JP3883540B2 - Photosensitive resin composition and use thereof - Google Patents
Photosensitive resin composition and use thereof Download PDFInfo
- Publication number
- JP3883540B2 JP3883540B2 JP2003575188A JP2003575188A JP3883540B2 JP 3883540 B2 JP3883540 B2 JP 3883540B2 JP 2003575188 A JP2003575188 A JP 2003575188A JP 2003575188 A JP2003575188 A JP 2003575188A JP 3883540 B2 JP3883540 B2 JP 3883540B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- integer
- general formula
- resin composition
- acrylate
- 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 - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 27
- 239000011347 resin Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- -1 2- (o-chlorophenyl) -4,5-diphenylimidazolyl Chemical class 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 23
- 238000011161 development Methods 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 238000010030 laminating Methods 0.000 claims description 12
- 229920001169 thermoplastic Polymers 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 8
- 238000000016 photochemical curing Methods 0.000 claims description 7
- 239000000539 dimer Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 239000010410 layer Substances 0.000 description 29
- 238000007747 plating Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 238000005530 etching Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 9
- 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 8
- 101710108306 Bifunctional dihydroflavonol 4-reductase/flavanone 4-reductase Proteins 0.000 description 8
- 101710170824 Dihydroflavonol 4-reductase Proteins 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 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 8
- 239000000975 dye Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MZGMQAMKOBOIDR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCO MZGMQAMKOBOIDR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- TVFJLSWPPLFHKR-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCCOCCOCC(O)OC1=CC=CC=C1 TVFJLSWPPLFHKR-UHFFFAOYSA-N 0.000 description 2
- DXVLAUMXGHQKAV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxypropoxy)propoxy]propoxy]propoxy]propoxy]propoxy]propoxy]propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)CO DXVLAUMXGHQKAV-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
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- 239000004793 Polystyrene Substances 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229940107698 malachite green Drugs 0.000 description 2
- 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 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene 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
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- 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
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- KWHNKGZVEXGCBF-UHFFFAOYSA-N 1-[1-[1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxy]-3-(4-octylphenoxy)propan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCC1=CC=C(OCC(O)COC(C)COC(C)COC(C)COC(C)CO)C=C1 KWHNKGZVEXGCBF-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
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-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
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical class C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-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
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-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
- IVLGFNUYEVNOJL-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethanol;1-[1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]propan-2-yloxy]-3-phenoxypropan-2-ol Chemical compound OCCOCCOCCOCCO.OCC(C)OCC(C)OCC(C)OCC(O)COC1=CC=CC=C1 IVLGFNUYEVNOJL-UHFFFAOYSA-N 0.000 description 1
- MCWMYICYUGCRDY-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCO MCWMYICYUGCRDY-UHFFFAOYSA-N 0.000 description 1
- OWRNLGZKEZSHGO-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-(2-hydroxypropoxy)propoxy]propoxy]propoxy]propoxy]propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)CO OWRNLGZKEZSHGO-UHFFFAOYSA-N 0.000 description 1
- XOLNSMTWLSOUQY-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]-1-(4-nonylphenoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCC1=CC=C(OC(O)COCCOCCOCCOCCOCCOCCOCCO)C=C1 XOLNSMTWLSOUQY-UHFFFAOYSA-N 0.000 description 1
- JDPZLHCKBWMLDH-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C=C JDPZLHCKBWMLDH-UHFFFAOYSA-N 0.000 description 1
- GLTGCYMDFZNUDK-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]benzoic acid Chemical compound CC(C)N(C(C)C)C1=CC=CC=C1C(O)=O GLTGCYMDFZNUDK-UHFFFAOYSA-N 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
- VVZWCWXLBDGDPJ-UHFFFAOYSA-N 2-fluorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(F)=CC=C3SC2=C1 VVZWCWXLBDGDPJ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-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
