JPS61201237A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPS61201237A JPS61201237A JP60042476A JP4247685A JPS61201237A JP S61201237 A JPS61201237 A JP S61201237A JP 60042476 A JP60042476 A JP 60042476A JP 4247685 A JP4247685 A JP 4247685A JP S61201237 A JPS61201237 A JP S61201237A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- titled composition
- resin composition
- parts
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 38
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- 229920003986 novolac Polymers 0.000 abstract description 6
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 229920001225 polyester resin Polymers 0.000 abstract description 4
- 239000004645 polyester resin Substances 0.000 abstract description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000005011 phenolic resin Substances 0.000 abstract description 2
- 229920006163 vinyl copolymer Polymers 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011253 protective coating Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- -1 polyethylene terephthalate Polymers 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl 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])C([H])([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
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- PASIEQDVKZQWRI-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol 3-hydroxy-2,2-dimethylpropanoic acid prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(C)(C)CO.OCC(C)(C)C(O)=O PASIEQDVKZQWRI-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- MAKLMMYWGTWPQM-UHFFFAOYSA-N 2-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCC)=CC=C3C(=O)C2=C1 MAKLMMYWGTWPQM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UAKWLVYMKBWHMX-UHFFFAOYSA-N SU4312 Chemical compound C1=CC(N(C)C)=CC=C1C=C1C2=CC=CC=C2NC1=O UAKWLVYMKBWHMX-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GXTJJXHLTYJRLX-UHFFFAOYSA-N butanedioic acid;2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO.OC(=O)CCC(O)=O GXTJJXHLTYJRLX-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
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に関し、更に詳しくは印刷配
線板製造、金属精密加工等に使用することのできる保護
被膜形成用の感光性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photosensitive resin composition, and more specifically to a photosensitive resin for forming a protective film that can be used in printed wiring board manufacturing, metal precision processing, etc. Regarding the composition.
（従来の技術）
印刷配線板を製造するに際し、エツチング、電解メッキ
などを行なうため、または回路の永久保護、半田付は領
域の限定、半田ブリッジの防止、電気絶縁性の保持、銅
導体の腐食防止、化学メッキなどを行なうために、保護
被膜が使用され、これらの保護被膜の形成には印刷イン
キ、感光性フィルムなどが使用されている。これらのう
ち印刷インキを用いる場合には、スクリーン印刷が行な
われるため印刷精度が悪いという欠点があり、また近年
、電子機器の小型化、軽量化に伴い、配線板回路の高密
度化が要求されていることから、このような配線板には
、感光性フィルム、例えばポリエチレンテレフタレート
フィルム等の支持体上に感光性組成物を塗工したフィル
ムが使用されるようになった。(Prior art) When manufacturing printed wiring boards, it is used to perform etching, electrolytic plating, etc., or to permanently protect circuits, limit the soldering area, prevent solder bridges, maintain electrical insulation, and corrode copper conductors. Protective films are used for prevention, chemical plating, etc., and printing inks, photosensitive films, etc. are used to form these protective films. Among these methods, when printing ink is used, there is a drawback that printing accuracy is poor because screen printing is performed, and in recent years, as electronic devices have become smaller and lighter, higher density wiring board circuits have been required. Therefore, for such wiring boards, photosensitive films such as polyethylene terephthalate films and other films coated with photosensitive compositions have come to be used.
このような感光性フィルムを使用して配線板を製造する
には、ポリエチレンテレフタレートフィルム等の支持体
上の感光性樹脂組成物面を銅張り積層板に加熱、加圧し
て密着させた後、支持体の他面上にネガフィルムを置き
、この上から紫外線′を照射させて露光し、次いで支持
体を感光性樹脂組成物から剥離し、現像およびエツチン
グを行なっている。In order to manufacture wiring boards using such a photosensitive film, the photosensitive resin composition surface on a support such as a polyethylene terephthalate film is heated and pressurized to bring it into close contact with a copper-clad laminate, and then the support is A negative film is placed on the other side of the body, exposed to ultraviolet light from above, and then the support is peeled off from the photosensitive resin composition and developed and etched.
これに対し、前記支持体を剥離させた後、感光性樹脂組
成物上に直接ネガフィルムを置いて露光、現像およびエ
ツチングを行なう方法や、支持体を用いずに、感光性樹
脂組成物を溶剤に熔解し、直接銅張り積層板等に塗工、
乾燥しく直接塗工法）、この感光性樹脂組成物上に直接
ネガフィルムを置いて露光、現像およびエツチングを行
なう方法も考えられる。これらの方法が採用できれば解
像度の向」二、配線板の高密度化、作業工程の簡略化等
を図ることができる。On the other hand, after peeling off the support, a negative film is placed directly on the photosensitive resin composition and exposed, developed and etched, or the photosensitive resin composition is removed using a solvent without using a support. melted and applied directly to copper-clad laminates, etc.
