JP6126851B2 - UV curable resin composition - Google Patents
UV curable resin composition Download PDFInfo
- Publication number
- JP6126851B2 JP6126851B2 JP2013013042A JP2013013042A JP6126851B2 JP 6126851 B2 JP6126851 B2 JP 6126851B2 JP 2013013042 A JP2013013042 A JP 2013013042A JP 2013013042 A JP2013013042 A JP 2013013042A JP 6126851 B2 JP6126851 B2 JP 6126851B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- curable resin
- ultraviolet curable
- group
- forming material
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 38
- 230000035945 sensitivity Effects 0.000 claims description 27
- 239000003504 photosensitizing agent Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 3
- -1 argon ion Chemical class 0.000 description 41
- 239000010410 layer Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 229920001577 copolymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- KLGVPAWHYZDGCX-UHFFFAOYSA-N 3-phenylcyclobut-3-ene-1,2-dione Chemical compound O=C1C(=O)C=C1C1=CC=CC=C1 KLGVPAWHYZDGCX-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 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
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- 150000005072 1,3,4-oxadiazoles Chemical class 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-BGYRXZFFSA-N 1-o-[(2r)-2-ethylhexyl] 2-o-[(2s)-2-ethylhexyl] benzene-1,2-dicarboxylate Chemical compound CCCC[C@H](CC)COC(=O)C1=CC=CC=C1C(=O)OC[C@H](CC)CCCC BJQHLKABXJIVAM-BGYRXZFFSA-N 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- WQMWHMMJVJNCAL-UHFFFAOYSA-N 2,4-dimethylpenta-1,4-dien-3-one Chemical compound CC(=C)C(=O)C(C)=C WQMWHMMJVJNCAL-UHFFFAOYSA-N 0.000 description 1
- GBOJZXLCJZDBKO-UHFFFAOYSA-N 2-(2-chlorophenyl)-2-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 GBOJZXLCJZDBKO-UHFFFAOYSA-N 0.000 description 1
- OBNDKPYBWSTKBI-UHFFFAOYSA-N 2-(2-fluorophenyl)-2-[2-(2-fluorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound FC1=CC=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)F)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 OBNDKPYBWSTKBI-UHFFFAOYSA-N 0.000 description 1
- DVZGSAUNAZEWAI-UHFFFAOYSA-N 2-(2-methoxyphenyl)-2-[2-(2-methoxyphenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound COC1=CC=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)OC)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 DVZGSAUNAZEWAI-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PNDRGJCVJPHPOZ-ONEGZZNKSA-N 2-[(e)-2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(\C=C\C=2OC=CC=2)=N1 PNDRGJCVJPHPOZ-ONEGZZNKSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KJCFAQDTHMIAAN-UHFFFAOYSA-N 2-methyl-1-phenylprop-2-en-1-one Chemical compound CC(=C)C(=O)C1=CC=CC=C1 KJCFAQDTHMIAAN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- HJEAHJPEXSXSIL-UHFFFAOYSA-N 3-(dimethylamino)-4-(1,5-dimethyl-3-oxo-2-phenylpyrazol-4-yl)cyclobut-3-ene-1,2-dione Chemical compound CN(C)c1c(-c2c(C)n(C)n(-c3ccccc3)c2=O)c(=O)c1=O HJEAHJPEXSXSIL-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- ITDSYODGBSEUPA-UHFFFAOYSA-N 3-piperidin-1-ylcyclobut-3-ene-1,2-dione Chemical compound O=C1C(=O)C=C1N1CCCCC1 ITDSYODGBSEUPA-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
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- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
- Laminated Bodies (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、スクアリリウム化合物からなる光増感剤と、重合開始剤と、エチレン性不飽和化合物と、を含有することを特徴とする紫外線硬化型樹脂組成物に関する。 The present invention relates to an ultraviolet curable resin composition comprising a photosensitizer comprising a squarylium compound, a polymerization initiator, and an ethylenically unsaturated compound.
従来、プリント配線板、液晶表示素子、プラズマディスプレイ、大規模集積回路、薄型トランジスタ、半導体パッケージ、カラーフィルター、有機エレクトロルミネッセンス、薄型トランジスタ等における導体回路や電極加工基板等の形成には、例えば、被加工基板上に感光性レジスト材層を有し、必要に応じてその上に保護層を有する画像形成材のその感光性レジスト材層を、マスクフィルムを通して紫外線照射して露光した後、マスクフィルムを剥離し、更に保護層を有する場合にはその保護層を剥離し、露光部と非露光部の現像液に対する溶解性の差を利用して現像してパターンを形成し、このパターン層をマスクとして被加工基板をエッチング加工或いはメッキ加工等した後、レジスト画像を除去することにより、被加工基板に回路パターンを形成するリソグラフィー法が広く用いられている。 Conventionally, the formation of conductor circuits and electrode processing substrates in printed wiring boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electroluminescence, thin transistors, etc. After exposing the photosensitive resist material layer of the image forming material having a photosensitive resist material layer on the processed substrate and, if necessary, a protective layer thereon by irradiating with ultraviolet rays through the mask film, If the protective layer is further peeled off, the protective layer is peeled off and developed using the difference in solubility in the developer between the exposed area and the unexposed area to form a pattern. Using this patterned layer as a mask After etching or plating the substrate to be processed, the resist image is removed so that a circuit is formed on the substrate to be processed. Lithography to form a turn has been widely used.
近年、露光光源にレーザー光を用いることにより、マスクフィルムを用いずに、コンピューター等のデジタル情報から直接画像を形成するレーザー直接描画法が、生産性のみならず、解像性や位置精度等の向上も図れることから注目されるに到り、それに伴い、リソグラフィー法においてもレーザー光の利用が盛んに研究されている。 In recent years, a laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using a laser beam as an exposure light source has not only improved productivity but also improved resolution and positional accuracy. As it can be improved, it has attracted attention, and accordingly, the use of laser light has been actively researched in lithography.
一方、レーザー光は、紫外から赤外までの種々の光源が知られているが、画像露光に利用できるレーザー光としては、出力、安定性、感光能力、及びコスト等の点から、アルゴンイオンレーザー、ヘリウムネオンレーザー、ＹＡＧレーザー、青紫色半導体レーザー、最近では、３５０〜４００ｎｍの紫外線発光ダイオードが好ましく用いられている。 On the other hand, various light sources from ultraviolet to infrared are known as laser light. As laser light that can be used for image exposure, an argon ion laser is used from the viewpoint of output, stability, photosensitive ability, and cost. , Helium neon laser, YAG laser, blue-violet semiconductor laser, and recently, an ultraviolet light emitting diode of 350 to 400 nm is preferably used.
