TWI771270B - 化學增幅型正型感光性樹脂組成物 - Google Patents
化學增幅型正型感光性樹脂組成物 Download PDFInfo
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- TWI771270B TWI771270B TW105106518A TW105106518A TWI771270B TW I771270 B TWI771270 B TW I771270B TW 105106518 A TW105106518 A TW 105106518A TW 105106518 A TW105106518 A TW 105106518A TW I771270 B TWI771270 B TW I771270B
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- acid
- photosensitive resin
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- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 239000011347 resin Substances 0.000 claims abstract description 101
- 239000002253 acid Substances 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 230000005855 radiation Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 7
- -1 fluoride compound Chemical class 0.000 claims description 125
- 125000004432 carbon atom Chemical group C* 0.000 claims description 70
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 17
- 125000003277 amino group Chemical group 0.000 claims description 16
- 125000001624 naphthyl group Chemical group 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 16
- 125000002252 acyl group Chemical group 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 239000004925 Acrylic resin Substances 0.000 claims description 11
- 229920000178 Acrylic resin Polymers 0.000 claims description 11
- 229920003986 novolac Polymers 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000011161 development Methods 0.000 claims description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 47
- 238000000465 moulding Methods 0.000 abstract description 7
- 230000006866 deterioration Effects 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 description 69
- 150000002430 hydrocarbons Chemical group 0.000 description 27
- 125000003118 aryl group Chemical group 0.000 description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 125000003545 alkoxy group Chemical group 0.000 description 16
- 229920002120 photoresistant polymer Polymers 0.000 description 16
- 125000001153 fluoro group Chemical group F* 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 125000002947 alkylene group Chemical group 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 8
- 150000001491 aromatic compounds Chemical group 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 150000002148 esters Chemical group 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- 150000001450 anions Chemical group 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 150000001768 cations Chemical group 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 125000004414 alkyl thio group Chemical group 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YGBVAGIVGBLKFE-UHFFFAOYSA-N 2-phenylbut-1-en-1-ol Chemical compound CCC(=CO)C1=CC=CC=C1 YGBVAGIVGBLKFE-UHFFFAOYSA-N 0.000 description 3
- MKHXOKALQIHXPI-UHFFFAOYSA-N 2-phenylprop-1-en-1-ol Chemical compound OC=C(C)C1=CC=CC=C1 MKHXOKALQIHXPI-UHFFFAOYSA-N 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 3
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
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- 125000005110 aryl thio group Chemical group 0.000 description 3
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical group NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
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- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000004010 onium ions Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
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- 229960004889 salicylic acid Drugs 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
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- 125000006713 (C5-C10) cycloalkyl group Chemical group 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