A dry direct coating method) and a method in which a negative film is placed directly on the photosensitive resin composition and then exposed, developed and etched are also considered. If these methods can be adopted, it will be possible to improve the resolution, increase the density of the wiring board, and simplify the work process.
しかしながら、従来の感光性樹脂組成物は粘着性を有し
、この上に直接ネガフィルムを置く場合には、ネガフィ
ルムが粘着して剥れにくくなり、またネガフィルムを汚
染して実用的でないという欠点があった。このように従
来の感光性樹脂組成物が粘着性を有するのは、組成物中
のビニル単量体が液状ないしは粘ちょう性の液体である
ことによると考えられる。However, conventional photosensitive resin compositions have adhesive properties, and when a negative film is placed directly on top of them, the negative film becomes sticky and difficult to peel off, and it also contaminates the negative film, making it impractical. There were drawbacks. The reason why conventional photosensitive resin compositions have such stickiness is thought to be because the vinyl monomer in the composition is a liquid or viscous liquid.
（発明が解決しようとする問題点）
本発明の目的は、前記従来技術の欠点を除去し、粘着性
を有さす、しかも前記直接塗工法も適用可能な、保護被
膜形成用の感光性樹脂組成物を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to eliminate the drawbacks of the prior art, and to provide a photosensitive resin composition for forming a protective film that has adhesive properties and is also applicable to the direct coating method. It's about providing things.
（問題点を解決するための手段）
本発明者らは、粘着性の原因となるビニル単量体の含有
量を少なくして組成物中の粘着性をなくし、少なくなっ
たビニル単量体の代わりに、粘着性がなく、かつ光重合
性を有する固形樹脂を使用することについて種々検討の
結果、光重合性固形樹脂であるエポキシエステル樹脂が
、カルボキシル基を有する化合物の共存下に、アルカリ
現像性ラス転移温度が４０℃以上の線状高分子化合物１
００重量部、（Ｂ）ノボラックエポキシ樹脂と１価不飽
和カルボン酸とを、エポキシ当量１に対してカルボン酸
当量０．４〜１．１の割合で反応させて得られる、軟化
点５０℃以上のエポキシエステル樹脂５〜１５０重量部
、（Ｃ）光重合可能なビニル単量体２５〜８０重量部お
よび（Ｄ）活性光線により遊離ラジカルを生成する増感
剤および（または）増感剤系を含有してなる感光性樹脂
組成物に関する。(Means for Solving the Problems) The present inventors have eliminated the stickiness in the composition by reducing the content of the vinyl monomer that causes stickiness, and the reduced vinyl monomer content has been reduced. As a result of various studies on using a non-tacky, photopolymerizable solid resin instead, we found that an epoxy ester resin, which is a photopolymerizable solid resin, was developed by alkaline development in the coexistence of a compound having a carboxyl group. Linear polymer compound 1 having a sexual lath transition temperature of 40°C or higher
00 parts by weight, (B) obtained by reacting a novolak epoxy resin and a monounsaturated carboxylic acid in a ratio of 0.4 to 1.1 carboxylic acid equivalents to 1 epoxy equivalent, with a softening point of 50°C or higher 5 to 150 parts by weight of an epoxy ester resin, (C) 25 to 80 parts by weight of a photopolymerizable vinyl monomer, and (D) a sensitizer and/or sensitizer system that generates free radicals when exposed to actinic radiation. It relates to a photosensitive resin composition comprising the following.
本発明の感光性樹脂組成物は、酸価８０〜２００で、カ
ルボキシル基を有し、かつガラス転移温度４０℃以上の
線状高分子化合物を必須成分（Ａ）として含有する。上
記高分子化合物の酸価が８０未満の場合は現像時間が長
くなり、２００を超えると耐現像液性が悪く、像が歪み
やくなる。またガラス転移温度が４０℃未満の場合には
感光性樹脂組成物が粘着性となる。ガラス転移温度は、
４０〜１２０℃の範囲が好ましい。The photosensitive resin composition of the present invention contains as an essential component (A) a linear polymer compound having an acid value of 80 to 200, a carboxyl group, and a glass transition temperature of 40° C. or higher. When the acid value of the polymer compound is less than 80, the development time becomes long, and when it exceeds 200, developer resistance is poor and the image becomes easily distorted. Moreover, when the glass transition temperature is less than 40°C, the photosensitive resin composition becomes sticky. The glass transition temperature is
The temperature range is preferably from 40 to 120°C.
上記線状高分子化合物は公知の化合物であり、例えばビ
ニル共重合線状高分子化合物、ポリエステル樹脂等があ
げられ、これらは単独で、または混合して用いられる。The above-mentioned linear polymer compound is a known compound, and includes, for example, a vinyl copolymer linear polymer compound, a polyester resin, etc., and these may be used alone or in combination.