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- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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Description
技術分野
本発明は、感光性樹脂組成物及び積層体、それを用いたレジストパターンの形成方法、ならびにプリント配線板、リードフレーム又は半導体パッケージの製造方法に関する。
背景技術
パソコンや携帯機器など電子機器には、部品や半導体などの実装用としてプリント配線板が使用されている。
これらのプリント配線板等の製造用レジストとして、従来、支持体と感光性樹脂層と保護層から成る、いわゆるドライフィルムレジスト（以下ＤＦＲと略称）が用いられている。ＤＦＲは、一般に支持体上に感光性樹脂層を積層し、さらに該感光性樹脂層上に保護層を積層することにより調製される。ここで用いられる感光性樹脂層としては、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ものが一般的である。
この感光性樹脂層としては、カルボキシル基を有する熱可塑性重合体、少なくとも１つの末端エチレン性不飽和基を含有する付加重合性モノマー、及び光重合開始剤を含有する組成物が一般的に用いられている。
このようなＤＦＲを用いてプリント配線板を作成するには、まず保護層を剥離した後、銅張積層板やフレキシブル基板等の永久回路作成用基板上にラミネーター等を用いＤＦＲを積層し、配線パターンマスクフィルム等を通し露光を行う。次に必要に応じて支持体を剥離し、現像液により未露光部分の感光性樹脂層を溶解、もしくは分散除去し、基板上にレジストパターンを形成させる。
レジストパターン形成後、回路を形成させるプロセスは、大きく２つの方法に分類される。第一の方法は、レジストパターンによって覆われていない銅張り積層板等の銅面をエッチング除去した後、レジストパターン部分を現像液よりも強いアルカリ水溶液で除去する方法である。第二の方法は、上記のレジストパターンによって覆われていない銅張り積層板等の銅面に銅、半田、ニッケルおよび錫等のめっき処理を行った後、第一の方法と同様にレジストパターン部分を除去し、さらに除去により現れた銅張り積層板等の銅面をエッチングする方法である。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。
ここで用いられるＤＦＲの特性としては、高解像性、高いテンティング特性や耐めっき性、良好な剥離性などが生産性、歩留まりの点から要求される。
従来、本発明者は、特定構造のウレタン構造を有するモノマーを用いることにより、耐エッチング性や耐めっき性、テンティング性（スルーホールを閉鎖保護する露光後ＤＦＲの現像、エッチング液等のスプレー圧力に対する耐久性）などが極めて改善されることを見出した（特開昭６３−１８４７４４号公報参照）。
本発明者は、一方で、特定構造の単官能モノマーを用いることにより、耐めっき性、剥離性が改善されることを見出している（特開平６−１６１１０３号公報参照）。
ただし、これら従来のＤＦＲについては、さらに、感度、解像度、またはテンティング性の観点でさらなる向上が望まれていた。
本発明の課題は、特定構造を持つ複数種のモノマーを併用することにより、テンティング性、耐めっき性、剥離性などの特性を維持しながら、感度が高い感光性樹脂組成物及び積層体、その感光性樹脂積層体を用いたレジストパターンの形成方法、ならびにプリント配線板、リードフレーム又は半導体パッケージの製造方法を提供することである。
発明の開示
即ち、本願は以下の発明を提供する。
（１）（ａ）カルボキシル基を有する熱可塑性重合体；
（ｂ）下記一般式１で示される化合物、下記一般式２で示される化合物、及び下記一般式３で示される化合物を含むエチレン性不飽和付加重合性モノマー；
（一般式１）
式（ａ）
（一般式２）
（一般式３）
（ｃ）２−（ｏ−クロロフェニル）−４、５−ジフェニルイミダゾリル二量体を含む光重合開始剤；及び
（ｄ）下記式４で示される化合物を含む染料、
（式４）
（２）支持体及びその上の上記（１）記載の感光性樹脂組成物の層を含む感光性樹脂積層体。
（３）上記（２）記載の感光性樹脂積層体を金属板、または金属被覆絶縁板の表面に積層し、紫外線露光した後、現像により未露光部を除去することを含むレジストパターンの形成方法。
（４）（２）に記載の感光性樹脂積層体を、回路形成用基板上に感光性樹脂組成物の層が密着するようにして積層し；
活性光線を画像状に照射し、露光部を光硬化させ；
未露光部を現像により除去して硬化レジストパターンを形成させ；そして
その後エッチング又はめっきする、
工程を含むプリント配線板の製造方法。
（５）（２）に記載の感光性樹脂積層体を、回路形成用基板上に感光性樹脂組成物の層が密着するようにして積層し；
活性光線を画像状に照射し、露光部を光硬化させ；
未露光部を現像により除去して硬化レジストパターンを形成させ；そして
その後エッチングする、
工程を含むリードフレームの製造方法。
（６）（２）に記載の感光性樹脂積層体を、回路形成用基板上に感光性樹脂組成物の層が密着するようにして積層し；
活性光線を画像状に照射し、露光部を光硬化させ；
未露光部を現像により除去して硬化レジストパターンを形成させ；そして
その後エッチング又はめっきする、
工程を含む半導体パッケージの製造方法。
発明を実施するための最良の形態
以下、本発明を詳細に説明する。
本発明において用いられる（ａ）成分のカルボキシル基を有する熱可塑性重合体としては、重合性不飽和カルボン酸の中から選ばれる少なくとも１種の第１単量体と、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリルアミドとその窒素上の水素をアルキル基またはアルコキシ基に置換した化合物、スチレン及びスチレン誘導体、（メタ）アクリロニトリル、及び（メタ）アクリル酸グリシジルの中から選ばれる少なくとも１種の第２単量体をビニル共重合して得られる化合物が挙げられる。
カルボキシル基を有する熱可塑性重合体の製造に用いられる第１単量体としては、具体的には、アクリル酸、メタクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、マレイン酸半エステル等が挙げられ、それぞれ単独で用いてもよいし２種以上を組み合わせてもよい。
カルボキシル基を有する熱可塑性重合体における第１単量体の割合は、１５重量％以上４０重量％以下、好ましくは２０重量％以上３５重量％以下である。その割合が１５重量％未満であると、アルカリ水溶液による現像が困難になる。また、その割合が４０重量％を越えると、重合中に溶媒に不溶となるため合成が困難になる。
カルボキシル基を有する熱可塑性重合体の製造に用いられる第２単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｎ−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、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−ブトキシメチルアクリルアミド、スチレン、ｐ−メチルスチレン、ｐ−クロロスチレン、（メタ）アクリロニトリル、（メタ）アクリル酸グリシジル等が挙げられ、それぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
カルボキシル基を有する熱可塑性重合体における第２単量体の割合は、６０重量％以上８５重量％以下、好ましくは６５重量％以上８０重量％以下である。
第２単量体の割合は、第１単量体の割合により自動的に決まるが、その割合が６０重量％未満であると、硬化膜の可とう性が悪化する。また、その割合が８５重量％を超えると、現像時間が長くなり好ましくない。
カルボキシル基を有する熱可塑性重合体の重量平均分子量は、２万以上３０万以下の範囲であり、好ましくは３万以上１５万以下である。この場合の重量平均分子量とはゲルパーミエーションクロマトグラフィー（ＧＰＣ）により標準ポリスチレンの検量線を用いて測定した重量平均分子量のことである。
この重量平均分子量が２万未満であると、硬化膜の強度が小さくなる。また、この重量平均分子量が３０万を越えると、感光性樹脂組成物の粘度が高くなりすぎ塗工性が低下する。
カルボキシル基を有する熱可塑性重合体は、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、過熱攪拌することにより合成することが好ましい。混合物の一部を反応液に滴下しながら合成する場合もある。また、反応終了後さらに溶剤を加えて、生成物を所望の濃度に調整する場合もある。合成手段としては、溶液重合以外にも、塊状重合、懸濁重合及び乳化重合も用いられる。
カルボキシル基を有する熱可塑性重合体の含有量は感光性樹脂組成物の全重量基準で３０重量％以上７５重量％以下の範囲が好ましく、より好ましくは４０重量％以上６５重量％以下である。この量が３０重量％未満であると、未露光の感光性樹脂組成物のアルカリ現像液に対する分散性が低下し現像時間が著しく長くなる。また、この量が７５重量％を越えると、感光性樹脂層の光硬化が不十分となり、レジストとしての耐性が低下する。
以上述べたカルボキシル基を有する熱可塑性重合体は、単独で用いても、２種以上を組み合わせて用いてもよい。
本発明に用いられる（ｂ）成分のエチレン性不飽和付加重合性モノマーとしては、下記一般式１の化合物、下記一般式２の化合物及び下記一般式３の化合物を含む。
（一般式１）
式（ａ）
（一般式２）
（一般式３）
上記の一般式１の化合物は、２置換のイソシアネート化合物と、アルキルオキシドの繰り返し単位を有するヒドロキシ（メタ）アクリレート化合物とのウレタン化物である。ここで、Ｗは、炭素数２以上２０以下の二価のアルキル基であり、Ｒ１及びＲ４は、水素またはメチル基である。Ｒ２及びＲ３は上記式（ａ）で表される残基であり、ｍは２から２５までの整数であり、ｎは０から１５までの整数であり、これらの基はランダムの形態にあってもブロックの形態にあってもよい。
上記の２置換のイソシアネート化合物としては、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、イソホロンジイソシアネートなどが挙げられるが、ヘキサメチレンジイシソシアネートがより好ましい。アルキルオキシドの繰り返し単位を有するヒドロキシ（メタ）アクリレート化合物としては、例えばヒドロキシプロピル（メタ）アクリレートや、ヒドロキシエチル（メタ）アクリレートにアルキレンオキシドを付加させた化合物が挙げられる。付加されるアルキレンオキシドとしては、プロピレンオキシドやエチレンオキシドが挙げられ、それらは単独で用いても、２種以上をランダムの形態で用いても、ブロックの形態で用いても構わない。好ましいものとしては、２−ヒドロキシプロピルメタクリレートにプロピレンオキシドを付加させた化合物、例えばブレンマーＰＰ１０００（日本油脂株式会社製）を挙げることができる。
