JP2005325180A - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- JP2005325180A JP2005325180A JP2004142798A JP2004142798A JP2005325180A JP 2005325180 A JP2005325180 A JP 2005325180A JP 2004142798 A JP2004142798 A JP 2004142798A JP 2004142798 A JP2004142798 A JP 2004142798A JP 2005325180 A JP2005325180 A JP 2005325180A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- sensitive adhesive
- pressure
- acrylic acid
- halogen
- 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.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims description 30
- 230000001070 adhesive effect Effects 0.000 title claims description 30
- 239000000203 mixture Substances 0.000 title claims description 22
- 239000000178 monomer Substances 0.000 claims abstract description 77
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 55
- 229920001577 copolymer Polymers 0.000 claims abstract description 37
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 36
- 150000002367 halogens Chemical class 0.000 claims abstract description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 239000000806 elastomer Substances 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 125000003277 amino group Chemical group 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 5
- 230000003068 static effect Effects 0.000 abstract description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract description 3
- 239000003292 glue Substances 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 43
- -1 acrylate ester Chemical class 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- LHEKBWMWMVRJMO-UHFFFAOYSA-N 3-methoxypropyl prop-2-enoate Chemical compound COCCCOC(=O)C=C LHEKBWMWMVRJMO-UHFFFAOYSA-N 0.000 description 2
- OYFJWLSZXKXLAT-UHFFFAOYSA-N 4-ethoxybutyl prop-2-enoate Chemical group CCOCCCCOC(=O)C=C OYFJWLSZXKXLAT-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 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
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 description 1
- YVOSZCZBCKHSBP-GORDUTHDSA-N (E)-2-(2-chloroethyl)but-2-enoic acid Chemical compound C\C=C(C(O)=O)/CCCl YVOSZCZBCKHSBP-GORDUTHDSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- DSZTYVZOIUIIGA-UHFFFAOYSA-N 1,2-Epoxyhexadecane Chemical compound CCCCCCCCCCCCCCC1CO1 DSZTYVZOIUIIGA-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 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
- VLJLXEKIAALSJE-UHFFFAOYSA-N 13-oxabicyclo[10.1.0]tridecane Chemical compound C1CCCCCCCCCC2OC21 VLJLXEKIAALSJE-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- QIBPJPNDSZRXRO-UHFFFAOYSA-N 2-(chloromethyl)prop-2-enenitrile Chemical compound ClCC(=C)C#N QIBPJPNDSZRXRO-UHFFFAOYSA-N 0.000 description 1
- AGIBHMPYXXPGAX-UHFFFAOYSA-N 2-(iodomethyl)oxirane Chemical compound ICC1CO1 AGIBHMPYXXPGAX-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- VMCOFBQXPQAQTE-UHFFFAOYSA-N 2-chloro-2-ethyl-3-methyloxirane Chemical compound CCC1(Cl)OC1C VMCOFBQXPQAQTE-UHFFFAOYSA-N 0.000 description 1
- RUYVEZRTTSFUPF-UHFFFAOYSA-N 2-chloro-9-(difluoromethyl)-1,3,4,4,5,5,6,6,7,8,8,9,10,10,11,12,12,12-octadecafluoro-3,11-bis(trifluoromethyl)dodec-1-ene Chemical compound FC(C(C(F)(F)F)(C(C(C(F)F)(C(C(C(C(C(C(C(F)(F)F)(C(=CF)Cl)F)(F)F)(F)F)(F)F)F)(F)F)F)(F)F)F)(F)F RUYVEZRTTSFUPF-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- KKZUMAMOMRDVKA-UHFFFAOYSA-N 2-chloropropane Chemical group [CH2]C(C)Cl KKZUMAMOMRDVKA-UHFFFAOYSA-N 0.000 description 1
- IOHJQSFEAYDZGF-UHFFFAOYSA-N 2-dodecyloxirane Chemical compound CCCCCCCCCCCCC1CO1 IOHJQSFEAYDZGF-UHFFFAOYSA-N 0.000 description 1
- QBJWYMFTMJFGOL-UHFFFAOYSA-N 2-hexadecyloxirane Chemical compound CCCCCCCCCCCCCCCCC1CO1 QBJWYMFTMJFGOL-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- BHZBVWCLMYQFQX-UHFFFAOYSA-N 2-octadecyloxirane Chemical compound CCCCCCCCCCCCCCCCCCC1CO1 BHZBVWCLMYQFQX-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CIIFBJOZSVHTOB-UHFFFAOYSA-N ClCC(=O)NCC(C(=O)N)=C Chemical compound ClCC(=O)NCC(C(=O)N)=C CIIFBJOZSVHTOB-UHFFFAOYSA-N 0.000 description 1
- CQQCDAGRLCRJCU-UHFFFAOYSA-N ClCC(=O)NCC=C(C(=O)N)C Chemical compound ClCC(=O)NCC=C(C(=O)N)C CQQCDAGRLCRJCU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- JVJUUTKHPUJINE-UHFFFAOYSA-N n-(chloromethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCl JVJUUTKHPUJINE-UHFFFAOYSA-N 0.000 description 1
- LZIWXMFWIBRDAB-UHFFFAOYSA-N n-(chloromethyl)prop-2-enamide Chemical compound ClCNC(=O)C=C LZIWXMFWIBRDAB-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dicing (AREA)
Abstract
【課題】従来の粘着シートには、近年のチツプサイズの微小化に対応する粘着力がなかった。ダイシングされたチツプに糊の付着があった。半導体部材ダイシング後のピツクアツプ時の剥離時に生じる静電気により、半導体部材が破壊してしまった。
【解決手段】本発明は、エラストマ１００質量部と、（メタ）アクリル酸エステル・アミン共重合体０．１〜３０質量部を備えたものである。エラストマがハロゲン含有モノマを少なくとも一種類共重合した共重合体であり、エラストマの０．１〜５５質量％がハロゲン含有モノマであり、（メタ）アクリル酸エステル・アミン共重合体が、（メタ）アクリル酸エステルモノマとアミン含有モノマを共重合させたものであり、さらに（メタ）アクリル酸エステル・アミン共重合体の０．１〜３０質量％が、アミン含有モノマである。
【選択図】なしA conventional pressure-sensitive adhesive sheet does not have a pressure-sensitive adhesive force corresponding to the recent miniaturization of chip size. There was glue adhesion on the diced chip. The semiconductor member was destroyed by static electricity generated during peeling after picking up the semiconductor member.
