanotubes include trade names “CVD-MWNT CM-95” manufactured by Irujin Nanotechnology, trade names “VGCF”, “VGCF-X”, “VGCF-H”, Nanocyl manufactured by Showa Denko K.K. The product name “Nanocyl NC-7000” manufactured by the company is preferred. The content of the carbon nanomaterial is preferably 0.01 to 20% by mass and more preferably 0.05 to 10% by mass in the solid content of the pressure-sensitive adhesive composition.
カーボンナノ材料は、好ましくは平均外周径が１〜１０００ｎｍ、平均長さが０．０１〜１００μｍであり、より好ましくは平均外周径が２〜５００ｎｍ、平均長さが０．１〜５０μｍであり、さらに好ましくは平均外周径が５〜２００ｎｍ、平均長さが０．５〜３０μｍである。 The carbon nanomaterial preferably has an average outer peripheral diameter of 1 to 1000 nm and an average length of 0.01 to 100 μm, more preferably an average outer peripheral diameter of 2 to 500 nm and an average length of 0.1 to 50 μm. More preferably, the average outer diameter is 5 to 200 nm and the average length is 0.5 to 30 μm.
ここで、平均外周径と平均長さは、電子顕微鏡を用いてカーボンナノ材料の任意の１００点につき各々測定した値の平均値とする。なお、平均外周径の測定は、カーボンナノ材料の長さ方向中央部について行う。また、カーボンナノ材料の形状が同心円の断面形状を有する円筒形状である場合は、外周径は、外側の円周の直径を意味する。また、カーボンナノ材料は、平均外周径に対する平均長さの比（平均長さ／平均外周径）が、１０〜６０００であることが好ましく、２０〜５００であることがより好ましい。 Here, let an average outer periphery diameter and average length be an average value of the value each measured about arbitrary 100 points | pieces of the carbon nanomaterial using the electron microscope. In addition, the measurement of an average outer periphery diameter is performed about the center part of the length direction of carbon nanomaterial. Moreover, when the shape of the carbon nanomaterial is a cylindrical shape having a concentric cross-sectional shape, the outer diameter means the diameter of the outer circumference. Moreover, as for carbon nanomaterial, ratio of the average length with respect to an average outer periphery diameter (average length / average outer periphery diameter) is preferably 10-6000, and more preferably 20-500.
さらに、粘着剤層にはエポキシ基含有化合物が配合されてなる。本発明で使用されるエポキシ基含有化合物としては、分子内に少なくとも１個のエポキシ基を有し、たとえばビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＳ型、ビフェニル型、フェノールノボラック型、クレゾールノボラック型のエポキシ樹脂などが挙げられる。 Furthermore, an epoxy group-containing compound is blended in the pressure-sensitive adhesive layer. The epoxy group-containing compound used in the present invention has at least one epoxy group in the molecule, such as bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, phenol novolak type, and cresol novolak type. An epoxy resin etc. are mentioned.
エポキシ基含有化合物の２３℃のおける粘度は、好ましくは７０００〜１８０００ｍＰａ・ｓ、さらに好ましくは８０００〜１６０００ｍＰａ・ｓ、特に好ましくは９０００〜１５０００ｍＰａ・ｓである。エポキシ基含有化合物の２３℃のおける粘度が上記範囲にあることで、カーボンナノ材料が粘着剤組成物中に、凝集せず均一に分散する。また、カーボンナノ材料を分散した後の粘着剤組成物において、カーボンナノ材料が沈降しづらく保管安定性に優れる。さらに、３本ロールミルでの混練が容易となる利点もある。 The viscosity at 23 ° C. of the epoxy group-containing compound is preferably 7000 to 18000 mPa · s, more preferably 8000 to 16000 mPa · s, and particularly preferably 9000 to 15000 mPa · s. When the viscosity at 23 ° C. of the epoxy group-containing compound is in the above range, the carbon nanomaterial is uniformly dispersed without being aggregated in the pressure-sensitive adhesive composition. In addition, in the pressure-sensitive adhesive composition after the carbon nanomaterial is dispersed, the carbon nanomaterial is difficult to settle and excellent in storage stability. Furthermore, there is an advantage that kneading with a three-roll mill is facilitated.
また、エポキシ基含有化合物の分子量は、比較的低いことが好ましく、１００〜２０００、好ましくは２００〜１０００、特に好ましくは３００〜５００である。分子量がこの範囲であれば、貼付後のチップと粘着剤の界面にエポキシ基含有化合物が存在しやすくなり、チップのピックアップ力を低減させる効果をもつ。 Moreover, it is preferable that the molecular weight of an epoxy group containing compound is comparatively low, and is 100-2000, Preferably it is 200-1000, Most preferably, it is 300-500. If the molecular weight is within this range, an epoxy group-containing compound is likely to be present at the interface between the chip and the pressure-sensitive adhesive after pasting, which has the effect of reducing the pick-up force of the chip.
エポキシ基含有化合物の配合割合は、エポキシ基含有化合物の種類により一概には決定できないが、一般的には粘着剤層を構成する全成分の合計１００質量部中（固形分中）に、０．１〜５０質量部、好ましくは０．２〜２５質量部、特に好ましくは０．５〜１０質量部程度用いられる。 The blending ratio of the epoxy group-containing compound cannot be determined unconditionally depending on the type of the epoxy group-containing compound, but is generally 0.001 in a total of 100 parts by mass (in the solid content) of all components constituting the pressure-sensitive adhesive layer. 1-50 mass parts, Preferably it is 0.2-25 mass parts, Most preferably, about 0.5-10 mass parts is used.
上記エポキシ基含有化合物は、粘着剤層中に遊離の状態で含まれていることが好ましい。すなわち、粘着剤層は、好ましくは“遊離のエポキシ基含有化合物”を含んでいる。ここで、遊離の状態とは、エポキシ基含有化合物が（メタ）アクリル酸エステル共重合体等の他の成分と実質的に未反応の状態にあることをいう。具体的には、粘着剤層のゾル成分のエポキシ基の滴定によって、未反応のエポキシ基含有化合物の有無が判断できる。 The epoxy group-containing compound is preferably contained in the pressure-sensitive adhesive layer in a free state. That is, the pressure-sensitive adhesive layer preferably contains a “free epoxy group-containing compound”. Here, the free state means that the epoxy group-containing compound is substantially unreacted with other components such as a (meth) acrylic acid ester copolymer. Specifically, the presence or absence of an unreacted epoxy group-containing compound can be determined by titration of the epoxy group of the sol component of the pressure-sensitive adhesive layer.