上記の一般式２の化合物は、アルキル置換フェノールにエチレンオキシド及び／又はプロピレンオキシドを付加させたモノオールとメタクリル酸、またはアクリル酸のエステル化物である。ここで、Ｒ５は炭素数１以上２０以下のアルキル基であり、Ｒ６は水素またはメチル基であり、ｐは０〜２０の整数、ｑは０〜２０の整数であり、且つｐとｑの合計は２〜２０の整数である。アルキル置換フェノールにエチレンオキシド及びプロピレンオキシドの両方を付加する場合、これらはブロックの形態にあっても、ランダムの形態にあっても構わない。
これらのうち、Ｒ５が炭素数８〜１５のアルキル基で、ｐが０〜５、ｑが５〜１２の化合物が好ましい。
上記の一般式３の化合物は、ポリプロピレンオキシドにエチレンオキシドを付加させたポリオールに、（メタ）アクリル酸をエステル化反応させるか、またはエステル交換反応により合成できる化合物である。ここで、Ｒ８及びＲ９は水素、またはメチル基であり、プロピレンオキシドの繰り返し単位数ｓは３〜２０であり、好ましくは８〜１５である。エチレンオキシドの繰り返し単位数ｒ及びｔは１〜１０であり、好ましくは２〜５である。
本発明に用いられる（ｂ）成分は、上記の一般式１〜３の化合物以外の化合物を含んでもよい。このような化合物としては、例えば、２−ヒドロキシ−３−フェノキシプロピルアクリレート、フェノキシテトラエチレングリコールアクリレート、α−ヒドロキシプロピル−β−（アクリロイルオキシ）プロピルフタレート、１，４−テトラメチレングリコールジ（メタ）アクリレート、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、ヘプタプロピレングリコールジ（メタ）アクリレート、グリセロール（メタ）アクリレート、２−ジ（ｐ−ヒドロキシフェニル）プロパンジ（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、ポリオキシプロピルトリメチロールプロパントリ（メタ）アクリレート、ポリオキシエチルトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、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、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、ジアリルフタレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、４−ノルマルオクチルフェノキシペンタプロピレングリコールアクリレート、ビス（トリエチレングリコールメタクリレート）ノナプロピレングリコール、ビス（テトラエチレングリコールメタクリレート）ポリプロピレングリコール、ビス（トリエチレングリコールメタクリレート）ポリプロピレングリコール、ビス（ジエチレングリコールアクリレート）ポリプロピレングリコール、４−ノルマルノニルフェノキシヘプタエチレングリコールジプロピレングリコール（メタ）アクリレート、フェノキシテトラプロピレングリコールテトラエチレングリコール（メタ）アクリレート、ビスフェノールＡ系（メタ）アクリル酸エステルモノマーの分子中にエチレンオキシド鎖を含む化合物、ビスフェノールＡ系（メタ）アクリル酸エステルモノマーの分子中にプロピレンオキシド鎖を含む化合物、ビスフェノールＡ系（メタ）アクリル酸エステルモノマーの分子中にエチレンオキシド鎖とプロピレンオキシド鎖の双方を含む化合物などが挙げられる。
上記の一般式１の化合物／上記の一般式２の化合物／上記の一般式３の化合物の比（重量％）は、１０〜８０／１０〜８０／１０〜８０、好ましくは１５〜７０／１５〜７０／１５〜７０である。
（ｂ）成分のエチレン性不飽和付加重合性モノマーの含有量は、感光性樹脂組成物の全重量基準で２０重量％以上６５重量％以下が好ましい。より好ましくは３０重量％以上６０重量％以下である。その割合が２０重量％未満であると、感光性樹脂の硬化が充分でなく、レジストとしての強度が不足する。一方、その割合が６５重量％を越えると、感光性樹脂積層体がロール状で保存された場合に、端面から感光性樹脂層が次第にはみだす現象、即ちエッジフュージョンが悪化する。
本発明においては、（ｃ）成分の光重合開始剤として、２−（ｏ−クロロフェニル）−４、５−ジフェニルイミダゾリル二量体を用いる。この化合物は、ロフィン二量体の慣用名で知られている。
また、本発明には、他の光重合開始剤を併用することは可能である。このような光重合開始剤としては、例えば、ベンジルジメチルケタール、ベンジルジエチルケタール、ベンジルジプロピルケタール、ベンジルジフェニルケタール、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインフェニルエーテル、チオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジイソプロピルチオキサントン、２−フルオロチオキサントン、４−フルオロチオキサントン、２−クロロチオキサントン、４−クロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、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［ミヒラーズケトン］、４，４’−ビス（ジエチルアミノ）ベンゾフェノン、２，２−ジメトキシ−２−フェニルアセトフェノンなどの芳香族ケトン類；２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾリル二量体等のビイミダゾール化合物；９−フェニルアクリジン等のアクリジン類；α，α−ジメトキシ−α−モルホリノ−メチルチオフェニルアセトフェノン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド、フェニルグリシン、Ｎ−フェニルグリシンさらに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、２，３−ジオキソ−３−フェニルプロピオン酸エチル−２−（ｏ−ベンゾイルカルボニル）−オキシム等のオキシムエステル類；ｐ−ジメチルアミノ安息香酸、ｐ−ジエチルアミノ安息香酸及びｐ−ジイソプロピルアミノ安息香酸及びこれらのアルコールとのエステル化物；ｐ−ヒドロキシ安息香酸エステルなどが挙げられる。その中でも特に２−（ｏ−クロロフェニル）−４、５−ジフェニルイミダゾリル二量体とミヒラーズケトン若しくは４，４’−ビス（ジエチルアミノ）ベンゾフェノンの組み合わせが好ましい。
本発明の（ｃ）成分の光重合開始剤の含有量は、感光性樹脂組成物の全質量基準で０．０１質量％以上２０質量％以下であることが好ましい。より好ましくは１質量％以上１０質量％以下である。この量が０．０１質量％より少ないと感度が十分でない。またこの量が２０質量％より多いと紫外線吸収率が高くなり、感光性樹脂層の底の部分の硬化が不十分になる。
本発明の感光性樹脂組成物は、（ｄ）成分の染料として、下記式４で示される化合物を含む。
（式４）
このＢａｓｉｃ Ｇｒｅｅｎ １の一種であるダイアモンドグリーン（商品名）は、アイゼン ダイアモンドグリーン ＧＨ（保土ヶ谷化学（株）製、製品名）として市販されている。ダイアモンドグリーンの添加量は感光性樹脂組成物の全質量基準で０．０１質量％以上０．１質量％未満が好ましく、０．０３質量％以上０．０７質量％未満が特に好ましい。０．０１質量％未満では、現像後の着色が小さいため検査がしずらく、０．１質量％を越えると、マスクを合わせて露光する場合に、基板のパターンと合わせずらくなり好ましくない。
一般に染料を添加すると感度が低下する傾向があるが、ダイアモンドグリーンはその程度が小さいので、より少ない露光量で所望の感度を得ることができる。
本発明の感光性樹脂組成物にはダイアモンドグリーン以外の染料、顔料等の着色物質が含有されていてもよい。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、パラマジェンタ、クリスタルバイオレット、メチルオレンジ、ナイルブルー２Ｂ、ビクトリアブルー、マラカイトグリーン、ベイシックブルー２０等が挙げられる。
本発明の感光性樹脂組成物の熱安定性、保存安定性を向上させるために、ラジカル重合禁止剤を含有させることは好ましい。このようなラジカル重合禁止剤としては、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、ｔ−ブチルカテコール、塩化第一銅、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２，２’メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、２，２’メチレンビス（４−メチル−６−ｔ−ブチルフェノール）等が挙げられる。
また、本発明の感光性樹脂組成物には光照射により発色する発色系染料を含有させてもよい。このような発色系染料としては、ロイコ染料とハロゲン化合物の組み合わせがよく知られている。ロイコ染料としては、例えば、トリス（４−ジメチルアミノ−２−メチルフェニル）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。一方、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、トリプ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等が挙げられる。
さらに、本発明の感光性樹脂組成物には、必要に応じて、可塑剤等の添加剤を含有させてもよい。このような添加剤としては、例えば、ジエチルフタレート等のフタル酸エステル類、ｏ−トルエンスルホン酸アミド、ｐ−トルエンスルホン酸アミド、クエン酸トリブチル、クエン酸トリエチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ−ｎ−プロピル、アセチルクエン酸トリ−ｎ−ブチル、ポリプロピレングリコール、ポリエチレングリコール、ポリエチレングリコールアルキルエーテル、ポリプロピレングリコールアルキルエーテル等が挙げられる。
本発明の感光性樹脂積層体における感光性樹脂層の膜厚は、１μｍ以上１５０μｍ以下であることが好ましく、さらには３μｍ以上８０μｍ以下が特に好ましい。製膜塗工性の観点から、感光性樹脂層の厚みは１μｍ以上が好ましく、現像後の画像の解像度、密着性の観点からは１５０μｍ以下が好ましい。
本発明の感光性樹脂積層体を作製する方法は、従来知られている方法で行うことができる。例えば、本発明の感光性樹脂組成物を溶剤と混ぜ合わせて均一な溶液とし、該溶液を支持体上にバーコーターやロールコーターを用いて塗布して乾燥することで、支持体上に感光性樹脂層を積層した本発明の感光性樹脂積層体を得ることができる。
本発明における感光性樹脂積層体で用いられる支持体は、活性光を透過する透明なものが望ましい。例えば、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレート、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。
