JP4617580B2 - Photosensitive resin composition and photosensitive element using the same - Google Patents
Photosensitive resin composition and photosensitive element using the same Download PDFInfo
- Publication number
- JP4617580B2 JP4617580B2 JP2001033569A JP2001033569A JP4617580B2 JP 4617580 B2 JP4617580 B2 JP 4617580B2 JP 2001033569 A JP2001033569 A JP 2001033569A JP 2001033569 A JP2001033569 A JP 2001033569A JP 4617580 B2 JP4617580 B2 JP 4617580B2
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- JP
- Japan
- Prior art keywords
- resin composition
- photosensitive resin
- photosensitive
- bis
- meth
- 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.)
- Expired - Fee Related
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- 239000011342 resin composition Substances 0.000 title claims description 30
- -1 amine compound Chemical class 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical class C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 3
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HLGNMOUJXWELKK-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C HLGNMOUJXWELKK-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NCLLUAZOPKRXQS-UHFFFAOYSA-N 3-amino-4,6,7-triethylchromen-2-one Chemical compound O1C(=O)C(N)=C(CC)C2=C1C=C(CC)C(CC)=C2 NCLLUAZOPKRXQS-UHFFFAOYSA-N 0.000 description 1
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 1
- LKJDPYZBJFUZNS-UHFFFAOYSA-N 4-methyl-7-(methylamino)chromen-2-one Chemical compound CC1=CC(=O)OC2=CC(NC)=CC=C21 LKJDPYZBJFUZNS-UHFFFAOYSA-N 0.000 description 1
- LCSNPEIXPRTDCL-UHFFFAOYSA-N 7-(diethylamino)-4,6-dimethylchromen-2-one Chemical compound O1C(=O)C=C(C)C2=C1C=C(N(CC)CC)C(C)=C2 LCSNPEIXPRTDCL-UHFFFAOYSA-N 0.000 description 1
- RIUSGHALMCFISX-UHFFFAOYSA-N 7-(dimethylamino)-2,3-dihydro-1h-cyclopenta[c]chromen-4-one Chemical compound O=C1OC2=CC(N(C)C)=CC=C2C2=C1CCC2 RIUSGHALMCFISX-UHFFFAOYSA-N 0.000 description 1
- GZEYLLPOQRZUDF-UHFFFAOYSA-N 7-(dimethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(N(C)C)=CC=C21 GZEYLLPOQRZUDF-UHFFFAOYSA-N 0.000 description 1
- QZXAEJGHNXJTSE-UHFFFAOYSA-N 7-(ethylamino)-4,6-dimethylchromen-2-one Chemical compound O1C(=O)C=C(C)C2=C1C=C(NCC)C(C)=C2 QZXAEJGHNXJTSE-UHFFFAOYSA-N 0.000 description 1
- OTNIKUTWXUODJZ-UHFFFAOYSA-N 7-(ethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(NCC)=CC=C21 OTNIKUTWXUODJZ-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 Cc(cc1)ccc1N(*)* Chemical compound Cc(cc1)ccc1N(*)* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UAKWLVYMKBWHMX-UHFFFAOYSA-N SU4312 Chemical compound C1=CC(N(C)C)=CC=C1C=C1C2=CC=CC=C2NC1=O UAKWLVYMKBWHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- HXTBYXIZCDULQI-UHFFFAOYSA-N bis[4-(methylamino)phenyl]methanone Chemical compound C1=CC(NC)=CC=C1C(=O)C1=CC=C(NC)C=C1 HXTBYXIZCDULQI-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 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
- 230000001680 brushing effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
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- GLNDAGDHSLMOKX-UHFFFAOYSA-N coumarin 120 Chemical compound C1=C(N)C=CC2=C1OC(=O)C=C2C GLNDAGDHSLMOKX-UHFFFAOYSA-N 0.000 description 1
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、感光性樹脂組成物及びそれを用いた感光性エレメントに関し、より詳細にはプリント配線板を製造する際に用いられるレジスト材料として有効な感光性樹脂組成物及びそれを用いた感光性エレメントに関する。
【０００２】
【従来の技術】
従来、プリント配線板の製造分野において、エッチング、めっき等に用いられるレジスト材料としては、感光性樹脂組成物及びそれに支持体と保護フィルムを用いる感光性エレメントが広く用いられている。プリント配線板は、感光性フィルムを銅基板上にラミネートして、パターン露光した後、未硬化部分を現像液で除去し、エッチング又はめっき処理を施して、パターンを形成させた後、硬化部分を基板上から剥離除去する方法によって製造されている。
【０００３】
感光性フィルムは、近年の印刷配線板の高密度化に伴い、従来の感光性フィルムに比べて高解像性・高密着性を示すものであるとする要求が益々高まっている。更に、ＢＧＡ（ボール・グリッド・アレー）、ＣＳＰ（チップ・サイズ・パッケージ）等の半導体チップが搭載される基板に対しては、米国半導体工業会のロードマップに見られるように、格別に高いレベルの解像性が要求されることが予想されている。
【０００４】
これまでの感光性樹脂組成物においては、水素供与性のアミン化合物系光開始剤や水素引き抜き型光開始剤等の光開始剤及び増感剤を配合して高解像性の樹脂組成物とすることが行われている。水素供与性のアミン化合物系光開始剤としては、ｐ−ジメチルアミノ安息香酸エチルエステル、ｐ−ジメチルアミノ安息香酸イソアミルエステル、Ｎ，Ｎ−ジエチルアニリン等が、水素引き抜き型光開始剤としては、２，４，５−トリフェニルイミダゾール二量体等が知られている。又、増感剤としては、ｐ−アミノフェニルケトン等が知られている。