ビニル共重合の線状高分子化合物はビニル単量体の重合
によって製造されるが、その製造に使用されるビニル単
量体としては、例えば（メタ）アクリル酸（アクリル酸
またはメタアクリル酸の意味。以下同じ）、（メタ）ア
クリル酸メチル、（メタ）アクリル酸エチル、（メタ）
アクリル酸プロピル、（メタ）アクリル酸ブチル、（メ
タ）アクリル酸イソブチル、２−ヒドロキシエチル（メ
タ）アクリレート（アクリレートまたはメタアクリレー
トの意味。以下同じ）、２−ヒドロキシプロピル（メタ
）アクリレート、２−エチルヘキシル（メタ）アクリレ
ート、オクタデシル（メタ）アクリレート、ラウリル（
メタ）アクリレート、トリデシル（メタ）アクリレート
、ステアリル（メタ）アクリレート、２−ヒドロキシド
デシル（メタ）アクリレート、スチレン、α−メチルス
チレン、アルリロニトリル、（メタ）アクリルアミド、
ダイア七トンアクリルアミド、 （メタ）アクリル酸メ
トキシエチル、（メタ）アクリル酸エトキシメチル、（
メタ）アクリル酸ブトキシエチル、テトラヒドロフルフ
リル（メタ）アクリレート等が挙げられる。これらの線
状高分子化合物の合成は通常、有機溶媒中で行なわれる
。Linear polymer compounds of vinyl copolymerization are produced by polymerizing vinyl monomers, and the vinyl monomers used for their production include, for example, (meth)acrylic acid (meaning acrylic acid or methacrylic acid). (same hereinafter), (meth)methyl acrylate, (meth)ethyl acrylate, (meth)
Propyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate (meaning acrylate or methacrylate; the same applies hereinafter), 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (
meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, 2-hydroxydodecyl(meth)acrylate, styrene, α-methylstyrene, alrylonitrile, (meth)acrylamide,
Diaseptone acrylamide, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, (
Examples include butoxyethyl meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like. Synthesis of these linear polymer compounds is usually carried out in an organic solvent.
ポリエステル樹脂はエチレングリコール、ネオペンチル
クリコール
ハク酸、アジピン酸、マレイン酸、無水マレイン酸、フ
タル酸、無水フタル酸などの２価のカルボン酸とのエス
テル化反応により得られる線状の飽和または不飽和のポ
リエステル樹脂が用いられる。Polyester resins are linear saturated or unsaturated resins obtained by esterification reaction with divalent carboxylic acids such as ethylene glycol, neopentyl glycol succinic acid, adipic acid, maleic acid, maleic anhydride, phthalic acid, and phthalic anhydride. A saturated polyester resin is used.
本発明の感光性樹脂組成物は、軟化点５０℃以上のエポ
キシエステル樹脂を、必須成分（Ｂ）として含有する。The photosensitive resin composition of the present invention contains an epoxy ester resin having a softening point of 50° C. or higher as an essential component (B).
軟化点（環球法で測定）が５０℃未満の場合には感光性
樹脂組成物が粘着性となる。When the softening point (measured by the ring and ball method) is less than 50°C, the photosensitive resin composition becomes sticky.
前記エポキシエステル樹脂は、ノボラックエポキシ樹脂
と１価不飽和カルボン酸とを、エポキシ当Ｎ１に対して
カルボン酸当量０．４〜１．１の割合で反応させて得ら
れる。カルボン酸当量が０．４未満の場合には反応性成
分が少ないため硬化性が悪く、１．１を超えると未反応
の不飽和カルボン酸が多くなる。The epoxy ester resin is obtained by reacting a novolak epoxy resin with a monovalent unsaturated carboxylic acid at a ratio of 0.4 to 1.1 carboxylic acid equivalents to N1 epoxy equivalents. When the carboxylic acid equivalent is less than 0.4, there are few reactive components, resulting in poor curability, and when it exceeds 1.1, there will be a large amount of unreacted unsaturated carboxylic acid.
ノボラックエポキシ樹脂と１価不飽和カルボン酸との反
応の反応温度は、反応時間および生成物の３次元化を防
止する点から７０〜１２０℃が好ましい。反応速度を高
めるために、３級アミン、第４級アンモニウム塩等を添
加することが好ましい。また反応系や反応生成物の安定
性を得る目的でハイドロキノンなどの安定剤を加えるこ
ともできる。反応は有機溶媒中で行なわれる。The reaction temperature for the reaction between the novolak epoxy resin and the monounsaturated carboxylic acid is preferably 70 to 120°C from the viewpoint of the reaction time and prevention of three-dimensionalization of the product. In order to increase the reaction rate, it is preferable to add a tertiary amine, a quaternary ammonium salt, etc. Furthermore, a stabilizer such as hydroquinone can be added for the purpose of stabilizing the reaction system and reaction products. The reaction is carried out in an organic solvent.