本発明の感光性樹脂積層体に用いられる支持体の厚みは、好ましくは１０μｍ以上４０μｍ以下であり、さらに好ましくは１２μｍ以上３０μｍである。取り扱いの観点から、支持体の厚みは１０μｍ以上が好ましく、解像度の点からは４０μｍ以下が好ましい。
また、本発明の感光性樹脂積層体の感光性樹脂上に、保護層をラミネートして、３層構造の感光性樹脂積層体を作製することもできる。この場合の保護層は厚みが１５μｍ以上５０μｍ以下が好ましく、さらには２５μｍ以上４５μｍ以下がより好ましい。最終製品の歩留まりの点からは、１５μｍ以上であることが好ましく、製造コストの点からは５０μｍ以下が好ましい。
保護層に用いられるフィルムとしては、ポリエチレンフィルムやポリプロピレンフィルム等のポリオレフィンフィルムやポリエステルフィルムあるいはシリコーン処理またはアルキッド処理により剥離性を向上させたポリエステルフィルム等を挙げることができる。特に、ポリエチレンフィルムが好ましい。
次に、本発明の感光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。
プリント配線板は、以下の各工程を経て製造される。
（１）感光性樹脂積層体を、その保護層を剥がしながら銅張積層板やフレキシブル基板等の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ラミネート工程。
（２）所望の配線パターンを有するマスクフィルムを支持体上に密着させ活性光線源を用いて露光を施す露光工程。
（３）支持体を剥離した後アルカリ現像液を用いて感光性樹脂層の未露光部分を溶解または分散除去し、レジストパターンを基板上に形成する現像工程。
（４）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、また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、ニッケルおよび錫等のめっき処理を行うめっき工程。
（５）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工程。
上記の露光工程において用いられる活性光線源としては、高圧水銀灯、超高圧水銀灯、紫外線蛍光灯、カーボンアーク灯、キセノンランプなどが挙げられる。また、より微細なレジストパターンを得るためには平行光光源を用いるのがより好ましい。ゴミや異物の影響を極力少なくしたい場合には、フォトマスクを支持体上から数十μｍ以上数百μｍ以下浮かせた状態で露光（プロキシミティー露光）する場合もある。
また、現像工程で用いられるアルカリ現像液としては、炭酸ナトリウム、炭酸カリウム等の水溶液が挙げられる。これらのアルカリ水溶液は感光性樹脂層の特性に合わせて選択されるが、一般的に０．５ｗｔ％以上３％ｗｔ以下の炭酸ナトリウム水溶液が用いられる。
エッチング工程は、酸性エッチング、アルカリエッチングなど、使用するＤＦＲに適した方法で行われる。
剥離工程で用いられるアルカリ剥離液としては、一般的に現像で用いたアルカリ水溶液よりも更に強いアルカリ性の水溶液、例えば１ｗｔ％以上５ｗｔ％以下の水酸化ナトリウム、水酸化カリウムの水溶液が挙げられる。
めっき工程を採用する場合には、レジストパターンを剥離後に、レジストパターンの下に現れた銅面をエッチングする場合もある。
また、本発明の感光性樹脂積層体を用いてリードフレームを製造する場合、前記の銅張り積層板やフレキシブル基板等の代わりに、銅、銅合金、鉄系合金等の金属板の両面に感光性樹脂層をラミネートし、露光、現像を行った後、エッチングする。最終的に硬化レジストの剥離を行い、所望のリードフレームを得る。
さらに、半導体パッケージを製造する場合、ＬＳＩとしての回路形成が終了したウェハに感光性樹脂層をラミネートし、露光、現像を行った後、開口部に銅、はんだ等の柱状のめっきを施す。次に硬化レジストの剥離を行い、柱状めっき以外の部分の薄い金属層をエッチングにより除去することにより、所望の半導体パッケージを得る。
以下、実施例により本発明の実施の形態をさらに詳しく説明する。
＜実施例１〜７及び比較例１〜４＞
実施例及び比較例における評価は次の方法により行った。
１）サンプルの基本作成条件
（感光性樹脂積層体の作成）
表１に示す組成の感光性樹脂組成物を混合し、厚さ１６μｍのポリエチレンテレフタレートフィルムにバーコーターを用いて均一に塗布し、９０℃の乾燥機中で２分間乾燥して感光性樹脂層を形成した。感光性樹脂層の厚みは４０μｍであった。表１の中の成分組成は固形分の質量部を表す。
感光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ポリエチレンフィルムを張り合わせて感光性樹脂積層体を得た。
（基板の整面）
銅箔厚みが３５μｍである銅張り積層板（板厚；１．６ｍｍ）を、サクランダムＲ＃２２０の砥粒（日本カーリット（株）製）を用いて、ジェットスクラブ研磨をした。
（ラミネート）
感光性樹脂積層体のポリエチレンフィルムを剥がしながら、前処理した銅合金基板に２段式ホットロールラミネーター（旭化成（株）製ＡＬ−７００）により前段ロール１００℃、後段ロール１００℃でラミネートした。ラミネーターのロール圧力はエアーゲージ表示で０．３０ＭＰａとし、ラミネート速度は２．０ｍ／ｍｉｎ．とした。
（露光）
感光性樹脂層に、マスクフィルムなしで、又は評価に必要なマスクフィルムを通して、超高圧水銀ランプ（オーク製作所製：ＨＭＷ−８０１）により６０ｍＪ／ｃｍ２で露光した。
（現像）
ポリエチレンテレフタレートフィルムを剥離した後、３０℃の１％炭酸ナトリウム水溶液を所定時間スプレーし、感光性樹脂層の未露光部分を溶解除去した。この際、未露光部分の感光性樹脂が完全に溶解するのに要する最も少ない時間を最小現像時間とし、所定現像時間はその１．５倍とした。
２）感度測定
フォトマスクとして、透明から黒色に２７段階に明度が変化している２７段ステップタブレット（旭化成（株）製、光学濃度Ｄ＝０．５０〜１．８０、１段あたりの濃度差＝０．０５）を用い露光、現像後に積層板の銅面が露出した位置に対応するステップタブレットの段数を調べた。
感度が１２段以上あると、実用上有効な範囲であり、１１段以下であると感度不足から露光量をさらに増やす必要があり、生産性が低下する。
３）解像度試験
１）のサンプルの基本作成条件の、ラミネート工程まで終わった基板に対して、ラインスペースが１０／３００μｍ〜１００／３００μｍ（５μｍ刻み）となるフォトマスクフィルムを、感光性樹脂積層体の支持体であるポリエチレンテレフタレートフィルム側に置き、フォトマスクフィルムを介して６０ｍＪ／ｃｍ２の露光量で露光した後、ポリエチレンテレフタレートフィルムを除去し、１ｗｔ％炭酸ナトリウム水溶液を３０℃で、スプレー圧が０．１５ＭＰａで８０秒間スプレーすることにより、未露光部を除去し、画像パターンを得た。得られた画像の分離されている、かつ流れの無い（即ち、画像パターンの蛇行、基板に密着していない部分等がない）最小ライン幅を解像度とした。
４）剥離性試験
３ｃｍ×５ｃｍエリア上に６０ｍＪ／ｃｍ２の露光量で露光、現像した基板を、５０℃に保った３ｗｔ％水酸化ナトリウム水溶液に浸漬し、硬化した感光性樹脂層が基材から剥がれるのに要する時間を剥離時間とした。
剥離時間が６０秒以下の場合を○、６０秒を越える場合を×とした。
５）耐めっき性試験
１）のサンプルの基本作成条件の露光工程で、回路パターン状のフォトマスクを用いて６０ｍＪ／ｃｍ２の露光量で露光、現像した基板を次の工程を経てめっき前処理した。
ａ）４０℃の酸性クリーナーＦＲ（アトテック社製、製品名）の１０ｗｔ％、硫酸２０ｗｔ％水溶液に４分間浸漬。
ｂ）室温で２００ｇ／Ｌの過硫酸アンモニウム水溶液に１分間浸浸。
ｃ）室温で１０ｗｔ％硫酸水溶液に２分間浸漬。
めっき前処理後、メルテックス社製「硫酸銅コンク」を１９ｗｔ％硫酸で３．６倍に希釈しためっき液中で、２．５Ａ／ｄｍ２の電流密度で室温下３０分間銅めっきを行った。さらに、マクダーミッド社製のはんだめっき液（錫／鉛＝６／４重量比）を用い２．０Ａ／ｄｍ２の電流密度で１０分間はんだめっきを行った。
この基板にＪＩＳ Ｋ ５６００−５−６法に準拠して、セロテープを貼り付け、引き剥がした後の硬化した感光性樹脂層の状態により、耐めっき性を次の様に評価した。
直径６ｍｍの円孔が約１０００個開いている銅張り積層板を用い、感光性樹脂積層体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じずに、前出のステップタブレット段数が１３段になる露光量で露光した。
これを最小現像時間の３倍の時間で現像処理し、さらにスプレー圧力０．３ＭＰａで１分間水洗した。円孔部の硬化膜の内、少なくとも片面が破れている円孔の数を数え、次の様にランク付けした。
○：破れ率 １０％未満
△：破れ率 １０％以上３０％未満
×：破れ率 ３０％以上
実施例及び比較例の結果を表１に示す。
なお、表１に示す組成（各成分量単位：重量部）及び支持体の略号は、以下に示すものである。
Ｐ−１：メタクリル酸メチル／メタクリル酸／アクリル酸ｎ−ブチル（質量比が６５／２５／１０）の組成を有し、重量平均分子量が１２万である共重合体の３０質量％メチルエチルケトン溶液
Ｍ−１：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ＰＰ−１０００）とのウレタン化物
Ｍ−２：ビス（トリエチレングリコールメタクリレート）ノナプロピレングリコール
Ｍ−３：４−ノルマルノニルフェノキシペンタエチレングリコールトリプロピレングリコールアクリレート
Ｍ−４：ノナエチレングリコールジアクリレート
Ｍ−５：フェノキシテトラエチレングリコールアクリレート
Ｍ−６：トリオキシエチルトリメチロールプロパントリアクリレート
Ｍ−７：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エチ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７０ＰＥＰ−３５０Ｐ）とのウレタン化物
Ｍ−８：４−ノルマルノニルフェノキシオクタエチレングリコールモノアクリレート
Ｍ−９：４−ノルマルノニルフェノキシヘキサプロピレングリコールモノアクリレート
Ｉ−１：ミヒラーズケトン
Ｉ−２：２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾリル二量体Ｄ−１：ダイヤモンドグリーン（保土ヶ谷化学（株）製）
Ｄ−２：マラカイトグリーン（保土ヶ谷化学（株）製）
Ｄ−３：ロイコクリスタルバイオレット
本発明による感光性樹脂組成物は、高感度、優れたテンティング性、耐めっき性、硬化膜の剥離性を有し、プリント配線板、リードフレームまたは半導体パッケージの製造に極めて有用である。Technical field
The present invention relates to a photosensitive resin composition and a laminate, a method for forming a resist pattern using the same, and a method for manufacturing a printed wiring board, a lead frame, or a semiconductor package.