【０００５】
しかし、上記水素供与性のアミン化合物系光開始剤と上記増感剤の組み合わせでは、解像性が低い。従って、開始剤としての２，４，５−トリフェニルイミダゾール二量体及び増感剤としてのｐ−アミノフェニルケトンを使用することにより高解像性を実現してきたが、現状では十分とは言えない。又、一方では、作業性の向上という点から、高感度、低めっき浴汚染性の感光性樹脂組成物が望まれており、これらの特性は、使用される光開始剤の種類及び量に依存する。
【０００６】
【発明が解決しようとする課題】
本発明は、以上の状況に鑑みてなされるものであり、高解像性、高密着性、高感度、めっき浴汚染性等に優れた感光性樹脂組成物及びそれを用いた感光性エレメントを提供することを目的とする。
【０００７】
【課題を解決するための手段】
上記目的を達成するために、本発明者らは鋭意研究を重ねた結果、光開始剤として芳香環を２個以上有するアミン系化合物と２，４，５−トリフェニルイミダゾール二量体等とを組み合わせて用いることにより、本発明の目的が達成されることを見いだして本発明に到達した。
【０００８】
すなわち、本発明は、バインダーポリマー（Ａ）、分子内に光重合可能なエチレン性不飽和基を有する光重合性化合物（Ｂ）並びに光開始剤（Ｃ）として下記一般式（Ｉ）で表される置換基を分子内に２個以上有し、アセトニトリル中で３６５ｎｍにおけるモル吸光係数が５００以下のアミン系化合物（Ｃ１）及び水素引き抜き型光開始剤（Ｃ２）を含有することを特徴とする感光性樹脂組成物を要旨とする。
【０００９】
【化４】
又、本発明の感光性樹脂組成物は、アミン系化合物（Ｃ１）が波長４００〜７００ｎｍの可視光線に吸収を持たない性質を有することを特徴とする。
【００１０】
更に、本発明は、バインダーポリマー（Ａ）、分子内に光重合可能なエチレン性不飽和基を有する光重合性化合物（Ｂ）並びに光開始剤（Ｃ）として下記一般式（II）で表されるアミン系化合物（Ｃ１）及び水素引き抜き型光開始剤（Ｃ２）を含有することを特徴とする感光性樹脂組成物を要旨とする。
【００１１】
【化５】
【００１２】
又、本発明の感光性樹脂組成物は、更に、増感剤（Ｄ）を含有することを特徴とする。
又、本発明の感光性樹脂組成物は、上記バインダーポリマ−（Ａ）は、その酸価が３０〜２００であり、その重量平均分子量が２０，０００〜３００，０００であることを特徴とする。
又、本発明の感光性樹脂組成物は、光重合性化合物（Ｂ）がビスフェノールＡポリオキシエチレンジアクリレート又はビスフェノールＡポリオキシエチレンジメタクリレートであることを特徴とする。
又、本発明の感光性樹脂組成物は、上記アミン系化合物（Ｃ１）が下記一般式（III)で表される化合物であり、上記水素引き抜き型光開始剤（Ｃ２）が２，４，５−トリフェニルイミダゾール二量体であることを特徴とする。
【００１３】
【化６】
【００１４】
更に、本発明は、上記いずれかの感光性樹脂組成物を支持体の上に塗布、乾燥してなる感光性エレメントを要旨とする。
【００１５】
【発明の実施の形態】
本発明で用いられるバインダーポリマー（Ａ）は、分子内にフリーのカルボキシ基を有するポリマーであることが望ましく、例えば、アクリル酸やメタクリル酸等の重合能を有する不飽和カルボン酸とアクリル酸若しくはメタクリル酸のエステル、アクリル酸若しくはメタクリル酸のアミド、ビニルスルホン酸、安息香酸ビニル、アクリロニトリル、スチレン、ビニルトルエン等の重合能を有する不飽和化合物との共重合体が挙げられる。以下に上記エステル、上記アミドの具体例を挙げるが、その中で（メタ）アクリレートとは、アクリレート及びそれに対応するメタクリレートを示す。
【００１６】
上記のエステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピル（メタ）アクリレート等が、上記のアミドとしては、例えば、（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド等が、それぞれ挙げられる。上記の重合能を有する不飽和化合物は１種に限らず、２種以上を選択して用いることができる。
【００１７】
バインダーポリマー（Ａ）は、酸価が３０〜２００であることが好ましく、又、重量平均分子量（ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、標準ポリスチレンを用いた検量線により換算）が２０，０００〜３００，０００であることが好ましい。酸価が３０未満では、現像時間が長くなる傾向があり、２００を超えると、光硬化したレジストの耐現像液性が低下する傾向がある。又、重量平均分子量が２０，０００未満では、光硬化したレジストの耐現像液性が低下する傾向があり、３００，０００を超えると、現像時間が長くなる傾向がある。
【００１８】
本発明で用いられる分子内に光重合可能なエチレン性不飽和基を有する光重合性化合物（Ｂ）としては、その分子内にアクリロイル基、メタクリロイル基、プロペノイル基等の末端ビニル基を持つアルケノイル基を有する化合物が挙げられ、それらを例示すると、γ−クロロ−ヒドロキシプロピル−β′−（メタ）アクリロイルオキシエチル−ｏ−フタレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ウレタンジ（メタ）アクリレート、ＥＯ（エチレンオキシド）変性ウレタンジ（メタ）アクリレート、ＥＯ，ＰＯ（プロピレンオキシド）変性ウレタンジ（メタ）アクリレート、トリス［（メタ）アクリロイルオキシ］テトラエチレングリコールイソシアナトヘキサメチレンイソシアヌレート、ビスフェノールＡポリオキシエチレンジ（メタ）アクリレート、トリメチロールプロパンエトキシトリ（メタ）アクリレート、トリメチロールプロパンＥＯ変性（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、１，１，１−トリス［プロペノイルオキシポリ （エチレンオキシ）メチル］プロパン、ノナエチレングリコールジ（メタ）アクリレート、２，２′−ビス［４−（（メタ）アクリロイルオキシ・ポリエトキシ）フェニル］プロパン、ノニルフェニル−４−エチレンオキシ（メタ）アクリレート等が挙げられる。これらの化合物（Ｂ）は、単独に限らず、それらの２種以上を組み合わせて用いることができる。
【００１９】
本発明で用いられる光開始剤（Ｃ）としてのアミン系化合物（Ｃ１）は、前記一般式（Ｉ）で表される置換基を分子内に２個以上有し、アセトニトリル中で３６５ｎｍにおけるモル吸光係数が５００以下化合物であるが、波長４００〜７００ｎｍの可視光線に吸収を持たない性質を有するものであるのが好ましい。
【００２０】
更に、アミン系化合物（Ｃ１）は、下記一般式（II) で表される化合物が望ましい。
【００２１】
【化７】
上記一般式（II) において、Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 は炭素数１〜６個のアルキル基又はヒドロキシアルキル基を示し、Ｘは炭素数１〜１２個、好ましくは炭素数３〜１２個、特に好ましくは炭素数５〜１０個のアルキレン基又はシクロアルキレン基を示す。
【００２３】
上記一般式（II) で表される化合物としては、２，２−ビス［４，４′−（Ｎ，Ｎ−ジメチルアミノフェニル）］プロパン、２，２−ビス［４，４′−（Ｎ，Ｎ−ジエチルアミノフェニル）］プロパン、３，３−ビス［４，４′−（Ｎ，Ｎ−ジメチルアミノフェニル）］ペンタン、３，３−ビス［４，４′−（Ｎ，Ｎ−ジエチルアミノフェニル）］ペンタン、２，２−ビス［４，４′−（Ｎ，Ｎ−ジヒドロキシエチルアミノフェニル）］プロパン、３，３−ビス［４，４′−（Ｎ，Ｎ−ジヒドロキシエチルアミノフェニル）］ペンタン、２，２−ビス［４，４′−（Ｎ−メチルアミノフェニル）］プロパン、３，３−ビス［４，４′−（Ｎ−メチルアミノフェニル）］ペンタン、２，２−ビス［４，４′−（Ｎ−エチルアミノフェニル）］プロパン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジメチルアミノフェニル）］シクロブタン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジメチルアミノフェニル）］シクロペンタン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジメチルアミノフェニル）］シクロヘキサン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジエチルアミノフェニル）］シクロブタン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジエチルアミノフェニル）］シクロペンタン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジエチルアミノフェニル）］シクロヘキサン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジヒドロキシエチルアミノフェニル）］シクロブタン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジヒドロキシエチルアミノフェニル）］シクロペンタン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジヒドロキシエチルアミノフェニル）］シクロヘキサン等が挙げられる。