The present invention comprises 100 parts by mass of an elastomer and 0.1 to 30 parts by mass of a (meth) acrylic acid ester / amine copolymer. The elastomer is a copolymer obtained by copolymerizing at least one halogen-containing monomer, 0.1 to 55% by mass of the elastomer is a halogen-containing monomer, and a (meth) acrylic acid ester / amine copolymer is (meth) An acrylic acid ester monomer and an amine-containing monomer are copolymerized, and 0.1 to 30% by mass of the (meth) acrylic acid ester / amine copolymer is an amine-containing monomer.
[Selection figure] None
Description
本発明は、粘着剤組成物及び粘着シートに係り、特に、粘着シートに貼り付けた半導体部材をチツプ状にダイシングしても該半導体部材をみだりに飛散させず、粘着剤の掻き上げを起こさせず、さらにダイシング後にチツプ化された半導体部材をピツクアツプしても静電気が生じない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 in particular, even when a semiconductor member affixed to a pressure-sensitive adhesive sheet is diced into chips, the semiconductor member is not scattered freely, and the pressure-sensitive adhesive is not raised. Furthermore, the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet that do not generate static electricity even when picked up after chipping a semiconductor member.
半導体基盤をダイシングして半導体部材にする際に用いられる粘着シートとして、特許文献１の半導体ウエハ固定用シートが知られている。 As a pressure-sensitive adhesive sheet used when dicing a semiconductor substrate into a semiconductor member, a semiconductor wafer fixing sheet of Patent Document 1 is known.
特許文献１記載の半導体ウエハ固定用粘着シートにあっては、チツプ飛び等が無くなったが、近年のチツプサイズの微小化により、さらなる粘着力の向上が必要になってきた。また、ダイシング時のブレード掻き上げによる半導体部材への糊付着に関してはフロンにて洗浄していたが、近年フロンの環境への影響が懸念され、糊の付着のないことが望まれている。 In the adhesive sheet for fixing a semiconductor wafer described in Patent Document 1, chip skipping or the like has been eliminated. However, due to the recent miniaturization of the chip size, it is necessary to further improve the adhesive force. In addition, adhesive adhesion to the semiconductor member by scraping the blade during dicing has been washed with chlorofluorocarbon. However, in recent years, there is a concern about the influence of chlorofluorocarbon on the environment, and it is desired that the adhesive does not adhere.
また、半導体部材ダイシング後のピツクアツプ時の剥離時に生じる静電気により、半導体部材が破壊してしまうという課題も発生している。 Further, there is a problem that the semiconductor member is destroyed due to static electricity generated at the time of peeling after picking up after the semiconductor member dicing.
したがって、本発明は、粘着シートに貼り付けた半導体部材をチツプ状にダイシングしても該半導体部材をみだりに飛散させず、粘着剤の掻き上げを起こさせず、さらにダイシング後にチツプ化された半導体部材をピツクアツプしても静電気が生じない粘着剤組成物及び粘着シートを提供することにある。 Therefore, the present invention does not cause the semiconductor member to be scattered freely even if the semiconductor member attached to the adhesive sheet is diced into chips, and does not cause the adhesive to be scraped up. Further, the semiconductor member is chipped after dicing. An object of the present invention is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet in which static electricity is not generated even when picking up the material.
したがって、本発明は、エラストマ１００質量部と、（メタ）アクリル酸エステル・アミン共重合体０．１〜３０質量部を備え、エラストマがハロゲン含有モノマを少なくとも一種類共重合した共重合体であり、エラストマの０．１〜５５質量％がハロゲン含有モノマであり、（メタ）アクリル酸エステル・アミン共重合体が、（メタ）アクリル酸エステルモノマとアミン含有モノマを共重合させたものであり、さらに（メタ）アクリル酸エステル・アミン共重合体の０．１〜３０質量％が、アミン含有モノマである粘着剤組成物である。 Accordingly, the present invention is a copolymer comprising 100 parts by mass of an elastomer and 0.1 to 30 parts by mass of a (meth) acrylic acid ester / amine copolymer, and the elastomer is a copolymer obtained by copolymerizing at least one halogen-containing monomer. 0.1 to 55% by mass of the elastomer is a halogen-containing monomer, and a (meth) acrylic acid ester / amine copolymer is a copolymer of a (meth) acrylic acid ester monomer and an amine-containing monomer, Furthermore, 0.1-30 mass% of (meth) acrylic acid ester-amine copolymer is an adhesive composition which is an amine-containing monomer.
他の発明は、シート状の基材と、基材の一方又は双方の面に粘着剤組成物を積層し、粘着剤組成物が、前記粘着剤組成物である粘着シートである。 Another invention is a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive composition is laminated on one or both surfaces of a sheet-like base material and the base material, and the pressure-sensitive adhesive composition is the pressure-sensitive adhesive composition.
本発明にあっては、粘着剤組成物を上記構成にすることにより、粘着シートに貼り付けた半導体部材をチツプ状にダイシングしても該半導体部材をみだりに飛散させず、粘着剤の掻き上げを起こさせず、さらにダイシング後にチツプ化された半導体部材をピツクアツプしても静電気が生じさせない。また、他の発明にあっては、粘着シートを上記構成とすることにより、粘着シートに当該効果を発揮させることができる。 In the present invention, by making the pressure-sensitive adhesive composition as described above, even if the semiconductor member affixed to the pressure-sensitive adhesive sheet is diced into chips, the semiconductor member is not scattered excessively, and the pressure-sensitive adhesive is scraped up. Static electricity is not generated even when picking up a semiconductor member chipped after dicing without picking up. Moreover, in other invention, the said effect can be exhibited at an adhesive sheet by setting an adhesive sheet as the said structure.
