JP4260463B2 - Photopolymerizable resin composition - Google Patents
Photopolymerizable resin composition Download PDFInfo
- Publication number
- JP4260463B2 JP4260463B2 JP2002338548A JP2002338548A JP4260463B2 JP 4260463 B2 JP4260463 B2 JP 4260463B2 JP 2002338548 A JP2002338548 A JP 2002338548A JP 2002338548 A JP2002338548 A JP 2002338548A JP 4260463 B2 JP4260463 B2 JP 4260463B2
- Authority
- JP
- Japan
- Prior art keywords
- photopolymerizable resin
- meth
- group
- mass
- 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.)
- Expired - Fee Related
Links
- 239000011342 resin composition Substances 0.000 title claims description 28
- 229920005989 resin Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 21
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 45
- -1 2-ethylhexyl Chemical group 0.000 description 22
- 239000000243 solution Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 239000011241 protective layer Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 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 6
- 238000005530 etching Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229940107698 malachite green Drugs 0.000 description 3
- 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 3
- 239000000693 micelle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 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
- 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
- LYCNQAIOLGIAFA-UHFFFAOYSA-N 4-[bis[4-(dimethylamino)-2-methylphenyl]methyl]-n,n,3-trimethylaniline Chemical compound CC1=CC(N(C)C)=CC=C1C(C=1C(=CC(=CC=1)N(C)C)C)C1=CC=C(N(C)C)C=C1C LYCNQAIOLGIAFA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SDTXSEXYPROZSZ-UHFFFAOYSA-N 1,2-dibromo-2-methylpropane Chemical compound CC(C)(Br)CBr SDTXSEXYPROZSZ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- FEWDXGMBVQULLN-UHFFFAOYSA-N 1-hydroxy-2-phenyl-1,5,6,7-tetrahydro-4H-benzimidazol-4-one Chemical compound ON1C=2CCCC(=O)C=2N=C1C1=CC=CC=C1 FEWDXGMBVQULLN-UHFFFAOYSA-N 0.000 description 1
- BTUGGGLMQBJCBN-UHFFFAOYSA-N 1-iodo-2-methylpropane Chemical compound CC(C)CI BTUGGGLMQBJCBN-UHFFFAOYSA-N 0.000 description 1
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical group C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-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
- 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
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(c(cc1)ccc1O)c(cc1)ccc1O* Chemical compound CC(C)(c(cc1)ccc1O)c(cc1)ccc1O* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WZKXBGJNNCGHIC-UHFFFAOYSA-N Leucomalachite green Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=CC=C1 WZKXBGJNNCGHIC-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- DMZOHLNSFFJNFS-UHFFFAOYSA-N [4-(butylamino)phenyl]-phenylmethanone Chemical compound C1=CC(NCCCC)=CC=C1C(=O)C1=CC=CC=C1 DMZOHLNSFFJNFS-UHFFFAOYSA-N 0.000 description 1
- BEUGBYXJXMVRFO-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1 BEUGBYXJXMVRFO-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- KSCQDDRPFHTIRL-UHFFFAOYSA-N auramine O Chemical compound [H+].[Cl-].C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 KSCQDDRPFHTIRL-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- FAJDWNKDRFAWLS-UHFFFAOYSA-N benzyl-[9-(diethylamino)benzo[a]phenoxazin-5-ylidene]azanium;chloride Chemical compound [Cl-].O1C2=CC(N(CC)CC)=CC=C2N=C(C2=CC=CC=C22)C1=CC2=[NH+]CC1=CC=CC=C1 FAJDWNKDRFAWLS-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- RUGJGIJOPOCYCH-UHFFFAOYSA-N bis[4-(dibutylamino)phenyl]methanone Chemical compound C1=CC(N(CCCC)CCCC)=CC=C1C(=O)C1=CC=C(N(CCCC)CCCC)C=C1 RUGJGIJOPOCYCH-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- OQROAIRCEOBYJA-UHFFFAOYSA-N bromodiphenylmethane Chemical compound C=1C=CC=CC=1C(Br)C1=CC=CC=C1 OQROAIRCEOBYJA-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004120 green S Substances 0.000 description 1
- 235000012701 green S Nutrition 0.000 description 1
- WDPIZEKLJKBSOZ-UHFFFAOYSA-M green s Chemical compound [Na+].C1=CC(N(C)C)=CC=C1C(C=1C2=CC=C(C=C2C=C(C=1O)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](C)C)C=C1 WDPIZEKLJKBSOZ-UHFFFAOYSA-M 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 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
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は光重合性樹脂組成物、光重合性樹脂積層体及びこれを用いたレジストパターンの形成方法に関し、更に詳しくはプリント回路板作製に適したアルカリ現像可能な光重合性樹脂組成物、光重合性樹脂積層体及びこれを用いたレジストパターンの形成方法に関する。
【０００２】
【従来の技術】
従来、プリント回路作製用のレジストとして、支持層と光重合性樹脂層から成る光重合性樹脂積層体、いわゆる、ドライフィルムレジスト（以下、ＤＦＲと略す）が用いられている。ＤＦＲは、一般に支持層上に光重合性樹脂組成物を積層し、多くの場合、さらに該組成物上に保護層を積層することにより作製される。
ここで用いられる光重合性樹脂組成物としては、現在、現像液として弱アルカリ水溶液を用いるアルカリ現像型の樹脂組成物が一般的である。
ＤＦＲを用いてのプリント配線板の作製は、以下のように行なわれる。