【００２４】
上記一般式（II) で表される化合物の中でも、特に下記一般式（III)で表される化合物が好ましい。一般式（III)において、Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 は上記と同意義である。
【００２５】
【化８】
該化合物としては、例えば、１，１−ビス［４，４′−（Ｎ，Ｎ−ジエチルアミノフェニル）］シクロヘキサン、１，１−ビス［４，４′−（Ｎ，Ｎ−ジヒドロキシエチルアミノフェニル）］シクロヘキサン等が挙げられる。
【００２７】
本発明で用いられる光開始剤（Ｃ）としての水素引き抜き型光開始剤（Ｃ２）としては、トリフェニルイミダゾール二量体、ベンゾフェノン、アントラキノン、エチルアントラキノン、ジエチルチオキサントン、イソプロピルチオキサントン、アクリジン系化合物等が挙げられ、アクリジン系化合物としては、９−フェニルアクリジン、下記一般式（IV) で表される化合物（Ｎ−１７１７）等が挙げられる。
【００２８】
【化９】
上記水素引き抜き型光開始剤（Ｃ２）の中でも、トリフェニルイミダゾール二量体が望ましく、特に下記一般式（Ｖ) で表される２，４，５−トリフェニルイミダゾール二量体が好ましい。
【００３０】
【化１０】
【００３１】
上記一般式（Ｖ) におけるＹ、Ｚ、Ｒ5 及びＲ6 のハロゲン原子としては、弗素、塩素、臭素等が挙げられる。
【００３２】
２，４，５−トリフェニルイミダゾール二量体の具体例としては、２，２′−ビス（２−クロロフェニル）−４，４′，５，５′−テトラフェニルビスイミダゾール、２，２′−ビス（２，３−ジクロロフェニル）−４，４′，５，５′−テトラフェニルビスイミダゾール、２，２′−ビス（２，４−ジクロロフェニル）−４，４′，５，５′−テトラフェニルビスイミダゾール、２，２′−ビス（２，６−ジクロロフェニル）−４，４′，５，５′−テトラフェニルビスイミダゾール、２，２′−ビス（２−ブロモフェニル）−４，４′，５，５′−テトラフェニルビスイミダゾール等が挙げられる。これらのイミダゾール二量体は、単独で用いてもよく、それらから選ばれる２種以上を用いてもよい。
【００３３】
本発明の感光性樹脂組成物は、上記バインダーポリマー（Ａ）、上記光重合性化合物（Ｂ）並びに光開始剤（Ｃ）としての上記アミン系化合物（Ｃ１）及び上記水素引き抜き型光開始剤（Ｃ２）を含有することからなるが、それらの配合割合は、バインダーポリマー（Ａ）及び光重合性化合物（Ｂ）１００質量部当り、バインダーポリマー（Ａ）が４０〜８０質量部、光重合性化合物（Ｂ）が６０〜２０質量部、アミン系化合物（Ｃ１）が０．１〜２．０質量部、特に０．３〜０．８質量部、水素引き抜き型光開始剤（Ｃ２）が１．０〜６．０質量部、特に２．０〜４．０質量部とするのが好ましい。
【００３４】
バインダーポリマー（Ａ）が４０質量部未満では、光硬化物が脆くなり易く、本感光性樹脂組成物を用いて感光性エレメントとした時に塗膜性に劣る傾向があり、８０質量部を超えると、感度が不十分となる傾向がある。光重合性化合物 （Ｂ）が２０質量部未満では、感度が不十分となる傾向があり、６０質量部を超えると、本感光性樹脂組成物を用いて感光性エレメントとした時に塗膜性に劣る傾向がある。又、アミン系化合物（Ｃ１）が０．１質量部未満では、感度が低下し、２．０質量部を超えると、解像性が低下する傾向がある。更に、水素引き抜き型光開始剤（Ｃ２）が１．０質量部未満では、感度が低下し、６．０質量部を超えると、解像性が低下する傾向がある。
【００３５】
本発明の感光性樹脂組成物は、光開始剤（Ｃ）の増感剤を配合するのが好ましい。該増感剤として、ｐ−アミノフェニルケトン化合物、クマリン化合物等を使用することができる。これらの化合物の例としては、４，４′−ジアミノベンゾフェノン、４，４′−ジメチルアミノベンゾフェノン、４，４′−ジエチルアミノベンゾフェノン、４，４′−（Ｎ−メチル−Ｎ−エチル）アミノベンゾフェノン、７−アミノ−４−メチルクマリン、７−ジメチルアミノ−４−メチルクマリン、７−ジエチルアミノ−４−メチルクマリン、７−メチルアミノ−４−メチルクマリン、７−エチルアミノ−４−メチルクマリン、７−ジメチルアミノシクロペンタ［ｃ］クマリン、７−アミノシクロペンタ［ｃ］クマリン、７−ジエチルアミノシクロペンタ［ｃ］クマリン、４，６−ジメチル−７−エチルアミノクマリン、４，６−ジエチル−７−エチルアミノクマリン、４，６−ジメチル−７−ジエチルアミノクマリン、４，６−ジメチル−７−ジメチルアミノクマリン、４，６−ジエチル−７−ジエチルアミノクマリン、４，６−ジエチル−７−ジメチルアミノクマリン等が挙げられる。
【００３６】
これらの増感剤は、バインダーポリマー（Ａ）及び光重合性化合物（Ｂ）１００質量部当り、０．０１〜０．３質量部、特に０．０３〜０．１質量部配合することが好ましい。この配合量が、０．０１質量部未満では、増感剤を配合することによる効果、すなわち感度向上が得られず、０．３質量部を超えると、解像度が低下する傾向がある。更に、本発明の感光性樹脂組成物は、重合禁止剤、発色剤、染料等の添加剤を、必要に応じて添加することができる。
【００３７】
本発明の感光性樹脂組成物は、上記バインダーポリマー（Ａ）、上記光重合性化合物（Ｂ）、上記アミン系化合物（Ｃ１）及び上記水素引き抜き型光開始剤 （Ｃ２）、更に上記増感剤や必要に応じて用いられる添加剤を、これらを溶解する溶剤、例えばトルエン、Ｎ，Ｎ′−ジメチルホルムアミド、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルセロソルブ、クロロホルム、塩化メチレン、メタノール、エタノール等に溶解、混合することにより、均一な溶液とすることができる。上記溶剤は、１種に限らず、２種以上を併用することができる。
【００３８】
更に、本発明は感光性エレメントを要旨とするが、該感光性エレメントは、上記感光性樹脂組成物を支持体の上に塗布、乾燥して感光層を設けたものである。
【００３９】
支持体としては、ポリエチレンテレフタレートフィルム、ポリプロピレンフィルム、ポリエチレンフィルム等の重合体フィルムが用いられ、中でもポリエチレンテレフタレートフィルムが好ましい。これらの重合体フィルムは、後に感光層から除去することが可能でなければならないため、除去を不可能とするような表面処理が施されたものであったり、材質であったりしてはならない。これらの重合体フィルムは、厚さが５〜１００μｍとすることが好ましく、１０〜４０μｍとすることがより好ましい。又、重合体フィルムは、その２つを感光層の両面に積層し、その１つを感光層の保護フィルムとすることができる。
【００４０】
本発明の感光性エレメントを用いて、フォトレジスト画像を製造する際、前記の保護フィルムが存在している場合には、保護フィルムを除去した後、感光層を加熱しながら基板に圧着させて積層する。積層される表面は、特に制限はないが、通常は金属面が用いられる。感光層の加熱温度は９０〜１３０℃とすることが好ましく、圧着圧力は０．１〜１ＭＰａとすることが好ましい。又、感光層を前記のように加熱すれば、予め基板を加熱処理することは必要ではないが、積層性を更に向上させるために、基板の予熱処理を行うこともできる。
【００４１】
このようにして積層が完了した感光層は、次いで、ネガフィルム、又はポジフィルムを用いて、活性光により画像的に露光される。この際、感光層上に存在する重合体フィルムが透明の場合は、そのまま露光してもよいが、不透明の場合は、重合体フィルムを当然に除去する必要がある。感光層の保護という観点からは、透明な重合体フィルムを用い、そのフィルムを残存させたまま、そのフィルムを通して露光するのが好ましい。
【００４２】
活性光としては、公知の活性光源、例えば、カーボンアーク、水銀蒸気アーク、キセノンアーク、写真用フラッド電球、太陽ランプ等から発生する光が用いられる。
【００４３】
次いで、露光後、感光層上に重合体フィルム等が存在している場合には、これを除去した後、アルカリ水溶液を用いて、例えば、スプレー、揺動浸漬、ブラッシング、スクラッピング等の公知の方法により、未露光部を除去して現像する。
【００４４】
アルカリ水溶液としては、リチウム、ナトリウム、カリウム等のアルカリ金属の水酸化物、炭酸塩、重炭酸塩、リン酸塩、ピロリン酸塩等の水溶液が使用可能であり、これらの中でも特に炭酸ナトリウムの水溶液が好ましい。アルカリ水溶液は、ｐＨが９〜１１のものが好ましく、現像時のアルカリ水溶液の温度は、感光層の現像性に合わせて調節することができる。又、アルカリ水溶液には、必要に応じて、表面活性剤、消泡剤、現像を促進するための少量の有機溶剤等を混入することができる。