しかしながら、通常、紫外線硬化型樹脂組成物には、光重合開始剤に加えて、光増感剤を併用することで、より好適に硬化物を得ることができる。
特許文献１には紫外線硬化型樹脂組成物に用いる光増感剤として、チオキサン系化合物、アミン系化合物が開示されているが、該化合物では紫外線に対して、十分な感度が得られない問題があった。
However, normally, a cured product can be obtained more suitably by using a photosensitizer in combination with a photopolymerization initiator in an ultraviolet curable resin composition.
Patent Document 1 discloses thioxan compounds and amine compounds as photosensitizers used in ultraviolet curable resin compositions. However, these compounds have a problem that sufficient sensitivity to ultraviolet rays cannot be obtained. there were.
そこで、紫外線に対して感度に優れる光増感剤を用いた紫外線硬化型樹脂組成物が求められている。 Therefore, there is a demand for an ultraviolet curable resin composition using a photosensitizer that is excellent in sensitivity to ultraviolet rays.
本発明の目的は、紫外線に対して感度の優れた紫外線硬化型樹脂組成物及び該紫外線硬化型樹脂組成物を用いて作製した画像形成材を提供することである。 An object of the present invention is to provide an ultraviolet curable resin composition excellent in sensitivity to ultraviolet rays and an image forming material produced using the ultraviolet curable resin composition.
本発明者らは、鋭意検討をした結果、光増感剤としてスクアリリウム化合物を用いた紫外線硬化型樹脂組成物が上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that an ultraviolet curable resin composition using a squarylium compound as a photosensitizer can solve the above problems, and have completed the present invention.
すなわち、本発明は以下に示すものである。 That is, the present invention is as follows.
第一の発明は、下記一般式（Ａ）又は（Ｂ）で表されるスクアリリウム化合物からなる光増感剤と、重合開始剤と、エチレン性不飽和化合物と、を含有することを特徴とする紫外線硬化型樹脂組成物である。 1st invention contains the photosensitizer which consists of a squarylium compound represented by the following general formula (A) or (B), a polymerization initiator, and an ethylenically unsaturated compound, It is characterized by the above-mentioned. It is an ultraviolet curable resin composition.
第二の発明は、一般式（Ａ）又は（Ｂ）で表されるスクアリリウム化合物からなる光増感剤が、３５０ｎｍ〜４００ｎｍに露光感度の極大ピークを有することを特徴とする第一の発明に記載の紫外線硬化型樹脂組成物である。 The second invention is characterized in that the photosensitizer comprising the squarylium compound represented by the general formula (A) or (B) has a maximum peak of exposure sensitivity at 350 nm to 400 nm. It is an ultraviolet curable resin composition of description.
第三の発明は、第一又は第二の発明に記載の紫外線硬化型樹脂組成物を、波長３５０ｎｍ〜４００ｎｍのレーザー光によって光硬化させることを特徴とする硬化物である。 3rd invention is a hardened | cured material characterized by photocuring the ultraviolet curable resin composition as described in 1st or 2nd invention with the laser beam of wavelength 350nm -400nm.
第四の発明は、仮支持フィルム上に、第一又は第二の発明に記載の紫外線硬化型樹脂組成物の層を形成させ、３５０ｎｍ〜４００ｎｍのレーザー光によって光硬化させて得られる硬化物層を有することを特徴とする画像形成材料である。 4th invention forms the layer of the ultraviolet curable resin composition as described in 1st or 2nd invention on a temporary support film, and the hardened | cured material layer obtained by photocuring with a 350-400 nm laser beam It is an image forming material characterized by having.
第五の発明は、被加工基板上に第四の発明に記載の画像形成材料が、硬化物層側で積層されてなることを特徴とする画像形成材である。 A fifth invention is an image forming material, wherein the image forming material according to the fourth invention is laminated on the substrate to be processed on the cured product layer side.
本発明によれば、紫外線発光ダイオードに対する感度に優れた紫外線硬化型樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the ultraviolet curable resin composition excellent in the sensitivity with respect to an ultraviolet light emitting diode can be provided.
本願発明は、一般式（Ａ）又は（Ｂ）で表されるスクアリリウム化合物からなる光増感剤と、重合開始剤と、エチレン性不飽和化合物と、を含有することを特徴とする紫外線硬化型樹脂組成物である。 The present invention comprises an ultraviolet curable type comprising a photosensitizer comprising a squarylium compound represented by the general formula (A) or (B), a polymerization initiator, and an ethylenically unsaturated compound. It is a resin composition.
＜光増感剤＞
本発明に用いる光増感剤は、一般式（Ａ）又は（Ｂ）で表されるスクアリリウム化合物を用いる。
<Photosensitizer>
The photosensitizer used in the present invention uses a squarylium compound represented by the general formula (A) or (B).
上記一般式（Ａ）又は（Ｂ）中、Ｒ１〜Ｒ９は、同一又は異なっても良い水素、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、フェニル基のいずれかを示し、Ｒ４とＲ５は連結して環を形成していてもよい。 In the general formula (A) or (B), R 1 to R 9 may be the same or different hydrogen, halogen atom, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, and phenyl group. R 4 and R 5 may be linked to form a ring.
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、好ましくはフッ素原子又は塩素原子が挙げられる。 As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom or a chlorine atom is mentioned.
上記炭素数１〜８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基等が挙げられる Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, and n-hexyl group. , N-heptyl group, n-octyl group and the like.
上記炭素数１〜８のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、２ーメトキシエトキシ基、ペンチルオキシ基、ヘキシルオキシ基、オクチルオキシ基、デシルオキシ基、メトキシメチル基、メトキシエチル基、メトキシプロピル基、メトキシブチル基、メトキシヘキシル基等が挙げられる。 Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methoxyethoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a decyloxy group. Methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxyhexyl group and the like.
一般式（Ａ）又は（Ｂ）で表されるスクアリリウム化合物の具体例（スクアリリウム化合物（１）〜（１４））を以下に示す。 Specific examples (squarylium compounds (1) to (14)) of the squarylium compound represented by the general formula (A) or (B) are shown below.
