JP2021043335A - Photosensitive resin composition, dry film having photosensitive resin composition, and printed wiring board having photocured product of photosensitive resin composition - Google Patents
Photosensitive resin composition, dry film having photosensitive resin composition, and printed wiring board having photocured product of photosensitive resin composition Download PDFInfo
- Publication number
- JP2021043335A JP2021043335A JP2019165371A JP2019165371A JP2021043335A JP 2021043335 A JP2021043335 A JP 2021043335A JP 2019165371 A JP2019165371 A JP 2019165371A JP 2019165371 A JP2019165371 A JP 2019165371A JP 2021043335 A JP2021043335 A JP 2021043335A
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- Prior art keywords
- photosensitive resin
- compound
- resin composition
- mass
- phenolic hydroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 123
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 48
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 46
- 239000011574 phosphorus Substances 0.000 claims abstract description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 40
- 239000011593 sulfur Substances 0.000 claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- -1 oxime ester Chemical class 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims 2
- 238000007747 plating Methods 0.000 abstract description 46
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052737 gold Inorganic materials 0.000 abstract description 29
- 239000010931 gold Substances 0.000 abstract description 29
- 230000035945 sensitivity Effects 0.000 abstract description 19
- 239000003513 alkali Substances 0.000 abstract description 18
- 239000010408 film Substances 0.000 description 74
- 239000003822 epoxy resin Substances 0.000 description 62
- 229920000647 polyepoxide Polymers 0.000 description 62
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 238000000576 coating method Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 229910000679 solder Inorganic materials 0.000 description 18
- 239000003086 colorant Substances 0.000 description 13
- 238000011161 development Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 150000007519 polyprotic acids Polymers 0.000 description 13
- 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 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000002530 phenolic antioxidant Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 125000001741 organic sulfur group Chemical group 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013039 cover film Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000040 green colorant Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000001061 orange colorant Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PJEUXMXPJGWZOZ-UHFFFAOYSA-L zinc;diphenylphosphinate Chemical compound [Zn+2].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 PJEUXMXPJGWZOZ-UHFFFAOYSA-L 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- LGNPNSQUCXPYKF-UHFFFAOYSA-N (methylideneamino) acetate Chemical compound CC(=O)ON=C LGNPNSQUCXPYKF-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- BVEIKFLZWBDLJG-UHFFFAOYSA-N 1-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCC BVEIKFLZWBDLJG-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 description 1
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YTXCAJNHPVBVDJ-UHFFFAOYSA-N octadecyl propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC YTXCAJNHPVBVDJ-UHFFFAOYSA-N 0.000 description 1
- OADYBSJSJUFUBR-UHFFFAOYSA-N octanedial Chemical compound O=CCCCCCCC=O OADYBSJSJUFUBR-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000008301 phosphite esters Chemical group 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 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 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- VRRIVXLVXXAHJA-UHFFFAOYSA-N tris(2,3,4-tribromophenyl) phosphate Chemical compound BrC1=C(Br)C(Br)=CC=C1OP(=O)(OC=1C(=C(Br)C(Br)=CC=1)Br)OC1=CC=C(Br)C(Br)=C1Br VRRIVXLVXXAHJA-UHFFFAOYSA-N 0.000 description 1
- MHEGXVLDEDJADA-UHFFFAOYSA-N tris(2,3,4-trimethylphenyl) phosphate Chemical compound CC1=C(C)C(C)=CC=C1OP(=O)(OC=1C(=C(C)C(C)=CC=1)C)OC1=CC=C(C)C(C)=C1C MHEGXVLDEDJADA-UHFFFAOYSA-N 0.000 description 1
- LRSNDFOWYYKLHB-UHFFFAOYSA-N tris(2,3-dibromophenyl) phosphate Chemical compound BrC1=CC=CC(OP(=O)(OC=2C(=C(Br)C=CC=2)Br)OC=2C(=C(Br)C=CC=2)Br)=C1Br LRSNDFOWYYKLHB-UHFFFAOYSA-N 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- SPUXJWDKFVXXBI-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SPUXJWDKFVXXBI-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—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 side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/144—Polymers containing more than one epoxy group per molecule
-
- 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
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本発明は、被覆材料、例えば、絶縁被覆材料に適した感光性樹脂組成物、感光性樹脂組成物をフィルムに塗布した塗膜を有するドライフィルム及び感光性樹脂組成物を光硬化させた光硬化物が被覆されたプリント配線板に関するものである。 The present invention is a photocurable coating material, for example, a photosensitive resin composition suitable for an insulating coating material, a dry film having a coating film coated with the photosensitive resin composition, and a photosensitive resin composition. It relates to a printed wiring board covered with an object.
基板上には導体(例えば、銅箔)の導体回路パターンが形成され、該回路パターンのはんだ付けランドに電子部品をはんだ付けにより搭載し、そのはんだ付けランドを除く回路部分は、保護膜としての絶縁被膜であるソルダーレジスト膜で被覆される。前記絶縁被膜として、カルボキシル基含有感光性樹脂と光重合開始剤とを含有する感光性樹脂組成物の光硬化膜が使用される。また、光硬化膜の黄変防止、光硬化反応時のハレーション防止、ビア開口部の形状安定化等のために、感光性樹脂組成物に酸化防止剤が配合されることがある。 A conductor circuit pattern of a conductor (for example, copper foil) is formed on the substrate, electronic components are mounted on the soldered lands of the circuit pattern by soldering, and the circuit portion excluding the soldered lands is used as a protective film. It is covered with a solder resist film, which is an insulating film. As the insulating film, a photocurable film of a photosensitive resin composition containing a carboxyl group-containing photosensitive resin and a photopolymerization initiator is used. Further, an antioxidant may be added to the photosensitive resin composition in order to prevent yellowing of the photocurable film, prevent halation during the photocuring reaction, stabilize the shape of the via opening, and the like.
そこで、光硬化膜の黄変防止、光硬化反応時のハレーション防止等のために、酸化防止剤を配合した感光性樹脂組成物として、例えば、(A)カルボキシル基含有感光性樹脂、(B)フェノール系化合物、(C)有機イオウ系化合物、(D)光重合開始剤、(E)希釈剤、(F)エポキシ化合物、及び(G)着色剤を含有する感光性樹脂組成物が提案されている(特許文献1)。特許文献1では、酸化防止剤として、(B)フェノール系化合物、(C)有機イオウ系化合物を配合することにより、光硬化膜の黄変防止、光硬化反応時のハレーションを防止するものである。 Therefore, in order to prevent yellowing of the photocurable film, prevent halation during the photocuring reaction, and the like, as a photosensitive resin composition containing an antioxidant, for example, (A) a carboxyl group-containing photosensitive resin, (B) A photosensitive resin composition containing a phenol-based compound, (C) an organic sulfur-based compound, (D) a photopolymerization initiator, (E) a diluent, (F) an epoxy compound, and (G) a colorant has been proposed. (Patent Document 1). In Patent Document 1, by blending (B) a phenolic compound and (C) an organic sulfur compound as an antioxidant, yellowing of the photocurable film is prevented and halation during the photocuring reaction is prevented. ..
一方で、プリント配線板に搭載される電子部品の小型化、高密度での電子部品の搭載等から、ソルダーレジスト膜には高い解像性が要求されることがある。ソルダーレジスト膜の解像性を向上させるために、紫外線に対して高感度化された感光性樹脂組成物が要求されることがある。感光性樹脂組成物を高感度化させるために、光重合開始剤として、オキシムエステル系光重合開始剤が使用されることがある。 On the other hand, the solder resist film may be required to have high resolution due to the miniaturization of electronic components mounted on the printed wiring board and the mounting of electronic components at high density. In order to improve the resolution of the solder resist film, a photosensitive resin composition having high sensitivity to ultraviolet rays may be required. In order to increase the sensitivity of the photosensitive resin composition, an oxime ester-based photopolymerization initiator may be used as the photopolymerization initiator.
しかし、オキシムエステル系光重合開始剤を使用すると、感光性樹脂組成物の感度が高くなりすぎて、フェノール系化合物や有機イオウ系化合物の酸化防止剤を配合しても、ハレーションを十分には抑制できず、例えば、小径のビア開口部が現像されないことなどから、アルカリ現像性に改善の余地があった。 However, when an oxime ester-based photopolymerization initiator is used, the sensitivity of the photosensitive resin composition becomes too high, and even if an antioxidant of a phenol-based compound or an organic sulfur-based compound is added, halation is sufficiently suppressed. There was room for improvement in alkali developability because, for example, the via opening having a small diameter was not developed.
また、酸素阻害の影響の少ない状況(例えば、PET等の樹脂フィルムを感光性樹脂組成物の塗膜上にラミネートした状態)等で感光性樹脂組成物を光硬化させる場合に、オキシムエステル系光重合開始剤を使用すると、紫外線が所望していない塗膜領域にまで回り込むことにより、塗膜の光硬化反応が過剰に進んでしまい、光硬化膜にスカム等の欠陥が発生することがある。光硬化膜にスカム等の欠陥が発生すると、例えば、導体上に形成した感光性樹脂組成物の光硬化膜では、金めっき等のめっき処理を施した場合、金めっき膜等のめっき膜にムラが生じ、さらには、めっき膜が未着となってしまうことがあった。従って、フェノール系化合物や有機イオウ系化合物の酸化防止剤を配合した従来の感光性樹脂組成物では、金めっき性等のめっき性に改善の余地があった。 Further, when the photosensitive resin composition is photocured in a situation where the influence of oxygen inhibition is small (for example, a resin film such as PET is laminated on the coating film of the photosensitive resin composition), the oxime ester-based light is used. When the polymerization initiator is used, the ultraviolet rays wrap around to the undesired coating film region, so that the photocuring reaction of the coating film proceeds excessively, and defects such as scum may occur in the photocured film. When defects such as scum occur in the photocurable film, for example, in the photocurable film of the photosensitive resin composition formed on the conductor, when plating treatment such as gold plating is performed, the plating film such as the gold plating film becomes uneven. In addition, the plating film may not be adhered. Therefore, in the conventional photosensitive resin composition containing an antioxidant of a phenol-based compound or an organic sulfur-based compound, there is room for improvement in plating properties such as gold plating property.
上記事情に鑑み、本発明の目的は、紫外線に対する高い感度を損なうことなく、アルカリ現像性、金めっき性等のめっき性に優れた光硬化膜を形成できる感光性樹脂組成物を提供することである。 In view of the above circumstances, an object of the present invention is to provide a photosensitive resin composition capable of forming a photocurable film having excellent plating properties such as alkali developability and gold plating property without impairing high sensitivity to ultraviolet rays. is there.