Background art
In electronic devices such as personal computers and portable devices, printed wiring boards are used for mounting components and semiconductors.
Conventionally, a so-called dry film resist (hereinafter abbreviated as DFR) composed of a support, a photosensitive resin layer, and a protective layer has been used as a resist for manufacturing such printed wiring boards. The DFR is generally prepared by laminating a photosensitive resin layer on a support and further laminating a protective layer on the photosensitive resin layer. As the photosensitive resin layer used here, an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used.
As the photosensitive resin layer, a thermoplastic polymer having a carboxyl group, an addition polymerizable monomer containing at least one terminal ethylenically unsaturated group, and a composition containing a photopolymerization initiator are generally used. ing.
To create a printed wiring board using such a DFR, the protective layer is first peeled off, and then a DFR is laminated on a permanent circuit creation board such as a copper-clad laminate or flexible board using a laminator, etc. Exposure is performed through a pattern mask film or the like. Next, if necessary, the support is peeled off, and the photosensitive resin layer in the unexposed portion is dissolved or dispersed and removed with a developing solution to form a resist pattern on the substrate.
The process of forming a circuit after forming a resist pattern is roughly classified into two methods. The first method is a method in which after removing a copper surface such as a copper-clad laminate not covered with a resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer. In the second method, after performing plating treatment of copper, solder, nickel, tin, etc. on a copper surface such as a copper clad laminate not covered with the resist pattern, the resist pattern portion is the same as in the first method. This is a method of etching the copper surface of the copper-clad laminate or the like that appears after the removal. For etching, cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used.
As the characteristics of the DFR used here, high resolution, high tenting characteristics, plating resistance, good peelability, and the like are required in terms of productivity and yield.
Conventionally, the present inventor has used a monomer having a urethane structure having a specific structure, so that etching resistance, plating resistance, and tenting properties (development of post-exposure DFR that closes and protects a through hole, spray pressure of an etching solution, etc.) It has been found that the durability of the toner is extremely improved (see Japanese Patent Application Laid-Open No. 63-184744).
On the other hand, the present inventor has found that the use of a monofunctional monomer having a specific structure improves the plating resistance and peelability (see JP-A-6-161103).
However, these conventional DFRs have been desired to be further improved in terms of sensitivity, resolution, or tenting properties.
An object of the present invention is to use a plurality of types of monomers having a specific structure in combination with a photosensitive resin composition and a laminate having high sensitivity while maintaining properties such as tenting property, plating resistance, and peelability. It is to provide a method for forming a resist pattern using the photosensitive resin laminate and a method for manufacturing a printed wiring board, a lead frame or a semiconductor package.
Disclosure of the invention
That is, this application provides the following invention.
(1) (a) a thermoplastic polymer having a carboxyl group;
(B) an ethylenically unsaturated addition polymerizable monomer containing a compound represented by the following general formula 1, a compound represented by the following general formula 2, and a compound represented by the following general formula 3;
(General formula 1)
Formula (a)
(General formula 2)
(General formula 3)
(C) a photoinitiator comprising 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer; and
(D) a dye containing a compound represented by the following formula 4,
(Formula 4)
(2) A photosensitive resin laminate comprising a support and a layer of the photosensitive resin composition according to (1) above.
(3) A method for forming a resist pattern, comprising: laminating the photosensitive resin laminate according to (2) above on the surface of a metal plate or a metal-coated insulating plate, exposing to ultraviolet rays, and then removing unexposed portions by development. .
(4) Laminating the photosensitive resin laminate according to (2) such that the layer of the photosensitive resin composition is in close contact with the circuit forming substrate;
Irradiating actinic rays in the form of an image and photocuring the exposed area;
Removing unexposed areas by development to form a cured resist pattern; and
Etching or plating afterwards,
A manufacturing method of a printed wiring board including a process.
(5) Laminating the photosensitive resin laminate according to (2) so that the layer of the photosensitive resin composition is in close contact with the circuit forming substrate;
Irradiating actinic rays in the form of an image and photocuring the exposed area;
Removing unexposed areas by development to form a cured resist pattern; and
Then etch,
A manufacturing method of a lead frame including a process.
(6) Laminating the photosensitive resin laminate according to (2) so that the layer of the photosensitive resin composition is in close contact with the circuit forming substrate;
Irradiating actinic rays in the form of an image and photocuring the exposed area;
Removing unexposed areas by development to form a cured resist pattern; and
Etching or plating afterwards,
A method of manufacturing a semiconductor package including a process.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
As the thermoplastic polymer having a carboxyl group as component (a) used in the present invention, at least one first monomer selected from polymerizable unsaturated carboxylic acids, alkyl (meth) acrylate, hydroxy Alkyl (meth) acrylate, (meth) acrylamide and a compound obtained by substituting hydrogen on the nitrogen with an alkyl group or an alkoxy group, styrene and a styrene derivative, (meth) acrylonitrile, and glycidyl (meth) acrylate at least Examples thereof include compounds obtained by vinyl copolymerization of one kind of second monomer.
Specific examples of the first monomer used for the production of the thermoplastic polymer having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester, and the like. And may be used alone or in combination of two or more.
The ratio of the 1st monomer in the thermoplastic polymer which has a carboxyl group is 15 to 40 weight%, Preferably it is 20 to 35 weight%. If the proportion is less than 15% by weight, development with an alkaline aqueous solution becomes difficult. On the other hand, if the ratio exceeds 40% by weight, it becomes insoluble in the solvent during the polymerization, making synthesis difficult.
Examples of the second monomer used in the production of the thermoplastic polymer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, cyclohexyl (meth) acrylate, and n-butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, (meth) acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, styrene, p-methylstyrene, p-chlorostyrene, (meth) acrylonitrile, (meth ) Glycidyl acrylate and the like, may be used alone or used in combination of two or more kinds.
The proportion of the second monomer in the thermoplastic polymer having a carboxyl group is 60% by weight or more and 85% by weight or less, preferably 65% by weight or more and 80% by weight or less.
The proportion of the second monomer is automatically determined by the proportion of the first monomer, but if the proportion is less than 60% by weight, the flexibility of the cured film is deteriorated. On the other hand, when the ratio exceeds 85% by weight, the development time becomes long, which is not preferable.
The weight average molecular weight of the thermoplastic polymer having a carboxyl group is in the range of 20,000 to 300,000, preferably 30,000 to 150,000. The weight average molecular weight in this case is a weight average molecular weight measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
When the weight average molecular weight is less than 20,000, the strength of the cured film is reduced. On the other hand, when the weight average molecular weight exceeds 300,000, the viscosity of the photosensitive resin composition becomes too high and the coating property is lowered.
A thermoplastic polymer having a carboxyl group is obtained by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting a mixture of monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to synthesize by heating and stirring. In some cases, a part of the mixture is synthesized while being dropped into the reaction solution. In addition, a solvent may be further added after the reaction to adjust the product to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization and emulsion polymerization are also used in addition to solution polymerization.