まず、保護層を剥離した後、銅張積層板等の永久回路作製用基板上にＤＦＲをラミネートし、配線パターンマスクフィルム等を通して露光を行う。
次に、必要に応じて支持層を剥離し、現像液により未露光部分の光重合性樹脂組成物を溶解又は分散除去し、基板上に硬化されたレジストパターンを形成させる。このレジストパターンをマスクとして、基板の金属表面をエッチング又はめっき処理し、最後にレジストパターンを強アルカリ水溶液を用いて剥離する。
【０００３】
近年は、工程の簡便さから、スルーホールを硬化された光重合性樹脂層（硬化膜）で覆ったのちにエッチングする、いわゆるテンティング法が多用されている。このエッチングには、塩化第二銅、塩化第二鉄、銅アンモニア錯体溶液等が用いられる。
ＤＦＲに要求される性能としては、テンティング用途では、硬化膜が強靭で破れのない良好なテンティング性が求められており、プリント配線板の配線パターンの微細化に伴って、レジストパターンの高解像度化も求められている。
【０００４】
ＤＦＲは、通常、プラスチック等の芯に固く巻きつけたロールの形態を取るため、光重合性樹脂層が軟らかすぎると、保存中に端面からのしみ出し（エッジフューズ）が起こり、取り扱い上好ましくない。このため、ラミネート時の基板への追従性を損なわない限りにおいて、エッジフューズ性が良い、つまり光重合性樹脂層が硬い方が取り扱いの観点から好ましい。
ＤＦＲに要求される性能としてはさらに、低凝集性であることが挙げられる。現像に際して、未露光の光重合性樹脂層は現像液に分散してミセルを形成するが、ミセルの安定性（低凝集性）が悪いと、現像運転中にミセルが容易に破壊されて非水溶性成分がオイル状や紛体状に凝集析出し、基板に付着して後工程における不良を生じたり、現像機内部に固着して運転に支障をきたすためである。
【０００５】
また、レジストの剥離性については、剥離片が大きくて砕けにくいと、剥離工程において搬送ロールに絡み付くなどのトラブルを生ずるため、剥離片の細かいことが工程上望ましい。
【０００６】
【発明が解決しようとする課題】
本発明の課題は、現像後のレジストパターンの解像性及び硬化膜のテンティング性に優れるとともに、エッジフューズ性、現像液分散時の低凝集性、剥離性にも優れる、アルカリ現像型プリント配線板作製用ＤＦＲとして有用な光重合性樹脂組成物及び光重合性樹脂積層体、及びこれを用いたレジストパターンの形成方法を提供することである。
【０００７】
【課題を解決するための手段】
上記の課題を解決すべく鋭意検討を重ねた結果、特定の光重合性樹脂組成物をＤＦＲに用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。
すなわち、本発明は以下の通りである。
（１）（ａ）カルボキシル基含有量が酸当量で１００〜６００でありかつ重量平均分子量が２万〜５０万の線状重合体からなるバインダー用樹脂を２０〜８０質量％、（ｂ）下記一般式（Ｉ）で表わされる化合物と下記一般式（ＩＩ）で表わされる化合物とを含み、さらに、下記一般式（ＩＩＩ）及び（ＩＶ）で表わされる化合物群から選ばれる少なくとも一種の化合物を含む光重合性不飽和化合物成分を５〜７０質量％、および（ｃ）光重合開始剤を０．１〜１５質量％含有することを特徴とする光重合性樹脂組成物。
【０００８】
【化６】
（式中、Ｒ1は（メタ）アクリロイル基を示し、Ａ1はＣ2Ｈ4又はＣ3Ｈ6を示し、Ａ2はシクロアルカン残基又は炭素数が６以下の鎖状炭化水素を示す。ｋは１〜６の整数である。）
【００１０】
【化７】
（式中、Ｒ2及びＲ3は（メタ）アクリロイル基を示し、Ａ3及びＡ4はＣ2Ｈ4又はＣ3Ｈ6を示す。ｍ、ｎ、ｐ及びｑは２≦ｍ＋ｎ＋ｐ＋ｑ≦４０となる０以上の整数である。）
【００１２】
【化８】
（式中、Ｒは水素原子又は（メタ）アクリロイル基を示し、１分子中に少なくとも４個以上の（メタ）アクリロイル基を含む。）
【００１４】
【化９】
（式中、Ｒ4は（メタ）アクリロイル基を示し、Ａ5は炭素数２０以下のアルキル基を示す。ｒは１〜３の整数、ｓは４〜２０の整数、ｔは０〜５の整数である。Ｃ2Ｈ4Ｏ及びＣ3Ｈ6Ｏの繰り返し単位の配列はブロックであってもランダムであっても良い。）
（２） （ｃ）光重合開始剤として、下記一般式（Ｖ）で表わされる２，４，５−トリアリールイミダゾール二量体を含有することを特徴とする、（１）に記載の光重合性樹脂組成物。
【００１６】
【化１０】
（式中、Ａ6、Ａ7及びＡ8は水素、アルキル基、アルコキシ基又はハロゲン基を示し、ｕ、ｖ、ｗは１〜５の整数である。）
（３） 支持層上に（１）又は（２）に記載の光重合性樹脂組成物からなる層を設けた光重合性樹脂積層体。
・ （３）に記載の光重合性樹脂積層体を用いて、基板上に光重合性樹脂層を形成し、露光し、現像する工程を含むレジストパターンの形成方法。
【００１８】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の光重合性樹脂組成物の（ａ）バインダー用樹脂に用いられる線状重合体に含まれるカルボキシル基の量は、酸当量で１００〜６００である必要があり、好ましくは３００〜４００である。（ａ）バインダー用樹脂の線状重合体に含まれるカルボキシル基は、ＤＦＲにアルカリ水溶液に対する適度な現像性や剥離性を与えるために必要である。
【００１９】
この酸当量が１００未満では、現像耐性が低下し、解像性及び密着性に悪影響を及ぼし、６００を超えると、現像性や剥離性が悪化する。ここで酸当量とは、その中に１当量のカルボキシル基を有するポリマーの質量を言い、その測定は、平沼産業（株）製平沼自動滴定装置（ＣＯＭ−５５５）を使用し、０．１ｍｏｌ／Ｌの水酸化ナトリウムを用いて電位差滴定法により行われる。
本発明の光重合性樹脂組成物の（ａ）バインダー用樹脂に用いられる線状重合体の分子量は、２万〜５０万である必要があり、好ましくは３万〜３０万、さらに好ましくは５万〜２５万である。この分子量が５０万を超えると、現像性が低下し、２万未満では硬化膜の強度やエッジフューズ性が悪化する。
【００２０】
分子量の測定は、日本分光（株）製ゲルパーミエーションクロマトグラフィー（ポンプ：Ｇｕｌｌｉｖｅｒ、ＰＵ−１５８０型、カラム：昭和電工（株）製Ｓｈｏｄｅｘ（登録商標）（ＫＦ−８０７、ＫＦ−８０６Ｍ、ＫＦ−８０６Ｍ、ＫＦ−８０２．５）４本直列、移動相溶媒：テトラヒドロフラン、ポリスチレン標準サンプルによる検量線使用）により、重量平均分子量（ポリスチレン換算）として求められる。
【００２１】
（ａ）バインダー用樹脂に用いられる線状重合体は、下記の二種類の単量体の中より各々一種又はそれ以上の単量体を共重合させることにより得られる。
第一の単量体は、分子中に重合性不飽和基を一個有するカルボン酸又は酸無水物で、例えば（メタ）アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、マレイン酸無水物、マレイン酸半エステル等がある。
第二の単量体は、非酸性で分子中に重合性不飽和基を一個有し、光重合性樹脂層の現像性、エッチング及びめっき工程での耐性、硬化膜の可撓性等の種々の特性を保持するように選ばれる。このようなものとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート類が挙げられる。また、フェニル基を有するビニル化合物（例えば、スチレン）も用いることができる。
【００２２】
（ａ）バインダー用樹脂に用いられる線状重合体の重合法としては、単量体の混合物をアセトン、メチルエチルケトン、イソプロパノール等の溶剤で希釈した溶液に、過酸化ベンゾイル、アゾビスイソブチロニトリル等のラジカル重合開始剤を適量添加し、加熱攪拌する方法が好ましい。
なお、混合物の一部を反応液に滴下しながら重合を行なったり、反応終了後さらに溶剤を加えて所望の濃度に調整する場合もある。また、重合法としては、上記の溶液重合以外に、塊状重合、懸濁重合及び乳化重合を用いても良い。
【００２３】
本発明において、（ａ）バインダー用樹脂の含有率は、光重合性樹脂組成物の全固形分の質量中、２０〜８０質量％であることが必要であり、好ましくは３０〜７０質量％、より好ましくは３５〜６５質量％である。（ａ）バインダー用樹脂が２０質量％未満であるか又は８０質量％を超えると、露光によって形成される硬化パターンがレジストとしての特性、例えば、テンティング、エッチング、各種めっき工程における耐性を十分に有しない。
【００２４】
本発明の光重合性樹脂組成物は、（ｂ）光重合性不飽和化合物成分として、下記一般式（Ｉ）で表わされる化合物、及び下記一般式（ＩＩ）で表わされる化合物が必須成分である。
【００２５】
【化１１】
（式中、Ｒ1は（メタ）アクリロイル基を示し、Ａ1はＣ2Ｈ4又はＣ3Ｈ6を示し、Ａ2は炭素数が６以下の鎖状炭化水素又はシクロアルカンを示す。ｋは１〜６の整数である。）
【００２７】
【化１２】
（式中、Ｒ2及びＲ3は（メタ）アクリロイル基を示し、Ａ3及びＡ4はＣ2Ｈ4又はＣ3Ｈ6を示す。ｍ、ｎ、ｐ及びｑは２≦ｍ＋ｎ＋ｐ＋ｑ≦４０となる０以上の整数である。）
一般式（Ｉ）で表わされる化合物において、ｋが６を超えると感度及び解像度が低下する。また、Ａ2が鎖状炭化水素の場合、その炭素数が６を超えると感度が低下する。Ａ2がシクロアルカンの場合は、シクロヘキサン環が好ましい。
【００２９】
本発明に用いられる一般式（Ｉ）で表わされる化合物の具体例としては、メタクリル酸のＥＯ付加物（平均２モル）とヘキサヒドロフタル酸とのハーフエステル等がある（ここでＥＯはエチレンオキサイドの略、以下同じ）。
一般式（ＩＩ）で表わされる化合物において、ｍ＋ｎ＋ｐ＋ｑが２未満だと硬化膜の柔軟性が低下して脆くなるとともに現像性が悪化し、４０を超えると感度及び解像度が低下する。
【００３０】
本発明に用いられる一般式（ＩＩ）で表わされる化合物の具体例としては、ビスフェノールＡのＥＯ付加物（両端に平均５モルずつ）のジメタクリレート（新中村化学工業（株）製ＮＫエスエルＢＰＥ−５００）や、ビスフェノールＡのアルキレンオキサイド付加物（両端に平均２モルずつのＰＯ及び平均１５モルずつのＥＯ）のジメタクリレート等がある（ここでＰＯはプロピレンオキサイドの略、以下同じ）。
【００３１】
また、（ｂ）光重合性不飽和化合物成分として、さらに、下記一般式（ＩＩＩ）及び（ＩＶ）で表わされる化合物群から選ばれる少なくとも一種が含有されていることは、本発明の好ましい実施形態である。
【００３２】
【化１３】
（式中、Ｒは水素原子又は（メタ）アクリロイル基を示し、１分子中に少なくとも４個以上の（メタ）アクリロイル基を含む。）
【００３４】
【化１４】
（式中、Ｒ4は（メタ）アクリロイル基を示し、Ａ5は炭素数２０以下のアルキル基を示す。ｒは１〜３の整数、ｓは４〜２０の整数、ｔは０〜５の整数である。Ｃ2Ｈ4Ｏ及びＣ3Ｈ6Ｏの繰り返し単位の配列はブロックであってもランダムであっても良い。）
