CN101303527B - Photocuring resin composition, dry film, curing product and print circuit board - Google Patents
Photocuring resin composition, dry film, curing product and print circuit board Download PDFInfo
- Publication number
- CN101303527B CN101303527B CN2008100818560A CN200810081856A CN101303527B CN 101303527 B CN101303527 B CN 101303527B CN 2008100818560 A CN2008100818560 A CN 2008100818560A CN 200810081856 A CN200810081856 A CN 200810081856A CN 101303527 B CN101303527 B CN 101303527B
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- CN
- China
- Prior art keywords
- carbon number
- alkyl
- resin composition
- photocurable resin
- phenyl
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 238000000016 photochemical curing Methods 0.000 title claims description 15
- 238000001723 curing Methods 0.000 title description 9
- -1 oxime ester Chemical class 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000001060 yellow colorant Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 57
- 229910052799 carbon Inorganic materials 0.000 claims description 56
- 125000000217 alkyl group Chemical group 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- 229910000679 solder Inorganic materials 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 238000013007 heat curing Methods 0.000 claims description 14
- 239000000038 blue colorant Substances 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 238000011161 development Methods 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 10
- 125000001589 carboacyl group Chemical group 0.000 claims description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 9
- 150000004056 anthraquinones Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 claims description 5
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 4
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 4
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 35
- 239000003999 initiator Substances 0.000 abstract 2
- 239000001062 red colorant Substances 0.000 abstract 2
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract 1
- 125000002009 alkene group Chemical group 0.000 abstract 1
- 230000036211 photosensitivity Effects 0.000 abstract 1
- 239000000049 pigment Substances 0.000 description 84
- 229920000647 polyepoxide Polymers 0.000 description 43
- 239000003822 epoxy resin Substances 0.000 description 35
- 239000010408 film Substances 0.000 description 22
- 239000003086 colorant Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 239000004593 Epoxy Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 238000004040 coloring Methods 0.000 description 11
- 229920003319 Araldite® Polymers 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 7
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 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 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000001029 thermal curing Methods 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- TVBNRFCUTVWHQB-UHFFFAOYSA-N 1-anilino-4-(methylamino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC=C1 TVBNRFCUTVWHQB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 206010034960 Photophobia Diseases 0.000 description 4
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 150000004294 cyclic thioethers Chemical class 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- WTIFIAZWCCBCGE-UUOKFMHZSA-N guanosine 2'-monophosphate Chemical compound C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1OP(O)(O)=O WTIFIAZWCCBCGE-UUOKFMHZSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 208000013469 light sensitivity Diseases 0.000 description 4
- 125000003566 oxetanyl group Chemical group 0.000 description 4
- 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 4
- 230000008569 process Effects 0.000 description 4
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- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
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- IBABXJRXGSAJLQ-UHFFFAOYSA-N 1,4-bis(2,6-diethyl-4-methylanilino)anthracene-9,10-dione Chemical compound CCC1=CC(C)=CC(CC)=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=C(CC)C=C(C)C=C1CC IBABXJRXGSAJLQ-UHFFFAOYSA-N 0.000 description 2
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- GBAJQXFGDKEDBM-UHFFFAOYSA-N 1-(methylamino)-4-(3-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC(C)=C1 GBAJQXFGDKEDBM-UHFFFAOYSA-N 0.000 description 2
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- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone powder Natural products C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/08—Epoxidised polymerised polyenes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Abstract
The invention provides a photocurable resin composition, dry film, cured substance and printed circuit board. The invention provides a photocurable resin composition which is fully coloured, has high photosensitivity under the exposure of ultraviolet ray and laser such that it has good curing depth, in the mean time, adjusting absorption in the ultraviolet region by using red or yellow colorant as well as oxime ester initiators. The photocurable resin composition which may develop through alkaline aqueous solution contains (A) carboxylic acid-containing resins, (B) red colorants, (C) oxime ester initiators and (D) compounds having more than two unsaturated alkene groups in the molecules.
Description
Technical field
The present invention relates to can be by the Photocurable resin composition of alkaline aqueous solution development, especially by the solder resist of ultraviolet exposure or laser explosure composition, its dry film, solidfied material and printed circuit board (PCB).
Background technology
Usually, form solder resist in order to protect copper circuit.Its effect also is to can't see the aspects such as the variable color, the defective on the copper circuit, dirt of the heat of copper circuit and variable color that moisture causes, electricity.
By being coated with solder resist at the glass epoxide base material that is formed with copper circuit, exposure forms image, and development, heat curing, thereby forms its film pattern.Owing to being formed with copper circuit on the base material, during therefore to its coating or lamination solder resist, its resist thickness is thick on the base material, thin on copper circuit, and is thinner in the marginal portion of copper circuit.
As a result, the edge part of the circuit of the easy attenuation of copper circuit is in the inadequate situation of colouring power, and there are the following problems: copper discoloration in the thermal history after solder resist forms, in appearance, only thin part variable color and seeing.
To this, in the past, improved colouring power by a large amount of colorants that cooperate in solder resist, thereby eliminated the marginal portion variable color of copper circuit only and the problem that can see.
But, when cooperating colorant in a large number, have the other problem that the following describes during exposure.
That is, common solder resist is painted to green and blueness, uses the phthalocyanine compound (with reference to patent documentation 1) of thermotolerance and chemical proofing excellence in this colorant.But phthalocyanine compound is large in the absorption of ultraviolet range, exists to obtain disadvantageous problem aspect the curing depth.
In addition, there is difference in commercially available ultraviolet exposure apparatus according because lamp causes ultraviolet wavelength to distribute.Therefore there are the following problems: the ultraviolet range (in the phthalocyanine compound that especially Change of absorption of 350nm～400nm) is large, is difficult to develop the solder resist that but has same resolution with different exposure device (lamp).
On the other hand, from the viewpoint of the accurate precision in position, laser scanning exposure is popularized in the exposure of solder resist.This laser explosure also requires to obtain the good Resist profile of high-resolution shape when requiring ISO.In addition, laser explosure is different from the UV-lamp exposure, is the light that utilizes single wavelength, and therefore importantly what degree the light absorption of resist has to its wavelength, decides light sensitivity by the light that makes Photoepolymerizationinitiater initiater effectively absorb employed light source.
Therefore, exist the light absorber as colorant can cause following problem: not only unfavorable to ISOization, also can hinder light and be transmitted to the bottom, cause undercutting.
As above-mentioned explanation, be added on the large phthalocyanine compound of light absorption of ultraviolet range in order to obtain can not obtaining desired curing depth for the sufficient colouring power of variable color of hiding the copper circuit marginal portion, produce undercutting.In order to prevent this phenomenon, reduce the amount of Photoepolymerizationinitiater initiater, can not the exposure of ISO ground.On the other hand, the amount of phthalocyanine compound is adjusted in the situation of the concentration that does not produce undercutting and improve Photoepolymerizationinitiater initiater, although can obtain sufficient photaesthesia luminosity, because colouring power is insufficient, therefore can not hides the variable color of copper circuit marginal portion.
Patent documentation 1: TOHKEMY 2000-7974, claims
Summary of the invention
Invent problem to be solved
Provide a kind of when therefore, the object of the invention is to adjust the absorption of ultraviolet range and have sufficient colouring power, under ultraviolet ray and laser explosure, be ISO and then the good composition of curing depth.
In addition, other purpose of the present invention is to provide a kind of composition, make resist become green, blueness even in above-mentioned composition, add again blue colorant or green colourant, with just having the colouring power that can fully suppress the bad orders such as variable color of copper circuit more in the past than the addition that lacked, for ISO and curing depth good.
For the method for dealing with problems
In order to realize this purpose, the present invention possesses following scheme.
(1) can be by the Photocurable resin composition of alkaline aqueous solution development, it is characterized in that, it contains (A), and to contain carboxylic acid resin, (B1) red stain, (C) oxime ester be the compound that has 2 above ethylenically unsaturated groups in Photoepolymerizationinitiater initiater, (D) molecule.
(2) can be by the Photocurable resin composition of alkaline aqueous solution development, it is characterized in that, it contains (A), and to contain carboxylic acid resin, (B2) yellow colorants, (C) oxime ester be the compound that has 2 above ethylenically unsaturated groups in Photoepolymerizationinitiater initiater, (D) molecule.
(3) can it is characterized in that by the Photocurable resin composition of alkaline aqueous solution development according to (1) is described, it also contains a kind or 2 kinds that is selected from yellow colorants (B2) and the blue colorant (B3).