本発明の構成の要旨は、以下の通りである。
[1](A)カルボキシル基含有感光性樹脂と、(B)酸化防止剤と、(C)光重合開始剤と、(D)反応性希釈剤と、(E)エポキシ化合物と、を含有する感光性樹脂組成物であって、
前記(B)酸化防止剤が、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物を含有する感光性樹脂組成物。
[2]前記(B)酸化防止剤が、前記(B1)フェノール性水酸基とリンとを有する化合物を含有する[1]に記載の感光性樹脂組成物。
[3]前記(B)酸化防止剤を、前記(A)カルボキシル基含有感光性樹脂100質量部に対して、0.40質量部以上12.0質量以下含有する[1]または[2]に記載の感光性樹脂組成物。
[4]前記(B1)フェノール性水酸基とリンとを有する化合物を、前記(A)カルボキシル基含有感光性樹脂100質量部に対して、2.0質量部以上6.0質量部以下含有する[2]に記載の感光性樹脂組成物。
[5]前記(B)酸化防止剤が、前記(B2)フェノール性水酸基と硫黄とを有する化合物を含有し、前記(B2)フェノール性水酸基と硫黄とを有する化合物を、前記(A)カルボキシル基含有感光性樹脂100質量部に対して、0.50質量部以上1.5質量部以下含有する[1]乃至[4]のいずれか1つに記載の感光性樹脂組成物。
[6]前記(B1)フェノール性水酸基とリンとを有する化合物が、下記式(1)
[7]前記(B2)フェノール性水酸基と硫黄とを有する化合物が、下記式(2)
[8]前記(C)光重合開始剤が、オキシムエステル系光重合開始剤を含有する[1]乃至[7]のいずれか1つに記載の感光性樹脂組成物。
[9][1]乃至[8]のいずれか1つに記載の感光性樹脂組成物の光硬化物。
[10][1]乃至[8]のいずれか1つに記載の感光性樹脂組成物を有するドライフィルム。
[11][1]乃至[8]のいずれか1つに記載の感光性樹脂組成物の光硬化物を有するプリント配線板。
The gist of the structure of the present invention is as follows.
[1] Contains (A) a carboxyl group-containing photosensitive resin, (B) an antioxidant, (C) a photopolymerization initiator, (D) a reactive diluent, and (E) an epoxy compound. It is a photosensitive resin composition and is
The (B) antioxidant contains at least one compound selected from the group consisting of (B1) a compound having a phenolic hydroxyl group and phosphorus and (B2) a compound having a phenolic hydroxyl group and sulfur. Sex resin composition.
[2] The photosensitive resin composition according to [1], wherein the (B) antioxidant contains the compound having the (B1) phenolic hydroxyl group and phosphorus.
[3] In [1] or [2], the (B) antioxidant is contained in an amount of 0.40 parts by mass or more and 12.0 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. The photosensitive resin composition according to the above.
[4] The compound having the (B1) phenolic hydroxyl group and phosphorus is contained in an amount of 2.0 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin [ 2] The photosensitive resin composition according to the above.
[5] The (B) antioxidant contains the compound having the (B2) phenolic hydroxyl group and sulfur, and the compound having the (B2) phenolic hydroxyl group and sulfur is the (A) carboxyl group. The photosensitive resin composition according to any one of [1] to [4], which contains 0.50 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the photosensitive resin contained.
[6] The compound having the (B1) phenolic hydroxyl group and phosphorus is the following formula (1).
[7] The compound having the (B2) phenolic hydroxyl group and sulfur is the following formula (2).
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the (C) photopolymerization initiator contains an oxime ester-based photopolymerization initiator.
[9] The photocured product of the photosensitive resin composition according to any one of [1] to [8].
[10] A dry film having the photosensitive resin composition according to any one of [1] to [8].
[11] A printed wiring board having a photocurable product of the photosensitive resin composition according to any one of [1] to [8].
本発明の態様によれば、(B)酸化防止剤が、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物を含有することにより、紫外線に対する高い感度を損なうことなく、金めっき性等のめっき性に優れた光硬化膜を形成できる感光性樹脂組成物を得ることができる。また、本発明の態様によれば、(B)酸化防止剤が、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物を含有することにより、優れたアルカリ現像性が得られるので、感光性樹脂組成物の塗膜の非露光部位を確実にアルカリ現像することができ、小径のビア開口部でも確実に塗膜をアルカリ現像で除去することができる。 According to an aspect of the present invention, the (B) antioxidant is at least one selected from the group consisting of (B1) a compound having a phenolic hydroxyl group and phosphorus and (B2) a compound having a phenolic hydroxyl group and sulfur. By containing the seed compound, it is possible to obtain a photosensitive resin composition capable of forming a photocurable film having excellent plating properties such as gold plating property without impairing high sensitivity to ultraviolet rays. Further, according to the aspect of the present invention, the (B) antioxidant was selected from the group consisting of (B1) a compound having a phenolic hydroxyl group and phosphorus and (B2) a compound having a phenolic hydroxyl group and sulfur. By containing at least one compound, excellent alkali developability can be obtained, so that the non-exposed portion of the coating film of the photosensitive resin composition can be reliably alkaline-developed, and even a small-diameter via opening can be reliably developed. The coating film can be removed by alkaline development.
本発明の態様によれば、(B)酸化防止剤が(B1)フェノール性水酸基とリンとを有する化合物を含有することにより、アルカリ現像性がさらに向上し、感光性樹脂組成物の塗膜の非露光部位をより確実にアルカリ現像することができる。 According to the aspect of the present invention, when the (B) antioxidant contains a compound having (B1) a phenolic hydroxyl group and phosphorus, the alkali developability is further improved, and the coating film of the photosensitive resin composition is further improved. The unexposed area can be more reliably alkaline-developed.
本発明の態様によれば、(B)酸化防止剤を、前記(A)カルボキシル基含有感光性樹脂100質量部に対して、0.40質量部以上12.0質量以下含有することにより、紫外線に対する感度が確実に向上しつつ、アルカリ現像性、金めっき性等のめっき性がさらに向上する。 According to the aspect of the present invention, by containing (B) an antioxidant in an amount of 0.40 parts by mass or more and 12.0 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin, ultraviolet rays are emitted. The plating property such as alkali developability and gold plating property is further improved while the sensitivity to UV light is surely improved.
本発明の態様によれば、(B1)フェノール性水酸基とリンとを有する化合物を、(A)カルボキシル基含有感光性樹脂100質量部に対して2.0質量部以上6.0質量部以下含有することにより、感度と金めっき性等のめっき性がバランスよく向上する。 According to the aspect of the present invention, the compound having (B1) a phenolic hydroxyl group and phosphorus is contained in an amount of 2.0 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. By doing so, the sensitivity and the plating property such as gold plating property are improved in a well-balanced manner.
本発明の態様によれば、(B)酸化防止剤が、(B2)フェノール性水酸基と硫黄とを有する化合物を含有し、(B2)フェノール性水酸基と硫黄とを有する化合物を、(A)カルボキシル基含有感光性樹脂100質量部に対して0.50質量部以上1.5質量部以下含有することにより、アルカリ現像性と金めっき性等のめっき性がバランスよく向上する。 According to the aspect of the present invention, (B) the antioxidant contains a compound having (B2) a phenolic hydroxyl group and sulfur, and (B2) a compound having a phenolic hydroxyl group and sulfur is (A) carboxyl. By containing 0.50 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the group-containing photosensitive resin, the plating properties such as alkali developability and gold plating property are improved in a well-balanced manner.
次に、本発明の感光性樹脂組成物について、以下に説明する。本発明の感光性樹脂組成物は、(A)カルボキシル基含有感光性樹脂と、(B)酸化防止剤と、(C)光重合開始剤と、(D)反応性希釈剤と、(E)エポキシ化合物と、を含有する感光性樹脂組成物であって、前記(B)酸化防止剤が、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物を含有する。 Next, the photosensitive resin composition of the present invention will be described below. The photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing photosensitive resin, (B) an antioxidant, (C) a photopolymerization initiator, (D) a reactive diluent, and (E). A photosensitive resin composition containing an epoxy compound, wherein the (B) antioxidant has (B1) a phenolic hydroxyl group and phosphorus, and (B2) a compound having a phenolic hydroxyl group and sulfur. Contains at least one compound selected from the group consisting of.
(A)カルボキシル基含有感光性樹脂
(A)成分であるカルボキシル基含有感光性樹脂の化学構造は、特に限定されず、例えば、1個以上の感光性の不飽和二重結合と遊離のカルボキシル基を有する樹脂が挙げられる。前記カルボキシル基含有感光性樹脂としては、例えば、1分子中にエポキシ基を2個以上有する多官能エポキシ樹脂のエポキシ基の少なくとも一部に、アクリル酸やメタクリル酸(以下、「(メタ)アクリル酸」ということがある。)等のラジカル重合性不飽和モノカルボン酸を反応させて、エポキシ(メタ)アクリレート等のラジカル重合性不飽和モノカルボン酸化エポキシ樹脂を得て、生成した水酸基に、多塩基酸及び/または多塩基酸無水物を反応させることで得られる、多塩基酸変性エポキシ(メタ)アクリレート等の多塩基酸変性ラジカル重合性不飽和モノカルボン酸化エポキシ樹脂などを挙げることができる。
(A) Carboxyl group-containing photosensitive resin The chemical structure of the carboxyl group-containing photosensitive resin as a component of (A) is not particularly limited, and for example, one or more photosensitive unsaturated double bonds and free carboxyl groups. Examples thereof include resins having. The carboxyl group-containing photosensitive resin includes, for example, acrylic acid or methacrylic acid (hereinafter, "(meth) acrylic acid") in at least a part of the epoxy groups of the polyfunctional epoxy resin having two or more epoxy groups in one molecule. A radically polymerizable unsaturated monocarboxylic acid such as epoxy (meth) acrylate is reacted to obtain a radically polymerizable unsaturated monocarboxylic oxide epoxy resin such as epoxy (meth) acrylate, and a polybase is added to the generated hydroxyl group. Examples thereof include a polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin such as a polybasic acid-modified epoxy (meth) acrylate obtained by reacting an acid and / or a polybasic acid anhydride.
前記多官能エポキシ樹脂は、2官能以上のエポキシ樹脂であれば、化学構造は、特に限定されない。また、多官能エポキシ樹脂のエポキシ当量は、特に限定されず、例えば、エポキシ当量の上限値は、3000g/eqが好ましく、2000g/eqがより好ましく、1500g/eqが特に好ましい。一方で、エポキシ当量の下限値は、100g/eqが好ましく、200g/eqが特に好ましい。 The chemical structure of the polyfunctional epoxy resin is not particularly limited as long as it is a bifunctional or higher functional epoxy resin. The epoxy equivalent of the polyfunctional epoxy resin is not particularly limited. For example, the upper limit of the epoxy equivalent is preferably 3000 g / eq, more preferably 2000 g / eq, and particularly preferably 1500 g / eq. On the other hand, the lower limit of the epoxy equivalent is preferably 100 g / eq, and particularly preferably 200 g / eq.
多官能エポキシ樹脂の樹脂種としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂等のフェノールノボラック型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、フェニルアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、シリコーン変性エポキシ樹脂等のゴム変性エポキシ樹脂、ε−カプロラクトン変性エポキシ樹脂、オルト−クレゾールノボラック型エポキシ樹脂等のクレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、環状脂肪族多官能エポキシ樹脂、グリシジルエステル型多官能エポキシ樹脂、グリシジルアミン型多官能エポキシ樹脂、複素環式多官能エポキシ樹脂、ビスフェノール変性ノボラック型エポキシ樹脂、多官能変性ノボラック型エポキシ樹脂等を挙げることができる。また、これらのエポキシ樹脂に、さらにBr、Cl等のハロゲン原子を導入したものを使用してもよい。これらの多官能エポキシ樹脂は、単独で使用してもよく、2種以上を併用してもよい。 Examples of the resin type of the polyfunctional epoxy resin include phenol novolac type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, and naphthalene type. Rubber-modified epoxy resin such as epoxy resin, dicyclopentadiene type epoxy resin, silicone-modified epoxy resin, cresol novolac type epoxy resin such as ε-caprolactone-modified epoxy resin, ortho-cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, Cyclic aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidylamine type polyfunctional epoxy resin, heterocyclic polyfunctional epoxy resin, bisphenol modified novolac type epoxy resin, polyfunctional modified novolac type epoxy resin, etc. Can be done. Further, those epoxy resins in which halogen atoms such as Br and Cl are further introduced may be used. These polyfunctional epoxy resins may be used alone or in combination of two or more.
