JP3945864B2 - New photosensitive resin laminate - Google Patents
New photosensitive resin laminate Download PDFInfo
- Publication number
- JP3945864B2 JP3945864B2 JP20737597A JP20737597A JP3945864B2 JP 3945864 B2 JP3945864 B2 JP 3945864B2 JP 20737597 A JP20737597 A JP 20737597A JP 20737597 A JP20737597 A JP 20737597A JP 3945864 B2 JP3945864 B2 JP 3945864B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- photosensitive resin
- meth
- alkyl
- 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
Links
- 229920005989 resin Polymers 0.000 title claims description 44
- 239000011347 resin Substances 0.000 title claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical group OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 150000003440 styrenes Chemical class 0.000 claims description 5
- 229920006163 vinyl copolymer Polymers 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 19
- 238000005530 etching Methods 0.000 description 18
- -1 lead frames Chemical class 0.000 description 16
- 150000002739 metals Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- SDTXSEXYPROZSZ-UHFFFAOYSA-N 1,2-dibromo-2-methylpropane Chemical compound CC(C)(Br)CBr SDTXSEXYPROZSZ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- AZUXKVXMJOIAOF-UHFFFAOYSA-N 1-(2-hydroxypropoxy)propan-2-ol Chemical group CC(O)COCC(C)O AZUXKVXMJOIAOF-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- FEWDXGMBVQULLN-UHFFFAOYSA-N 1-hydroxy-2-phenyl-1,5,6,7-tetrahydro-4H-benzimidazol-4-one Chemical compound ON1C=2CCCC(=O)C=2N=C1C1=CC=CC=C1 FEWDXGMBVQULLN-UHFFFAOYSA-N 0.000 description 1
- BTUGGGLMQBJCBN-UHFFFAOYSA-N 1-iodo-2-methylpropane Chemical compound CC(C)CI BTUGGGLMQBJCBN-UHFFFAOYSA-N 0.000 description 1
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 description 1
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- LTMPEYZFRFPAMX-UHFFFAOYSA-N 2-(2,4-dichloroanilino)acetic acid Chemical compound OC(=O)CNC1=CC=C(Cl)C=C1Cl LTMPEYZFRFPAMX-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- UIHRWPYOTGCOJP-UHFFFAOYSA-N 2-(2-fluorophenyl)-4,5-diphenyl-1h-imidazole Chemical class FC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 UIHRWPYOTGCOJP-UHFFFAOYSA-N 0.000 description 1
- DRMOCHGNKTXIBF-UHFFFAOYSA-N 2-(2-methoxyanilino)acetic acid Chemical compound COC1=CC=CC=C1NCC(O)=O DRMOCHGNKTXIBF-UHFFFAOYSA-N 0.000 description 1
- XIOGJAPOAUEYJO-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 XIOGJAPOAUEYJO-UHFFFAOYSA-N 0.000 description 1
- DYPOHVRBXIPFIK-UHFFFAOYSA-N 2-(2-methylanilino)acetic acid Chemical compound CC1=CC=CC=C1NCC(O)=O DYPOHVRBXIPFIK-UHFFFAOYSA-N 0.000 description 1
- LGBCEZSPCHBRFQ-UHFFFAOYSA-N 2-(2-nitroanilino)acetic acid Chemical compound OC(=O)CNC1=CC=CC=C1[N+]([O-])=O LGBCEZSPCHBRFQ-UHFFFAOYSA-N 0.000 description 1
- KZXFAYGKDCLTER-UHFFFAOYSA-N 2-(3-chloroanilino)acetic acid Chemical compound OC(=O)CNC1=CC=CC(Cl)=C1 KZXFAYGKDCLTER-UHFFFAOYSA-N 0.000 description 1
- AEXFITBEFOTRCS-UHFFFAOYSA-N 2-(4-acetylanilino)acetic acid Chemical compound CC(=O)C1=CC=C(NCC(O)=O)C=C1 AEXFITBEFOTRCS-UHFFFAOYSA-N 0.000 description 1
- VYFGVOMFCZSJPI-UHFFFAOYSA-N 2-(4-carbamoylanilino)acetic acid Chemical compound NC(=O)C1=CC=C(NCC(O)=O)C=C1 VYFGVOMFCZSJPI-UHFFFAOYSA-N 0.000 description 1
- FWALJUXKWWBNEO-UHFFFAOYSA-N 2-(4-chloroanilino)acetic acid Chemical compound OC(=O)CNC1=CC=C(Cl)C=C1 FWALJUXKWWBNEO-UHFFFAOYSA-N 0.000 description 1
- SNFCQJAJPFWBDJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 SNFCQJAJPFWBDJ-UHFFFAOYSA-N 0.000 description 1
- BUWHNKZFUTUGJW-UHFFFAOYSA-N 2-(4-methoxyphenyl)-5-phenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC=C(C=2C=CC=CC=2)N1 BUWHNKZFUTUGJW-UHFFFAOYSA-N 0.000 description 1