本発明の粘着剤組成物の配合物として、エラストマとして「ハロゲン含有モノマを少なくとも一種類共重合した共重合体」と、（メタ）アクリル酸エステル・アミン共重合体を採用したのは、ハロゲン成分とアミン成分が反応してアンモニウム塩を形成することで粘着剤自体の凝集性の向上、粘着剤表面の表面抵抗値の低下及び粘着力の向上が図れることを見出したからである。ハロゲン成分としては、例えば塩素、フツ素、臭素、ヨウ素があり、分子量的に軽く、活性度が高いため生成時のイオン交換をし易いことから、フツ素、塩素が好ましく、特に好ましくは塩素が良い。 As the composition of the pressure-sensitive adhesive composition of the present invention, “a copolymer obtained by copolymerizing at least one halogen-containing monomer” and a (meth) acrylic acid ester / amine copolymer are employed as an elastomer. This is because it has been found that the cohesiveness of the pressure-sensitive adhesive itself can be improved, the surface resistance value of the pressure-sensitive adhesive surface can be lowered, and the pressure-sensitive adhesive force can be improved by forming an ammonium salt by reacting with the amine component. Examples of the halogen component include chlorine, fluorine, bromine, and iodine. Since the molecular weight is light and the activity is high, ion exchange at the time of production is easy. Therefore, fluorine and chlorine are preferable, and chlorine is particularly preferable. good.
エラストマの０．１〜５５質量％をハロゲン含有モノマとしたのは、０．１質量％未満であると架橋による凝集力の向上が望めず被着体に対し糊残りが生じてしまうと共に粘着剤の表面抵抗値が高くなる傾向にあり、５５質量％を超えると粘着力が低下してしまうと共にハロゲン成分が被着体に移行する傾向にあるからである。含有率の好ましい下限は３質量％であり、好ましい上限は３０質量％である。 The reason why the halogen-containing monomer is 0.1 to 55% by mass of the elastomer is that the content is less than 0.1% by mass. This is because the surface resistance value tends to increase, and if it exceeds 55% by mass, the adhesive strength decreases and the halogen component tends to migrate to the adherend. The minimum with preferable content rate is 3 mass%, and a preferable upper limit is 30 mass%.
「ハロゲン含有モノマを少なくとも一種類共重合した共重合体」としては、エピハロヒドリンゴム、フツ素ゴム、「ハロゲン含有モノマと（メタ）アクリル酸エステルモノマとの共重合体」があり、特に好ましくは半導体部材への粘着性の高さから、「ハロゲン含有モノマと（メタ）アクリル酸エステルモノマとの共重合体」が良い。 Examples of the “copolymer obtained by copolymerizing at least one halogen-containing monomer” include epihalohydrin rubber, fluorine rubber, and “copolymer of halogen-containing monomer and (meth) acrylate ester monomer”, particularly preferably a semiconductor. A “copolymer of a halogen-containing monomer and a (meth) acrylate monomer” is preferable because of its high adhesiveness to the member.
エピハロヒドリンゴムを大別すると、ハロゲン含有モノマのみを共重合体させたものと、ハロゲン含有モノマとハロゲン非含有モノマを共重合させたものがある。エピハロヒドリンゴムのハロゲン含有モノマとしては、例えばエピハロヒドリンがある。エピハロヒドリンとしては、例えばエピクロロヒドリン、エピブロモヒドリン、エピヨードヒドリン、β−メチルエピクロロヒドリンがある。エピハロヒドリンゴムのハロゲン非含有モノマとしては、例えばアルキレンオキサイド、不飽和エポキシドがある。アルキレンオキサイドとしては、例えばエチレンオキシド、プロピレンオキシド、１，２−エポキシブタン、１，２−エポキシ−ｉｓｏ−ブタン、２，３−エポキシブタン、１，２−エポキシへキサン、１，２−エポキシオクタン、１，２−エポキシデカン、１，２−エポキシテトラデカン、１，２−エポキシヘキサデカン、１，２−エポキシオクタデカン、１，２−エポキシエイコサン、１，２−エポキシシクロペンタン、１，２−エポキシシクロへキサン、１，２−エポキシシクロドデカン、１，２−エポキシ−イソブタン、２，３−エポキシ−イソブタン、２，３−エポキシ−３−クロロペンタンがある。 Epihalohydrin rubbers are roughly classified into those obtained by copolymerizing only halogen-containing monomers and those obtained by copolymerizing halogen-containing monomers and halogen-free monomers. Examples of the halogen-containing monomer of the epihalohydrin rubber include epihalohydrin. Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and β-methylepichlorohydrin. Examples of the halogen-free monomer of the epihalohydrin rubber include alkylene oxide and unsaturated epoxide. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-iso-butane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane There are hexane, 1,2-epoxycyclododecane, 1,2-epoxy-isobutane, 2,3-epoxy-isobutane, 2,3-epoxy-3-chloropentane.
フツ素ゴムを大別すると、ハロゲン含有モノマのみを共重合体させたものと、ハロゲン含有モノマとハロゲン非含有モノマを共重合させたものがある。フツ素ゴムのハロゲン含有モノマとしてはフツ素モノマがある。フツ素モノマとしては、例えばビニリデンフルオライド、ヘキサフルオロプロピレン、ペンタフルオロプロピレン、クロロトリフルオロエチレン、テトラフルオロエチレン、ヘキサフルオロプロピレン、ビニルフルオライド、パーフルオロメチルビニルエーテル、パーフルオロプロピルビニリデンがある。フツ素ゴムのハロゲン非含有モノマとしては、例えばアクリル酸エステル、プロピレン、エチレン、ジエンがある。フツ素ゴムにおける「ハロゲン含有モノマとハロゲン非含有モノマを共重合させたもの」としては、例えばテトラフルオロエチレン・プロピレン共重合体、ヘキサフルオロプロピレン・エチレン共重合体がある。 Fluorine rubber is roughly classified into one obtained by copolymerizing only halogen-containing monomers and one obtained by copolymerizing halogen-containing monomers and halogen-free monomers. As a halogen-containing monomer of fluorine rubber, there is a fluorine monomer. Examples of fluorine monomers include vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl fluoride, perfluoromethyl vinyl ether, and perfluoropropyl vinylidene. Examples of fluorine-free monomers of fluorine rubber include acrylic acid esters, propylene, ethylene, and dienes. Examples of the “copolymerized halogen-containing monomer and non-halogen-containing monomer” in fluorine rubber include, for example, tetrafluoroethylene / propylene copolymer and hexafluoropropylene / ethylene copolymer.