したがって、本発明における粘着剤層には、上記エポキシ基含有化合物と反応する物質（エポキシ硬化剤）および反応を促進する物質（反応触媒）は実質的に含まれないことが好ましい。粘着剤層中にエポキシ硬化剤および反応触媒が含まれると、半導体ウエハの貼付後、エポキシ基含有化合物が反応して硬化し、遊離のエポキシ基含有化合物が減少するため本発明の効果が得られないことがある。また、半導体ウエハと粘着剤層とが接着することがあり、ピックアップ不良の原因となる。実質的に含まれることのないエポキシ硬化剤および反応触媒としては、アミン類、有機酸、酸無水物、フェノール樹脂、尿素樹脂、ポリアミドがあげられる。 Therefore, it is preferable that the pressure-sensitive adhesive layer in the present invention does not substantially contain a substance that reacts with the epoxy group-containing compound (epoxy curing agent) and a substance that promotes the reaction (reaction catalyst). When an epoxy curing agent and a reaction catalyst are contained in the pressure-sensitive adhesive layer, the epoxy group-containing compound reacts and cures after the semiconductor wafer is stuck, and the effect of the present invention is obtained because the free epoxy group-containing compound is reduced. There may not be. In addition, the semiconductor wafer and the pressure-sensitive adhesive layer may adhere to each other, causing a pickup failure. Examples of the epoxy curing agent and reaction catalyst which are not substantially contained include amines, organic acids, acid anhydrides, phenol resins, urea resins, and polyamides.
上記のように本発明における粘着剤層は、実質的に粘着剤、カーボンナノ材料およびエポキシ基含有化合物からなる。また、本発明における粘着剤層は、エネルギー線硬化性の粘着剤であってもよい。 As described above, the pressure-sensitive adhesive layer in the present invention substantially comprises a pressure-sensitive adhesive, a carbon nanomaterial, and an epoxy group-containing compound. The pressure-sensitive adhesive layer in the present invention may be an energy ray-curable pressure-sensitive adhesive.
本発明の粘着剤組成物を、エネルギー線を照射することにより硬化させる場合は、粘着剤組成物中にエネルギー線重合性基を有する化合物を含有するエネルギー線硬化型粘着剤を用いる。 When the pressure-sensitive adhesive composition of the present invention is cured by irradiation with energy rays, an energy ray-curable pressure-sensitive adhesive containing a compound having an energy ray polymerizable group in the pressure-sensitive adhesive composition is used.
エネルギー線重合性基を有する化合物としては、例えば、エネルギー線重合性基を有する粘着剤の主剤、エネルギー線重合性基を有するモノマーやオリゴマーなどが挙げられる。エネルギー線重合性基を有する粘着剤の主剤の例としては、（メタ）アクリル酸エステル共重合体中の水酸基やカルボキシル基（アクリル酸等）と反応する官能基及びエネルギー線重合性基を有する化合物を、（メタ）アクリル酸エステル共重合体に付加させたものなどが挙げられる。このような付加する化合物の例としては、２−メタクリロイルオキシエチルイソシアナートやメタクリル酸グリシジルなどが挙げられる。 Examples of the compound having an energy beam polymerizable group include a main component of a pressure-sensitive adhesive having an energy beam polymerizable group, a monomer and an oligomer having an energy beam polymerizable group, and the like. Examples of the main component of the pressure-sensitive adhesive having an energy ray-polymerizable group include a compound having a functional group and an energy ray-polymerizable group that react with a hydroxyl group or a carboxyl group (acrylic acid or the like) in a (meth) acrylic acid ester copolymer. And the like added to a (meth) acrylic acid ester copolymer. Examples of such a compound to be added include 2-methacryloyloxyethyl isocyanate and glycidyl methacrylate.
エネルギー線硬化型粘着剤に含有させるエネルギー線重合性基を有するモノマー及び／又はオリゴマーとしては、例えば、多官能アクリレート、ウレタンアクリレートやポリエステルアクリレート等の２官能基以上を有する多官能のエネルギー線硬化型のアクリル系化合物が挙げられ、ウレタンアクリレート系オリゴマーやポリエステルアクリレート系オリゴマーが好ましく、ウレタンアクリレート系オリゴマーが特に好ましい。 Examples of the monomer and / or oligomer having an energy ray polymerizable group to be contained in the energy ray curable pressure-sensitive adhesive include a polyfunctional energy ray curable type having two or more functional groups such as polyfunctional acrylate, urethane acrylate, and polyester acrylate. Acrylic acrylate oligomers and polyester acrylate oligomers are preferred, and urethane acrylate oligomers are particularly preferred.
エネルギー線重合性基を有するオリゴマーの分子量（重量平均分子量）は、１０００〜１０万が好ましい。特に、ウレタンアクリレート系オリゴマーの分子量は、１０００〜５００００が好ましく、２０００〜３００００がより好ましい。 As for the molecular weight (weight average molecular weight) of the oligomer which has an energy-beam polymeric group, 1000-100,000 are preferable. In particular, the molecular weight of the urethane acrylate oligomer is preferably 1000 to 50000, more preferably 2000 to 30000.
エネルギー線重合性基を有するモノマー及び／又はオリゴマーは、１種単独で使用してもよいし、２種以上を組合せて用いてもよい。エネルギー線重合性基を有するモノマー及び／又はオリゴマーの含有量は、特に制限ないが、粘着剤組成物の固形分中５〜８０質量％が好ましく、１５〜６０質量％がより好ましい。ここで、固形分とは、粘着剤層を形成する際に、乾燥により除去される成分、具体的には、後述する溶剤や分散媒を除いた成分をいう。 Monomers and / or oligomers having an energy beam polymerizable group may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in content of the monomer and / or oligomer which has an energy-beam polymeric group, 5-80 mass% is preferable in solid content of an adhesive composition, and 15-60 mass% is more preferable. Here, the solid content refers to a component removed by drying when forming the pressure-sensitive adhesive layer, specifically, a component excluding a solvent and a dispersion medium described later.