- DVYVBENBIMEAJZ-UHFFFAOYSA-N 2-(n-methylanilino)acetic acid Chemical compound OC(=O)CN(C)C1=CC=CC=C1 DVYVBENBIMEAJZ-UHFFFAOYSA-N 0.000 description 1
- ZXEFJAWHZVPDKS-UHFFFAOYSA-N 2-[(3-cyanophenyl)azaniumyl]acetate Chemical compound OC(=O)CNC1=CC=CC(C#N)=C1 ZXEFJAWHZVPDKS-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- VZMLJEYQUZKERO-UHFFFAOYSA-N 2-hydroxy-1-(2-methylphenyl)-2-phenylethanone Chemical compound CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 VZMLJEYQUZKERO-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
- QISZCVLALJOROC-UHFFFAOYSA-N 3-(2-hydroxyethyl)-4-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OCCC1=C(CCOC(=O)C=C)C=CC(C(O)=O)=C1C(O)=O QISZCVLALJOROC-UHFFFAOYSA-N 0.000 description 1
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- OKJSFKIUVDXFMS-UHFFFAOYSA-N 4-[bis[4-(diethylamino)-2-methylphenyl]methyl]-n,n-diethyl-3-methylaniline Chemical compound CC1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)N(CC)CC)C)C1=CC=C(N(CC)CC)C=C1C OKJSFKIUVDXFMS-UHFFFAOYSA-N 0.000 description 1
- VKDMWMYGKLGAHI-UHFFFAOYSA-N 9-phenoxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC1=CC=CC=C1 VKDMWMYGKLGAHI-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
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は新規な感光性樹脂積層体に関する。更に詳しくはプリント配線板の製造、金属の精密加工等に用いられるエッチングレジスト又はメッキレジストとして耐薬品性に優れる感光性樹脂積層体に関する。
【０００２】
【従来の技術】
プリント配線板の製造やリードフレーム等金属の微細加工に、感光性樹脂積層体を使用することは以前より知られている。これらの製造、加工に於いては、感光性樹脂層を金属表面に支持体と共に熱圧着（ラミネート）させた後、フォトマスクを介して露光し、支持体を剥がして現像して、レジストパターンを得た後に金属をエッチング又はメッキして所望の金属パターンを形成するのが一般的である。
【０００３】
而して、この分野においても近年の電子機器の小型、高性能化に対応した解像度に優れる感光性樹脂組成物が提供されており、それにともなって感光性樹脂組成物の用途が拡大し、４２アロイ材等の銅以外の金属の微細加工へ適用が進むとともに感光性樹脂組成物の金属に対する密着性、耐エッチング性、解像性がますます重要となってきている。
【０００４】
それに応じて、これまでにも感光層を多層化する技術が開発されており、例えば特公昭６０−３２１７３号公報、特公昭６１−３１８５５号公報、特開昭５６−２５７３２号公報、特開昭５８−１３６０２７号公報、特開平０３−１７６５０号公報のような多層化した感光性樹脂積層体が知られている。
また、特開平４−３５３８４９号公報や特開平４−３４０５５１号公報には耐エッチング性を改良する感光性樹脂組成物も提案されている。
【０００５】
【発明が解決しようとする課題】
しかしながら、前者の感光層の多層化によって得られる感光性樹脂積層体は、耐エッチング性が不十分であり、エッチング液がしみ込んで金属が変色するという問題点があった。特に、リードフレーム等金属の微細加工に於いては、４２アロイ材等の銅以外の金属に対する密着性が不十分なためエッチング中にレジストパターンが剥がれるという現象が見られ、これらの感光性樹脂積層体に対して金属に対する良好な密着性と耐エッチング性が求められていたのである。
【０００６】
一方、耐エッチング性を改良することを目的とした後者の技術（特開平４−３５３８４９号公報、特開平４−３４０５５１号公報）によって得られたレジストパターンは、解像度が不十分で、且つ、銅以外の金属に対する密着性が不十分なため、金属の微細加工には適用できなかった。
また、上記技術を組合せ（感光性樹脂層の多層化技術と耐エッチング性改良技術）ても、得られる感光性樹脂積層体の銅以外の金属に対する密着性と耐エッチング性はやはり不十分であった。
【０００７】
本発明は、以上説明した従来技術の問題点を解決し、解像性が優れ、金属に対する密着性がよく、耐エッチング性に優れた感光性樹脂組成物及びこれを用いた感光性樹脂積層体の開発を課題とするものである。
【０００８】
【課題を解決するための手段】
そこで、本発明者らは、上記従来技術の問題点を解決すべく、プリント配線板の製造や金属の微細加工に好適な感光性樹脂積層体について鋭意研究を重ねるなかで、スチレン及びスチレン誘導体の中から選ばれる少なくとも１種の単量体を含むビニル共重合体を用いた感光性樹脂組成物が解像性と密着性が優れること、しかし、該感光性樹脂組成物はまだ支持体との接着性が低く、感光性樹脂層から支持体が剥がれやすいという問題があることを知った。
【０００９】
そこでさらに研究を重ねた結果、その感光性樹脂組組成物の層の他に、スチレン及びスチレン誘導体を含まないビニル共重合体を支持体上の第１の感光性樹脂組成物の層として用いて、２層の感光性樹脂積層体とする事で支持体との接着性が向上し、且つ、解像性と密着性も維持されることを見い出したのである。
しかも、驚くべき事に、上記感光性樹脂組成物に特定のモノマーを含有させることで金属に対する密着性と耐エッチング性が飛躍的に向上することがわかり、解像性、密着性、耐エッチング性に優れた本発明の感光性樹脂積層体を完成することができたのである。
【００１０】
即ち、本発明は、支持体上に第一の感光性樹脂層及び第二の感光性樹脂層を順次積層してなる感光性樹脂積層体であって、
第一の感光性樹脂層が、
（Ａ）α，β−不飽和カルボン酸の中から選ばれる少なくとも１種の単量体と、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミドとその窒素上の水素がアルキル基又はアルコキシ基で置換された化合物、及びメタクリル酸グリシジルの中から選ばれる少なくとも１種の単量体を共重合して得られる重量平均分子量３０，０００から２８０，０００のビニル共重合体、
（Ｂ）下記式（１）で示される分子量が１０００以下の光重合性モノマー、
【００１１】
【化３】
【００１２】
（Ｃ）エチレン性不飽和二重結合を２個以上含有する光重合性モノマー及び、
（Ｄ）光重合開始剤を含有し、
第二の感光性樹脂層が、
（Ｅ）スチレン及びスチレン誘導体の中から選ばれる少なくとも１種の単量体と、α、β−不飽和カルボン酸の中から選ばれる少なくとも１種の単量体と、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミドとその窒素上の水素がアルキル基又はアルコキシ基で置換された化合物、及びメタクリル酸グリシジルの中から選ばれる少なくとも１種の単量体を共重合して得られる重量平均分子量３０，０００から１５０，０００のビニル共重合体、
（Ｆ）下記式（１）で示される分子量が１０００以下の光重合性モノマー、
【００１３】
【化４】
【００１４】
（Ｇ）エチレン性不飽和二重結合を２個以上含有する光重合性モノマー及び、（Ｈ）光重合開始剤