「ハロゲン含有モノマと（メタ）アクリル酸エステルモノマとの共重合体」を採用する際のハロゲン含有モノマとしては、例えばクロロメチル（メタ）アクリレート、１−クロロエチル（メタ）アクリレート、２−クロロエチル（メタ）アクリレート、１，２−ジクロロエチル（メタ）アクリレート、２−クロロプロピル（メタ）アクリレート、３−クロロプロピル（メタ）アクリレート、２，３−ジクロロプロピル（メタ）アクリレート、２−クロロブチル（メタ）アクリレート、３−クロロブチル（メタ）アクリレート、４−クロロブチル（メタ）アクリレート、３，４−ジクロロブチル（メタ）アクリレートなどのハロアルキル（メタ）アクリレート類；クロロアセトキシメチル（メタ）アクリレート、２−（クロロアセトキシ）エチル（メタ）アクリレート、３−（クロロアセトキシ）プロピル（メタ）アクリレート、４−（クロロアセトキシ）ブチル（メタ）アクリレート等のハロアシロキシアルキル（メタ）アクリレート類；クロロアセチルカルバモイルオキシメチル（メタ）アクリレート、２−（クロロアセチルカルバモイルオキシ）エチル（メタ）アクリレート、３−（クロロアセチルカルバモイルオキシ）プロピル（メタ）アクリレート、３−（ヒドロキシシクロヘキシルアセトキシ）プロピル（メタ）アクリレート、４−（ヒドロキシシクロヘキシルアセトキシ）プロピル（メタ）アクリレート等の他のハロゲン含有（メタ）アクリレート類；エタクリル酸２−クロロエチル、クロトン酸２−クロロエチル、ケイ皮酸２−クロロエチル等の他の不飽和カルボン酸ハロアルキル類；α−クロロアクリルニトリル、α−クロロメチルアクリロニトリル等のハロゲン含有不飽和ニトリル類；Ｎ−クロロメチルアクリルアミド、Ｎ−クロロメチルメタクリルアミド、クロロアセトアミドメチルアクリルアミド、クロロアセトアミドメチルメタクリルアミド等のハロゲン含有不飽和アミド類がある。 Examples of the halogen-containing monomer used in the case of adopting “a copolymer of a halogen-containing monomer and a (meth) acrylic acid ester monomer” include, for example, chloromethyl (meth) acrylate, 1-chloroethyl (meth) acrylate, 2-chloroethyl (meta ) Acrylate, 1,2-dichloroethyl (meth) acrylate, 2-chloropropyl (meth) acrylate, 3-chloropropyl (meth) acrylate, 2,3-dichloropropyl (meth) acrylate, 2-chlorobutyl (meth) acrylate Haloalkyl (meth) acrylates such as 3-chlorobutyl (meth) acrylate, 4-chlorobutyl (meth) acrylate and 3,4-dichlorobutyl (meth) acrylate; chloroacetoxymethyl (meth) acrylate, 2- (chloroacetoxy) Echi Haloacyloxyalkyl (meth) acrylates such as (meth) acrylate, 3- (chloroacetoxy) propyl (meth) acrylate, 4- (chloroacetoxy) butyl (meth) acrylate; chloroacetylcarbamoyloxymethyl (meth) acrylate, 2 -(Chloroacetylcarbamoyloxy) ethyl (meth) acrylate, 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylate, 3- (hydroxycyclohexylacetoxy) propyl (meth) acrylate, 4- (hydroxycyclohexylacetoxy) propyl (meth) ) Other halogen-containing (meth) acrylates such as acrylates; other unsaturated carboxylic acids such as 2-chloroethyl ethacrylate, 2-chloroethyl crotonic acid, 2-chloroethyl cinnamate, etc. Haloalkyls; Halogen-containing unsaturated nitriles such as α-chloroacrylonitrile and α-chloromethylacrylonitrile; Halogens such as N-chloromethylacrylamide, N-chloromethylmethacrylamide, chloroacetamidomethylacrylamide, chloroacetamidomethylmethacrylamide There are unsaturated amides.
フツ素ゴム、「ハロゲン含有モノマと（メタ）アクリル酸エステルモノマとの共重合体」を採用する際の「ハロゲン非含有モノマ」としてのアクリル酸エステルとしては、主モノマ、コモノマ等を有する共重合体、官能基を有するモノマ等の重合体がある。 As acrylic acid ester as “halogen-free monomer” when adopting fluorine rubber, “copolymer of halogen-containing monomer and (meth) acrylic acid ester monomer”, copolymer having main monomer, comonomer, etc. There are polymers such as polymers and monomers having functional groups.
主モノマとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−メトキシプロピル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸２−メトキシブチル、（メタ）アクリル酸４−メトキシブチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸３−エトキシプロピル、（メタ）アクリル酸４−エトキシブチルがある。コモノマとしては、例えばアクリロニトリル、スチレンがある。官能基を有するモノマとしては、例えば（メタ）アクリル酸、（メタ）アクリル酸β−カルボキシエチル、イタコン酸、クロトン酸、マレイン酸、フマル酸等のカルボキシル基含有モノマ；（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル等の水酸基含有モノマ；（メタ）アクリル酸グリシジルエーテル等のエポキシ基含有モノマがある。 Examples of the main monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, (meth) 3-methoxypropyl acrylate, 2-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, (meth) There is 4-ethoxybutyl acrylate. Examples of the comonomer include acrylonitrile and styrene. Examples of the monomer having a functional group include (meth) acrylic acid, (meth) acrylic acid β-carboxyethyl, itaconic acid, crotonic acid, maleic acid, fumaric acid and other carboxyl group-containing monomers; (meth) acrylic acid 2- There are hydroxyl group-containing monomers such as hydroxyethyl and 2-hydroxypropyl (meth) acrylate; and epoxy group-containing monomers such as (meth) acrylic acid glycidyl ether.