【００４５】
更に、印刷配線板を製造するに際しては、現像されたフォトレジスト画像をマスクして、露光している基板の表面を、エッッチング、めっき等の公知の方法で処理する。次いで、フォトレジスト画像は、通常、現像に用いたアルカリ水溶液よりも更に強アルカリ性の水溶液で剥離される。この強アルカリ性の水溶液としては、濃度が１〜５質量％の前記のアルカリ水溶液が好ましく、例えば、水酸化ナトリウム、水酸化カリウム等が用いられる。
【００４６】
【実施例】
以下、本発明を実施例により、詳細に説明する。なお、実施例及び比較例における部及び％は質量基準である。実施例及び比較例で用いた各成分は、下記の通りである。
【００４７】
バインダーポリマー（Ａ）
メタクリル酸（３０部）−メタクリル酸メチル（４５部）−スチレン（２５部）共重合体（酸価：２０、重量平均分子量：５万）のメチルセロソルブ−トルエン溶液（固形分：４５％）
光重合性化合物（Ｂ）
（Ｂ−１）：１，１，１−トリス［プロペノイルオキシポリ（エチレンオキシ）メチル］プロパン（Ａ−ＴＭＰＴ−３ＥＯ；新中村化学工業社製，商品名）
（Ｂ−２）：ノナエチレングリコールジメタクリレート（９Ｇ；新中村化学工業社製，商品名）
（Ｂ−３）：２，２′−ビス［４−（メタクリロイルオキシ・ポリエトキシ）フェニル］プロパン（ＢＰＥ−５００；新中村化学工業社製，商品名）
（Ｂ−４）：ノニルフェニル−４−エチレンオキシアクリレート（ＮＰ−４ＥＡ；共栄社製，商品名）
アミン系化合物（Ｃ１）
１，１−ビス［４，４′−（Ｎ，Ｎ−ジメチルアミノフェニル）］シクロヘキサン（ＤＭＡＨ；シグマ−アルドリッチ社製，商品名）
水素引き抜き型光開始剤（Ｃ２）
２，２′−ビス（２−クロロフェニル）−４，４′，５，５′−テトラフェニルビスイミダゾール
増感剤
４，４′−ビス（Ｎ，Ｎ−ジエチルアミノ）ベンゾフェノン
光開始剤
ＥＰＡ：ｐ−ジメチルアミノ安息香酸エチルエステル（日本化薬社製，商品名）
ＤＭＢＩ：ｐ−ジメチルアミノ安息香酸イソアミルエステル（日本化薬社製，商品名）
ＤＥＡ：Ｎ，Ｎ−ジエチルアニリン（東京化成工業社製，商品名）
（合成例）
ＤＭＡＨを１２ｍｇ、２，２′−ビス（２−クロロフェニル）−４，４′，５，５′−テトラフェニルビスイミダゾールを５０ｍｇ、ＢＰＥ−５００を１０ｇ及びＮ，Ｎ−ジメチルホルムアミドを３ｇを混合して、それらの溶液を得た。この溶液１１．７ｍｇをアルミニウム製サンプルパン上に採取し、光化学反応熱熱量計（セイコーインストルメンツ社製、ＰＤＣ１２１）にて光ラジカル重合熱を計測した。測定条件は以下の通りである。
光源：２００Ｗ 水銀／キセノンランプ（全光照射）
照度：５０ｍＷ／ｃｍ2
雰囲気：窒素気流下
測定温度：２５℃
光照射により反応熱が観測された。反応熱は、ΔＨ＝１７ｍＪ／ｍｇであった。又、ＤＭＡＨ１０ｍｇをアセトニトリル１ｌに溶解した溶液を調製し、３６５ｎｍにおけるモル吸光係数を求めたところ、ε＝１６０であった。
【００４９】
（実施例１）
上記各成分を表１に示す割合で混合し、それらの溶液を得た。得られた溶液に、Ｃ１成分を表２に示す割合で用いて溶解させ、本発明の感光性樹脂組成物の溶液を調製した。なお、ＤＭＡＨ（Ｃ１）０．５ｇをアセトン１０ｇ、トルエン７ｇ、ＤＭＦ３ｇ及びメタノール３ｇに溶解させた溶液は、波長４００〜７００ｎｍの可視光線に吸収を持たなかった。
上記で得られた感光性樹脂組成物の溶液を、１６μｍのポリエチレンテレフタレートフィルム上に、均一に塗布し、１００℃の熱風対流式乾燥器で、１０分間乾燥して、表面に感光層を持つ感光性エレメントを得た。感光層の膜厚は３０μｍであった。
【００５０】
一方、厚さ３５μｍの銅箔を両面に積層したガラスエポキシ材である銅張り積層板（日立化成工業社製、商品名：ＭＣＬ−Ｅ−６１）の銅表面を、＃６００相当のブラシを持つ研磨機（三啓社製）を用いて研磨し、水洗後、空気流で乾燥し、その銅張り積層板を８０℃に加温し、その銅表面上に、上記感光性エレメントの感光層を１１０℃の加熱しながらラミネートした。
【００５１】
次に、高圧水銀灯ランプを有する露光機（オーク社製、露光機５９０）を用いて、ネガとしてストーファー４１段ステップタブレットを試験片の上に置いて、６０ｍＪ／ｃｍ2 、１２０ｍＪ／ｃｍ2 、２４０ｍＪ／ｃｍ2 露光した。
【００５２】
次に、ポリエチレンテレフタレートフィルムを剥離し、３０℃で１％の炭酸ナトリウム水溶液を２０秒間スプレーすることにより、未露光部を除去した。
【００５３】
更に、銅張り積層板上に形成された光硬化膜のステップタブレットの段数を測定し、対数回帰計算によってステップタブレット１５段が残る露光量を感度とした。その結果を表３に示した。感度は、露光量が少ないほど高いことを示す。
【００５４】
又、ステップタブレット１５段が残る露光量を、ガラスネガマスクパターン （日立化成エレクトロニクス社製）を通して露光して現像後得られたパターンを観察し、ライン・アンド・スペース幅（μｍ）から解像度（μｍ）を求めた。その結果を表３に示した。この値が小さいほど、解像度が高いことを示す。
【００５５】
（比較例１〜４）
実施例１で各成分を表１に示す割合で混合して得られた溶液に、表２に示す光開始剤を配合しないか、表２に示す光開始剤を表２に示す割合で配合して溶解させ、感光性樹脂組成物の溶液を調製した。これらの溶液を用いて、実施例１と同様にして感光性エレメントを製造し、更にそれらの感光性エレメントについて、実施例１と同様にして感度及び解像度を求め、それらの結果を表３に示した。
【００５６】
【表１】
表３から明らかのように、実施例に係る感光性エレメントは、比較例に係る感光性エレメントに比べて、感度及び解像度共に優れていることが判る。
【００５８】
【発明の効果】
本発明の感光性樹脂組成物は、特に解像性に優れると共に、光感度、密着性、耐薬品性、柔軟性、めっき浴汚染性、低臭気性等に優れ、更にアルカリ現像液による現像性や機械的強度が良好であり、しかも作業性に優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive resin composition and a photosensitive element using the same, and more specifically, a photosensitive resin composition effective as a resist material used in manufacturing a printed wiring board and a photosensitive property using the same. Regarding elements.
[0002]
[Prior art]
Conventionally, in the field of printed wiring board production, as a resist material used for etching, plating and the like, a photosensitive resin composition and a photosensitive element using a support and a protective film are widely used. The printed wiring board is formed by laminating a photosensitive film on a copper substrate, pattern exposure, removing uncured portions with a developer, etching or plating, forming a pattern, and then curing the cured portions. It is manufactured by a method of peeling off from the substrate.
[0003]
With the recent increase in the density of printed wiring boards, there has been an increasing demand for photosensitive films to exhibit higher resolution and higher adhesion than conventional photosensitive films. Furthermore, for boards on which semiconductor chips such as BGA (Ball Grid Array) and CSP (Chip Size Package) are mounted, as shown in the road map of the American Semiconductor Industry Association, the level is exceptionally high. It is expected that the resolution will be required.