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- GYQQFWWMZYBCIB-UHFFFAOYSA-N 1-[diazo-(4-methylphenyl)sulfonylmethyl]sulfonyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=C(C)C=C1 GYQQFWWMZYBCIB-UHFFFAOYSA-N 0.000 description 2
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Abstract
本發明係提供使用化學增幅型正型感光性樹脂組成物,在基板上形成成為鍍敷成形物之模之阻劑圖型的情形,即使使用透鏡開口數(NA)高之曝光裝置的情形,也可抑制阻劑圖型之非阻劑部之剖面之形狀劣化的化學增幅型正型感光性樹脂組成物、使用該感光性樹脂組成物之附模基板之製造方法及使用該附模基板之鍍敷成形物之製造方法。
本發明之化學增幅型正型感光性樹脂組成物,其係在具有金屬表面之基板的前述金屬表面上製作鍍敷成形物(plated molded article)用的化學增幅型正型感光性樹脂組成物,其係含有(A)藉由活性光線或放射線之照射產生酸的酸產生劑、(B)因酸之作用而增大對鹼之溶解性的樹脂及(C)以下述式(1)表示的茀化合物。
Description
本發明係有關化學增幅型正型感光性樹脂組成物、使用該化學增幅型正型感光性樹脂組成物之附模基板之製造方法及使用該附模基板之鍍敷成形物之製造方法。
現今,感光蝕刻加工(photofabrication)已成精密微細加工技術的主流。「感光蝕刻加工」係指將光阻組成物塗佈於被加工物表面形成光阻層,利用光微影技術使光阻層進行圖型化,再以經圖型化的光阻層(光阻圖型)作為遮罩進行化學蝕刻、電解蝕刻、或以電鍍為主體的電成形等,製造半導體組件(semiconductor package)等各種精密零件之技術的總稱。
又,近年,隨著電子機器之小型化,半導體封裝之高密度組裝技術進展,試圖依據封裝之多針腳薄膜組裝化、封裝尺寸之小型化、採覆晶方式之二維組裝技術、三維組裝技術提高組裝密度。在這種高密度組裝技術中,在基板上高精密度地配置連接由作為連接端子例如突
出於封裝體上之凸塊等的突起電極(組裝端子)、晶圓上之週邊端子延伸的再配線與組裝端子的金屬柱(Metal Post)等。
如上述之感光蝕刻加工係使用光阻組成物,這種光阻組成物,已知有包含酸產生劑的化學增幅型光阻組成物(參照例如專利文獻1、2等)。化學增幅型光阻組成物係藉由放射線照射(曝光)而由酸產生劑產生酸,以加熱處理促進酸的擴散,對於組成物中之基質樹脂等產生酸觸媒反應,而改變其鹼溶解性者。
這種化學增幅型正型光阻組成物被使用於例如藉由鍍敷步驟形成如凸塊或金屬柱之鍍敷成形物等。具體而言,使用化學增幅型光阻組成物,在金屬基板等支撐體上形成所望之膜厚的光阻層,經由特定之遮罩圖型進行曝光、顯影,形成作為形成凸塊或金屬柱之部分被選擇性去除(剝離)模使用的光阻圖型。然後,藉由鍍敷將銅等的導體埋入於此被去除的部分(非阻劑部)後,藉由去除其周圍的光阻圖型,可形成凸塊或金屬柱。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開平9-176112號公報
[專利文獻2]日本特開平11-52562號公報
進一步要求高密度組裝中,而要求圖型之微細化或高膜厚化。
為了圖型之微細化,有時使用透鏡開口數(NA)更高的曝光裝置。但是使用透鏡開口數高的曝光裝置進行曝光的情形,高膜厚之阻劑圖型,有時會因光學密度不同產生形狀劣化。
使用如專利文獻1、2等所揭示之習知化學增幅型正型光阻組成物,將成作凸塊或金屬柱等形成用之模的光阻圖型形成於金屬基板上的情形,難以形成阻劑圖型之非阻劑部之剖面未產生形狀劣化的阻劑圖型。
本發明係有鑑於上述課題而完成者,本發明之目的係提供使用化學增幅型正型感光性樹脂組成物,在基板上形成成為鍍敷成形物之模之阻劑圖型的情形,即使使用透鏡開口數(NA)高之曝光裝置的情形,也可抑制阻劑圖型之非阻劑部之剖面之形狀劣化的化學增幅型正型感光性樹脂組成物、使用該感光性樹脂組成物之附模基板之製造方法及使用該附模基板之鍍敷成形物之製造方法。
本發明人等為了達成上述目的而精心研究的結果,發現藉由在化學增幅型正型感光性樹脂組成物中含有特定結構的茀化合物,可解決上述課題,而完成本發
明。具體而言,本發明係提供如以下者。
本發明之第一態樣係一種化學增幅型正型感光性樹脂組成物,其係在具有金屬表面之基板的前述金屬表面上製作鍍敷成形物用的化學增幅型正型感光性樹脂組成物,其係含有(A)藉由活性光線或放射線之照射產生酸的酸產生劑、(B)因酸之作用而增大對鹼之溶解性的樹脂及(C)以下述式(1)表示的茀化合物。
(式中,環Z1及環Z2獨立表示苯環或萘環,X1及X2獨立表示單鍵或-S-,R1、R2、R3及R4獨立表示一價烴基、羥基、(甲基)丙烯醯氧基、以-OR4a表示之基、以-SR4b表示之基、醯基、烷氧基羰基、鹵素原子、硝基、氰基、巰基、羧基、胺基、胺基甲醯基、以-NHR4c表示之基、以-N(R4d)2表示之基、(甲基)丙烯醯氧基、磺基、或一價烴基、以-OR4a表示之基、以-SR4b表示之基、醯基、烷氧基羰基、以-NHR4c表示之基、或表示鍵結於以-N(R4d)2表示之基所含有之碳原子之氫原子的至少一部分被一價烴基、羥基、以-OR4a表示之基、以-SR4b表示之基、醯基、
烷氧基羰基、鹵素原子、硝基、氰基、巰基、羧基、胺基、胺基甲醯基、以-NHR4c表示之基、以-N(R4d)2表示之基、(甲基)丙烯醯氧基、甲磺醯氧基、或磺基所取代之基,R4a~R4d獨立表示一價烴基,k1、k2、k3及k4獨立表示0~4之整數)。
本發明之第二態樣係一種附模基板之製造方法,其係含有:在具有金屬表面之基板的前述金屬表面上,層合由如第一態樣之化學增幅型正型感光性樹脂組成物所成之感光性樹脂層的層合步驟,將活性光線或放射線照射於前述感光性樹脂層的曝光步驟,將曝光後之前述感光性樹脂層進行顯影製作形成鍍敷成形物用之模的顯影步驟。
本發明之第三態樣係一種鍍敷成形物之製造方法,其係含有:對於藉由如第二態樣之方法所製造之前述附模基板施予鍍敷,在前述模內形成鍍敷成形物的步驟。
依據本發明時,可提供使用化學增幅型正型感光性樹脂組成物,在基板上形成成為鍍敷成形物之模之阻劑圖型的情形,即使使用透鏡開口數(NA)高之曝光裝置的情形,也可抑制阻劑圖型之非阻劑部之剖面之形狀劣化
的化學增幅型正型感光性樹脂組成物、使用該感光性樹脂組成物之附模基板之製造方法及使用該附模基板之鍍敷成形物之製造方法。
[實施發明之形態]
≪化學增幅型正型感光性樹脂組成物≫
本發明之化學增幅型正型感光性樹脂組成物(以下也稱為「感光性樹脂組成物」)係在具有金屬表面之基板的前述金屬表面上製作鍍敷成形物用的感光性樹脂組成物,其係含有(A)藉由活性光線或放射線之照射產生酸的酸產生劑(以下也稱為「(A)酸產生劑」)、(B)因酸之作用而增大對鹼之溶解性的樹脂(以下也稱為「(B)樹脂」)及(C)以下述式(1)表示的茀化合物(本說明書中,也稱為「(C)茀化合物」)。感光性樹脂組成物必要時,也可含有(D)鹼可溶性樹脂、(E)酸擴散控制劑、及(S)有機溶劑等之成分。
使用感光性樹脂組成物形成之阻劑圖型的膜厚無特別限定,惟感光性樹脂組成物較佳使用於厚膜之阻劑圖案之形成。使用感光性樹脂組成物所形成之阻劑圖案的膜厚,具體而言,較佳為10μm以上,更佳為10~150μm,特佳為20~120μm,最佳為20~80μm。
以下,說明感光性樹脂組成物所包含之必須或任意的成分及感光性樹脂組成物的製造方法。
<(A)酸產生劑>
(A)酸產生劑係藉由照射活性光線或放射線產生酸的化合物,只要為可藉由光直接或間接地產生酸的化合物則不特別限定。(A)酸產生劑較佳為以下所說明之第一~第五形態的酸產生劑。以下,感光性樹脂組成物中適合使用之(A)酸產生劑當中,較佳者以第一至第五態樣來說明。
(A)酸產生劑之第一形態,可舉出下述式(a1)所示之化合物。
上述式(a1)中,X1a表示原子價g的硫原子或碘原子,g為1或2。h表示括弧內之結構的重複單元數。R1a為與X1a鍵結的有機基,表示碳原子數6~30之芳基、碳原子數4~30之雜環基、碳原子數1~30之烷基、碳原子數2~30之烯基、或碳原子數2~30之炔基,R1a可被選自由烷基、羥基、烷氧基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、芳硫基羰基、醯氧基、芳硫基、烷硫基、芳基、雜環、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、伸烷氧基、胺基、氰基、硝基之各基、及鹵素所成群之至少1種所取代。R1a的個數為g+h(g-1)+1,R1a可分別彼此相同或相異。又,2個以上之R1a可彼此直接鍵結、或經由-O-、-S-、-SO-、-SO2-、