を含有してなる事を特徴とする感光性樹脂積層体が提供するものである。
【００１５】
以下、本発明を詳しく説明する。
本発明の第一の感光性樹脂組成層の（Ａ）成分の共重合に用いられるα，β−不飽和カルボン酸の中から選ばれる少なくとも１種の単量体としてはアクリル酸、メタクリル酸等が挙げられる。
【００１６】
（Ａ）成分の今一つの単量体であるアルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミドとその窒素上の水素がアルキル基又はアルコキシ基で置換された化合物、及びメタクリル酸グリシジルの中から選ばれる少なくとも１種の単量体としては、例えば、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ｎ−プロピルアクリレート、ｎ−プロピルメタクリレート、シクロヘキシルアクリレート、シクロヘキシルメタクリレート、ブチルアクリレート、ブチルメタクリレート、２−エチルヘキシルアクリレート、２−エチルヘキシルメタクリレート等が挙げられる。これらは単独で又は２種以上を組み合わせて用いられる。
【００１７】
（Ａ）成分の含有量は感光性樹脂組成物の全重量基準で５〜９０重量％、好ましくは２０〜８５重量％、より好ましくは４５〜７５重量％である。
（Ａ）成分の使用量が少なすぎると現像性が低下し、多すぎると光感度が低下する。
【００１８】
本発明で用いる（Ｂ）成分は下記式（１）で示される分子量が１０００以下の光重合性モノマーである。
【００１９】
【化５】
【００２０】
Ｒ1 の例としては上記した水素原子、メチル基が挙げられる。
Ｒ2 の例としては、オキシノニル基、エチレンオキシド２単位とプロピレンオキシド５単位の共重合体残基、エチレンオキシド５単位とプロピレンオキシド２単位の共重合体残基、カルボン酸エチルエステル基、カルボン酸−２−ヒドロキシプロピルエステル基、２−ヒドロキシプロピルオキシ基、ネオペンチルグリコール基が挙げられる。
Ｒ3 の例としては、水素原子、臭素原子、ノニル基、カルボン酸−２−ヒドロキシエチルエステル基が挙げられる。
【００２１】
そして（Ｂ）成分の例としては、フェノキシノニルアクリレート（Ｒ1 ：水素原子、Ｒ2 ：オキシノニル基、Ｒ3 ：水素原子）、２−ヒドロキシ−３−フェノキシプロピルアクリレート（Ｒ1 ：水素原子、Ｒ2 ：２−ヒドロキシプロピルオキシド基、Ｒ3 ：水素原子）、アクリロイルオキシエチル−２−ヒドロキシプロピルフタレート（Ｒ1 ：水素原子、Ｒ2 ：カルボン酸エチルエステル基、Ｒ3 ：カルボン酸２−ヒドロキシプロピルエステル基）、ディスパノールＬＳ−１００Ａ（Ｒ1 ：水素原子、Ｒ2 ：エチレンオキシド２単位とプロピレンオキシド５単位の共重合体残基、Ｒ3 ：ノニル基）、２−アクリロイルオキシエチル−２−ヒドロキシ エチルフタル酸（Ｒ1 ：水素原子、Ｒ2 ：カルボン酸エチルエステル基、Ｒ3 ：カルボン酸−２−ヒドロキシエチルエステル基）等が挙げられる。
【００２２】
（Ｂ）成分の含有量は感光性樹脂組成物の全重量基準で３〜３０重量％、好ましくは５〜３０重量％、より好ましくは５〜２０重量％である。
（Ｂ）成分の含有量が３重量％未満である場合には耐エッチング性が不足し、３０重量％を越える場合には光重合した感光性樹脂組成物から得られるレジストパターンの硬化が不足する。
【００２３】
本発明で用いる（Ｃ）及び（Ｇ）成分としては、分子内にエチレン性不飽和二重結合を２個以上含有する公知の光重合性モノマーを用いることができる。その例としては、ポリオールのアクリル酸もしくはメタクリル酸エステル、ポリアミンより得られるアクリルアミド類、ウレタン基を含有する化合物、ポリオールとジイソシアネートとを反応させて得られる化合物に更にβ−ヒドロキシアルキル（メタ）アクリレートを反応させて得られるアクリルウレタンオリゴマー、ビスフェノールＡから変性誘導されたアクリル酸もしくはメタクリル酸エステル類等の内エチレン性不飽和二重結合を２個以上含有する物を用いることができる。
（Ｃ）及び（Ｇ）成分の含有量はそれぞれ感光性樹脂組成物の全重量基準で５〜６０重量％、好ましくは５〜５０重量％、より好ましくは１０〜３５重量％である。
【００２４】
本発明で用いられる光重合性モノマー（Ｂ）及び（Ｃ）成分の全含有量は感光性樹脂組成物の全重量基準で８〜９０重量％、好ましくは１０〜８０重量％、より好ましくは１５〜５５重量％である。この使用量が少なすぎると耐現像液性が低下し、多すぎると感光性樹脂組成物としての粘度が低下し、感光性樹脂積層体としてロール状に巻いたときに感光性樹脂組成層がはみ出し接着する（エッジフュージョン現象）。
【００２５】
本発明で用いる（Ｄ）及び（Ｈ）成分の光重合開始剤は、特に限定されるものでなく、公知の光重合開始剤を用いることができる。好ましい例として、ベンゾフェノン、アンスラキノン、ミヒラーズケトン、４−メトキシ−４’−ジメチルアミノベンゾフェノン、２−エチルアントラキノン等の芳香族ケトン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテルなどのベンゾインエーテル、メチルベンゾイン、エチルベンゾインなどのベンゾイン、ベンジルジメチルケタールなどのベンジル誘導体、
【００２６】
２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−５−フェニルイミダゾール二量体、２−（ｐ−メチルメルカプトフェニル）−４，５−ジフェニルイミダゾール二量体等の２，４，５−トリアリールイミダゾール二量体等のイミダゾール二量体、９−フェニルアクリジン、１，７−ビス（９，９’−アクリジニル）ヘプタン等のアクリジン誘導体、
【００２７】
Ｎ−フェニルグリシン、Ｎ−（３−クロロフェニル）グリシン、Ｎ−（２，４−ジクロルフェニル）グリシン、Ｎ−（２−ニトロフェニル）グリシン、Ｎ−（４−アセチルフェニル）グリシン、Ｎ−（４−ニトロフェニリル）グリシン、Ｎ−（４−シアノフェニリル）グリシン、Ｎ−（４−クロロフェニル）グリシン、Ｎ−（２−メチルフェニル）グリシン、Ｎ−（２−メトキシフェニル）グリシン、Ｎ−メチル−Ｎ−フェニルグリシン、Ｎ−（３−シアノフェニル）グリシン、Ｎ−（４−カルバモイルフェニル）グリシン、Ｎ−（４−スルファモイルフェニル）グリシン等のフェニルグリシン誘導体、ジアゾニウム化合物、クロルチオキサントン等のチオキサントン誘導体等を使用することができる。
【００２８】
（Ｄ）及び（Ｈ）成分の含有量はそれぞれ感光性樹脂組成物の全重量基準で、０．０１〜３０重量％、好ましくは０．０１〜２０重量％、より好ましくは０．０５〜１５重量％である。この使用量が少なすぎると、十分な光感度が得られない傾向があり、多すぎると露光の際に感光性樹脂組成の表面での光吸収が増加して内部の光硬化が不足する傾向がある。
【００２９】
本発明の第二の感光性樹脂組成層の（Ｅ）成分の共重合体に用いられるスチレン及びスチレン誘導体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−エチルスチレン、ｐ−メトキシスチレン、ｐ−エトキシスチレン、ｐ−クロロスチレン、ｐ−ブロモスチレン等を挙げることができ、スチレンが好ましく用いられる。スチレン及びスチレン誘導体の含有率は５〜３０％が好ましい。５％より低いと解像性が悪化し、３０％より多いと現像に要する時間がいちじるしく長くなる。
【００３０】
α，β−不飽和カルボン酸の中から選ばれる単量体としてはアクリル酸、メタクリル酸等が挙げられる。
アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミドとその窒素上の水素がアルキル基又はアルコキシ基で置換された化合物、及びメタクリル酸グリシジルの中から選ばれる少なくとも１種の単量体としては、例えば、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ｎ−プロピルアクリレート、ｎ−プロピルメタクリレート、シクロヘキシルアクリレート、シクロヘキシルメタクリレート、ブチルアクリレート、ブチルメタクリレート、２−エチルヘキシルアクリレート、２−エチルヘキシルメタクリレートが挙げられ、これらビニル単量体は任意に用いることがでる。
上記（Ｅ）成分のビニル共重合体の含有量は感光性樹脂組成物の全重量基準で、５〜９０重量％、好ましくは２０〜８５重量％、より好ましくは４５〜７５重量％である。
【００３１】