ラジカル重合性不飽和モノカルボン酸は、特に限定されず、例えば、(メタ)アクリル酸、クロトン酸、チグリン酸、アンゲリカ酸、桂皮酸等を挙げることができる。これらのうち、入手と取り扱い性の点から、(メタ)アクリル酸が好ましい。これらのラジカル重合性不飽和モノカルボン酸は、単独で使用してもよく、2種以上を併用してもよい。 The radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, tiglic acid, angelic acid, and cinnamic acid. Of these, (meth) acrylic acid is preferable from the viewpoint of availability and handleability. These radically polymerizable unsaturated monocarboxylic acids may be used alone or in combination of two or more.
多官能エポキシ樹脂とラジカル重合性不飽和モノカルボン酸とを反応させる方法は、特に限定されず、例えば、多官能エポキシ樹脂とラジカル重合性不飽和モノカルボン酸とを有機溶媒等の非反応性希釈剤中で溶解させて加熱する方法等が挙げられる。 The method for reacting the polyfunctional epoxy resin with the radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and for example, the polyfunctional epoxy resin and the radically polymerizable unsaturated monocarboxylic acid are non-reactively diluted with an organic solvent or the like. Examples thereof include a method of dissolving in an agent and heating.
多塩基酸及び/または多塩基酸無水物が、多官能エポキシ樹脂とラジカル重合性不飽和モノカルボン酸との反応により生成した水酸基に付加反応することで、ラジカル重合性不飽和モノカルボン酸化エポキシ樹脂に遊離のカルボキシル基が導入される。多塩基酸及び多塩基酸無水物の化学構造は、いずれも特に限定されず、飽和、不飽和のいずれでも使用可能である。多塩基酸としては、例えば、コハク酸、マレイン酸、アジピン酸、クエン酸、フタル酸、テトラヒドロフタル酸、3−メチルテトラヒドロフタル酸、4−メチルテトラヒドロフタル酸、3−エチルテトラヒドロフタル酸、4−エチルテトラヒドロフタル酸等のテトラヒドロフタル酸類、ヘキサヒドロフタル酸、3−メチルヘキサヒドロフタル酸、4−メチルヘキサヒドロフタル酸、3−エチルヘキサヒドロフタル酸、4−エチルヘキサヒドロフタル酸等のヘキサヒドロフタル酸類、メチルテトラヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、メチルエンドメチレンテトラヒドロフタル酸等のテトラヒドロフタル酸類、トリメリット酸、ピロメリット酸及びジグリコール酸等が挙げられる。多塩基酸無水物としては、上記した各種多塩基酸の無水物が挙げられる。これらの化合物は、単独で使用してもよく、2種以上を併用してもよい。 A radically polymerizable unsaturated monocarboxylic oxide epoxy resin by addition reaction of a polybasic acid and / or a polybasic acid anhydride to a hydroxyl group generated by a reaction between a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid. A free carboxyl group is introduced into the. The chemical structures of the polybasic acid and the polybasic acid anhydride are not particularly limited, and either saturated or unsaturated can be used. Examples of polybasic acids include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-. Tetrahydrophthalates such as ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, hexahydro such as 4-ethylhexahydrophthalic acid Examples thereof include tetrahydrophthalic acids such as phthalic acids, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid and methylendomethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid and diglycolic acid. Examples of the polybasic acid anhydride include the above-mentioned anhydrides of various polybasic acids. These compounds may be used alone or in combination of two or more.
ラジカル重合性不飽和モノカルボン酸化エポキシ樹脂と多塩基酸及び/または多塩基酸無水物とを反応させる方法は、特に限定されず、例えば、ラジカル重合性不飽和モノカルボン酸化エポキシ樹脂と多塩基酸及び/または多塩基酸無水物とを有機溶媒等の非反応性希釈剤中で溶解させて加熱する方法等が挙げられる。 The method for reacting the radically polymerizable unsaturated monocarboxylic oxide epoxy resin with the polybasic acid and / or the polybasic acid anhydride is not particularly limited, and for example, the radically polymerizable unsaturated monocarboxylic oxide epoxy resin and the polybasic acid are not particularly limited. And / or a method in which the polybasic acid anhydride is dissolved in a non-reactive diluent such as an organic solvent and heated.
上記した多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂がカルボキシル基含有感光性樹脂として使用できる。また、上記のようにして得られた多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂のカルボキシル基の一部に、1つ以上のラジカル重合性不飽和基とエポキシ基とを有する化合物を付加反応させて得られる、ラジカル重合性不飽和基をさらに付加した多塩基酸変性ラジカル重合性不飽和モノカルボン酸化エポキシ樹脂を、カルボキシル基含有感光性樹脂として使用してもよい。ラジカル重合性不飽和基をさらに付加した多塩基酸変性ラジカル重合性不飽和モノカルボン酸化エポキシ樹脂は、多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂の側鎖にラジカル重合性不飽和基がさらに導入されている化学構造を有している。従って、多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂よりも、感光性がさらに向上したカルボキシル基含有感光性樹脂である。 The above-mentioned polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin can be used as the carboxyl group-containing photosensitive resin. Further, a compound having one or more radically polymerizable unsaturated groups and an epoxy group is added to a part of the carboxyl groups of the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin obtained as described above. The polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin to which a radically polymerizable unsaturated group is further added may be used as the carboxyl group-containing photosensitive resin. In the polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin to which a radically polymerizable unsaturated group is further added, a radically polymerizable unsaturated group is further introduced into the side chain of the polybasic acid-modified unsaturated monocarboxylic oxidized epoxy resin. Has a chemical structure that has been modified. Therefore, it is a carboxyl group-containing photosensitive resin having further improved photosensitivity as compared with the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin.
1つ以上のラジカル重合性不飽和基とエポキシ基とを有する化合物としては、例えば、グリシジル化合物を挙げることができる。グリシジル化合物としては、例えば、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、ペンタエリスリトールトリアクリレートモノグリシジルエーテル、ペンタエリスリトールトリメタクリレートモノグリシジルエーテル等が挙げられる。グリシジル化合物のグリシジル基は、1分子中に1つ有していてもよく、複数有していてもよい。また、1つ以上のラジカル重合性不飽和基とエポキシ基とを有する化合物は、単独で使用してもよく、2種以上を併用してもよい。 Examples of the compound having one or more radically polymerizable unsaturated groups and an epoxy group include glycidyl compounds. Examples of the glycidyl compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, pentaerythritol trimethacrylate monoglycidyl ether and the like. The glycidyl group of the glycidyl compound may have one or a plurality of glycidyl groups in one molecule. Further, the compound having one or more radically polymerizable unsaturated groups and an epoxy group may be used alone or in combination of two or more.
多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂と、グリシジル化合物等の1つ以上のラジカル重合性不飽和基とエポキシ基とを有する化合物と、を反応させる方法は、特に限定されず、例えば、多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂と1つ以上のラジカル重合性不飽和基とエポキシ基を有する化合物とを、有機溶媒等の非反応性希釈剤中で溶解させて加熱する方法等が挙げられる。 The method for reacting the polybasic acid-modified unsaturated monocarboxylic oxidized epoxy resin with a compound having one or more radically polymerizable unsaturated groups such as a glycidyl compound and an epoxy group is not particularly limited, and for example, many Examples include a method in which a basic acid-modified unsaturated monocarboxylic oxidized epoxy resin and a compound having one or more radically polymerizable unsaturated groups and an epoxy group are dissolved in a non-reactive diluent such as an organic solvent and heated. Be done.
カルボキシル基含有感光性樹脂の酸価は、特に限定されず、例えば、その下限値は、アルカリによる現像の点から30mgKOH/gが好ましく、40mgKOH/gが特に好ましい。一方で、カルボキシル基含有感光性樹脂の酸価の上限値は、例えば、アルカリ現像液による露光部の溶解防止の点から200mgKOH/gが好ましく、光硬化物の耐湿性と絶縁信頼性の低下を確実に防止する点から150mgKOH/gが特に好ましい。 The acid value of the carboxyl group-containing photosensitive resin is not particularly limited, and for example, the lower limit thereof is preferably 30 mgKOH / g and particularly preferably 40 mgKOH / g from the viewpoint of development with an alkali. On the other hand, the upper limit of the acid value of the carboxyl group-containing photosensitive resin is preferably 200 mgKOH / g from the viewpoint of preventing dissolution of the exposed portion by the alkaline developer, for example, and reduces the moisture resistance and insulation reliability of the photocured product. 150 mgKOH / g is particularly preferable from the viewpoint of reliably preventing it.
カルボキシル基含有感光性樹脂の質量平均分子量は、特に限定されず、例えば、その下限値は、光硬化物の強靭性及び指触乾燥性の点から6000が好ましく、7000がより好ましく、8000が特に好ましい。一方で、カルボキシル基含有感光性樹脂の質量平均分子量の上限値は、例えば、アルカリによる現像の点から200000が好ましく、100000がより好ましく、50000が特に好ましい。なお、「質量平均分子量」とは、ゲルパーミエーションクロマトグラフィー(GPC)を用いて、常温で測定し、ポリスチレン換算にて算出される質量平均分子量を意味する。 The mass average molecular weight of the carboxyl group-containing photosensitive resin is not particularly limited, and for example, the lower limit thereof is preferably 6000, more preferably 7000, and particularly 8000 from the viewpoint of toughness and dryness to the touch of the photocured product. preferable. On the other hand, the upper limit of the mass average molecular weight of the carboxyl group-containing photosensitive resin is preferably 200,000, more preferably 100,000, and particularly preferably 50,000, for example, from the viewpoint of development with an alkali. The "mass average molecular weight" means a mass average molecular weight measured at room temperature using gel permeation chromatography (GPC) and calculated in terms of polystyrene.
カルボキシル基含有感光性樹脂は、上記各成分を用いて上記反応工程にて調製してもよく、上市されているカルボキシル基含有感光性樹脂を使用してもよい。上市されているカルボキシル基含有感光性樹脂としては、例えば、「KAYARAD ZAR−2000」、「KAYARAD ZFR−1122」、「KAYARAD FLX−2089」、「KAYARAD ZCR−1569H」(以上、日本化薬株式会社)、「サイクロマーP(ACA)Z−250」(ダイセル・オルネクス株式会社)、「SP−4621」(昭和電工株式会社)等を挙げることができる。また、これらのカルボキシル基含有感光性樹脂は、単独で使用してもよく、2種以上を併用してもよい。 The carboxyl group-containing photosensitive resin may be prepared in the above reaction step using each of the above components, or a commercially available carboxyl group-containing photosensitive resin may be used. Examples of the carboxyl group-containing photosensitive resin on the market include "KAYARAD ZAR-2000", "KAYARAD ZFR-1122", "KAYARAD FLX-2089", and "KAYARAD ZCR-1569H" (above, Nippon Kayaku Co., Ltd.). ), "Cyclomer P (ACA) Z-250" (Dycel Ornex Co., Ltd.), "SP-4621" (Showa Denko KK), and the like. Further, these carboxyl group-containing photosensitive resins may be used alone or in combination of two or more.