-NH-、-NR2a-、-CO-、-COO-、-CONH-、碳原子數1~3之伸烷基或伸苯基進行鍵結,形成包含X1a的環結構。R2a為碳原子數1~5之烷基或碳原子數6~10之芳基。
X2a為下述式(a2)所示的結構。
上述式(a2)中,X4a表示碳原子數1~8之伸烷基、碳原子數6~20之伸芳基、或碳原子數8~20之雜環化合物之2價基,X4a可被選自由碳原子數1~8之烷基、碳原子數1~8之烷氧基、碳原子數6~10之芳基、羥基、氰基、硝基之各基、及鹵素所成群之至少1種所取代。X5a表示-O-、-S-、-SO-、-SO2-、-NH-、-NR2a-、-CO-、-COO-、-CONH-、碳原子數1~3之伸烷基、或伸苯基。h表示括弧內之結構的重複單元數。h+1個X4a及h個X5a可分別相同或相異。R2a係與前述定義相同。
X3a-為鎓之對離子,可舉出以下述式(a17)所示之氟化烷基氟磷酸陰離子或以下述式(a18)所示之硼酸陰離子。
上述式(a17)中,R3a表示氫原子之80%以上被氟原子取代的烷基。j表示其個數,為1~5之整數。j個R3a各自可相同或相異。
上述式(a18)中,R4a~R7a各自獨立表示氟原子或苯基,該苯基之氫原子之一部分或全部可被選自由氟原子及三氟甲基所成群之至少1種所取代。
上述式(a1)所示之化合物中的鎓離子,可舉出三苯基鋶、三-對甲苯基鋶、4-(苯硫基)苯基二苯基鋶、雙[4-(二苯基鋶基)苯基]硫醚、雙[4-{雙[4-(2-羥基乙氧基)苯基]鋶基}苯基]硫醚、雙{4-[雙(4-氟苯基)鋶基]苯基}硫醚、4-(4-苯甲醯基-2-氯苯硫基)苯基雙(4-氟苯基)鋶、7-異丙基-9-側氧-10-硫雜-9,10-二氫蒽-2-基二-對甲苯基鋶、7-異丙基-9-側氧-10-硫雜-9,10-二氫蒽-2-基二苯基鋶、2-[(二苯基)鋶基]噻噸酮、4-[4-(4-三級丁基苯甲醯基)苯硫基]苯基二-對甲苯基鋶、4-(4-苯甲醯基苯硫基)苯基二苯基鋶、二苯基苯甲醯甲基鋶、4-羥基苯基甲基苄基鋶、2-萘基甲基(1-乙氧基羰基)乙基鋶、4-羥基苯基甲基苯甲醯甲基鋶、苯基[4-(4-聯苯硫基)苯基]4-聯苯基鋶、苯基[4-(4-聯苯硫基)苯基]3-聯苯基鋶、[4-(4-乙醯苯硫基)苯基]二
苯基鋶、十八烷基甲基苯甲醯甲基鋶、二苯基錪、二-p-甲苯基錪、雙(4-十二烷基苯基)錪、雙(4-甲氧基苯基)錪、(4-辛氧基苯基)苯基錪、雙(4-癸氧基)苯基錪、4-(2-羥基十四烷氧基)苯基苯基錪、4-異丙基苯基(p-甲苯基)錪、或4-異丁基苯基(p-甲苯基)錪等。
上述式(a1)所示之化合物中的鎓離子中,較佳之鎓離子可舉出下述式(a19)所示之鋶離子。
上述式(a19)中,R8a各自獨立表示選自由氫原子、烷基、羥基、烷氧基、烷基羰基、烷基羰氧基、烷氧基羰基、鹵素原子、可具取代基之芳基、芳基羰基所成群之基。X2a表示與上述式(a1)中之X2a相同意義。
上述式(a19)所示之鋶離子的具體例,可舉出4-(苯硫基)苯基二苯基鋶、4-(4-苯甲醯基-2-氯苯硫基)苯基雙(4-氟苯基)鋶、4-(4-苯甲醯基苯硫基)苯基二苯基鋶、苯基[4-(4-聯苯硫基)苯基]4-聯苯基鋶、苯基[4-(4-聯苯硫基)苯基]3-聯苯基鋶、[4-(4-乙醯苯硫基)苯基]二苯基鋶、二苯基[4-(p-三聯苯硫基)苯基]二苯基鋶。
上述式(a17)所示之氟化烷基氟磷酸陰離子中,R3a表示經氟原于取代的烷基,較佳之碳原子數為1~8,更佳之碳原子數為1~4。烷基之具體實例,可舉出甲基、乙基、丙基、丁基、戊基、辛基等直鏈烷基;異丙基、異丁基、sec-丁基、tert-丁基等之分支烷基;及環丙基、環丁基、環戊基、環己基等之環烷基等,烷基之氫原子被取代成氟原子的比例,通常為80%以上,較佳為90%以上,又更佳為100%。氟原子之取代率若未達80%的情形,上述式(a1)所示之鎓氟化烷基氟磷酸鹽的酸強度會降低。
特佳之R3a為碳原子數為1~4,且氟原子之取代率為100%之直鏈狀或分支狀的全氟烷基,具體實例可舉出CF3、CF3CF2、(CF3)2CF、CF3CF2CF2、CF3CF2CF2CF2、(CF3)2CFCF2、CF3CF2(CF3)CF、(CF3)3C。R3a的個數j為1~5之整數,較佳為2~4,特佳為2或3。
較佳之氟化烷基氟磷酸陰離子的具體實例,可舉出[(CF3CF2)2PF4]-、[(CF3CF2)3PF3]-、[((CF3)2CF)2PF4]-、[((CF3)2CF)3PF3]-、[(CF3CF2CF2)2PF4]-、[(CF3CF2CF2)3PF3]-、[((CF3)2CFCF2)2PF4]-、[((CF3)2CFCF2)3PF3]-、[(CF3CF2CF2CF2)2PF4]-、或[(CF3CF2CF2)3PF3]-,此等之中,特佳為[(CF3CF2)3PF3]-、[(CF3CF2CF2)3PF3]-、[((CF3)2CF)3PF3]-、[((CF3)2CF)2PF4]-、[((CF3)2CFCF2)3PF3]-、或[((CF3)2CFCF2)2PF4]-。
上述式(a18)所示之硼酸根陰離子的較佳具體
實例,可舉出肆(五氟苯基)硼酸陰離子([B(C6F5)4]-)、肆[(三氟甲基)苯基]硼酸陰離子([B(C6H4CF3)4]-)、二氟雙(五氟苯基)硼酸陰離子([(C6F5)2BF2]-)、三氟(五氟苯基)硼酸陰離子([(C6F5)BF3]-)、肆(二氟苯基)硼酸陰離子([B(C6H3F2)4]-)等。此等當中,特佳為肆(五氟苯基)硼酸陰離子([B(C6F5)4]-)。
酸產生劑(A)之第二態樣,可舉出2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(2-呋喃基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基-2-呋喃基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(5-乙基-2-呋喃基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(5-丙基-2-呋喃基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(3,5-二甲氧基苯基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(3,5-二乙氧基苯基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(3,5-二丙氧基苯基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(3-甲氧基-5-乙氧基苯基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(3-甲氧基-5-丙氧基苯基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-亞甲二氧基苯基)乙烯基]-s-三嗪、2,4-雙(三氯甲基)-6-(3,4-亞甲二氧基苯基)-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-s-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基萘基)-4,6-雙(三
氯甲基)-1,3,5-三嗪、2-[2-(2-呋喃基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-[2-(5-甲基-2-呋喃基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-[2-(3,5-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(3,4-亞甲二氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、參(1,3-二溴丙基)-1,3,5-三嗪、參(2,3-二溴丙基)-1,3,5-三嗪等含鹵素之三嗪化合物及參(2,3-二溴丙基)三聚異氰酸酯等之下述式(a3)所示之含鹵素之三嗪化合物。
上述式(a3)中,R9a、R10a、R11a各自獨立表示鹵烷基。
又,(A)酸產生劑之第三態樣,可舉出α-(對甲苯磺醯氧基亞胺基)-苯基乙腈、α-(苯磺醯氧基亞胺基)-2,4-二氯苯基乙腈、α-(苯磺醯氧基亞胺基)-2,6-二氯苯基乙腈、α-(2-氯苯磺醯氧基亞胺基)-4-甲氧基苯基乙腈、α-(乙基磺醯氧基亞胺基)-1-環戊烯基乙腈及含有肟磺酸酯基的下述式(a4)所示之化合物。