本発明に用いられる（Ｆ）成分は、上記した（Ｂ）成分と同じ光重合性モノマーが用いられる。（Ｆ）成分の含有量は感光性樹脂組成物の全重量基準で３〜３０重量％、好ましくは５〜３０重量％、より好ましくは５〜２０重量％である。本発明で用いられる光重合性モノマー（Ｆ）及び（Ｇ）成分の全含有量は感光性樹脂組成物の全重量基準で８〜９０重量％、好ましくは１０〜８０重量％、より好ましくは１５〜５５重量％である。
【００３２】
本発明で用いる感光性樹脂組成物には、染料、顔料などの着色物質を含有させても良い。例えば、フクシン、オーラミン塩基、カルコキシドグリーンＳ、パラマジェンタ、クリスタルバイオレット、メチルオレンジ、ナイルブルー２Ｂ、ビクトリアブルー、マラカイトグリーン、ベイシックブルー２０、ダイヤモンドグリーンなどを用いることができる。
【００３３】
本発明で用いる感光性樹脂組成物には、光硬化部分を未硬化部分と区別するために、光照射により発色する発色系染料を含有させても良い。発色系染料としては、ロイコ染料とハロゲン化合物の組み合わせが良く知られている。ロイコ染料としては、例えばトリス（４−ジメチルアミノ−２−メチルフェニル）、トリス（４−ジエチルアミノ−２−メチルフェニル）メタン等が挙げられる。ハロゲン化合物としては、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンザル、臭化メチレン、トリブロモメチルフェニルスルフォン、４臭化炭素、トリス（２，３−ジブロモプロピル）ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、１，１，１−トリクロロ−２，２−ビス（ｐ−クロロフェニル）エタン、ヘキサクロロエタン等が挙げられる。
【００３４】
本発明で用いる感光性樹脂組成物には、必要に応じてラジカル重合禁止剤を含有させ、熱安定性、保存安定性を向上、調節することができる。ラジカル重合禁止剤の例としてはハイドロキノン、ｐ−メトキシフェノール、ｔ−ブチルカテコール、ピロガロール、ピクリン酸、ｐ−トルイジン、ニトロソフェニルヒドロキシアミンアルミニウム塩等が挙げられる。
【００３５】
また、本発明で用いる感光性樹脂組成物には必要に応じて可塑剤などの添加剤を含有することができる。このような添加剤としては、例えばジエチルフタレート等のフタル酸エステル類、ｏ−トルエンスルホン酸アミド、ｐ−トルエンスルホン酸アミド、クエン酸トリブチル、クエン酸トリエチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ−ｎ−プロピル、アセチルクエン酸トリ−ｎ−ブチル、ポリプロピレングリコール等が挙げられる。
【００３６】
本発明で用いる感光性樹脂組成物は、組成の各成分を、これらを溶解する溶剤、例えば、トルエン、アセトン、メチルエチルケトン、メチルイソブチルケトン、クロロホルム、塩化メチレン、メチルアルコール、エチルアルコール等に溶解、混合させることにより均一な溶液とすることができる。
【００３７】
本発明の感光性樹脂積層体に用いられる支持体としては、ポリエチレン、ポリプロピレン、ポリ酢酸ビニル、ポリ塩化ビニル、ポリエチレンテレフタレート、ポリビニルアルコール、ポリ塩化ビニリデン、ポリメタクリル酸メチル、ポリスチレン、ポリアクリロニトリル、スチレン共重合体、ポリアミド、セルロース誘導体等のフィルムを使用することができる。
【００３８】
本発明に於いて、感光性樹脂層の塗設は従来から採用されている方法で行うことができる。例えば、前述の溶剤を用いて溶液とした第一の感光性樹脂層を支持体上に塗布、乾燥後、第二の感光性樹脂層の溶液を塗布、乾燥して塗設することができる。また、Ｔダイ、キスディッピング等により連続して塗設することもできる。
【００３９】
【発明の実施の形態】
以下、実施例を挙げて本発明の実施の形態を説明するが、本発明はこれら実施例により限定されない。
＜感光性樹脂組成物の調製＞
表１に示す成分を用いて、表２〜４に示す配合（単位はグラム）で感光性樹脂組成物の溶液を調製した。なお、表２〜４に示す組成成分の略号は、表１に示す通りのものを表わしている。
【００４０】
【実施例】
実施例１〜８及び比較例１〜３
＜感光性樹脂積層体＞
第一の感光性樹脂組成物の溶液を２０μｍ厚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、対流式乾燥機で８０℃にて約３分間乾燥させ、厚み３μｍの第一の感光性樹脂組成物からなる感光性樹脂積層体を得た。次に、第二の感光性樹脂組成物の溶液を上記積層体の感光性樹脂層面に均一に塗布し、１００℃で約３分間乾燥させて感光性樹脂層を形成、二層合わせて厚み３０μｍの第一及び第二の感光性樹脂層からなる感光性樹脂積層体を得た。
【００４１】
比較例４、５
感光性樹脂組成物の溶液を２０μｍ厚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℃で約３分間乾燥させて感光性樹脂層を形成し、厚み３０μｍの感光性樹脂層からなる感光性樹脂積層体を得た。
【００４２】
＜解像性＞
厚み２００μｍの４２アロイ基板（日立金属（株）製）を１％苛性ソーダ水溶液に１分間浸漬し、水洗、送風乾燥し得られた基板を６０℃に加温し、この金属表面に前記感光性樹脂積層体をホットロールラミネーター（旭化成工業（株）製）を用いて１２０℃に加熱しながらラミネートした。次に、高圧水銀灯ランプを有する露光機（オーク（株）製）ＨＭＷ−２０１ＫＢを用いてライン：スペース＝１：１ライン幅２０〜１００μｍのネガマスクパターンを支持体であるポリエチレンテレフタレートフィルム上に置き、このフィルムを介して８０ｍＪ／ｃｍ2 で露光した。次にポリエチレンテレフタレートフィルムを剥離し、３０℃１重量％炭酸ナトリウム水溶液を６０秒間スプレーすることにより、未露光部分を除去し解像性を観察した。結果を表５、６にまとめた。
【００４３】
＜耐エッチング性＞
上記と同様にして、ライン＆スペース５０μｍのネガマスクパターンを用いて露光、現像した後、スプレーエッチング装置（東京加工機（株）製）により、塩化第二鉄水溶液（液の比重４７ボーメ、塩酸濃度０．２％、温度５０℃）をスプレー圧力２．０ｋｇ／ｃｍ2 で１０分間スプレー、エッチングし、レジストパターンの剥がれを観察した。その後、レジストを剥離し金属ラインの表面状態を観察した。結果を表５、６にまとめた。
【００４４】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
上記表５、表６中の＊、＊＊、＊＊＊の意味は次の通りである。
＊市販の引っ張り試験機を用いて支持体を感光性樹脂層から剥離する時の１８０度ピール強度を測定した。
【発明の効果】
本発明の感光性樹脂積層体は感光性樹脂層を多層化し特定のモノマーを含有させる事で、解像性、金属面への密着性、耐エッチング性に優れ、プリント配線板の製造、リードフレーム等金属の微細加工等に極めて好適に用いる事ができるという効果を有している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel photosensitive resin laminate. More specifically, the present invention relates to a photosensitive resin laminate excellent in chemical resistance as an etching resist or a plating resist used in the production of printed wiring boards, precision metal processing, and the like.
[0002]
[Prior art]
It has long been known to use a photosensitive resin laminate for the production of printed wiring boards and fine processing of metals such as lead frames. In these manufacturing and processing, after the photosensitive resin layer is thermocompression bonded (laminated) with a support on a metal surface, it is exposed through a photomask, and the support is peeled off and developed to form a resist pattern. After being obtained, the metal is generally etched or plated to form a desired metal pattern.