エネルギー線としては、紫外線、電子線、α線、β線、γ線などが挙げられる。紫外線を使用する場合は、硬化性組成物には、光重合開始剤を含有することが好ましい。光重合開始剤としては、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、メトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシアセトフェノンなどのアセトフェノン系化合物、ベンゾフェノン、ベンゾイル安息香酸、３，３’−ジメチル−４−メトキシベンゾフェノンなどのベンゾフェノン系化合物、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アニソインメチルエーテルなどのベンゾインエーテル系化合物、ベンジルジメチルケタールなどのケタール系化合物、２−ナフタレンスルホニルクロリドなどの芳香族スルホニルクロリド系化合物、１−フェノン−１，１−プロパンジオン−２−（ｏ−エトキシカルボニル）オキシムなどの光活性オキシム系化合物などの公知の光重合開始剤を用いることができ、また、オリゴマー型光重合開始剤を用いることもできる。 Examples of energy rays include ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used, the curable composition preferably contains a photopolymerization initiator. As the photopolymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenone compounds such as diethoxyacetophenone, benzophenone, benzoylbenzoic acid, benzophenone compounds such as 3,3′-dimethyl-4-methoxybenzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, anisoin methyl ether, etc. Benzoin ether compounds, ketal compounds such as benzyldimethyl ketal, aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride, 1-phenone-1,1-propanedione-2- (o-eth Aryloxycarbonyl) may be a known photopolymerization initiator such as light-active oxime compounds such as oximes, it may also be used an oligomer type photopolymerization initiator.
光重合開始剤は、１種単独で使用してもよいし、２種以上を組合せて用いてもよい。光重合開始剤の配合量は、エネルギー線重合性基を有する化合物１００質量部に対して０．１〜１５質量部が好ましく、０．２〜１０質量部がより好ましく、０．５〜５質量部がさらに好ましい。 A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type. 0.1-15 mass parts is preferable with respect to 100 mass parts of compounds which have an energy-beam polymeric group, as for the compounding quantity of a photoinitiator, 0.2-10 mass parts is more preferable, 0.5-5 masses Part is more preferred.
粘着剤中に、カーボンナノ材料をエポキシ基含有化合物により均一に分散させるには、分散媒中に粘着剤、カーボンナノ材料、エポキシ基含有化合物を混合して粘着剤分散液を得て、その粘着剤分散液をよく撹拌することが好ましい。さらに、カーボンナノ材料の分散性を向上するためには、カーボンナノ材料とエポキシ基含有化合物とを混合した後に、粘着剤を混合することが好ましい。撹拌は、公知の撹拌方法で行うことが出来るが、特に好ましくは超音波振動を与えて撹拌することが好ましい。撹拌時間は、特に制限ないが、通常０．５〜５時間が好ましい。 To uniformly disperse the carbon nanomaterial with the epoxy group-containing compound in the pressure-sensitive adhesive, the pressure-sensitive adhesive dispersion is obtained by mixing the pressure-sensitive adhesive, the carbon nanomaterial, and the epoxy group-containing compound in the dispersion medium. It is preferable to stir the agent dispersion well. Furthermore, in order to improve the dispersibility of the carbon nanomaterial, it is preferable to mix the carbon nanomaterial and the epoxy group-containing compound and then mix the adhesive. Stirring can be performed by a known stirring method, but it is particularly preferable to stir by applying ultrasonic vibration. The stirring time is not particularly limited but is usually preferably 0.5 to 5 hours.
粘着剤中に、カーボンナノ材料をエポキシ樹脂により、一層均一に分散させるには、予めカーボンナノ材料とエポキシ樹脂を、３本ロールミルなどを用いて、混練してカーボンナノ材料分散液を得て、次いで、そのカーボンナノ材料分散液を粘着剤に混合することが好ましい。粘着剤は、分散媒あるいはエネルギー線重合性基を有するモノマー及び／又はオリゴマーに分散または溶解された粘着剤分散液または粘着剤溶液の状態で使用することが好ましい。 In order to disperse the carbon nanomaterial more uniformly with the epoxy resin in the adhesive, the carbon nanomaterial and the epoxy resin are kneaded in advance using a three-roll mill to obtain a carbon nanomaterial dispersion liquid, Subsequently, it is preferable to mix the carbon nanomaterial dispersion liquid with the pressure-sensitive adhesive. The pressure-sensitive adhesive is preferably used in the state of a pressure-sensitive adhesive dispersion or pressure-sensitive adhesive solution dispersed or dissolved in a dispersion medium or a monomer and / or oligomer having an energy beam polymerizable group.
分散媒としては、有機溶剤が好ましい。有機溶剤としては、イソブタノール、イソプロパノールなどのアルコール類、ベンゼン、トルエン、キシレンなどの芳香族炭化水素、ヘキサン、ヘプタン、オクタン、ノナン、デカンなどの脂肪族炭化水素、酢酸エチル、酢酸ブチルなどのエステル、メチルエチルケトン、ジエチルケトン、ジイソプロピルケトン等のケトン、エチルセロソルブなどのセロソルブ系溶剤、プロピレングリコールモノメチルエーテルなどのグリコールエーテル系溶剤等が挙げられる。これらの内、芳香族溶剤が好ましい。 As the dispersion medium, an organic solvent is preferable. Organic solvents include alcohols such as isobutanol and isopropanol, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, nonane and decane, and esters such as ethyl acetate and butyl acetate. And ketones such as methyl ethyl ketone, diethyl ketone and diisopropyl ketone, cellosolv solvents such as ethyl cellosolve, glycol ether solvents such as propylene glycol monomethyl ether, and the like. Of these, aromatic solvents are preferred.
この場合、カーボンナノ材料分散液中のカーボンナノ材料の含有量は、０．０１〜２０質量％が好ましく、０．１〜１０質量％がより好ましく、１〜５質量％が特に好ましい。カーボンナノ材料分散液は、撹拌してカーボンナノ材料を均一に分散させることが好ましい。撹拌は、公知の撹拌方法で行うことが出来るが、特に好ましくは超音波振動を与えて撹拌することが好ましい。撹拌時間は、特に制限ないが、通常０．５〜５時間が好ましい。 In this case, the content of the carbon nanomaterial in the carbon nanomaterial dispersion liquid is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 1 to 5% by mass. The carbon nanomaterial dispersion liquid is preferably stirred to uniformly disperse the carbon nanomaterial. Stirring can be performed by a known stirring method, but it is particularly preferable to stir by applying ultrasonic vibration. The stirring time is not particularly limited but is usually preferably 0.5 to 5 hours.