(B)酸化防止剤
(B)成分である酸化防止剤として、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物が使用される。(B)成分の酸化防止剤として、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物が使用されることにより、紫外線等の活性エネルギー線に対する高い感度を損なうことなく、金めっき性等のめっき性に優れた光硬化膜を形成できる感光性樹脂組成物を得ることができ、また、ハレーションを十分に防止して優れたアルカリ現像性が得られるので、感光性樹脂組成物の塗膜の非露光部位を確実にアルカリ現像にて除去することができ、例えば、小径のビア開口部や微細パット部でも確実に塗膜をアルカリ現像にて除去することができる。
(B) Antioxidant As an antioxidant as a component of (B), at least selected from the group consisting of (B1) a compound having a phenolic hydroxyl group and phosphorus and (B2) a compound having a phenolic hydroxyl group and sulfur. One compound is used. As the antioxidant of the component (B), at least one compound selected from the group consisting of (B1) a compound having a phenolic hydroxyl group and phosphorus and (B2) a compound having a phenolic hydroxyl group and sulfur is used. As a result, it is possible to obtain a photosensitive resin composition capable of forming a photocurable film having excellent plating properties such as gold plating without impairing high sensitivity to active energy rays such as ultraviolet rays, and sufficient halation. Since excellent alkaline developability can be obtained, the unexposed portion of the coating film of the photosensitive resin composition can be reliably removed by alkaline development. For example, a small-diameter via opening or a fine pad portion can be removed. However, the coating film can be reliably removed by alkaline development.
(B1)成分であるフェノール性水酸基とリンとを有する化合物としては、例えば、フェノール性水酸基とP(OR1)(OR2)(OR3)(R1、R2、R3は、有機基)で表される亜燐酸エステル(ホスファイト)構造とを骨格中に備えた化合物が挙げられる。フェノール性水酸基とP(OR1)(OR2)(OR3)で表される亜燐酸エステル構造とを骨格中に備えた化合物としては、例えば、下記式(1)で表される化合物が挙げられる。
また、上記式(1)のブチル基に代えて、水素、炭素数1〜3のアルキル基、炭素数5〜10アルキル基であるフェノール性水酸基とリンとを有する化合物でもよく、上記式(1)のメチル基に代えて、水素、炭素数2〜10のアルキル基であるフェノール性水酸基とリンとを有する化合物でもよい。上記式(1)で表される化合物として、「SumilizerGP」(住友化学株式会社)を挙げることができる。 Further, instead of the butyl group of the above formula (1), a compound having hydrogen, an alkyl group having 1 to 3 carbon atoms, a phenolic hydroxyl group having 5 to 10 carbon atoms and phosphorus may be used, and the above formula (1) may be used. ) May be replaced with a compound having hydrogen, a phenolic hydroxyl group which is an alkyl group having 2 to 10 carbon atoms, and phosphorus. Examples of the compound represented by the above formula (1) include "Sumilizer GP" (Sumitomo Chemical Co., Ltd.).
(B2)成分であるフェノール性水酸基と硫黄とを有する化合物としては、例えば、フェノールが、−R4−S−R5(式中、R4は炭素数1〜5、好ましくは炭素数1〜3の炭化水素、R5は炭素数5〜20、好ましくは炭素数10〜15の炭化水素を表す。)の置換基で置換された化合物を挙げることができる。置換基−R4−S−R5の数は、少なくとも1つであり、2つが好ましい。 As a compound having a phenolic hydroxyl group and sulfur as the component (B2), for example, phenol is -R 4- S-R 5 (in the formula, R 4 has 1 to 5 carbon atoms, preferably 1 to 1 carbon atoms. 3 hydrocarbon, R 5 is 5 to 20 carbon atoms, preferable examples thereof include compounds substituted with substituents represented.) hydrocarbons having 10 to 15 carbon atoms. The number of substituents -R 4- S-R 5 is at least one, preferably two.
フェノールが−R4−S−R5で置換された化合物としては、例えば、下記式(2)で表される化合物が挙げられる。
上記式(2)で表される化合物として、「Irganox1726」(BASF社)を挙げることができる。 Examples of the compound represented by the above formula (2) include "Irganox1726" (BASF, Inc.).
本発明の感光性樹脂組成物では、フェノール性水酸基とリンとを有する化合物とフェノール性水酸基と硫黄とを有する化合物を併用してもよく、フェノール性水酸基とリンとを有する化合物とフェノール性水酸基と硫黄とを有する化合物のいずれか一方を使用してもよい。このうち、アルカリ現像性がさらに向上して感光性樹脂組成物の塗膜の非露光部位をより確実にアルカリ現像にて除去することができる点から、フェノール性水酸基とリンとを有する化合物が好ましい。 In the photosensitive resin composition of the present invention, a compound having a phenolic hydroxyl group and phosphorus and a compound having a phenolic hydroxyl group and sulfur may be used in combination, and the compound having a phenolic hydroxyl group and phosphorus and the phenolic hydroxyl group Either one of the compounds having sulfur may be used. Of these, a compound having a phenolic hydroxyl group and phosphorus is preferable because the alkali developability is further improved and the unexposed portion of the coating film of the photosensitive resin composition can be more reliably removed by alkaline development. ..
フェノール性水酸基とリンとを有する化合物及びフェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物の配合量は、特に限定されないが、その下限値は、金めっき性等のめっき性がさらに向上する点から、カルボキシル基含有感光性樹脂100質量部(固形分、以下同じ)に対して、0.40質量部が好ましく、0.50質量部がより好ましく、1.0質量部がさらに好ましく、2.0質量部が特に好ましい。一方で、フェノール性水酸基とリンとを有する化合物及びフェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物の配合量の上限値は、紫外線に対する感度が確実に向上しつつ、優れたアルカリ現像性を得る点から、カルボキシル基含有感光性樹脂100質量部に対して、12.0質量が好ましく、10.0質量部がより好ましく、5.0質量部が特に好ましい。 The blending amount of at least one compound selected from the group consisting of a compound having a phenolic hydroxyl group and phosphorus and a compound having a phenolic hydroxyl group and sulfur is not particularly limited, but the lower limit thereof is gold plating property and the like. 0.40 parts by mass, more preferably 0.50 parts by mass, and 1.0 parts by mass with respect to 100 parts by mass (solid content, the same applies hereinafter) of the carboxyl group-containing photosensitive resin from the viewpoint of further improving the plating property of the above. The parts by mass are more preferable, and 2.0 parts by mass is particularly preferable. On the other hand, the upper limit of the blending amount of at least one compound selected from the group consisting of the compound having a phenolic hydroxyl group and phosphorus and the compound having a phenolic hydroxyl group and sulfur surely improves the sensitivity to ultraviolet rays. On the other hand, from the viewpoint of obtaining excellent alkali developability, 12.0 parts by mass is preferable, 10.0 parts by mass is more preferable, and 5.0 parts by mass is particularly preferable with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin.
また、フェノール性水酸基とリンとを有する化合物を配合し、フェノール性水酸基と硫黄とを有する化合物を配合しない場合には、フェノール性水酸基とリンとを有する化合物の配合量の下限値は、金めっき性等のめっき性がさらに向上する点から、カルボキシル基含有感光性樹脂100質量部に対して1.0質量部が好ましく、1.5質量部がより好ましく、2.0質量部が特に好ましい。一方で、フェノール性水酸基とリンとを有する化合物を配合し、フェノール性水酸基と硫黄とを有する化合物を配合しない場合の、フェノール性水酸基とリンとを有する化合物の配合量の上限値は、感度をさらに向上させる点から、カルボキシル基含有感光性樹脂100質量部に対して10.0質量部が好ましく、7.5質量部がより好ましく、6.0質量部がさらに好ましく、5.0質量部が特に好ましい。 When a compound having a phenolic hydroxyl group and phosphorus is blended and a compound having a phenolic hydroxyl group and sulfur is not blended, the lower limit of the blending amount of the compound having a phenolic hydroxyl group and phosphorus is gold plating. From the viewpoint of further improving the plating property such as properties, 1.0 part by mass is preferable, 1.5 parts by mass is more preferable, and 2.0 parts by mass is particularly preferable with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. On the other hand, when a compound having a phenolic hydroxyl group and phosphorus is blended and a compound having a phenolic hydroxyl group and sulfur is not blended, the upper limit of the blending amount of the compound having a phenolic hydroxyl group and phosphorus determines the sensitivity. From the viewpoint of further improvement, 10.0 parts by mass is preferable, 7.5 parts by mass is more preferable, 6.0 parts by mass is further preferable, and 5.0 parts by mass is preferable with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. Especially preferable.
また、フェノール性水酸基と硫黄とを有する化合物を配合し、フェノール性水酸基とリンとを有する化合物を配合しない場合には、フェノール性水酸基と硫黄とを有する化合物の下限値は、金めっき性等のめっき性がさらに向上する点から、カルボキシル基含有感光性樹脂100質量部に対して0.50質量部が好ましく、0.75質量部が特に好ましい。一方で、フェノール性水酸基と硫黄とを有する化合物を配合し、フェノール性水酸基とリンとを有する化合物を配合しない場合の、フェノール性水酸基と硫黄とを有する化合物の上限値は、アルカリ現像性がさらに向上する点から、カルボキシル基含有感光性樹脂100質量部に対して2.5質量部が好ましく、2.0質量部がより好ましく、1.5質量部が特に好ましい。 When a compound having a phenolic hydroxyl group and sulfur is blended and a compound having a phenolic hydroxyl group and phosphorus is not blended, the lower limit of the compound having a phenolic hydroxyl group and sulfur is gold plating property or the like. From the viewpoint of further improving the plating property, 0.50 parts by mass is preferable with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin, and 0.75 parts by mass is particularly preferable. On the other hand, when a compound having a phenolic hydroxyl group and sulfur is blended and a compound having a phenolic hydroxyl group and phosphorus is not blended, the upper limit of the compound having a phenolic hydroxyl group and sulfur is further alkaline developability. From the viewpoint of improvement, 2.5 parts by mass is preferable, 2.0 parts by mass is more preferable, and 1.5 parts by mass is particularly preferable with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin.
また、(B)酸化防止剤として、必要に応じて、(B1)フェノール性水酸基とリンとを有する化合物及び/または(B2)フェノール性水酸基と硫黄とを有する化合物と、(B1)成分及び(B2)成分以外の酸化防止剤(以下、「他の酸化防止剤」ということがある。)と、を併用してもよい。併用される他の酸化防止剤としては、例えば、リンも硫黄も含まないフェノール系酸化防止剤(以下、「フェノール系酸化防止剤」ということがある。)、フェノール性水酸基を有さないリン系酸化防止剤(以下、「リン系酸化防止剤」ということがある。)、フェノール性水酸基を有さない硫黄系酸化防止剤(以下、「硫黄系酸化防止剤」ということがある。)等を挙げることができる。 Further, as (B) antioxidant, if necessary, a compound having (B1) phenolic hydroxyl group and phosphorus and / or a compound having (B2) phenolic hydroxyl group and sulfur, (B1) component and (B1) component and ( B2) An antioxidant other than the component (hereinafter, may be referred to as "another antioxidant") may be used in combination. Other antioxidants used in combination include, for example, a phenolic antioxidant containing neither phosphorus nor sulfur (hereinafter, may be referred to as "phenolic antioxidant"), and a phosphorus-based agent having no phenolic hydroxyl group. Antioxidants (hereinafter, may be referred to as "phosphory-based antioxidants"), sulfur-based antioxidants which do not have phenolic hydroxyl groups (hereinafter, may be referred to as "sulfur-based antioxidants"), etc. Can be mentioned.
