JPH03221956A - Photosensitive resin composition and laminate using same - Google Patents
Photosensitive resin composition and laminate using sameInfo
- Publication number
- JPH03221956A JPH03221956A JP1850690A JP1850690A JPH03221956A JP H03221956 A JPH03221956 A JP H03221956A JP 1850690 A JP1850690 A JP 1850690A JP 1850690 A JP1850690 A JP 1850690A JP H03221956 A JPH03221956 A JP H03221956A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- monomer
- resin composition
- binder
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 31
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 125000004429 atom Chemical group 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 27
- 239000003513 alkali Substances 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 abstract description 4
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- -1 ethylhexyl Chemical group 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000000034 method Methods 0.000 description 8
- 206010034972 Photosensitivity reaction Diseases 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000036211 photosensitivity Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920006027 ternary co-polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000018109 developmental process 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
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 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
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- 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
- RXAYEPUDXSKVHS-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(3-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC(C2=C(NC(=N2)C=2C(=CC=CC=2)Cl)C=2C=C(OC)C=CC=2)=C1 RXAYEPUDXSKVHS-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 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
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-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
- 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
- HXARQZVREPYHOX-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOc1ccccc1.C=CC(=O)OCCOc1ccccc1 HXARQZVREPYHOX-UHFFFAOYSA-N 0.000 description 1
- NGZVRPKOTMGHAY-UHFFFAOYSA-N 2-phenoxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OC1=CC=CC=C1 NGZVRPKOTMGHAY-UHFFFAOYSA-N 0.000 description 1
- KVPYIEPKUGXISR-UHFFFAOYSA-N 2-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCC(C)OC1=CC=CC=C1 KVPYIEPKUGXISR-UHFFFAOYSA-N 0.000 description 1
- YFKMFQHIZCWXJD-UHFFFAOYSA-N 3-acridin-9-ylprop-2-enoic acid Chemical compound C1=CC=C2C(C=CC(=O)O)=C(C=CC=C3)C3=NC2=C1 YFKMFQHIZCWXJD-UHFFFAOYSA-N 0.000 description 1
- JNRPOURQJNXRPA-UHFFFAOYSA-N 3-phenoxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC1=CC=CC=C1 JNRPOURQJNXRPA-UHFFFAOYSA-N 0.000 description 1
- JRJNSEMUYTUGLA-UHFFFAOYSA-N 3-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC1=CC=CC=C1 JRJNSEMUYTUGLA-UHFFFAOYSA-N 0.000 description 1
- ZEWLHMQYEZXSBH-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)CCC(O)=O ZEWLHMQYEZXSBH-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-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
- JQPNFFYPPWWWCH-UHFFFAOYSA-N 9-pyridin-2-ylacridine Chemical compound N1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 JQPNFFYPPWWWCH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- RKOPRXMOOHDZFV-UHFFFAOYSA-N NC(=O)OCC.CC(C(C)(C)N=C=O)CCCCN=C=O Chemical compound NC(=O)OCC.CC(C(C)(C)N=C=O)CCCCN=C=O RKOPRXMOOHDZFV-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ARNIZPSLPHFDED-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 ARNIZPSLPHFDED-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、感光性樹脂組成物及びこれを用いた感光性樹
脂組成物積層体（以下、単に「感光性フィルム」とよぶ
）に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photosensitive resin composition and a photosensitive resin composition laminate (hereinafter simply referred to as "photosensitive film") using the same.
さらに詳しくは、コールドフローが少なく、有機溶剤を
使用しない弱アルカリ水溶液によって短時間で解像度良
く現像でき、その光硬化物が、密着性、可とう性が良好
で、耐アルカリエツチング性が優れ、剥離時間が短り、
シかも剥離片形状が小さい優れた感光性樹脂組放物及び
該組成物を用いた感光性フィルムに関する。More specifically, it has little cold flow, can be developed in a short time with high resolution using a weak alkaline aqueous solution without using organic solvents, and the photocured product has good adhesion, flexibility, excellent alkali etching resistance, and is easy to peel. Time is short;
The present invention relates to an excellent photosensitive resin composition having a small peelable piece shape and a photosensitive film using the composition.
（従来の技術）
従来、印刷配線板の製造、金属の精密加工等の分野にか
いて、エツチング、めっき等に用いられるレジスト材料
としては、感光性樹脂組成物およびこれを用いて得られ
る感光性フィルムが広く用いられている。この感光性フ
ィルムには、塩素系有機溶剤を用いて現像する溶剤現像
型感光性フィルムと、アルカリ水溶液を用いて現像する
アルカリ現像型感光性フィルムとがあるが、コスト、作
業環境等の面からアルカリ現像型感光性フィルムが多く
使用されている。(Prior Art) Conventionally, in fields such as manufacturing of printed wiring boards and precision processing of metals, photosensitive resin compositions and photosensitive resin compositions obtained using the same have been used as resist materials for etching, plating, etc. Film is widely used. There are two types of photosensitive films: solvent-developable photosensitive films that are developed using chlorinated organic solvents and alkaline-developable photosensitive films that are developed using alkaline aqueous solutions. Alkaline developable photosensitive films are often used.
しかし、このアルカリ現像型感光性フィルムは従来の有
機溶剤現像型感光性フィルムに比ベエッチング特に、ア
ルカリエツチングに対する耐性が低いため処理に制約が
多く、使用に際して問題となることが多かった。エツチ
ング液には大別して。However, this alkali-developable photosensitive film has low resistance to etching, especially alkali etching, compared to conventional organic solvent-developable photosensitive films, and therefore has many limitations in processing and often causes problems in use. Broadly divided into etching liquids.
２種類有シ、１）酸性エツチング液２例えば、塩化第２
銅、塩化第２鉄、２）アルカリ性エツチング液。There are two types: 1) Acidic etching solution 2 For example, dichloride
Copper, ferric chloride, 2) alkaline etching solution.
例えば、アンモニアをベースとしたアルカリエツチング
液が多く使用されている。従来の有機溶剤現像型感光性
フィルムは、この２種のエツチング液に対し同等の耐性
を示すが、アルカリ現像型感光性フィルムは、フィルム
性付与ポリマにカルボキシル基を多く含有した高分子量
体を用いているため弱アルカリ性の現像液に対しては耐
性があるが、エツチング液である比較的強いアルカリエ
ツチング液に対し、耐性が十分でなくアルカリエツチン
グ液のｐＨ，温度、エツチング時間等に極めて敏感であ
わ２作業条件の裕度が非常に狭いことが問題であった。For example, ammonia-based alkaline etching solutions are often used. Conventional organic solvent-developable photosensitive films exhibit equivalent resistance to these two types of etching solutions, but alkaline-developable photosensitive films use a high molecular weight material containing a large number of carboxyl groups as a polymer that imparts film properties. Because of this, it is resistant to weakly alkaline developers, but it is not sufficiently resistant to relatively strong alkaline etching solutions and is extremely sensitive to the pH, temperature, etching time, etc. of the alkaline etching solution. The problem was that the latitude for foam 2 working conditions was very narrow.