本発明の粘着シートは、基材シートの片面又は両面に、上記粘着剤組成物からなる粘着剤層が設けられている。基材シートとしては、種々のプラスチックシート、フィルムが使用できる。基材シートの具体例としては、例えばポリエチレン樹脂、ポリプロピレン樹脂などのポリオレフィン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリブチレンテレフタレート樹脂などのポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン樹脂、ポリウレタン樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリイミド樹脂、フッ素系樹脂などの各種合成樹脂のシート、フィルムが挙げられ、特に、高強度であり安価であることから、ポリエチレンテレフタレート樹脂などのポリエステル樹脂より成るシート、フィルムが好ましい。基材シートは、単層であってもよいし、同種又は異種の２層以上の多層であってもよい。さらに、これらフィルムを着色したもの、あるいは印刷を施したものであってもよく、硬化性樹脂を薄膜化、硬化してシート化したものが使われてもよい。なお、粘着剤としてエネルギー線硬化型粘着剤を用いる場合には、エネルギー線を透過する基材シートが好ましい。 As for the adhesive sheet of this invention, the adhesive layer which consists of the said adhesive composition is provided in the single side | surface or both surfaces of the base material sheet. Various plastic sheets and films can be used as the base sheet. Specific examples of the substrate sheet include, for example, polyolefin resins such as polyethylene resin and polypropylene resin, polyester resins such as polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin, polyvinyl chloride resin, polystyrene resin, polyurethane resin, and polycarbonate. Examples include sheets and films of various synthetic resins such as resins, polyamide resins, polyimide resins, and fluorine resins. Particularly, sheets and films made of polyester resins such as polyethylene terephthalate resin are preferable because of their high strength and low cost. . The base sheet may be a single layer or a multilayer of two or more layers of the same type or different types. Furthermore, the film may be colored or printed, or a curable resin formed into a thin film and cured into a sheet may be used. In addition, when using an energy ray hardening-type adhesive as an adhesive, the base material sheet which permeate | transmits an energy ray is preferable.
基材シートの厚みは、特に制限ないが、通常１０〜３５０μｍが好ましく、２５〜３００μｍがより好ましく、５０〜２５０μｍが特に好ましい。基材シートの表面は、易接着処理を施してもよい。易接着処理としては、特に制限ないが、例えば、コロナ放電処理等が挙げられる。本発明の粘着シートにおいては、基材シートの片面又は両面に、上記粘着剤組成物からなる粘着剤層が形成されている。粘着剤層の厚みは、特に制限されないが、通常乾燥後の膜厚が３〜１５０μｍが好ましく、５〜１００μｍがより好ましく、１０〜６０μｍがさらに好ましい。 Although there is no restriction | limiting in particular in the thickness of a base material sheet, Usually, 10-350 micrometers is preferable, 25-300 micrometers is more preferable, 50-250 micrometers is especially preferable. The surface of the base sheet may be subjected to an easy adhesion treatment. The easy adhesion treatment is not particularly limited, and examples thereof include corona discharge treatment. In the adhesive sheet of this invention, the adhesive layer which consists of the said adhesive composition is formed in the single side | surface or both surfaces of a base material sheet. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but the film thickness after drying is usually preferably 3 to 150 μm, more preferably 5 to 100 μm, further preferably 10 to 60 μm.
基材シートの片面又は両面に、上記粘着剤組成物からなる粘着剤層を形成するには、基材シートの片面又は両面に、上記粘着剤組成物を塗布して、必要に応じて乾燥することにより、形成できる。上記粘着剤組成物の基材シートへの塗布方法は、例えば、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法、カーテンコート法など従来公知の方法が挙げられる。乾燥は、通常２０〜１５０℃で行うことが好ましい。 In order to form the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition on one side or both sides of the base sheet, the pressure-sensitive adhesive composition is applied to one side or both sides of the base sheet and dried as necessary. Can be formed. Examples of the method for applying the pressure-sensitive adhesive composition to the substrate sheet include conventionally known methods such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, and a curtain coating method. It is done. It is preferable to perform drying normally at 20 to 150 ° C.
本発明の粘着シートは、被着体に貼付して使用され、帯電防止性又は導電性が要求される分野であれば、その用途は限定されない。本発明の粘着シートは、粘着シートを被着体に貼付した後、エネルギー線を照射しない用途に使用することもできるし、粘着シートを被着体に貼付し、処理工程を経た後、エネルギー線を照射して、粘着力を低減して、被着体から剥離し、除去して使用することもできる。後者の用途としては、例えば、半導体ウエハを接着固定し、形成素子を小片に切断、分割し、その素子小片をピックアップ方式で自動回収するダイシング工程において、半導体ウエハの裏面に貼付してウエハを保持するために用いられるウエハダイシングシートや、半導体ウエハの裏面研削工程において、半導体ウエハ表面を保護するために用いられる表面保護シート（裏面研削シート）などが挙げられる。 The application of the pressure-sensitive adhesive sheet of the present invention is not limited as long as it is used in a field in which an antistatic property or conductivity is required by being attached to an adherend. The pressure-sensitive adhesive sheet of the present invention can be used for applications in which an energy ray is not irradiated after the pressure-sensitive adhesive sheet is attached to an adherend, or after the pressure-sensitive adhesive sheet is attached to the adherend and undergoing a treatment step, Can be used by reducing the adhesive strength, peeling off from the adherend and removing it. As the latter application, for example, in a dicing process in which a semiconductor wafer is bonded and fixed, a forming element is cut and divided into small pieces, and the element small pieces are automatically collected by a pickup method, the wafer is attached to the back surface of the semiconductor wafer to hold the wafer. Examples thereof include a wafer dicing sheet used for the purpose, and a surface protective sheet (back surface grinding sheet) used for protecting the semiconductor wafer surface in the back surface grinding process of the semiconductor wafer.
照射されるエネルギー線としては、種々のエネルギー線発生装置から発生するエネルギー線が用いられる。例えば、紫外線としては、通常は紫外線ランプから輻射される紫外線が用いられる。この紫外線ランプとしては、通常波長３００〜４００ｎｍの領域にスペクトル分布を有する紫外線を発光する、高圧水銀ランプ、ヒュ−ジョンＨランプ、キセノンランプ等の紫外線ランプが用いられ、照射量は通常５０〜３０００ｍＪ／ｃｍ２が好ましい。 As the irradiated energy rays, energy rays generated from various energy ray generators are used. For example, as ultraviolet rays, ultraviolet rays radiated from an ultraviolet lamp are usually used. As this ultraviolet lamp, an ultraviolet lamp such as a high-pressure mercury lamp, a fusion H lamp, or a xenon lamp that emits ultraviolet light having a spectral distribution in a wavelength range of 300 to 400 nm is usually used, and the irradiation amount is usually 50 to 3000 mJ. / Cm 2 is preferred.
次に、本発明を実施例によりさらに具体的に説明する。なお、本発明は、これらの例によって何ら制限されるものではない。 Next, the present invention will be described more specifically with reference to examples. In addition, this invention is not restrict | limited at all by these examples.