上述式(a4)中,R12a表示1價、2價、或3價有機基,R13a表示經取代或未取代之飽和烴基、不飽和烴基、或芳香族性化合物基,n表示括弧內之結構的重複單元數。
上述式(a4)中,芳香族性化合物基表示芳香族化合物顯示特有的物理、化學性質之化合物之基,可列舉例如苯基、萘基等之芳基、或呋喃基、噻吩基等之雜芳基。此等亦可在環上具有1個以上之適當的取代基,例如鹵素原子、烷基、烷氧基、硝基等。又,R13a特佳為碳原子數1~6之烷基,可舉出甲基、乙基、丙基、丁基。特別是R12a為芳香族性化合物基,R13a為碳原子數1~4之烷基的化合物為佳。
上述式(a4)所示之酸產生劑,當n=1時,R12a為苯基、甲基苯基、甲氧基苯基之任一,R13a為甲基的化合物,具體而言,可舉出α-(甲磺醯氧基亞胺基)-1-苯基乙腈、α-(甲磺醯氧基亞胺基)-1-(p-甲基苯基)乙腈、α-(甲磺醯氧基亞胺基)-1-(p-甲氧基苯基)乙腈、[2-(丙基磺醯氧基亞胺基)-2,3-二羥基噻吩-3-亞基](o-甲苯基)乙腈等。當n=2時,上述式(a4)所示之酸產生劑,具體而言,可舉出下述式所示之酸產生劑。
另外,(A)酸產生劑之第四態樣,可舉出在陽離子部具有萘環的鎓鹽。此「具有萘環」係指具有來自萘之結構,意指至少2個環的結構,且可維持彼等之芳香族性。此萘環亦可具有碳原子數1~6之直鏈狀或分支狀的烷基、羥基、碳原子數1~6之直鏈狀或分支狀的烷氧基等的取代基。來自萘環之結構可為1價基(游離原子價為1),亦可為2價基(游離原子價為2)以上,較佳為1價基(惟,此時係扣除與上述取代基鍵結部分來計算游離原子價者)。萘環數較佳為1~3。
此種在陽離子部具有萘環之鎓鹽的陽離子部,較佳為以下述式(a5)所示之結構。
上述式(a5)中,R14a、R15a、R16a中至少1個表示下述式(a6)所示之基,其餘表示碳原子數1~6之直鏈
狀或分支狀的烷基、可具取代基之苯基、羥基、或碳原子數1~6之直鏈狀或分支狀的烷氧基。或R14a、R15a、R16a中之一個為下述式(a6)所示之基,其餘兩個各自獨立為碳原子數1~6之直鏈狀或分支狀的伸烷基,此等之末端可鍵結形成環狀。
上述式(a6)中,R17a、R18a各自獨立表示羥基、碳原子數1~6之直鏈狀或分支狀的烷氧基、或碳原子數1~6之直鏈狀或分支狀的烷基,R19a表示單鍵或可具取代基之碳原子數1~6之直鏈狀或分支狀的伸烷基。l及m各自獨立表示0~2之整數,l+m為3以下。但是當R17a存在複數個的情形,彼等可彼此相同或相異。又,當R18a存在複數個的情形,彼等可彼此相同或相異。
上述R14a、R15a、R16a之中,上述式(a6)所示之基的數目,從化合物穩定性的觀點,較佳為1個,其餘為碳原子數1~6之直鏈狀或分支狀的伸烷基,此等末端可鍵結形成環狀。此時,上述2個伸烷基包含硫原子,構成3~9員環。構成環的原子(包含硫原子)之數,較佳為5~6。
又,上述伸烷基可具有的取代基,可舉出氧原子(此時,與構成伸烷基的碳原子共同形成羰基)、羥基等。
又,苯基可具有的取代基,可舉出羥基、碳原子數1~6之直鏈狀或分支狀的烷氧基、碳原子數1~6之直鏈狀或分支狀的烷基等。
適合作為此等之陽離子部者,可列舉以下述式(a7)、(a8)表示者,特佳為以下述式(a8)表示之結構。
這種陽離子部可為錪鹽或鋶鹽;但是從酸產生效率等的觀點,較佳為鋶鹽。
因此,適合作為陽離子部具有萘環之鎓鹽的陰離子部者,較佳為可形成鋶鹽的陰離子。
這種酸產生劑的陰離子部係氫原子之一部分或全部經氟化的氟烷基磺酸離子或芳基磺酸離子。
氟烷基磺酸離子中的烷基可為碳原子數1~20之直鏈狀、分支狀或環狀,因產生之酸的體積大小及其擴散距離,較佳為碳原子數1~10。特別是分支狀或環狀者因擴散距離短,故較佳。又,由於可廉價地合成而言,可舉出較佳者為甲基、乙基、丙基、丁基、辛基等。
芳基磺酸離子中的芳基為碳原子數6~20之芳基,可舉出可經烷基、鹵素原子取代或未取代之苯基、萘基。特別是由可廉價地合成而言,較佳為碳原子數6~10之芳基。較佳者的具體實例,可舉出苯基、甲苯磺醯基、乙基苯基、萘基、甲基萘基等。
上述氟烷基磺酸離子或芳基磺酸離子中,氫原子之一部分或全部經氟化時的氟化率,較佳為10~100%,更佳為50~100%,特別是全部氫原子以氟原子取代者,因酸的強度增強,故較佳。此類者具體而言,可舉出三氟甲磺酸酯、全氟丁磺酸酯、全氟辛磺酸酯、全氟苯磺酸酯等。
此等之中,較佳之陰離子部,可舉出下述式(a9)所示者。
【化13】R 20a SO 3 - (a9)
上述式(a9)中,R20a為下述式(a10)、(a11)、及(a12)所示之基。
上述式(a10)中,x表示1~4之整數。又,上述式(a11)中,R21a表示氫原子、羥基、碳原子數1~6之直鏈狀或分支狀的烷基、或碳原子數1~6之直鏈狀或分支狀的烷氧基,y表示1~3之整數。此等之中,由安全性的觀點,較佳為三氟甲磺酸酯、全氟丁磺酸酯。
又,陰離子部亦可使用下述式(a13)、(a14)所示之含氮者。
上述式(a13)、(a14)中,Xa表示至少1個氫原子經氟原子取代之直鏈狀或分支狀的伸烷基,該伸烷基之碳原子數為2~6,較佳為3~5,最佳為碳原子數為3。又,Ya、Za各自獨立表示至少1個氫原子經氟原子取代之直鏈狀或分支狀的烷基,該烷基的碳原子數為1~10,較佳為1~7,更佳為1~3。
Xa之伸烷基的碳原子數、或Ya、Za之烷基的碳原子數愈小,對有機溶劑的溶解性愈良好,因此較佳。
又,Xa之伸烷基或Ya、Za之烷基中,經氟原子取代之氫原子之數目愈多,酸的強度愈強,因此較佳。該伸烷基或烷基中之氟原子的比例,亦即氟化率,較佳為70~100%,更佳為90~100%,最佳為全部的氫原子經氟原子取代的全氟伸烷基或全氟烷基。
作為這種陽離子部具有萘環之鎓鹽較佳者,可舉出下述式(a15)、(a16)所示之化合物。
又,(A)酸產生劑之第五態樣,可列舉雙(p-甲苯磺醯基)重氮甲烷、雙(1,1-二甲基乙基磺醯基)重氮甲烷、雙(環己基磺醯基)重氮甲烷、雙(2,4-二甲基苯基磺醯基)重氮甲烷等之雙磺醯基重氮甲烷類;p-甲苯磺酸2-硝基苄酯、p-甲苯磺酸2,6-二硝基苄酯、硝基苄基甲苯磺酸酯、二硝基苄基甲苯磺酸酯、硝基苄基磺酸鹽、硝基苄基碳酸酯、二硝基苄基碳酸酯等之硝基苄酯衍生物;焦拮酚三氟甲磺酸酯、焦拮酚三甲苯磺酸酯、苄基甲苯磺酸酯、苄基磺酸鹽、N-甲基磺醯氧基丁二醯亞胺、N-三氯甲基磺醯氧基丁二醯亞胺、N-苯基磺醯氧基馬來醯亞胺、N-甲基磺醯氧基酞醯亞胺等之磺酸酯類;N-羥基酞醯亞胺、N-羥基萘醯亞胺等之三氟甲烷磺酸酯類;二苯基錪六氟磷酸酯、(4-甲氧基苯基)苯基錪三氟甲烷磺酸酯、雙(p-tert-丁基苯基)錪三氟甲烷磺酸鹽、三苯基鋶六氟磷酸酯、(4-甲氧基苯基)二苯基鋶三氟甲烷磺酸鹽、(p-tert-丁基苯基)二苯基鋶三氟甲烷磺酸酯等之鎓鹽類;苯偶因甲苯磺酸酯、
α-甲基苯偶因甲苯磺酸酯等之苯偶因對甲苯磺酸酯類;其他之二苯基錪鹽、三苯基鋶鹽、苯基重氮鎓鹽、苄基碳酸酯等。
此(A)酸產生劑可單獨使用,亦可組合2種以上使用。又,(A)酸產生劑的含量係相對於感光性樹脂組成物之全質量,較佳為0.1~10質量%,更佳為0.5~3質量%。藉由將(A)酸產生劑之使用量設為上述範圍,可容易調製具備良好感度、均勻的溶液,且保存穩定性優良的感光性樹脂組成物。
<(B)樹脂>
(B)藉由酸之作用而增大對鹼之溶解性的樹脂,無特別限定,可使用藉由酸之作用而增大對鹼之溶解性的任意樹脂。其中,較佳為含有選自由(B1)酚醛清漆樹脂、(B2)聚羥基苯乙烯樹脂及(B3)丙烯酸樹脂所成群之至少1種樹脂。
[(B1)酚醛清漆樹脂]
(B1)酚醛清漆樹脂可使用含有下述式(b1)表示之構成單元的樹脂。
上述式(b1)中,R1b表示酸解離性溶解抑制基,R2b、R3b各自獨立表示氫原子或碳原子數1~6之烷基。
上述R1b表示之酸解離性溶解抑制基,較佳為以下述式(b2)、(b3)表示之基、碳原子數1~6之直鏈狀、分支狀、或環狀之烷基、乙烯氧基乙基、四氫吡喃基、四呋喃基、或三烷基甲矽烷基。
上述式(b2)、(b3)中,R4b、R5b各自獨立表示氫原子、或碳原子數1~6之直鏈狀或分支狀之烷基,R6b表示碳原子數1~10之直鏈狀、分支狀、或環狀之烷基,R7b表示碳原子數1~6之直鏈狀、分支狀、或環狀之烷基,o表示0或1。
上述直鏈狀或分支狀之烷基,可列舉甲基、乙基、丙基、異丙基、n-丁基、異丁基、tert-丁基、戊基、異戊基、新戊基等。又,上述環狀之烷基可列舉環戊
基、環己基等。
在此,上述式(b2)表示之酸解離性溶解抑制基,具體而言,可列舉甲氧基乙基、乙氧基乙基、n-丙氧基乙基、異丙氧基乙基、n-丁氧基乙基、異丁氧基乙基、tert-丁氧基乙基、環己氧基乙基、甲氧基丙基、乙氧基丙基、1-甲氧基-1-甲基-乙基、1-乙氧基-1-甲基乙基等。又,上述式(b3)表示之酸解離性溶解抑制基,具體而言,可列舉tert-丁氧基羰基、tert-丁氧基羰基甲基等。又,上述三烷基甲矽烷基可列舉三甲基甲矽烷基、三-tert-丁基二甲基甲矽烷基等之各烷基之碳原子數為1~6者。