また、アルカリ現像型感光性フィルムは、有機溶剤現像
型感光性樹脂組成物に比ベエッチング又はメツキによる
パターン形成後のレジストの剥離性が劣っていることも
問題とされていた。すなわち、有機溶剤現像型感光性フ
ィルムを使用した場合、そのレジストの剥離は一般的に
塩化メチレンのような溶剤で行なわれ、剥離片が細片と
なり。Another problem with alkali-developable photosensitive films is that they are inferior in resist removability after pattern formation by etching or plating compared to organic solvent-developable photosensitive resin compositions. That is, when an organic solvent developable photosensitive film is used, the resist is generally removed using a solvent such as methylene chloride, and the peeled pieces become fine pieces.
印刷配線板の洗浄が容易で剥離液又は剥離機のメンテナ
ンスが簡単である。一方、アルカリ現像型感光性フィル
ムを使用した場合、そのレジストの剥離は一般的に加温
した水酸化ナトリウム水溶液又は水酸化カリウム水溶液
によって行なわれるが。The printed wiring board is easy to clean, and the stripping solution or stripping machine is easy to maintain. On the other hand, when an alkali-developable photosensitive film is used, the resist is generally removed using a heated aqueous solution of sodium hydroxide or aqueous potassium hydroxide.
剥離片は細分化せず、いわゆる“ワカメ”状となう印刷
配線板に再付着し、また、剥離液のろ過による再生が困
難であることが作業上大きな問題となっている。The peeled pieces do not break into small pieces, but re-adhere to the printed wiring board in a so-called "seaweed" shape, and it is difficult to regenerate the peeling solution by filtration, which poses a major operational problem.
アルカリ現像型感光性樹脂組成物に関し特公昭４６−３
２７１４号（結合剤は例えばメタクリル酸メチル／メタ
クリル酸共重合体である）、特公昭５４−３４３２７号
（結合剤は例えばメタクリ−
ル酸メチル／メタクリル酸２−エチルヘキシル／メタク
リル酸の三元共重合体である）、特公昭５５−３８９６
１号（結合剤は例えばスチレン／マレイン酸モノｎ−ブ
チルエステル共重合体である）１％公昭５６−３３４１
３号（結合剤は例えばメタクリル酸エチル／アクリル酸
エチル／メタクリル酸の三元共重合体である）、特公昭
５４２５９５７号（結合剤は例えばスチレン／メタクリ
ル酸メチル／アクリル酸エチル／メタクリル酸の四元共
重合体である）、特開昭５２−９９８１０号（結合剤は
例えばメタクリル酸ベンジル／メタクリル酸共重合体で
ある）、特公昭５８−１２５７７号（結合剤は例えばア
クリロニトリル／メタクリル酸２−エチルヘキシル／メ
タクリル酸の三元共重合体である）９％公昭５５−６２
１０号（結合剤は例えばメタクリル酸メチル／アクリル
酸エチル／アクリル酸三元共重合体とインプロハノール
テ一部分エステル化シタスチレン／マレイン酸無水共重
合体の２種である）９％公昭６０−１５９７４３号（結
合剤は例えばペンジルメタ６−
クリレート／メタクリル酸メチル／メタクリル酸の三元
共重合体である）９％公昭６２−２９２８１５号、特公
昭６２−２９２８１６号（結合剤は例えばアクリル酸２
−フェノキシエチル／メタクリル酸／メタクリル酸メチ
ルの三元共重合体である）には９種々の結合剤を使用し
たアルカリ現像型感光性樹脂組放物が記載されるが、こ
れらはアルカリエツチングの耐性、現像時間、はくｂ性
、銅との密着、コールドフロー、可とり性のすべての粋
性を同時に満足することができていないのが現状である
。Regarding alkali-developable photosensitive resin compositions, Special Publication No. 46-3
No. 2714 (the binder is, for example, a methyl methacrylate/methacrylic acid copolymer), Japanese Patent Publication No. 54-34327 (the binder is, for example, a terpolymer of methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid). (combination), Special Publication Showa 55-3896
No. 1 (the binder is, for example, styrene/maleic acid mono-n-butyl ester copolymer) 1% Kosho 56-3341
No. 3 (the binder is, for example, a ternary copolymer of ethyl methacrylate/ethyl acrylate/methacrylic acid), and Japanese Patent Publication No. 5425957 (the binder is, for example, a ternary copolymer of styrene/methyl methacrylate/ethyl acrylate/methacrylic acid). JP-A-52-99810 (the binder is, for example, benzyl methacrylate/methacrylic acid copolymer), JP-A-58-12577 (the binder is, for example, acrylonitrile/methacrylic acid 2- terpolymer of ethylhexyl/methacrylic acid) 9% Kosho 55-62
No. 10 (Binders are two types, for example, methyl methacrylate/ethyl acrylate/acrylic acid ternary copolymer and Improhanolte partially esterified sitastyrene/maleic anhydride copolymer) 9% Kosho 60-159743 No. 62-292815 (the binder is, for example, a terpolymer of pendyl meth 6-acrylate/methyl methacrylate/methacrylic acid);
- phenoxyethyl/methacrylic acid/methyl methacrylate ternary copolymer), alkali-developable photosensitive resin assemblies using nine different binders are described, but these are resistant to alkaline etching. At present, it is not possible to simultaneously satisfy all the requirements of development time, peelability, adhesion to copper, cold flow, and removability.
（発明が解決しようとする課題）
本発明の目的は、従来のアルカリ現像型感光性樹脂組放
物及びこれを用いた感光性フィルムの上述した問題点を
克服し、アルカリエツチングに対し強い耐性が有り、短
時間で現像でき、短時間で剥離でき、かつ剥離片が小さ
く、感光性フィルムとして基板に積層するに十分な可と
う性を持ち。(Problems to be Solved by the Invention) The purpose of the present invention is to overcome the above-mentioned problems of the conventional alkali-developable photosensitive resin assembly and the photosensitive film using the same, and to provide strong resistance to alkali etching. Yes, it can be developed in a short time, can be peeled off in a short time, has small peeling pieces, and has sufficient flexibility to be laminated to a substrate as a photosensitive film.
そしてその基板に対して強い密着力を有し、會たコール
ドフローの少ない感光性組成物及びこれを用いた感光性
フィルムを提供することにある。Another object of the present invention is to provide a photosensitive composition that has strong adhesion to the substrate and has little cold flow, and a photosensitive film using the same.
（課題を解決するための手段） 本発明は。(Means for solving problems) The present invention is.