（実施例１）
（１）カーボンナノチューブ分散エポキシ樹脂の調製
カーボンナノチューブ（昭和電工社製、商品名「ＶＧＣＦ」、円筒状の中空の繊維状形状、平均外周径（外側の円周の平均直径）１５０ｎｍ、平均長さ８μｍ、平均外周径に対する平均長さの比５３）２．８ｇを、ビスフェノールＡ型エポキシ樹脂（三菱化学社製、商品名「エピコート８２８」９７．２ｇに添加し、３本ロールミルで混練し、カーボンナノチューブがエポキシ樹脂中に分散された、カーボンナノチューブ分散エポキシ樹脂を得た。なお、多層カーボンナノチューブの平均外周径（外側の円周の平均直径）及び平均長さの値は、走査型電子顕微鏡（日立ハイテクノロジーズ社製、商品名「Ｓ−４７００」）を用いて、各々５万倍、１５０００倍の倍率で観察したものである。
Example 1
(1) Preparation of carbon nanotube-dispersed epoxy resin Carbon nanotube (manufactured by Showa Denko KK, trade name “VGCF”, cylindrical hollow fiber shape, average outer diameter (average diameter of outer circumference) 150 nm, average length 2.8 g of 8 μm, ratio of average length to average outer diameter 53) is added to 97.2 g of a bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Mitsubishi Chemical Corporation), and kneaded with a three-roll mill. A carbon nanotube-dispersed epoxy resin was obtained in which nanotubes were dispersed in an epoxy resin, and the average outer diameter (average diameter of the outer circumference) and average length of multi-walled carbon nanotubes were measured with a scanning electron microscope ( Using Hitachi High-Technologies Corporation, trade name “S-4700”), the images were observed at magnifications of 50,000 times and 15000 times, respectively.
（２）粘着剤組成物の調製
粘着剤樹脂の主剤としてアクリル酸エステル共重合体樹脂（アクリル酸ｎ−ブチル／メタクリル酸メチル／アクリル酸／２−ヒドロキシエチルアクリレート＝８４／１０／１／５（質量比）、重量平均分子量７０万、溶剤トルエン、固形分濃度４０質量％）１００質量部に、イソシアナート系架橋剤（東洋インキ製造社製、商品名「オリバインＢＨＳ８５１５」、固形分濃度３７．５質量％）８質量部に、上記（１）で調製されたカーボンナノチューブ分散エポキシ樹脂１．５４質量部を配合して混合し、粘着剤組成物を調製した。粘着剤組成物の固形分中のカーボンナノチューブ含有量は０．１質量％であった。
(2) Preparation of pressure-sensitive adhesive composition Acrylic ester copolymer resin (n-butyl acrylate / methyl methacrylate / acrylic acid / 2-hydroxyethyl acrylate = 84/10/1/5 ( (Mass ratio), weight average molecular weight 700,000, solvent toluene, solid content concentration 40% by mass) and 100 parts by mass of isocyanate-based cross-linking agent (manufactured by Toyo Ink Manufacturing Co., Ltd., trade name “Olivein BHS8515”, solid content concentration 37.5) (Mass%) 8 parts by mass of 1.54 parts by mass of the carbon nanotube-dispersed epoxy resin prepared in the above (1) was mixed and mixed to prepare an adhesive composition. The carbon nanotube content in the solid content of the pressure-sensitive adhesive composition was 0.1% by mass.
（３）粘着シートの作成
上記（２）で調製した粘着剤組成物を、剥離コートフィルムに乾燥膜厚が４０μｍになるように塗布し、乾燥させ、剥離コートフィルム上に、粘着剤組成物の単層シート（いわゆるノンキャリアフィルム）を作成した。
(3) Preparation of pressure-sensitive adhesive sheet The pressure-sensitive adhesive composition prepared in the above (2) was applied to a release coat film so that the dry film thickness was 40 μm, dried, and the pressure-sensitive adhesive composition was formed on the release coat film. A single layer sheet (so-called non-carrier film) was prepared.
（実施例２）
（１）カーボンナノチューブ分散エポキシ樹脂の調製
実施例１と同様にしてカーボンナノチューブ分散エポキシ樹脂を調製した。
(Example 2)
(1) Preparation of carbon nanotube-dispersed epoxy resin A carbon nanotube-dispersed epoxy resin was prepared in the same manner as in Example 1.
（２）粘着剤組成物の調製
粘着剤樹脂の主剤としてアクリル酸エステル共重合体樹脂（アクリル酸ｎ−ブチル／アクリル酸＝９０／１０（質量比）、重量平均分子量７０万、溶剤トルエン、固形分濃度３３質量％）１００質量部に、イソシアナート系架橋剤（東洋インキ製造社製、商品名「オリバインＢＨＳ８５１５」、固形分濃度３７．５質量％）１０質量部、エネルギー線重合性基含有オリゴマーとしてウレタンアクリレート系オリゴマー（大日精化工業社製、商品名「セイカビームＥＸＬ−８１０ＴＬ」、重量平均分子量１００００、固形分濃度６１質量％）７０質量部、光重合開始剤として１−ヒドロキシ−シクロヘキシルフェニルケトン（チバスペシャリティーケミカルズ社製、商品名「イルガキュア１８４」）１．２６質量部を混合し、次に、上記（１）で調製されたカーボンナノチューブ分散エポキシ樹脂溶液３．０質量部を配合して混合し、エネルギー線硬化型の粘着剤組成物を調製した。粘着剤組成物の固形分中のカーボンナノチューブ含有量は０．１質量％であった。
(2) Preparation of pressure-sensitive adhesive composition Acrylic ester copolymer resin (n-butyl acrylate / acrylic acid = 90/10 (mass ratio), weight average molecular weight 700,000, solvent toluene, solid as a main component of pressure-sensitive adhesive resin 10 parts by mass of isocyanate-based cross-linking agent (trade name “Olivein BHS8515”, solid concentration 37.5% by mass, solid content concentration 37.5% by mass, manufactured by Toyo Ink Co., Ltd.) As urethane acrylate oligomer (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name “SEICA BEAM EXL-810TL”, weight average molecular weight 10,000, solid content concentration 61% by mass), 1-hydroxy-cyclohexyl phenyl ketone as photopolymerization initiator (Ciba Specialty Chemicals, trade name “Irgacure 184”) 1.26 parts by mass Next, 3.0 parts by mass of the carbon nanotube-dispersed epoxy resin solution prepared in the above (1) was blended and mixed to prepare an energy ray-curable pressure-sensitive adhesive composition. The carbon nanotube content in the solid content of the pressure-sensitive adhesive composition was 0.1% by mass.