フェノール系酸化防止剤としては、例えば、3,9−ビス{2−[3−(3−t−ブチル−4−ヒドロキシ−5−メチルフエニル)プロピオニルオキシ]−1,1−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、3,9−ビス{2−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]−1,1−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、3,9−ビス{2−[3−(3−iso−ブチル−4−ヒドロキシ−5−メチルフエニル)プロピオニルオキシ]1,1′−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、3,9−ビス{2−[3−(4−ヒドロキシ−5−メチルフエニル)プロピオニルオキシ]1,1′−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、3,9−ビス{2−[3−(3−t−ブチル−5−エチル−4−ヒドロキシフェニル)プロピオニルオキシ]1,1′−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオン酸ステアリル等のヒンダードフェノール系酸化防止剤が挙げられる。上市されているヒンダードフェノール系酸化防止剤として、例えば、「Irganox 1010」(BASF社)を挙げることができる。 Examples of the phenolic antioxidant include 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2, 4,8,10-Tetraoxaspiro [5,5] undecane, 3,9-bis {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1,1 -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis {2- [3- (3-iso-butyl-4-hydroxy-5-methylphenyl) propionyl) Oxy] 1,1'-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis {2- [3- (4-hydroxy-5-methylphenyl) propionyl) Oxy] 1,1'-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis {2- [3- (3-t-butyl-5-ethyl) -4-Hydroxyphenyl) propionyloxy] 1,1'-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 3- (3,5-di-tert-butyl-4) −Hydroxyphenyl) Examples include hindered phenolic antioxidants such as stearyl propionate. Examples of the hindered phenolic antioxidants on the market include "Irganox 1010" (BASF).
リン系酸化防止剤としては、例えば、「Irgafos 168」(BASF社)として上市されているトリス(2,4−di−tert−ブチルフェニル)フォスファイト等が挙げられる。 Examples of the phosphorus-based antioxidant include tris (2,4-di-tert-butylphenyl) phosphite marketed as "Irgafos 168" (BASF).
硫黄系酸化防止剤としては、例えば、下記一般式(I)で表わされる有機硫黄系化合物が挙げられる。
(R6-S-CH2CH2COOCH2)4C・・・・(I)
(式(I)中、R6は、炭素数10〜20のアルキル基を示し、4個のR6は、同一でも異なっていてもよい。)R6である炭素数10〜20のアルキル基としては、例えば、ラウリル基、ミリスチル基、パルミチル基、基、ステアリル基などが挙げられる。上市されている硫黄系酸化防止剤としては、例えば、「Sumilizer TP−D」(住友化学株式会社)が挙げられる。
Examples of the sulfur-based antioxidant include an organic sulfur-based compound represented by the following general formula (I).
(R 6 -S-CH 2 CH 2 COOCH 2 ) 4 C ... (I)
(In the formula (I), R 6 represents an alkyl group having 10 to 20 carbon atoms, and the four R 6s may be the same or different.) An alkyl group having 10 to 20 carbon atoms, which is R 6. Examples thereof include a lauryl group, a myristyl group, a palmityl group, a group, a stearyl group and the like. Examples of the sulfur-based antioxidants on the market include "Sumilizer TP-D" (Sumitomo Chemical Co., Ltd.).
他の酸化防止剤の配合量は、特に限定されないが、その下限値は、ハレーションの抑制に確実に寄与する点から、カルボキシル基含有感光性樹脂100質量部に対して0.05質量部が好ましく、0.10質量部が特に好ましい。一方で、他の酸化防止剤の配合量の上限値は、高い感度を確実に維持する点から、カルボキシル基含有感光性樹脂100質量部に対して2.0質量部が好ましく、1.0質量部が特に好ましい。 The amount of the other antioxidant is not particularly limited, but the lower limit thereof is preferably 0.05 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin from the viewpoint of surely contributing to the suppression of halation. , 0.10 parts by mass is particularly preferable. On the other hand, the upper limit of the blending amount of the other antioxidant is preferably 2.0 parts by mass and 1.0 part by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin from the viewpoint of reliably maintaining high sensitivity. Part is particularly preferable.
(C)光重合開始剤
(C)成分である光重合開始剤は、特に限定されず、いずれも使用することができる。光重合開始剤としては、例えば、1,2−オクタンジオン,1−〔4−(フェニルチオ)−2−(O−ベンゾイルオキシム)〕、エタノン,1−[9−エチル−6−(2−メチルベンゾイル)-9H−カルバゾール−3−イル]−,1−(O−アセチルオキシム)、2−(アセチルオキシイミノメチル)チオキサンテン−9−オン、1,8−オクタンジオン,1,8−ビス[9−エチル−6−ニトロ−9H−カルバゾール−3−イル]−,1,8−ビス(O−アセチルオキシム)、1,8−オクタンジオン,1,8−ビス[9−(2−エチルヘキシル)−6−ニトロ−9H−カルバゾール−3−イル]−,1,8−ビス(O−アセチルオキシム)、(Z) −(9−エチル−6−ニトロ−9H−カルバゾール−3−イル)(4−((1−メトキシプロパン−2−イル)オキシ) −2−メチルフェニル)メタノン O−アセチルオキシム等のオキシムエステル系光重合開始剤が挙げられる。これらの化合物は、単独で使用してもよく、2種以上を併用してもよい。オキシムエステル系光重合開始剤は、感光性樹脂組成物に紫外線等の活性エネルギー線に対する高い感度を付与することができる。
(C) Photopolymerization Initiator The photopolymerization initiator as the component (C) is not particularly limited, and any of them can be used. Examples of the photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), 2- (acetyloxyiminomethyl) thioxanthene-9-one, 1,8-octanedione, 1,8-bis [ 9-Ethyl-6-nitro-9H-carbazole-3-yl]-, 1,8-bis (O-acetyloxime), 1,8-octanedione, 1,8-bis [9- (2-ethylhexyl)] -6-Nitro-9H-carbazole-3-yl]-, 1,8-bis (O-acetyloxime), (Z)-(9-ethyl-6-nitro-9H-carbazole-3-yl) (4) Examples thereof include an oxime ester-based photopolymerization initiator such as − ((1-methoxypropan-2-yl) oxy) -2-methylphenyl) methanone O-acetyloxime. These compounds may be used alone or in combination of two or more. The oxime ester-based photopolymerization initiator can impart high sensitivity to active energy rays such as ultraviolet rays to the photosensitive resin composition.
本発明では、オキシムエステル系光重合開始剤が配合されても、(B)酸化防止剤が、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物を含有することで、光硬化反応時のハレーションを防止でき、アルカリ現像性、金めっき性等のめっき性に優れた光硬化膜を形成できる。 In the present invention, even if an oxime ester-based photopolymerization initiator is blended, the (B) antioxidant is a compound having (B1) a phenolic hydroxyl group and phosphorus and (B2) a compound having a phenolic hydroxyl group and sulfur. By containing at least one compound selected from the group consisting of, it is possible to prevent halation during the photocuring reaction and to form a photocured film having excellent plating properties such as alkali developability and gold plating property.
また、オキシムエステル系光重合開始剤以外の光重合開始剤を使用してもよく、例えば、フェニルビス(2,4,6−トリメチルベンゾイル)ホスフィンオキシド、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−n−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、2,2−ジメトキシ−2−フェニルアセトフェノン、2,2−ジエトキシ−2−フェニルアセトフェノン、1−ベンジル−1−(ジメチルアミノ)プロピル−4−モルフォリノフェニル−ケトン、2−メチル−4’−(メチルチオ)−2−モルフォリノプロピオフェノン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタノン−1、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、1−ヒドロキシシクロヘキシルフェニルケトン、4−(2−ヒドロキシエトキシ)フェニル−2−(ヒドロキシ−2−プロピル)ケトン、ベンゾフェノン、p−フェニルベンゾフェノン、4,4′−ビス(ジエチルアミノ)ベンゾフェノン、ジクロルベンゾフェノン、2−メチルアントラキノン、2−エチルアントラキノン、2−ターシャリーブチルアントラキノン、2−アミノアントラキノン、2−メチルチオキサントン、2−エチルチオキサントン、2−クロルチオキサントン、2,4−ジメチルチオキサントン、2,4−ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、P−ジメチルアミノ安息香酸エチルエステル等が挙げられる。これらの化合物は、単独で使用してもよく、2種以上を併用してもよい。 Further, a photopolymerization initiator other than the oxime ester-based photopolymerization initiator may be used, for example, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin. Isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-benzyl-1- (dimethylamino) ) Propyl-4-morpholinophenyl-ketone, 2-methyl-4'-(methylthio) -2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1,2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p. -Phenylbenzophenone, 4,4'-bis (diethylamino) benzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tersary butyl anthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone , 2-Chlorthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenonedimethylketal, P-dimethylaminobenzoic acid ethyl ester and the like. These compounds may be used alone or in combination of two or more.
光重合開始剤の含有量は、特に限定されないが、カルボキシル基含有感光性樹脂100質量部に対して、0.10〜10質量部が好ましく、0.50〜5.0質量部が特に好ましい。 The content of the photopolymerization initiator is not particularly limited, but is preferably 0.10 to 10 parts by mass and particularly preferably 0.50 to 5.0 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin.
(D)反応性希釈剤
(D)成分である反応性希釈剤は、例えば、光重合性モノマーであり、1分子当たり少なくとも1つ、好ましくは2つ以上の重合性二重結合を有する化合物である。反応性希釈剤は、感光性樹脂組成物の光硬化を十分にして、光硬化物の耐酸性、耐熱性、耐アルカリ性等の向上に寄与する。
(D) Reactive Diluent The reactive diluent as the component (D) is, for example, a photopolymerizable monomer, which is a compound having at least one, preferably two or more polymerizable double bonds per molecule. is there. The reactive diluent sufficiently photocures the photosensitive resin composition and contributes to the improvement of acid resistance, heat resistance, alkali resistance and the like of the photocured product.
反応性希釈剤としては、例えば、単官能の(メタ)アクリレートモノマー、2官能以上の(メタ)アクリレートモノマーを挙げることができる。単官能の(メタ)アクリレートモノマーとして、例えば、(メタ)アクリル酸2−ヒドロキシエチル、フェノキシエチル(メタ)アクリレート、ジエチレングルコールモノ(メタ)アクリレート、2−ヒドロキシ−3−フェノキシプロピル(メタ)アクリルレート、カプロラクトン変性(メタ)アクリレートが挙げられる。また、2官能以上の(メタ)アクリレートモノマーとして、例えば、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールアジペートジ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、ジシクロペンタニルジ(メタ)アクリレート、エチレンオキサイド変性燐酸ジ(メタ)アクリレート、アリル化シクロヘキシルジ(メタ)アクリレート、イソシアヌレートジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、プロピレンオキシド変性トリメチロールプロパントリ(メタ)アクリレート、トリス(アクリロキシエチル)イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ウレタン(メタ)アクリレート等が挙げられる。これらの化合物は、単独で使用してもよく、2種以上を併用してもよい。 Examples of the reactive diluent include a monofunctional (meth) acrylate monomer and a bifunctional or higher functional (meth) acrylate monomer. Examples of the monofunctional (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, diethylene glucol mono (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylic. Examples include rates and caprolactone-modified (meth) acrylates. Further, as the bifunctional or higher functional (meth) acrylate monomer, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (Meta) acrylate, neopentyl glycol adipate di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyldi (meth) acrylate, ethylene oxide-modified di (meth) acrylate of phosphate, cyclohexyl allylated Di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropan tri (meth) acrylate, ditrimethylolpropantetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene Examples thereof include oxide-modified trimethylolpropantri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and urethane (meth) acrylate. .. These compounds may be used alone or in combination of two or more.
反応性希釈剤の配合量は、特に限定されないが、カルボキシル基含有感光性樹脂100質量部に対して、5.0〜100質量部が好ましく、10〜30質量部が特に好ましい。 The amount of the reactive diluent is not particularly limited, but is preferably 5.0 to 100 parts by mass and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin.
(E)エポキシ化合物
(E)成分であるエポキシ化合物は、感光性樹脂組成物の光硬化物の架橋密度を上げて、十分な機械的強度を有する光硬化膜を得るためのものである。エポキシ化合物としては、例えば、エポキシ樹脂を挙げることができる。エポキシ樹脂としては、例えば、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、テトラメチルビスフェノールF型エポキシ樹脂等のビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、アダマンタン型エポキシ樹脂を挙げることができる。これらのうち、ポットライフをさらに向上させる点から、ビスフェノールA型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビスフェノールF型エポキシ樹脂が好ましく、ビフェニル型エポキシ樹脂、テトラメチルビスフェノールF型エポキシ樹脂が特に好ましい。これらの化合物は単独で使用してもよく、2種以上を併用してもよい。
(E) Epoxy compound The epoxy compound as the component (E) is for increasing the crosslink density of the photocured product of the photosensitive resin composition to obtain a photocurable film having sufficient mechanical strength. Examples of the epoxy compound include an epoxy resin. Examples of the epoxy resin include biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, bisphenol A type epoxy resin, tetramethyl bisphenol F type epoxy resin and other bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. , Dicyclopentadiene type epoxy resin, Adamantane type epoxy resin can be mentioned. Of these, bisphenol A type epoxy resin, biphenyl type epoxy resin, and tetramethyl bisphenol F type epoxy resin are preferable, and biphenyl type epoxy resin and tetramethyl bisphenol F type epoxy resin are particularly preferable, from the viewpoint of further improving the pot life. These compounds may be used alone or in combination of two or more.
エポキシ化合物の配合量は、特に限定されず、十分な機械的強度の光硬化物を確実に得る点から、カルボキシル基含有感光性樹脂100質量部に対して、5.0〜100質量部が好ましく、10〜50質量部が特に好ましい。 The blending amount of the epoxy compound is not particularly limited, and is preferably 5.0 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin from the viewpoint of surely obtaining a photocured product having sufficient mechanical strength. , 10 to 50 parts by mass is particularly preferable.
本発明の感光性樹脂組成物には、上記した(A)〜(E)成分の他に、必要に応じて、他の成分、例えば、体質顔料、難燃剤、硬化促進剤、添加剤、着色剤、非反応性希釈剤等を、適宜、配合してもよい。 In addition to the above-mentioned components (A) to (E), the photosensitive resin composition of the present invention contains other components, for example, extender pigments, flame retardants, curing accelerators, additives, and colorings, if necessary. Agents, non-reactive diluents and the like may be blended as appropriate.
体質顔料としては、タルク、硫酸バリウム、疎水性シリカ、アルミナ、水酸化アルミニウム、マイカ等を挙げることができる。難燃剤は、本発明の感光性樹脂組成物の光硬化物に難燃性を付与するためのものであり、例えば、リン系の難燃剤を挙げることができる。リン系の難燃剤としては、例えば、トリス(クロロエチル)ホスフェート、トリス(2,3−ジクロロプロピル)ホスフェート、トリス(2−クロロプロピル)ホスフェート、トリス(2,3−ブロモプロピル)ホスフェート、トリス(ブロモクロロプロピル)ホスフェート、2,3−ジブロモプロピル−2,3−クロロプロピルホスフェート、トリス(トリブロモフェニル)ホスフェート、トリス(ジブロモフェニル)ホスフェート、トリス(トリブロモネオペンチル)ホスフェートなどの含ハロゲン系リン酸エステル;トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリブトキシエチルホスフェートなどのノンハロゲン系脂肪族リン酸エステル;トリフェニルホスフェート、クレジルジフェニルホスフェート、ジクレジルフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、キシレニルジフェニルホスフェート、トリス(イソプロピルフェニル)ホスフェート、イソプロピルフェニルジフェニルホスフェート、ジイソプロピルフェニルフェニルホスフェート、トリス(トリメチルフェニル)ホスフェート、トリス(t−ブチルフェニル)ホスフェート、ヒドロキシフェニルジフェニルホスフェート、オクチルジフェニルホスフェートなどのノンハロゲン系芳香族リン酸エステル;トリスジエチルホスフィン酸アルミニウム、トリスメチルエチルホスフィン酸アルミニウム、トリスジフェニルホスフィン酸アルミニウム、ビスジエチルホスフィン酸亜鉛、ビスメチルエチルホスフィン酸亜鉛、ビスジフェニルホスフィン酸亜鉛、ビスジエチルホスフィン酸チタニル、テトラキスジエチルホスフィン酸チタン、ビスメチルエチルホスフィン酸チタニル、テトラキスメチルエチルホスフィン酸チタン、ビスジフェニルホスフィン酸チタニル、テトラキスジフェニルホスフィン酸チタンなどのホスフィン酸の金属塩、9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド(以下HCA)、HCAとアクリル酸エステルの付加反応生成物、HCAとエポキシ樹脂の付加反応生成物、HCAとハイドロキノンの付加反応生成物等のHCA変性型化合物、ジフェニルビニルホスフィンオキサイド、トリフェニルホスフィンオキサイド、トリアルキルホスフィンオキサイド、トリス(ヒドロキシアルキル)ホスフィンオキサイド等のホスフィンオキサイド系化合物等が挙げられる。このうち、有機リン酸塩系の難燃剤が好ましい。 Examples of the extender pigment include talc, barium sulfate, hydrophobic silica, alumina, aluminum hydroxide, mica and the like. The flame retardant is for imparting flame retardancy to the photocurable product of the photosensitive resin composition of the present invention, and examples thereof include phosphorus-based flame retardants. Examples of phosphorus-based flame retardants include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, and tris (bromo). Halogen-containing phosphoric acids such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, and tris (tribromoneopentyl) phosphate. Esters; non-halogen aliphatic phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresil diphenyl phosphate, dicredyl phenyl phosphate, tricresyl phosphate, trixylate Nylphosphate, xylenyldiphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyldiphenyl phosphate, diisopropylphenylphenyl phosphate, tris (trimethylphenyl) phosphate, tris (t-butylphenyl) phosphate, hydroxyphenyldiphenyl phosphate, octyldiphenyl phosphate Non-halogen aromatic phosphate esters such as: Aluminum Trisdiethylphosphinate, Aluminum Trismethylethylphosphinate, Aluminum Trisdiphenylphosphinate, Zinc bisdiphenylphosphinate, Zinc bismethylethylphosphinate, Zinc bisdiphenylphosphinate, Bisdiethyl Metal salts of phosphinic acids such as titanyl phosphinate, titanium tetrakisdiphenylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphite, 9,10-dihydro-9 HCA modification of −oxa-10-phosphaphenanthrene-10-oxide (hereinafter HCA), addition reaction product of HCA and acrylate ester, addition reaction product of HCA and epoxy resin, addition reaction product of HCA and hydroquinone, etc. Type compounds, diphenylvinylphosphine oxide, triphenylphosphine oxide, trialkylphosphine oxide, tris (hydroxyalkyl) phos Examples thereof include phosphine oxide compounds such as fin oxide. Of these, organic phosphate-based flame retardants are preferable.
硬化促進剤としては、メルカプトベンゾオキサザール及びその誘導体、ジシアンジアミド(DICY)及びその誘導体、メラミン及びその誘導体、三フッ化ホウ素−アミンコンプレックス、有機酸ヒドラジド、ジアミノマレオニトリル(DAMN)及びその誘導体、グアナミン及びその誘導体、アミンイミド(AI)並びにポリアミン等が挙げられる。添加剤としては、シリコーン系、炭化水素系及びアクリル系等の消泡剤、ポリカルボン酸アマイド等のチキソ剤等が挙げられる。 Curing accelerators include mercaptobenzoxalal and its derivatives, dicyandiamide (DICY) and its derivatives, melamine and its derivatives, boron trifluoride-amine complex, organic acid hydrazide, diaminomaleonitrile (DAMN) and its derivatives, guanamine. And its derivatives, amineimide (AI), polyamines and the like. Examples of the additive include antifoaming agents such as silicone-based, hydrocarbon-based and acrylic-based, thixotropic agents such as polycarboxylic acid amide, and the like.
着色剤は、顔料、色素等、特に限定されず、また、白色着色剤、青色着色剤、緑色着色剤、黄色着色剤、紫色着色剤、黒色着色剤、橙色着色剤等、いずれの色彩の着色剤も使用可能である。上記着色剤には、例えば、白色着色剤である酸化チタン(ルチル型、アナターゼ型)、黒色着色剤であるカーボンブラック、アセチレンブラック等の無機系着色剤や、緑色着色剤であるフタロシアニングリーン及び青色着色剤であるフタロシアニンブルーやリオノールブルー等のフタロシアニン系、アントラキノン系、橙色着色剤であるクロモフタルオレンジ等のジケトピロロピロール系等の有機系着色剤などを挙げることができる。 The colorant is not particularly limited to pigments, pigments, etc., and any color such as white colorant, blue colorant, green colorant, yellow colorant, purple colorant, black colorant, orange colorant, etc. is colored. Agents can also be used. Examples of the colorant include inorganic colorants such as titanium oxide (rutyl type, anatase type) which is a white colorant, carbon black and acetylene black which are black colorants, and phthalocyanine green and blue which are green colorants. Examples thereof include phthalocyanine-based colorants such as phthalocyanine blue and lionol blue, anthraquinone-based colorants, and diketopyrrolopyrrole-based organic colorants such as chromoftal orange, which is an orange colorant.
非反応性希釈剤は、感光性樹脂組成物の塗工性や乾燥性を調節するためのものである。非反応性希釈剤として、例えば、有機溶剤を挙げることができる。有機溶剤には、例えば、メチルエチルケトン、シクロヘキサン等のケトン類、トルエン、キシレン等の芳香族炭化水素類、メタノール、エタノール、プロパノール、シクロヘキサノール等のアルコール類、シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類、石油エーテル、石油ナフサ等の石油系溶剤、セロソルブ、ブチルセロソルブ等のセロソルブ類、カルビトール、ブチルカルビトール等のカルビトール類、酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、エチレングリコールアセテート、エチルジグリコールアセテート等のエステル類等を挙げることができる。これらは、単独で使用してもよく、2種以上を併用してもよい。 The non-reactive diluent is for adjusting the coatability and drying property of the photosensitive resin composition. Examples of the non-reactive diluent include organic solvents. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol and cyclohexanol, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Classes, petroleum ethers, petroleum solvents such as petroleum naphtha, cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl Examples thereof include esters such as carbitol acetate, ethylene glycol acetate, and ethyl diglycol acetate. These may be used alone or in combination of two or more.
上記した本発明の感光性樹脂組成物の製造方法は、特定の方法に限定されず、例えば、上記各成分を所定割合で配合後、室温(常温)にて、三本ロール、ボールミル、サンドミル等の混練手段、またはスーパーミキサー、プラネタリーミキサー等の攪拌手段により混練または混合して製造することができる。また、前記混練または混合の前に、必要に応じて、室温(常温)にて、予備混練または予備混合を行ってもよい。 The method for producing the photosensitive resin composition of the present invention described above is not limited to a specific method. For example, after blending each of the above components in a predetermined ratio, at room temperature (normal temperature), a three-roll, ball mill, sand mill, etc. It can be produced by kneading or mixing by a kneading means of the above, or a stirring means such as a super mixer or a planetary mixer. Further, prior to the kneading or mixing, pre-kneading or pre-mixing may be performed at room temperature (normal temperature), if necessary.