[0003]
Thus, also in this field, a photosensitive resin composition excellent in resolution corresponding to the recent downsizing and high performance of electronic devices has been provided, and the use of the photosensitive resin composition has been expanded accordingly. As application to fine processing of metals other than copper such as alloy materials progresses, adhesion, etching resistance, and resolution of photosensitive resin compositions to metals are becoming increasingly important.
[0004]
Accordingly, techniques for multilayering photosensitive layers have been developed so far, for example, Japanese Patent Publication No. 60-32173, Japanese Patent Publication No. 61-31855, Japanese Patent Publication No. 56-25732, Japanese Unexamined Patent Publication No. Sho-05. There are known multilayered photosensitive resin laminates such as 58-136027 and JP 03-17650.
JP-A-4-353849 and JP-A-4-340551 also propose a photosensitive resin composition that improves etching resistance.
[0005]
[Problems to be solved by the invention]
However, the photosensitive resin laminate obtained by multilayering the former photosensitive layer has a problem that etching resistance is insufficient and the etching solution penetrates and the metal is discolored. In particular, in the fine processing of metals such as lead frames, there is a phenomenon that the resist pattern is peeled off during etching due to insufficient adhesion to metals other than copper such as 42 alloy material. There was a demand for good adhesion to metal and etching resistance to the body.
[0006]
On the other hand, the resist pattern obtained by the latter technique (JP-A-4-353549, JP-A-4-340551) for improving the etching resistance has insufficient resolution and copper. Due to insufficient adhesion to other metals, it could not be applied to fine metal processing.
In addition, even when the above technologies are combined (photosensitive resin layer multilayering technology and etching resistance improvement technology), the adhesion and etching resistance of the resulting photosensitive resin laminate to metals other than copper are still insufficient. It was.
[0007]
The present invention solves the problems of the prior art described above, has excellent resolution, good adhesion to metals, and has excellent etching resistance, and a photosensitive resin laminate using the same Development is a challenge.
[0008]
[Means for Solving the Problems]
Therefore, in order to solve the above-mentioned problems of the prior art, the present inventors have conducted intensive research on photosensitive resin laminates suitable for the production of printed wiring boards and metal microfabrication. A photosensitive resin composition using a vinyl copolymer containing at least one monomer selected from among them has excellent resolution and adhesion, but the photosensitive resin composition is still in contact with the support. It has been found that there is a problem that the adhesiveness is low and the support is easily peeled off from the photosensitive resin layer.
[0009]
Therefore, as a result of further research, in addition to the photosensitive resin assembly layer, a vinyl copolymer containing no styrene and styrene derivative was used as the first photosensitive resin composition layer on the support. It has been found that by using a two-layer photosensitive resin laminate, the adhesion to the support is improved, and the resolution and adhesion are maintained.