（３）粘着シートの作成
上記（２）で調製した粘着剤組成物を、剥離フィルムの片面に乾燥膜厚が１０μｍになるように塗布し、乾燥させ、粘着剤層を形成した。粘着剤層を導電コート付ポリオレフィン基材と貼り合わせ、転写することで粘着シートを作成した。
(3) Preparation of pressure-sensitive adhesive sheet The pressure-sensitive adhesive composition prepared in (2) above was applied to one side of a release film so that the dry film thickness was 10 μm and dried to form a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer was bonded to a polyolefin substrate with a conductive coat and transferred to prepare a pressure-sensitive adhesive sheet.
（実施例３）
実施例２（１）において、カーボンナノチューブ（昭和電工社製、商品名「ＶＧＣＦ」）の使用量を３．０ｇとして、エポキシ樹脂をビスフェノールＡ型エポキシ樹脂（三菱化学社製、商品名「エピコート８２７」９７．０ｇに変更した以外は、実施例２と同様にしてカーボンナノチューブ分散エポキシ樹脂を調製した。得られたカーボンナノチューブ分散エポキシ樹脂を用いて、実施例２と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Example 3)
In Example 2 (1), the amount of carbon nanotubes (trade name “VGCF” manufactured by Showa Denko KK) used is 3.0 g, and the epoxy resin is bisphenol A type epoxy resin (trade name “Epicoat 827” manufactured by Mitsubishi Chemical Corporation). A carbon nanotube-dispersed epoxy resin was prepared in the same manner as in Example 2 except that the amount was changed to 97.0 g. Using the obtained carbon nanotube-dispersed epoxy resin, a pressure-sensitive adhesive composition was prepared in the same manner as in Example 2. The pressure-sensitive adhesive sheet was prepared.
（実施例４）
実施例２（１）において、カーボンナノチューブとして、昭和電工社製、商品名「ＶＧＣＦ−Ｘ」（円筒状の中空の繊維状形状、平均外周径１５０ｎｍ、平均長さ６μｍ、平均外周径に対する平均長さの比４０）３．０ｇを用い、ビスフェノールＡ型エポキシ樹脂（三菱化学社製、商品名「エピコート８２８」９７．０ｇを用いた以外は、実施例２と同様にしてカーボンナノチューブ分散エポキシ樹脂を調製した。得られたカーボンナノチューブ分散エポキシ樹脂を用いて、実施例２と同様にして粘着剤組成物を調製し、粘着シートを作成した。
Example 4
In Example 2 (1), as a carbon nanotube, trade name “VGCF-X” (cylindrical hollow fiber shape, average outer diameter 150 nm, average length 6 μm, average length with respect to average outer diameter, manufactured by Showa Denko KK The carbon nanotube-dispersed epoxy resin was treated in the same manner as in Example 2 except that 3.0 g of the ratio 40) was used, and 97.0 g of a bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Mitsubishi Chemical Corporation) was used. Using the obtained carbon nanotube-dispersed epoxy resin, a pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 to prepare a pressure-sensitive adhesive sheet.
（実施例５）
実施例２（１）において、カーボンナノチューブとして、昭和電工社製、商品名「ＶＧＣＦ−Ｈ」（円筒状の中空の繊維状形状、平均外周径１５ｎｍ、平均長さ３μｍ、平均外周径に対する平均長さの比２０）３．０ｇを用い、ビスフェノールＡ型エポキシ樹脂（三菱化学社製、商品名「エピコート８２８」９７．０ｇを用いた以外は、実施例２と同様にしてカーボンナノチューブ分散エポキシ樹脂を調製した。得られたカーボンナノチューブ分散エポキシ樹脂を用いて、実施例２と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Example 5)
In Example 2 (1), as a carbon nanotube, trade name “VGCF-H” (cylindrical hollow fiber shape, average outer diameter 15 nm, average length 3 μm, average length with respect to average outer diameter, manufactured by Showa Denko KK The carbon nanotube-dispersed epoxy resin was treated in the same manner as in Example 2 except that 3.0 g of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name “Epicoat 828” 97.0 g) was used. Using the obtained carbon nanotube-dispersed epoxy resin, a pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 to prepare a pressure-sensitive adhesive sheet.
（実施例６）
実施例５において、粘着剤組成物中に配合するカーボンナノチューブ分散エポキシ樹脂の使用量を１．５質量部とした以外は、実施例５と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Example 6)
In Example 5, the pressure-sensitive adhesive composition was prepared in the same manner as in Example 5 except that the amount of the carbon nanotube-dispersed epoxy resin blended in the pressure-sensitive adhesive composition was 1.5 parts by mass. Created.
（実施例７）
実施例５において、粘着剤組成物中に配合するカーボンナノチューブ分散エポキシ樹脂の使用量を０．３質量部とした以外は、実施例５と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Example 7)
In Example 5, a pressure-sensitive adhesive composition was prepared in the same manner as in Example 5 except that the amount of the carbon nanotube-dispersed epoxy resin blended in the pressure-sensitive adhesive composition was 0.3 parts by mass. Created.
（実施例８）
実施例２（１）において、カーボンナノチューブとして、Ｎａｎｏｃｙｌ社製、商品名「Ｎａｎｏｃｙｌ ＮＣ−７０００」（円筒状の中空の繊維状形状、平均外周径９．５ｎｍ、平均長さ１．５μｍ、平均外周径に対する平均長さの比１５８）３．０ｇを用い、ビスフェノールＡ型エポキシ樹脂（三菱化学社製、商品名「エピコート８２８」９７．０ｇを用いた以外は、実施例２と同様にしてカーボンナノチューブ分散エポキシ樹脂を調製した。得られたカーボンナノチューブ分散エポキシ樹脂を用いて、実施例２と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Example 8)
In Example 2 (1), as a carbon nanotube, a product name “Nanocyl NC-7000” (cylindrical hollow fiber shape, average outer diameter 9.5 nm, average length 1.5 μm, average outer diameter, manufactured by Nanocyl Co., Ltd. Carbon nanotubes in the same manner as in Example 2, except that 3.0 g of the average length to diameter 158) and 97.0 g of bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Mitsubishi Chemical Corporation) were used. A dispersion epoxy resin was prepared, and a pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 using the obtained carbon nanotube-dispersed epoxy resin to prepare a pressure-sensitive adhesive sheet.