上記ノボラックエポキシ樹脂としては、例えばフェノー
ル、クレゾール等とホルムアルデヒドとを酸性触媒を用
いて縮合させて得られるノボラックフェノール樹脂に、
エピクロルヒドリンを反応させて得られるものが用いら
れる。また１価不飽和カルボン酸としては、例えばアク
リル酸、メタアクリル酸等が用いられ、これらの混合物
も用いることができる。As the novolac epoxy resin, for example, a novolac phenol resin obtained by condensing phenol, cresol, etc. and formaldehyde using an acidic catalyst,
The one obtained by reacting epichlorohydrin is used. Further, as the monovalent unsaturated carboxylic acid, for example, acrylic acid, methacrylic acid, etc. are used, and mixtures thereof can also be used.
前記エポキシエステル樹脂の配合割合は、前記線状高分
子化合物１００重量部に対して５〜１５０重量部である
。この配合割合が５重量部未満の場合には組成物中の反
応性成分が少ないため、硬化性が悪（、１５０重量部を
超えると現像時間が長くなる。The blending ratio of the epoxy ester resin is 5 to 150 parts by weight based on 100 parts by weight of the linear polymer compound. When this blending ratio is less than 5 parts by weight, the amount of reactive components in the composition is small, resulting in poor curability (and when it exceeds 150 parts by weight, the development time becomes long).
本発明の感光性樹脂組成物は、光重合可能なビニル単量
体を必須成分（Ｃ）として含有する。The photosensitive resin composition of the present invention contains a photopolymerizable vinyl monomer as an essential component (C).
光重合可能なビニル単量体としては、例えばテトラエチ
レングリコールジ（メタ）アクリレート等のポリエチレ
ングリコールジ（メタ）アクリレ− Ｉ−、プロピレン
グリコールジ（メタ）アクリレート、ジプロピレングリ
コールジ（メタ）アクリレート等のポリプロピングリコ
ールジ（メタ）アクリレート、２，２−ビス（４−（メ
タ）アクリロキシ・ジェトキシフェニル〉プロパン等の
ビスフェノールＡとエチレンオキサイドとから得られる
ジアルコールと（メタ）アクリル酸とのジエステル、ト
リメチロールプロパントリ （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、ジ
ペンタエリスリトールペンタ（メタ）アクリレート、ジ
ペンタエリスリトールヘキサ（メタ）アクリレート、β
１−メタクリロイルオキシエチル−γークロルーβーヒ
ドロキシプロピル−〇ーフタレート、フタル酸または無
水フタル酸と２価アルコール（例えばエチレングリコー
ル等）と（メタ）アクリル酸とから得られるポリエステ
ル型ジ（メタ）アクリレート、ネオペンチルグリコール
ジアクリレート、ヒドロキシピバリン酸ネオペンチルグ
リコールジアクリレート、エチレングリコールジグリシ
ジルエーテルジ（メタ）アクリレート、グリセリントリ
グリシジルエーテルトリ （メタ）アクリレート等のエ
ポキシ環に（メタ）アクリル酸を付加して得られるエポ
キシエステルが用いられる。これらは単独で、または２
種以上混合して使用される。Examples of photopolymerizable vinyl monomers include polyethylene glycol di(meth)acrylate I- such as tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and the like. polypropylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloxy jetoxyphenyl) diester of dialcohol obtained from bisphenol A such as propane and ethylene oxide and (meth)acrylic acid. , trimethylolpropane tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, β
1-methacryloyloxyethyl-γ-chloro-β-hydroxypropyl-〇-phthalate, a polyester type di(meth)acrylate obtained from phthalic acid or phthalic anhydride, a dihydric alcohol (e.g. ethylene glycol, etc.) and (meth)acrylic acid, Products obtained by adding (meth)acrylic acid to the epoxy ring of neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, ethylene glycol diglycidyl ether di(meth)acrylate, glycerin triglycidyl ether tri(meth)acrylate, etc. Epoxy esters are used. These can be used alone or in combination
Used as a mixture of more than one species.
ビニル単量体の配合割合は、前記線状高分子化合物１０
０重量部に対して２５〜８０重量部である。この配合割
合が２５重量部未満の場合には組成物中の反応性成分が
少ないため、硬化性が悪く、かつ現像時間が長く、８０
重量部を超えると組成物が粘着性になる。The blending ratio of the vinyl monomer is 10% of the linear polymer compound described above.
The amount is 25 to 80 parts by weight relative to 0 parts by weight. If this blending ratio is less than 25 parts by weight, the amount of reactive components in the composition is small, resulting in poor curability and long development time.
If the amount exceeds parts by weight, the composition becomes sticky.
本発明の感光性樹脂組成物は、活性光線により遊離ラジ
カルを生成する増感剤および（または）増感剤系を必須
成分（Ｄ）として含有する。The photosensitive resin composition of the present invention contains as an essential component (D) a sensitizer and/or a sensitizer system that generates free radicals when exposed to actinic rays.