[0004]
In the conventional photosensitive resin composition, a photo-initiator such as a hydrogen-donating amine compound photoinitiator or a hydrogen abstraction type photoinitiator and a sensitizer are blended to obtain a high-resolution resin composition To be done. Examples of hydrogen-donating amine compound photoinitiators include p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, N, N-diethylaniline, and the like. , 4,5-triphenylimidazole dimer and the like are known. Moreover, p-aminophenyl ketone etc. are known as a sensitizer.
[0005]
However, the combination of the hydrogen-donating amine compound photoinitiator and the sensitizer has low resolution. Therefore, although high resolution has been realized by using 2,4,5-triphenylimidazole dimer as an initiator and p-aminophenyl ketone as a sensitizer, it can be said that it is sufficient at present. Absent. On the other hand, from the viewpoint of improving workability, a photosensitive resin composition with high sensitivity and low plating bath contamination is desired, and these characteristics depend on the type and amount of the photoinitiator used. To do.
[0006]
[Problems to be solved by the invention]
The present invention is made in view of the above situation, and a photosensitive resin composition excellent in high resolution, high adhesion, high sensitivity, plating bath contamination, and the like, and a photosensitive element using the same. The purpose is to provide.
[0007]
[Means for Solving the Problems]
In order to achieve the above-mentioned object, the present inventors have conducted extensive research, and as a result, an amine compound having two or more aromatic rings as a photoinitiator, a 2,4,5-triphenylimidazole dimer, and the like. The inventors have found that the object of the present invention can be achieved by using in combination, and have reached the present invention.
[0008]
That is, the present invention is represented by the following general formula (I) as a binder polymer (A), a photopolymerizable compound (B) having a photopolymerizable ethylenically unsaturated group in the molecule, and a photoinitiator (C). Which contains at least two substituents in the molecule, an amine compound (C1) having a molar extinction coefficient at 365 nm in acetonitrile of 500 or less and a hydrogen abstraction type photoinitiator (C2) in acetonitrile. The gist of the resin composition is as follows.
[0009]
[Formula 4]
The photosensitive resin composition of the present invention is characterized in that the amine compound (C1) has a property of not absorbing visible light having a wavelength of 400 to 700 nm.
[0010]
Further, the present invention is represented by the following general formula (II) as a binder polymer (A), a photopolymerizable compound (B) having a photopolymerizable ethylenically unsaturated group in the molecule, and a photoinitiator (C). The gist of the present invention is a photosensitive resin composition comprising an amine compound (C1) and a hydrogen abstraction type photoinitiator (C2).
[0011]
[Chemical formula 5]
[0012]
The photosensitive resin composition of the present invention further contains a sensitizer (D).
In the photosensitive resin composition of the present invention, the binder polymer (A) has an acid value of 30 to 200 and a weight average molecular weight of 20,000 to 300,000. .
The photosensitive resin composition of the present invention is characterized in that the photopolymerizable compound (B) is bisphenol A polyoxyethylene diacrylate or bisphenol A polyoxyethylene dimethacrylate.
In the photosensitive resin composition of the present invention, the amine compound (C1) is a compound represented by the following general formula (III), and the hydrogen abstraction type photoinitiator (C2) is 2,4,5. -Triphenylimidazole dimer.