(4) according to each described Photocurable resin composition of (1)～(3); it is characterized in that; aforementioned oxime ester is that Photoepolymerizationinitiater initiater (C) is Photoepolymerizationinitiater initiater for the oxime ester shown in the following general formula (I), and also containing the alpha-aminoacetophenone shown in the following general formula (II) is that the acylphosphine oxide shown in Photoepolymerizationinitiater initiater and the following general formula (III) is a kind or 2 kinds of Photoepolymerizationinitiater initiater.
(in the formula; R1 represents that the alkyl of hydrogen atom, phenyl (can be replaced by the alkyl of carbon number 1～6, phenyl or halogen atom), carbon number 1～20 (can be replaced by 1 above hydroxyl; can have 1 above oxygen atom in the middle of the alkyl chain), the naphthenic base of carbon number 5～8, alkanoyl or the benzoyl (can be replaced by the alkyl or phenyl of carbon number 1～6) of carbon number 2～20
R2 represents the alkyl (can be had 1 above oxygen atom in the middle of 1 above hydroxyl replacement, the alkyl chain) of phenyl (can be replaced by the alkyl of carbon number 1～6, phenyl or halogen atom), carbon number 1～20, the naphthenic base of carbon number 5～8, alkanoyl or the benzoyl (can be replaced by the alkyl or phenyl of carbon number 1～6) of carbon number 2～20.)
(in the formula, R3 and R4 represent alkyl or the aralkyl of carbon number 1～12 independently of one another,
R5 and R6 represent the alkyl of hydrogen atom, carbon number 1～6 or the ring-type alkane ether of R5 and two combinations of R6 independently of one another.)
(in the formula, R7 and R8 represent straight chain shape or alkyl, cyclohexyl, cyclopentyl, aryl, the alkoxy of a chain or the aryl that is replaced by halogen atom, alkyl or alkoxy of carbon number 1～10 independently of one another, wherein, among R7 and the R8 one can represent R-C (=O)-Ji (at this, R is the alkyl of carbon number 1～20).))
(5) according to (4) described Photocurable resin composition, it is characterized in that, the oxime ester shown in the aforementioned formula (I) is that Photoepolymerizationinitiater initiater (C) is Photoepolymerizationinitiater initiater for the oxime ester shown in the following formula (IV).
(6) according to (4) described Photocurable resin composition, it is characterized in that, the oxime ester shown in the aforementioned formula (I) is that Photoepolymerizationinitiater initiater (C) is Photoepolymerizationinitiater initiater for the oxime ester shown in the following general formula (V).
(in the formula; R9 represents that (carbon number that consists of the alkyl of alkoxy is 2 when above for the alkanoyl of alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, the carbon number 2～12 of hydrogen atom, halogen atom, carbon number 1～12, the alkoxy carbonyl group of carbon number 2～12; alkyl can be replaced by 1 above hydroxyl; can have 1 above oxygen atom in the middle of the alkyl chain) or carbobenzoxy
R10, R12 represent the alkyl (can be had 1 above oxygen atom in the middle of 1 above hydroxyl replacement, the alkyl chain) of phenyl (can be replaced by the alkyl of carbon number 1～6, phenyl or halogen atom), carbon number 1～20, the naphthenic base of carbon number 5～8, alkanoyl or the benzoyl (can be replaced by the alkyl or phenyl of carbon number 1～6) of carbon number 2～20 independently of one another
R11 represents the alkyl (can be had 1 above oxygen atom in the middle of 1 above hydroxyl replacement, the alkyl chain) of hydrogen atom, phenyl (can be replaced by the alkyl of carbon number 1～6, phenyl or halogen atom), carbon number 1～20, the naphthenic base of carbon number 5～8, alkanoyl or the benzoyl (can be replaced by the alkyl or phenyl of carbon number 1～6) of carbon number 2～20.)
(7) according to each described Photocurable resin composition of (1)～(6), it is characterized in that, also contain (E) heat curing composition.
(8) according to (1)～(7) described Photocurable resin compositions, it is characterized in that, composition is the solder resist that is selected from the tone in blueness, green, the orange and purple.
(9) a kind of dry film of photo-curable, it is by being applied to each described Photocurable resin composition of (1)～(3) on the carrier thin film and dry obtaining.
(10) a kind of solidfied material, it is by obtaining each described Photocurable resin composition of (1)～(8) or (9) described dry film photocuring.
(11) a kind of solidfied material, it is by obtaining each described Photocurable resin composition of (1)～(8) or (9) described dry film photocuring.
(12) a kind of printed circuit board (PCB), it is by with after each described Photocurable resin composition of (1)～(8) or (9) described dry film photocuring, heat curing and obtaining.
(13) a kind of printed circuit board (PCB), it has insulation course, and this insulation course contains red stain (B1).
The definition of the color of composition and solder resist
The color of composition and solder resist can be used based on the hue circle of JISZ8721 and the represented mark of Meng Saier hue circle (juridical person Japan color study is edited new Essential colour watch series 2 Meng Saier system day true qualities and ground the distribution of cause Co., Ltd.) and distinguish (the Meng Saier hue circle is with reference to Fig. 1).
Red 7RP is to the scope of not enough 9R
Orange 9R is to the scope of not enough 7YR
Yellow 7YR is to the scope of not enough 9Y
Green 9Y is to the scope of not enough 5BG
Blue 5BG is to the scope of not enough 3P
Purple 3P is to the scope of not enough 7RP
In addition, lightness, chroma are respectively according to substrate (glass epoxide base material or copper circuit and surface-treated copper circuit) and different, preferred chroma is that 1 above less than 16, lightness are 1 above less than 9, and further preferred chroma is that 2 above less thaies 15, lightness are 2 above less thaies 9 (lightness, chroma are based on JISZ8102 JISZ8721).
Further suitable condition determination is preferably on the copper circuit of thick 20～30 μ m of solder resist.
In addition, in the present invention, printed circuit board (PCB) refers to use the printing technologies such as silk screen print method, photoetching process to form the substrate of conductive pattern on the surface of electrical insulating property substrate, is divided into rigid circuit board and flexible electric circuit board.
The invention effect
In the present invention, be Photoepolymerizationinitiater initiater by using redness or yellow colorant and oxime ester, provide when adjusting the absorption of ultraviolet range have fully painted, be ISO and the good composition of curing depth in ultraviolet ray and laser explosure.In addition, also can provide a kind of ISO and curing depth good composition, even if it adds blue colorant or green colourant and makes resist become green, blueness in these compositions, use more in the past than the addition that lacked just to have the colouring power that can fully suppress the bad orders such as variable color of copper circuit.
Description of drawings
Fig. 1 is the key diagram of expression Meng Saier hue circle.
Fig. 2 is the schematic diagram by the cross sectional shape of the resulting resin combination of exposure imaging, and A～E represents the shape of different separately evaluations.
Symbol description
The design load of 1a live width
Resin combination behind the 1b exposure imaging
The 1c substrate
Embodiment
Below, each constituent of Photocurable resin composition of the present invention is elaborated.
(A) contain the carboxylic acid resin
As Photocurable resin composition of the present invention contained contain carboxylic acid resin (A), can use the resin compound known commonly used that contains carboxylic acid in the molecule.And then from photo-curable and anti-development aspect, what more preferably have ethylenical unsaturated double bonds in the molecule contains carboxylic acid photoresist (A ').
Particularly, can list the following resin of enumerating.