（実施例９）
実施例２（１）において、カーボンナノチューブ（昭和電工社製、商品名「ＶＧＣＦ」）の使用量を３．０ｇとして、エポキシ樹脂をビスフェノールＡ型エポキシ樹脂（新日鐵化学社製、商品名「ＹＤ−８２５ＧＳＨ」９７．０ｇに変更した以外は、実施例２と同様にしてカーボンナノチューブ分散エポキシ樹脂を調製した。得られたカーボンナノチューブ分散エポキシ樹脂を用いて、実施例２と同様にして粘着剤組成物を調製し、粘着シートを作成した。
Example 9
In Example 2 (1), the amount of carbon nanotubes (made by Showa Denko, trade name “VGCF”) used is 3.0 g, and the epoxy resin is bisphenol A type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name “ A carbon nanotube-dispersed epoxy resin was prepared in the same manner as in Example 2, except that the YD-825GSH "was changed to 97.0 g.Adhesive was obtained in the same manner as in Example 2 by using the obtained carbon nanotube-dispersed epoxy resin. The composition was prepared and the adhesive sheet was created.
（比較例１）
実施例１において、カーボンナノチューブ分散エポキシ樹脂を配合しない以外は実施例１と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Comparative Example 1)
In Example 1, a pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the carbon nanotube-dispersed epoxy resin was not blended, and a pressure-sensitive adhesive sheet was prepared.
（比較例２）
実施例２において、カーボンナノチューブ分散エポキシ樹脂を配合しない以外は実施例２と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Comparative Example 2)
In Example 2, a pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 except that the carbon nanotube-dispersed epoxy resin was not blended, and a pressure-sensitive adhesive sheet was prepared.
（比較例３）
実施例２において、カーボンナノチューブ分散エポキシ樹脂を配合せずに、カーボンナノチューブ０．１質量％を粘着剤に直接配合した以外は実施例２と同様にして粘着剤組成物を調製し、粘着シートを作成した。
(Comparative Example 3)
In Example 2, a pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 except that 0.1% by mass of carbon nanotubes were directly blended in the pressure-sensitive adhesive without blending the carbon nanotube-dispersed epoxy resin. Created.
（粘着力測定）
２３℃、５０％ＲＨの環境下、実施例および比較例の粘着シートを２５ｍｍ幅にカットし、直径６インチ、厚さ６００μｍのシリコンウエハの裏面（ミラー面）に貼付し、１８０度剥離粘着力（紫外線照射前）を測定した。同様にして、シリコンウエハの粘着シートを貼付後、リンテック社製紫外線照射装置ＲＡＤ−２０００を用いて１２０ｍＷ／ｃｍ２、７０ｍＪ／ｃｍ２で基材面から紫外線照射し、３０分間放置した後、１８０度剥離粘着力（紫外線照射後）を測定した。なお、実施例１および比較例１の粘着シートは、粘着剤組成物だけからなるノンキャリアフィルムなので、粘着力の測定を行わなかった。比較例３の粘着シートは、カーボンナノチューブの凝集物が多く、正常な表面状態の粘着剤層が得られなかったため、粘着力の測定は行わなかった。
(Adhesive strength measurement)
In an environment of 23 ° C. and 50% RH, the adhesive sheets of Examples and Comparative Examples were cut to a width of 25 mm and attached to the back surface (mirror surface) of a silicon wafer having a diameter of 6 inches and a thickness of 600 μm. (Before UV irradiation) was measured. Similarly, after sticking a pressure-sensitive adhesive sheet of the silicon wafer, irradiated with ultraviolet rays from the substrate surface at 120mW / cm 2, 70mJ / cm 2 using LINTEC Corporation ultraviolet irradiation apparatus RAD-2000, after standing for 30 minutes, 180 Degree of peel adhesion (after UV irradiation) was measured. In addition, since the adhesive sheet of Example 1 and Comparative Example 1 was a non-carrier film consisting only of the adhesive composition, the adhesive strength was not measured. Since the pressure-sensitive adhesive sheet of Comparative Example 3 had many aggregates of carbon nanotubes and a pressure-sensitive adhesive layer having a normal surface state could not be obtained, the adhesive strength was not measured.
（ダイシング試験）
実施例の粘着シートを、直径８インチ、厚さ３５０μｍのシリコンウエハの裏面に貼付し、以下の条件でウエハのダイシングを行った後、エネルギー線硬化型の粘着剤においては、さらにリンテック社製紫外線照射装置ＲＡＤ−２０００を用いて１２０ｍＷ／ｃｍ２、７０ｍＪ／ｃｍ２で基材面から紫外線照射した。いずれの粘着シートにおいても、ダイシング工程においてチップ飛びは起こらず、ウエハおよびチップを保持、固定することができた。
(Dicing test)
The pressure-sensitive adhesive sheet of the example was affixed to the back surface of a silicon wafer having a diameter of 8 inches and a thickness of 350 μm, and the wafer was diced under the following conditions. was irradiated with ultraviolet rays from the substrate surface at 120mW / cm 2, 70mJ / cm 2 using an irradiation device RAD-2000. In any pressure-sensitive adhesive sheet, no chip jump occurred in the dicing process, and the wafer and the chip could be held and fixed.
ダイシング条件
装置：東京精密社製、商品名「ＡＷＤ−４００８Ｂ」
ダイシングブレード：ディスコ社製、商品名「ＮＢＣ−ＺＨ２０５０ ２ＨＥＣＣ」
ブレード回転数：３００００ｒｐｍ
ダイシングスピード：１００ｍｍ／秒
ダイシングサイズ（チップサイズ）：１０ｍｍ×１０ｍｍ
カットモード：ダウンカット
Dicing conditions Equipment: Tokyo Seimitsu Co., Ltd., trade name "AWD-4008B"
Dicing blade: Product name “NBC-ZH2050 2HECC” manufactured by Disco Corporation
Blade rotation speed: 30000 rpm
Dicing speed: 100 mm / second Dicing size (chip size): 10 mm × 10 mm
Cut mode: Down cut
（ピックアップ力測定）
上記ダイシング試験を行った後、リンテック社製紫外線照射装置ＲＡＤ−２０００を用いて１２０ｍＷ／ｃｍ２、７０ｍＪ／ｃｍ２で基材面から紫外線照射し、４ピン突き上げ法によりピックアップ力を測定した。実施例の粘着シートにおいては、いずれもピックアップ不良は生じず、ピックアップ可能であった。ダイシング中の回路面への研削水の浸入の有無および、ピックアップ力およびピックアップに要した時間を表に記載した。なお、実施例１および比較例１は、粘着剤組成物だけからなるノンキャリアフィルムなので、ダイシング試験およびピックアップ力測定を行わなかった。比較例３の粘着シートは、カーボンナノチューブの凝集物が多く、正常な表面状態の粘着剤層が得られなかったため、ダイシング試験およびピックアップ力測定を行わなかった。
(Pickup force measurement)
After the dicing test, ultraviolet irradiation from the substrate surface at 120mW / cm 2, 70mJ / cm 2 using LINTEC Corporation ultraviolet irradiation apparatus RAD-2000, was determined pickup force by 4-pin push-up method. In the pressure-sensitive adhesive sheets of the examples, any pick-up failure did not occur, and pick-up was possible. The presence / absence of intrusion of grinding water into the circuit surface during dicing, the pick-up force and the time required for pick-up are listed in the table. In addition, since Example 1 and Comparative Example 1 are non-carrier films consisting only of the pressure-sensitive adhesive composition, no dicing test and pickup force measurement were performed. Since the pressure-sensitive adhesive sheet of Comparative Example 3 had many carbon nanotube aggregates and a pressure-sensitive adhesive layer having a normal surface state could not be obtained, the dicing test and the pickup force measurement were not performed.