（ｉ）結合剤
（ｉ１） ビニル単量体
及び
（Ｉｌｌ） 光開始剤
を含有する感光性樹脂組成物であって、前記（ｉ）結合
剤が、下記一般式（Ｉ）で示される単量体（Ａ）及び下
記一般式（ｎ）で示される単量体（Ｂ）を含む単量体成
分を共重合してなる多元共重合体である感光性樹脂組成
物に関する。A photosensitive resin composition containing (i) a binder (i1) a vinyl monomer and (Ill) a photoinitiator, wherein the (i) binder contains a monomer represented by the following general formula (I). The present invention relates to a photosensitive resin composition which is a multi-component copolymer obtained by copolymerizing monomer components including a monomer (A) and a monomer (B) represented by the following general formula (n).
Ｒ＋
ＯＯ
（式中、Ｒ□は水素原子又はメチル基を示し＋ Ｒ２は
＋（＆４ （ただし９ｍは１〜８の整数を示す）又（式
中＋ Ｒ１及びＲ４は、各々独立して水素原子又はメチ
ル基を示し、 Ｒ３は炭素原子数１〜５のアルキレン基
を示し、ｎは１〜１０の整数を示す）また９本発明は、
前記感光性樹脂組成物を支持フィルム上に積層してなる
感光性樹脂組成物積層体に関する。R+ OO (in the formula, R□ represents a hydrogen atom or a methyl group + R2 is +(&4 (however, 9m represents an integer of 1 to 8) or (in the formula + R1 and R4 each independently represent a hydrogen atom) or a methyl group, R3 represents an alkylene group having 1 to 5 carbon atoms, and n represents an integer of 1 to 10).
The present invention relates to a photosensitive resin composition laminate formed by laminating the photosensitive resin composition on a support film.
以下９本発明を詳述する。The following nine inventions will be described in detail.
本発明における（ｉ）結合剤の多元共重合体を構成する
のに使用される単量体成分に含筐れる単量体について説
明する。The monomers contained in the monomer component used to constitute the multi-component copolymer of the binder (i) in the present invention will be explained.
一般式（ｉ）で示される単量体（Ａ）は多元共重合体を
構成するのに使用される単量体成分中に必須成分として
台筐れる。The monomer (A) represented by the general formula (i) is present as an essential component in the monomer components used to construct the multi-component copolymer.
一般式（ｉ１におけるｍは１〜８である。ｍ＝ｏのもの
は入手困難であう９ｍが９以上のものは共重合性が劣る
。In the general formula (i1, m is 1 to 8. Those with m=o are difficult to obtain. Those with 9m or more have poor copolymerizability.
単量体（Ａ）としては９例えば、β−アクリロイルオキ
シエチルハイドロジエンサクシネート、β−メタクリロ
イルオキシエチルハイドロジエンサクシネート、β−メ
タクリロイルオキシエチルハイ９
ドロジエンフタレート等を挙げることができる。Examples of the monomer (A) include β-acryloyloxyethylhydrodiene succinate, β-methacryloyloxyethylhydrodiene succinate, and β-methacryloyloxyethylhydrodiene phthalate.
β−アクリロイルオキシエチルハイドロジエンサクシネ
ート及びβ−メタクリロイルオキシエチルハイドロジエ
ンサクシネートが好ましい。β-acryloyloxyethyl hydrogen succinate and β-methacryloyloxyethyl hydrogen succinate are preferred.
これらの単量体は、新中村化学工業社等から商業的に入
手可能である。These monomers are commercially available from Shin-Nakamura Chemical Industries, Ltd., etc.
単量体（Ａ）は多元共重合体を構成するのに使用される
単量体成分中に１０〜４０重量優の範囲で台筐れること
が好ましい。１０重量多未満では現像性が、４０重量多
を超えるとコールドフローが起こる傾向がある。It is preferable that the monomer (A) is contained in the monomer component used to constitute the multi-component copolymer in an amount of 10 to 40% by weight. If the amount is less than 10% by weight, developability tends to be poor, and if it is more than 40% by weight, cold flow tends to occur.
一般式（Ｉｔ）で示される単量体（Ｂ）は多元共重合体
を構成するのに使用される単量体成分中に必須成分とし
て含１れる。The monomer (B) represented by the general formula (It) is contained as an essential component in the monomer components used to constitute the multi-component copolymer.
一般式（■）にかけるｎは１〜１０である。ｎ ＝ ０
のものは入手困難であり、ｎが１１以上のものは共重合
性が劣る。n applied to the general formula (■) is 1 to 10. n = 0
Those with n of 11 or more have poor copolymerizability.
また、一般式（］Ｉ）におけるＲ３は炭素原子数が１〜
５のアルキレン基を示す。炭素原子数が６以上のものは
共重合性が劣る。Further, R3 in general formula (]I) has 1 to 1 carbon atoms.
5 shows the alkylene group. Those having 6 or more carbon atoms have poor copolymerizability.
１０
単量体（Ｂ）としては９例えば、アクリル酸２−フェノ
キシエチル、メタクリル酸２−フェノキシエチル、アク
リル酸２−フェノキシプロピル、アクリル酸３−フェノ
キシプロピル、アクリル酸フェノキシジェトキシ、アク
リル酸フェノキシトリエトキシ、アクリル酸フエノキシ
ジブロボキシ、メタクリル酸２−フェノキシプロピル、
メタクリル酸３−フェノキシプロピル、メタクリル酸フ
ェノキシジェトキシ、メタクリル酸フェノキシトリエト
キシ、メタクリル酸フェノキシジプロポキシ等を挙げる
ことができる。アクリル酸２−フェノキシエチル及びメ
タクリル酸２−フェノキシエチルが好ましい。10 Examples of the monomer (B) include 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 2-phenoxypropyl acrylate, 3-phenoxypropyl acrylate, phenoxyjethoxy acrylate, and phenoxytriacrylate. Ethoxy, phenoxydibroboxy acrylate, 2-phenoxypropyl methacrylate,
Examples include 3-phenoxypropyl methacrylate, phenoxyjethoxy methacrylate, phenoxytriethoxy methacrylate, and phenoxydipropoxy methacrylate. 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate are preferred.
成分（Ｂｌは多元共重合体を構成するのに使用される単
量体成分中に５〜６０重量多の範囲で含まれることが好
ましい。５単量体未満では耐アルカリエツチング性が悪
化し、６０重量幅を超えると現像性が劣る傾向がある。The component (Bl) is preferably contained in the monomer component used to constitute the multi-component copolymer in an amount of 5 to 60% by weight.If the amount is less than 5 monomers, the alkali etching resistance will deteriorate; When the weight range exceeds 60, developability tends to be poor.
上記単量体（Ａｌ及び単量体（Ｂ）以外の単量体（単量
体（Ｃ）と呼ぶ）を特性を悪化させない範囲で必要に応
じて用いることができる。Monomers other than the above-mentioned monomers (Al and monomer (B) (referred to as monomer (C)) can be used as necessary within a range that does not deteriorate the properties.