[0013]
[Chemical 6]
[0014]
Furthermore, the gist of the present invention is a photosensitive element obtained by coating any one of the above photosensitive resin compositions on a support and drying.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The binder polymer (A) used in the present invention is preferably a polymer having a free carboxy group in the molecule. For example, an unsaturated carboxylic acid having a polymerization ability such as acrylic acid or methacrylic acid and acrylic acid or methacrylic acid. Examples include an ester of an acid, an amide of acrylic acid or methacrylic acid, vinyl sulfonic acid, vinyl benzoate, acrylonitrile, styrene, vinyl toluene, and a copolymer with an unsaturated compound having a polymerization ability. Specific examples of the ester and the amide are given below, and (meth) acrylate indicates acrylate and the corresponding methacrylate.
[0016]
Examples of the ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydro Furfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate Examples of the amide include (meth) acrylamide, diacetone (meth) acrylamide and the like. The unsaturated compound having the above-mentioned polymerization ability is not limited to one type, and two or more types can be selected and used.
[0017]
The binder polymer (A) preferably has an acid value of 30 to 200, and has a weight average molecular weight (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) of 20, It is preferable that it is 000-300,000. When the acid value is less than 30, the development time tends to be long, and when it exceeds 200, the developer resistance of the photocured resist tends to be lowered. Further, when the weight average molecular weight is less than 20,000, the developing solution resistance of the photocured resist tends to be lowered, and when it exceeds 300,000, the developing time tends to be longer.
[0018]
The photopolymerizable compound (B) having an ethylenically unsaturated group that can be photopolymerized in the molecule used in the present invention includes an alkenoyl group having a terminal vinyl group such as an acryloyl group, a methacryloyl group, or a propenoyl group in the molecule. Examples thereof include γ-chloro-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, urethane di (Meth) acrylate, EO (ethylene oxide) modified urethane di (meth) acrylate, EO, PO (propylene oxide) modified urethane di (meth) acrylate, tris [(meth) acryloyloxy] tetraethylene glycol isocyanatohexamethylene iso Cyanurate, bisphenol A polyoxyethylene di (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane EO modified (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,1,1-tris [ Propenoyloxypoly (ethyleneoxy) methyl] propane, nonaethylene glycol di (meth) acrylate, 2,2'-bis [4-((meth) acryloyloxy polyethoxy) phenyl] propane, nonylphenyl-4-ethyleneoxy (Meth) acrylate etc. are mentioned. These compounds (B) can be used not only independently but in combination of 2 or more types thereof.
[0019]
The amine compound (C1) as the photoinitiator (C) used in the present invention has two or more substituents represented by the general formula (I) in the molecule, and molar absorption at 365 nm in acetonitrile. A compound having a coefficient of 500 or less, but preferably has a property of not absorbing visible light having a wavelength of 400 to 700 nm.
[0020]
Further, the amine compound (C1) is preferably a compound represented by the following general formula (II).
[0021]
[Chemical 7]
In the above general formula (II), R1, R2, RThreeAnd RFourRepresents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group, and X represents an alkylene group or cycloalkylene having 1 to 12 carbon atoms, preferably 3 to 12 carbon atoms, particularly preferably 5 to 10 carbon atoms. Indicates a group.
[0023]
Examples of the compound represented by the general formula (II) include 2,2-bis [4,4 ′-(N, N-dimethylaminophenyl)] propane and 2,2-bis [4,4 ′-(N , N-diethylaminophenyl)] propane, 3,3-bis [4,4 '-(N, N-dimethylaminophenyl)] pentane, 3,3-bis [4,4'-(N, N-diethylaminophenyl) ]] Pentane, 2,2-bis [4,4 '-(N, N-dihydroxyethylaminophenyl)] propane, 3,3-bis [4,4'-(N, N-dihydroxyethylaminophenyl)] Pentane, 2,2-bis [4,4 '-(N-methylaminophenyl)] propane, 3,3-bis [4,4'-(N-methylaminophenyl)] pentane, 2,2-bis [ 4,4 '-(N-ethylaminophenyl)] pro Bread, 1,1-bis [4,4 ′-(N, N-dimethylaminophenyl)] cyclobutane, 1,1-bis [4,4 ′-(N, N-dimethylaminophenyl)] cyclopentane, , 1-bis [4,4 ′-(N, N-dimethylaminophenyl)] cyclohexane, 1,1-bis [4,4 ′-(N, N-diethylaminophenyl)] cyclobutane, 1,1-bis [ 4,4 '-(N, N-diethylaminophenyl)] cyclopentane, 1,1-bis [4,4'-(N, N-diethylaminophenyl)] cyclohexane, 1,1-bis [4,4'- (N, N-dihydroxyethylaminophenyl)] cyclobutane, 1,1-bis [4,4 '-(N, N-dihydroxyethylaminophenyl)] cyclopentane, 1,1-bis [4,4'-( N, N-Dig B carboxyethyl aminophenyl) cyclohexane.
[0024]
Among the compounds represented by the general formula (II), a compound represented by the following general formula (III) is particularly preferable. In general formula (III), R1, R2, RThreeAnd RFourIs as defined above.
[0025]
[Chemical 8]
Examples of the compound include 1,1-bis [4,4 ′-(N, N-diethylaminophenyl)] cyclohexane, 1,1-bis [4,4 ′-(N, N-dihydroxyethylaminophenyl). ] Cyclohexane etc. are mentioned.
[0027]
Examples of the hydrogen abstraction type photoinitiator (C2) as the photoinitiator (C) used in the present invention include triphenylimidazole dimer, benzophenone, anthraquinone, ethylanthraquinone, diethylthioxanthone, isopropylthioxanthone, acridine compounds and the like. Examples of the acridine compound include 9-phenylacridine, a compound (N-1717) represented by the following general formula (IV), and the like.
[0028]
[Chemical 9]
Among the hydrogen abstraction type photoinitiators (C2), a triphenylimidazole dimer is preferable, and a 2,4,5-triphenylimidazole dimer represented by the following general formula (V) is particularly preferable.
[0030]
Embedded image
[0031]
Y, Z, R in the general formula (V)FiveAnd R6Examples of the halogen atom include fluorine, chlorine, bromine and the like.
[0032]
Specific examples of 2,4,5-triphenylimidazole dimer include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'- Bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl Bisimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbisimidazole and the like can be mentioned. These imidazole dimers may be used alone or in combination of two or more selected from them.
[0033]
The photosensitive resin composition of the present invention comprises the binder polymer (A), the photopolymerizable compound (B), the amine compound (C1) as a photoinitiator (C), and the hydrogen abstraction photoinitiator ( C2), but the blending ratio thereof is 40 to 80 parts by mass of the binder polymer (A) per 100 parts by mass of the binder polymer (A) and the photopolymerizable compound (B). (B) is 60 to 20 parts by mass, the amine compound (C1) is 0.1 to 2.0 parts by mass, particularly 0.3 to 0.8 parts by mass, and the hydrogen abstraction type photoinitiator (C2) is 1. It is preferable to set it as 0-6.0 mass parts, especially 2.0-4.0 mass parts.