Moreover, surprisingly, it can be seen that the adhesion to metal and the etching resistance are drastically improved by adding a specific monomer to the photosensitive resin composition, and the resolution, adhesion, and etching resistance are improved. The photosensitive resin laminate of the present invention that was excellent in the quality of the present invention could be completed.
[0010]
That is, the present invention is a photosensitive resin laminate obtained by sequentially laminating a first photosensitive resin layer and a second photosensitive resin layer on a support,
The first photosensitive resin layer
(A) at least one monomer selected from α, β-unsaturated carboxylic acids, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and nitrogen thereof Vinyl having a weight average molecular weight of 30,000 to 280,000 obtained by copolymerizing a compound in which the above hydrogen is substituted with an alkyl group or an alkoxy group, and at least one monomer selected from glycidyl methacrylate Copolymer,
(B) a photopolymerizable monomer having a molecular weight of 1000 or less represented by the following formula (1),
[0011]
[Chemical 3]
[0012]
(C) a photopolymerizable monomer containing two or more ethylenically unsaturated double bonds, and
(D) contains a photopolymerization initiator,
The second photosensitive resin layer is
(E) at least one monomer selected from styrene and styrene derivatives, at least one monomer selected from α, β-unsaturated carboxylic acids, alkyl (meth) acrylate, hydroxy At least one monomer selected from alkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and a compound in which hydrogen on the nitrogen is substituted with an alkyl group or an alkoxy group, and glycidyl methacrylate. A vinyl copolymer having a weight average molecular weight of 30,000 to 150,000 obtained by copolymerization;
(F) a photopolymerizable monomer having a molecular weight of 1000 or less represented by the following formula (1),
[0013]
[Formula 4]
[0014]
A photosensitive resin laminate comprising (G) a photopolymerizable monomer containing two or more ethylenically unsaturated double bonds and (H) a photopolymerization initiator is provided. .
[0015]
Hereinafter, the present invention will be described in detail.
As at least one monomer selected from α, β-unsaturated carboxylic acids used for copolymerization of the component (A) of the first photosensitive resin composition layer of the present invention, acrylic acid, methacrylic acid, etc. Is mentioned.
[0016]
Alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and hydrogen on the nitrogen, which are the other monomers of component (A), are substituted with alkyl groups or alkoxy groups. Examples of the compound and at least one monomer selected from glycidyl methacrylate include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. Butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and the like. These may be used alone or in combination of two or more.
[0017]
The content of the component (A) is 5 to 90% by weight, preferably 20 to 85% by weight, more preferably 45 to 75% by weight, based on the total weight of the photosensitive resin composition.
When the amount of the component (A) is too small, the developability is lowered, and when too large, the photosensitivity is lowered.
[0018]
The component (B) used in the present invention is a photopolymerizable monomer having a molecular weight of 1000 or less represented by the following formula (1).
[0019]
[Chemical formula 5]
[0020]
Examples of R 1 include the above-described hydrogen atom and methyl group.
Examples of R 2 include oxynonyl group, copolymer residue of 2 units of ethylene oxide and 5 units of propylene, copolymer residue of 5 units of ethylene oxide and 2 units of propylene oxide, ethyl ester group of carboxylic acid, carboxylic acid-2 -Hydroxypropyl ester group, 2-hydroxypropyloxy group, neopentyl glycol group are mentioned.
Examples of R 3 include a hydrogen atom, a bromine atom, a nonyl group, and a carboxylic acid-2-hydroxyethyl ester group.
[0021]
Examples of the component (B) include phenoxynonyl acrylate (R 1 : hydrogen atom, R 2 : oxynonyl group, R 3 : hydrogen atom), 2-hydroxy-3-phenoxypropyl acrylate (R 1 : hydrogen atom, R 2 : 2-hydroxypropyl oxide group, R 3 : hydrogen atom), acryloyloxyethyl-2-hydroxypropyl phthalate (R 1 : hydrogen atom, R 2 : carboxylic acid ethyl ester group, R 3 : 2-hydroxypropyl carboxylate) Ester group), dispanol LS-100A (R 1 : hydrogen atom, R 2 : copolymer residue of 2 units of ethylene oxide and 5 units of propylene oxide, R 3 : nonyl group), 2-acryloyloxyethyl-2-hydroxy Ethylphthalic acid (R 1 : hydrogen atom, R 2 : carboxylic acid ethyl ester group, R 3 : carboxylic acid- 2-hydroxyethyl ester group) and the like.
[0022]
The content of the component (B) is 3 to 30% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight based on the total weight of the photosensitive resin composition.
When the content of the component (B) is less than 3% by weight, the etching resistance is insufficient, and when it exceeds 30% by weight, the resist pattern obtained from the photopolymerized photosensitive resin composition is insufficiently cured. .
[0023]
As (C) and (G) component used by this invention, the well-known photopolymerizable monomer which contains two or more ethylenically unsaturated double bonds in a molecule | numerator can be used. For example, acrylic acid or methacrylic acid ester of polyol, acrylamide obtained from polyamine, compound containing urethane group, compound obtained by reacting polyol and diisocyanate, and β-hydroxyalkyl (meth) acrylate are further added. An acrylic urethane oligomer obtained by the reaction, or a substance containing two or more ethylenically unsaturated double bonds such as acrylic acid or methacrylic acid ester modified from bisphenol A can be used.
Content of (C) and (G) component is 5-60 weight% on the basis of the total weight of the photosensitive resin composition, respectively, Preferably it is 5-50 weight%, More preferably, it is 10-35 weight%.
[0024]
The total content of the photopolymerizable monomers (B) and (C) used in the present invention is 8 to 90% by weight, preferably 10 to 80% by weight, more preferably 15 based on the total weight of the photosensitive resin composition. ~ 55% by weight. If the amount used is too small, the developer resistance decreases, and if it is too large, the viscosity as the photosensitive resin composition decreases, and the photosensitive resin composition layer protrudes when rolled into a roll as the photosensitive resin laminate. Adhere (edge fusion phenomenon).