一般式（ＩＩＩ）で表わされる化合物において、１分子中の（メタ）アクリロイル基の数が４個未満だと十分な感度と硬化膜強度が得られない。本発明に用いられる一般式（ＩＩＩ）で表わされる化合物の具体例としては、ジペンタエリスリトールヘキサアクリレート［ダイセル・ユーシービー（株）製ＤＰＨＡ］等がある。
【００３６】
一般式（ＩＶ）で表わされる化合物において、Ａ5の炭素数が２０を超えたり、ｒが３を超えると現像性が悪化する。ｓが４未満だと凝集性が悪化し、２０を超えると感度や解像性が低下する。ｔが５を超えると凝集性が悪化する。
本発明に用いられる一般式（ＩＶ）で表わされる化合物の具体例としては、ノニルフェノールのＥＯ付加物（平均８モル）のアクリレート（東亞合成（株）製アロニックス（登録商標）Ｍ−１１４）や、ノニルフェノールのアルキレンオキサイド付加物（平均２モルのＰＯ及び平均７モルのＥＯ）のアクリレート等がある。
【００３７】
（ｂ）光重合性不飽和化合物としては、さらに、下記一般式（ＶＩ）で表わされる化合物を含んでも良い。
【００３８】
【化１５】
（式中、Ｒ5及びＲ6は（メタ）アクリロイル基を示し、Ａ9はＣ2Ｈ4又はＣ3Ｈ6を示し、Ａ10は炭素数４〜１２のイソシアネート残基を示す。ｈ及びｊは２≦ｈ＋ｊ≦３０となる０以上の整数である。）
一般式（ＶＩ）で表わされる化合物において、ｈ＋ｊが２未満だと硬化膜の柔軟性が低下して脆くなり、３０を超えると感度及び解像度が低下する。
本発明に用いられる一般式（ＶＩ）で表わされる化合物の具体例としては、ヘキサメチレンジイソシアネートとオリゴプロピレングリコールモノメタクリレート［日本油脂（株）製ブレンマーＰＰ１０００］との反応物等がある。
【００４０】
本発明に用いられる（ｂ）光重合性不飽和化合物成分としては、上記以外に、下記化合物を同時に併用することもできる。
例えば、１，６−ヘキサンジオールジ（メタ）アクリレート、１，４−シクロヘキサンジオールジ（メタ）アクリレート、グリセロールトリ（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、ＥＯ（ＰＯ）付加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トリグリシジルエーテルトリ（メタ）アクリレート、フェノキシポリエチレングリコールモノ（メタ）アクリレート、β−ヒドロキシプロピル−β’−アクリロキシプロピルフタレート等が挙げられる。
【００４１】
（ｂ）光重合性不飽和化合物成分の含有量は、光重合性樹脂組成物の全固形分の質量中、５〜７０質量％であることが必要であり、好ましくは１０〜６５質量％、より好ましくは１５〜６０質量％である。この量が、５質量％未満では感度が不十分で、７０質量％を超えるとエッジフューズ性が悪化する。
本発明に用いられる（ｃ）光重合開始剤としては、解像性の点で、２，４，５−トリアリールイミダゾール二量体を含むことが好ましい。２，４，５−トリアリールイミダゾール二量体は下記一般式（Ｖ）で表わされる。
【００４２】
【化１６】
（式中、Ａ6、Ａ7及びＡ8は水素、アルキル基、アルコキシ基又はハロゲン基を示し、ｕ、ｖ、ｗは１〜５の整数である。）
２個のロフィン基を結合する共有結合は、１，１’−、１，２’−、１，４’−、２，２’−、２，４’−又は４，４’−位についているが、１，２’−位に共有結合がついている化合物が好ましい。
２，４，５−トリアリールイミダゾール二量体には、例えば、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ビス−（ｍ−メトキシフェニル）イミダゾール二量体、２−（ｐ−メトシキフェニル）−４，５−ジフェニルイミダゾール二量体等がある。
【００４４】
また、これらとｐ−アミノフェニルケトンとを併用する系は好ましく、例えば、ｐ−アミノベンゾフェノン、ｐ−ブチルアミノベンゾフェノン、ｐ−ジメチルアミノアセトフェノン、ｐ−ジメチルアミノベンゾフェノン、４，４’−ビス（エチルアミノ）ベンゾフェノン、４，４’−ビス（ジメチルアミノ）ベンゾフェノン、４，４’−ビス（ジエチルアミノ）ベンゾフェノン、４，４’−ビス（ジブチルアミノ）ベンゾフェノン等が挙げられる。
【００４５】
また、（ｃ）光重合開始剤には、上記で示された化合物以外に、他の光重合開始剤との併用も可能である。ここでの光重合開始剤とは、各種の活性光線、例えば紫外線等により活性化しうる、重合を開始する公知の化合物である。
このような化合物としては、例えば、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン等のキノン類、ベンゾフェノン等の芳香族ケトン類、Ｎ−フェニルグリシン等のＮ−アリールアミノ酸類、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル等のベンゾインエーテル類、ベンジルジメチルケタール、ベンジルジエチルケタール等が挙げられる。
【００４６】
また、例えば、チオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン等のチオキサントン類と、ジメチルアミノ安息香酸アルキルエステル化合物等の三級アミン化合物との組み合わせも挙げられる。
また、例えば、９−フェニルアクリジン等のアクリジン類、１−フェニル−１，２−プロパンジオン−２−（ｏ−ベンゾイル）オキシム、１−フェニル−１，２−プロパンジオン−２−（ｏ−エトキシカルボニル）オキシム等のオキシムエステル類等も挙げられる。
【００４７】
（ｃ）光重合開始剤の含有量は、光重合性樹脂組成物の全固形分の質量中、０．１〜１５質量％であることが必要であり、好ましくは０．５〜１０質量％である。この量が、１５質量％を超えると光重合性樹脂組成物の活性吸収率が高くなり、光重合性樹脂積層体として用いた場合、光重合性樹脂層の底部の重合硬化が不十分になる。また、この量が、０．１質量％未満では十分な感度が出ない。
さらに、本発明の光重合性樹脂組成物に、熱安定性及び保存安定性を向上させるためのラジカル重合禁止剤を含有させることは好ましく、例えば、ｐ−メトキシフェノール、ハイドロキノン、ピロガロール、ナフチルアミン、ｔｅｒｔ−ブチルカテコール、塩化第一銅、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、Ｎ−ニトロソフェニルヒドロキシルアミンアルミニウム塩、ジフェニルニトロソアミン等が挙げられる。
【００４８】
本発明の光重合性樹脂組成物に染料や顔料等の着色物質を含有させることもできる。このような着色物質としては、例えば、フクシン、フタロシアニングリーン、オーラミン塩基、カルコキシドグリーンＳ、パラマジエンタ、クリスタルバイオレット、メチルオレンジ、ナイルブルー２Ｂ、ビクトリアブルー、マラカイトグリーン、ベイシックブルー２０、ダイアモンドグリーン等が挙げられる。
また、本発明の光重合性樹脂組成物に、光照射により発色する発色系染料を含有させることもできる。このような発色系染料としては、ロイコ染料又はフルオラン染料とハロゲン化合物との組み合わせがある。
【００４９】
ロイコ染料としては、例えば、トリス（４−ジメチルアミノ−２−メチルフェニル）メタン［ロイコクリスタルバイオレット］、トリス（４−ジメチルアミノ−２−メチルフェニル）メタン［ロイコマラカイトグリーン］等が挙げられる。
また、ハロゲン化合物としては、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンザル、臭化メチレン、トリブロモメチルフェニルスルホン、四臭化炭素、トリス（２，３−ジブロモプロピル）ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、１，１，１−トリクロロ−２，２−ビス（ｐ−クロロフェニル）エタン、ヘキサクロロエタン、トリアジン化合物等が挙げられる。
【００５０】
なお、トリアジン化合物としては、２，４，６−トリス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン等が挙げられる。
このような発色系染料の中でも、ロイコ染料とトリブロモメチルフェニルスルホンとの組み合わせや、ロイコ染料とトリアジン化合物との組み合わせが有用である。
【００５１】
また、本発明の光重合性樹脂組成物には、必要に応じて可塑剤等の添加剤を含有させることもできる。このような添加剤としては、例えば、ジエチルフタレート等のフタル酸エステル類、ｐ−トルエンスルホンアミド等が挙げられる。
光重合性樹脂積層体を作製する場合には、上記光重合性樹脂組成物を支持層上に塗布する。
ここで用いられる支持層としては、活性光を透過する透明なものが望ましく、例えば、ポリエチレンテレフタレートフィルム、ポリビニルアルコールフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリ塩化ビニリデンフィルム、塩化ビニリデン共重合体フィルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、セルロース誘導体フィルム等が挙げられる。
【００５２】
これらのフィルムは、必要に応じ延伸されたものも使用可能である。その厚みは薄い方が画像形成性や経済性の面で有利であるが、強度を維持する必要もあり、１０〜３０μｍのものが一般的である。また、支持層のヘーズは５％以下であることが好ましい。
支持層に塗布した光重合性樹脂層の表面には、必要に応じて保護層を積層する。支持層よりも保護層の方が光重合性樹脂層との密着力が十分小さく容易に剥離できることがこの保護層としての重要な特性である。このような保護層としては、例えばポリエチレンフィルム、ポリプロピレンフィルム等が挙げられる。
光重合性樹脂層の厚みは用途において異なるが、プリント配線板作製用には、５〜１００μｍ、好ましくは５〜５０μｍである。光重合性樹脂層が薄いほど解像力が向上し、また、光重合性樹脂層が厚いほど硬化膜強度が向上する。
【００５３】
次に、本発明の光重合性樹脂積層体を用いてプリント配線板を製造する方法の一例を説明する。
製造工程は、通常、次の（Ａ）〜（Ｅ）の工程よりなり、順次行う。
（Ａ）ラミネート工程：光重合性樹脂積層体に保護層がある場合には、保護層を剥がしながら基板上にホットロールラミネーターを用いて密着させる。この時の加熱温度は一般的に４０〜１６０℃である。
（Ｂ）露光工程：所望の配線パターンを有するフォトマスクを介して、活性光線源を用いて光重合性樹脂層に露光を施す。支持層を剥離して露光しても良いし、支持層がついたまま露光してもよい。