[(B2)聚羥基苯乙烯樹脂]
(B2)聚羥基苯乙烯樹脂可使用含有下述式(b4)表示之構成單元的樹脂。
上述式(b4)中,R8b表示氫原子或碳原子數1~6之烷基,R9b表示酸解離性溶解抑制基。
上述碳原子數1~6之烷基,例如碳原子數1~6之直鏈狀、分支狀、或環狀之烷基。直鏈狀或分支狀之烷
基,可列舉甲基、乙基、丙基、異丙基、n-丁基、異丁基、tert-丁基、戊基、異戊基、新戊基等,環狀之烷基可列舉環戊基、環己基等。
上述以R9b表示之酸解離性溶解抑制基,可使用與上述式(b2)、(b3)所例示者同樣的酸解離性溶解抑制基。
此外,(B2)聚羥基苯乙烯樹脂,為了適度控制物理、化學特性為目的,可包含其他的聚合性化合物作為構成單元。這種聚合性化合物,可舉出公知之自由基聚合性化合物、或陰離子聚合性化合物。又,這種聚合性化合物,可舉出例如丙烯酸、甲基丙烯酸、巴豆酸等單羧酸類;馬來酸、富馬酸、衣康酸等二羧酸類;2-甲基丙烯醯氧乙基琥珀酸、2-甲基丙烯醯氧乙基馬來酸、2-甲基丙烯醯氧乙基鄰苯二甲酸、2-甲基丙烯醯氧乙基六氫鄰苯二甲酸等具羧基及酯鍵之甲基丙烯酸衍生物類;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等(甲基)丙烯酸烷基酯類;(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯等(甲基)丙烯酸羥基烷基酯類;(甲基)丙烯酸苯酯、(甲基)丙烯酸苯甲酯等(甲基)丙烯酸芳基酯類;馬來酸二乙酯、富馬酸二丁酯等二羧酸二酯類;苯乙烯、α-甲基苯乙烯、氯苯乙烯、氯甲基苯乙烯、乙烯基甲苯、羥基苯乙烯、α-甲基羥基苯乙烯、α-乙基羥基苯乙烯等含乙烯基之芳香族化合物類;乙酸乙烯酯等含乙烯基之脂肪族化合物類;丁二烯、異戊二烯等共軛二烯烴類;丙烯腈、甲
基丙烯腈等含腈基之聚合性化合物類;氯乙烯、偏二氯乙烯等含氯聚合性化合物;丙烯醯胺、甲基丙烯醯胺等含醯胺鍵之聚合性化合物類;等。
[(B3)丙烯酸樹脂]
(B3)丙烯酸樹脂可使用包含下述式(b5)~(b7)所示之構成單元的樹脂。
上述式(b5)~(b7)中,R10b、及R14b~R19b各自獨立表示氫原子、碳原子數1~6之直鏈狀或分支狀的烷基、氟原子、或碳原子數1~6之直鏈狀或分支狀之氟化烷基,R11b~R13b各自獨立表示碳原子數1~6之直鏈狀或分支
狀的烷基、或碳原子數1~6之直鏈狀或分支狀之氟化烷基,R12b及R13b可彼此鍵結,與兩者所鍵結的碳原子共同形成碳原子數5~20之烴環,Yb表示可具取代基之脂肪族環式基或烷基,p表示0~4之整數,q表示0或1。
此外,作為上述直鏈狀或分支狀的烷基,可舉出甲基、乙基、丙基、異丙基、正丁基、異丁基、tert-丁基、戊基、異戊基、新戊基等。又,氟化烷基係指上述烷基之氫原子之一部分或全部經氟原子取代者。
上述R12b及R13b未彼此鍵結而形成烴環的情形,上述R11b、R12b、及R13b,由高對比、解析度、焦點深度寬等良好的觀點,較佳為碳原子數2~4之直鏈狀或分支狀的烷基。上述R15b、R16b、R18b、R19b較佳為氫原子或甲基。
上述R12b及R13b可與兩者所鍵結的碳原子共同形成碳原子數5~20之脂肪族環式基。這種脂肪族環式基的具體例,可舉出由單環烷、二環烷、三環烷、四環烷等多環烷中去除1個以上之氫原子的基。具體而言,可舉出由環戊烷、環己烷、環庚烷、環辛烷等之單環烷、或金剛烷、降莰烷、異莰烷(isobornane)、三環癸烷、四環十二烷等之多環烷中去除1個以上之氫原子的基。特別是由環己烷、金剛烷中去除1個以上之氫原子的基(可進一步具有取代基)為佳。
再者,上述R12b及R13b所形成的脂肪族環式基,在其環骨架上具有取代基的情形,該取代基之例,可
舉出羥基、羧基、氰基、氧原子(=O)等之極性基、或碳原子數1~4之直鏈狀或分支狀的烷基。極性基特佳為氧原子(=O)。
上述Yb為脂肪族環式基或烷基,可舉出由單環烷、二環烷、三環烷、四環烷等之多環烷中去除1個以上之氫原子的基等。具體而言,可舉出由環戊烷、環己烷、環庚烷、環辛烷等單環烷、或金剛烷、降莰烷、異莰烷、三環癸烷、四環十二烷等之多環烷中去除1個以上之氫原子的基等。特佳為由金剛烷中去除1個以上之氫原子的基(可進一步具有取代基)。
再者,上述Yb之脂肪族環式基在其環骨架上具有取代基的情形,該取代基之例,可舉出羥基、羧基、氰基、氧原子(=O)等之極性基、或碳原子數1~4之直鏈狀或分支狀的烷基。極性基特佳為氧原子(=O)。
又,Yb為烷基的情形,為碳原子數1~20、較佳為6~15之直鏈狀或分支狀的烷基。這種烷基特佳為烷氧基烷基,這種烷氧基烷基,可舉出1-甲氧基乙基、1-乙氧基乙基、1-n-丙氧基乙基、1-異丙氧基乙基、1-n-丁氧基乙基、1-異丁氧基乙基、1-tert-丁氧基乙基、1-甲氧基丙基、1-乙氧基丙基、1-甲氧基-1-甲基-乙基、1-乙氧基-1-甲基乙基等。
上述式(b5)所示之構成單元之較佳具體例,可舉出下述式(b5-1)~(b5-33)所示者。
上述式(b5-1)~(b5-33)中,R20b表示氫原子或甲基。
上述式(b6)表示之構成單元之較佳具體例,可列舉下述式(b6-1)~(b6-24)表示者。
上述式(b6-1)~(b6-24)中,R20b表示氫原子或甲基。
上述式(b7)表示之構成單元之較佳具體例,可列舉下述式(b7-1)~(b7-15)表示者。
上述式(b7-1)~(b7-15)中,R20b表示氫原子或甲基。
此外,(B3)丙烯酸樹脂相對於上述式(b5)~(b7)表示之構成單元,進一步包含由具有醚鍵之聚合性化合物所衍生之構成單元之共聚物所成的樹脂為佳。
上述具有醚鍵之聚合性化合物,可列舉例如具有醚鍵及酯鍵之(甲基)丙烯酸衍生物等之自由基聚合性化合物,具體例可列舉2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、3-甲氧基丁基(甲基)丙烯酸酯、乙基卡必醇(甲基)
丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯等。又,上述具有醚鍵之聚合性化合物,較佳為2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯。此等之聚合性化合物,可單獨使用,亦可組合2種以上使用。
此外,(B3)丙烯酸樹脂中,為了適度控制物理、化學特性為目的,可包含其他的聚合性化合物作為構成單元。此種聚合性化合物,可舉出公知之自由基聚合性化合物或陰離子聚合性化合物。
這種聚合性化合物,可舉出例如丙烯酸、甲基丙烯酸、巴豆酸等之單羧酸類;馬來酸、富馬酸、衣康酸等之二羧酸類;2-甲基丙烯醯氧乙基琥珀酸、2-甲基丙烯醯氧乙基馬來酸、2-甲基丙烯醯氧乙基鄰苯二甲酸、2-甲基丙烯醯氧乙基六氫鄰苯二甲酸等之具羧基及酯鍵之甲基丙烯酸衍生物類;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸環己酯等之(甲基)丙烯酸烷基酯類;(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯等(甲基)丙烯酸羥基烷基酯類;(甲基)丙烯酸苯酯、(甲基)丙烯酸苯甲酯等(甲基)丙烯酸芳基酯類;馬來酸二乙酯、富馬酸二丁酯等之二羧酸二酯類;苯乙烯、α-甲基苯乙烯、氯苯乙烯、氯甲基苯乙烯、乙烯基甲苯、羥基苯乙烯、α-甲基羥基苯乙烯、α-乙基羥基苯乙烯等之含
乙烯基之芳香族化合物類;乙酸乙烯酯等之含乙烯基之脂肪族化合物類;丁二烯、異戊二烯等之共軛二烯烴類;丙烯腈、甲基丙烯腈等之含腈基之聚合性化合物類;氯乙烯、偏二氯乙烯等之含氯聚合性化合物;丙烯醯胺、甲基丙烯醯胺等之含醯胺鍵之聚合性化合物類;等。
又,作為聚合性化合物,可舉出具有酸非解離性之脂肪族多環式基之(甲基)丙烯酸酯類、含乙烯基之芳香族化合物類等。酸非解離性之脂肪族多環式基,特別是三環癸基、金剛烷基、四環十二烷基、異莰基、降莰基等,工業上容易取得等的觀點而言,較佳。此等脂肪族多環式基亦可具有碳原子數1~5之直鏈狀或分支鏈狀的烷基作為取代基。
具酸非解離性之脂肪族多環式基的(甲基)丙烯酸酯類,具體而言,可例示下述式(b8-1)~(b8-5)之結構者。
上述式(b8-1)~(b8-5)中,R21b表示氫原子或甲基。
上述(B)樹脂當中,較佳使用(B3)丙烯酸樹脂。這種(B3)丙烯酸樹脂之中,較佳為具有上述式(b5)所示之構成單元、自(甲基)丙烯衍生酸之構成單元、自(甲基)丙烯酸烷基酯類衍生的構成單元、及自(甲基)丙烯酸芳基酯類衍生的構成單元的共聚物。
這種類共聚物較佳為下述式(b9)所示之共聚物。