これらの中でも特に紫外線における光増感剤として、感光性が大きい点より、化合物（１）、（２）、（９）、（１０）が好ましく挙げられ、特に（１）又は（２）が好ましく挙げられる。 Among these, compounds (1), (2), (9) and (10) are preferred as photosensitizers particularly for ultraviolet rays, and (1) or (2) is particularly preferred because of their high photosensitivity. Can be mentioned.
本発明に用いるスクアリリウム化合物である光増感剤は有機溶媒に対する溶解性が良好であり、紫外線に対して、感光性に優れる特徴を有している。 The photosensitizer, which is a squarylium compound used in the present invention, has good solubility in an organic solvent and has excellent photosensitivity to ultraviolet rays.
＜光重合開始剤＞
光重合開始剤は、スクアリリウム化合物である光増感剤との共存下で光照射されたときに、光増感剤の光励起エネルギーを受け取って活性ラジカルを発生し、エチレン性不飽和化合物を重合に到らしめるラジカル発生剤であって、例えば、ヘキサアリールビイミダゾール系化合物、チタノセン系化合物、ハロメチル化ｓ−トリアジン誘導体、ハロメチル化１，３，４−オキサジアゾール誘導体、ジアリールヨードニウム塩、有機硼素酸塩、及び有機過酸化物等が挙げられる。紫外線硬化型樹脂組成物としての感度、基板に対する密着性及び保存安定性等の面から、ヘキサアリールビイミダゾール系化合物、チタノセン系化合物が好ましく、ヘキサアリールビイミダゾール系化合物が特に好ましく挙げられる。
<Photopolymerization initiator>
When photoinitiator is irradiated with light in the presence of a photosensitizer, which is a squarylium compound, it receives the photoexcitation energy of the photosensitizer and generates active radicals to polymerize the ethylenically unsaturated compound. Radical generators to be achieved, such as hexaarylbiimidazole compounds, titanocene compounds, halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, diaryliodonium salts, organoboric acids A salt, an organic peroxide, etc. are mentioned. In terms of sensitivity as an ultraviolet curable resin composition, adhesion to a substrate, storage stability, and the like, hexaarylbiimidazole compounds and titanocene compounds are preferable, and hexaarylbiimidazole compounds are particularly preferable.
ヘキサアリールビイミダゾール系化合物としては、具体的には、例えば、２，２’−ビス（ｏ−メトキシフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｐ−メトキシフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（フルオロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−メチルフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジメトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ，ｐ−ジクロロフェニル）−４，４’，５，５’−テトラ（ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−エトキシカルボニルフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−クロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ，ｐ−ジクロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−フルオロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジブロモフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｐ−ヨードフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｏ−クロロ−ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−クロロナフチル）ビイミダゾール等が挙げられる。 Specific examples of the hexaarylbiimidazole compound include 2,2′-bis (o-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis. (P-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p -Methylphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4 4 ', 5,5'-tetra (o, p-dimethoxyphenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (p-methoxyphenyl) ) Biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4 , 4 ′, 5,5′-tetra (p-chlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4, 4 ', , 5′-tetra (p-fluorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dibromophenyl) biimidazole, 2, 2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o-chloro-p-methoxyphenyl) bi Examples include imidazole and 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) biimidazole.
チタノセン系化合物としては、具体的には、例えば、ジシクロペンタジエニルチタニウムジクロライド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，４−ジフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，６−ジフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，４，６−トリフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６−テトラフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６−ペンタフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６−ジフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６−ペンタフルオロフェニル）、ジシクロペンタジエニルチタニウムビス〔２，６−ジフルオロ−３−（１−ピロリル）フェニル〕等が挙げられる。 Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadi. Enyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl) ), Dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadi) Enyl) titanium bis (2,3,4,5,6-penta) Ruorofeniru), dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like.
＜エチレン性不飽和化合物＞
上記エチレン性不飽和化合物とは、紫外線硬化型樹脂組成物が紫外線の照射を受けたときに、光重合開始剤を含む光重合開始系の作用により付加重合し、場合により架橋、硬化するようなラジカル重合性のエチレン性不飽和結合を分子内に少なくとも１個有する化合物である。
<Ethylenically unsaturated compound>
The ethylenically unsaturated compound is such that when the ultraviolet curable resin composition is irradiated with ultraviolet rays, it undergoes addition polymerization by the action of a photopolymerization initiation system containing a photopolymerization initiator, and in some cases, crosslinks and cures. It is a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule.
エチレン性不飽和化合物としては、エチレン性不飽和基を有する化合物（モノマー又はポリマー）である。例えば、（メタ）アクリル酸、クロトン酸、イソクロトン酸、マレイン酸、イタコン酸、シトラコン酸等の不飽和カルボン酸、及びそのアルキルエステル、（メタ）アクリロニトリル、（メタ）アクリルアミド、スチレン等が挙げられ、重合性や露光部と非露光部の現像液溶解性の差異を拡大できる等の点から、エチレン性不飽和結合を分子内に２個以上有する化合物であることが好ましく挙げられる。 The ethylenically unsaturated compound is a compound (monomer or polymer) having an ethylenically unsaturated group. Examples include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, and the like. A compound having two or more ethylenically unsaturated bonds in the molecule is preferred from the viewpoints of polymerizability and the difference in developer solubility between exposed and unexposed areas.
エチレン不飽和基を有する化合物（モノマー）の具体例としては、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、トリメチロールプロパントリアクリレート、イソシアヌル酸ＥＯ変性トリアクリレート、トリメチルロールプロパンＥＯ変性トリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジトリメチロールプロパンテトラアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（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、イソシアヌル酸ＥＯ変性トリ（メタ）アクリレート、トリメチルロールプロパンＥＯ変性トリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等のアクリル系モノマーが挙げられる。 Specific examples of the compound (monomer) having an ethylenically unsaturated group include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, isocyanuric acid EO-modified triacrylate, trimethylolpropane EO-modified triacrylate, dipentaerythritol. Hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, trimethyl Roll propane EO modified tri (meth) acrylate, dipentaerythritol pen Data (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and acrylic monomers such as pentaerythritol tetra (meth) acrylate.