増感剤としては、２−エチルアントラキノン、２−１−
ブチルアントラキノン、オクタメチルアントラキノン、
１．２−ベンズアントラキノン、２．３−ジフェニルア
ンＩ・ラキノン等の置換または非置換の多核キノン類、
ジアセチル、ベンジル等のケ１−アルドニル化合物、ヘ
ンジイン、ピハロン等のα−ケタルドニルアルコール類
およびエーテル類、α−フェニルーヘンゾイン、α５
α−ジェトキシアセトフェノン等のα−炭化水素置換芳
香族アシロイン類、ヘンシフエノン、４．４−ビスジア
ルキルアミノヘンシフエノン、２．４−ジエチルチオキ
サントン等の芳香族ケトン類などが使用される。これら
は単独で、または２種以上混合して使用される。As a sensitizer, 2-ethylanthraquinone, 2-1-
Butylanthraquinone, octamethylanthraquinone,
1. Substituted or unsubstituted polynuclear quinones such as 2-benzanthraquinone and 2.3-diphenylune I/laquinone;
Ke1-aldonyl compounds such as diacetyl and benzyl, α-ketaldonyl alcohols and ethers such as hengeine and pyhalon, α-phenyl-henzoin, α5
Used are α-hydrocarbon-substituted aromatic acyloins such as α-jethoxyacetophenone, aromatic ketones such as hensifhenone, 4,4-bisdialkylaminohensiphenone, and 2,4-diethylthioxanthone. These may be used alone or in combination of two or more.
増感剤系としては、例えば２． ２． ５−１−リアリ
ールイミダゾールニ量体と２＝メルカプトベンゾキナゾ
ール、ロイコクリスクルハイオレソト、トリス（４−ジ
エチルアミノ−２−メチルフェニル）メタン等との組合
わせが使用される。またそれ自体では光重合開始性はな
いが、前記物質と組合わせて用いることにより全体とし
て光重合開始性能の良好な増感剤系となるような添加剤
を使用することもできる。例えばベンゾフェノンに対す
るトリエタノールアミン等の３級アミンなどである。Examples of the sensitizer system include 2. 2. Combinations of 5-1-rearylimidazole dimer and 2=mercaptobenzoquinazole, leucocriscle hiolesotho, tris(4-diethylamino-2-methylphenyl)methane, etc. are used. It is also possible to use additives which do not have photopolymerization initiating properties by themselves, but which, when used in combination with the above substances, form a sensitizer system with good photopolymerization initiating performance as a whole. Examples include tertiary amines such as triethanolamine for benzophenone.
これらの増感剤および（または）増感剤系は上記の線状
高分子化合物、エポキシエステル樹脂および光重合可能
なビニル単量体１００重量部に対して０．５〜１０重量
部の割合で含有させることが好ましい。These sensitizers and/or sensitizer systems are used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the above-mentioned linear polymer compound, epoxy ester resin and photopolymerizable vinyl monomer. It is preferable to include it.
本発明の感光性樹脂組成物は、シリコン樹脂等の表面張
力改質剤、発泡防止剤、染料、着色顔料、トリエチレン
グリコールジアセテート等の可塑剤などを含有させるこ
とができる。The photosensitive resin composition of the present invention can contain a surface tension modifier such as a silicone resin, an antifoaming agent, a dye, a coloring pigment, a plasticizer such as triethylene glycol diacetate, and the like.
本発明の感光性樹脂組成物に前記直接塗工法を適用して
、ロールコータ−、カーテンフローコーター、ディッピ
ング塗工法などで直接銅張り積層板に塗工後、溶剤を乾
燥させ、次いで感光性樹脂組成物上に直接ネガフィルム
を当て、露光、現像およびエツチングを行なって配線板
を得ることができる。The above-mentioned direct coating method is applied to the photosensitive resin composition of the present invention, and after coating the copper-clad laminate directly with a roll coater, curtain flow coater, dipping coating method, etc., the solvent is dried, and then the photosensitive resin A wiring board can be obtained by applying a negative film directly onto the composition, exposing it to light, developing it and etching it.
また本発明の感光性樹脂組成物をポリエステルフィルＪ
、などの支持体上に塗工、乾燥させた後、銅張り積層板
に密着させ、前記支持体を感光性樹脂組成物から剥離し
、以下前記と同様にして配線板を得ることもできる。Further, the photosensitive resin composition of the present invention may be used as polyester film J.
It is also possible to obtain a wiring board by coating the composition on a support such as .
更に従来の感光性フィルムの場合と同様に、本発明の感
光性樹脂組成物をポリエステルフィルムなどの支持体上
に塗布、乾燥させた後、銅張り積層板に密着させ、前記
支持体を剥離させずに、その支持体上にネガフィルムを
置き、露光し、更に前記支持体を剥離後、現像およびエ
ツチングを行なって配線板を得ることもできる。Further, as in the case of conventional photosensitive films, the photosensitive resin composition of the present invention is applied onto a support such as a polyester film, dried, and then brought into close contact with a copper-clad laminate, and the support is peeled off. A wiring board can also be obtained by placing a negative film on the support, exposing it to light, peeling off the support, and then developing and etching it.