次に、本発明の感光性樹脂組成物の使用方法例について説明する。ここでは、まず、導体箔をエッチングして形成した回路パターンを有するプリント配線板上に、本発明の感光性樹脂組成物を塗工したドライフィルムを用いて、ソルダーレジスト膜を形成する方法について説明する。 Next, an example of how to use the photosensitive resin composition of the present invention will be described. Here, first, a method of forming a solder resist film on a printed wiring board having a circuit pattern formed by etching a conductor foil using a dry film coated with the photosensitive resin composition of the present invention will be described. To do.
ドライフィルムは、支持フィルム(例えば、ポリエチレンテレフタレートフィルム、ポリエステルフィルム等の熱可塑性フィルム)と、該支持フィルムに塗工されたソルダーレジスト層と、該ソルダーレジスト層を保護するカバーフィルム(例えば、ポリエチレンフィルム、ポリプロピレンフィルム)と、を有する積層構造となっている。支持フィルム上に本発明の感光性樹脂組成物を、ローラコート法、バーコータ法等の公知の方法で塗工して塗膜を形成後、該塗膜を乾燥処理することで、支持フィルム上にソルダーレジスト層を形成する。その後、形成したソルダーレジスト層上にカバーフィルムを積層することで、本発明の感光性樹脂組成物の塗膜を有するドライフィルムを作製できる。 The dry film includes a support film (for example, a thermoplastic film such as a polyethylene terephthalate film or a polyester film), a solder resist layer coated on the support film, and a cover film (for example, a polyethylene film) that protects the solder resist layer. , Polyester film), and has a laminated structure. The photosensitive resin composition of the present invention is applied onto the support film by a known method such as a roller coating method or a bar coater method to form a coating film, and then the coating film is dried to obtain the coating film on the support film. A solder resist layer is formed. Then, by laminating a cover film on the formed solder resist layer, a dry film having a coating film of the photosensitive resin composition of the present invention can be produced.
上記ドライフィルムのカバーフィルムを剥がしながらソルダーレジスト層とプリント配線板をはり合わせることで、プリント配線板上にソルダーレジスト膜を形成する。その後、必要に応じて、感光性樹脂組成物中の非反応性希釈剤(有機溶剤)を揮散させるために70〜120℃程度の温度で1〜20分間程度加熱する予備乾燥を行い、感光性樹脂組成物から非反応性希釈剤(有機溶剤)を揮発させてソルダーレジスト膜の表面をタックフリーの状態にする。形成したソルダーレジスト膜上に、回路パターンのランド以外を透光性にしたパターンを有するネガフィルムを密着させ、ネガフィルムの上から紫外線(例えば、波長300〜400nmの範囲)を照射させる。その後、前記ランドに対応する非露光領域を希アルカリ水溶液で除去することによりソルダーレジスト膜が現像される。現像方法には、スプレー法、シャワー法等が用いられ、使用される希アルカリ水溶液としては、例えば、0.5〜5質量%の炭酸ナトリウム水溶液が挙げられる。現像後、130〜170℃の熱風循環式の乾燥機等で20〜80分間ポストキュア(熱硬化処理)を行うことにより、プリント配線板上に、目的とするパターンを有するソルダーレジスト膜を形成させることができる。 A solder resist film is formed on the printed wiring board by sticking the solder resist layer and the printed wiring board together while peeling off the cover film of the dry film. Then, if necessary, pre-drying is performed by heating at a temperature of about 70 to 120 ° C. for about 1 to 20 minutes in order to volatilize the non-reactive diluent (organic solvent) in the photosensitive resin composition. The non-reactive diluent (organic solvent) is volatilized from the resin composition to make the surface of the solder resist film tack-free. A negative film having a translucent pattern other than the land of the circuit pattern is brought into close contact with the formed solder resist film, and ultraviolet rays (for example, a wavelength in the range of 300 to 400 nm) are irradiated from above the negative film. Then, the solder resist film is developed by removing the non-exposed region corresponding to the land with a dilute alkaline aqueous solution. A spray method, a shower method, or the like is used as the developing method, and examples of the dilute alkaline aqueous solution used include a 0.5 to 5% by mass sodium carbonate aqueous solution. After development, post-cure (thermosetting treatment) is performed for 20 to 80 minutes in a hot air circulation type dryer or the like at 130 to 170 ° C. to form a solder resist film having a desired pattern on the printed wiring board. be able to.
次に、本発明の感光性樹脂組成物の使用方法例として、感光性樹脂組成物をプリント配線板に塗工して絶縁保護膜(例えば、ソルダーレジスト膜)を形成する方法について説明する。上記のようにして得られた本発明の感光性樹脂組成物を、回路パターンを有するプリント配線板上に、スクリーン印刷法、スプレー塗工、バーコータ法、アプリケータ法、ブレードコータ法、ナイフコータ法、ロールコータ法、グラビアコータ法等、他の公知の塗工方法にて、所望の厚さで塗布して塗膜を形成する。次に、必要に応じて、非反応性希釈剤を揮散させるために、60〜100℃程度の温度で15〜60分間程度加熱する予備乾燥を行って、タックフリーの塗膜を形成する。次に、塗膜上に回路パターンのランド以外を透光性にしたパターンを有するネガフィルムを密着させ、ネガフィルムの上から紫外線(例えば、波長300〜400nmの範囲)を照射させて塗膜を光硬化させる。そして、前記ランドに対応する非露光領域を希アルカリ水溶液で除去することにより塗膜が現像される。現像方法には、スプレー法、シャワー法等が用いられ、使用する希アルカリ水溶液としては、例えば、0.5〜5質量%の炭酸ナトリウム水溶液が挙げられる。次いで、130〜170℃の熱風循環式の乾燥機等で20〜80分間ポストキュア(熱硬化処理)を行うことにより、プリント配線板上に目的とするソルダーレジスト膜を形成させることができる。 Next, as an example of how to use the photosensitive resin composition of the present invention, a method of applying the photosensitive resin composition to a printed wiring board to form an insulating protective film (for example, a solder resist film) will be described. The photosensitive resin composition of the present invention obtained as described above is applied onto a printed wiring board having a circuit pattern by a screen printing method, a spray coating method, a bar coater method, an applicator method, a blade coater method, a knife coater method, and the like. A coating film is formed by applying to a desired thickness by another known coating method such as a roll coater method or a gravure coater method. Next, if necessary, in order to volatilize the non-reactive diluent, pre-drying is performed by heating at a temperature of about 60 to 100 ° C. for about 15 to 60 minutes to form a tack-free coating film. Next, a negative film having a pattern other than the land of the circuit pattern is brought into close contact with the coating film, and ultraviolet rays (for example, a wavelength in the range of 300 to 400 nm) are irradiated from above the negative film to form the coating film. Light cure. Then, the coating film is developed by removing the non-exposed region corresponding to the land with a dilute alkaline aqueous solution. A spray method, a shower method, or the like is used as the developing method, and examples of the dilute alkaline aqueous solution used include a 0.5 to 5% by mass sodium carbonate aqueous solution. Next, a target solder resist film can be formed on the printed wiring board by performing post-cure (thermosetting treatment) for 20 to 80 minutes in a hot air circulation type dryer or the like at 130 to 170 ° C.
次に、本発明の実施例を説明するが、本発明はその趣旨を超えない限り、これらの例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.
実施例1〜9、比較例1〜3
下記表1に示す各成分を下記表1に示す配合割合にて配合し、3本ロールを用いて室温(25℃)にて混合分散させて、実施例1〜9、比較例1〜3にて使用する感光性樹脂組成物を調製した。下記表1に示す各成分の配合量は、特に断りのない限り質量部を示す。なお、下記表1中の配合量の空欄部は、配合なしを意味する。
Examples 1-9, Comparative Examples 1-3
Each component shown in Table 1 below was blended in the blending ratio shown in Table 1 below, mixed and dispersed at room temperature (25 ° C.) using three rolls, and in Examples 1 to 9 and Comparative Examples 1 to 3. A photosensitive resin composition to be used was prepared. Unless otherwise specified, the blending amount of each component shown in Table 1 below is shown in parts by mass. In addition, the blank part of the compounding amount in Table 1 below means that there is no compounding.
なお、下記表1中の各成分についての詳細は、以下の通りである。
(A)カルボキシル基含有感光性樹脂
・KAYARAD ZAR−2000:固形分(樹脂分)65質量%、日本化薬株式会社
KAYARAD ZAR−2000は、エポキシ樹脂(ビスフェノールA型エポキシ樹脂)のエポキシ基の少なくとも一部に、アクリル酸を反応させて、エポキシアクリレートを得、エポキシアクリレートの生成した水酸基に多塩基酸を反応させて得られる、多塩基酸変性エポキシアクリレート樹脂である。
(B)酸化防止剤
・SumilizerGP:式(1)化合物、住友化学株式会社
・Irganox1726:式(2)化合物、BASF社
・Irganox 1010:フェノール系酸化防止剤、BASF社
・Irgafos 168:リン系酸化防止剤、BASF社
(C)光重合開始剤
・NCI−831:オキシムエステル系光重合開始剤、ADEKA社
・OXE−02:オキシムエステル系光重合開始剤、BASF社
(D)反応性希釈剤
・EBERCRYL8405:ダイセル・サイテック株式会社
(E)エポキシ化合物
・EPICRON 850−S:DIC社
The details of each component in Table 1 below are as follows.
(A) Carboxyl group-containing photosensitive resin-KAYARAD ZAR-2000: Solid content (resin content) 65% by mass, Nippon Kayaku Co., Ltd. KAYARAD ZAR-2000 is at least the epoxy group of the epoxy resin (bisphenol A type epoxy resin). It is a polybasic acid-modified epoxy acrylate resin obtained by partially reacting an acrylic acid to obtain an epoxy acrylate and reacting a hydroxyl group produced by the epoxy acrylate with a polybasic acid.
(B) Antioxidant / SumiiserGP: Formula (1) Compound, Sumitomo Chemical Co., Ltd. / Irganox 1726: Formula (2) Compound, BASF / Irganox 1010: Phenol Antioxidant, BASF / Irgafos 168: Phosphorus Antioxidant Agent, BASF (C) Photopolymerization Initiator, NCI-831: Oxymester Photopolymerization Initiator, ADEKA, OXE-02: Oxymester Photopolymerization Initiator, BASF (D) Reactive Diluter, EBERCRYL8405 : Daicel Cytec Co., Ltd. (E) Epoxy compound, EPICRON 850-S: DIC
体質顔料
・ハイジライト H42M:昭和電工株式会社
難燃剤
・エクソリット OP−935:クラリアントジャパン社
硬化促進剤
・メラミン:日産化学工業株式会社
・DICY−7:三菱化学株式会社
添加剤
・X−50−1095C:消泡剤、信越化学工業株式会社
着色剤
・クロモフタルDPPオレンジTR:チバスペシャルティケミカルズ社
非反応性希釈剤
・EDGAC:三洋化成品株式会社
Constituent pigment, Heidilite H42M: Showa Denko Co., Ltd. Flame retardant, Exolit OP-935: Clariant Japan, Inc. Hardening accelerator, Melamine: Nissan Chemical Industries, Ltd., DICY-7: Mitsubishi Chemical Industries, Ltd. Additive, X-50-1095C : Defoamer, Shin-Etsu Chemical Co., Ltd. Colorant / Clariant DPP Orange TR: Ciba Specialty Chemicals Co., Ltd. Non-reactive diluent / EDGAC: Sanyo Kasei Co., Ltd.