また、エチレン性不飽和基を有する化合物（ポリマー）の具体例としては、ヒドロキシエチルアクリレート、ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチルアクリレート、４−ヒドロキシブチル（メタ）アクリレート等のアクリル系モノマーとポリエステル系、ポリエーテル系、ポリアクリル系、ポリカーボネート系等のポリオールをヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、プロピレンジイソシアネート、ブチレンジイソシアネート等の脂肪族イソシアネート、シクロヘキサンジイソシアネート、メチレン（ビスシクロヘキシルイソシアネート）、イソホロンジイソシアネート等の脂環式イソシアネート、トリレンジジイソシアネート等の芳香族イソシアネート等のイソシアネート系硬化剤で重合し作製したウレタンアクリレート樹脂等が挙げられる。 Specific examples of the compound (polymer) having an ethylenically unsaturated group include acrylic monomers such as hydroxyethyl acrylate, hydroxyethyl (meth) acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Polyester, polyether, polyacrylic, polycarbonate and other polyols such as hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate and other aliphatic isocyanates, cyclohexane diisocyanate, methylene (biscyclohexyl isocyanate), isophorone diisocyanate, etc. Isocyanate curing agents such as aromatic isocyanates such as alicyclic isocyanate and tolylene diisocyanate Combined fabricated urethane acrylate resins.
また、必要に応じて、バインダー、添加剤（重合加速剤、熱重合禁止剤、可塑剤等）を用いることができる。 Moreover, a binder and additives (a polymerization accelerator, a thermal polymerization inhibitor, a plasticizer, etc.) can be used as needed.
バインダーとしては、例えば、ポリメタクリル酸エステル、ポリアクリル酸エステル、ポリ酢酸ビニル、酢酸ビニルとエチレンとの共重合体、ポリスチレン、ポリビニルホルマール、ポリビニルブチラール、ポリクロロプレン、ポリ塩化ビニル、塩素化ポリエチレン、塩素化ポリプロピレン、フェノールノボラック樹脂、ポリビニルフェノール、ビニルフェノールとメタクリル酸エステルとの共重合体、ポリエチレンオキサイド、ポリメチルイソプロペニルケトン、メタクリル酸エステルとフェニルイソプロペニルケトンとの共重合体、ポリウレタン、ポリアミド、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、アセチルセルロース、アセチルブチルセルロース、ニトロセルロース、ポリビニルカルバゾール、ビニルカルバゾールとスチレンとの共重合体、ビニルカルバゾールとメタクリル酸エステルとの共重合体、ビニルカルバゾールとアクリル酸エステルとの共重合体等が挙げられる。 Examples of the binder include polymethacrylic acid ester, polyacrylic acid ester, polyvinyl acetate, copolymer of vinyl acetate and ethylene, polystyrene, polyvinyl formal, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, and chlorine. Polypropylene, phenol novolac resin, polyvinyl phenol, copolymer of vinyl phenol and methacrylic acid ester, polyethylene oxide, polymethyl isopropenyl ketone, copolymer of methacrylic acid ester and phenyl isopropenyl ketone, polyurethane, polyamide, polycarbonate , Polyethylene terephthalate, polybutylene terephthalate, acetylcellulose, acetylbutylcellulose, nitrocellulose, polyvinylcarbazo , Copolymers of vinyl carbazole and styrene, a copolymer of vinylcarbazole and methacrylic acid esters, copolymers of vinyl carbazole and acrylic acid esters.
重合加速剤としては、例えば、２−メルカプトベンゾチアゾール等が挙げられる。熱重合禁止剤としては、例えば、ｐ−ｔｅｒｔ−ブチルカテコール、ハイドロキノン、クロラニル等が挙げられる。可塑剤としては、例えば、ジエチルヘキシルフタレート、ジイソブチルフタレート、トリクレシルホスフェート、ジエチルヘキシルセバケート、ジエチルヘキシルアジペート等が挙げられる。熱硬化性化合物としては、例えば、エポキシ基を少なくとも一つ以上有するメタクリレートモノマー又はアクリレートモノマー、エポキシ基を少なくとも一つ以上有するスチレンモノマー、他に反応性基を含まないポリグリシジル化合物等が挙げられ、さらにエポキシ基を二つ以上有するポリマー、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ウレタン変性エポキシ樹脂、エポキシ基含有共重合体等がそれぞれ挙げられる。 Examples of the polymerization accelerator include 2-mercaptobenzothiazole. Examples of the thermal polymerization inhibitor include p-tert-butylcatechol, hydroquinone, chloranil and the like. Examples of the plasticizer include diethyl hexyl phthalate, diisobutyl phthalate, tricresyl phosphate, diethyl hexyl sebacate, diethyl hexyl adipate, and the like. Examples of the thermosetting compound include a methacrylate monomer or acrylate monomer having at least one epoxy group, a styrene monomer having at least one epoxy group, and a polyglycidyl compound having no other reactive group. Further, polymers having two or more epoxy groups, such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, urethane modified epoxy resins, epoxy group-containing copolymers, etc., respectively Can be mentioned.
本発明の紫外線硬化型樹脂組成物を調製する際に使用する溶剤としては、各成分に対して良好な溶解性又は良好な分散性を有していることが望まれ、例えば、メチルセロソルブ、エチルセロソルブ、ブチルソロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、酢酸エチル、酢酸ブチル、メタノール、エタノール、２−プロパノール、Ｎ、Ｎ−ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、シクロヘキサン、トルエン、これらの混合溶媒等があげられる。 As a solvent used in preparing the ultraviolet curable resin composition of the present invention, it is desired that the solvent has good solubility or good dispersibility with respect to each component. For example, methyl cellosolve, ethyl Cellosolve, butyl solosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl acetate, butyl acetate, methanol, ethanol, 2-propanol, N, N-dimethylformamide, dimethylacetamide, N -Methylpyrrolidone, cyclohexane, toluene, a mixed solvent thereof and the like.
本発明の紫外線硬化型樹脂組成物における光増感剤の使用量は、全組成物１００質量部に対して、０．００１〜５質量部が好ましく、０．０１〜２質量部がより好ましく挙げられる。光重合開始剤は、光増感剤１質量部に対して、０．１〜１００質量部が好ましく、１〜５０質量部がより好ましく挙げられる。エチレン性不飽和化合物は、光増感剤１質量部に対して、２〜１０００質量部が好ましく、２０〜２００質量部がより好ましく挙げられる。 The amount of the photosensitizer used in the ultraviolet curable resin composition of the present invention is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total composition. It is done. 0.1-100 mass parts is preferable with respect to 1 mass part of photosensitizers, and 1-50 mass parts is mentioned more preferably with a photoinitiator. 2-1000 mass parts is preferable with respect to 1 mass part of photosensitizers, and, as for an ethylenically unsaturated compound, 20-200 mass parts is mentioned more preferably.