（メタ）アクリル酸エステル・アミン共重合体の配合量は、０．１質量部未満であるとハロゲン成分とアミン成分が反応してできるアンモニウム塩の形成が少なく粘着剤自体の凝集性の向上、粘着剤表面の表面抵抗値の低下及び粘着力の向上が図れない傾向にあり、３０質部を超えると粘着力が低下する傾向にあるため、０．１〜３０質量部であり、好ましい下限は３質量部、好ましい上限は１０質量部である。 When the blending amount of the (meth) acrylic acid ester / amine copolymer is less than 0.1 parts by mass, the formation of an ammonium salt formed by the reaction between the halogen component and the amine component is less, and the cohesiveness of the adhesive itself is improved. There is a tendency that the surface resistance value of the pressure-sensitive adhesive surface cannot be lowered and the adhesive force cannot be improved, and if it exceeds 30 parts, the adhesive force tends to decrease. Therefore, the preferred lower limit is 0.1 to 30 parts by mass. 3 parts by mass, the preferred upper limit is 10 parts by mass.
（メタ）アクリル酸エステル・アミン共重合体のアミン含有モノマの配合量は、０．１質量％未満であると粘着力の向上、反応による凝集力の向上及び粘着剤表面抵抗値の低下が望めない傾向にあり、３０質量％を超えると粘着力が低下する傾向にあるため、０．１〜３０質量％であり、好ましい下限は３質量％、好ましい上限は１０質量％である。 If the amount of the amine-containing monomer in the (meth) acrylic acid ester / amine copolymer is less than 0.1% by mass, the adhesive strength can be improved, the cohesive strength can be improved by the reaction, and the adhesive surface resistance can be reduced. Since there exists a tendency for adhesive force to fall when it exceeds 30 mass%, it is 0.1-30 mass%, a preferable minimum is 3 mass%, and a preferable upper limit is 10 mass%.
（メタ）アクリル酸エステル・アミン共重合体に配合されるアミン含有モノマは、分子内中にアミノ基、アミド基、そのいずれかを少なくとも一つ含有しているモノマをいい、アミノ基含有モノマ、アミド基含有モノマ、アミノ基・アミド基両方を含有するモノマがあり、この中でもハロゲン含有エラストマとの反応性が良好なアミノ基含有モノマが良い。 The amine-containing monomer compounded in the (meth) acrylic acid ester / amine copolymer refers to a monomer containing at least one of an amino group and an amide group in the molecule, an amino group-containing monomer, There are amide group-containing monomers and monomers containing both amino groups and amide groups. Among these, amino group-containing monomers having good reactivity with halogen-containing elastomers are preferred.
アミノ基含有モノマとしては、例えばアミノエチル（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、ビニルピリジン、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレートがある。アミド基含有モノマとしては、例えば（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、アクリロイルモルホリン、アクリルアマイドがある。アミノ基・アミド基両方を含有するモノマとしては、例えばＮ，Ｎ−ジメチルアミノプロピルアクリルアミドがある。 Examples of amino group-containing monomers include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, vinylpyridine, N, N-diethylaminoethyl (meta). ) Acrylate. Examples of the amide group-containing monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, acryloylmorpholine, and acrylamide. Examples of the monomer containing both amino group and amide group include N, N-dimethylaminopropylacrylamide.
（メタ）アクリル酸エステルとしては、以下に説明する主モノマ、コモノマ等を有する共重合体、官能基を有するモノマ等の重合体がある。 Examples of the (meth) acrylic acid ester include a copolymer having a main monomer and a comonomer described below, and a polymer such as a monomer having a functional group.
主モノマとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−メトキシプロピル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸２−メトキシブチル、（メタ）アクリル酸４−メトキシブチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸３−エトキシプロピル、（メタ）アクリル酸４−エトキシブチルがある。コモノマとしては、例えばアクリロニトリル、スチレンがある。官能基を有するモノマとしては、例えば（メタ）アクリル酸、（メタ）アクリル酸β−カルボキシエチル、イタコン酸、クロトン酸、マレイン酸、フマル酸等のカルボキシル基含有モノマ；（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル等の水酸基含有モノマ；（メタ）アクリル酸グリシジルエーテル等のエポキシ基含有モノマがある。 Examples of the main monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, (meth) 3-methoxypropyl acrylate, 2-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, (meth) There is 4-ethoxybutyl acrylate. Examples of the comonomer include acrylonitrile and styrene. Examples of the monomer having a functional group include (meth) acrylic acid, (meth) acrylic acid β-carboxyethyl, itaconic acid, crotonic acid, maleic acid, fumaric acid and other carboxyl group-containing monomers; (meth) acrylic acid 2- There are hydroxyl group-containing monomers such as hydroxyethyl and 2-hydroxypropyl (meth) acrylate; and epoxy group-containing monomers such as (meth) acrylic acid glycidyl ether.
本発明の粘着剤組成物には、本発明の目的が損なわれない範囲で、従来公知の添加剤、例えば紫外線重合性オリゴマ、紫外線重合性モノマ、重合開始剤、粘着付与剤、硬化剤、軟化剤、老化防止剤、充填剤、紫外線吸収剤及び光安定剤を適宜選択して配合できる。 In the pressure-sensitive adhesive composition of the present invention, conventionally known additives such as UV-polymerizable oligomers, UV-polymerizable monomers, polymerization initiators, tackifiers, curing agents, softening agents are used as long as the object of the present invention is not impaired. An agent, an anti-aging agent, a filler, an ultraviolet absorber and a light stabilizer can be appropriately selected and blended.
本発明に係る粘着シートのシート状の基材の厚みは、用途に応じて適宜選択でき、シート状だけでなく、フィルム状も含めることができる。基材の素材としては、用途に応じて従来公知の合成樹脂を適宜選択して使用でき、具体的にはポリ塩化ビニル、ポリエチレン、ポリプロピレン、ポリエステル、エチレンビニルアルコールがある。 The thickness of the sheet-like base material of the pressure-sensitive adhesive sheet according to the present invention can be appropriately selected depending on the application, and can include not only a sheet shape but also a film shape. As the material of the base material, conventionally known synthetic resins can be appropriately selected and used according to applications, and specifically, there are polyvinyl chloride, polyethylene, polypropylene, polyester, and ethylene vinyl alcohol.