本発明の感光性樹脂組成物の銅張り積層板への乾燥後の
塗布厚さは、特に限定されないが、通常５〜６０μｍ程
度で、特に１０〜２０μｍが好ましい。この塗布厚さが
薄すぎるとゴミなどが付着して塗膜にピンホールが生じ
易いなど、異物に対する管理が難しくなり、また厚すぎ
ると解像度が悪くなる。The coating thickness of the photosensitive resin composition of the present invention after drying on a copper-clad laminate is not particularly limited, but is usually about 5 to 60 μm, and preferably 10 to 20 μm. If the coating thickness is too thin, it will be difficult to control foreign matter, such as dirt and the like, which will easily cause pinholes in the coating film, and if it is too thick, the resolution will deteriorate.
本発明の感光性樹脂組成物の乾燥条件には特に制限はな
いが、乾燥時間は主として塗膜厚さと乾燥温度に左右さ
れる。高温で長時間加熱すると、熱重合を起こして現像
できなくなることがあるため、１２０℃以下で３０分以
下乾燥することが好ましい。Although there are no particular restrictions on the drying conditions for the photosensitive resin composition of the present invention, the drying time mainly depends on the coating thickness and drying temperature. If heated at high temperature for a long time, thermal polymerization may occur and development may become impossible, so it is preferable to dry at 120° C. or lower for 30 minutes or less.
本発明の感光性樹脂組成物に対する露光量は、硬化の度
合および解像度の点から１００〜５００ｍ Ｊ ／ ｃ
ｓＡが好ましい。The exposure amount for the photosensitive resin composition of the present invention is 100 to 500 mJ/c in terms of degree of curing and resolution.
sA is preferred.
現像に際しては、現像液として炭酸ソーダ、苛性ソーダ
等のアルカリ水溶液が使用されるが、トリエタノールア
ミン等のアミン、ブチルセロソルブ等の有機溶剤を前記
現像液に添加することもできる。In the development, an alkaline aqueous solution such as soda carbonate or caustic soda is used as a developer, but an amine such as triethanolamine or an organic solvent such as butyl cellosolve may also be added to the developer.
エツチング溶液としては、塩化第２鉄溶液、塩化第２銅
水溶液等が使用される。As the etching solution, a ferric chloride solution, a cupric chloride aqueous solution, etc. are used.
本発明の感光性樹脂組成物を用いて塗工、乾燥、露光、
現像およびエンチングを行なって得られる配線板の銅面
には、本発明の感光性樹脂組成物が残存しているが、苛
性ソーダ等のアルカリ水溶液または有機溶剤に浸漬する
ことによりこれを除去することができる。Coating, drying, exposing using the photosensitive resin composition of the present invention,
The photosensitive resin composition of the present invention remains on the copper surface of the wiring board obtained by developing and etching, but this can be removed by immersion in an aqueous alkaline solution such as caustic soda or an organic solvent. can.
（発明の効果）
本発明の感光性樹脂組成物は、粘着性を有しないため、
この感光性樹脂組成物上に直接ネガフィルムを置いて露
光、現像およびエツチングを行なうことができ、ネガフ
ィルムの汚染を生じることがないという効果を有する。(Effect of the invention) Since the photosensitive resin composition of the invention does not have adhesiveness,
Exposure, development and etching can be performed by placing a negative film directly on this photosensitive resin composition, which has the effect that the negative film is not contaminated.
この結果、本発明の感光性樹脂組成物を使用することに
より、解像度の向上した、また高密度化された配線板を
得ることができる。特に本発明の感光性樹脂組成物は、
支持体を用いずに、直接銅張り積層板等に塗工する直接
塗工法を適用することができるため、支持体フィルムの
節約、作業工程の簡略化等を図ることができ、極めて経
済的に配線板を製造することができる。As a result, by using the photosensitive resin composition of the present invention, a wiring board with improved resolution and high density can be obtained. In particular, the photosensitive resin composition of the present invention is
Since it is possible to apply the direct coating method to directly coat copper-clad laminates, etc. without using a support, it is possible to save on support film and simplify the work process, making it extremely economical. Wiring boards can be manufactured.
（実施例） 実施例中の部は重量部を意味する。(Example) Parts in the examples mean parts by weight.
実施例１
（エポキシエステル樹脂の合成）
攪拌機、温度計付き四つ目フラスコに、ＥＯＣＮ−１０
４３（日本化薬（株）製、ノボラックエポキシ樹脂）５
２３部、アクリル酸 １２３部（エポキシ当量１に対し
てカルボン酸当量０．７５）、エチレングリコールモノ
エチルエーテルアセテート ３５０部、ハイドロキノン
０．３部およびカヤキュアーＤＭＢＩ（日本化薬（株
）ｉ！！、芳香族３級アミン）５２部を仕込み、９０
”Ｃで酸価が２になるまで反応を行ない、エポキシエス
テル樹脂溶液（加熱残分６７重量％、固形化した樹脂の
軟化点約７０℃）を得た。Example 1 (Synthesis of epoxy ester resin) EOCN-10 was placed in a fourth flask equipped with a stirrer and a thermometer.