[0034]
When the binder polymer (A) is less than 40 parts by mass, the photocured product tends to be brittle, and when the photosensitive resin composition is used as a photosensitive element, the coating property tends to be inferior, and when it exceeds 80 parts by mass. , The sensitivity tends to be insufficient. When the photopolymerizable compound (B) is less than 20 parts by mass, the sensitivity tends to be insufficient. When the photopolymerizable compound (B) exceeds 60 parts by mass, when the photosensitive element is used as a photosensitive element, the coating property is improved. There is a tendency to be inferior. Moreover, when the amine compound (C1) is less than 0.1 parts by mass, the sensitivity is lowered, and when it exceeds 2.0 parts by mass, the resolution tends to be lowered. Furthermore, when the hydrogen abstraction type photoinitiator (C2) is less than 1.0 part by mass, the sensitivity is lowered, and when it exceeds 6.0 parts by mass, the resolution tends to be lowered.
[0035]
The photosensitive resin composition of the present invention preferably contains a photoinitiator (C) sensitizer. As the sensitizer, a p-aminophenyl ketone compound, a coumarin compound, or the like can be used. Examples of these compounds include 4,4′-diaminobenzophenone, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 4,4 ′-(N-methyl-N-ethyl) aminobenzophenone, 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7- Dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethyl Aminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl 7-dimethylamino coumarin, 4,6-diethyl-7-diethylamino coumarin, 4,6-diethyl-7-dimethylamino coumarin, and the like.
[0036]
These sensitizers are preferably blended in an amount of 0.01 to 0.3 parts by weight, particularly 0.03 to 0.1 parts by weight, per 100 parts by weight of the binder polymer (A) and the photopolymerizable compound (B). . If the blending amount is less than 0.01 parts by mass, the effect of blending the sensitizer, that is, the sensitivity cannot be improved, and if it exceeds 0.3 parts by mass, the resolution tends to decrease. Furthermore, additives such as a polymerization inhibitor, a color former and a dye can be added to the photosensitive resin composition of the present invention as necessary.
[0037]
The photosensitive resin composition of the present invention includes the binder polymer (A), the photopolymerizable compound (B), the amine compound (C1), the hydrogen abstraction type photoinitiator (C2), and the sensitizer. Or additives used as necessary, in solvents such as toluene, N, N'-dimethylformamide, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, chloroform, methylene chloride, methanol, ethanol, etc. By mixing, a uniform solution can be obtained. The said solvent is not restricted to 1 type, but can use 2 or more types together.
[0038]
Further, the gist of the present invention is a photosensitive element, wherein the photosensitive element is obtained by coating the photosensitive resin composition on a support and drying to provide a photosensitive layer.
[0039]
As the support, a polymer film such as a polyethylene terephthalate film, a polypropylene film, or a polyethylene film is used, and a polyethylene terephthalate film is particularly preferable. Since these polymer films must be removable from the photosensitive layer later, they should not be subjected to a surface treatment or a material which makes removal impossible. These polymer films preferably have a thickness of 5 to 100 μm, and more preferably 10 to 40 μm. Further, two polymer films can be laminated on both sides of the photosensitive layer, and one of them can be used as a protective film for the photosensitive layer.
[0040]
When producing a photoresist image using the photosensitive element of the present invention, if the protective film is present, the protective film is removed, and then the photosensitive layer is heated and bonded to the substrate while being laminated. To do. The surface to be laminated is not particularly limited, but a metal surface is usually used. The heating temperature of the photosensitive layer is preferably 90 to 130 ° C., and the pressure bonding pressure is preferably 0.1 to 1 MPa. If the photosensitive layer is heated as described above, it is not necessary to heat the substrate in advance. However, in order to further improve the laminating property, the substrate can be preheated.
[0041]
The photosensitive layer thus laminated is then imagewise exposed to actinic light using a negative film or a positive film. At this time, if the polymer film present on the photosensitive layer is transparent, it may be exposed as it is, but if it is opaque, the polymer film needs to be naturally removed. From the viewpoint of protecting the photosensitive layer, it is preferable to use a transparent polymer film and expose the film while leaving the film remaining.
[0042]
As the active light, light generated from a known active light source such as a carbon arc, a mercury vapor arc, a xenon arc, a photographic flood bulb, a solar lamp, or the like is used.
[0043]
Next, after exposure, if a polymer film or the like is present on the photosensitive layer, it is removed, and then an alkaline aqueous solution is used, for example, a known method such as spraying, rocking dipping, brushing, scraping or the like. By the method, the unexposed portion is removed and developed.
[0044]
As the alkaline aqueous solution, alkaline metal hydroxides such as lithium, sodium and potassium, carbonates, bicarbonates, phosphates, pyrophosphates and other aqueous solutions can be used. Is preferred. The aqueous alkaline solution preferably has a pH of 9 to 11, and the temperature of the aqueous alkaline solution during development can be adjusted according to the developability of the photosensitive layer. Moreover, a surface active agent, a defoaming agent, a small amount of organic solvent for accelerating development, and the like can be mixed in the alkaline aqueous solution as necessary.
[0045]
Furthermore, when manufacturing a printed wiring board, the developed photoresist image is masked, and the exposed surface of the substrate is processed by a known method such as etching or plating. Next, the photoresist image is usually peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, the above alkaline aqueous solution having a concentration of 1 to 5% by mass is preferable. For example, sodium hydroxide, potassium hydroxide or the like is used.
[0046]
【Example】
Hereinafter, the present invention will be described in detail by way of examples. In addition, the part and% in an Example and a comparative example are mass references | standards. Each component used in the Examples and Comparative Examples is as follows.
[0047]
Binder polymer (A)
Methyl cellosolve-toluene solution (solid content: 45%) of methacrylic acid (30 parts) -methyl methacrylate (45 parts) -styrene (25 parts) copolymer (acid value: 20, weight average molecular weight: 50,000)
Photopolymerizable compound (B)
(B-1): 1,1,1-tris [propenoyloxypoly (ethyleneoxy) methyl] propane (A-TMPT-3EO; manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)
(B-2): Nonaethylene glycol dimethacrylate (9G; manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)
(B-3): 2,2′-bis [4- (methacryloyloxy / polyethoxy) phenyl] propane (BPE-500; manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)
(B-4): Nonylphenyl-4-ethyleneoxyacrylate (NP-4EA; manufactured by Kyoeisha, trade name)
Amine compound (C1)
1,1-bis [4,4 '-(N, N-dimethylaminophenyl)] cyclohexane (DMAH; manufactured by Sigma-Aldrich, trade name)
Hydrogen abstraction type photoinitiator (C2)
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole
Sensitizer
4,4'-bis (N, N-diethylamino) benzophenone
Photoinitiator
EPA: p-dimethylaminobenzoic acid ethyl ester (trade name, manufactured by Nippon Kayaku Co., Ltd.)
DMBI: p-dimethylaminobenzoic acid isoamyl ester (trade name, manufactured by Nippon Kayaku Co., Ltd.)