本発明の紫外線硬化型樹脂組成物の好ましい分光感度の極大ピークは、３００〜４２０ｎｍが好ましく、３３０〜４１０ｎｍがさらに好ましく、３５０〜４００ｎｍが特に好ましく挙げられる。３００ｎｍ未満又は４２０ｎｍ超では、紫外線発光ダイオードに対する感度が低くなる欠点がある。 The maximum spectral sensitivity peak of the ultraviolet curable resin composition of the present invention is preferably 300 to 420 nm, more preferably 330 to 410 nm, and particularly preferably 350 to 400 nm. If it is less than 300 nm or more than 420 nm, there is a drawback that the sensitivity to the ultraviolet light-emitting diode is lowered.
なお、本発明に用いる３５０〜４００ｎｍのレーザー光としては、紫外線発光ダイオードによるレーザー光が好ましく挙げられる。 In addition, as a 350-400 nm laser beam used for this invention, the laser beam by an ultraviolet light emitting diode is mentioned preferably.
本発明における分光感度の極大ピークとは、基板表面上に光硬化性組成物層を形成した光硬化性画像形成材試料を、分光感度測定装置を用い、キセノンランプ又はタングステンランプ等の光源から分光した光を横軸方向に露光した後、現像処理することにより、各露光波長の感度に応じた画像が得られ、その画像高さから画像形成可能な露光エネルギーを算出し、横軸に波長、縦軸にその露光エネルギーの逆数をプロットすることにより得られる分光感度曲線における極大ピークを指す。 The maximum spectral sensitivity peak in the present invention refers to a photocurable image-forming material sample having a photocurable composition layer formed on the surface of a substrate, which is spectrally separated from a light source such as a xenon lamp or a tungsten lamp using a spectral sensitivity measuring device. After exposing the light to the horizontal axis direction and developing it, an image corresponding to the sensitivity of each exposure wavelength is obtained, and the exposure energy capable of image formation is calculated from the image height, and the horizontal axis represents the wavelength, The maximum peak in the spectral sensitivity curve obtained by plotting the reciprocal of the exposure energy on the vertical axis.
次に画像形成材料について説明する。 Next, the image forming material will be described.
画像形成材料は、通常、前記各成分を適当な溶剤に溶解又は分散させた塗布液として、仮支持フィルム上に塗布し乾燥させ、必要に応じて、形成された紫外線硬化型樹脂組成物を用いて作製した硬化物の層表面を被覆フィルムで覆うことにより形成される。この様な画像形成材料としては、例えばドライフィルムレジスト材等が挙げられる。 The image forming material is usually applied onto a temporary support film as a coating solution in which the above-described components are dissolved or dispersed in an appropriate solvent and dried. If necessary, an ultraviolet curable resin composition formed is used. It is formed by covering the layer surface of the cured product prepared in this way with a coating film. Examples of such an image forming material include a dry film resist material.
また、上記画像形成材料は、本発明の画像形成材を形成するのに用いることができる。画像形成材は、通常、２タイプの作製方法がある。一つは、画像形成材料の紫外線硬化樹脂組成物層側を、被覆フィルムで覆われている場合にはその被覆フィルムを剥離して、被加工基板上に積層することにより作成される。もう一つは、以下の手順で作成される。
（１）前記の紫外線硬化型樹脂組成物の各成分を適当な溶剤に溶解或いは分散させた塗布液とする。（２）被加工基板上に直接に塗布し乾燥させる。（３）被加工基板上に紫外線硬化型樹脂組成物を硬化させた硬化物の層が形成される。
更に、画像形成材は、以下の画像形成方法に好適に用いられる。即ち、画像形成材の紫外線硬化型樹脂組成物の層を、例えば波長３５０〜４００ｎｍの紫外線発光ダイオードにより走査露光し、現像処理して画像を現出させる。
The image forming material can be used to form the image forming material of the present invention. There are generally two types of image forming materials. One is created by peeling off the coating film when the ultraviolet curable resin composition layer side of the image forming material is covered with a coating film and laminating it on the substrate to be processed. The other is created by the following procedure.
(1) A coating solution is prepared by dissolving or dispersing each component of the ultraviolet curable resin composition in an appropriate solvent. (2) Apply directly on the substrate to be processed and dry. (3) A layer of a cured product obtained by curing the ultraviolet curable resin composition is formed on the substrate to be processed.
Furthermore, the image forming material is suitably used in the following image forming method. That is, the layer of the ultraviolet curable resin composition of the image forming material is subjected to scanning exposure with an ultraviolet light emitting diode having a wavelength of 350 to 400 nm, for example, and developed to reveal an image.
そのドライフィルムレジスト材等として用いられる場合における仮支持フィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等の従来公知のフィルムが用いられる。その際、それらのフィルムがドライフィルムレジスト材の作製時に必要な耐溶剤性や耐熱性等を有しているものであるときは、それらの仮支持フィルム上に直接に紫外線硬化型樹脂組成物の塗布液を塗布し乾燥させてドライフィルムレジスト材を作製することができ、又、それらのフィルムが耐溶剤性や耐熱性等の低いものであっても、例えば、ポリテトラフルオロエチレンフィルムや離型フィルム等の離型性を有するフィルム上に先ず紫外線硬化型樹脂組成物層を形成した後、その層上に耐溶剤性や耐熱性等の低い仮支持フィルムを積層し、しかる後、離型性を有するフィルムを剥離することにより、ドライフィルムレジスト材を作製することもできる。 As the temporary support film when used as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. In that case, when those films have the solvent resistance and heat resistance necessary for the production of the dry film resist material, the ultraviolet curable resin composition is directly applied on the temporary support film. A dry film resist material can be produced by applying and drying a coating solution. Even if those films have low solvent resistance or heat resistance, for example, polytetrafluoroethylene film or mold release First, an ultraviolet curable resin composition layer is formed on a film having releasability such as a film, and then a temporary support film having low solvent resistance and heat resistance is laminated on the layer, and then releasability is obtained. A dry film resist material can also be produced by peeling the film having s.