（表面抵抗率の測定）
２３℃、５０％ＲＨの環境下、１００ｍｍ×１００ｍｍサイズの粘着シートを、表面抵抗計（（株）ＡＤＶＡＮＴＥＳＴ製、商品名「Ｒ８２５２ ＥＬＥＣＴＲＯＭＥＴＥＲ」）に設置し、粘着シートの粘着剤面の表面抵抗率を測定し、紫外線（ＵＶ）照射前の表面抵抗値とした。
(Measurement of surface resistivity)
In an environment of 23 ° C. and 50% RH, a 100 mm × 100 mm size pressure-sensitive adhesive sheet was placed on a surface resistance meter (trade name “R8252 ELECTROMETER” manufactured by ADVANTEST Co., Ltd.), and the surface resistivity of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet Was measured as a surface resistance value before ultraviolet (UV) irradiation.
また、同様な粘着シートを、リンテック社製紫外線照射装置ＲＡＤ−２０００を用いて１２０ｍＷ／ｃｍ２、７０ｍＪ／ｃｍ２で基材面から紫外線照射し、その紫外線照射後の粘着シートの粘着剤面の表面抵抗率を上記と同様な方法で測定した。なお、比較例３の粘着シートは、カーボンナノチューブの凝集物が多く、正常な表面状態の粘着剤層が得られなかったため、表面抵抗率の測定を行わなかった。 Further, a similar adhesive sheet with ultraviolet irradiation from the substrate surface at 120mW / cm 2, 70mJ / cm 2 using LINTEC Corporation ultraviolet irradiation apparatus RAD-2000, the adhesive surface of the adhesive sheet after the ultraviolet irradiation The surface resistivity was measured by the same method as described above. In addition, since the adhesive sheet of Comparative Example 3 had many carbon nanotube aggregates and a normal surface-state adhesive layer was not obtained, the surface resistivity was not measured.
（帯電圧の測定）
２３℃、５０％ＲＨの環境下、４０ｍｍ×４０ｍｍサイズの粘着シートを、電荷減衰測定装置（（株）宍戸商会製、商品名「ＳＴＡＴＩＣ ＨＯＮＥＳＴＭＥＲ」）の上に粘着剤層面を上向きに設置し、１３００ｒｐｍで回転させ、粘着剤面に１０ｋＶの電圧を印加させて、印加６０秒後の粘着剤面の帯電圧を測定し、紫外線（ＵＶ）照射前の帯電圧とした。
(Measurement of charged voltage)
Under an environment of 23 ° C. and 50% RH, an adhesive sheet having a size of 40 mm × 40 mm was placed on a charge attenuation measuring device (manufactured by Shishido Shokai Co., Ltd., trade name “STATIC HONESTMER”) with the adhesive layer surface facing upward. It was rotated at 1300 rpm, a voltage of 10 kV was applied to the pressure-sensitive adhesive surface, and the charged voltage on the pressure-sensitive adhesive surface 60 seconds after application was measured to obtain a charged voltage before ultraviolet (UV) irradiation.
また、同様な粘着シートを、リンテック社製紫外線照射装置ＲＡＤ−２０００を用いて１２０ｍＷ／ｃｍ２、７０ｍＪ／ｃｍ２で基材面から紫外線照射し、その紫外線照射後の粘着シートの帯電圧を上記と同様な方法で測定した。 Also, similar to the adhesive sheet, and ultraviolet radiation from the substrate surface at 120mW / cm 2, 70mJ / cm 2 using LINTEC Corporation ultraviolet irradiation apparatus RAD-2000, the the charged voltage of the pressure-sensitive adhesive sheet after the ultraviolet irradiation It was measured by the same method.
（帯電圧の半減期測定）
２３℃、５０％ＲＨの環境下、４０ｍｍ×４０ｍｍサイズの粘着シートを、電荷減衰測定装置（（株）宍戸商会製、商品名「ＳＴＡＴＩＣ ＨＯＮＥＳＴＭＥＲ」）の上に粘着剤面を上向きに設置し、１３００ｒｐｍで回転させ、粘着剤面に１０ｋＶの電圧を印加させて粘着剤面の帯電圧を測定した。印加開始から６０秒後に電圧の印加を停止し、その時点から帯電圧の値が半分になるまでの時間を測定した。この時間を紫外線（ＵＶ）照射前の半減期とした。
(Measurement of half-life of charged voltage)
Under an environment of 23 ° C. and 50% RH, an adhesive sheet having a size of 40 mm × 40 mm was placed on a charge attenuation measuring device (manufactured by Shishido Shokai Co., Ltd., trade name “STATIC HONESTMER”) with the adhesive surface facing upward. By rotating at 1300 rpm, a voltage of 10 kV was applied to the pressure-sensitive adhesive surface, and the voltage on the pressure-sensitive adhesive surface was measured. The application of voltage was stopped 60 seconds after the start of application, and the time from that point until the value of the charged voltage was halved was measured. This time was defined as the half-life before ultraviolet (UV) irradiation.
また、同様な粘着シートを、リンテック社製紫外線照射装置ＲＡＤ−２０００を用いて１２０ｍＷ／ｃｍ２、７０ｍＪ／ｃｍ２で基材面から紫外線照射し、その紫外線照射後の粘着シートの帯電圧の半減期を上記と同様な方法で測定した。
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| WO2016136685A1 (en) * | 2015-02-23 | 2016-09-01 | リンテック オブ アメリカ インク | Adhesive sheet |
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| JP2017082146A (en) * | 2015-10-30 | 2017-05-18 | 東洋インキＳｃホールディングス株式会社 | Conductive adhesive and method for producing the same |
| WO2020116284A1 (en) * | 2018-12-05 | 2020-06-11 | リンテック株式会社 | Protective film forming composite sheet and method for manufacturing semiconductor chip |
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