Can list:
(1) by containing the carboxyl acid copolymer resin with unsaturated carboxylic acids such as (methyl) acrylic acid with more than a kind except what the compound with unsaturated double-bond it carried out that copolymerization obtains;
(2) the unsaturated carboxylic acids such as (methyl) acrylic acid and more than a kind on the multipolymer of the compound with unsaturated double-bond it, by (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters etc. has the addition ethylenically unsaturated groups such as the compound, (methyl) acryloyl chloride of epoxy radicals and unsaturated double-bond as side chain, thus obtain contain the carboxylic acid photoresist;
(3) make (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters etc. have the compound of epoxy radicals and unsaturated double-bond with except the compound copolymerization with unsaturated double-bond it, make the unsaturated carboxylic acids reactions such as this multipolymer and (methyl) acrylic acid, the secondary hydroxyl that generates reacts with multi-anhydride and the photosensitive carboxyl acid copolymer resin that contains that obtains;
(4) make maleic anhydride etc. have the acid anhydrides of unsaturated double-bond with except the compound copolymerization with unsaturated double-bond it, the compound that makes this multipolymer and (methyl) acrylic acid 2-hydroxyl ethyl ester etc. have hydroxyl and unsaturated double-bond react and obtain contain the carboxylic acid photoresist;
(5) make the reaction of multi-group epoxy compound and unsaturated monocarboxylic, the hydroxyl that generates and saturated or unsaturated multi-anhydride react and obtain contain the carboxylic acid photoresist;
(6) make the reaction of the hydroxyl polymer-containing such as polyvinyl alcohol derivative and saturated or unsaturated multi-anhydride, the compound that has epoxy radicals and unsaturated double-bond in the carboxylic acid that then makes generation and a part reacts and the hydroxyl that obtains and the photoresist of carboxylic acid;
(7) make the compound reaction of the reactive group beyond the alcoholic extract hydroxyl group that has at least 1 alcoholic extract hydroxyl group and 1 and epoxy reaction in multi-group epoxy compound, unsaturated monocarboxylic, a part, this reaction product and saturated or unsaturated multi-anhydride are reacted and obtain contain the carboxylic acid photoresist;
(8) make the reaction of the polyfunctional group oxetane compound that has at least 2 oxetanes rings in a part and unsaturated monocarboxylic, what make that primary hydroxyl and saturated or unsaturated multi-anhydride in the modification oxetane resin of gained react gained contains the carboxylic acid photoresist; And
(9) make the reaction of polyfunctional epoxy resin and unsaturated monocarboxylic, then make the reaction of itself and multi-anhydride and obtain contain the carboxylic acid photoresist again with molecule in have that thereby the compound reaction of 1 oxirane ring and 1 above ethylenically unsaturated group obtains contain carboxylic acid photoresist etc., but not limited by these.
As preferred in these illustrations, be the carboxylic acid resin that contains of above-mentioned (2), (5), (7), from photo-curable, cured coating film characteristic aspect, especially preferably above-mentioned (9) contains the carboxylic acid photoresist.
In addition, in this manual, (methyl) acrylate is the term of general designation acrylate, methacrylate and their potpourri, similarly expresses too for other.
Above-mentioned contains carboxylic acid resin (A) owing to having a plurality of free carboxyls on the side chain of trunk polymer, therefore can utilize alkaline aqueous solution to develop.
In addition, the above-mentioned carboxylic acid resin's of containing (A) acid number is the scope of 40～200mgKOH/g, more preferably the scope of 45～120mgKOH/g.The words that contain carboxylic acid resin's the not enough 40mgKOH/g of acid number, alkali develops and becomes difficulty, on the other hand, surpass 200mgKOH/g, can excessively the expose dissolving of section of developer solution, so line becomes meticulous, according to circumstances, exposure section and unexposed are dissolved by the developing as broad as longly and peel off, normal corrosion-resisting pattern describe difficult, therefore not preferred.
In addition, the above-mentioned weight-average molecular weight that contains carboxylic acid resin (A) is according to resin matrix and different, preferably be generally 2000～150000, further be 5000～100000 scope contain carboxylic acid resin (A).Weight-average molecular weight less than 2000, tack-free poor performance, the moisture-proof of filming after the exposure is bad and produce film when developing and reduce, and resolution is very bad.On the other hand, weight-average molecular weight surpasses 150000, the non-constant of development, poor storage stability.
The use level that contains carboxylic acid resin (A) like this is 20～60 quality % in whole compositions, be preferably 30～50 quality %.When lacking than above-mentioned scope, coating strength reduces, therefore not preferred.On the other hand, therefore the reductions such as when manying than above-mentioned scope, viscosity uprises, coating are not preferred.
(B) colorant
Colorant can use known material commonly used, can be in pigment, dyestuff, the pigment any one.Particularly, can use following material.
(B1) red stain
As red stain, monoazo system, bisdiazo system, azo lake system, benzimidazolone Xi, perylene system, diketopyrrolo-pyrrole system, condensation azo system, anthraquinone system, quinacridone etc. are arranged, specifically can enumerate following colorant.
(monoazo system)
Paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269
(bisdiazo system)
Pigment red 37,38,41
(monoazo color lake)
Pigment red 4 8:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68
(benzimidazolone)
Paratonere 171, paratonere 175, paratonere 176, paratonere 185, paratonere 208
The (perylene)
Solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, pigment red179, paratonere 190, paratonere 194, paratonere 224
(diketopyrrolo-pyrrole system)
Paratonere 254, paratonere 255, paratonere 264, paratonere 270, paratonere 272
(condensation azo)
Paratonere 220, paratonere 144, paratonere 166, pigment red 21 4, paratonere 220, paratonere 221, paratonere 242
(anthraquinone system)
Paratonere 168, paratonere 177, pigment red 21 6, solvent red 149, solvent red 150, solvent red 52, solvent red 207
(quinacridone)
Pigment red 122, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209
In these red stains, especially absorb red stain little and that Change of absorption 350～400nm is little in the ultraviolet range suitable.In addition, from the environmental pollution aspect, colorant and non-halogen compounds beyond the preferred azo based compound.
As suitable red stain, can list paratonere 177, paratonere 264 etc.
Consider coloring and UVA amount, it is 0.01～5.0 mass parts that the use level of red stain contains carboxylic acid resin (A) with respect to 100 mass parts, is preferably 0.05～3.0 mass parts.
(B2) yellow colorants
As yellow colorants monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc. are arranged, specifically can list following colorant.
(anthraquinone system)
Solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202
(isoindolinone system)
Pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment yellow 185
(condensation azo system)
Pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment Yellow 12 8, pigment yellow 155, pigment yellow 166, pigment yellow 180
(benzimidazolone)
Pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment yellow 17 5, pigment yellow 181
(monoazo)
Pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183
(bisdiazo)
Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198
In these yellow colorants, special its is that the absorption yellow colorants little and that Change of absorption 350～400nm is little of ultraviolet range is suitable.In addition, from the environmental pollution aspect, colorant and non-halogen compounds beyond the preferred azo based compound.
As suitable yellow colorants, can list solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202, pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment yellow 185, pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment yellow 17 5, pigment yellow 181 etc.
Consider coloring and UVA amount, it is 0.01～5 mass parts that the use level of yellow colorants contains carboxylic acid resin (A) with respect to 100 mass parts, be preferably 0.05～3 mass parts.
(B3) blue colorant
For the tone that makes composition is green, blueness or orange, cooperation blue colorant.
The blue colorant that cooperates has phthalocyanine system, anthraquinone system, and pigment system can list the compound that is classified into pigment (Pigment), specifically with following chromaticity index (C.I.; The distribution of The Society of Dyers and Colourists society) material of sequence number.
Pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 16, pigment blue 60
As dyestuff system, can use solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc.Except above-mentioned, also can use metal to replace or without the phthalocyanine compound that replaces.
In these blue colorant, especially the absorption of ultraviolet range blue colorant little and that Change of absorption 350～400nm is little is suitable.
As suitable blue colorant, can list pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 16, pigment blue 60, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc.
Consider coloring and UVA amount, it is 0.01～5 mass parts that the use level of blue colorant contains the carboxylic acid resin with respect to 100 mass parts, be preferably 0.05～3 mass parts.
Be green or blue in order to make form and aspect, consider coloring and UVA amount, the use level that is coupled to the blue colorant in red stain, the yellow colorants contains carboxylic acid resin (A) with respect to 100 mass parts, and the total amount of colorant is 0.5～5 mass parts, be preferably 0.5～4 mass parts.
(colorant of other tone)
The present invention for the tone that makes composition for green, blue or orange, in the scope that does not hinder purpose of the present invention, can add the colorant of the tones such as green beyond above-mentioned, purple, orange, dark brown, black.
As green colourant, phthalocyanine system, anthraquinone system are arranged, can use particularly that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.Except above-mentioned, also can use metal to replace or without the phthalocyanine compound that replaces.
Other colorant as beyond the green can list pigment violet 19,23,29,32,36,38,42, solvent violet 13,36, C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. pigment brown 23, C.I. pigment brown 25; C.I. pigment black 1, C.I. pigment black 7 etc.
(C) the oxime ester is Photoepolymerizationinitiater initiater
In the present invention, can use arbitrarily that the oxime ester is Photoepolymerizationinitiater initiater, the oxime ester that especially preferably has the group shown in the above-mentioned general formula (I) is Photoepolymerizationinitiater initiater.In addition, preferably use that to be selected from the alpha-aminoacetophenone with the group shown in the above-mentioned general formula (II) be that Photoepolymerizationinitiater initiater and the acylphosphine oxide with the group shown in the above-mentioned general formula (III) are the Photoepolymerizationinitiater initiater more than a kind in the Photoepolymerizationinitiater initiater.The Photoepolymerizationinitiater initiater that has the group shown in general formula (II) or the general formula (III) by use for long wavelength's light source, has the effect that enlarges photosensitive region.