本発明にかかる粘着シートの被着体の一例である半導体部材とは、ＢＧＡ（ボール・グリッド・アレイ）基盤、シリコンウエハ、ガリウム−砒素、ガラス、エポキシ基盤、ベクトラ基盤がある。 The semiconductor member which is an example of the adherend of the pressure-sensitive adhesive sheet according to the present invention includes a BGA (ball grid array) substrate, a silicon wafer, gallium arsenide, glass, an epoxy substrate, and a vector substrate.
以下、本発明の実施例について、比較例と対比しつつ、表１を参照しながら説明する。 Hereinafter, examples of the present invention will be described with reference to Table 1 in comparison with comparative examples.
表１のダイシング性（チツプ飛び）は、試験体である実施例・比較例にかかる粘着シートを、パツケージ成形用モールド樹脂によりモールドされた半導体部材に気泡が入らないよう貼り付け、１０分放置後に５ｍｍ□にダイシングし、この作業を５回繰り返した際のチツプ総数１００個あたりのチツプ飛び個数である。この値は、数値が小さいほど良く、０が好ましい。 The dicing properties (chip skipping) in Table 1 are as follows. The pressure-sensitive adhesive sheets according to Examples and Comparative Examples, which are test specimens, are attached to a semiconductor member molded with a package molding mold resin so that no air bubbles enter and left for 10 minutes. The number of chips skipped per 100 total chips when dicing to 5 mm □ and repeating this operation five times. This value is better as the numerical value is smaller, and 0 is preferable.
表１の粘着剤掻き上げは、試験体である実施例・比較例にかかる粘着シートを、パツケージ成形用モールド樹脂によりモールドされた半導体部材に気泡が入らないよう貼り付け、１０分放置後に５ｍｍ□にダイシングし、この作業を５回繰り返し、チツプ総数１００個に対するチツプ側面に粘着剤の付着が確認された個数である。この値は、数値が小さいほど良く、０が好ましい。 The adhesives in Table 1 are prepared by sticking the pressure-sensitive adhesive sheets according to Examples and Comparative Examples, which are test specimens, to a semiconductor member molded with a packaging molding resin so that no air bubbles enter, and after leaving for 10 minutes, 5 mm □ This process is repeated 5 times, and the number of adhesives confirmed to be attached to the side surface of the chip with respect to 100 total chips. This value is better as the numerical value is smaller, and 0 is preferable.
表１の粘着力には、試験体である実施例・比較例にかかる粘着シートを、パツケージ成形用モールド樹脂によりモールドされた半導体部品に、両者の間に気泡が入らないよう貼り付け、ＪＩＳ Ｚ ０２３７に準じて測定したものである。この値は、５．０Ｎ／２０ｍｍ以上でなければならない。 For the adhesive strength of Table 1, the adhesive sheets according to the examples and comparative examples as test specimens are attached to a semiconductor component molded with a packaging molding mold resin so that no air bubbles enter between them. Measured according to 0237. This value must be at least 5.0 N / 20 mm.
表１の表面抵抗値は、試験体である実施例・比較例にかかる粘着シートを、温度２３℃、湿度５５％の雰囲気下で表面抵抗測定器（アドバンテスト社Ｒ８３４０Ａ）を用いて粘着剤表面の抵抗値を測定したものである。この値は１．０×１０１２Ω／□以下でなければならない。 The surface resistance values in Table 1 are the values of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet according to Examples and Comparative Examples, which are test specimens, using a surface resistance measuring instrument (Advantest R8340A) in an atmosphere at a temperature of 23 ° C. and a humidity of 55%. The resistance value is measured. This value must be less than 1.0 × 10 12 Ω / □.
表１のハロゲン元素抽出量は、試験体である実施例・比較例にかかる粘着シート１００ｃｍ２をコニカルビーカーに入れ、超純水１００ｍｌに浸漬し、ホットプレートを用いて１００℃で２時間抽出、イオンクロマトグラフィー（ＤＩＯＮＥＸ社ＤＸ−ＡＱ）にて塩素イオン量の分析を行ったものである。ハロゲン元素抽出量が多いと部材金属配線部に腐食を生じてしまうため、０．１ｐ．ｐ．ｍ．未満でなければならない。そのため、０．１ｐ．ｐ．ｍ．未満を○、０．１ｐ．ｐ．ｍ．以上のものを×とした。 The amount of halogen element extracted in Table 1 is 100 cm 2 of pressure-sensitive adhesive sheets according to Examples and Comparative Examples as test specimens, placed in a conical beaker, immersed in 100 ml of ultrapure water, and extracted at 100 ° C. for 2 hours using a hot plate. The amount of chloride ion was analyzed by ion chromatography (DX-AQ, DIONEX). If the amount of extracted halogen element is large, corrosion will occur in the metal wiring part of the member. p. m. Must be less than Therefore, 0.1 p. p. m. Less than ○, 0.1 p. p. m. The above was marked as x.
実施例１について、説明する。本発明にかかる実施例１の粘着剤組成物は、エラストマとしてハロゲン含有モノマの含有率が５質量％のアクリル酸アルキルエステル・アクリル酸アルコキシアルキルエステル共重合体１００質量部、紫外線架橋性オリゴマ（根上工業社製アートレジンＵＮ３３２０）３０質量部、光重合開始剤（チバガイギー製イルガキュア１８４）３質量部及び（メタ）アクリル酸エステル・アミン共重合体としてメタクリル酸メチルとＮ，Ｎ−ジメチルアミノエチルアクリレート共重合体（ジメチルアミノエチルアクリレートモノマ量４質量％）を５質量部配合したものである。 Example 1 will be described. The pressure-sensitive adhesive composition of Example 1 according to the present invention comprises 100 parts by mass of an acrylic acid alkyl ester / acrylic acid alkoxyalkyl ester copolymer having a halogen-containing monomer content of 5% by mass as an elastomer, an ultraviolet-crosslinkable oligomer (Negami). 30 parts by mass of Art Resin UN3320 manufactured by Kogyo Co., Ltd., 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy), and methyl methacrylate and N, N-dimethylaminoethyl acrylate as a (meth) acrylate ester / amine copolymer 5 parts by mass of polymer (dimethylaminoethyl acrylate monomer amount 4% by mass) is blended.