また、塗布液に用いられる溶剤としては、使用成分に対して十分な溶解度を持ち、良好な塗膜性を与えるものであれば特に制限はないが、例えば、メチルセロソルブアセテート、エチルセロソルブアセテート等のセロソルブ系溶剤、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールジメチルエーテル等のプロピレングリコール系溶剤、酢酸ブチル、酢酸アミル、酪酸エチル、酪酸ブチル、ジエチルオキサレート、ピルビン酸エチル、エチル−２−ヒドロキシブチレート、エチルアセトアセテート、乳酸メチル、乳酸エチル、３−メトキシプロピオン酸メチル等のエステル系溶剤、メタノール、イソプロパノール、ヘプタノール、ヘキサノール、ジアセトンアルコール、フルフリルアルコール等のアルコール系溶剤、シクロヘキサノン、メチルエチルケトン等のケトン系溶剤、トルエン等の芳香族系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の高極性溶剤、或いはこれらの混合溶剤、更にはこれらに芳香族炭化水素を添加したもの等が挙げられる。これらの中で、溶解能、表面張力、粘度、乾燥のし易さ等の点から、メチルエチルケトン、メタノール、イソプロパノール、トルエン等の単独或いは混合溶剤が好適である。溶剤の使用割合は、紫外線硬化型樹脂組成物の総量に対して、質量比で０．５〜２倍程度の範囲である。 The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. For example, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether and other propylene glycol solvents, Butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate Ester solvents such as ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as methanol, isopropanol, heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketones such as cyclohexanone, methyl ethyl ketone, etc. Examples thereof include a system solvent, an aromatic solvent such as toluene, a highly polar solvent such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, a mixed solvent thereof, and those obtained by adding an aromatic hydrocarbon thereto. Among these, from the standpoints of solubility, surface tension, viscosity, ease of drying, and the like, single or mixed solvents such as methyl ethyl ketone, methanol, isopropanol, and toluene are preferable. The use ratio of the solvent is in a range of about 0.5 to 2 times by mass ratio with respect to the total amount of the ultraviolet curable resin composition.
塗布方法としては、例えば、ダイコート法、ナイフコート法、ロールコート法、スプレーコート法、スピンコート法等が挙げられる。その際の塗布量は、画像形成性及びそれに引き続くエッチングやメッキ等の加工性等の面から、乾燥膜厚として、通常５μｍ以上であり、ドライフィルムレジスト材としては１０μｍ以上であるのが好ましく、１５μｍ以上であるのが更に好ましく、感度等の面から、２００μｍ以下であるのが好ましく、１００μｍ以下であるのが更に好ましい。 Examples of the coating method include a die coating method, a knife coating method, a roll coating method, a spray coating method, and a spin coating method. In this case, the coating amount is usually 5 μm or more as a dry film thickness, and preferably 10 μm or more as a dry film resist material, from the viewpoints of image formability and subsequent processability such as etching and plating. More preferably, it is 15 μm or more, and in terms of sensitivity and the like, it is preferably 200 μm or less, and more preferably 100 μm or less.
ドライフィルムレジスト材等として用いられる場合には、それが被加工基板に積層されるまでの間、形成された紫外線硬化型樹脂組成物を用いて作製した硬化物の層表面を被覆フィルムで覆うことが好ましく、その被覆フィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム、ポリテトラフルオロエチレンフィルム等の従来公知のフィルムが用いられる。 When used as a dry film resist material, etc., cover the layer surface of the cured product prepared using the formed ultraviolet curable resin composition with a coating film until it is laminated on the substrate to be processed. As the covering film, a conventionally known film such as a polyethylene film, a polypropylene film, or a polytetrafluoroethylene film is used.
前記ドライフィルムレジスト材の紫外線硬化型樹脂組成物層側を、被覆フィルムで覆われている場合にはその被覆フィルムを剥離して、加熱、加圧等して積層することにより、又は、紫外線硬化型樹脂組成物の塗布液を直接に塗布し乾燥させることにより、レジスト画像形成材を作製するにおける被加工基板は、その上に形成される紫外線硬化型樹脂組成物の層を紫外線発光ダイオードにより露光し現像処理することによって現出された画像をレジストとしてエッチング加工或いはメッキ加工等することにより、その表面に回路や電極等のパターンが形成されるものであり、銅、アルミニウム、金、銀、クロム、亜鉛、錫、鉛、ニッケル等の金属板そのものであってもよいが、通常、例えば、エポキシ樹脂、ポリイミド樹脂、ビスマレイミド樹脂、不飽和ポリエステル樹脂、フェノール樹脂、メラミン樹脂等の熱硬化性樹脂、飽和ポリエステル樹脂、ポリカーボネート樹脂、ポリスルホン樹脂、アクリル樹脂、ポリアミド樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリオレフィン樹脂、弗素樹脂等の熱可塑性樹脂等の樹脂、紙、ガラス、及び、アルミナ、シリカ、硫酸バリウム、炭酸カルシウム等の無機物、又は、ガラス布基材エポキシ樹脂、ガラス不織布基材エポキシ樹脂、紙基材エポキシ樹脂、紙基材フェノール樹脂等の複合材料等からなり、その厚さが０．０２〜１０ｍｍ程度の絶縁性支持体表面に、前記金属或いは酸化インジウム、酸化錫、酸化インジウムドープ酸化錫等の金属酸化物等の金属箔を加熱、圧着ラミネートするか、金属をスパッタリング、蒸着、メッキする等の方法により、その厚さが１〜１００μｍ程度の導電層を形成した金属張積層板が、好ましく用いられる。 When the UV curable resin composition layer side of the dry film resist material is covered with a coating film, the coating film is peeled off and laminated by heating, pressing, or the like, or UV curing The substrate to be processed in producing a resist image forming material by directly applying and drying a coating solution of a mold resin composition is exposed to an ultraviolet light emitting diode on the layer of the ultraviolet curable resin composition formed thereon. Then, the pattern of circuits, electrodes, etc. is formed on the surface by etching processing or plating processing using the developed image as a resist. Copper, aluminum, gold, silver, chrome It may be a metal plate itself such as zinc, tin, lead, nickel, etc., but usually, for example, epoxy resin, polyimide resin, bismaleimide Thermosetting resin such as fat, unsaturated polyester resin, phenol resin, melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, fluorine resin, etc. Resin such as thermoplastic resin, paper, glass, and inorganic substances such as alumina, silica, barium sulfate, calcium carbonate, or glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base It is made of a composite material such as a phenol resin, and the metal or a metal oxide such as indium oxide, tin oxide, indium oxide doped tin oxide, etc. on the surface of the insulating support having a thickness of about 0.02 to 10 mm. Heating and pressure laminating metal foil or sputtering, vapor deposition, and metal By a method such as that, the thickness of the metal-clad laminate in which a conductive layer of about 1~100μm is preferably used.