Be Photoepolymerizationinitiater initiater as the oxime ester with the group shown in the above-mentioned general formula (I), more preferably (acetoxyl group iminomethyl) thioxanthene-9-one of the 2-shown in the above-mentioned formula (IV) and compound with the group shown in the above-mentioned general formula (V).As commercially available product, can list CGI-325, IRGACURE OXE01 that Ciba Specialty Chemicals company produces, IRGACURE OXE02 etc.These oxime esters are that Photoepolymerizationinitiater initiater can use more than 2 kinds alone or in combination.
Be Photoepolymerizationinitiater initiater as the alpha-aminoacetophenone with the group shown in the aforementioned formula (II), can list 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino acetophenone etc.As commercially available product, can list IRGACURE907, IRGACURE369 that Ciba SpecialtyChemicals company produces, IRGACURE379 etc.
Be Photoepolymerizationinitiater initiater as the acylphosphine oxide with the group shown in the aforementioned formula (III); can list 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2; 4,4-trimethyl-amyl group phosphine oxide etc.As commercially available product, can list Lucirin TPO, the IRGACURE819 that Ciba SpecialtyChemicals company produces etc. that BASF AG produces.
The use level of such Photoepolymerizationinitiater initiater (C) is with respect to the aforementioned carboxylic acid resin A that contains of 100 mass parts) can be from 0.01～30 mass parts, preferably select from the scope of 0.5～15 mass parts.Less than 0.01 mass parts, photo-curable on the copper is not enough, films to peel off or the coating characteristic such as chemical proofing reduces, therefore not preferred.On the other hand, surpass 30 mass parts, Photoepolymerizationinitiater initiater (C) is arranged in the light absorption fierceness of solder resist film coated surface, the tendency that the property reduction is solidified in the deep, therefore not preferred.
In addition, when the oxime ester that use has a group shown in the aforementioned formula (I) is Photoepolymerizationinitiater initiater, its use level with respect to the aforementioned carboxylic acid resin of containing of 100 mass parts (A) preferably from 0.01～20 mass parts, more preferably to select from the scope of 0.01～5 mass parts be desirable.
(D) has the compound of 2 above ethylenically unsaturated groups in the molecule
Have the compound (D) of 2 above ethylenically unsaturated groups in the employed molecule of Photocurable resin composition of the present invention by active energy beam irradiation photocuring, make the aforementioned carboxylic acid resin of containing (A) in alkaline aqueous solution, not dissolve or help and do not dissolve.As such compound, can list the diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; Polyvalent alcohol or the multicomponent methacrylate classes such as these ethylene oxide adduct or propylene oxide adduct such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethyl isocyanuric acid ester; The multicomponent methacrylate classes such as the ethylene oxide adduct of acrylic acid benzene oxygen ester, bisphenol a diacrylate and these phenols or propylene oxide adduct; The multicomponent methacrylate class of the glycidol ethers such as glycerine diglycidyl ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; And melamine acrylate and/or each methyl acrylic ester corresponding with the aforesaid propylene acid esters etc.
The epoxy urethane acrylate compound that half urethane ester compounds of the diisocyanate such as the hydroxy acrylate such as the hydroxyl that in addition, can enumerate the Epocryl of the polyfunctional epoxy resin such as the cresols phenolic resin varnish type epoxy resin of sening as an envoy to and acrylic acid reaction and make this Epocryl and pentaerythritol triacrylate and isophorone diisocyanate reacts etc.Such epoxy acrylate is that resin does not make the dry to touch reduction, can improve photo-curable.
The use level that has the compound (D) of 2 above ethylenically unsaturated groups in such molecule is 5～100 mass parts, the ratio of 1～70 mass parts more preferably with respect to the aforementioned carboxylic acid resin of containing of 100 mass parts (A).In the situation of aforementioned use level less than 5 mass parts, photo-curable reduces, and is difficult to after the active energy beam irradiation form pattern by the alkali development, therefore not preferred.On the other hand, when surpassing 100 mass parts, to the dissolubility reduction of alkaline aqueous solution, filming becomes fragile, therefore not preferred.
When using aforementioned potpourri; contain carboxylic acid resin (A) with respect to 100 mass parts, the oxime ester that is selected from the group shown in (I) that has general formula is that Photoepolymerizationinitiater initiater and the alpha-aminoacetophenone with the group shown in the general formula (II) are that Photoepolymerizationinitiater initiater and the acylphosphine oxide with the group shown in the general formula (III) are that Photoepolymerizationinitiater initiater more than a kind in the Photoepolymerizationinitiater initiater is 1～15 mass parts, is preferably 3～10 mass parts.
(E) heat curing composition
In order to give thermotolerance, photosensitive composite of the present invention can add the heat curing composition.Particularly preferably be and have 2 above ring-type ethers and/or cyclic thioether base in the molecule Thermocurable composition (E) of (following, referred to as ring-type (sulphur) ether).
The Thermocurable composition (E) that has 2 above ring-types (sulphur) ether in such molecule is to have 2 above ternarys in the molecule, quaternary or pentacyclic ring-type ether, or any one or the compound of 2 kinds of groups in the cyclic thioether base, for example can list, have the compound of at least 2 above epoxy radicals in the molecule, be multi-group epoxy compound (E1), the compound that has at least 2 above oxetanyls in the molecule, be polyfunctional group oxetane compound (E2), the compound that has 2 above thioether groups in the molecule, it is episulfide resin resin (E3) etc.
As aforementioned multi-group epoxy compound (E1), for example can list, bisphenol A type epoxy resin, such as Japan Epoxy Resins Co., Ltd. the Epikote 828 that makes, Epikote 834, Epikote 1001, Epikote 1004, the Epiclon 840 that large Japanese ink chemical industrial company makes, Epiclon 850, Epiclon 1050, Epiclon 2055, Dongdu changes into the Epotote YD-011 that company makes, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical company makes, D.E.R.331, D.E.R.661, D.E.R.664, the Araldite 6071 of Ciba Specialty Chemicals company, Araldite 6084, AralditeGY250, AralditeGY260, the Sumiepoxy ESA-011 that Sumitomo Chemical Co. Ltd. makes, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name); Brominated epoxy resin, such as Japan Epoxy Resins Co., Ltd. the EpikoteYL903 that makes, the Epiclon152 that large Japanese ink chemical industrial company makes, Epiclon 165, Dongdu changes into the Epotote YDB-400 that company makes, YDB-500, the D.E.R.542 that Dow Chemical company makes, the Araldite 8011 that Ciba SpecialtyChemicals company makes, the Sumiepoxy ESB-400 that Sumitomo Chemical Co. Ltd. makes, ESB-700, the A.E.R.711 that industrial group of Asahi Chemical Industry makes, A.E.R.714 etc. (being trade name); Phenolic resin varnish type epoxy resin, such as Japan Epoxy Resins Co., Ltd. the Epikote 152 that makes, Epikote 154, the D.E.N.431 that Dow Chemical company makes, D.E.N.438, the Epiclon N-730 that large Japanese ink chemical industrial company makes, Epiclon N-770, EpiclonN-865, Dongdu changes into the Epotote YDCN-701 that company makes, YDCN-704, the Araldite ECN1235 that Ciba Specialty Chemicals company makes, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, the EPPN-201 that Japan chemical drug company makes, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the SumiepoxyESCN-195X that Sumitomo Chemical Co. Ltd. makes, ESCN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299 etc. (being trade name); Bisphenol f type epoxy resin, the Epiclon830 that makes such as large Japanese ink chemical industrial company, Japan Epoxy ResinsCo., Ltd. the Epikote807 that makes, Dongdu changes into Epotote YDF-170, YDF-175, the YDF-2004 that company makes, (being trade name) such as Araldite XPY306 that Ciba Specialty Chemicals company makes; Bisphenol-A epoxy resin changes into Epotote ST-2004, ST-2007 that company makes, ST-3000 (trade name) etc. such as Dongdu; Glycidyl amine type epoxy resin, such as Japan EpoxyResins Co., Ltd. the Epikote604 that makes, Dongdu changes into the EpototeYH-434 that company makes, the Araldite MY720 that Ciba Specialty Chemicals company makes, (being trade name) such as Sumiepoxy ELM-120 that Sumitomo Chemical Co. Ltd. makes; The hydantoins type epoxy resin such as Araldite CY-350 (trade name) that Ciba Specialty Chemicals company makes; DAICEL CHEMICALINDUSTRIES, the Celoxide2021 that LTD. makes, (being trade name) alicyclic epoxy resins such as Araldite CY175, CY179 that Ciba SpecialtyChemicals company makes; Japan Epoxy Resins Co., the YL-933 that Ltd. makes, (being trade name) trihydroxy benzene methylmethane type epoxy resin such as T.E.N., the EPPN-501 that Dow Chemical