上述式(b9)中,R22b表示氫原子或甲基,R23b表示碳原子數2~4之直鏈狀或分支狀的烷基,Xb表示與其所鍵結的碳原子共同形成的碳原子數5~20之烴環,R24b表示碳原子數1~6之直鏈狀或分支狀的烷基或碳原子數1~6之烷氧基烷基,R25b表示碳原子數6~12之芳基。
此外,上述式(b9)所示之共聚物中,s、t、u、v表示各自之構成單元的莫耳比,s為8~45莫耳%,t為10~65莫耳%,u為3~25莫耳%,v為6~25莫耳%。
(B)樹脂之聚苯乙烯換算質量平均分子量,較佳為10000~600000,更佳為20000~400000,又更佳為
30000~300000。藉由設為此種質量平均分子量,不會降低與基板表面的剝離性,可保持感光性樹脂層之充分的強度,甚而可防止鍍敷時圖形之膨脹、或龜裂之產生。
又,(B)樹脂較佳為分散度為1.05以上的樹脂。於此,分散度係指質量平均分子量除以數量平均分子量所得的值。藉由設為這種分散度,可避免所期望之對鍍敷之應力耐性、或藉由鍍敷處理所得之金屬層容易膨脹的問題。
(B)樹脂之含量係相對於感光性樹脂組成物之全質量,較佳為5~60質量%。
<(C)茀化合物>
(C)茀化合物係以下述式(1)表示。
(式中,環Z1及環Z2獨立表示苯環或萘環,X1及X2獨立表示單鍵或-S-,R1、R2、R3及R4獨立表示一價烴基、羥基、(甲基)丙烯醯氧基、以-OR4a表示之基、以-SR4b表示之基、醯基、烷氧基羰基、鹵素原子、硝基、氰基、
巰基、羧基、胺基、胺基甲醯基、以-NHR4c表示之基、以-N(R4d)2表示之基、(甲基)丙烯醯氧基、磺基、或一價烴基、以-OR4a表示之基、以-SR4b表示之基、醯基、烷氧基羰基、以-NHR4c表示之基、或表示鍵結於以-N(R4d)2表示之基所含有之碳原子之氫原子的至少一部分被一價烴基、羥基、以-OR4a表示之基、以-SR4b表示之基、醯基、烷氧基羰基、鹵素原子、硝基、氰基、巰基、羧基、胺基、胺基甲醯基、以-NHR4c表示之基、以-N(R4d)2表示之基、(甲基)丙烯醯氧基、甲磺醯氧基、或磺基所取代之基,R4a~R4d獨立表示一價烴基,k1、k2、k3及k4獨立表示0~4之整數)。
環Z1及環Z2獨立表示苯環或萘環,但是更佳為環Z1及環Z2皆為苯環,或皆為萘環。
上述一般式(1)中,X1及X2獨立表示單鍵或-S-表示之基,典型為單鍵。
上述一般式(1)中,R1、R2、R3及R4可列舉例如烷基(例如、甲基、乙基、丙基、異丙基、丁基等之C1-12烷基、較佳為C1-8烷基、更佳為C1-6烷基等)、環烷基(環己基等之C5-10環烷基、較佳為C5-8環烷基、更佳為C5-6環烷基等)、芳基(例如苯基、甲苯基、二甲苯基、萘基等之C6-14芳基、較佳為C6-10芳基、更佳為C6-8芳基等)、芳烷基(苄基、苯乙基等之C6-10芳基-C1-4烷基等)等之一價烴基;羥基;烷氧基(甲氧基、乙氧基、丙氧基、丁氧基等之C1-12烷氧基、較佳為C1-8烷氧基、更佳為C1-6烷
氧基等)、環烷氧基(環己氧基等之C5-10環烷氧基等)、芳氧基(苯氧基等之C6-10芳氧基)、芳烷基氧基(例如、苄氧基等之C6-10芳基-C1-4烷氧基)等之-OR4a表示之基[式中,R4a表示一價烴基(上述例示之一價烴基等)。];烷基硫基(甲基硫基、乙基硫基、丙基硫基、丁基硫基等之C1-12烷基硫基、較佳為C1-8烷基硫基、更佳為C1-6烷基硫基等)、環烷基硫基(環己基硫基等之C5-10環烷基硫基等)、芳基硫基(苯硫基等之C6-10芳基硫基)、芳烷基硫基(例如、苄基硫基等之C6-10芳基-C1-4烷基硫基)等之-SR4b表示之基[式中,R4b表示一價烴基(上述例示之一價烴基等)。];醯基(乙醯基等之C1-6醯基等);烷氧基羰基(甲氧基羰基等之C1-4烷氧基-羰基等);鹵素原子(氟原子、氯原子、溴原子、碘原子等);硝基;氰基;巰基;羧基;胺基;胺基甲醯基;烷基胺基(甲基胺基、乙基胺基、丙基胺基、丁基胺基等之C1-12烷基胺基、較佳為C1-8烷基胺基、更佳為C1-6烷基胺基等)、環烷基胺基(環己基胺基等之C5-10環烷基胺基等)、芳基胺基(苯基胺基等之C6-10芳基胺基)、芳烷基胺基(例如、苄基胺基等之C6-10芳基-C1-4烷基胺基)等之-NHR4c表示之基[式中,R4c表示一價烴基(上述例示之一價烴基等)。];二烷基胺基(二甲基胺基、二乙基胺基、二丙基胺基、二丁基胺基等之二(C1-12烷基)胺基、較佳為二(C1-8烷基)胺基、更佳為二(C1-6烷基)胺基等)、二環烷基胺基(二環己基胺基等之二(C5-10環烷基)胺基等)、二芳基胺基(二苯基胺基等之二(C6-10芳基)胺基)、
二芳烷基胺基(例如、二苄基胺基等之二(C6-10芳基-C1-4烷基)胺基)等之-N(R4d)2表示之基[式中,R4d獨立表示一價烴基(上述例示之一價烴基等)。];(甲基)丙烯醯氧基;磺基;或經上述之一價烴基、-OR4a表示之基、-SR4b表示之基、醯基、烷氧基羰基、-NHR4c表示之基、或表示鍵結於以-N(R4d)2表示之基所含有之碳原子之氫原子的至少一部分被上述之一價烴基、羥基、-OR4a表示之基、-SR4b表示之基、醯基、烷氧基羰基、鹵素原子、硝基、氰基、巰基、羧基、胺基、胺基甲醯基、-NHR4c表示之基、-N(R4d)2表示之基、(甲基)丙烯醯氧基、甲磺醯氧基、或磺基所取代之基[例如,烷氧基芳基(例如、甲氧基苯基等之C1-4烷氧基C6-10芳基)、烷氧基羰基芳基(例如,甲氧基羰基苯基、乙氧基羰基苯基等之C1-4烷氧基-羰基C6-10芳基等)]等。
此等之中,代表性而言,R1、R2、R3及R4也可為羥基、碳數1~4之羥基烷基、(甲基)丙烯醯氧基、一價烴基、-OR4a表示之基、-SR4b表示之基、醯基、烷氧基羰基、鹵素原子、硝基、氰基、-NHR4c表示之基、-N(R4d)2表示之基等。
較佳之R1及R2為羥基、碳數1~4之羥基烷基、(甲基)丙烯醯氧基,特佳為羥基、(甲基)丙烯醯氧基。
較佳之R3及R4,可列舉一價烴基[例如、烷基(例如,C1-6烷基)、環烷基(例如,C5-8環烷基)、芳基(例如,C6-10芳基)、芳烷基(例如,C6-8芳基-C1-2烷基)等]、烷氧基(C1-4烷氧基等)等。特別是R2a及R2b為烷基
[C1-4烷基(特別是甲基)等]、芳基[例如,C6-10芳基(特別是苯基)等]等之一價烴基(特別是烷基)為佳。
又,k1、k2、k3及k4之合計為2以上之整數的情形,各自對應之R1、R2、R3及R4可彼此相同或相異,例如,環Z1所含有之R1與環Z2所含有之R2、又,R3與R4互相可相同或相異。R1之環Z1中之取代位置、R2之環Z2中之取代位置、R3之苯並(benzo)環中之取代位置、R4之苯並環中之取代位置,各自無特別限定。
上述一般式(1)中,k1、k2、k3及k4可配合環Z1及環Z2之種類來選擇,例如可為0~4之整數、較佳為0~3之整數、更佳為0~2之整數。k1、k2、k3及k4係獨立,因此,彼此可相同或相異。
(C)茀化合物之含量係相對於感光性樹脂組成物之全質量,較佳為1~50質量%,更佳為5~40質量%,特佳為10~30質量%。
依據本實施態樣時,藉由含有(C)茀化合物,其作用機構雖不明確,但是可形成DOF餘裕廣,且矩形性高的圖型。
<(D)鹼可溶性樹脂>
感光性樹脂組成物為了提升龜裂耐性,因此進一步含有(D)鹼可溶性樹脂為佳。在此,「鹼可溶性樹脂」係指藉由樹脂濃度20質量%之樹脂溶液(溶劑:丙二醇單甲醚乙酸酯),於基板上形成膜厚1μm的樹脂膜,於2.38質量
%的TMAH水溶液中浸漬1分鐘時,溶解0.01μm以上者。(D)鹼可溶性樹脂較佳為選自由(D1)酚醛清漆樹脂、(D2)聚羥基苯乙烯樹脂及(D3)丙烯酸樹脂所成群之至少1種樹脂。
[(D1)酚醛清漆樹脂]
酚醛清漆樹脂可藉由例如將具有酚性羥基之芳香族化合物(以下僅稱為「酚類」)與醛類在酸觸媒下進行加成縮合而得。
上述酚類可舉出例如酚、鄰甲酚、間甲酚、對甲酚、鄰乙酚、間乙酚、對乙酚、鄰丁酚、間丁酚、對丁酚、2,3-二甲酚、2,4-二甲酚、2,5-二甲酚、2,6-二甲酚、3,4-二甲酚、3,5-二甲酚、2,3,5-三甲酚、3,4,5-三甲酚、對苯酚、間苯二酚、對苯二酚、對苯二酚單甲醚、連苯三酚(pyrogallol)、間苯三酚、羥基二苯基、雙酚A、沒食子酸、沒食子酸酯、α-萘酚、β-萘酚等。
上述醛類可舉出例如甲醛、糠醛、苯甲醛、硝基苯甲醛、乙醛等。
加成縮合反應時之觸媒無特別限定,例如酸觸媒可使用鹽酸、硝酸、硫酸、甲酸、草酸、乙酸等。
此外,藉由使用鄰甲酚;將樹脂中之羥基之氫原子取代成其他的取代基;或使用大體積的醛類,可進一步提升酚醛清漆樹脂的柔軟性。
(D1)酚醛清漆樹脂之質量平均分子量,在不妨
礙本發明目的之範圍內無特別限定,較佳為1000~50000。
[(D2)聚羥基苯乙烯樹脂]
構成(D2)聚羥基苯乙烯樹脂之羥基苯乙烯系化合物,可舉出對羥基苯乙烯、α-甲基羥基苯乙烯、α-乙基羥基苯乙烯等。