The content of the thermoplastic polymer having a carboxyl group is preferably in the range of 30 wt% to 75 wt%, more preferably 40 wt% to 65 wt%, based on the total weight of the photosensitive resin composition. When this amount is less than 30% by weight, the dispersibility of the unexposed photosensitive resin composition in an alkaline developer is lowered, and the development time is significantly increased. On the other hand, when the amount exceeds 75% by weight, photo-curing of the photosensitive resin layer becomes insufficient, and the resistance as a resist is lowered.
The above-mentioned thermoplastic polymers having a carboxyl group may be used alone or in combination of two or more.
The ethylenically unsaturated addition polymerizable monomer of component (b) used in the present invention includes a compound of the following general formula 1, a compound of the following general formula 2, and a compound of the following general formula 3.
(General formula 1)
Formula (a)
(General formula 2)
(General formula 3)
The compound of the above general formula 1 is a urethanized product of a disubstituted isocyanate compound and a hydroxy (meth) acrylate compound having an alkyl oxide repeating unit. Here, W is a divalent alkyl group having 2 to 20 carbon atoms, and R 1 And R 4 Is hydrogen or a methyl group. R 2 And R 3 Is a residue represented by the above formula (a), m is an integer from 2 to 25, n is an integer from 0 to 15, and even if these groups are in random form, It may be in form.
Examples of the disubstituted isocyanate compound include hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate, and hexamethylene diisocyanate is more preferable. Examples of the hydroxy (meth) acrylate compound having an alkyl oxide repeating unit include hydroxypropyl (meth) acrylate and compounds obtained by adding alkylene oxide to hydroxyethyl (meth) acrylate. Examples of the alkylene oxide to be added include propylene oxide and ethylene oxide. These may be used alone, or two or more of them may be used in random form or in block form. Preferable examples include compounds obtained by adding propylene oxide to 2-hydroxypropyl methacrylate, such as Blenmer PP1000 (manufactured by NOF Corporation).
The compound of the above general formula 2 is an esterified product of monool and methacrylic acid or acrylic acid obtained by adding ethylene oxide and / or propylene oxide to alkyl-substituted phenol. Where R 5 Is an alkyl group having 1 to 20 carbon atoms, R 6 Is hydrogen or a methyl group, p is an integer of 0-20, q is an integer of 0-20, and the sum of p and q is an integer of 2-20. When both ethylene oxide and propylene oxide are added to an alkyl-substituted phenol, they can be in block or random form.
Of these, R 5 Is an alkyl group having 8 to 15 carbon atoms, and a compound in which p is 0 to 5 and q is 5 to 12 is preferable.
The compound of the above general formula 3 is a compound that can be synthesized by subjecting a polyol obtained by adding ethylene oxide to polypropylene oxide to an esterification reaction of (meth) acrylic acid or by a transesterification reaction. Where R 8 And R 9 Is hydrogen or a methyl group, and the number of repeating units s of propylene oxide is 3 to 20, preferably 8 to 15. The number of repeating units r and t of ethylene oxide is 1 to 10, preferably 2 to 5.
(B) component used for this invention may also contain compounds other than the compound of said General formula 1-3. Examples of such compounds include 2-hydroxy-3-phenoxypropyl acrylate, phenoxytetraethylene glycol acrylate, α-hydroxypropyl-β- (acryloyloxy) propyl phthalate, 1,4-tetramethylene glycol di (meth). Acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, heptapropylene glycol di (meth) acrylate, glycerol (meth) acrylate, 2-di (p-hydroxyphenyl) Propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polio Xylethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) Acrylate, diallyl phthalate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 4-normal octylphenoxypentapropylene glycol acrylate, bis (triethylene glycol methacrylate) nonapropylene glycol, bis (tetraethylene glycol methacrylate) polypropylene Glycol, bis (triethylene glycol methacrylate) polypro Of lenglycol, bis (diethylene glycol acrylate) polypropylene glycol, 4-normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate, phenoxytetrapropylene glycol tetraethylene glycol (meth) acrylate, bisphenol A (meth) acrylic acid ester monomer Compound containing ethylene oxide chain in molecule, compound containing propylene oxide chain in molecule of bisphenol A (meth) acrylate monomer, ethylene oxide chain and propylene oxide chain in molecule of bisphenol A (meth) acrylate monomer And compounds containing both of them.
The ratio (% by weight) of the compound of the general formula 1 / the compound of the general formula 2 / the compound of the general formula 3 is 10 to 80/10 to 80/10 to 80, preferably 15 to 70/15. -70 / 15-70.
The content of the ethylenically unsaturated addition polymerizable monomer (b) is preferably 20% by weight or more and 65% by weight or less based on the total weight of the photosensitive resin composition. More preferably, it is 30 wt% or more and 60 wt% or less. When the proportion is less than 20% by weight, the photosensitive resin is not sufficiently cured, and the strength as a resist is insufficient. On the other hand, when the proportion exceeds 65% by weight, the phenomenon that the photosensitive resin layer gradually protrudes from the end face when the photosensitive resin laminate is stored in a roll shape, that is, edge fusion is deteriorated.
In the present invention, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is used as the photopolymerization initiator of the component (c). This compound is known by the common name of lophine dimer.
In the present invention, other photopolymerization initiators can be used in combination. Examples of such a photopolymerization initiator include benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl diphenyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, thioxanthone, 2, 4 -Dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1- Chloro-4-propoxythioxanthone, benzophenone, 4,4'-bis (dimethylamino) benzophenone [Michler's ketone ], 4,4'-bis (diethylamino) benzophenone, aromatic ketones such as 2,2-dimethoxy-2-phenylacetophenone; bi (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and the like Imidazole compounds; acridines such as 9-phenylacridine; α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylglycine, N-phenylglycine and 1-phenyl- Oxime esters such as 1,2-propanedione-2-o-benzoyloxime, ethyl 2,3-dioxo-3-phenylpropionate-2- (o-benzoylcarbonyl) -oxime; p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and p- Examples include diisopropylaminobenzoic acid and esterified products thereof with these alcohols; p-hydroxybenzoic acid ester and the like. Among them, a combination of 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and Michler's ketone or 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The content of the photopolymerization initiator of the component (c) of the present invention is preferably 0.01% by mass or more and 20% by mass or less based on the total mass of the photosensitive resin composition. More preferably, it is 1 mass% or more and 10 mass% or less. If this amount is less than 0.01% by mass, the sensitivity is not sufficient. On the other hand, when the amount is more than 20% by mass, the ultraviolet absorptance is increased, and the bottom portion of the photosensitive resin layer is not sufficiently cured.
The photosensitive resin composition of this invention contains the compound shown by following formula 4 as dye of (d) component.
(Formula 4)
Diamond Green (trade name), which is a kind of Basic Green 1, is commercially available as Eisen Diamond Green GH (product name, manufactured by Hodogaya Chemical Co., Ltd.). The addition amount of diamond green is preferably 0.01% by mass or more and less than 0.1% by mass, and particularly preferably 0.03% by mass or more and less than 0.07% by mass based on the total mass of the photosensitive resin composition. If it is less than 0.01% by mass, the color after development is small and inspection is difficult, and if it exceeds 0.1% by mass, it is difficult to align with the pattern of the substrate when the mask is exposed.
In general, when a dye is added, the sensitivity tends to decrease, but since the degree of diamond green is small, a desired sensitivity can be obtained with a smaller exposure amount.
The photosensitive resin composition of the present invention may contain coloring substances such as dyes and pigments other than diamond green. Examples of such coloring substances include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, paramagenta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue 20 and the like.
In order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, it is preferable to contain a radical polymerization inhibitor. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2 Examples include 'methylenebis (4-ethyl-6-t-butylphenol), 2,2'methylenebis (4-methyl-6-t-butylphenol), and the like.
Further, the photosensitive resin composition of the present invention may contain a coloring dye that develops color when irradiated with light. As such a coloring dye, a combination of a leuco dye and a halogen compound is well known. 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. On the other hand, as halogen compounds, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tripromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane and the like.
Furthermore, you may make the photosensitive resin composition of this invention contain additives, such as a plasticizer, as needed. Such additives include, for example, phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri -N-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like.
The film thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 1 μm to 150 μm, more preferably 3 μm to 80 μm. From the viewpoint of film-forming coating property, the thickness of the photosensitive resin layer is preferably 1 μm or more, and from the viewpoint of image resolution and adhesion after development, 150 μm or less is preferable.