company makes, EPPN-502; Japan Epoxy ResinsCo., di-cresols type or united phenol-type epoxy resin or their potpourris such as YL-6056, the YX-4000 that Ltd. makes, YL-6121 (being trade name); The EBPS-200 that Japan chemical drug company makes, the bisphenol-s epoxy resins such as EXA-1514 (trade name) that the EPX-30 that Asahi Electro-Chemical Co. Ltd makes, large Japanese ink chemical industrial company make; Japan Epoxy Resins Co., the bisphenol-A phenolic varnish type epoxy resin such as Epikote 157S (trade name) that Ltd. makes; Japan Epoxy ResinsCo., (being trade name) four hydroxyphenyl ethane type epoxy resin such as Araldite 163 that the Epikote YL-931 that Ltd. makes, Ciba Specialty Chemicals company make; (being trade name) hetero ring type epoxy resin such as TEPIC that the Araldite PT810 that Ciba Specialty Chemicals company makes, daily output chemical industrial company make; The o-phthalic acid diglycidyl ester resins such as Blemmer DGT that Nof Corp. makes; Dongdu changes into four glycidyl group dimethylbenzene acyl group ethane (the tetraglycidyl xylenoyl ethane) resins such as ZX-1063 that company makes; ESN-190, ESN-360 that chemical company of Nippon Steel makes, HP-4032, the EXA-4750 that large Japanese ink chemical industrial company makes, EXA-4700 etc. contain the epoxy resin of naphthyl; HP-7200, the HP-7200H etc. that large Japanese ink chemical industrial company makes have the epoxy resin of bicyclopentadiene skeleton; The glycidyl methacrylate copolymerization such as CP-50S, CP-50M that Nof Corp. makes are epoxy resin; Further can enumerate the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate; Epoxide modified polybutadiene rubber derivant (DAICEL CHEMICALINDUSTRIES for example, LTD. the PB-3600 that makes etc.), CTBN modified epoxy (changing into YR-102, the YR-450 etc. that company makes such as Dongdu) etc., but be not limited to these materials.These epoxy resin can be used alone or in combination of two or more kinds.Particularly preferably phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri in the middle of these.
As aforementioned multifunctional oxetane compound (E2), can list two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, Isosorbide-5-Nitrae-two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, the polyfunctional group oxetanes classes such as their oligomer or multipolymer, and oxetanes alcohol and novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calixresorcinarene) class or silsesquioxane (silsesquioxane) etc. have the etherate etc. of the resin of hydroxyl.In addition, can also enumerate the multipolymer etc. of unsaturated monomer with oxetanes ring and (methyl) alkyl acrylate.
Compound (E3) as having 2 above cyclic thioether bases in the aforementioned molecule for example can list, Japan Epoxy Resins Co., the bisphenol A-type episulfide resin resin YL7000 that Ltd. produces etc.In addition, also can use same synthetic method, the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced to episulfide resin resin of sulphur atom etc.
The use level that has the Thermocurable composition (E) of 2 above ring-types (sulphur) ether in the aforementioned molecule is preferably 0.6～2.5 equivalent, the scope of 0.8～2.0 equivalent more preferably with respect to the aforementioned carboxylic acid resin's of containing 1 equivalent carboxyl.When having the use level less than 0.6 of Thermocurable composition (E) of 2 above ring-types (sulphur) ether in the molecule, residual in the soldering-resistance layer have carboxyl, and the reduction such as thermotolerance, alkali resistance, electrical insulating property, therefore not preferred.On the other hand, when surpassing 2.5 equivalent, low-molecular-weight ring-type (sulphur) ether remains in the dry coating, causes the reductions such as intensity of filming, therefore not preferred.
When using the heat curing composition (E) that has 2 above ring-types (sulphur) ether in the above-mentioned molecule, preferably contain thermal curing catalyst.As such thermal curing catalyst, for example can list imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-the cyanoethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, the amines such as N-dimethyl benzyl amine; The hydrazide compound such as adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds such as triphenylphosphine etc., and can list four countries for example as commercially available product and change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 2P4MHZ (all being the trade name of imidazole compound) that industrial group makes, U-CAT3503N, U-CAT3502T (all being the trade name of the block isocyanate compound of dimethyl amine) that SAN-APRO company makes, DBU, DBN, U-CATSA102, U-CAT5002 (all being two ring type amidine compound and salt thereof) etc.Be not particularly limited in these compounds, so long as the thermal curing catalyst of epoxy resin or oxetane compound or promote epoxy radicals and/or the material of the reaction of oxetanyl and carboxyl just can, can use separately or mix use more than 2 kinds.In addition, also can use guanamine, methyl guanamines, benzoguanamine, melamine, 2,4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-4,6-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2,4-diamido-6-methacryloxyethyl-the Striazine derivatives such as s-triazine isocyanuric acid addition product preferably also is used in combination these as compound and the aforementioned hot curing catalysts that tackifiers works.
The use level of these thermal curing catalysts is just enough with the ratio of common amount, for example, contain the Thermocurable composition (E) that has 2 above ring-types (sulphur) ether in carboxylic acid resin (A) or the molecule with respect to 100 mass parts, be preferably 0.1～20 mass parts, 0.5～15.0 mass parts more preferably.
Filler
In order to improve this physical strength of filming etc., Photocurable composition of the present invention can cooperate filler as required.As such filler, can use known inorganic or organic filler commonly used, particularly preferably use barium sulphate, spherical silicon dioxide and talcum.NANOPOX (trade name) XP 0516, XP 0525, XP0314 (being the product line name) that NANOCRYL (trade name) XP 0396, XP0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (being the product line name), the Hanse-Chemie company that in addition, also can use the Hanse-Chemie company of dispersing nanometer silicon dioxide in the compound that has 2 above ethylenically unsaturated groups in molecule or the aforementioned polyfunctional epoxy resin (E1) to produce produces.These can separately or cooperate use more than 2 kinds.
The use level of these fillers with respect to the above-mentioned carboxylic acid resin of containing of 100 mass parts (A) be preferably 300 mass parts following, more preferably 0.1～300 mass parts, be particularly preferably 0.1～150 mass parts.When the use level of filler surpassed 300 mass parts, the viscosity of Photocurable composition uprised and printing reduces, and solidfied material becomes fragile, therefore not preferred.
Organic solvent
In addition, for the adjustment of the above-mentioned carboxylic acid resin's of containing (A) synthetic and composition or in order to adjust viscosity in order to be applied on substrate or the carrier thin film, Photocurable resin composition of the present invention can be with an organic solvent.
As such organic solvent, can list ketone, aromatic hydrocarbons, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc.In particular, be the ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; The glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; The ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents such as sherwood oil, naphtha, hydrotreated naphtha, solvent naphtha etc.Such organic solvent can use separately or with the form of potpourri more than 2 kinds.
Other gradation composition
Photocurable resin composition of the present invention can also cooperate the known hot polymerization inhibitors commonly used such as quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine as required, the known thickening agents commonly used such as fine particle silica, organobentonite, polynite, defoamer and/or the levelling agents such as silicone-based, fluorine system, macromolecular, the known additive kinds commonly used such as silane coupling agent, antioxidant, rust preventive such as imidazoles system, thiazole system, triazole system.
In addition, in the scope that does not hinder purpose of the present invention, the present invention can cooperate take benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthones compound, ketal compound, benzophenone cpd, xanthone compound and tertiary amine compound etc. as other Photoepolymerizationinitiater initiater of representative, light-initiated auxiliary agent and sensitizer.
This Photocurable resin composition among the present invention, its tone is preferably green or blueness.By cooperating single colorant or the potpourri of a plurality of colorants, can suitably obtain such tone.
Dry film, solidfied material, printed circuit board (PCB)
This Photocurable resin composition among the present invention who obtains like this in carrier thin film coating, drying, can obtain the dry film of photo-curable by conventional process thus.