（Ｃ）現像工程：支持層が残っている場合にはこれを剥離した後、アルカリ現像液を用いて光重合性樹脂層の未露光部分を溶解又は分散除去し、レジストパターンを基板上に形成する。
ここで用いられる現像液は、光重合性樹脂層の特性に合わせて選択され、０．５〜３質量％の炭酸ナトリウムや炭酸カリウムの水溶液が一般的である。
【００５４】
（Ｄ）回路形成工程：形成されたレジストパターン上からエッチング液を吹き付け、レジストパターンによって覆われていない銅面をエッチングするエッチング工程、又はレジストパターンによって覆われていない銅面に銅、半田、ニッケル、金及び錫等のめっき処理を行うめっき工程。
（Ｅ）剥離工程：レジストパターンを、アルカリ剥離液を用いて基板から除去する。剥離液は現像液よりも更に強いアルカリ性水溶液で、１〜５質量％の水酸化ナトリウムや水酸化カリウムの水溶液が一般的に用いられる。
なお、現像液や剥離液に消泡剤等の少量の水溶性有機溶媒を加える事も可能である。
【００５５】
【実施例】
以下、本発明の具体的実施形態について、実施例および比較例に基き説明する。
（実施例１〜９及び比較例１〜２）
表１に示す組成物を均一に溶解し、混合溶液を得た。表１中の記号については、下記の＜記号説明＞に示す。得られた混合溶液を、厚さ２０μｍのポリエチレンテレフタレートフィルム（支持層）にバーコーターを用いて均一塗布した。これを９５℃の乾燥機中で約４分間乾燥して光重合性樹脂層の厚み４０μｍの光重合性樹脂積層体を得た。その後、光重合性樹脂層のポリエチレンテレフタレートフィルムを積層していない表面上に２５μｍのポリエチレンフィルム（保護層）を張り合わせて光重合性樹脂積層体を作製した。
【００５６】
上記で得た光重合性樹脂積層体を用いてのレジストパターンの作成は、次に示す（イ）〜（ハ）の工程によった。
＜レジストパターン作成方法＞
（イ）ラミネート
３５μｍ圧延銅箔を積層した銅張積層板表面を湿式バフロール研磨（スリーエム社製、スコッチブライト（登録商標）＃６００、２連）し、得られた光重合性樹脂積層体を、この銅面に光重合性樹脂層が面するようにポリエチレンフィルムを剥がしながらホットロール式ラミネーターによりラミネート速度１．５ｍ／ｍｉｎ、ロール温度１０５℃、エア圧力０．３５ＭＰａの条件でラミネートした。
（ロ）露光
マスクフィルムを通して、超高圧水銀ランプ（（株）オーク製作所ＨＭＷ−２０１ＫＢ）により光重合性樹脂層を６０ｍＪ／ｃｍ2で露光した。
（ハ）現像
ポリエチレンテレフタレートフィルムを除去した後、１質量％炭酸ナトリウム水溶液（３０℃）を最小現像時間の２倍の時間スプレーして未露光部分を溶解除去し、光重合性樹脂層をパターニングした。ここで、最小現像時間は、銅張積層板に光重合性樹脂層をラミネートし、これを露光せずに支持層を剥離して現像したとき、光重合性樹脂層が溶解する最小時間のことである。
【００５７】
なお、実施例における（１）エッジフューズ性、（２）解像度、（３）テンティング性、（４）現像凝集性、（５）剥離片形状は、以下に示す方法により評価した。
（１）エッジフューズ性
ロール状の光重合性樹脂積層体を２３℃、湿度５０％で保存し、端面からの光重合性樹脂層のしみ出し具合により以下のようにランク付け評価した。
○：３ヶ月以上、端面からのしみ出し無しで保存可能
△：１ヶ月以上３ヶ月未満、端面からのしみ出し無しで保存可能
×：１ヶ月未満のうちに端面からのしみ出しが生じる。
（２）解像度
銅張積層板に光重合性樹脂層をラミネートし、これを種々のライン幅（ライン幅：スペ−ス幅＝１：１）パターンの印刷されたマスクフィルムを通して露光し、支持層を剥離したのち現像した。得られた画像の分離し得る最小ライン幅を解像度とした。
【００５８】
（３）テンティング性
直径６ｍｍの円孔が約１０００個開いている銅張積層板を用い、光重合性樹脂層を基板の両面に逐次ラミネートし、両面からそれぞれパターンマスクを通さず直接に露光した。これを最小現像時間の３倍の時間で現像し、さらに、スプレー圧力０．３ＭＰａで約１分間水洗した。両面の硬化膜のいずれかが破れている円孔を数え、以下の通りランク付けした。
○：破れ率１０％未満
△：破れ率１０％以上３０％未満
×：破れ率３０％以上
【００５９】
（４）現像凝集性
３０℃、１質量％の炭酸ナトリウム水溶液に、４０μｍ膜厚換算で０．６ｍ2／Ｌの未露光の光重合性樹脂層を溶解させ、溶液２００ｍＬを０．２ＭＰａの圧力でスプレーしながら、溶液循環を３時間行なった。
その後、槽内の凝集物（粉体状ないしオイル状）発生の状態を目視で判定し、以下の通りランク付けした。
○：液面に浮遊物がなく、溶液を除去後の槽底にも全く凝集物の発生がない
△：液面や槽底に、ごくわずかに凝集物の発生が認められる
×：液面や槽底に、多量の凝集物発生が認められる
【００６０】
（５）剥離片形状
銅張積層板に光重合性樹脂層をラミネートし、これをパターンマスクを通さず直接に露光した。さらに現像した後、これを５ｃｍ角に裁断し、評価基板とした。評価基板を５０℃の３％水酸化ナトリウム水溶液に浸漬し、基板から剥がれた硬化膜（剥離片）の形状を以下のようにランク付けした。
ＬＬ：亀裂を生ずること無くシート状に剥がれる
Ｌ：亀裂を生じて剥がれた後、１０〜２０ｍｍ角程度の形状となる
Ｍ：亀裂を生じて剥がれた後、５〜１０ｍｍ角程度の細片となる
Ｓ：亀裂を多数生じて剥がれた後、５ｍｍ角以下の微細片となる
結果をまとめて表１に示す。
【００６１】
なお、比較例１は、（ｂ）光重合性不飽和化合物の一般式（Ｉ）で表わされる化合物を含んでいないため、要件を欠いている。また、比較例２は、（ｂ）光重合性不飽和化合物の一般式（ＩＩ）で表わされる化合物を含んでいないため、要件を欠いている。
＜記号説明＞
Ｐ−１：メタクリル酸メチル６５質量％、メタクリル酸２５質量％、アクリル酸ブチル１０質量％の三元共重合体のメチルエチルケトン溶液（固形分濃度３４質量％、重量平均分子量７．５万、酸当量３４４）
Ｐ−２：メタクリル酸メチル６７質量％、メタクリル酸２３質量％、アクリル酸ブチル１０質量％の三元共重合体のメチルエチルケトン溶液（固形分濃度２５質量％、重量平均分子量２０万、酸当量３７４）
Ｐ−３：メタクリル酸メチル５０質量％、メタクリル酸２５質量％、スチレン２５質量％の三元共重合体のメチルエチルケトン溶液（固形分濃度３５質量％、重量平均分子量５万、酸当量３４４）
【００６２】
Ｍ−１：一般式（Ｉ）で表わされる化合物、メタクリル酸のＥＯ付加物（平均２モル）とヘキサヒドロフタル酸とのハーフエステル
Ｍ−２：一般式（ＩＩ）で表わされる化合物、ビスフェノールＡのＥＯ付加物（両端に平均５モルずつ）のジメタクリレート（新中村化学工業（株）製ＮＫエステルＢＰＥ−５００）
Ｍ−３：一般式（ＩＩ）で表わされる化合物、ビスフェノールＡのアルキレンオキサイド付加物（両端に平均２モルずつのＰＯ及び平均１５モルずつのＥＯ）のジメタクリレート
Ｍ−４：ポリエチレングリコール（ＥＯ単位数平均４モル）ジアクリレート（新中村化学工業（株）製ＮＫエステル４Ｇ）
Ｍ−５：ポリプロピレングリコール（ＰＯ単位数平均７モル）ジメタクリレート（新中村化学工業（株）製ＮＫエステル９ＰＧ）
Ｍ−６：ポリプロピレングリコール（ＰＯ単位数平均１２モル）のＥＯ付加物（両端に平均３モルずつ）のジメタクリレート
Ｍ−７：一般式（ＶＩ）で表わされる化合物、ヘキサメチレンジイソシアネートとオリゴプロピレングリコールモノメタクリレート（日本油脂（株）製ブレンマーＰＰ１０００）との反応物
Ｍ−８：一般式（ＩＩＩ）で表わされる化合物、ジペンタエリスリトールヘキサアクリレート（ダイセル・ユーシービー（株）製ＤＰＨＡ）
Ｍ−９：一般式（ＩＶ）で表わされる化合物、ノニルフェノールのアルキレンオキサイド付加物（平均２モルのＰＯ及び平均７モルのＥＯ）のアクリレート
【００６３】
Ａ−１：ベンゾフェノン
Ａ−２：４，４’−ビス（ジエチルアミノ）ベンゾフェノン
Ａ−３：一般式（Ｖ）で表わされる化合物、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体
【００６４】
Ｂ−１：マラカイトグリーン（保土ヶ谷化学（株）製ＡＩＺＥＮ（登録商標）ＭＡＬＡＣＨＩＴＥ ＧＲＥＥＮ）
Ｂ−２：ロイコクリスタルバイオレット
Ｂ−３：トリブロモメチルフェニルスルホン
【００６５】
【表１】
【発明の効果】
本発明の光重合性樹脂組成物を用いたＤＦＲは、現像後のレジストパターンの解像性及び硬化膜のテンティング性に優れるとともに、エッジフューズ性、現像液分散時の低凝集性、剥離性にも優れ、アルカリ現像型プリント配線板作製用ＤＦＲとして有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photopolymerizable resin composition, a photopolymerizable resin laminate, and a method of forming a resist pattern using the same, and more particularly, an alkali developable photopolymerizable resin composition suitable for the production of a printed circuit board, light The present invention relates to a polymerizable resin laminate and a resist pattern forming method using the same.
[0002]
[Prior art]
Conventionally, a photopolymerizable resin laminate comprising a support layer and a photopolymerizable resin layer, a so-called dry film resist (hereinafter abbreviated as DFR), has been used as a resist for producing printed circuits. The DFR is generally produced by laminating a photopolymerizable resin composition on a support layer, and in many cases, further laminating a protective layer on the composition.