DEA: N, N-diethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd., trade name)
(Synthesis example)
Mix 12 mg of DMAH, 50 mg of 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 10 g of BPE-500 and 3 g of N, N-dimethylformamide. These solutions were obtained. 11.7 mg of this solution was collected on an aluminum sample pan, and the photoradical polymerization heat was measured with a photochemical reaction calorimeter (PDC121, manufactured by Seiko Instruments Inc.). The measurement conditions are as follows.
Light source: 200W mercury / xenon lamp (all-light irradiation)
Illuminance: 50 mW / cm2
Atmosphere: under nitrogen flow
Measurement temperature: 25 ° C
Reaction heat was observed by light irradiation. The heat of reaction was ΔH = 17 mJ / mg. In addition, a solution in which 10 mg of DMAH was dissolved in 1 l of acetonitrile was prepared, and the molar extinction coefficient at 365 nm was determined. As a result, ε = 160.
[0049]
Example 1
The above components were mixed in the proportions shown in Table 1 to obtain solutions. In the obtained solution, the C1 component was dissolved in the ratio shown in Table 2 to prepare a solution of the photosensitive resin composition of the present invention. A solution prepared by dissolving 0.5 g of DMAH (C1) in 10 g of acetone, 7 g of toluene, 3 g of DMF and 3 g of methanol did not absorb visible light having a wavelength of 400 to 700 nm.
The photosensitive resin composition solution obtained above is uniformly coated on a 16 μm polyethylene terephthalate film, dried for 10 minutes in a 100 ° C. hot air convection dryer, and has a photosensitive layer on the surface. A sex element was obtained. The film thickness of the photosensitive layer was 30 μm.
[0050]
On the other hand, the copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-61), which is a glass epoxy material having a 35 μm thick copper foil laminated on both sides, has a brush equivalent to # 600. Polishing using a polishing machine (manufactured by Sankeisha), washing with water, drying with air flow, heating the copper-clad laminate to 80 ° C., and forming the photosensitive layer of the photosensitive element on the copper surface Lamination was performed while heating at 110 ° C.
[0051]
Next, using an exposure machine having a high-pressure mercury lamp lamp (Oak Co., Ltd., exposure machine 590), a 41-step stove tablet as a negative was placed on the test piece, and 60 mJ / cm.2, 120mJ / cm2240 mJ / cm2Exposed.
[0052]
Next, the polyethylene terephthalate film was peeled off, and a 1% sodium carbonate aqueous solution was sprayed at 30 ° C. for 20 seconds to remove unexposed portions.
[0053]
Furthermore, the number of steps of the step tablet of the photocured film formed on the copper-clad laminate was measured, and the exposure amount at which 15 steps of the step tablet remained by logarithmic regression calculation was defined as the sensitivity. The results are shown in Table 3. The sensitivity indicates that the smaller the exposure amount, the higher the sensitivity.
[0054]
Also, the exposure amount remaining on the step tablet 15 steps is exposed through a glass negative mask pattern (manufactured by Hitachi Chemical Electronics Co., Ltd.), and the pattern obtained after development is observed, and the resolution from the line and space width (μm) to the resolution (μm ) The results are shown in Table 3. A smaller value indicates a higher resolution.
[0055]
(Comparative Examples 1-4)
In the solution obtained by mixing each component in Example 1 in the ratio shown in Table 1, the photoinitiator shown in Table 2 is not blended, or the photoinitiator shown in Table 2 is blended in the ratio shown in Table 2. Then, a solution of the photosensitive resin composition was prepared. Using these solutions, photosensitive elements were produced in the same manner as in Example 1. Further, the sensitivity and resolution of these photosensitive elements were determined in the same manner as in Example 1, and the results are shown in Table 3. It was.
[0056]
[Table 1]
As is apparent from Table 3, it can be seen that the photosensitive element according to the example is superior in both sensitivity and resolution as compared with the photosensitive element according to the comparative example.
[0058]
【The invention's effect】
The photosensitive resin composition of the present invention is particularly excellent in resolution, photosensitivity, adhesion, chemical resistance, flexibility, plating bath contamination, low odor, etc., and developability with an alkaline developer. In addition, the mechanical strength is good and the workability is excellent.
Claims (5)
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| JP2005221739A (en) * | 2004-02-05 | 2005-08-18 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element obtained by using same, method for producing photoresist pattern and method for producing printed wiring board |
| CN102459171B (en) | 2009-06-17 | 2014-07-09 | 东洋油墨Sc控股株式会社 | Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern |
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| JPS52130701A (en) * | 1976-04-26 | 1977-11-02 | Dynachem Corp | Dye componds of new photootropy and photoosensitive composition containing same |
| JPH10104826A (en) * | 1996-09-25 | 1998-04-24 | Kansai Paint Co Ltd | Photopolymerizable composition |
| JPH10207061A (en) * | 1996-12-17 | 1998-08-07 | Kolon Ind Inc | Photosensitive resin composition containing diamine compound and photosensitive film applying it |
| JPH11102070A (en) * | 1997-09-26 | 1999-04-13 | Nippon Synthetic Chem Ind Co Ltd:The | Photosensitive resin composition |
| JP2000007715A (en) * | 1998-06-22 | 2000-01-11 | Kansai Paint Co Ltd | Visible-ray-curable resin composition and its use |
| JP2000105455A (en) * | 1998-09-29 | 2000-04-11 | Nippon Synthetic Chem Ind Co Ltd:The | Photosensitive resin composition |
| JP2000321767A (en) * | 1999-05-07 | 2000-11-24 | Nichigo Morton Co Ltd | Photosensitive resin composition and dry film resist using the same |
| JP2002226441A (en) * | 2001-01-30 | 2002-08-14 | Hodogaya Chem Co Ltd | Method for producing bis (alkylaminophenyl) cyclohexane derivative |
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2001
- 2001-02-09 JP JP2001033569A patent/JP4617580B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52130701A (en) * | 1976-04-26 | 1977-11-02 | Dynachem Corp | Dye componds of new photootropy and photoosensitive composition containing same |
| JPH10104826A (en) * | 1996-09-25 | 1998-04-24 | Kansai Paint Co Ltd | Photopolymerizable composition |
| JPH10207061A (en) * | 1996-12-17 | 1998-08-07 | Kolon Ind Inc | Photosensitive resin composition containing diamine compound and photosensitive film applying it |
| JPH11102070A (en) * | 1997-09-26 | 1999-04-13 | Nippon Synthetic Chem Ind Co Ltd:The | Photosensitive resin composition |
| JP2000007715A (en) * | 1998-06-22 | 2000-01-11 | Kansai Paint Co Ltd | Visible-ray-curable resin composition and its use |
| JP2000105455A (en) * | 1998-09-29 | 2000-04-11 | Nippon Synthetic Chem Ind Co Ltd:The | Photosensitive resin composition |
| JP2000321767A (en) * | 1999-05-07 | 2000-11-24 | Nichigo Morton Co Ltd | Photosensitive resin composition and dry film resist using the same |
| JP2002226441A (en) * | 2001-01-30 | 2002-08-14 | Hodogaya Chem Co Ltd | Method for producing bis (alkylaminophenyl) cyclohexane derivative |
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