This Photocurable resin composition or this dry film among the present invention become solidfied material by photocuring to copper.Photocuring can utilize ultraviolet exposure apparatus according to carry out, and utilizes lasing fluorescence light source, the especially laser of wavelength 350～410nm to make its curing.Printed circuit board (PCB) of the present invention can obtain by heat curing behind this photocuring.
Particularly as following, form dry film, solidfied material, printed circuit board (PCB).Namely, Photocurable resin composition of the present invention, for example be adjusted into the viscosity that is suitable for coating process with aforementioned organic solvent, the methods such as method, silk screen print method, curtain-type rubbing method that are coated with by dip coating, flow coat method, rolling method, rod are applied on the base material, make organic solvent volatile dry contained in the composition (temporary transient dry) in about 60～100 ℃ temperature, can form tack-free filming.In addition, be applied to above-mentioned composition on the carrier thin film and make its drying, as winding film, it is attached on the base material, can form resin insulating barrier thus.Then, by contact (or cordless), by forming figuratum photomask, utilize active energy beam optionally to expose or utilize the direct pattern exposure of the direct exposure machine of laser, unexposed is developed with alkaline aqueous solution (for example 0.3～3% aqueous sodium carbonate), form corrosion-resisting pattern.In addition, in the situation for the composition that contains heat curing composition (E), for example be heated to approximately 140～180 ℃ temperature and heat curing, the Thermocurable composition (E) that has 2 above ring-type ethers and/or cyclic thioether base in the aforementioned carboxylic acid resin's of containing (A) carboxyl and the molecule reacts, and can form the cured coating film of the various characteristics excellences such as thermotolerance, chemical proofing, anti-hydroscopicity, adaptation, electrical characteristics.
In addition, even if when not containing Thermocurable composition (E), by thermal treatment, carry out the hot radical polymerization with the residual ethylenic unsaturated bond of unreacted state when making exposure, coating characteristic improves, and therefore according to the purpose purposes, also can heat-treat (heat curing).
As above-mentioned base material, can enumerate the high-frequency circuit that makes paper using phenolics, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/nonwoven fabrics epoxy resin, glass cloth/paper epoxy resin, synthon epoxy resin, fluorine tygon polyphenylene oxide (PPO) cyanate etc. with the copper clad laminate of all series (FR-4 etc.) of the materials such as copper clad laminate, and Kapton, pet film (PET film), glass substrate, ceramic substrate, wafer board etc.
Be coated with the volatile dry that carries out after the Photocurable resin composition of the present invention, can use heated air circulation type drying oven, IR stove, electric hot plate, convection oven etc. (use possess utilize steam carry out air heat mode thermal source device and make hot blast in the dryer carry out the method for convection current contact and blow to mode on the supporter by nozzle) and carry out.
As following, be coated with after Photocurable resin composition of the present invention and the volatile dry, to filming of gained expose (irradiation of active energy beam).The exposure section of filming (part of being shone by active energy beam) solidifies.
Shine employed exposure machine as above-mentioned active energy beam, can use the exposure machine, the exposure machine that has carried (surpassing) high-pressure sodium lamp that have carried the direct drawing apparatus of laser (laser direct imaging system), carried metal halide lamp, carried the exposure machine of mercury short arc lamp or use the direct drawing apparatus of the UV-lamp such as (surpassing) high-pressure sodium lamp.As active energy beam, be the laser of the scope of 350～410nm as long as use maximum wavelength, so gas laser, Solid State Laser can.In addition, its exposure can be 5～200mJ/cm usually according to thickness etc. and different
2, be preferably 5～100mJ/cm
2, 5～50mJ/cm more preferably
2Scope in.As above-mentioned direct drawing apparatus, for example can use Orbotech Japan Co., the device that Ltd. produces, PENTAX company produces etc. just can use arbitrarily and installs so long as the vibration maximum wavelength is the device of the laser of 350～410nm.
As aforementioned developing method, can utilize infusion process, spray process, gunite, brushing method etc., as developer solution, can use the alkaline aqueous solution of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc.
Embodiment
Below embodiment is shown and comparative example is specifically described the present invention, the present invention is not limited to following embodiment certainly.
Resin synthesis example 1
In possessing 2 liters of removable flasks of stirring machine, thermometer, backflow cooling tube, tap funnel and nitrogen ingress pipe, import 660g cresols phenolic resin varnish type epoxy resin (Japanese chemical drug (strain) manufacturing, EOCN-104S, 92 ℃ of softening points, epoxide equivalent 220), 421.3g carbitol acetic acid esters and 180.6g solvent naphtha, add thermal agitation at 90 ℃, dissolving.Then, be cooled to for the time being 60 ℃, add 216g acrylic acid, 4.0g triphenylphosphine, 1.3g methylnaphthohydroquinone 100 ℃ of reactions 12 hours, obtain the reaction product that acid number is 0.2mgKOH/g.It is added the 241.7g tetrabydrophthalic anhydride, be heated to 90 ℃, reacted 6 hours.Thus, obtain the solution that contains carboxylic acid resin (A) of acid number 50mgKOH/g, two key equivalent (the g weight of the resin of per 1 mole of unsaturated group) 400, weight-average molecular weight 7,000.Below, this solution that contains the carboxylic acid resin is called A-1 varnish.
Cooperate example and embodiment
Cooperate the various compositions shown in the comparative example according to the ratio (mass parts) that cooperates example, by the stirring machine ready-mixed, then use 3 roll-type roller mills mixing, modulation solder resist photosensitive polymer combination.At this, the dispersion degree of the Photocurable resin composition of gained is estimated in the granulometry that the grindmeter that produces by ERICHSEN company carries out, and the result is below the 15 μ m.
In addition, the numerical value of the composition in the table all represents mass parts.Table 1,2 comparative example 1 be that to cooperate the oxime ester be Photoepolymerizationinitiater initiater but do not cooperate the example of red stain or yellow colorants, and comparative example 2 is that to cooperate red stain or yellow colorants but do not cooperate the oxime ester be the example of Photoepolymerizationinitiater initiater.Table 3,4 comparative example 1 be that to cooperate the oxime ester be Photoepolymerizationinitiater initiater but do not cooperate the example of red stain or yellow colorants, and comparative example 2 is that the oxime ester is the example that Photoepolymerizationinitiater initiater, red stain or yellow colorants all no cooperation.
Cooperate example
154 parts in A composition A-1 varnish (100 parts of solid constituents)
B composition amino anthraquinones compound subordinate list
C composition Photoepolymerizationinitiater initiater subordinate list
20 parts of D composition dipentaerythritol acrylates (Japanese chemical drug manufacturing)
E composition phenol novolak type epoxy resin
(Dow Chemical company makes DEN-431) 15 parts
Di-toluene phenol-type epoxy resin
(Japan Epoxy Resins Co., Ltd. produces YX-4000) 25 parts
Other composition
100 parts in barium sulphate (Sakai chemical company produces barium sulphate B30)
0.3 part of thermal curing catalyst dicyandiamide
5 parts of thermal curing catalyst melamines
The pigment subordinate list
3 parts of silicone-based defoamers
5 parts of DPM (dipropylene glycol monomethyl ether)
Table 1 also illustrates except above-mentioned cooperation example in 2 and has added (B) (C) and the embodiment of the composition of colorant and comparative example.The evaluating characteristics of this moment uses Orbotech Japan Co., and the 355nm laser explosure machine that Ltd. produces is estimated characteristic.
*1:2-(acetoxyl group iminomethyl) thioxanthene-9-one
*2:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone
*3:2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
*4:Irg907 (production of Ciba Specialty Chemicals company)
Table 3, the 4th, the 355nm laser explosure machine that substitution list 1,2 employed Orbotech Japan Co., Ltd. produce and estimate characteristic with the EXP-2960 of the ORC company of having carried mercury short arc lamp.
Performance evaluation:
＜optimum exposure/light sensitivity 〉
After the circuit pattern substrate polishing of the thick 35 μ m of copper ground, washing, drying, the Photocurable resin composition by silk screen print method whole coating previous embodiment and comparative example then was with 80 ℃ heated air circulation type kiln drieds 60 minutes.Then, use carried maximum wavelength 355nm semiconductor laser direct drawing apparatus or carry the exposure device of mercury short arc lamp, (Kodak No.2) exposes across stage metraster, develop (30 ℃, 0.2MPa, 1 quality % aqueous sodium carbonate) when the pattern of residual stage metraster is 7 sections in the time of 60 seconds as optimum exposure.