As the photopolymerizable resin composition used here, an alkali development type resin composition using a weak alkaline aqueous solution as a developer is generally used.
Fabrication of a printed wiring board using DFR is performed as follows.
First, after the protective layer is peeled off, DFR is laminated on a permanent circuit fabrication substrate such as a copper clad laminate and exposed through a wiring pattern mask film or the like.
Next, if necessary, the support layer is peeled off, and the unpolymerized portion of the photopolymerizable resin composition is dissolved or dispersed and removed by a developer to form a cured resist pattern on the substrate. Using this resist pattern as a mask, the metal surface of the substrate is etched or plated, and finally the resist pattern is peeled off using a strong alkaline aqueous solution.
[0003]
In recent years, a so-called tenting method in which etching is performed after covering a through hole with a cured photopolymerizable resin layer (cured film) has been widely used because of the simplicity of the process. For this etching, cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used.
As for the performance required for DFR, in tenting applications, the cured film is tough and good tenting properties without tearing are required. As the wiring pattern of the printed wiring board becomes finer, the resist pattern becomes higher. There is also a demand for higher resolution.
[0004]
Since DFR usually takes the form of a roll tightly wound around a core such as plastic, if the photopolymerizable resin layer is too soft, bleeding from the end surface (edge fuse) occurs during storage, which is not preferable for handling. . For this reason, as long as the followability to the substrate during lamination is not impaired, it is preferable from the viewpoint of handling that the edge fuse property is good, that is, the photopolymerizable resin layer is hard.
The performance required for DFR further includes low cohesion. During development, the unexposed photopolymerizable resin layer is dispersed in the developer to form micelles. However, if the micelle stability (low cohesion) is poor, the micelles are easily destroyed during the development operation and are not water-soluble. This is because the chemical component aggregates and precipitates in the form of an oil or powder and adheres to the substrate to cause a defect in a later process, or adheres to the inside of the developing machine and hinders the operation.
[0005]
Further, regarding the peelability of the resist, if the peeled piece is large and difficult to break, troubles such as entanglement with the transport roll occur in the peeling step, and therefore it is desirable in the process that the peeled piece is fine.
[0006]
[Problems to be solved by the invention]
An object of the present invention is an alkali development type printed wiring which is excellent in resolution of a resist pattern after development and tenting of a cured film, as well as edge fuse, low agglomeration at the time of dispersion of a developer, and exfoliation. A photopolymerizable resin composition and a photopolymerizable resin laminate useful as a DFR for producing a plate, and a method for forming a resist pattern using the same.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, it has been found that the above problems can be solved by using a specific photopolymerizable resin composition for DFR, and the present invention has been completed.
That is, the present invention is as follows.
(1) (a) 20-80% by mass of a binder resin comprising a linear polymer having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 20,000 to 500,000, (b) Including a compound represented by the general formula (I) and a compound represented by the following general formula (II), and further comprising at least one compound selected from the group of compounds represented by the following general formulas (III) and (IV) A photopolymerizable resin composition comprising 5-70% by mass of a photopolymerizable unsaturated compound component and 0.1-15% by mass of (c) a photopolymerization initiator.
[0008]
[Chemical 6]
(In the formula, R 1 represents a (meth) acryloyl group, A 1 represents C 2 H 4 or C 3 H 6 , and A 2 represents a cycloalkane residue or a chain hydrocarbon having 6 or less carbon atoms. K is an integer from 1 to 6.)
[0010]
[Chemical 7]
(In the formula, R 2 and R 3 represent a (meth) acryloyl group, A 3 and A 4 represent C 2 H 4 or C 3 H 6, and m, n, p, and q are 2 ≦ m + n + p + q ≦ 40. It is an integer greater than or equal to 0. )
[0012]
[Chemical 8]
(In the formula, R represents a hydrogen atom or a (meth) acryloyl group, and includes at least 4 (meth) acryloyl groups in one molecule).