[0025]
The photopolymerization initiators (D) and (H) used in the present invention are not particularly limited, and known photopolymerization initiators can be used. Preferred examples include aromatic ketones such as benzophenone, anthraquinone, Michler's ketone, 4-methoxy-4'-dimethylaminobenzophenone and 2-ethylanthraquinone, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, methyl benzoin , Benzoins such as ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal,
[0026]
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (p-methylmercaptophenyl) ) -4,5-diphenylimidazole dimer and other 2,4,5-triarylimidazole dimer and other imidazole dimers, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) Acridine derivatives such as heptane,
[0027]
N-phenylglycine, N- (3-chlorophenyl) glycine, N- (2,4-dichlorophenyl) glycine, N- (2-nitrophenyl) glycine, N- (4-acetylphenyl) glycine, N- ( 4-nitrophenylyl) glycine, N- (4-cyanophenylyl) glycine, N- (4-chlorophenyl) glycine, N- (2-methylphenyl) glycine, N- (2-methoxyphenyl) glycine, N- Phenylglycine derivatives such as methyl-N-phenylglycine, N- (3-cyanophenyl) glycine, N- (4-carbamoylphenyl) glycine, N- (4-sulfamoylphenyl) glycine, diazonium compounds, chlorothioxanthone, etc. Thioxanthone derivatives of the above can be used.
[0028]
The contents of the components (D) and (H) are each 0.01 to 30% by weight, preferably 0.01 to 20% by weight, more preferably 0.05 to 15%, based on the total weight of the photosensitive resin composition. % By weight. If the amount used is too small, there is a tendency that sufficient photosensitivity cannot be obtained, and if it is too large, light absorption on the surface of the photosensitive resin composition increases during exposure and the internal photocuring tends to be insufficient. is there.
[0029]
Examples of styrene and styrene derivatives used in the copolymer of component (E) of the second photosensitive resin composition layer of the present invention include styrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxy. Examples thereof include styrene, p-ethoxystyrene, p-chlorostyrene, p-bromostyrene, and styrene is preferably used. The content of styrene and styrene derivatives is preferably 5 to 30%. If it is lower than 5%, the resolution deteriorates, and if it exceeds 30%, the time required for development becomes extremely long.
[0030]
Examples of the monomer selected from α, β-unsaturated carboxylic acids include acrylic acid and methacrylic acid.
Alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and a compound in which hydrogen on nitrogen is substituted with an alkyl group or an alkoxy group, and at least selected from glycidyl methacrylate As one kind of monomer, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate is mentioned, and these vinyl monomers can be used arbitrarily.
The content of the vinyl copolymer as the component (E) is 5 to 90% by weight, preferably 20 to 85% by weight, more preferably 45 to 75% by weight, based on the total weight of the photosensitive resin composition.
[0031]
The component (F) used in the present invention is the same photopolymerizable monomer as the component (B) described above. The content of the component (F) is 3 to 30% by weight, preferably 5 to 30% by weight, and more preferably 5 to 20% by weight based on the total weight of the photosensitive resin composition. The total content of the photopolymerizable monomers (F) and (G) used in the present invention is 8 to 90% by weight, preferably 10 to 80% by weight, more preferably 15 based on the total weight of the photosensitive resin composition. ~ 55% by weight.
[0032]
The photosensitive resin composition used in the present invention may contain coloring substances such as dyes and pigments. For example, fuchsin, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green and the like can be used.
[0033]
In order to distinguish the photocured part from the uncured part, the photosensitive resin composition used in the present invention may contain a coloring dye that develops color by light irradiation. A combination of a leuco dye and a halogen compound is well known as a coloring dye. Examples of leuco dyes include tris (4-dimethylamino-2-methylphenyl) and tris (4-diethylamino-2-methylphenyl) methane. Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3 -Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane and the like.
[0034]
The photosensitive resin composition used in the present invention can contain a radical polymerization inhibitor as required, and the thermal stability and storage stability can be improved and adjusted. Examples of the radical polymerization inhibitor include hydroquinone, p-methoxyphenol, t-butylcatechol, pyrogallol, picric acid, p-toluidine, nitrosophenylhydroxyamine aluminum salt and the like.
[0035]
Moreover, the photosensitive resin composition used by this invention can contain additives, such as a plasticizer, as needed. Examples of such additives include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples include n-propyl, tri-n-butyl acetylcitrate, and polypropylene glycol.
[0036]
The photosensitive resin composition used in the present invention dissolves and mixes each component of the composition in a solvent for dissolving them, such as toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, methylene chloride, methyl alcohol, ethyl alcohol, and the like. By making it, it can be set as a uniform solution.
[0037]
Supports used in the photosensitive resin laminate of the present invention include polyethylene, polypropylene, polyvinyl acetate, polyvinyl chloride, polyethylene terephthalate, polyvinyl alcohol, polyvinylidene chloride, polymethyl methacrylate, polystyrene, polyacrylonitrile, and styrene. Films of polymers, polyamides, cellulose derivatives, etc. can be used.
[0038]
In the present invention, the coating of the photosensitive resin layer can be performed by a conventionally employed method. For example, the first photosensitive resin layer formed as a solution using the above-mentioned solvent can be applied on the support and dried, and then the second photosensitive resin layer solution can be applied and dried. Moreover, it can also coat continuously by T die | dye, kiss dipping, etc.
[0039]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Hereinafter, although an Example is given and embodiment of this invention is described, this invention is not limited by these Examples.
<Preparation of photosensitive resin composition>
Using the components shown in Table 1, photosensitive resin composition solutions were prepared with the formulations shown in Tables 2 to 4 (unit: grams). In addition, the symbol of the composition component shown in Tables 2-4 represents the thing as shown in Table 1.
[0040]
【Example】
Examples 1-8 and Comparative Examples 1-3
<Photosensitive resin laminate>
The first photosensitive resin composition solution is uniformly coated on a 20 μm-thick polyethylene terephthalate film and dried at 80 ° C. for about 3 minutes by a convection dryer, and the first photosensitive resin composition having a thickness of 3 μm. The photosensitive resin laminated body which consists of was obtained. Next, a solution of the second photosensitive resin composition is uniformly applied to the photosensitive resin layer surface of the laminate, and dried at 100 ° C. for about 3 minutes to form a photosensitive resin layer. The two layers are combined, and the thickness is 30 μm. A photosensitive resin laminate comprising the first and second photosensitive resin layers was obtained.
[0041]
Comparative Examples 4 and 5
The photosensitive resin composition solution is uniformly coated on a 20 μm thick polyethylene terephthalate film, dried at 100 ° C. for about 3 minutes to form a photosensitive resin layer, and a photosensitive resin comprising a photosensitive resin layer having a thickness of 30 μm. A laminate was obtained.