単量体（Ｃ）としては９例えば、メチルメタクリレート
、メチルアクリレート、エチルメタクリレート、エチル
アクリレート、ｎ−プロピルアクリレート、ｎ−プロピ
ルアクリレート、シクロヘキシルメタクリレート、シク
ロヘキシルアクリレート等を挙げることができ、メチル
アクリレート及びメチルメタクリレートが好せしい。Examples of the monomer (C) include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl acrylate, n-propyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, and the like.Methyl acrylate and methyl methacrylate is good.
単量体（Ｃ）は多元共重合体を構成するのに使用される
単量体成分中に５〜４０重量多の範囲で含咬れることが
好普しい。単量体（Ｃ）の含有量が多い場合コールドフ
ロー等の特性が悪化しやすい。単量体（Ｃ）を使用する
と価格、可とう性等の点で有効であるので、単量体（Ｃ
）の含有量が少ないと、特別な利点はなく多元共重合体
の製造工程を煩雑にするだけである。Monomer (C) is preferably included in the monomer component used to constitute the multi-component copolymer in an amount of 5 to 40% by weight. When the content of monomer (C) is large, properties such as cold flow tend to deteriorate. The use of monomer (C) is effective in terms of cost, flexibility, etc.
) is not particularly advantageous and only complicates the production process of the multi-component copolymer.
多元共重合体を構成するのに使用される単量体成分は、
単量体（Ａ）が１０〜４０重量φ、単量体（Ｂ）が５〜
６０重量嘔及び単量体（Ｃ）が５〜４０重量係であって
、かつ単量体（Ａ）、 （Ｂ）及び（Ｃ）の総量が１０
０重量単量体るように含有されているものが好ましい。The monomer components used to construct the multi-component copolymer are:
Monomer (A) has a weight of 10 to 40 φ, and monomer (B) has a weight of 5 to 40
60% by weight and the monomer (C) is 5 to 40% by weight, and the total amount of monomers (A), (B) and (C) is 10% by weight.
It is preferable that the amount of the monomer is 0 by weight.
本発明における（ｉ）結合剤は９以上に示した単量体を
用いて、溶液重合法、懸濁重合法、乳化重合法、塊状重
合法等の公知の重合技術によって容易に製造することが
できる。The binder (i) in the present invention can be easily produced by known polymerization techniques such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization using the monomers shown in 9 and above. can.
（ｉ）結合剤の重量平均分子量（ＧＰＣによるポリスチ
レン換算）は、１０，０００〜５００，０００の範囲で
あることが好筐しい。１０，０００未満では。(i) The weight average molecular weight (in terms of polystyrene by GPC) of the binder is preferably in the range of 10,000 to 500,000. Less than 10,000.
耐現像液性が低く、５００，０００を超えると現像性が
劣る傾向がある。Developer resistance is low, and if it exceeds 500,000, developability tends to be poor.
（ｉ）結合剤の酸価は、６０〜２００ｍｇＫＯＨ／ｇの
範囲であることが好’Ｅ Ｌ ＜ 、 ６０〜１００ｍ
ｇＫＯＨ／Ｈの範囲であることがより好鵞しく、６５〜
８５ｍｇＫＯＨ／９の範囲であることが特に好ましい。(i) The acid value of the binder is preferably in the range of 60 to 200 mgKOH/g.
It is more preferable that it is in the range of gKOH/H, 65 to
A range of 85 mg KOH/9 is particularly preferred.
酸価が小さすぎると現像性が劣シ、酸価が太きすぎると
耐アルカリエツチング性が劣る傾向がある。If the acid value is too low, the developability tends to be poor, and if the acid value is too high, the alkali etching resistance tends to be poor.
次に１本発明における（ｉ）結合剤として用いられる重
合体を第１表として例示する（これらは、アゾビスイソ
ブチロニトリルを重合開始剤とし、ラジカル溶液重合法
で得ることができる）。Next, the polymers used as (i) the binder in the present invention are illustrated in Table 1 (these can be obtained by a radical solution polymerization method using azobisisobutyronitrile as a polymerization initiator).
３
本発明にかける（ＩＩ）ビニル単量体としては１例えば
、多価アルコールにα、β−不飽和カルボン酸を反応さ
せて得られる化合物９例えば、ポリエチレングリコール
ジ（メタ）アクリレート（エチレン基の数が２〜１４の
もの）、トリメチロールプロパンジ（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
、トリメチロールプロパンエトキシトリ（メタ）アクリ
レート。3 Vinyl monomers (II) used in the present invention include 1, for example, a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid; 9, for example, polyethylene glycol di(meth)acrylate (with an ethylene group); trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate.
トリメチロールプロパンプロポキシトリ（メタ）アクリ
レート、テトラメチロールメタントリ（メタ）アクリレ
ート、テトラメチロールメタンテトラ（メタ）アクリレ
ート、ポリプロピレングリコールジ（メタ）アクリレー
ト（プロピレン基の数が２〜１４のもの）、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
リスリトールへキサ（メタ）アクリレート等、ビスフェ
ノールＡポリオキジエチレンジ（メタ）アクリレート、
創見ば、ビスフェノールＡジオキシエチレンジ（メタ）
アクリレート、ビスフェノールＡトリオキシエチレンジ
（メタ）アクリレート、ビスフェノールＡデカオキジエ
チレンジ（メタ）アクリレート等、グリシジル基含有化
合物にα、β−不飽和カルボン酸を付加して得られる化
合物９例えばトリメチロールプロパントリグリシジルエ
ーテルトリアクリレート、ビスフェノールＡジグリシジ
ルエーテルジアクリレート等、多価カルボン酸。Trimethylolpropane propoxy tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, polypropylene glycol di(meth)acrylate (having 2 to 14 propylene groups), dipenta Erythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc., bisphenol A polyoxydiethylene di(meth)acrylate,
Soumiba, bisphenol A dioxyethylene di(meth)
Compound 9 obtained by adding α,β-unsaturated carboxylic acid to a glycidyl group-containing compound such as acrylate, bisphenol A trioxyethylene di(meth)acrylate, bisphenol A decaoxyethylene di(meth)acrylate, etc.9 For example, trimethylolpropane Polyhydric carboxylic acids such as triglycidyl ether triacrylate and bisphenol A diglycidyl ether diacrylate.
例えば無水フタル酸等と水酸基及びエチレン性不飽和基
を有する物質１例えばβ−ヒドロキシエチル（メタ）ア
クリレート等とのエステル化物、アクリル酸若しくはメ
タクリル酸のアルキルエステル、例えば（メタ）アクリ
ル酸メチルエステル。For example, an esterified product of phthalic anhydride or the like with a substance having a hydroxyl group and an ethylenically unsaturated group, such as β-hydroxyethyl (meth)acrylate, or an alkyl ester of acrylic acid or methacrylic acid, such as methyl (meth)acrylate.