[0014]
[Chemical 9]
(In the formula, R 4 represents a (meth) acryloyl group, A 5 represents an alkyl group having 20 or less carbon atoms, r is an integer of 1 to 3, s is an integer of 4 to 20, and t is 0 to 5) (It is an integer. The arrangement of repeating units of C 2 H 4 O and C 3 H 6 O may be a block or random.)
( 2 ) (c) The photopolymerization according to (1 ) , wherein the photopolymerization initiator contains a 2,4,5-triarylimidazole dimer represented by the following general formula (V): Resin composition.
[0016]
[Chemical Formula 10]
(In the formula, A 6 , A 7 and A 8 represent hydrogen, an alkyl group, an alkoxy group or a halogen group, and u, v and w are integers of 1 to 5)
( 3 ) A photopolymerizable resin laminate in which a layer made of the photopolymerizable resin composition according to (1) or ( 2) is provided on a support layer.
A method for forming a resist pattern, including a step of forming a photopolymerizable resin layer on a substrate using the photopolymerizable resin laminate according to ( 3 ), exposing, and developing.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The amount of the carboxyl group contained in the linear polymer used in the (a) binder resin of the photopolymerizable resin composition of the present invention needs to be 100 to 600 in terms of acid equivalent, preferably 300 to 400. is there. (A) The carboxyl group contained in the linear polymer of the binder resin is necessary to give the DFR suitable developability and releasability to an alkaline aqueous solution.
[0019]
When the acid equivalent is less than 100, the development resistance is lowered, adversely affecting the resolution and adhesion, and when it exceeds 600, the developability and peelability are deteriorated. Here, the acid equivalent refers to the mass of a polymer having one equivalent of a carboxyl group therein, and the measurement is carried out using a Hiranuma Titanium Hiratuma automatic titrator (COM-555), and 0.1 mol / This is carried out by potentiometric titration using L sodium hydroxide.
The molecular weight of the linear polymer used in the binder resin (a) of the photopolymerizable resin composition of the present invention needs to be 20,000 to 500,000, preferably 30,000 to 300,000, more preferably 5 10,000 to 250,000. When this molecular weight exceeds 500,000, the developability decreases, and when it is less than 20,000, the strength of the cured film and the edge fuse property deteriorate.
[0020]
The molecular weight was measured by gel permeation chromatography manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF- 806M, KF-802.5) 4 in series, mobile phase solvent: tetrahydrofuran, using a calibration curve with a polystyrene standard sample), the weight average molecular weight (polystyrene conversion).
[0021]
(A) The linear polymer used for the binder resin is obtained by copolymerizing one or more monomers from the following two types of monomers.
The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule, such as (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride. Products, maleic acid half esters, and the like.
The second monomer is non-acidic and has one polymerizable unsaturated group in the molecule. Various properties such as developability of the photopolymerizable resin layer, resistance to etching and plating processes, flexibility of the cured film, etc. Chosen to retain the characteristics of As such a thing, alkyl (meth) acrylates, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, are mentioned, for example. A vinyl compound having a phenyl group (for example, styrene) can also be used.
[0022]
(A) As a polymerization method of the linear polymer used for the binder resin, benzoyl peroxide, azobisisobutyronitrile, etc., in a solution obtained by diluting a mixture of monomers with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc. A method of adding an appropriate amount of the radical polymerization initiator and stirring with heating is preferred.
In some cases, polymerization may be performed while dropping a part of the mixture into the reaction solution, or a solvent may be added after the reaction to adjust the concentration to a desired level. As the polymerization method, bulk polymerization, suspension polymerization, and emulsion polymerization may be used in addition to the above solution polymerization.
[0023]
In the present invention, (a) the content of the binder resin needs to be 20 to 80% by mass, preferably 30 to 70% by mass, based on the total solid content of the photopolymerizable resin composition. More preferably, it is 35-65 mass%. (A) When the binder resin is less than 20% by mass or exceeds 80% by mass, the cured pattern formed by exposure has sufficient characteristics as a resist, such as tenting, etching, and resistance in various plating processes. I don't have it.
[0024]
In the photopolymerizable resin composition of the present invention, as the (b) photopolymerizable unsaturated compound component, a compound represented by the following general formula (I) and a compound represented by the following general formula (II) are essential components. .
[0025]
Embedded image
(In the formula, R 1 represents a (meth) acryloyl group, A 1 represents C 2 H 4 or C 3 H 6 , and A 2 represents a chain hydrocarbon or cycloalkane having 6 or less carbon atoms. K Is an integer from 1 to 6.)
[0027]
Embedded image
(In the formula, R 2 and R 3 represent a (meth) acryloyl group, A 3 and A 4 represent C 2 H 4 or C 3 H 6, and m, n, p, and q are 2 ≦ m + n + p + q ≦ 40. (It is an integer of 0 or more.)
In the compound represented by the general formula (I), when k exceeds 6, sensitivity and resolution are lowered. In addition, when A 2 is a chain hydrocarbon, the sensitivity decreases when the number of carbon atoms exceeds 6. When A 2 is cycloalkane, a cyclohexane ring is preferred.
[0029]
Specific examples of the compound represented by the general formula (I) used in the present invention include an EO adduct of methacrylic acid (average 2 mol) and a half ester of hexahydrophthalic acid (where EO is ethylene oxide). Abbreviation, the same shall apply hereinafter).
In the compound represented by the general formula (II), if m + n + p + q is less than 2, the flexibility of the cured film is reduced and the brittleness is deteriorated and developability is deteriorated.
[0030]
Specific examples of the compound represented by the general formula (II) used in the present invention include bisphenol A EO adduct (average of 5 mol at both ends) dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK SL BPE- 500), dimethacrylate of alkylene oxide adduct of bisphenol A (average of 2 moles of PO and 15 moles of EO at both ends) (PO is an abbreviation of propylene oxide, the same shall apply hereinafter).
[0031]
Moreover, it is preferable that at least one selected from the group of compounds represented by the following general formulas (III) and (IV) is further contained as the (b) photopolymerizable unsaturated compound component. It is.
[0032]
Embedded image
(In the formula, R represents a hydrogen atom or a (meth) acryloyl group, and includes at least 4 (meth) acryloyl groups in one molecule).
[0034]
Embedded image
(In the formula, R 4 represents a (meth) acryloyl group, A 5 represents an alkyl group having 20 or less carbon atoms, r is an integer of 1 to 3, s is an integer of 4 to 20, and t is 0 to 5) (It is an integer. The arrangement of repeating units of C 2 H 4 O and C 3 H 6 O may be a block or random.)
In the compound represented by the general formula (III), if the number of (meth) acryloyl groups in one molecule is less than 4, sufficient sensitivity and cured film strength cannot be obtained. Specific examples of the compound represented by the general formula (III) used in the present invention include dipentaerythritol hexaacrylate [DPHA manufactured by Daicel UCB Co., Ltd.].
[0036]
In the compound represented by the general formula (IV), if the carbon number of A 5 exceeds 20 or r exceeds 3, developability deteriorates. When s is less than 4, the cohesiveness is deteriorated, and when it exceeds 20, sensitivity and resolution are deteriorated. When t exceeds 5, the cohesiveness deteriorates.
Specific examples of the compound represented by the general formula (IV) used in the present invention include acrylate of nonylphenol EO adduct (average 8 mol) (Aronix (registered trademark) M-114 manufactured by Toagosei Co., Ltd.), Nonylphenol alkylene oxide adducts (average 2 mol PO and average 7 mol EO) acrylates, and the like.
[0037]
(B) The photopolymerizable unsaturated compound may further include a compound represented by the following general formula (VI).
[0038]
Embedded image
(Wherein R 5 and R 6 represent a (meth) acryloyl group, A 9 represents C 2 H 4 or C 3 H 6 , and A 10 represents an isocyanate residue having 4 to 12 carbon atoms. H and j is an integer of 0 or more which satisfies 2 ≦ h + j ≦ 30.)
In the compound represented by the general formula (VI), when h + j is less than 2, the flexibility of the cured film is lowered and becomes brittle, and when it exceeds 30, sensitivity and resolution are lowered.
Specific examples of the compound represented by the general formula (VI) used in the present invention include a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate [Nippon Yushi Co., Ltd. Blenmer PP1000].
[0040]
As the (b) photopolymerizable unsaturated compound component used in the present invention, in addition to the above, the following compounds may be used in combination.