[0042]
<Resolution>
A 42 alloy substrate (manufactured by Hitachi Metals Co., Ltd.) having a thickness of 200 μm was immersed in a 1% aqueous solution of caustic soda for 1 minute, washed with water and dried by blowing air, and the substrate was heated to 60 ° C. The laminate was laminated while being heated to 120 ° C. using a hot roll laminator (manufactured by Asahi Kasei Corporation). Next, a negative mask pattern with a line: space = 1: 1 line width of 20 to 100 μm is placed on a polyethylene terephthalate film as a support using an exposure machine (manufactured by Oak Co., Ltd.) HMW-201KB having a high-pressure mercury lamp. The film was exposed at 80 mJ / cm 2 through this film. Next, the polyethylene terephthalate film was peeled off, and an unexposed portion was removed and the resolution was observed by spraying a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 60 seconds. The results are summarized in Tables 5 and 6.
[0043]
<Etching resistance>
In the same manner as described above, after exposure and development using a negative mask pattern with a line and space of 50 μm, an aqueous ferric chloride solution (specific gravity of 47 baume of liquid, hydrochloric acid) was applied by a spray etching apparatus (manufactured by Tokyo Processing Machine Co., Ltd.). The resist pattern peeling was observed by spraying and etching at a spray pressure of 2.0 kg / cm 2 for 10 minutes. Then, the resist was peeled and the surface state of the metal line was observed. The results are summarized in Tables 5 and 6.
[0044]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
The meanings of *, **, and *** in Tables 5 and 6 are as follows.
* 180 degree peel strength was measured when the support was peeled from the photosensitive resin layer using a commercially available tensile tester.
【The invention's effect】
The photosensitive resin laminate of the present invention has a multi-layered photosensitive resin layer and contains a specific monomer, so that it has excellent resolution, adhesion to a metal surface, and etching resistance. It has the effect that it can be used very suitably for the fine processing of metals, etc.
Claims (1)
第一の感光性樹脂層が、
（Ａ）α，β−不飽和カルボン酸の中から選ばれる少なくとも１種の単量体と、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミドとその窒素上の水素がアルキル基又はアルコキシ基で置換された化合物、及びメタクリル酸グリシジルの中から選ばれる少なくとも１種の単量体を共重合して得られる重量平均分子量３０，０００から２８０，０００のビニル共重合体、
（Ｂ）下記式（１）で示される分子量が１０００以下の光重合性モノマー、
（Ｃ）エチレン性不飽和二重結合を２個以上含有する光重合性モノマー及び、
（Ｄ）光重合開始剤を含有し、
第二の感光性樹脂層が、
（Ｅ）スチレン及びスチレン誘導体の中から選ばれる少なくとも１種の単量体と、α，β−不飽和カルボン酸の中から選ばれる少なくとも１種の単量体と、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミドとその窒素上の水素がアルキル基又はアルコキシ基で置換された化合物、及びメタクリル酸グリシジルの中から選ばれる少なくとも１種の単量体を共重合して得られる重量平均分子量３０，０００から１５０，０００のビニル共重合体、
（Ｆ）下記式（１）で示される分子量が１０００以下の光重合性モノマー、
（Ｇ）エチレン性不飽和二重結合を２個以上含有する光重合性モノマー及び、
（Ｈ）光重合開始剤
を含有してなる事を特徴とする感光性樹脂積層体。A photosensitive resin laminate in which a first photosensitive resin layer and a second photosensitive resin layer are sequentially laminated on a support,
The first photosensitive resin layer
(A) At least one monomer selected from α, β-unsaturated carboxylic acid, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and nitrogen thereof Vinyl having a weight average molecular weight of 30,000 to 280,000 obtained by copolymerizing a compound in which the above hydrogen is substituted with an alkyl group or an alkoxy group, and at least one monomer selected from glycidyl methacrylate Copolymer,
(B) a photopolymerizable monomer having a molecular weight of 1000 or less represented by the following formula (1),
(C) a photopolymerizable monomer containing two or more ethylenically unsaturated double bonds, and
(D) contains a photopolymerization initiator,
The second photosensitive resin layer is
(E) at least one monomer selected from styrene and styrene derivatives, at least one monomer selected from α, β-unsaturated carboxylic acids, alkyl (meth) acrylate, hydroxy At least one monomer selected from alkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and a compound in which hydrogen on the nitrogen is substituted with an alkyl group or an alkoxy group, and glycidyl methacrylate. A vinyl copolymer having a weight average molecular weight of 30,000 to 150,000 obtained by copolymerization;
(F) a photopolymerizable monomer having a molecular weight of 1000 or less represented by the following formula (1),
(G) a photopolymerizable monomer containing two or more ethylenically unsaturated double bonds, and
(H) A photosensitive resin laminate comprising a photopolymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20737597A JP3945864B2 (en) | 1996-07-31 | 1997-07-17 | New photosensitive resin laminate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21686296 | 1996-07-31 | ||
| JP8-216862 | 1996-07-31 | ||
| JP20737597A JP3945864B2 (en) | 1996-07-31 | 1997-07-17 | New photosensitive resin laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10111573A JPH10111573A (en) | 1998-04-28 |
| JP3945864B2 true JP3945864B2 (en) | 2007-07-18 |
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| JP20737597A Expired - Fee Related JP3945864B2 (en) | 1996-07-31 | 1997-07-17 | New photosensitive resin laminate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1489460A3 (en) * | 2003-06-20 | 2008-07-09 | FUJIFILM Corporation | Light-sensitive sheet comprising support, first light-sensitive layer and second light-sensitive layer |
| US7288345B2 (en) | 2005-03-31 | 2007-10-30 | Toyo Ink Mfg. Co., Ltd. | Photosensitive colored composition and color filter |
| JP6225053B2 (en) | 2014-03-20 | 2017-11-01 | 富士フイルム株式会社 | Photosensitive laminate, transfer material, patterned photosensitive laminate and method for producing the same, touch panel, and image display device |
| CN112770907A (en) * | 2018-09-28 | 2021-05-07 | 富士胶片株式会社 | Laminate, method for manufacturing laminate, and capacitance-type input device |
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| JPH10111573A (en) | 1998-04-28 |
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