此外,(D2)聚羥基苯乙烯樹脂較佳為與苯乙烯樹脂的共聚物。構成此種苯乙烯樹脂的苯乙烯系化合物,可舉出苯乙烯、氯苯乙烯、氯甲基苯乙烯、乙烯基甲苯、α-甲基苯乙烯等。
(D2)聚羥基苯乙烯樹脂之質量平均分子量,在不妨礙本發明目的之範圍內不特別限定,較佳為1000~50000。
[(D3)丙烯酸樹脂]
(D3)丙烯酸樹脂較佳為包含由具醚鍵之聚合性化合物所衍生的構成單元、及由具羧基之聚合性化合物所衍生的構成單元。
上述具醚鍵之聚合性化合物,可例示2-甲氧基乙基(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、3-甲氧基丁基(甲基)丙烯酸酯、乙基卡必醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯等之具有醚
鍵及酯鍵之(甲基)丙烯酸衍生物等。上述具醚鍵之聚合性化合物,較佳為2-甲氧基乙基丙烯酸酯、甲氧基三乙二醇丙烯酸酯。此等聚合性化合物可單獨使用,亦可組合2種以上使用。
上述具羧基之聚合性化合物,可例示丙烯酸、甲基丙烯酸、巴豆酸等之單羧酸類;馬來酸、富馬酸、衣康酸等之二羧酸類;2-甲基丙烯醯氧乙基琥珀酸、2-甲基丙烯醯氧乙基馬來酸、2-甲基丙烯醯氧乙基鄰苯二甲酸、2-甲基丙烯醯氧乙基六氫鄰苯二甲酸等之具羧基及酯鍵之化合物;等。上述具羧基之聚合性化合物,較佳為丙烯酸、甲基丙烯酸。此等聚合性化合物可單獨使用,亦可組合2種以上使用。
(D3)丙烯酸樹脂之質量平均分子量,在不妨礙本發明目的之範圍內不特別限定,較佳為30000~800000。
(D)鹼可溶性樹脂的含量係上述(B)樹脂與(D)鹼可溶性樹脂之合計設為100質量份的情形,較佳為0~80質量份,更佳為0~60質量份。藉由將(D)鹼可溶性樹脂的含量設為上述範圍,可提升龜裂耐性,而有可防止顯影時之膜減少的傾向。
<(E)酸擴散控制劑>
感光性樹脂組成物為了作為模使用之阻劑圖案的形狀、或提高感光性樹脂膜之放置安定性等,進一步含有
(E)酸擴散控制劑為佳。(E)酸擴散控制劑,較佳為(E1)含氮化合物,可進一步視需求可含有(E2)有機羧酸、或磷之含氧酸或其衍生物。
[(E1)含氮化合物]
(E1)含氮化合物可列舉三甲基胺、二乙基胺、三乙基胺、二-n-丙基胺、三-n-丙基胺、三-n-戊基胺、三-n-己基胺、三-n-庚基胺、三-n-辛基胺、三-n-壬基胺、三-n-癸基胺、三苄基胺、二乙醇胺、三乙醇胺、n-己基胺、n-庚基胺、n-辛基胺、n-壬基胺、n-癸基胺、乙二胺、N,N,N’,N’-四甲基乙二胺、四亞甲基二胺、六亞甲基二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、4,4’-二胺基二苯甲酮、4,4’-二胺基二苯基胺、甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、丙醯胺、苯甲醯胺、吡咯烷酮、N-甲基吡咯烷酮、甲基脲、1,1-二甲基脲、1,3-二甲基脲、1,1,3,3,-四甲基脲、1,3-二苯基脲、咪唑、苯並咪唑、4-甲基咪唑、8-羥基喹啉、吖啶、嘌呤、吡咯烷、哌啶、2,4,6-三(2-吡啶基)-S-三嗪、嗎啉、4-甲基嗎啉、哌嗪、1,4-二甲基哌嗪、1,4-二氮雜雙環[2.2.2]辛烷、吡啶等。此等可單獨使用或組合2種以上使用。
(E1)含氮化合物係相對於上述(B)樹脂及上述(D)鹼可溶性樹脂之合計質量100質量份,通常在0~5質量份之範圍使用,特佳為在0~3質量份之範圍使用。
[(E2)有機羧酸、或磷之含氧酸或其衍生物]
(E2)有機羧酸、或磷之含氧酸或其衍生物之中,有機羧酸,具體而言,較佳為丙二酸、檸檬酸、蘋果酸、琥珀酸、苯甲酸、水楊酸等,特佳為水楊酸。
磷之含氧酸或其衍生物,可列舉磷酸、磷酸二-n-丁基酯、磷酸二苯基酯等之磷酸及彼等之酯之衍生物;膦酸、膦酸二甲基酯、膦酸-二-n-丁基酯、苯基膦酸、膦酸二苯基酯、膦酸二苄基酯等之膦酸及彼等之酯之衍生物;次磷酸、苯基次磷酸等之次磷酸及彼等之酯之衍生物;等。此等之中,特佳為膦酸。此等可單獨使用或組合2種以上使用。
(E2)有機羧酸、或磷之含氧酸或其衍生物係相對於上述(B)樹脂及上述(D)鹼可溶性樹脂之合計質量100質量份,通常在0~5質量份之範圍使用,特佳為在0~3質量份之範圍使用。
又,為了使形成鹽使安定,(E2)有機羧酸、或磷之含氧酸或其衍生物,較佳為使用與上述(E1)含氮化合物同等量。
<(S)有機溶劑>
感光性樹脂組成物含有(S)有機溶劑。(S)有機溶劑之種類,在不阻礙本發明之目的之範圍內,無特別限定,可由以往使用於正型感光性樹脂組成物之有機溶劑中,適宜
選擇使用。
(S)有機溶劑之具體例,可列舉丙酮、甲基乙基酮、環己酮、甲基異戊基酮、2-庚酮等之酮類;乙二醇、乙二醇單乙酸酯、二乙二醇、二乙二醇單乙酸酯、丙二醇、丙二醇單乙酸酯、二丙二醇、二丙二醇單乙酸酯之單甲基醚、單乙基醚、單丙基醚、單丁基醚、單苯基醚等之多元醇類及其衍生物;二噁烷等之環式醚類;甲酸乙酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸甲酯、乙醯乙酸甲酯、乙醯乙酸乙酯、丙酮酸乙酯、乙氧基乙酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯等之酯類;甲苯、二甲苯等之芳香族烴類;等。此等可單獨使用或混合2種以上使用。
(S)有機溶劑之含量,在不阻礙本發明之目的之範圍內,無特別限定。在藉由旋轉塗佈法等所得之感光性樹脂層之膜厚成為10μm以上的厚膜用途,使用感光性樹脂組成物的情形,在感光性樹脂組成物之固體成分濃度成為30~70質量%的範圍內,使用(S)有機溶劑為佳。
<其他之成分>
感光性樹脂組成物為了提高可塑性,可進一步含有聚乙烯基樹脂。聚乙烯基樹脂之具體例,可列舉聚氯乙烯、聚苯乙烯、聚羥基苯乙烯、聚乙酸乙烯酯、聚乙烯基苯甲
酸、聚乙烯基甲基醚、聚乙烯基乙基醚、聚乙烯醇、聚乙烯基吡咯烷酮、聚乙烯基酚及此等之共聚物等。聚乙烯基樹脂從玻璃轉移溫度低的觀點,較佳為聚乙烯基甲基醚。
又,感光性樹脂組成物為了提高使用感光性樹脂組成物所形成之模與金屬基板之接著性,可進一步含有接著助劑。
又,感光性樹脂組成物為了提高塗佈性、消泡性、平坦性等,可進一步含有界面活性劑。界面活性劑之具體例,可列舉BM-1000、BM-1100(均為BM Chmie公司製)、MegafacF142D、MegafacF172、MegafacF173、MegafacF183(均為大日本油墨化學工業公司製)、FluoradFC-135、FluoradFC-170C、FluoradFC-430、FluoradFC-431(均為住友3M公司製)、SurflonS-112、SurflonS-113、SurflonS-131、SurflonS-141、SurflonS-145(均為旭硝子公司製)、SH-28PA、SH-190、SH-193、SZ-6032、SF-8428(均為東麗聚矽氧公司製)等之市售之氟系界面活性劑,但是不限定於此等。
又,感光性樹脂組成物為了對顯影液之溶解性之微調整,可進一步含有酸、酸酐、或高沸點溶劑。
酸及酸酐的具體實例,可舉出乙酸、丙酸、正丁酸、異丁酸、正戊酸、異戊酸、苯甲酸、桂皮酸等之單羧酸類;乳酸、2-羥基丁酸、3-羥基丁酸、水楊酸、間羥基苯甲酸、對羥基苯甲酸、2-羥基桂皮酸、3-羥基桂皮酸、4-羥基桂皮酸、5-羥基間苯二甲酸、丁香酸等之羥基
單羧酸類;草酸、琥珀酸、戊二酸、己二酸、馬來酸、衣康酸、六氫鄰苯二甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2-環己烷二羧酸、1,2,4-環己烷三羧酸、丁烷四羧酸、偏苯三甲酸、苯均四酸、環戊烷四羧酸、丁烷四羧酸、1,2,5,8-萘四羧酸等之多元羧酸類;衣康酸酐、琥珀酸酐、檸康酸酐、十二烯基琥珀酸酐、丙烷三羧酸酐、馬來酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、降莰烯二酸酐、1,2,3,4-丁烷四羧酸酐、環戊烷四羧酸二酐、鄰苯二甲酸酐、苯均四甲酸酐、偏苯三甲酸酐、二苯甲酮四羧酸酐、乙二醇雙偏苯三甲酸酐、丙三醇三偏苯三甲酸酐等酸酐;等。
又,高沸點溶劑之具體例,可舉出N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮、二甲基亞碸、苯甲基***、二己醚、乙醯基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、苯甲醇、乙酸苯甲酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、苯基賽路蘇乙酸酯等。
又,感光性樹脂組成物,為了提升感度,亦可進一步含有增感劑。
<化學增幅型正型感光性樹脂組成物的調製方法>