For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO (PO) -added trimethylolpropane Examples include tri (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, β-hydroxypropyl-β′-acryloxypropyl phthalate, and the like.
[0041]
(B) The content of the photopolymerizable unsaturated compound component needs to be 5 to 70% by mass, preferably 10 to 65% by mass, based on the total solid content of the photopolymerizable resin composition. More preferably, it is 15-60 mass%. If this amount is less than 5% by mass, the sensitivity is insufficient, and if it exceeds 70% by mass, the edge fuse property deteriorates.
The (c) photopolymerization initiator used in the present invention preferably contains a 2,4,5-triarylimidazole dimer from the viewpoint of resolution. The 2,4,5-triarylimidazole dimer is represented by the following general formula (V).
[0042]
Embedded image
(In the formula, A 6 , A 7 and A 8 represent hydrogen, an alkyl group, an alkoxy group or a halogen group, and u, v and w are integers of 1 to 5)
The covalent bond connecting the two lophine groups is in the 1,1'-, 1,2'-, 1,4'-, 2,2'-, 2,4'- or 4,4'-position. However, compounds having a covalent bond at the 1,2′-position are preferred.
Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- ( m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.
[0044]
Moreover, the system which uses these and p-aminophenyl ketone together is preferable, for example, p-aminobenzophenone, p-butylaminobenzophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, 4,4′-bis (ethyl). Amino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dibutylamino) benzophenone and the like.
[0045]
In addition to the compounds shown above, (c) the photopolymerization initiator can be used in combination with other photopolymerization initiators. A photoinitiator here is a well-known compound which starts superposition | polymerization which can be activated by various active rays, for example, ultraviolet rays.
Examples of such compounds include quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, N-aryl amino acids such as N-phenylglycine, benzoin and benzoin methyl ether. Benzoin ethers such as benzoin ethyl ether, benzyl dimethyl ketal, benzyl diethyl ketal and the like.
[0046]
Moreover, for example, combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds are also included.
Further, for example, acridines such as 9-phenylacridine, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxy) And oxime esters such as carbonyl) oxime.
[0047]
(C) Content of a photoinitiator needs to be 0.1-15 mass% in the mass of the total solid of a photopolymerizable resin composition, Preferably it is 0.5-10 mass%. It is. When this amount exceeds 15% by mass, the active absorptivity of the photopolymerizable resin composition increases, and when used as a photopolymerizable resin laminate, the polymerization and curing at the bottom of the photopolymerizable resin layer becomes insufficient. . If this amount is less than 0.1% by mass, sufficient sensitivity cannot be obtained.
Furthermore, it is preferable that the photopolymerizable resin composition of the present invention contains a radical polymerization inhibitor for improving thermal stability and storage stability. For example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert -Butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4- Methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine and the like.
[0048]
The photopolymerizable resin composition of the present invention may contain a coloring substance such as a dye or a pigment. Examples of such coloring substances include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, paramadienta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green and the like. It is done.
Further, the photopolymerizable resin composition of the present invention may contain a coloring dye that develops color when irradiated with light. Such coloring dyes include a combination of a leuco dye or a fluorane dye and a halogen compound.
[0049]
Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like.
Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like.
[0050]
Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, and the like.
Among such coloring dyes, a combination of a leuco dye and tribromomethylphenyl sulfone or a combination of a leuco dye and a triazine compound is useful.
[0051]
Moreover, the photopolymerizable resin composition of the present invention may contain an additive such as a plasticizer as necessary. Examples of such additives include phthalic esters such as diethyl phthalate, p-toluenesulfonamide, and the like.
When producing a photopolymerizable resin laminate, the photopolymerizable resin composition is applied onto a support layer.
The support layer used here is preferably a transparent layer that transmits active light. For example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, and a vinylidene chloride copolymer are used. Examples include a polymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film.
[0052]
These films can be stretched if necessary. A thinner thickness is more advantageous in terms of image formation and economy, but it is necessary to maintain strength, and a thickness of 10 to 30 μm is common. The haze of the support layer is preferably 5% or less.
A protective layer is laminated on the surface of the photopolymerizable resin layer applied to the support layer as necessary. An important characteristic of this protective layer is that the protective layer has a sufficiently small adhesion to the photopolymerizable resin layer and can be easily peeled off than the support layer. Examples of such a protective layer include a polyethylene film and a polypropylene film.
Although the thickness of the photopolymerizable resin layer varies depending on the application, it is 5 to 100 μm, preferably 5 to 50 μm, for producing a printed wiring board. The thinner the photopolymerizable resin layer, the better the resolution, and the thicker the photopolymerizable resin layer, the better the cured film strength.
[0053]
Next, an example of a method for producing a printed wiring board using the photopolymerizable resin laminate of the present invention will be described.
The manufacturing process usually comprises the following steps (A) to (E) and is performed sequentially.
(A) Lamination process: When a photopolymerizable resin laminated body has a protective layer, it adheres on a board | substrate using a hot roll laminator, peeling off a protective layer. The heating temperature at this time is generally 40 to 160 ° C.
(B) Exposure process: The photopolymerizable resin layer is exposed using an actinic ray source through a photomask having a desired wiring pattern. The support layer may be peeled off and exposed, or the support layer may be exposed.
(C) Development step: If the support layer remains, after peeling it off, an alkali developer is used to dissolve or disperse the unexposed portions of the photopolymerizable resin layer to form a resist pattern on the substrate. To do.
The developing solution used here is selected according to the characteristics of the photopolymerizable resin layer, and an aqueous solution of 0.5 to 3% by mass of sodium carbonate or potassium carbonate is generally used.
[0054]
(D) Circuit formation process: An etching process in which an etching solution is sprayed on the formed resist pattern to etch the copper surface not covered with the resist pattern, or copper, solder, nickel on the copper surface not covered with the resist pattern A plating process for plating gold, tin and the like.
(E) Stripping step: The resist pattern is removed from the substrate using an alkali stripping solution. The stripper is an alkaline aqueous solution that is stronger than the developer, and an aqueous solution of 1 to 5% by mass of sodium hydroxide or potassium hydroxide is generally used.
It is also possible to add a small amount of a water-soluble organic solvent such as an antifoaming agent to the developer or stripping solution.
[0055]
【Example】
Hereinafter, specific embodiments of the present invention will be described based on examples and comparative examples.
(Examples 1-9 and Comparative Examples 1-2)
The composition shown in Table 1 was uniformly dissolved to obtain a mixed solution. The symbols in Table 1 are shown in <Explanation of symbols> below. The obtained mixed solution was uniformly applied to a polyethylene terephthalate film (support layer) having a thickness of 20 μm using a bar coater. This was dried in a dryer at 95 ° C. for about 4 minutes to obtain a photopolymerizable resin laminate having a photopolymerizable resin layer thickness of 40 μm. Thereafter, a 25 μm polyethylene film (protective layer) was laminated on the surface of the photopolymerizable resin layer on which the polyethylene terephthalate film was not laminated to prepare a photopolymerizable resin laminate.
[0056]
Creation of the resist pattern using the photopolymerizable resin laminate obtained above was performed according to the following steps (a) to (c).
<Resist pattern creation method>
(I) Laminating 35 μm rolled copper foil laminated copper clad laminate surface wet buffol polishing (manufactured by 3M, Scotch Bright (registered trademark) # 600, 2 series), the resulting photopolymerizable resin laminate, While peeling the polyethylene film so that the photopolymerizable resin layer faces this copper surface, the film was laminated by a hot roll laminator at a lamination speed of 1.5 m / min, a roll temperature of 105 ° C., and an air pressure of 0.35 MPa.
(B) The photopolymerizable resin layer was exposed at 60 mJ / cm 2 through an exposure mask film using an ultrahigh pressure mercury lamp (Oak Seisakusho HMW-201KB).
(C) After removing the developed polyethylene terephthalate film, a 1% by weight aqueous sodium carbonate solution (30 ° C.) was sprayed for twice the minimum development time to dissolve and remove unexposed portions, and the photopolymerizable resin layer was patterned. . Here, the minimum development time is the minimum time for the photopolymerizable resin layer to dissolve when the photopolymerizable resin layer is laminated on a copper-clad laminate and the support layer is peeled off and developed without exposing it. It is.
[0057]
In the examples, (1) edge fuse property, (2) resolution, (3) tenting property, (4) development aggregation property, and (5) peeled piece shape were evaluated by the following methods.
(1) The photopolymerizable resin laminate in the form of an edge fuse roll was stored at 23 ° C. and a humidity of 50%, and was ranked and evaluated as follows according to the extent of the photopolymerizable resin layer oozing from the end face.