＜resolution and wire shaped 〉
After the circuit pattern substrate polishing of line/be spaced apart 300/300, the thick 35 μ m of copper ground, washing, drying, then the Photocurable resin composition by whole of silk screen print method coating previous embodiment and comparative example was with 80 ℃ heated air circulation type kiln drieds 30 minutes.After the drying, use the direct drawing apparatus of the semiconductor laser that has carried maximum wavelength 355nm or the exposure device of lift-launch mercury short arc lamp to expose.Exposing patterns uses directly the retouching with data or photomask of line of describing 20/30/40/50/60/70/80/90/100 μ m in interval parts.Be that the mode of the optimum exposure of Photocurable resin composition is shone active energy beam according to exposure.After the exposure, develop by 30 ℃ 1 quality % aqueous sodium carbonates and to describe pattern, thereby the heat curing of carrying out 150 ℃ * 60 minutes obtains cured coating film.
Use is adjusted into 200 times optical microscope, the solder resist minimum residual wires (resolution) of the cured coating film of Photocurable resin composition of obtaining gained.In addition, cut off the line central portion, carry out minute surface finishing, then use to be adjusted into 1000 times optical microscope, measure footpath, top, footpath, bottom, the thickness of the minimum residual wires of cured coating film.As shown in the figure, the shape of this moment is carried out the evaluation (wire shaped) of A～E.Schematic diagram when accompanying drawing represents following phenomenon occurs.When especially A estimates, no matter depart from line top, bottom all in 5 μ m apart from design load.
A estimates: the perfect condition as the design width
B estimates: anti-development deficiency waits and causes the superficial layer corrosion
C estimates: the undercutting state
D estimates: halation etc. cause the line chap
E estimates: the line chap of superficial layer and generation undercutting
At this, be not only A and estimate, C estimates, D estimates all is can be as the level of soldering-resistance layer.Relative therewith, the surface cure of the soldering-resistance layer that B estimates is insufficient, and outward appearance and electrical characteristics are poor, and the soldering-resistance layer that E estimates is that the level as soldering-resistance layer is easily peeled off, is difficult to line, undercut portions.
Attribute testing:
Estimate the substrate preparation method: forming on the figuratum copper clad laminate, with whole coating of the composition of the various embodiments described above and comparative example, 80 ℃ of dryings 20 minutes, placing cool to room temperature with serigraphy.Use carried maximum wavelength 355nm semiconductor laser direct drawing apparatus or carry the exposure device of mercury short arc lamp, to this substrate with optimum exposure exposure solder resist pattern, with 30 ℃ 1%Na
2CO
3Aqueous solution is carried out development in 60 seconds under the condition of spray pressure 0.2MPa, obtain corrosion-resisting pattern.With the UV conveyor oven at cumulative exposure amount 1000mJ/cm
2Condition under to this substrate irradiation ultraviolet radiation, then 150 ℃ of heating 60 minutes, solidify.Printed circuit board (PCB) (evaluation substrate) to gained is estimated characteristic as following.
＜the color of filming 〉
The color of the solidfied material of visual solder resist to above-described embodiment and comparative example is judged.
＜solder heat resistance 〉
In being redefined for 260 ℃ solder bath, dip coated has the evaluation substrate of rosin series solder flux, and with modification alcohol washing solder flux, then visual expansion to resist layer is peeled off and estimated.Judgment standard is as follows.
Zero: even if repeatedly flood more than 3 times, flooded for 10 seconds at every turn, also can't see and peel off.
△: repeatedly flood more than 3 times, flooded for 10 seconds at every turn, peel off a little.
*: flood 3 times with interior, when flooding for 10 second at every turn, resist layer just has expansion, peels off.
＜electrochemical corrosion resistant 〉
Replace copper clad laminate and use the comb-type electrode B print of IPC B-25, substrate is estimated in preparation under these conditions, this comb electrode is applied the bias voltage of DC100V, and affirmation has non-migratory in 85 ℃, the constant temperature and humidity cabinet of 85%R.H. after 1000 hours.Judgment standard is as follows.
Zero: can't see variation fully
△: only a little change
*: move
＜anti-electroless gold plating 〉
Use the commercially available product electroless nickel plating to bathe and the electroless gold plating bath, under the condition of nickel 0.5 μ m, golden 0.03 μ m, carry out plating, peel off by band, estimate resist layer and have or not the infiltration of peeling off and having or not plating, then under the test condition of aforementioned solder heat resistance, flooded for 10 seconds in solder bath, then washing, drying are peeled off evaluation by band and are had or not peeling off of resist layer.Judgment standard is as follows.
Zero: can't see variation fully.
△: can see the infiltration of a little behind the plating, can see peeling off behind the solder heat resistance.
*: peel off behind the plating.
＜acid resistance 〉
At room temperature will estimate substrate and be impregnated into 10vol%H
2SO
4In the aqueous solution 30 minutes, observe the stripping and the band that infiltrate, film and peel off peeling off of causing.Judgment standard is as follows.
Zero: do not have infiltration, stripping and peel off.
△: see a little infiltration, stripping or peel off.
*: see a large amount of infiltrations, stripping or peel off.
＜copper circuit variable color 〉
To estimate substrate again 150 ℃ of heating 2 hours, as the degree of the variable color on the copper circuit that judges.
◎: do not have variable color fully.
Zero: with prima facies than a little variable color, but the thin part of resist does not have difference fully with thick part.
△: can be observed variable color, but the thin part of resist does not have difference fully with thick part.
*: the part that resist is thin can be observed variable color, with the significant difference of thick part.
By the result shown in table 1～table 4 as can be known, the light sensitivity of embodiments of the invention, resolution, wire shaped, copper circuit variable color aspect are all excellent.Relative therewith, mismatch the comparative example of the colorant among the present invention, all light sensitivity, resolution, wire shaped, copper circuit variable color are all excellent unlike embodiments of the invention.
In addition, as supplementary test, replace carrying the exposure device of high-pressure sodium lamp and use the direct drawing apparatus (DAINIPPON SCREEN MFG.CO., the Mercurex that LTD. makes) that carries ultrahigh pressure mercury lamp, use the composition preparation of embodiment 9～15 to estimate substrate.Carry out the coating characteristic evaluation, when the result uses the exposure machine that carries mercury short arc lamp, can obtain identical result.
Claims (20)
1. the Photocurable resin composition that can develop by alkaline aqueous solution that uses to the copper of photocuring, it is characterized in that, it is the compound (D) that has 2 above ethylenically unsaturated groups in Photoepolymerizationinitiater initiater (C), the molecule that its ultraviolet range of containing carboxylic acid resin (A), 350～400nm absorbs red stain (B1), oxime ester little and that Change of absorption is little
Described red stain (B1) is at least any one red stain in azo lake Xi, perylene system, diketopyrrolo-pyrrole system, anthraquinone system and the quinacridone.
2. according to claim 1 can it is characterized in that by the Photocurable resin composition of alkaline aqueous solution development, it also contains a kind or 2 kinds that is selected from yellow colorants (B2) and the blue colorant (B3).
3. Photocurable resin composition according to claim 1 and 2; it is characterized in that; aforementioned oxime ester is that Photoepolymerizationinitiater initiater (C) is Photoepolymerizationinitiater initiater for the oxime ester with the group shown in the following general formula (I); also containing the alpha-aminoacetophenone with the group shown in the following general formula (II) is that Photoepolymerizationinitiater initiater and the acylphosphine oxide with the group shown in the following general formula (III) are a kind or 2 kinds of Photoepolymerizationinitiater initiater
In the formula, R
1The expression hydrogen atom; Can be by the phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom replacement; Can by the alkyl of the carbon number 1～20 of 1 above hydroxyl replacement, wherein, can have 1 above oxygen atom in the middle of the alkyl chain; The naphthenic base of carbon number 5～8; The alkanoyl of carbon number 2～20; Perhaps, the benzoyl that can be replaced by the alkyl or phenyl of carbon number 1～6,
R
2Expression can be by the phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom replacement; Can by the alkyl of the carbon number 1～20 of 1 above hydroxyl replacement, wherein, can have 1 above oxygen atom in the middle of the alkyl chain; The naphthenic base of carbon number 5～8; The alkanoyl of carbon number 2～20; Perhaps, the benzoyl that can be replaced by the alkyl or phenyl of carbon number 1～6,
In the formula, R
3And R
4The alkyl or the aralkyl that represent independently of one another carbon number 1～12,
R
5And R
6The alkyl or the R that represent independently of one another hydrogen atom, carbon number 1～6
5With R
6The ring-type alkane ether of two combinations,
In the formula, R
7And R
8The straight chain shape or alkyl, cyclohexyl, cyclopentyl, aryl, the alkoxy of a chain or the aryl that is replaced by halogen atom, alkyl or alkoxy that represent independently of one another carbon number 1～10, wherein, R
7And R
8In one can represent R-C (=O)-Ji, at this, R is the alkyl of carbon number 1～20.