感光性樹脂組成物係將上述各成分以常用方法混合、攪拌而調製。將上述各成分混合、攪拌時可使用的裝置,
可舉出溶解機、均質機、三輥磨機等。可將上述各成分均勻混合後,進一步利用篩網、薄膜過濾器等過濾所得之混合物。
≪附模基板的製造方法≫
使用上述說明之感光性樹脂組成物,在具有金屬表面之基板的金屬表面上,形成鍍敷成形物用之模的阻劑圖案的方法,無特別限定。
較佳的方法,可舉出一種附模基板之製造方法,其係含有:
在具有金屬表面之基板的前述金屬表面上,層合由感光性樹脂組成物所成之感光性樹脂層的層合步驟,將活性光線或放射線照射於感光性樹脂層的曝光步驟,及將曝光後之感光性樹脂層進行顯影製作形成鍍敷成形物用之模的顯影步驟。
層合感光性樹脂層的基板,無特別限定,可使用以往周知者,可例示例如電子零件用之基板、或於其上形成有特定配線圖型者等。該基板可使用具有金屬表面者,但是構成金屬表面之金屬物種,較佳為銅、金、鋁,更佳為銅。
感光性樹脂層係例如以下方式層合於基板上。亦即,將液狀的感光性樹脂組成物塗佈於基板上,藉由加熱去除溶劑而形成所期望之膜厚的感光性樹脂層。感光性樹脂層的厚度,只要可以所期望之膜厚形成作為模的
阻劑圖型時,即無特別限定。感光性樹脂層的膜厚無特別限定,較佳為10μm以上,更佳為10~150μm,特佳為20~120μm,最佳為20~100μm。
在基板上塗佈感光性樹脂組成物的方法,可採用旋轉塗佈法、狹縫塗佈法、輥塗佈法、網版印刷法、塗佈機(applicator)法等方法。對於感光性樹脂層進行預烘烤為佳。預烘烤條件係因感光性樹脂組成物中之各成分的種類、摻合比例、塗佈膜厚等而異,惟通常為70~150℃,較佳為80~140℃、2~60分鐘左右。
對於如上述形成的感光性樹脂層,經由特定圖型的遮罩,選擇性照射(曝光)活性光線或放射線,例如波長為300~500nm的紫外線或可見光線。
放射線之線源,可使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵素燈、氬氣雷射等。又,放射線包含微波、紅外線、可見光線、紫外線、X射線、γ射線、電子束、質子束、中子束、離子束等。放射線照射量係因感光性樹脂組成物之組成或感光性樹脂層的膜厚等而異,例如使用超高壓水銀燈的情形,為100~10000mJ/cm2。又,放射線中為了使產生酸,而包含使(A)酸產生劑活化的光線。
曝光後,藉由採用周知方法,對感光性樹脂層加熱促進酸之擴散,在感光性樹脂膜中之經曝光的部分,使感光性樹脂層之鹼溶解性改變。
其次,藉由將曝光後的感光性樹脂層,依據
習知方法進行顯影,溶解去除不溶的部分,形成特定之阻劑圖型。此時,顯影液使用鹼性水溶液。
顯影液可使用例如氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水、乙胺、正丙胺、二乙胺、二正丙胺、三乙胺、甲基二乙胺、二甲基乙醇胺、三乙醇胺、氫氧化四甲銨、氫氧化四乙銨、吡咯、哌啶、1,8-二氮雜雙環[5,4,0]-7-十一碳烯、1,5-二氮雜雙環[4,3,0]-5-壬烷等之鹼類的水溶液。又,亦可在上述鹼類之水溶液中適量添加了甲醇、乙醇等水溶性有機溶劑或界面活性劑的水溶液也可作為顯影液使用。
顯影時間係因感光性樹脂組成物的組成或感光性樹脂層的膜厚等而異,通常為1~30分鐘。顯影方法可為盛液法、浸漬法、槳式法、噴塗顯影法等任一種。
顯影後,進行流水洗淨30~90秒,使用空氣噴槍或烘箱等使乾燥。如此,即可製造在具有金屬表面之基板的金屬表面上,具備成為模之阻劑圖型之附模板基板。
≪鍍敷成形物的製造方法≫
於藉由以上述方法所形成之附模基板之模中的非阻劑部(以顯影液去除的部分),利用鍍敷埋入金屬等之導體,可形成例如凸塊或金屬柱等連接端子的鍍敷成形物。此外,鍍敷處理方法不特別限制,可採用以往周知的各種方法。鍍敷液特別適合使用鍍錫、鍍銅、鍍金、鍍鎳液。殘
餘的模,最終依據常用方法使用剝離液等去除。
根據上述方法時,可抑制腳化(footing),同時形成作為模之阻劑圖型。藉由使用如此製作之具備腳化被抑制之模的基板,可製造對基板之密接性優異的鍍敷成形物。
[實施例]
以下,根據實施例更詳細地說明本發明,惟本發明非限定於此等實施例者。
[實施例1~11及比較例1~3]
實施例、及比較例中,(A)酸產生劑使用下述式的化合物。
實施例、及比較例中,(B)藉由酸之作用,增大對鹼之溶解性的樹脂,使用藉由將以下之單體進行共聚合所得之樹脂B-1(n/m/l/o/p=20/35/20/5/20[質量比]、質量平均分子量[Mw]40,000、Mw/Mn=2.6)或樹脂B-2(n/m/l/o/p=20/35/20/5/20[質量比]、質量平均分子量
[Mw]40,000、Mw/Mn=2.6)。各樹脂中之n~p表示各樹脂中之構成單元之含量(質量%)。
實施例、及比較例中,(D)鹼可溶性樹脂使用以下之樹脂D-1、及D-2。
D-1:聚羥基苯乙烯樹脂(p-羥基苯乙烯/苯乙烯=85/15(質量比)、質量平均分子量2,500、Mw/Mn=2.4)
D-2:酚醛清漆樹脂(以m-甲酚與p-甲酚與m-甲酚/p-甲酚=60/40(質量比)混合,在甲醛及酸觸媒之存在下,進行加成縮合而得到的酚醛清漆樹脂(質量平均分子量8000))
實施例、及比較例中,(C)茀化合物使用以下之C-1、C-2或C-3的化合物。下述式表示A1及A2為羥基萘基者為C-1、羥基苯基者為C-2、丙烯醯氧基萘基者為C-3。又,比較例1係於感光性樹脂組成物中未加入茀
化合物。
實施例、及比較例中,使用下述式之化合物A作為添加劑。
將如表1所示之種類及含量之樹脂及茀化合物及酸產生劑2.0質量份、三-n-癸基胺0.03質量份、化合物A 0.05質量份溶解於3-甲氧基丁基乙酸酯(MA)/乙酸丁酯(BA)=5/5(質量比)的溶劑中,使固體成分濃度成為50質量%,得到各實施例及比較例之感光性樹脂組成物。
[非阻劑部之剖面形狀之評價]
使用旋轉塗佈機,將各實施例及比較例之感光性樹脂
組成物塗佈於表面以銅濺鍍之8吋之基板上,形成膜厚50μm的感光性樹脂層。然後,將此感光性樹脂層以130℃預烘烤5分鐘。預烘烤後,使用孔圖型之遮罩,以NA0.50之I線進行圖型曝光。接著,將基板以85℃進行3分鐘之曝光後加熱(PEB)。然後,使用2.38%四甲基銨氫氧化物(TMAH)水溶液顯影。然後,流水洗淨得到具有40μm直徑之接觸孔(contact hole)圖型的厚膜阻劑圖型。
<剖面形狀之評價基準>
以掃描型電子顯微鏡(SEM)觀察孔圖型之剖面形狀,進行目視評價。
○:剖面形狀大致為矩形
×:剖面形狀非矩形
[焦點深度(DOF)餘裕]
形成有孔圖型之EOP中,適度上下移動焦點深度,與上述同樣形成阻劑圖型,求得可形成矩形圖型之焦點深度之寬度(μm)。
<剖面形狀之評價基準>
○:焦點深度之寬度為5μm以上
×:焦點深度之寬度未達5μm
由表1可知,含有茀化合物的各實施例,相較於不含有茀化合物之比較例1時,所得之阻劑圖型之非阻劑部的剖面形狀及焦點深度(DOF)餘裕均較優異。
具體而言,由比較例1與實施例2、4及5可知,即使茀化合物的種類不同,但是所得之阻劑圖型之非阻劑部的剖面形狀及焦點深度(DOF)餘裕均較優異。
由實施例2與實施例6可知,即使茀化合物之含量不同,但是所得之阻劑圖型之非阻劑部的剖面形狀及焦點深度(DOF)餘裕均優異。
由實施例2與實施例3可知,即使摻合之樹脂的種類不同,但是只要是含有茀化合物的組成物時,所得之阻劑圖型之非阻劑部的剖面形狀及焦點深度(DOF)餘裕均優異。
Claims (5)
- 一種不含金屬氧化物粒子之化學增幅型正型感光性樹脂組成物,其係在具有金屬表面之基板的前述金屬表面上製作鍍敷成形物用,鍍敷成形物製作後被除去的化學增幅型正型感光性樹脂組成物,其係含有(A)藉由活性光線或放射線之照射產生酸的酸產生劑0.1~10質量%、(B)因酸之作用而增大對鹼之溶解性的樹脂5~60質量%及(C)以下述式(1)表示的茀化合物1~50質量%,
- 如申請專利範圍第1項之化學增幅型正型感光性樹脂組成物,其中進一步含有(D)鹼可溶性樹脂。
- 如申請專利範圍第2項之化學增幅型正型感光性樹脂組成物,其中前述(D)鹼可溶性樹脂包含選自由(D1)酚醛清漆樹脂、(D2)聚羥基苯乙烯樹脂、及(D3)丙烯酸樹脂所成群之至少1種樹脂。
- 一種附模基板之製造方法,其係含有:在具有金屬表面之基板的前述金屬表面上,層合由如申請專利範圍第1~3項中任一項之化學增幅型正型感光性樹脂組成物所成之感光性樹脂層的層合步驟,將活性光線或放射線照射於前述感光性樹脂層的曝光步驟,及將曝光後之前述感光性樹脂層進行顯影製作形成鍍敷成形物用之模的顯影步驟。
- 一種鍍敷成形物之製造方法,其係含有:對於藉由如申請專利範圍第4項之方法所製造之前述附模基板施予鍍敷,在前述模內形成鍍敷成形物的步驟。
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