○: Can be stored for 3 months or more without exudation from the end face. Δ: 1 month or more and less than 3 months can be stored without exudation from the end face. ×: Exudation from the end face occurs within less than 1 month.
(2) A photopolymerizable resin layer is laminated on a resolution copper-clad laminate, which is exposed through a mask film on which various line width (line width: space width = 1: 1) patterns are printed, and a support layer. The film was peeled and developed. The minimum line width from which the obtained image can be separated was defined as the resolution.
[0058]
(3) Tenting ability A copper-clad laminate with about 1000 circular holes with a diameter of 6 mm is used, and a photopolymerizable resin layer is sequentially laminated on both sides of the substrate and exposed directly from both sides without passing through a pattern mask. did. This was developed for 3 times the minimum development time, and further washed with water at a spray pressure of 0.3 MPa for about 1 minute. The round holes in which either one of the cured films on both sides was broken were counted and ranked as follows.
○: Tear rate less than 10% △: Tear rate 10% or more and less than 30% ×: Tear rate 30% or more
(4) Development cohesion 30 ° C. An unexposed photopolymerizable resin layer of 0.6 m 2 / L in terms of a film thickness of 40 μm is dissolved in a 1% by mass sodium carbonate aqueous solution, and 200 mL of the solution is dissolved at a pressure of 0.2 MPa. While spraying, the solution was circulated for 3 hours.
Thereafter, the state of occurrence of agglomerates (powder or oil) in the tank was visually determined and ranked as follows.
○: There is no suspended solids on the liquid surface, and no agglomerates are generated at the bottom of the tank after removing the solution. Δ: Very slight agglomerates are observed on the liquid surface or the bottom of the tank. A large amount of agglomerates are observed at the bottom of the tank.
(5) A photopolymerizable resin layer was laminated on the peeled piece-shaped copper-clad laminate, and this was directly exposed without passing through a pattern mask. After further development, this was cut into a 5 cm square to obtain an evaluation substrate. The evaluation substrate was immersed in a 3% aqueous sodium hydroxide solution at 50 ° C., and the shapes of the cured films (peeled pieces) peeled from the substrate were ranked as follows.
LL: Peeled into a sheet without cracking L: After cracking and peeling, it becomes a shape of about 10 to 20 mm square M: After cracking and peeling, it becomes a strip of about 5 to 10 mm square S: Table 1 summarizes the results of forming fine pieces of 5 mm square or less after many cracks were generated and peeled.
[0061]
In addition, since the comparative example 1 does not contain the compound represented by general formula (I) of (b) photopolymerizable unsaturated compound, it lacks requirements. Moreover, since the comparative example 2 does not contain the compound represented by general formula (II) of (b) photopolymerizable unsaturated compound, it lacks requirements.
<Symbol explanation>
P-1: Methyl ethyl ketone solution of ternary copolymer of 65% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 10% by mass of butyl acrylate (solid content concentration 34% by mass, weight average molecular weight 75,000, acid equivalent 344)
P-2: A methyl ethyl ketone solution of a terpolymer of 67% by mass of methyl methacrylate, 23% by mass of methacrylic acid and 10% by mass of butyl acrylate (solid content concentration 25% by mass, weight average molecular weight 200,000, acid equivalent 374)
P-3: Methyl ethyl ketone solution of ternary copolymer of methyl methacrylate 50 mass%, methacrylic acid 25 mass%, styrene 25 mass% (solid content concentration 35 mass%, weight average molecular weight 50,000, acid equivalent 344)
[0062]
M-1: Compound represented by general formula (I), EO adduct of methacrylic acid (average 2 mol) and hexahydrophthalic acid half ester M-2: Compound represented by general formula (II), bisphenol A Dimethacrylate (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-3: Dimethacrylate M-4: Polyethylene glycol (EO unit) of compound represented by general formula (II), alkylene oxide adduct of bisphenol A (average of 2 moles of PO and 15 moles of EO at both ends) Number average 4 mol) diacrylate (NK ester 4G manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-5: Polypropylene glycol (average number of PO units: 7 mol) dimethacrylate (NK ester 9PG manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-6: Dimethacrylate of polypropylene glycol (average number of PO units: 12 moles) EO adduct (average of 3 moles at both ends) M-7: Compound represented by formula (VI), hexamethylene diisocyanate and oligopropylene glycol Reaction product M-8 with monomethacrylate (Nippon Yushi Co., Ltd., Bremer PP1000): compound represented by general formula (III), dipentaerythritol hexaacrylate (DPHA, manufactured by Daicel UCB)
M-9: Compound represented by general formula (IV), acrylate of alkylene oxide adduct of nonylphenol (average 2 mol PO and average 7 mol EO)
A-1: Benzophenone A-2: 4,4′-bis (diethylamino) benzophenone A-3: a compound represented by the general formula (V), 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer [0064]
B-1: Malachite Green (AIZEN (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.)
B-2: Leuco Crystal Violet B-3: Tribromomethylphenylsulfone
[Table 1]
【The invention's effect】
The DFR using the photopolymerizable resin composition of the present invention is excellent in resolution of a resist pattern after development and tenting of a cured film, as well as edge fuse, low agglomeration when dispersed in a developer, and peelability. And is useful as a DFR for preparing an alkali development type printed wiring board.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002338548A JP4260463B2 (en) | 2002-11-21 | 2002-11-21 | Photopolymerizable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002338548A JP4260463B2 (en) | 2002-11-21 | 2002-11-21 | Photopolymerizable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004170816A JP2004170816A (en) | 2004-06-17 |
| JP4260463B2 true JP4260463B2 (en) | 2009-04-30 |
Family
ID=32701757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002338548A Expired - Fee Related JP4260463B2 (en) | 2002-11-21 | 2002-11-21 | Photopolymerizable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4260463B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004034416A1 (en) * | 2004-07-15 | 2006-02-02 | "Stiftung Caesar" (Center Of Advanced European Studies And Research) | Liquid, radiation-curing compositions |
| JP4780988B2 (en) * | 2005-03-28 | 2011-09-28 | 旭化成イーマテリアルズ株式会社 | Photopolymerizable resin laminate and glass substrate with black matrix |
| JP4679356B2 (en) * | 2005-06-28 | 2011-04-27 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and photosensitive resin laminate using the same |
-
2002
- 2002-11-21 JP JP2002338548A patent/JP4260463B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004170816A (en) | 2004-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4778588B2 (en) | Photosensitive resin laminate | |
| JP3549015B2 (en) | Photopolymerizable composition | |
| EP1282010A1 (en) | Photosensitive resin composition, photosensitive element comprising the same, method for producing resist pattern, and method for producing printed wiring board | |
| JP3508819B2 (en) | Photopolymerizable composition | |
| US4543318A (en) | Photopolymerizable composition containing heterocyclic additives | |
| JP4230227B2 (en) | Photopolymerizable resin composition | |
| JP3957513B2 (en) | Photopolymerizable resin composition | |
| JP4578269B2 (en) | Photopolymerizable resin composition | |
| JP4614858B2 (en) | Photosensitive resin composition and laminate thereof | |
| JP4260463B2 (en) | Photopolymerizable resin composition | |
| JP4493385B2 (en) | Photosensitive resin composition and use thereof | |
| JP4259855B2 (en) | Photosensitive resin composition | |
| JP2006234995A5 (en) | ||
| JP2002053621A (en) | Photopolymerizable resin composition and laminate | |
| JP3267703B2 (en) | New photopolymerizable resin laminate | |
| JP3957502B2 (en) | Photosensitive resin composition | |
| JP4197445B2 (en) | Photosensitive resin composition and laminate | |
| JP3640869B2 (en) | Photopolymerizable composition | |
| JP5612862B2 (en) | Dry film resist roll | |
| JP3824508B2 (en) | Dry film resist and manufacturing method thereof | |
| JP4201555B2 (en) | Photosensitive resin composition | |
| JP4515123B2 (en) | Photosensitive resin laminate and use thereof | |
| JP4488601B2 (en) | Photosensitive resin laminate | |
| JP4569700B2 (en) | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method | |
| JP4033571B2 (en) | Novel photopolymerizable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051027 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081001 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081007 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081205 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090203 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090204 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120220 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20090401 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120220 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120220 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| A072 | Dismissal of procedure |
Free format text: JAPANESE INTERMEDIATE CODE: A072 Effective date: 20090728 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120220 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130220 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140220 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |