JP2008299293A - Photosensitive resin composition and flexible wiring board obtained using the same - Google Patents
Photosensitive resin composition and flexible wiring board obtained using the same Download PDFInfo
- Publication number
- JP2008299293A JP2008299293A JP2007148647A JP2007148647A JP2008299293A JP 2008299293 A JP2008299293 A JP 2008299293A JP 2007148647 A JP2007148647 A JP 2007148647A JP 2007148647 A JP2007148647 A JP 2007148647A JP 2008299293 A JP2008299293 A JP 2008299293A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- resin composition
- photosensitive resin
- photopolymerization initiator
- 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
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 80
- -1 oxime ester Chemical class 0.000 claims abstract description 72
- 239000003999 initiator Substances 0.000 claims abstract description 51
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002923 oximes Chemical class 0.000 claims abstract description 9
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 7
- 239000004305 biphenyl Substances 0.000 claims abstract description 7
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- 239000003822 epoxy resin Substances 0.000 claims description 54
- 229920000647 polyepoxide Polymers 0.000 claims description 54
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 21
- 229910000679 solder Inorganic materials 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000002252 acyl group Chemical group 0.000 claims description 11
- 239000003063 flame retardant Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 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 claims description 10
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000005011 alkyl ether group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 125000006678 phenoxycarbonyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 63
- 150000001875 compounds Chemical class 0.000 description 34
- 239000000126 substance Substances 0.000 description 26
- 239000000758 substrate Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 13
- 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 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000013039 cover film Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical group S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 150000004294 cyclic thioethers Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000004292 cyclic ethers Chemical group 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003553 thiiranes Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HHOJVZAEHZGDRB-UHFFFAOYSA-N 2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=NC(N)=NC(N)=N1 HHOJVZAEHZGDRB-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 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
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- 239000002585 base Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 230000001851 biosynthetic effect Effects 0.000 description 2
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000019000 fluorine Nutrition 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 150000002921 oxetanes Chemical class 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- RSHKWPIEJYAPCL-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(CC)COC1 RSHKWPIEJYAPCL-UHFFFAOYSA-N 0.000 description 1
- 0 *P1(Oc(cccc2)c2-c2c1cccc2)=O Chemical compound *P1(Oc(cccc2)c2-c2c1cccc2)=O 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
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-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
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 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
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- DYJPQQUZBUUKAH-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethoxymethoxymethyl]oxetane Chemical compound C1OCC1(CC)COCOCOCC1(CC)COC1 DYJPQQUZBUUKAH-UHFFFAOYSA-N 0.000 description 1
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- AOXLOPQXIGICOF-UHFFFAOYSA-N 3-methyl-3-[(3-methyloxetan-3-yl)methoxymethoxymethoxymethyl]oxetane Chemical compound C1OCC1(C)COCOCOCC1(C)COC1 AOXLOPQXIGICOF-UHFFFAOYSA-N 0.000 description 1
- UVJGOUQARONWII-UHFFFAOYSA-N 3-methyl-3-[[4-[(3-methyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(C)COC2)C=CC=1COCC1(C)COC1 UVJGOUQARONWII-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UDGNCGOMVIKQOW-UHFFFAOYSA-N 4-[(dimethylamino)methyl]-n,n-dimethylaniline Chemical compound CN(C)CC1=CC=C(N(C)C)C=C1 UDGNCGOMVIKQOW-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical compound N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- ZCEYMOIPAHPDOR-UHFFFAOYSA-N 7-(diethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21.CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 ZCEYMOIPAHPDOR-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UAKWLVYMKBWHMX-UHFFFAOYSA-N SU4312 Chemical compound C1=CC(N(C)C)=CC=C1C=C1C2=CC=CC=C2NC1=O UAKWLVYMKBWHMX-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- VMKBJESZDNXQHG-UHFFFAOYSA-N [(9-oxothioxanthen-2-yl)methylideneamino] acetate Chemical compound C1=CC=C2C(=O)C3=CC(C=NOC(=O)C)=CC=C3SC2=C1 VMKBJESZDNXQHG-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- HXTBYXIZCDULQI-UHFFFAOYSA-N bis[4-(methylamino)phenyl]methanone Chemical compound C1=CC(NC)=CC=C1C(=O)C1=CC=C(NC)C=C1 HXTBYXIZCDULQI-UHFFFAOYSA-N 0.000 description 1
- DDPMGIMJSRUULN-UHFFFAOYSA-N buphedrone Chemical compound CCC(NC)C(=O)C1=CC=CC=C1 DDPMGIMJSRUULN-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- JAOPKYRWYXCGOQ-UHFFFAOYSA-N n,n-dimethyl-1-(4-methylphenyl)methanamine Chemical compound CN(C)CC1=CC=C(C)C=C1 JAOPKYRWYXCGOQ-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- WZESLRDFSNLECD-UHFFFAOYSA-N phenyl prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1 WZESLRDFSNLECD-UHFFFAOYSA-N 0.000 description 1
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-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
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- 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
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、希アルカリ水溶液により現像可能な感光性樹脂組成物、その硬化物及びそれを用いて得られるレジストパターンを有するフレキシブル配線板に関する。 The present invention relates to a photosensitive resin composition that can be developed with a dilute alkaline aqueous solution, a cured product thereof, and a flexible wiring board having a resist pattern obtained using the same.