（メタ）アクリル酸エチルエステル、（メタ）アクリル
酸ブチルエステル、（メタ）アクリル酸２−エチルヘキ
シルエステル、トリレンジイソシアネートと２−ヒドロ
キシエチル（メタ）アクリル酸エステルとの反応物やト
リメチルへキサメチレンジイソシアネートとシクロヘキ
サンジメタツールと２−ヒドロキシエチル（メタ）アク
リル酸エステルとの反応物等のウレタン（メタ）アクリ
レート、前記一般式（Ｉ）及び一般式（Ｉ［）で示され
る単量体などが挙げられる。これらは、２種以上を混合
して用いることができる。(meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, reaction product of tolylene diisocyanate and 2-hydroxyethyl (meth)acrylic acid ester, trimethylhexamethylene diisocyanate Urethane (meth)acrylates such as reaction products of It will be done. These can be used in combination of two or more types.
本発明に用いられる（ｉｉり光開始剤としては９例えば
、ベンゾフェノン、Ｎ、Ｎ’−テトラメチル−４，４′
−ジアミノベンゾフェノン（ミヒラーケトン）。Examples of photoinitiators used in the present invention include benzophenone, N,N'-tetramethyl-4,4'
-Diaminobenzophenone (Michler's ketone).
Ｎ、Ｎ−テトラメチル−４，４′−ジアミノベンゾフェ
ノン、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、フェナントレンキノ
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等
のベンゾインエーテル。Aromatic ketones such as N,N-tetramethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether etc. benzoin ether.
メチルベンゾイン、エチルベンゾイン等のベンゾイン、
β−（アクリジン−９−イル）アクリル酸のジエステル
化合物、９−フェニルアクリジン。Benzoin such as methylbenzoin and ethylbenzoin,
Diester compound of β-(acridin-9-yl)acrylic acid, 9-phenylacridine.
９−ピリジルアクリジン等のアクリジン化合物。Acridine compounds such as 9-pyridyl acridine.
２−（ｏ−クロロフェニル）−４，５−シフェニルイミ
ダゾールニ量体、２−（ｏ−クロロフェニル）−４，５
−ジ（ｍ−メトキシフェニル）イミダゾールニ量体、２
−（０−フルオロフェニル）−４，５−ジフェニルイミ
ダゾールニ量体、２−（ｏ−メ８−
トキシフェニル）−４，５−ジンエニルイミダゾー＃二
ｉ体、２− （ｐ−メトキシフェニル）−４，５−ジフ
ェニルイミダゾールニ量体、ス４−ジ（ｐ−メトキシフ
ェニル）５−フェニルイミダゾール二量体、２−（２，
４−ジメトキシフェニル）−４゜５−ジフェニルイミダ
ゾールニ量体、２−（ｐ−メチルメルカプトフェニル）
−４，５−シフェニルイミダゾールニ量体等の２．４
．５−トリアリールイミダゾールニ量体などが挙げられ
る。これらは。2-(o-chlorophenyl)-4,5-cyphenylimidazole dimer, 2-(o-chlorophenyl)-4,5
-di(m-methoxyphenyl)imidazole dimer, 2
-(0-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-me8-toxyphenyl)-4,5-dienylimidazo #di, 2-(p-methoxyphenyl )-4,5-diphenylimidazole dimer, 4-di(p-methoxyphenyl)5-phenylimidazole dimer, 2-(2,
4-dimethoxyphenyl)-4゜5-diphenylimidazole dimer, 2-(p-methylmercaptophenyl)
2.4 of -4,5-cyphenylimidazole dimer etc.
．． Examples include 5-triarylimidazole dimer. these are.
２種以上を混合して用いることができる。A mixture of two or more types can be used.
本発明における（＋１結合剤、 （ＩＩ）ビニル単量体
及び＋ｌ＋＋＋光開始剤の各々の使用量は、（ｉ）結合
剤及び（ｉ１）ビニル単量体の総量１００重量部に対し
て、ビニル単量体１０〜８０重量部とすることが好筐し
く。In the present invention, the amounts of each of (+1 binder, (II) vinyl monomer and +1+++ photoinitiator used are as follows: Preferably, the monomer content is 10 to 80 parts by weight.
２０〜５０重量部とすることがよシ好ましい。（ｉ１結
合剤は２０〜９０重量部とすることが好ましく。It is more preferable to use 20 to 50 parts by weight. (The amount of the i1 binder is preferably 20 to 90 parts by weight.
５０〜８０重量部とすることがよシ好ｔＬ＜、６５〜７
５重量部とすることが特に好ましい。（ｉ１）ビニル単
量体の使用量が少なすぎると、光硬化物（露光されたレ
ジスト）が脆く充分な物性が得られず。It is preferable to use 50 to 80 parts by weight tL<, 65 to 7
Particularly preferred is 5 parts by weight. (i1) If the amount of vinyl monomer used is too small, the photocured product (exposed resist) will be brittle and sufficient physical properties will not be obtained.
９− 多すぎると充分な光感度が得られないことがある。9- If it is too large, sufficient photosensitivity may not be obtained.
１１ｉ１光開始剤の使用量は、（Ｉ）結合剤及び（Ｉｌ
ｌビニル単量体の総量１００重量部に対して０．０３〜
２０重量部とすることが好ましく、０．０５〜１０重量
部とすることがよう好オしい。この使用量が少なすぎる
と、充分な光感度が得られず、多すぎると。The amount of 11i1 photoinitiator used is determined by the amount of (I) binder and (Il
0.03 to 100 parts by weight of the total vinyl monomer
The amount is preferably 20 parts by weight, and more preferably 0.05 to 10 parts by weight. If the amount used is too small, sufficient photosensitivity will not be obtained, and if it is too large.
露光の際に組成物の表面での光吸収が増加して内部の光
硬化が不充分となることがある。During exposure, light absorption at the surface of the composition may increase, resulting in insufficient photocuring of the interior.
本発明の感光性樹脂組成物は、必要に応じて。The photosensitive resin composition of the present invention may be prepared as necessary.
可塑剤、熱重合禁止剤、染料、顔料、充填剤、密着性付
与剤等を配合することができる。Plasticizers, thermal polymerization inhibitors, dyes, pigments, fillers, adhesion agents, etc. can be blended.
本発明の感光性樹脂組成物は、金属面９例えば銅、ニッ
ケル、クロム、好壕しくは銅の上に、液状レジストとし
て塗布して乾燥後、保護フィルムを被覆して用いるか、
または感光性フィルムとして用いられる。感光性樹脂組
成物層の厚みは用途によシ異なるが、乾燥後の厚みで１
０〜１００μｍ程度である。液状レジストとした場合は
、保護フィルムとしてポリエチレン、ポリプロピレン等
の不活性なポリオレフィンフィルムが用いられる。The photosensitive resin composition of the present invention can be used by applying it as a liquid resist onto a metal surface 9 such as copper, nickel, chromium, or copper, and after drying, covering it with a protective film.