43 (manufactured by Nippon Kayaku Co., Ltd., novolac epoxy resin) 5
23 parts of acrylic acid (carboxylic acid equivalent: 0.75 to 1 epoxy equivalent), 350 parts of ethylene glycol monoethyl ether acetate, 0.3 part of hydroquinone, and Kayacure DMBI (Nippon Kayaku Co., Ltd. i!!). Add 52 parts of aromatic tertiary amine) and
The reaction was carried out with C until the acid value reached 2 to obtain an epoxy ester resin solution (heated residue: 67% by weight, softening point of solidified resin: about 70°C).
（感光性樹脂組成物の調製）
線状高分子化合物溶液（メタクリル酸／スチレン／メタ
クリル酸メチル／メタクリル酸エチル−２０／２０１５
０／１０重量比の共重合体、ガラス転移温度約９０℃、
分子量約３万、酸価１２７）、エチレングリコールモノ
エチルエーテル溶液、（加熱残分４５重量％）８６部、
前記エポキシエステル樹脂 ３５部、テトラエチレング
リコールジアクリレート ８部、トリメチロールプロパ
ントリアクリレート ６部、カヤキュアＤＭＢ Ｉ２部
、２，４−ジエチルチオキサントン １．５部、ビクト
リアピュアブルー０．２部、メチルエチルケトン ８部
およびメタノール ７部を均一に混合して本発明の感光
性樹脂組成物を得た。(Preparation of photosensitive resin composition) Linear polymer compound solution (methacrylic acid/styrene/methyl methacrylate/ethyl methacrylate-20/2015
0/10 weight ratio copolymer, glass transition temperature approximately 90°C,
Molecular weight approximately 30,000, acid value 127), ethylene glycol monoethyl ether solution, (heating residue 45% by weight) 86 parts,
35 parts of the above epoxy ester resin, 8 parts of tetraethylene glycol diacrylate, 6 parts of trimethylolpropane triacrylate, 2 parts of Kayacure DMB I, 1.5 parts of 2,4-diethylthioxanthone, 0.2 parts of Victoria Pure Blue, 8 parts of methyl ethyl ketone. and 7 parts of methanol were uniformly mixed to obtain a photosensitive resin composition of the present invention.
（配線板の製造）
表面を研摩した銅張り積層板に、塗工器（ＢＡＫＥＲＦ
ＩＬＭＡＰＰＬＩＣＡＴＯＲ（上品製作所（株）製）を
用いて前記感光性樹脂組成物を直接塗布し、１００℃で
２分間乾燥して得られた膜の厚さは約１０μｍで、全く
粘着性はなかった。(Manufacture of wiring boards) A coating machine (BAKERF
The photosensitive resin composition was directly coated using ILMAPPLICATOR (manufactured by Jyuji Seisakusho Co., Ltd.) and dried at 100° C. for 2 minutes. The resulting film had a thickness of about 10 μm and had no tackiness at all.
この感光性樹脂組成物上に直接ネガフィルムを置き、真
空下に、ネガフィルムをよく密着させ３ＫＷの超高圧水
銀灯（オーク製作所（株）製、フエニソクス−３０００
）を用いて２００ｍＪ／−で露光を行なった。ネガフィ
ルムは感光性樹脂組成物から容易に取れ、ネガフィルム
を全く汚染する１に
とはなかった。A negative film was placed directly on this photosensitive resin composition, and under vacuum, the negative film was placed in close contact with a 3KW ultra-high pressure mercury lamp (manufactured by Oak Seisakusho Co., Ltd., Fenisox-3000).
) was used for exposure at 200 mJ/-. The negative film was easily removed from the photosensitive resin composition and did not contaminate the negative film at all.
次いで３０℃の２％炭酸ソーダ水溶液で１００秒間スプ
レー現像した後、４０°ボーメ塩化第２鉄溶液を用いて
エツチングを行い、５％苛性ソーダ水溶液で感光性樹脂
組成物を剥離して配線板を得た。得られた配線板はネガ
フィルムに忠実であり、その解像度は３０μｍ以上であ
った。Next, spray development was performed for 100 seconds with a 2% sodium carbonate aqueous solution at 30°C, etching was performed using a 40° Baume ferric chloride solution, and the photosensitive resin composition was peeled off with a 5% caustic soda aqueous solution to obtain a wiring board. Ta. The obtained wiring board was faithful to the negative film, and its resolution was 30 μm or more.