表１における評価にあっては、実施例１の粘着剤組成物を、基材としての厚さ１５０μｍのポリエチレン製シートの一方の面に、厚さ２５μｍになるように積層して粘着剤層を設けることにより作成した粘着シートで行った。後述する実施例・比較例は、特に言及した部分以外は、本実施例と同様である。 In the evaluation in Table 1, the pressure-sensitive adhesive composition of Example 1 was laminated on one surface of a polyethylene sheet having a thickness of 150 μm as a base material so as to have a thickness of 25 μm. It carried out with the adhesive sheet created by providing. Examples and comparative examples to be described later are the same as those of the present example except for the parts specifically mentioned.
本実施例における粘着シートはチツプ飛び、粘着剤の掻き上げは確認されず、表面抵抗値が６．０×１０１１Ω／□、塩素イオン抽出量が０．１ｐ．ｐ．ｍ．未満であり、良好であった。 The pressure-sensitive adhesive sheet in this example was skipped, and the adhesive was not scraped, the surface resistance value was 6.0 × 10 11 Ω / □, and the chlorine ion extraction amount was 0.1 p. p. m. It was less than it was good.
実施例２について、説明する。実施例２は、実施例１の粘着剤層のエラストマとしてのアクリル酸アルキルエステル・アクリル酸アルコキシアルキルエステル共重合体をビニリデンフルオライド・ヘキサフルオロプロピレン共重合体に変更したものである。実施例３は、実施例１の（メタ）アクリル酸エステル・アミン共重合体としてのＮ，Ｎ−ジメチルアミノエチルアクリレートをメタアクリルアマイドに変更したものである。いずれの実施例も、良好な値であった。 Example 2 will be described. In Example 2, the acrylic acid alkyl ester / acrylic acid alkoxyalkyl ester copolymer as the elastomer of the pressure-sensitive adhesive layer of Example 1 was changed to vinylidene fluoride / hexafluoropropylene copolymer. In Example 3, N, N-dimethylaminoethyl acrylate as the (meth) acrylic acid ester / amine copolymer in Example 1 was changed to methacrylamide. All examples were good values.
以下、比較例について、説明する。比較例１は実施例における（メタ）アクリル酸エステル・アミン共重合体を０．０５質量部にしたものであり、比較例２は実施例における（メタ）アクリル酸エステル・アミン共重合体を３５質量部にしたものである。比較例３は実施例におけるエラストマに塩素基を有するモノマを含有しなかったものであり、比較例４は実施例におけるエラストマにハロゲン含有モノマの含有率を０．０５質量％にしたものである。比較例５は実施例におけるエラストマにハロゲン含有モノマの含有率を６０質量％にしたものである。比較例６は実施例における（メタ）アクリル酸エステル・アミン共重合体のアミン含有モノマの含有率を０．０５質量％にしたものである。比較例７は実施例における（メタ）アクリル酸エステル・アミン共重合体のアミン含有モノマの含有率を３５質量％にしたものである。 Hereinafter, a comparative example will be described. In Comparative Example 1, 0.05 part by mass of the (meth) acrylic acid ester / amine copolymer in the example was used, and in Comparative Example 2, the (meth) acrylic acid ester / amine copolymer in the example was 35%. It is a mass part. In Comparative Example 3, the elastomer in the example did not contain a monomer having a chlorine group, and in Comparative Example 4, the content of the halogen-containing monomer in the elastomer in the example was 0.05% by mass. In Comparative Example 5, the content of the halogen-containing monomer is 60% by mass in the elastomer in the examples. In Comparative Example 6, the content of the amine-containing monomer of the (meth) acrylic acid ester / amine copolymer in the examples was 0.05% by mass. In Comparative Example 7, the content of the amine-containing monomer of the (meth) acrylic acid ester / amine copolymer in the examples was 35% by mass.
比較例１は、粘着剤の掻き上げ、および粘着剤表面抵抗値が悪かった。比較例２は、粘着剤の掻き上げはなく、粘着剤表面抵抗値は良好なものの、粘着力が低く、チツプ飛びが多くみられた。比較例３は、塩素イオン抽出量は少ないものの、粘着剤表面抵抗値が悪かった。比較例４は、塩素イオン抽出量は少ないものの、粘着剤表面抵抗値が悪かった。比較例５は、粘着剤の掻き上げはないものの、塩素イオン抽出量が多く、チツプ飛びも多くみられた。比較例６は、粘着剤の掻き上げ、および粘着剤表面抵抗値が悪かった。比較例７は、粘着剤の掻き上げはなく、粘着剤表面抵抗値は良好なものの、粘着力が低く、チツプ飛びが多くみられた。 In Comparative Example 1, the adhesive was scraped up and the adhesive surface resistance value was poor. In Comparative Example 2, the pressure-sensitive adhesive was not scraped up, and the pressure-sensitive adhesive surface resistance value was good, but the pressure-sensitive adhesive force was low, and many chip skips were observed. Although the comparative example 3 had little chlorine ion extraction amount, the adhesive surface resistance value was bad. Although the comparative example 4 had little chloride ion extraction amount, the adhesive surface resistance value was bad. In Comparative Example 5, although the adhesive was not scraped up, the amount of extracted chlorine ions was large and chip skipping was also observed. In Comparative Example 6, the pressure-sensitive adhesive scraping and the pressure-sensitive adhesive surface resistance were poor. In Comparative Example 7, the pressure-sensitive adhesive was not scraped and the pressure-sensitive adhesive surface resistance value was good, but the pressure-sensitive adhesive force was low, and many chip skips were observed.