Or used as a photosensitive film. The thickness of the photosensitive resin composition layer varies depending on the application, but the thickness after drying is 1.
It is about 0 to 100 μm. When a liquid resist is used, an inert polyolefin film such as polyethylene or polypropylene is used as a protective film.
感光性フィルムは、ポリエステル等の支持フィルム上に
感光性樹脂組成物を塗布、乾燥してその層を積層し、必
要によりポリエチレン等の保護フィルムを積層して得ら
れる。感光性樹脂組成物は必要に応じて他の溶剤と混合
して溶液として塗布してもよい。The photosensitive film is obtained by coating a photosensitive resin composition on a support film such as polyester, drying and laminating the layers, and, if necessary, laminating a protective film such as polyethylene. The photosensitive resin composition may be mixed with other solvents and applied as a solution, if necessary.
前記の感光性樹脂組成物層は、アートワークあるいはネ
ガフィルムと呼ばれるネガまたはポジマスクパターンを
通して活性光線が照射された後。The photosensitive resin composition layer is irradiated with actinic rays through a negative or positive mask pattern called artwork or negative film.
現像液で現像され、レジストパターンとされる。It is developed with a developer to form a resist pattern.
この際用いられる活性光線としては１例えばカーボンア
ーク灯、超高圧水銀灯、高圧水銀灯、キセノンランプ等
の紫外線を有効に放射するものが用いられる。The active light used in this case is one that effectively emits ultraviolet rays, such as a carbon arc lamp, an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, or a xenon lamp.
現像液としては、安全かつ安定であシ、操作性が良好な
ものが用いられ、その具体的な例としては、水酸化リチ
ウム、水酸化ナトリウム、水酸化カリウム、炭酸ナトリ
ウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カ
リウム、ケイ酸ナトリウム、リン酸ナトリウム、メタケ
イ酸ナトリウム等の水溶液が挙げられる。特に、炭酸ナ
トリウムの１〜２φ水溶液が好ましい。As the developer, one that is safe, stable, and has good operability is used. Specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and hydrogen carbonate. Examples include aqueous solutions of sodium, potassium hydrogen carbonate, sodium silicate, sodium phosphate, sodium metasilicate, and the like. Particularly preferred is a 1 to 2 φ aqueous solution of sodium carbonate.
現像の方法には、デイツプ方式、パドル方式。Development methods include dip method and paddle method.
スプレ一方式等があυ、高圧スプレ一方式が解像度向上
のためには最も適している。Although there are one-sided spray systems, etc., one-sided high-pressure spray systems are most suitable for improving resolution.
（実施例） 以下、実施例によって本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
〔結合剤の多元共重合体としての重合体１の合成〕以下
のようにして先に示した第１表の重合体番号が１の重合
体（重合体１）を合成した。[Synthesis of Polymer 1 as a multi-component copolymer of binder] The polymer having the polymer number 1 in Table 1 shown above (Polymer 1) was synthesized as follows.
攪拌機、温度計、還流冷却器及び窒素ガス導入管を装着
した２での４つロフラスコに、エチレングリコールモノ
メチルエーテル／トルエン（重量比６／４）の重合溶媒
としての混合溶媒（以下混合溶媒Ａとする）９００９を
投入し８０℃に加温し、８０℃で１時間保温後、アクリ
ル酸２−フェノキシエチル２１０９．β−メタクリロイ
ルオキシエチルハイドロジエンサクシネート１８０９゜
２
した溶液を、温度を８０℃に保ちフラスコ内を攪拌しな
がら、４時間かけてフラスコ内に滴下した。A mixed solvent (hereinafter referred to as mixed solvent A) of ethylene glycol monomethyl ether/toluene (weight ratio 6/4) as a polymerization solvent was placed in a four-bottle flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. 2-phenoxyethyl acrylate 2-phenoxyethyl acrylate 2109. A solution of β-methacryloyloxyethylhydrogen succinate (1809°C) was added dropwise into the flask over 4 hours while the temperature was kept at 80°C and the flask was stirred.
滴下終了後混合溶媒Ａを６０９添加し８０℃で４時間保
温後冷却し９重合体１の溶液を得た。この重合体１の重
量平均分子量をＧＰＣで測定したところ９０，０００（
ポリスチレン換算）であった。After the dropwise addition was completed, 60% of mixed solvent A was added, kept at 80° C. for 4 hours, and then cooled to obtain a solution of 9 polymers 1. The weight average molecular weight of this polymer 1 was measured by GPC and was 90,000 (
(polystyrene equivalent).
また酸価は７３ （ＩｎｇＫＯＨ／ ９ ）であった。Further, the acid value was 73 (IngKOH/9).
重合体１の合成と同様にして前記第１表に示した重合体
４９重合体７及び重合体１０を合成した。Polymer 49, Polymer 7, and Polymer 10 shown in Table 1 above were synthesized in the same manner as in the synthesis of Polymer 1.
また９重合体１の合成と同様にして次の第２表の本発明
の範囲外の比較用の重合体である９重合体１３９重合体
１４９重合体１５及び重合体１６を合成した。In addition, in the same manner as the synthesis of 9-polymer 1, 9-polymer 139, polymer 149, polymer 15, and polymer 16, which are comparative polymers outside the scope of the present invention, shown in Table 2 below were synthesized.
２３
実施例１〜４及び比較例１〜４
実施例１〜４は結合剤として第１表記載の重合体の重合
体１，４．７及び１０を、また比較例１〜４は結合剤と
して第２表記載の重合体の重合体１３．１４．１５及び
１６を使用した。23 Examples 1 to 4 and Comparative Examples 1 to 4 Examples 1 to 4 used Polymers 1, 4.7, and 10 of the polymers listed in Table 1 as the binder, and Comparative Examples 1 to 4 used the polymers 1, 4.7, and 10 as the binder. Polymers 13, 14, 15 and 16 of the polymers listed in Table 2 were used.