The method for producing the photosensitive resin laminate of the present invention can be performed by a conventionally known method. For example, the photosensitive resin composition of the present invention is mixed with a solvent to form a uniform solution, and the solution is coated on the support using a bar coater or a roll coater and dried, whereby the photosensitivity is formed on the support. The photosensitive resin laminated body of this invention which laminated | stacked the resin layer can be obtained.
The support used in the photosensitive resin laminate in the present invention is preferably a transparent one that transmits active light. For example, polyethylene terephthalate film, polyethylene naphthalate, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, poly Examples include acrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film.
The thickness of the support used in the photosensitive resin laminate of the present invention is preferably 10 μm or more and 40 μm or less, and more preferably 12 μm or more and 30 μm. From the viewpoint of handling, the thickness of the support is preferably 10 μm or more, and preferably 40 μm or less from the viewpoint of resolution.
In addition, a protective layer can be laminated on the photosensitive resin of the photosensitive resin laminate of the present invention to produce a photosensitive resin laminate having a three-layer structure. In this case, the protective layer preferably has a thickness of 15 μm to 50 μm, and more preferably 25 μm to 45 μm. From the viewpoint of the yield of the final product, it is preferably 15 μm or more, and from the viewpoint of manufacturing cost, it is preferably 50 μm or less.
Examples of the film used for the protective layer include a polyolefin film such as a polyethylene film and a polypropylene film, a polyester film, a polyester film whose peelability is improved by a silicone treatment or an alkyd treatment, and the like. In particular, a polyethylene film is preferable.
Next, an example of a method for producing a printed wiring board using the photosensitive resin laminate of the present invention will be described.
A printed wiring board is manufactured through the following steps.
(1) A laminating step in which the photosensitive resin laminate is adhered to a substrate such as a copper clad laminate or a flexible substrate using a hot roll laminator while peeling off the protective layer.
(2) An exposure process in which a mask film having a desired wiring pattern is brought into close contact with the support and exposed using an actinic ray source.
(3) A development process in which after the support is peeled off, an unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed using an alkali developer to form a resist pattern on the substrate.
(4) An etching process in which an etching solution is sprayed on the formed resist pattern to etch a copper surface not covered with the resist pattern, or copper, solder, nickel, tin, or the like is plated on the copper surface not covered with the resist pattern Plating process for processing.
(5) A peeling step of removing the resist pattern from the substrate using an alkaline stripping solution.
Examples of the actinic ray source used in the exposure process include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp. In order to obtain a finer resist pattern, it is more preferable to use a parallel light source. When it is desired to reduce the influence of dust or foreign matter as much as possible, exposure (proximity exposure) may be performed in a state where the photomask is floated from several tens of micrometers to several hundreds of micrometers from the support.
Examples of the alkali developer used in the development step include aqueous solutions of sodium carbonate, potassium carbonate and the like. These alkaline aqueous solutions are selected in accordance with the characteristics of the photosensitive resin layer, but in general, an aqueous sodium carbonate solution of 0.5 wt% or more and 3% wt or less is used.
An etching process is performed by the method suitable for DFR to be used, such as acidic etching and alkali etching.
Examples of the alkaline stripping solution used in the stripping step include alkaline aqueous solutions that are generally stronger than the alkaline aqueous solution used in development, for example, 1 wt% to 5 wt% of sodium hydroxide and potassium hydroxide.
When the plating process is employed, the copper surface that appears under the resist pattern may be etched after the resist pattern is removed.
In addition, when producing a lead frame using the photosensitive resin laminate of the present invention, it is sensitive to both sides of a metal plate such as copper, copper alloy, iron-based alloy, etc. instead of the copper-clad laminate or flexible substrate. The conductive resin layer is laminated, exposed and developed, and then etched. Finally, the cured resist is peeled off to obtain a desired lead frame.
Furthermore, when manufacturing a semiconductor package, a photosensitive resin layer is laminated on a wafer on which circuit formation as an LSI has been completed, and after exposure and development, columnar plating such as copper or solder is applied to the opening. Next, the cured resist is peeled off, and the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.
Hereinafter, the embodiments of the present invention will be described in more detail by way of examples.
<Examples 1-7 and Comparative Examples 1-4>
Evaluation in Examples and Comparative Examples was performed by the following method.
1) Basic sample creation conditions
(Preparation of photosensitive resin laminate)
The photosensitive resin composition having the composition shown in Table 1 is mixed, and uniformly applied to a polyethylene terephthalate film having a thickness of 16 μm using a bar coater, followed by drying in a dryer at 90 ° C. for 2 minutes to form a photosensitive resin layer. Formed. The thickness of the photosensitive resin layer was 40 μm. The component composition in Table 1 represents parts by mass of solid content.
A polyethylene film was laminated on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.
(Smoothing of substrate)
A copper clad laminate (thickness: 1.6 mm) having a copper foil thickness of 35 μm was subjected to jet scrub polishing using abrasive grains of Sac Random R # 220 (manufactured by Nippon Carlit Co., Ltd.).
(laminate)
While peeling the polyethylene film of the photosensitive resin laminate, the pre-treated copper alloy substrate was laminated at a front roll 100 ° C. and a rear roll 100 ° C. by a two-stage hot roll laminator (AL-700 manufactured by Asahi Kasei Co., Ltd.). The laminator roll pressure is 0.30 MPa in terms of air gauge, and the laminating speed is 2.0 m / min. It was.
(exposure)
60 mJ / cm with a super high pressure mercury lamp (OMW Mfg. Co., Ltd .: HMW-801) without a mask film or through a mask film necessary for evaluation on the photosensitive resin layer. 2 And exposed.
(developing)
After peeling the polyethylene terephthalate film, a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin in the unexposed portion was set as the minimum development time, and the predetermined development time was set to 1.5 times that time.
2) Sensitivity measurement
As a photomask, a 27-step tablet whose brightness changes from transparent to black in 27 steps (manufactured by Asahi Kasei Co., Ltd., optical density D = 0.50-1.80, density difference per stage = 0.05 ) Was used to examine the number of steps of the step tablet corresponding to the position where the copper surface of the laminated plate was exposed after exposure and development.
If the sensitivity is 12 steps or more, it is a practically effective range, and if it is 11 steps or less, it is necessary to further increase the exposure amount due to insufficient sensitivity, and productivity is lowered.
3) Resolution test
A photomask film in which the line space is 10/300 μm to 100/300 μm (in 5 μm increments) with respect to the substrate that has been subjected to the lamination process of the basic preparation conditions of the sample of 1) is a support of a photosensitive resin laminate. Place it on the polyethylene terephthalate film side and pass through the photomask film to 60mJ / cm 2 Then, the polyethylene terephthalate film was removed, and a 1 wt% aqueous sodium carbonate solution was sprayed at 30 ° C. and a spray pressure of 0.15 MPa for 80 seconds to remove the unexposed area and obtain an image pattern. It was. The resolution was defined as the minimum line width in which the obtained image was separated and there was no flow (that is, there was no meandering of the image pattern, no portion not in close contact with the substrate, etc.).
4) Peelability test
60mJ / cm on 3cm x 5cm area 2 The substrate exposed and developed with the exposure amount was immersed in a 3 wt% aqueous sodium hydroxide solution maintained at 50 ° C., and the time required for the cured photosensitive resin layer to peel from the substrate was defined as the peeling time.
The case where the peeling time was 60 seconds or less was marked with ◯, and the case where the peeling time exceeded 60 seconds was marked with x.
5) Plating resistance test
In the exposure process under the basic preparation conditions of the sample of 1), using a circuit pattern photomask, 60 mJ / cm 2 The substrate exposed and developed with an exposure amount of 1 was pre-plated through the following steps.
a) Immersion for 4 minutes in a 10 wt% aqueous solution of acidic cleaner FR (product name, manufactured by Atotech Co., Ltd.) at 40 ° C. and 20 wt% sulfuric acid.
b) Immerse in 200 g / L ammonium persulfate aqueous solution for 1 minute at room temperature.
c) Immerse in a 10 wt% aqueous sulfuric acid solution at room temperature for 2 minutes.