本発明にかかる粘着剤組成物は、一枚の板に複数個作成された電子部材を個々にダイシングする際、当該板の背面に貼り付けられる粘着シートに採用されるものである。他の発明に係る粘着シートは、当該分野に採用されるものである。
The pressure-sensitive adhesive composition according to the present invention is employed in a pressure-sensitive adhesive sheet that is affixed to the back surface of a board when a plurality of electronic members formed on a single board are individually diced. The pressure-sensitive adhesive sheet according to another invention is employed in this field.
Claims (6)
The pressure-sensitive adhesive sheet according to claim 5, wherein the pressure-sensitive adhesive sheet is for fixing a semiconductor member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004142798A JP2005325180A (en) | 2004-05-12 | 2004-05-12 | Adhesive composition and adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004142798A JP2005325180A (en) | 2004-05-12 | 2004-05-12 | Adhesive composition and adhesive sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005325180A true JP2005325180A (en) | 2005-11-24 |
Family
ID=35471780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004142798A Pending JP2005325180A (en) | 2004-05-12 | 2004-05-12 | Adhesive composition and adhesive sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005325180A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007220694A (en) * | 2005-05-16 | 2007-08-30 | Nitto Denko Corp | Dicing pressure-sensitive adhesive sheet and processing method of workpiece using the same |
| JP2008069185A (en) * | 2006-09-12 | 2008-03-27 | Denki Kagaku Kogyo Kk | An adhesive sheet for fixing an electronic component and a method for manufacturing an electronic component using the same. |
| WO2015005387A1 (en) * | 2013-07-09 | 2015-01-15 | 日東電工株式会社 | Adhesive-agent composition |
| WO2015141986A1 (en) * | 2014-03-19 | 2015-09-24 | 동우 화인켐 주식회사 | Adhesive composition and polarizing plate comprising same |
| WO2016006875A1 (en) * | 2014-07-11 | 2016-01-14 | 동우 화인켐 주식회사 | Ultra-thin polarising plate and liquid crystal display device equipped with same |
-
2004
- 2004-05-12 JP JP2004142798A patent/JP2005325180A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007220694A (en) * | 2005-05-16 | 2007-08-30 | Nitto Denko Corp | Dicing pressure-sensitive adhesive sheet and processing method of workpiece using the same |
| JP2008069185A (en) * | 2006-09-12 | 2008-03-27 | Denki Kagaku Kogyo Kk | An adhesive sheet for fixing an electronic component and a method for manufacturing an electronic component using the same. |
| WO2015005387A1 (en) * | 2013-07-09 | 2015-01-15 | 日東電工株式会社 | Adhesive-agent composition |
| JPWO2015005387A1 (en) * | 2013-07-09 | 2017-03-02 | 日東電工株式会社 | Adhesive composition |
| US9605189B2 (en) | 2013-07-09 | 2017-03-28 | Nitto Denko Corporation | Pressure-sensitive adhesive composition |
| WO2015141986A1 (en) * | 2014-03-19 | 2015-09-24 | 동우 화인켐 주식회사 | Adhesive composition and polarizing plate comprising same |
| WO2016006875A1 (en) * | 2014-07-11 | 2016-01-14 | 동우 화인켐 주식회사 | Ultra-thin polarising plate and liquid crystal display device equipped with same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101768415B (en) | Antistatic adhesive composition, adhesive film using the same, method for producing the adhesive film, and method of fabricating liquid crystal display | |
| CN109643662B (en) | Die attach paste and semiconductor devices | |
| KR101552741B1 (en) | Pressure-sensitive adhesive composition for touch panel, pressure-sensitive adhesive film and touch panel | |
| KR101392535B1 (en) | Adhesive tape for surface protection of a semiconductor wafer and method of producing a semiconductor wafer using the same | |
| KR20120036829A (en) | Pressure-sensitive adhesive compositon, pressure-sensitive adhesive, pressure-sensitive adhesive for optical member, and optical member with pressure-sensitive adhesive layer obtained using same | |
| US20090136748A1 (en) | Adhesive compostion for die bonding in semiconductor assembly, adhesive film prepared therefrom, dicing die-bonding film prepared therefrom, device package including the same, and associated methods | |
| JP2013523941A (en) | Touch panel adhesive film and touch panel | |
| JP2012244115A (en) | Backgrind-underfill integrated tape, and mounting method of semiconductor chip | |
| JP2009260332A (en) | Adhesive tape with antistatic property for fixing semiconductor wafer | |
| CN106574161A (en) | Adhesive composition, adhesive obtained by crosslinking same, adhesive for masking films, adhesive for heat-resistant adhesive films, heat-resistant adhesive film for masking, and method for using heat-resistant adhesive film for masking | |
| JP2007161909A (en) | Photopolymerizable adhesive composition and adhesive sheet using the same | |
| CN1394930A (en) | Anti-electrostatic cutting band | |
| JP2005325180A (en) | Adhesive composition and adhesive sheet | |
| JP5407247B2 (en) | Adhesive, adhesive film, and surface protective film for optical member | |
| JP5419318B2 (en) | Resin composition and semiconductor device produced using resin composition | |
| JP6894282B2 (en) | Adhesive tape and adhesive tape for fixing electronic device parts | |
| KR101248008B1 (en) | Adhesive film composition for semiconductor package | |
| KR100956721B1 (en) | Adhesive film for semiconductor assembly and dicing die bonding film comprising the same | |
| JP2000256635A (en) | Substrate with adhesive layer and adhesive film using acrylic resin | |
| JP2005281510A (en) | Adhesive composition and adhesive sheet | |
| JP4676297B2 (en) | An adhesive, an adhesive sheet using the adhesive, and an electronic component manufacturing method using the adhesive sheet. | |
| JP5888839B2 (en) | Acrylic pressure-sensitive adhesive manufacturing method, pressure-sensitive adhesive sheet manufacturing method | |
| JP4229817B2 (en) | Electronic member fixing sheet | |
| JP5066671B2 (en) | Photopolymerizable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same | |
| JP4640966B2 (en) | An adhesive, an adhesive sheet using the adhesive, and an electronic component manufacturing method using the adhesive sheet. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060404 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20100223 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Effective date: 20100421 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A02 | Decision of refusal |
Effective date: 20100518 Free format text: JAPANESE INTERMEDIATE CODE: A02 |