フェニルスルフォンｏ、ｓｇ、 ロイコクリスタルバ
イオレット１９．マラカイトグリーン０．８９ ： ｌ
１ｌ）光開始剤としてのＮ、 Ｎ’−テトラエチル−４
，４′−ジアミノ−ベンゾフェノン０．１５９．ベンゾ
フェノン３．５９．ｐ−ジメチルアミノ安息香酸エチル
エステル３．５９；メチルエチルケトン２５ｇ、メタノ
ール３９ ： （ｌｉ）ビニル単量体としてのＢＰＥ−
１０（新中村化学工業■社製商品名、ビスフェノールＡ
ポリオキシエチレンジメタクリレート）２５９゜ＭＥＣ
ＨＰＰ （大阪有機化学工業■社製商品名、γ−クロロ
ーβ−ヒドロキシプロピル−β′−メタクリロイルオキ
シエチル−〇−フタレート）１０９を配合して感光性樹
脂組成物の溶液を得た。Phenylsulfone o, sg, leuco crystal violet 19. Malachite green 0.89: l
1l) N,N'-tetraethyl-4 as photoinitiator
, 4'-diamino-benzophenone 0.159. Benzophenone 3.59. p-dimethylaminobenzoic acid ethyl ester 3.59; methyl ethyl ketone 25 g, methanol 39: (li) BPE- as vinyl monomer
10 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name, bisphenol A)
polyoxyethylene dimethacrylate) 259°MEC
HPP (trade name, manufactured by Osaka Organic Chemical Industry ■, γ-chloroβ-hydroxypropyl-β′-methacryloyloxyethyl-〇-phthalate) 109 was blended to obtain a solution of a photosensitive resin composition.
５
〔特性評価用試料の作成〕
前記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１−に塗布し、１００℃の
熱風対流式乾燥機で約１０分間乾燥して感光性フィルム
を得た。感光性樹脂組成物層の乾燥後の膜厚は４０μｍ
であった。5 [Preparation of sample for characteristic evaluation] A solution of the photosensitive resin composition was applied onto a 20 μm thick polyethylene terephthalate film 1-, and dried for about 10 minutes in a hot air convection dryer at 100° C. to form a photosensitive film. Obtained. The film thickness of the photosensitive resin composition layer after drying is 40 μm
Met.
一方、銅はく（厚さ３５μｍ）を両面に積層したガラス
エポキシ材である銅張り積層板（日立化成工業社製、Ｍ
ＣＬ−Ｅ−６１）の銅表面をφ８００のサンドペーパー
で研磨し、水洗して空気流で乾燥し、得られた銅張り積
層板を６０℃に加温し、その銅面上に前記感光性樹脂組
成物層を。On the other hand, a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., M
The copper surface of CL-E-61) was polished with φ800 sandpaper, washed with water, and dried with air flow. The resulting copper-clad laminate was heated to 60°C, and the photosensitive material was applied on the copper surface. resin composition layer.
１２０℃に加熱し々からラミネートレ特性評価用試料を
得た。After heating to 120° C., a sample for evaluation of laminated resin properties was obtained.
この特性評価用試料を用いて以下の（ａ−１）。The following (a-1) was performed using this characteristic evaluation sample.
（ａ−２）及び（ａ−３）に示したようにして種々の特
性を評価した。Various properties were evaluated as shown in (a-2) and (a-3).
（ａ−１）
特性評価用試料に、ネガフィルムを適用し、３ｋＷ高圧
水銀灯（オーク製作新製、ＨＭＷ−２０１２６−
Ｂ）で１００ ｍＪ／ｃｍ２の露光を行なった。この際
光感度を評価できるように、光透過量が段階的に少なく
なるように作られたネガフィルム（光学密度０．０５を
１段目とし、１段ごとに光学密度が０．１５ずつ増加す
る２１段のステップタブレット）を用いた。(a-1) A negative film was applied to a sample for characteristic evaluation, and exposure was performed at 100 mJ/cm 2 using a 3 kW high-pressure mercury lamp (manufactured by Oak Seisaku Shin, HMW-20126-B). At this time, in order to evaluate the photosensitivity, a negative film made so that the amount of light transmission decreases in stages (the first stage has an optical density of 0.05, and the optical density increases by 0.15 with each stage) A 21-step step tablet) was used.
次イでホリエチレンテレフタレートフイルムを除去し、
３０℃で１％炭酸す） ＩＪウム水溶液を５０〜１２０
秒間スプレーすることにより、未露光部分を除去した。In the next step, remove the polyethylene terephthalate film,
(1% carbonic acid at 30℃) IJum aqueous solution 50-120
Unexposed areas were removed by spraying for seconds.
またことで１２０秒間スプレーしても未露光部が除去で
きないサンプルは、第５表現像性の評価を×とした（そ
れ以外良好なサンプルは○とした）。さらに銅張シ積層
板上に形成された光硬化膜のステップタブレットの段数
を測定することによう、感光性樹脂組放物の光感度を評
価した。その結果を第５表に示す。光感度はステップタ
ブレットの段数で示され、このステップタブレットの段
数が高いほど光感度が高いことを示している。解像度は
、解像できる最小のライン幅と間隔をμｍ単位で示した
もので、数字が小２７一
さいほど解像度が良好なことを示している。In addition, for samples whose unexposed areas could not be removed even after spraying for 120 seconds, the evaluation of the fifth expressive image quality was rated as × (other samples with good performance were rated as ○). Furthermore, the photosensitivity of the photosensitive resin assembly was evaluated by measuring the number of step tablets of the photocured film formed on the copper-clad laminate. The results are shown in Table 5. The photosensitivity is indicated by the number of steps on the step tablet, and the higher the number of steps on the step tablet, the higher the photosensitivity. Resolution indicates the minimum resolvable line width and interval in μm, and the smaller the number, the better the resolution.
次いで現像したものを、アルカリエツチングを行ない、
その後２つの評価法で耐アルカリエツチング性を調べた
。咬ず、密着性を調べる為、光硬化膜にセロテープを貼
り、これを垂直方向にすばやく引き剥がして（９０°ビ
ールオフ試験）光硬化膜の剥がれのありなしを調べた。Next, the developed material is subjected to alkaline etching,
Thereafter, the alkali etching resistance was examined using two evaluation methods. To examine adhesion and non-biting, cellophane tape was applied to the photocured film, and this was quickly peeled off in the vertical direction (90° beer-off test) to check for peeling of the photocured film.
筐た。電子顕微鏡にて光硬化膜のリフティング（銅はく
と光硬化膜が密着してからす９両者間にすき１があり光
硬化膜が鋼はくから浮き上がってみえる現象）のあシな
しを観察した。その結果を第５表に示す。なお、アルカ
リエツチングは、メルテツクス製のＡプロセスをアルカ
リエツチング液として用い、５０℃、１２５秒にてエツ
チングした。It was a cabinet. Using an electron microscope, observe the lifting of the photocured film (a phenomenon in which the copper foil and the photocured film are in close contact with each other, with a gap of 1 between them, and the photocured film appears to be lifted from the steel foil). did. The results are shown in Table 5. Incidentally, the alkali etching was performed at 50° C. for 125 seconds using Process A manufactured by Meltex as an alkaline etching solution.
（ａ−−２）
特性評価用資料に５ｃｍＸ７ｃｍの長方形の開口部（光
透過部）を有するネガフィルムを適用して（ａ−１）と
同様にして露光し、（ａ−１）と同様にして現像した。(a--2) A negative film having a rectangular opening (light transmitting part) of 5 cm x 7 cm was applied to the material for characteristic evaluation, and exposed in the same manner as in (a-1); I developed it.