After plating pretreatment, 2.5A / dm in plating solution diluted with Meltex's "copper sulfate conch" with 19wt% sulfuric acid 3.6 times 2 Copper plating was performed at room temperature for 30 minutes at a current density of. Furthermore, using a solder plating solution (tin / lead = 6/4 weight ratio) manufactured by McDermid, 2.0 A / dm 2 Solder plating was performed at a current density of 10 minutes.
In accordance with JIS K 5600-5-6 method, the plating resistance was evaluated as follows according to the state of the cured photosensitive resin layer after the cellophane was affixed to the substrate and peeled off.
Using a copper-clad laminate with about 1000 circular holes with a diameter of 6 mm, the photosensitive resin laminate was sequentially laminated on both sides of the substrate, and the number of step tablet steps described above was 13 without passing through a pattern mask from each side. The exposure was performed with a stepwise exposure amount.
This was developed for 3 times the minimum development time, and further washed with water at a spray pressure of 0.3 MPa for 1 minute. Of the cured film in the circular hole portion, the number of circular holes in which at least one side was broken was counted and ranked as follows.
○: Breaking rate less than 10%
Δ: Breaking rate 10% or more and less than 30%
×: Tear rate 30% or more
The results of Examples and Comparative Examples are shown in Table 1.
In addition, the composition (each component amount unit: part by weight) and the abbreviation of the support shown in Table 1 are shown below.
P-1: 30% by mass methyl ethyl ketone solution of a copolymer having a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (mass ratio 65/25/10) and having a weight average molecular weight of 120,000
M-1: Urethane product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Blenmer PP-1000 manufactured by NOF Corporation)
M-2: Bis (triethylene glycol methacrylate) nonapropylene glycol
M-3: 4-normal nonylphenoxypentaethylene glycol tripropylene glycol acrylate
M-4: Nonaethylene glycol diacrylate
M-5: Phenoxytetraethylene glycol acrylate
M-6: trioxyethyltrimethylolpropane triacrylate
M-7: Urethane product of hexamethylene diisocyanate and oligopropylene glycol ethylene glycol monomethacrylate (Blemmer 70PEP-350P manufactured by NOF Corporation)
M-8: 4-normal nonylphenoxy octaethylene glycol monoacrylate
M-9: 4-Normal nonylphenoxyhexapropylene glycol monoacrylate
I-1: Michler's ketone
I-2: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer D-1: Diamond green (manufactured by Hodogaya Chemical Co., Ltd.)
D-2: Malachite green (Hodogaya Chemical Co., Ltd.)
D-3: leuco crystal violet
The photosensitive resin composition according to the present invention has high sensitivity, excellent tenting properties, plating resistance, and peelability of a cured film, and is extremely useful for the production of printed wiring boards, lead frames or semiconductor packages.
Claims (6)
（ｂ）下記一般式１で示される化合物、下記一般式２で示される化合物、及び下記一般式３で示される化合物を含むエチレン性不飽和付加重合性モノマー；
（一般式１）
式（ａ）
（一般式２）
（一般式３）
（ｃ）２−（ｏ−クロロフェニル）−４、５−ジフェニルイミダゾリル二量体を含む光重合開始剤；及び
（ｄ）下記式４で示される化合物を含む染料、
（式４）
(B) an ethylenically unsaturated addition polymerizable monomer containing a compound represented by the following general formula 1, a compound represented by the following general formula 2, and a compound represented by the following general formula 3;
(General formula 1)
Formula (a)
(General formula 2)
(General formula 3)
(C) a photopolymerization initiator containing 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer; and (d) a dye containing a compound represented by the following formula 4:
(Formula 4)
活性光線を画像状に照射し、露光部を光硬化させ；
未露光部を現像により除去して硬化レジストパターンを形成させ；そして
その後エッチング又はめっきする、
工程を含むプリント配線板の製造方法。Laminating the photosensitive resin laminate according to claim 2 on a circuit forming substrate so that the layer of the photosensitive resin composition is in close contact;
Irradiating actinic rays in the form of an image and photocuring the exposed area;
Unexposed areas are removed by development to form a cured resist pattern; and then etched or plated,
A manufacturing method of a printed wiring board including a process.
活性光線を画像状に照射し、露光部を光硬化させ；
未露光部を現像により除去して硬化レジストパターンを形成させ；そして
その後エッチングする、
工程を含むリードフレームの製造方法。Laminating the photosensitive resin laminate according to claim 2 on a circuit forming substrate so that the layer of the photosensitive resin composition is in close contact;
Irradiating actinic rays in the form of an image and photocuring the exposed area;
Unexposed areas are removed by development to form a cured resist pattern; and then etched.
A manufacturing method of a lead frame including a process.
活性光線を画像状に照射し、露光部を光硬化させ；
未露光部を現像により除去して硬化レジストパターンを形成させ；そして
その後エッチング又はめっきする、
工程を含む半導体パッケージの製造方法。Laminating the photosensitive resin laminate according to claim 2 on a circuit forming substrate so that the layer of the photosensitive resin composition is in close contact;
Irradiating actinic rays in the form of an image and photocuring the exposed area;
Unexposed areas are removed by development to form a cured resist pattern; and then etched or plated,
A method of manufacturing a semiconductor package including a process.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002067116 | 2002-03-12 | ||
| JP2002067116 | 2002-03-12 | ||
| PCT/JP2003/002800 WO2003077035A1 (en) | 2002-03-12 | 2003-03-10 | Photosensitive resin composition and use thereof |
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| Publication Number | Publication Date |
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| JPWO2003077035A1 JPWO2003077035A1 (en) | 2005-07-07 |
| JP3883540B2 true JP3883540B2 (en) | 2007-02-21 |
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| JP2003575188A Expired - Lifetime JP3883540B2 (en) | 2002-03-12 | 2003-03-10 | Photosensitive resin composition and use thereof |
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|---|---|
| JP (1) | JP3883540B2 (en) |
| CN (1) | CN1310088C (en) |
| AU (1) | AU2003213432A1 (en) |
| WO (1) | WO2003077035A1 (en) |
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| CN100434948C (en) * | 2004-11-16 | 2008-11-19 | 奇美实业股份有限公司 | Photosensitive resin composition for colour filter |
| CN101401036B (en) * | 2006-03-14 | 2011-12-07 | 旭化成电子材料株式会社 | Photosensitive-resin layered product |
| JP5376043B2 (en) * | 2010-03-19 | 2013-12-25 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method |
| CN103282829B (en) * | 2010-12-24 | 2016-08-17 | 旭化成株式会社 | Photosensitive polymer combination |
| JP6512532B2 (en) * | 2015-06-05 | 2019-05-15 | 日油株式会社 | Photosensitive resin composition for urethane (meth) acrylate and dry film resist |
| JP6567952B2 (en) * | 2015-10-26 | 2019-08-28 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, and resist pattern forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539286A (en) * | 1983-06-06 | 1985-09-03 | Dynachem Corporation | Flexible, fast processing, photopolymerizable composition |
| JP2548016B2 (en) * | 1986-09-09 | 1996-10-30 | 旭化成工業株式会社 | Photopolymerizable laminate |
| JP3267703B2 (en) * | 1992-11-19 | 2002-03-25 | 旭化成株式会社 | New photopolymerizable resin laminate |
| JP2000214583A (en) * | 1999-01-22 | 2000-08-04 | Hitachi Chem Co Ltd | Photosensitive resin composition, and photosensitive element using same and manufacture of resist pattern and printed circuit board |
| JP3473696B2 (en) * | 1999-03-03 | 2003-12-08 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, and method for producing printed wiring board |
| JP2001142201A (en) * | 1999-11-17 | 2001-05-25 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using same and method for producing color filter |
| JP4475730B2 (en) * | 2000-04-06 | 2010-06-09 | ニチゴー・モートン株式会社 | Photosensitive resin composition and photosensitive film using the same |
| JP4716347B2 (en) * | 2001-04-05 | 2011-07-06 | 旭化成イーマテリアルズ株式会社 | Dry film resist |
-
2003
- 2003-03-10 WO PCT/JP2003/002800 patent/WO2003077035A1/en active Application Filing
- 2003-03-10 JP JP2003575188A patent/JP3883540B2/en not_active Expired - Lifetime
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| JPWO2003077035A1 (en) | 2005-07-07 |
| CN1643451A (en) | 2005-07-20 |
| CN1310088C (en) | 2007-04-11 |
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