紫外線硬化型樹脂組成物の塗布液を直接に塗布し乾燥させることにより、レジスト画像形成材を作製した場合には、前記被加工基板上に形成された紫外線硬化型樹脂組成物層の酸素による重合禁止作用を防止する等のために、その紫外線硬化型樹脂組成物層上に、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンオキサイド、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース等の溶液の塗布、乾燥により形成した保護層が設けられてもよい。 When a resist image forming material is produced by directly applying and drying a coating solution of the UV curable resin composition, polymerization of the UV curable resin composition layer formed on the substrate to be processed is performed with oxygen. In order to prevent the prohibiting action, etc., a protection formed by applying a solution of, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and the like on the UV curable resin composition layer A layer may be provided.
以下、本発明を実施例に基づいてより詳細に説明する。なお、本発明は本実施例によりなんら限定されない。実施例中の「部」は「質量部」を表す。 Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited at all by this Example. “Part” in the examples represents “part by mass”.
なお、本発明に用いたスクアリリウム化合物（１）、（２）、（９）、（１０）は上述したスクアリリウム化合物に対応するものである。 The squarylium compounds (1), (2), (9) and (10) used in the present invention correspond to the above-mentioned squarylium compounds.
実施例１〜４は光増感剤としてスクアリリウム（１）、（２）、（９）、（１０）を用い、比較例１、２は光増感剤として、２，４−ジエチルチオキサントン（比較例１）、４，４’−ジメチルアミノベンゾフェノン（比較例２）を用いた。 Examples 1 to 4 use squarylium (1), (2), (9), and (10) as photosensitizers, and Comparative Examples 1 and 2 use 2,4-diethylthioxanthone (comparative) as photosensitizers. Example 1), 4,4′-dimethylaminobenzophenone (Comparative Example 2) was used.
（実施例１）
＜紫外線用硬化樹脂組成物と画像形成材の製造＞
ペンタエリスリトールアクリレート１００部、ポリビニルピロリドン１００部、２−［２−（フラン−２−イル）ビニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン１０部、３−（２，３−ジヒドロ−１，５−ジメチル−３−オキソ−２−フェニル−１Ｈ−ピラゾール−４−イル）−４−（ジメチルアミノ）−３−シクロブテン−１，２−ジオン（ＭｉｃｒｏＣｏｍｂｉＣｈｅｍ社製）（スクアリリウム化合物（１））０．１部をメチルセロソルブ９００部に溶解して紫外線硬化樹脂組成物を得た。得られた紫外線硬化樹脂組成物をポリエステルフィルムにスピンコーターを用いて塗布し、乾燥させて、画像形成材（膜厚２μｍ）を作製した。
Example 1
<Manufacture of UV-curable resin composition and image forming material>
100 parts of pentaerythritol acrylate, 100 parts of polyvinylpyrrolidone, 10 parts of 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 3- (2 , 3-Dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl) -4- (dimethylamino) -3-cyclobutene-1,2-dione (manufactured by MicroCombiChem) 0.1 part of squarylium compound (1)) was dissolved in 900 parts of methyl cellosolve to obtain an ultraviolet curable resin composition. The obtained ultraviolet curable resin composition was applied to a polyester film using a spin coater and dried to prepare an image forming material (film thickness: 2 μm).
＜分光感度の極大ピーク＞
画像形成材を５０×６０ｍｍの大きさに切り出したサンプルを、回折分光照射装置を用い、キセノンランプ（ウシオ電機社製「ＵＩ−５０１Ｃ」）を光源として３００〜５００ｎｍの波長域で分光した光を横軸方向に露光波長が直線的に、縦軸方向に露光強度が対数的に変化するように設定して１０秒間照射して露光し、次いで２５℃の０．７質量％炭酸ナトリウム水溶液を現像液として０．１５ＭＰａとなるように吹き付け、最小現像時間の１．５倍の時間でスプレー現像することにより、各露光波長の感度に応じた画像が得られ、その画像高さから画像形成可能な露光エネルギーを算出し、横軸に波長、縦軸にその露光エネルギーの逆数をプロットすることにより得られる分光感度曲線における極大ピークを読みとった。露光感度の極大ピーク（ｎｍ）の波長を表１に示す。
<Maximum peak of spectral sensitivity>
A sample obtained by cutting an image forming material into a size of 50 × 60 mm is obtained by using a diffraction spectroscopic irradiation apparatus and using a xenon lamp (“UI-501C” manufactured by Ushio Electric Co., Ltd.) as a light source to split light in a wavelength range of 300 to 500 nm. The exposure wavelength is set linearly in the horizontal axis direction, and the exposure intensity is changed logarithmically in the vertical axis direction. The exposure is performed by irradiating for 10 seconds, and then a 0.7 mass% sodium carbonate aqueous solution at 25 ° C. is developed By spraying as a liquid at 0.15 MPa and spray development in 1.5 times the minimum development time, an image corresponding to the sensitivity of each exposure wavelength can be obtained, and an image can be formed from the image height The exposure energy was calculated, and the maximum peak in the spectral sensitivity curve obtained by plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis was read. The wavelength of the maximum peak (nm) of exposure sensitivity is shown in Table 1.
＜露光感度の測定＞
紫外線硬化樹脂組成物を用いて作製した硬化物層を、中心波長３７０ｎｍ、レーザー出力５ｍＷの紫外線発光ダイオードを用いて、像面照度２ｍＷ、ビームスポット径２μｍで、ビーム走査間隔及び走査速度を変えながら操作露光し、次いで、３０℃の１質量％炭酸ナトリウム水溶液を現像液として０．１５ＭＰａとなるように吹き付け、最小現像時間の２倍の時間でスプレー現像することによりネガ画像を現出させた。得られた画像について２０μｍの線幅が再現するのに要する露光量を求め露光感度とした。露光感度の測定結果を表１に示す。
<Measurement of exposure sensitivity>
Using a UV light emitting diode having a center wavelength of 370 nm and a laser output of 5 mW, a cured product layer prepared using the UV curable resin composition was changed with a beam scanning interval and a scanning speed at an image plane illuminance of 2 mW and a beam spot diameter of 2 μm. Operation exposure was performed, and then a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed as a developing solution to a pressure of 0.15 MPa, and a negative image was revealed by spray development in a time twice as long as the minimum development time. With respect to the obtained image, an exposure amount required for reproducing a line width of 20 μm was obtained and used as exposure sensitivity. Table 1 shows the measurement results of exposure sensitivity.