ついで、５０℃２％の水酸化す） ＩＪウム水溶液を入
れたビーカーに現像後の資料を浸漬しレジスト（光硬化
被膜）を剥離し、剥離片の大きさと、剥離終了筐でに要
した剥離終了時間（秒）を測定した。剥離片の大きさの
評価基準を第３表に示した。Next, the developed material was immersed in a beaker containing 2% hydroxide at 50°C and the resist (photocured film) was peeled off. The completion time (seconds) was measured. Table 3 shows the evaluation criteria for the size of peeled pieces.
第 ３ 表
（ａ−３）
特性評価用資料にネガフィルムを適用せずにベタで（即
ち全面に）（ａ−１）と同様にして露光しく、 １００
ｍＪ／ｃ１ｎり’、その後（ａ−１）と同様にして現
像した。ついでＪＩ８−に５４００の方法で、クロスカ
ット性を評価した。評価基準を第４表に示した。Table 3 (a-3) The material for characteristic evaluation was exposed solidly (that is, on the entire surface) in the same manner as in (a-1) without applying a negative film, and 100
mJ/c1n, and then developed in the same manner as (a-1). Then, cross-cutting properties were evaluated using the JI8-5400 method. The evaluation criteria are shown in Table 4.
第
表
クロスカット性の評価点数が高いものは可とう性及び密
着性に優れる。Products with high evaluation scores for cross-cutting properties in Table 1 have excellent flexibility and adhesion.
０− １− 第５表の結果から本発明の感光性樹脂組成物は。0- 1- From the results in Table 5, the photosensitive resin composition of the present invention.
下地金属（銅はく）への密着性が良好で耐アルカリエツ
チング性、剥離性及びクロスカット性に優れていること
がわかった。It was found that it had good adhesion to the underlying metal (copper foil) and was excellent in alkali etching resistance, peelability, and cross-cutting properties.
（発明の効果）
本発明の感光性樹脂組成物及びこれを用いた感光性フィ
ルムは良好な光感度、解像度を有しておりコールド７０
−も少なく、曾た金属、特に印刷配線板に用いられる銅
張ジ積層板に対し優れた密着性を有し、剥離性及び可と
う性（クロスカット性）も良好であシ、耐アルカリエツ
チング性に極めて優れ、銅はくの厚さが比較的厚い銅張
シ積眉板（銅はくの薄いものに比べてエツチング時間が
長い）におけるアルカリエツチング工法にも好適に使用
できるものである。(Effect of the invention) The photosensitive resin composition of the present invention and the photosensitive film using the same have good photosensitivity and resolution, and have a cold 70%
It has excellent adhesion to traditional metals, especially copper-clad laminates used in printed wiring boards, has good peelability and flexibility (cross-cutting properties), and is resistant to alkali etching. It has excellent properties and can be suitably used in the alkaline etching method for copper-clad laminate boards with relatively thick copper foil (the etching time is longer than with thin copper foil).
３２−32-
Claims (1)
剤が、下記一般式（ I ）で示される単量体（Ａ）及び
下記一般式（II）で示される単量体（Ａ）を含む単量体
成分を共重合してなる多元共重合体である感光性樹脂組
成物。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１は水素原子又はメチル基を示し、Ｒ＿２
は▲数式、化学式、表等があります▼（ただし、ｍは１
〜８の整数を示す）又はベンゼン環を示す） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１及びＲ＿４は、各々独立して水素原子又
はメチル基を示し、Ｒ＿３は炭素原子数１〜５のアルキ
レン基を示し、ｎは１〜１０の整数を示す）２、（ｉ）
結合剤の多元共重合体が、重量平均分子量１０，０００
〜５００，０００の多元共重合体である請求項１記載の
感光性樹脂組成物。 ３、（ｉ）結合剤の多元共重合体が、酸価６０〜２００
ｍｇＫＯＨ／ｇ多元共重合体である請求項１又は２記載
の感光性樹脂組成物。 ４、単量体成物が、単量体（Ａ）を１０〜４０重量％、
単量体（Ｂ）を５〜６０重量％含む単量体成分である請
求項１、２又は３記載の感光性樹脂組成物。 ５、請求項１、２、３又は４記載の感光性樹脂組成物の
層を支持フィルム上に積層してなる感光性樹脂組成物積
層体。[Scope of Claims] 1. A photosensitive resin composition containing (i) a binder, (ii) a vinyl monomer, and (iii) a photoinitiator, wherein the (i) binder has the following general formula: A photosensitive resin composition that is a multicomponent copolymer obtained by copolymerizing a monomer component containing a monomer (A) represented by (I) and a monomer (A) represented by the following general formula (II). thing. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom or a methyl group, and R_2
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, m is 1
(indicates an integer of ~8) or a benzene ring) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_1 and R_4 each independently represent a hydrogen atom or a methyl group, and R_3 is a carbon represents an alkylene group having 1 to 5 atoms, n represents an integer of 1 to 10)2, (i)
The multi-element copolymer of the binder has a weight average molecular weight of 10,000
The photosensitive resin composition according to claim 1, which is a multicomponent copolymer of 500,000 to 500,000. 3. (i) The multicomponent copolymer of the binder has an acid value of 60 to 200
3. The photosensitive resin composition according to claim 1 or 2, which is a multicomponent copolymer. 4. The monomer composition contains 10 to 40% by weight of monomer (A),
The photosensitive resin composition according to claim 1, 2 or 3, which is a monomer component containing 5 to 60% by weight of monomer (B). 5. A photosensitive resin composition laminate comprising a layer of the photosensitive resin composition according to claim 1, 2, 3 or 4 laminated on a support film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1850690A JPH03221956A (en) | 1990-01-29 | 1990-01-29 | Photosensitive resin composition and laminate using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1850690A JPH03221956A (en) | 1990-01-29 | 1990-01-29 | Photosensitive resin composition and laminate using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03221956A true JPH03221956A (en) | 1991-09-30 |
Family
ID=11973512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1850690A Pending JPH03221956A (en) | 1990-01-29 | 1990-01-29 | Photosensitive resin composition and laminate using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03221956A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000052529A1 (en) * | 1999-03-03 | 2000-09-08 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element comprising the same, process for producing resist pattern, and process for producing printed circuit board |
-
1990
- 1990-01-29 JP JP1850690A patent/JPH03221956A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000052529A1 (en) * | 1999-03-03 | 2000-09-08 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element comprising the same, process for producing resist pattern, and process for producing printed circuit board |
| US7022462B1 (en) | 1999-03-03 | 2006-04-04 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element using the same, process for producing resist pattern, and process for producing printed wiring board |
| CN1332266C (en) * | 1999-03-03 | 2007-08-15 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive element comprising the same, process for producing resist pattern, and process for producing printed circuit board |
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