4. Photocurable resin composition according to claim 3 is characterized in that, the oxime ester with the group shown in the aforementioned formula (I) is that Photoepolymerizationinitiater initiater (C) is Photoepolymerizationinitiater initiater for the oxime ester shown in the following formula (IV).
5. Photocurable resin composition according to claim 3 is characterized in that, the oxime ester with the group shown in the aforementioned formula (I) is that Photoepolymerizationinitiater initiater (C) is Photoepolymerizationinitiater initiater for the oxime ester shown in the following general formula (V),
In the formula, R
9The expression hydrogen atom; Halogen atom; The alkyl of carbon number 1～12; Cyclopentyl; Cyclohexyl; Phenyl; Benzyl; Benzoyl; The alkanoyl of carbon number 2～12; Carbobenzoxy; The perhaps alkoxy carbonyl group of carbon number 2～12, wherein, the carbon number that consists of the alkyl of alkoxy is 2 when above, and alkyl can be replaced by 1 above hydroxyl, and the alkyl chain centre can have 1 above oxygen atom,
R
10, R
12Independently of one another expression can be by the phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom replacement; Can by the alkyl of the carbon number 1～20 of 1 above hydroxyl replacement, wherein, can have 1 above oxygen atom in the middle of the alkyl chain; The naphthenic base of carbon number 5～8; The alkanoyl of carbon number 2～20; Perhaps, the benzoyl that can be replaced by the alkyl or phenyl of carbon number 1～6,
R
11The expression hydrogen atom; Can be by the phenyl of the alkyl of carbon number 1～6, phenyl or halogen atom replacement; Can by the alkyl of the carbon number 1～20 of 1 above hydroxyl replacement, wherein, can have 1 above oxygen atom in the middle of the alkyl chain; The naphthenic base of carbon number 5～8; The alkanoyl of carbon number 2～20; Perhaps, can be by the benzoyl of the alkyl or phenyl of carbon number 1～6 replacement.
6. Photocurable resin composition according to claim 1 and 2 is characterized in that, also contains heat curing composition (E).
7. Photocurable resin composition according to claim 2 is characterized in that, composition is that tone is selected from the solder resist in blueness, green, the orange and purple.
8. Photocurable resin composition according to claim 1 and 2 is characterized in that, in whole compositions, the use level that contains carboxylic acid resin (A) is 20～60 quality %; Contain carboxylic acid resin (A) with respect to 100 mass parts, the use level of Photoepolymerizationinitiater initiater (C) is 0.01～30 mass parts, and the use level that has the compound (D) of 2 above ethylenically unsaturated groups in the molecule is 5～100 mass parts.
9. Photocurable resin composition according to claim 1 is characterized in that, contains carboxylic acid resin (A) with respect to 100 mass parts, and the use level of red stain (B1) is 0.01～5.0 mass parts.
10. Photocurable resin composition according to claim 1 is characterized in that, aforementioned red stain (B1) is any one the red stain that does not contain in halogen and the azo group.
11. Photocurable resin composition according to claim 2 is characterized in that, contains carboxylic acid resin (A) with respect to 100 mass parts, the use level of blue colorant (B3) is 0.01～5 mass parts.
12. the dry film of a photo-curable, it is by being applied on the carrier film claim 1 or 2 described Photocurable resin compositions and dry obtaining.
13. a solidfied material, it is by obtaining claim 1 or 2 described Photocurable resin composition photocurings.
14. a solidfied material, it is by obtaining the described dry film photocuring of claim 12.
15. a solidfied material, it is by obtaining claim 1 or 2 described Photocurable resin composition photocurings to copper.
16. a solidfied material, it is by obtaining the described dry film photocuring of claim 12 to copper.
17. a printed circuit board (PCB), it has insulation course, and this insulation course is by obtaining heat curing after claim 1 or the 2 described Photocurable resin composition photocurings.
18. printed circuit board (PCB), it has insulation course, and this insulation course is by obtaining heat curing after the described dry film photocuring of claim 12.
19. printed circuit board (PCB), it has insulation course, and this insulation course contains any at least a red stain (B1) in azo lake Xi, perylene system, diketopyrrolo-pyrrole system, anthraquinone system and the quinacridone, contains carboxylic acid resin (A), the oxime ester is the compound (D) that has 2 above ethylenically unsaturated groups in Photoepolymerizationinitiater initiater (C) and the molecule.
20. printed circuit board (PCB) according to claim 19, aforementioned red stain (B1) are any one the red stains that does not contain in halogen and the azo group.
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| JP2009239181A (en) * | 2008-03-28 | 2009-10-15 | Taiyo Ink Mfg Ltd | Resin composition for printed circuit board, dry film, and printed circuit board |
| JP5317809B2 (en) * | 2009-04-20 | 2013-10-16 | 富士フイルム株式会社 | Colored curable composition, colored pattern forming method, color filter, and liquid crystal display device |
| JP5475350B2 (en) * | 2009-07-02 | 2014-04-16 | 太陽ホールディングス株式会社 | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them |
| JP5559999B2 (en) * | 2009-07-21 | 2014-07-23 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP5620656B2 (en) * | 2009-08-19 | 2014-11-05 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP5672698B2 (en) * | 2009-12-28 | 2015-02-18 | セイコーエプソン株式会社 | Recording method |
| US9081276B2 (en) | 2010-09-29 | 2015-07-14 | Kaneka Corporation | Photosensitive resin composition production kit, and use thereof |
| JP6084353B2 (en) * | 2010-12-28 | 2017-02-22 | 太陽インキ製造株式会社 | Photocurable resin composition manufacturing method, dry film manufacturing method, cured product manufacturing method, and printed wiring board manufacturing method |
| KR20140018280A (en) * | 2011-04-13 | 2014-02-12 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable resin composition, dry film, cured product, and printed wiring board |
| JP6001922B2 (en) * | 2011-05-27 | 2016-10-05 | 太陽インキ製造株式会社 | Thermosetting resin composition, dry film and printed wiring board using the same |
| JP5315441B1 (en) * | 2012-03-30 | 2013-10-16 | 太陽インキ製造株式会社 | Photocurable resin composition, dry film, cured product and printed wiring board |
| JP6185742B2 (en) * | 2013-04-19 | 2017-08-23 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, and joined body |
| CN104427742B (en) * | 2013-08-28 | 2017-08-22 | 鹏鼎控股(深圳)股份有限公司 | Cover layer and circuit board |
| CN104950574A (en) * | 2014-03-31 | 2015-09-30 | 太阳油墨（苏州）有限公司 | Photocuring and thermosetting resin composition, dry film, cured product and printed circuit board |
| JP2016027384A (en) * | 2014-06-25 | 2016-02-18 | Jsr株式会社 | Photosensitive composition for bezel formation, bezel, and display device |
| JP6704224B2 (en) * | 2015-04-15 | 2020-06-03 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product and printed wiring board |
| CN106444282A (en) * | 2015-08-13 | 2017-02-22 | 常州强力先端电子材料有限公司 | Photosensitive resin composition containing oxime ester photoinitiator and application of photosensitive resin composition |
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| JP7429283B2 (en) | 2020-02-20 | 2024-02-07 | 富士フイルム株式会社 | Colored compositions, films, color filters, solid-state imaging devices, and image display devices |
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| TWI400565B (en) | 2013-07-01 |
| KR101022073B1 (en) | 2011-03-17 |
| CN101303527A (en) | 2008-11-12 |
| TW200910006A (en) | 2009-03-01 |
| KR101120300B1 (en) | 2012-03-06 |
| JP2008281653A (en) | 2008-11-20 |
| CN102393603A (en) | 2012-03-28 |
| CN102393603B (en) | 2014-11-05 |
| KR20080099181A (en) | 2008-11-12 |
| JP4663679B2 (en) | 2011-04-06 |
| KR20110013342A (en) | 2011-02-09 |
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Application publication date: 20081112 Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Holding Co., Ltd. Contract record no.: 2011990000116 Denomination of invention: Photocuring resin composition, dry film, curing product and print circuit board Granted publication date: 20130213 License type: Common License Record date: 20110302 |
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