（実施例２）
実施例１に記載の３−（２，３−ジヒドロ−１，５−ジメチル−３−オキソ−２−フェニル−１Ｈ−ピラゾール−４−イル）−４−（ジメチルアミノ）−３−シクロブテン−１，２−ジオン（ＭｉｃｒｏＣｏｍｂｉＣｈｅｍ社製）（スクアリリウム化合物（１））を、３−（２，３−ジヒドロ−１，５−ジメチル−３−オキソ−２−フェニル−１Ｈ−ピラゾール−４−イル）−４−（１−ピペリジニル）−３−シクロブテン−１，２−ジオン（ＭｉｃｒｏＣｏｍｂｉＣｈｅｍ社製）（スクアリリウム化合物（２））に代えた以外は、実施例１と同様にして画像形成材を製造し、分光感度の極大ピークと露光感度を測定した。
(Example 2)
3- (2,3-Dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl) -4- (dimethylamino) -3-cyclobutene-1 as described in Example 1 , 2-dione (manufactured by MicroCombiChem) (squarylium compound (1)) is converted into 3- (2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)- An image forming material was produced in the same manner as in Example 1 except that 4- (1-piperidinyl) -3-cyclobutene-1,2-dione (manufactured by MicroCombiChem) (squarylium compound (2)) was used. The maximum sensitivity peak and exposure sensitivity were measured.
（実施例３）
実施例１に記載の３−（２，３−ジヒドロ−１，５−ジメチル−３−オキソ−２−フェニル−１Ｈ−ピラゾール−４−イル）−４−（ジメチルアミノ）−３−シクロブテン−１，２−ジオン（ＭｉｃｒｏＣｏｍｂｉＣｈｅｍ社製）（スクアリリウム化合物（１））を、３−（２，３−ジヒドロ−１，５−ジメチル−３−オキソ−２−フェニル−１Ｈ−ピラゾール−４−イル）−４−フェニル−３−シクロブテン−１，２−ジオン（ＭｉｃｒｏＣｏｍｂｉＣｈｅｍ社製）（スクアリリウム化合物（９））に代えた以外は、実施例１と同様にして画像形成材を製造し、分光感度の極大ピークと露光感度を測定した。
(Example 3)
3- (2,3-Dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl) -4- (dimethylamino) -3-cyclobutene-1 as described in Example 1 , 2-dione (manufactured by MicroCombiChem) (squarylium compound (1)) is converted into 3- (2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)- An image forming material was produced in the same manner as in Example 1 except that 4-phenyl-3-cyclobutene-1,2-dione (manufactured by MicroCombiChem) (squarylium compound (9)) was used. And the exposure sensitivity was measured.
（実施例４）
実施例１に記載の３−（２，３−ジヒドロ−１，５−ジメチル−３−オキソ−２−フェニル−１Ｈ−ピラゾール−４−イル）−４−（ジメチルアミノ）−３−シクロブテン−１，２−ジオン（ＭｉｃｒｏＣｏｍｂｉＣｈｅｍ社製）（スクアリリウム化合物（１））を、３−（２，３−ジヒドロ−１，５−ジエチル−３−オキソ−２−フェニル−１Ｈ−ピラゾール−４−イル）−４−フェニル−３−シクロブテン−１，２−ジオン（ＭｉｃｒｏＣｏｍｂｉＣｈｅｍ社製）（スクアリリウム化合物（１０））に代えた以外は、実施例１と同様にして画像形成材を製造し、分光感度の極大ピークと露光感度を測定した。
Example 4
3- (2,3-Dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl) -4- (dimethylamino) -3-cyclobutene-1 as described in Example 1 , 2-dione (manufactured by MicroCombiChem) (squarylium compound (1)) is converted to 3- (2,3-dihydro-1,5-diethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)- An image forming material was produced in the same manner as in Example 1 except that 4-phenyl-3-cyclobutene-1,2-dione (manufactured by MicroCombiChem) (squarylium compound (10)) was used, and the maximum peak of spectral sensitivity was obtained. And the exposure sensitivity was measured.
表１より、比較例１、２に比べ、実施例１〜４の方が紫外線発光ダイオードに対して優れた感度を有していることがわかる。 From Table 1, it can be seen that Examples 1 to 4 have superior sensitivity to ultraviolet light-emitting diodes as compared to Comparative Examples 1 and 2.
本発明の紫外線硬化樹脂組成物は、液晶表示素子、プラズマディスプレイ、大規模集積回路、薄型トランジスタ、半導体パッケージ、カラーフィルター、有機エレクトロルミネッセンス等に適用できる。 The ultraviolet curable resin composition of the present invention can be applied to liquid crystal display elements, plasma displays, large scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electroluminescence, and the like.
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| WO1994001806A1 (en) * | 1992-07-13 | 1994-01-20 | Kyowa Hakko Kogyo Co., Ltd. | Photopolymerizable composition |
| US5756258A (en) * | 1992-07-13 | 1998-05-26 | Kyowa Hakko Co., Ltd. | Photopolymerizable composition containing an addition polymerizable compound, a radical-producing agent and a squarylium compound |
| JP2006241459A (en) * | 2002-06-10 | 2006-09-14 | Mitsubishi Chemicals Corp | Electronic display-use filter and electronic display unit using the filter |
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| JP2006063034A (en) * | 2004-08-27 | 2006-03-09 | Kyowa Hakko Chemical Co Ltd | Photoelectric conversion material, photoelectric transducer and photoelectrochemical cell |
| JP4817286B2 (en) * | 2005-07-19 | 2011-11-16 | 日本カーリット株式会社 | Metal-containing squarylium compound and optical recording medium using the compound |
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| JP2009138175A (en) * | 2007-11-12 | 2009-06-25 | Kyowa Hakko Chemical Co Ltd | Squarylium compound and photo-polymerizable composition for short-wavelength light source using the same |
| JP5550136B2 (en) * | 2010-03-05 | 2014-07-16 | カーリットホールディングス株式会社 | Photosensitive composition for blue-violet semiconductor laser |
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