実施例２
線状高分子化合物の使用量８６部を６１部とし、かつエ
ポキシエステル樹脂の使用量３５部を５８部とし、その
他は実施例１と同様に処理して銅張り積層板に塗布し、
１００℃で２分間乾燥して得られた膜の厚さは約５μｍ
であった。以下実施例１と同様にして露光を行なったが
、ネガフィルムは感光性樹脂組成物から容易に取れ、ネ
ガフィルムを汚染することもなかった。Example 2 The amount of the linear polymer compound used was changed from 86 parts to 61 parts, and the amount of the epoxy ester resin used was changed from 35 parts to 58 parts, and otherwise treated in the same manner as in Example 1 and applied to a copper-clad laminate. ,
The thickness of the film obtained by drying at 100°C for 2 minutes is approximately 5 μm.
Met. Exposure was carried out in the same manner as in Example 1, but the negative film was easily removed from the photosensitive resin composition and was not contaminated.
Claims (1)
し、かつガラス転移温度が４０℃以上の線状高分子化合
物１００重量部、（Ｂ）ノボラックエポキシ樹脂と１価
不飽和カルボン酸とを、エポキシ当量１に対してカルボ
ン酸当量０．４〜１．１の割合で反応させて得られる、
軟化点５０℃以上のエポキシエステル樹脂５〜１５０重
量部、（Ｃ）光重合可能なビニル単量体２５〜８０重量
部および（Ｄ）活性光線により遊離ラジカルを生成する
増感剤および（または）増感剤系を含有してなる感光性
樹脂組成物。1. (A) 100 parts by weight of a linear polymer compound with an acid value of 80 to 200, a carboxyl group, and a glass transition temperature of 40°C or higher, (B) novolac epoxy resin and monounsaturated carboxylic acid obtained by reacting with the epoxy equivalent in a ratio of 0.4 to 1.1 carboxylic acid equivalent to 1,
5 to 150 parts by weight of an epoxy ester resin with a softening point of 50°C or higher, (C) 25 to 80 parts by weight of a photopolymerizable vinyl monomer, and (D) a sensitizer that generates free radicals when exposed to actinic rays and/or A photosensitive resin composition containing a sensitizer system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60042476A JPS61201237A (en) | 1985-03-04 | 1985-03-04 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60042476A JPS61201237A (en) | 1985-03-04 | 1985-03-04 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61201237A true JPS61201237A (en) | 1986-09-05 |
Family
ID=12637111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60042476A Pending JPS61201237A (en) | 1985-03-04 | 1985-03-04 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61201237A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS646943A (en) * | 1987-02-25 | 1989-01-11 | Tokyo Ohka Kogyo Co Ltd | Heat resistant photosensitive resin composition |
| JPS646944A (en) * | 1987-03-25 | 1989-01-11 | Tokyo Ohka Kogyo Co Ltd | Heat resistant photosensitive resin composition |
| JPH021859A (en) * | 1988-06-13 | 1990-01-08 | Toyobo Co Ltd | Photosensitive resin composition |
| JPH024255A (en) * | 1988-06-22 | 1990-01-09 | Toyobo Co Ltd | Photosensitive resin composition |
| JPH02230149A (en) * | 1987-12-16 | 1990-09-12 | Nippon Synthetic Chem Ind Co Ltd:The | Image forming method |
| JPH05257281A (en) * | 1991-06-12 | 1993-10-08 | Mitsui Toatsu Chem Inc | Photosensitive resin composition and photosensitive liquid composition and photosensitive film |
| JP2007010835A (en) * | 2005-06-29 | 2007-01-18 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| WO2011037182A1 (en) * | 2009-09-25 | 2011-03-31 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition for resist material, and photosensitive resin laminate |
-
1985
- 1985-03-04 JP JP60042476A patent/JPS61201237A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS646943A (en) * | 1987-02-25 | 1989-01-11 | Tokyo Ohka Kogyo Co Ltd | Heat resistant photosensitive resin composition |
| JPS646944A (en) * | 1987-03-25 | 1989-01-11 | Tokyo Ohka Kogyo Co Ltd | Heat resistant photosensitive resin composition |
| JPH02230149A (en) * | 1987-12-16 | 1990-09-12 | Nippon Synthetic Chem Ind Co Ltd:The | Image forming method |
| JPH021859A (en) * | 1988-06-13 | 1990-01-08 | Toyobo Co Ltd | Photosensitive resin composition |
| JPH024255A (en) * | 1988-06-22 | 1990-01-09 | Toyobo Co Ltd | Photosensitive resin composition |
| JPH05257281A (en) * | 1991-06-12 | 1993-10-08 | Mitsui Toatsu Chem Inc | Photosensitive resin composition and photosensitive liquid composition and photosensitive film |
| JP2007010835A (en) * | 2005-06-29 | 2007-01-18 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| WO2011037182A1 (en) * | 2009-09-25 | 2011-03-31 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition for resist material, and photosensitive resin laminate |
| CN102549498A (en) * | 2009-09-25 | 2012-07-04 | 旭化成电子材料株式会社 | Photosensitive resin composition for resist material, and photosensitive resin laminate |
| JPWO2011037182A1 (en) * | 2009-09-25 | 2013-02-21 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition for resist material and photosensitive resin laminate |
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