試験体作製工程
調製した感光性樹脂組成物を用いて以下のように試験体を作製した。
基板:ガラスエポキシ基板、「FR4」、銅箔厚み25μm
基板表面処理:5質量%硫酸処理
塗工:スクリーン印刷
予備乾燥:BOX炉にて、80℃、20分
露光:直描露光機(Nuvogo 800、Orbotech社)を用いて、露光条件100〜300mJ/cm2にて露光処理
アルカリ現像:1質量%のNa2CO3水溶液、液温30℃、スプレー圧0.2MPa、現像時間60秒
ポストキュア(本硬化の加熱処理):150℃、60分
Specimen preparation process A test specimen was prepared as follows using the prepared photosensitive resin composition.
Substrate: Glass epoxy substrate, "FR4", copper foil thickness 25 μm
Substrate surface treatment: 5 mass% sulfuric acid treatment Coating: Screen printing Pre-drying: In a BOX furnace, exposure at 80 ° C. for 20 minutes: Using a direct drawing exposure machine (Nuvogo 800, Orbotech), exposure conditions 100 to 300 mJ / Exposure treatment at cm 2 Alkaline development: 1 mass% Na 2 CO 3 aqueous solution, liquid temperature 30 ° C., spray pressure 0.2 MPa, development time 60 seconds Post-cure (heat treatment for main curing): 150 ° C., 60 minutes
上記のようにして得られた試験体の光硬化膜の厚さは、20〜23μmであった。 The thickness of the photocurable film of the test piece obtained as described above was 20 to 23 μm.
評価項目
(1)感度
上記試験体作製工程にて、80℃、20分の予備乾燥を行った後の塗工基板について、感度測定用ステップタブレット(コダック社、21段)を設置し、ステップタブレットを通して100mJ/cm2露光したものをテストピ−スとした。露光後、1質量%のNa2CO3水溶液を用い、スプレー圧0.2MPa、現像時間60秒にて現像を行った後の露光部分の除去されない部分を、数字(ステップ数)で表した。ステップ数が大きいほど感光特性が良好であることを示す。
Evaluation items (1) Sensitivity A step tablet for sensitivity measurement (Kodak, 21 steps) was installed on the coated substrate after pre-drying at 80 ° C. for 20 minutes in the above test specimen manufacturing process, and the step tablet was installed. The test piece was exposed to 100 mJ / cm 2 through the test. After the exposure, the exposed portion was represented by a number (number of steps) after the development was carried out using a 1% by mass Na 2 CO 3 aqueous solution at a spray pressure of 0.2 MPa and a development time of 60 seconds. The larger the number of steps, the better the photosensitive characteristics.
(2)アルカリ現像性
試験体作製工程において、スクリーン印刷に代えてスプレー塗工法にて感光性樹脂組成物を塗布後、80℃にて、20分〜80分間、10分間隔で予備乾燥したものを試験体とした。予備乾燥炉から試験体を取り出し、上記試験体作製工程のアルカリ現像条件にて現像を行い、現像後の塗膜の除去状態を目視により観察し、塗膜が除去された試験体の最長の予備乾燥時間を計測した。
(2) Alkaline developability In the process of preparing a test piece, a photosensitive resin composition is applied by a spray coating method instead of screen printing, and then pre-dried at 80 ° C. for 20 to 80 minutes at 10-minute intervals. Was used as a test body. The test piece is taken out from the pre-drying furnace, developed under the alkaline development conditions of the test piece preparation process, and the state of removal of the coating film after development is visually observed, and the longest reserve of the test piece from which the coating film has been removed is observed. The drying time was measured.
(3)金めっき性
市販(奥野製薬工業株式会社)の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル0.5μm、金0.03μmの条件でめっきを行った。金めっきの状態を目視にて観察し、金めっき性を以下の4段階で評価した。
○:金めっき表面に異常なし。
△:若干金めっきムラあり。
×:全体的に金めっきムラあり。
××:金めっき未着発生
(3) Gold Plating Using a commercially available electroless nickel plating bath and an electroless gold plating bath (Okuno Pharmaceutical Co., Ltd.), plating was performed under the conditions of nickel 0.5 μm and gold 0.03 μm. The state of gold plating was visually observed, and the gold plating property was evaluated in the following four stages.
◯: No abnormality on the gold-plated surface.
Δ: There is some uneven gold plating.
×: There is uneven gold plating on the whole.
XX: Gold plating has not arrived
上記評価の結果を下記表1に示す。 The results of the above evaluation are shown in Table 1 below.
上記表1に示すように、酸化防止剤として、(B1)成分であるフェノール性水酸基とリンとを有する化合物または(B2)成分であるフェノール性水酸基と硫黄とを有する化合物を配合した実施例1〜9では、優れた感度を有しつつ、アルカリ現像性と金めっき性に優れた光硬化物を得ることができた。なお、実施例4、7から、フェノール系酸化防止剤を併用しても、優れた感度を有しつつ、アルカリ現像性と金めっき性に優れた光硬化物を得ることができた。特に、実施例1〜4、8と実施例5〜7、9の比較から、(B1)成分であるフェノール性水酸基とリンとを有する化合物は(B2)成分であるフェノール性水酸基と硫黄とを有する化合物と比較して、予備乾燥時間を長くしても塗膜の除去が可能であり、アルカリ現像性がさらに向上した。 As shown in Table 1 above, Example 1 in which a compound having a phenolic hydroxyl group and phosphorus as a component (B1) or a compound having a phenolic hydroxyl group and sulfur as a component (B2) was blended as an antioxidant. In Nos. 9 to 9, a photocurable product having excellent alkali developability and gold plating property could be obtained while having excellent sensitivity. From Examples 4 and 7, even when a phenolic antioxidant was used in combination, a photocurable product having excellent sensitivity and excellent alkali developability and gold plating property could be obtained. In particular, from the comparison between Examples 1 to 4 and 8 and Examples 5 to 7 and 9, the compound having the phenolic hydroxyl group and phosphorus as the component (B1) contains the phenolic hydroxyl group and sulfur as the component (B2). Compared with the compound having, the coating film can be removed even if the pre-drying time is lengthened, and the alkali developability is further improved.
また、カルボキシル基含有感光性樹脂100質量部に対して、(B1)フェノール性水酸基とリンとを有する化合物を約2質量部配合した実施例2は、(B1)フェノール性水酸基とリンとを有する化合物を約5質量部配合した実施例1、(B1)フェノール性水酸基とリンとを有する化合物を約10質量部配合した実施例8と比較して、感度がさらに向上した。また、カルボキシル基含有感光性樹脂100質量部に対して、(B1)フェノール性水酸基とリンとを有する化合物を約2質量部配合した実施例2は、(B1)フェノール性水酸基とリンとを有する化合物を約1質量部配合した実施例4と比較して、300mJ/cm2での金めっき性がさらに向上した。 Further, Example 2 in which about 2 parts by mass of a compound having (B1) phenolic hydroxyl group and phosphorus is blended with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin has (B1) phenolic hydroxyl group and phosphorus. The sensitivity was further improved as compared with Example 1 in which about 5 parts by mass of the compound was blended, and Example 8 in which about 10 parts by mass of the compound having (B1) phenolic hydroxyl group and phosphorus was blended. Further, Example 2 in which about 2 parts by mass of a compound having (B1) phenolic hydroxyl group and phosphorus is blended with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin has (B1) phenolic hydroxyl group and phosphorus. Compared with Example 4 in which about 1 part by mass of the compound was blended, the gold plating property at 300 mJ / cm 2 was further improved.
また、カルボキシル基含有感光性樹脂100質量部に対して、(B2)フェノール性水酸基と硫黄とを有する化合物を約1質量部配合した実施例5は、(B2)フェノール性水酸基と硫黄とを有する化合物を約2質量部配合した実施例9と比較して、アルカリ現像性がさらに向上した。また、カルボキシル基含有感光性樹脂100質量部に対して、(B2)フェノール性水酸基と硫黄とを有する化合物を約1質量部配合した実施例5は、(B2)フェノール性水酸基と硫黄とを有する化合物を約0.5質量部配合した実施例6と比較して、300mJ/cm2での金めっき性がさらに向上した。 Further, Example 5 in which about 1 part by mass of a compound having (B2) phenolic hydroxyl group and sulfur is blended with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin has (B2) phenolic hydroxyl group and sulfur. Compared with Example 9 in which about 2 parts by mass of the compound was blended, the alkali developability was further improved. Further, Example 5 in which about 1 part by mass of a compound having (B2) phenolic hydroxyl group and sulfur is blended with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin has (B2) phenolic hydroxyl group and sulfur. Compared with Example 6 in which about 0.5 parts by mass of the compound was blended, the gold plating property at 300 mJ / cm 2 was further improved.
一方で、酸化防止剤を配合しなかった比較例1では金めっき性が得られず、酸化防止剤としてフェノール系酸化防止剤を使用した比較例2、リン系酸化防止剤を使用した比較例3では、200mJ/cm2、300mJ/cm2での金めっき性が得られなかった。 On the other hand, in Comparative Example 1 in which no antioxidant was blended, gold plating property was not obtained, and Comparative Example 2 in which a phenolic antioxidant was used as an antioxidant and Comparative Example 3 in which a phosphorus-based antioxidant was used. Then, the gold plating property at 200 mJ / cm 2 and 300 mJ / cm 2 could not be obtained.
本発明の感光性樹脂組成物は、紫外線に対する高い感度を損なうことなく、アルカリ現像性、金めっき性等のめっき性に優れた光硬化膜を形成できるので、プリント配線板に形成するソルダーレジスト等の保護膜の分野、特に、高感度化された感光性樹脂組成物にてソルダーレジスト等の保護膜を形成する分野で利用価値が高い。
Since the photosensitive resin composition of the present invention can form a photocurable film having excellent plating properties such as alkali developability and gold plating property without impairing high sensitivity to ultraviolet rays, a solder resist or the like formed on a printed wiring board or the like can be formed. It is highly useful in the field of protective film, particularly in the field of forming a protective film such as solder resist with a highly sensitive photosensitive resin composition.
Claims (11)
前記(B)酸化防止剤が、(B1)フェノール性水酸基とリンとを有する化合物及び(B2)フェノール性水酸基と硫黄とを有する化合物からなる群から選択された少なくとも1種の化合物を含有する感光性樹脂組成物。 A photosensitive resin containing (A) a carboxyl group-containing photosensitive resin, (B) an antioxidant, (C) a photopolymerization initiator, (D) a reactive diluent, and (E) an epoxy compound. It ’s a composition,
The (B) antioxidant contains at least one compound selected from the group consisting of (B1) a compound having a phenolic hydroxyl group and phosphorus and (B2) a compound having a phenolic hydroxyl group and sulfur. Sex resin composition.
A printed wiring board having a photocurable product of the photosensitive resin composition according to any one of claims 1 to 8.
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JP2019165371A JP6986534B2 (en) | 2019-09-11 | 2019-09-11 | A printed wiring board having a photosensitive resin composition, a dry film having a photosensitive resin composition, and a photocured product of the photosensitive resin composition. |
KR1020200108473A KR20210031374A (en) | 2019-09-11 | 2020-08-27 | A photosensitive resin composition, dry films comprising the composition, and a printed circuit board comprising a product produced by photo-cure of the composition |
TW109131053A TW202121055A (en) | 2019-09-11 | 2020-09-10 | Photosensitive resin composition, dried film including the same and printed circuit board including photocurable film having the same including a photosensitive resin containing a carboxyl group, an antioxidant, a photopolymerization initiator, a reactive diluent and an epoxy compound |
CN202010956244.2A CN112485968A (en) | 2019-09-11 | 2020-09-11 | Photosensitive resin composition, dry film, and printed wiring board having photo-cured product of photosensitive resin composition |
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