従来、フレキシブル配線板（ＦＰＣ）は、カバーレイといわれるポリイミドフィルムに接着剤を塗布した絶縁フィルムをプレス打ち抜き加工してラミネートし、さらにプレスで加圧条件下熱硬化することにより、回路形成されたフレキシブル基板の表面のカバー層としていた。このカバーレイはポリイミドフィルムをベースに低収縮熱硬化性樹脂で構成されていることから、ラミネート後及びプレス硬化後の反りは非常に小さく、さらにはその後の補強板の貼り付け、熱硬化後や実装のリフロー時の反りも非常に少なくすることができ、ＦＰＣ用途に大量に使用されている。 Conventionally, a flexible printed circuit board (FPC) has been formed into a circuit by press punching and laminating an insulating film obtained by applying an adhesive to a polyimide film called a coverlay, and further thermosetting under pressure under a press. It was a cover layer on the surface of the flexible substrate. Since this cover lay is composed of a low shrinkage thermosetting resin based on a polyimide film, the warpage after lamination and press curing is very small. The warpage during the reflow of the mounting can be extremely reduced, and it is used in a large amount for FPC applications.
しかしながら、プレスにて打ち抜き加工するために、微細な加工が困難であり、かつ、回路形成された配線板とのラミネートの際に位置合せ精度がよくないという欠点がある。
それに対し、感光性カバーレイとしてアルカリ現像性感光性樹脂組成物やそのドライフィルムが提案されている（特許文献１参照）。
However, since punching is performed with a press, fine processing is difficult, and there is a disadvantage that alignment accuracy is not good when laminating with a circuit board on which a circuit is formed.
On the other hand, an alkali-developable photosensitive resin composition and its dry film have been proposed as a photosensitive coverlay (see Patent Document 1).
一方、ＦＰＣは電子機器に搭載されるため難燃性の要求があり、このＦＰＣ用途のソルダーレジストにも要求されている。ＦＰＣは、通常、ポリイミド基板であり、ガラスエポキシ基板のプリント配線板とは異なり、薄膜である。しかしながら、塗布されるべきソルダーレジストは、プリント配線板もＦＰＣも同じ膜厚であるため、相対的にソルダーレジストへの難燃化の負担が大きくなる。これに対してハロゲン化芳香環と重合可能な不飽和二重結合を有する化合物を有するＦＰＣ用ソルダーレジストの組成が提案されているが（特許文献２参照）、ハロゲン化合物の使用は環境負荷の観点から好ましくない。
本発明は、前記したような従来技術の問題を解消すべくなされたものであり、その主たる目的は、ノンハロゲン組成で環境負荷が少なく、しかも十分な難燃性を発揮すると共に、その硬化物は可撓性に優れるＦＰＣ用の感光性樹脂組成物を提供することにある。
さらに本発明の目的は、このような感光性樹脂組成物を用いることによって得られる、難燃性や可撓性に優れる硬化物及びレジストパターンを有するフレキシブル配線板を提供することにある。
The present invention has been made to solve the problems of the prior art as described above, and its main purpose is to have a non-halogen composition with a low environmental load and exhibit sufficient flame retardancy, and its cured product is It is providing the photosensitive resin composition for FPC which is excellent in flexibility.
Furthermore, the objective of this invention is providing the flexible wiring board which has a hardened | cured material excellent in a flame retardance and flexibility obtained by using such a photosensitive resin composition, and a resist pattern.
前記目的を達成するために、本発明によれば、（Ａ）カルボキシル基含有樹脂、（Ｂ）リン元素含有アクリレート、（Ｃ）光重合開始剤を含有することを特徴とする感光性樹脂組成物が提供される。 In order to achieve the above object, according to the present invention, a photosensitive resin composition comprising (A) a carboxyl group-containing resin, (B) a phosphorus element-containing acrylate, and (C) a photopolymerization initiator. Is provided.
好適な態様においては、前記光重合開始剤（Ｃ）は、オキシム系光重合開始剤（Ｃ’）、特に後述する一般式（II）で表されるオキシムエステル系光重合開始剤（Ｃ１）、又は、該オキシムエステル系光重合開始剤（Ｃ１）と、後述する一般式（III）で表されるアミノアセトフェノン系光重合開始剤（Ｃ２）及び／又は下記一般式（IV）で表されるアシルホスフィンオキサイド系光重合開始剤（Ｃ３）との混合物であることが好ましい。 In a preferred embodiment, the photopolymerization initiator (C) is an oxime photopolymerization initiator (C ′), particularly an oxime ester photopolymerization initiator (C1) represented by the general formula (II) described later, Alternatively, the oxime ester photopolymerization initiator (C1), an aminoacetophenone photopolymerization initiator (C2) represented by the following general formula (III) and / or an acyl represented by the following general formula (IV) A mixture with a phosphine oxide photopolymerization initiator (C3) is preferred.
また、他の好適な態様においては、前記カルボキシル基含有樹脂（Ａ）は、ビスフェノールＡ骨格、ビスフェノールＦ骨格、ビフェニル骨格、ビキシレノール骨格もしくはその水添骨格である構造を有する樹脂であることが好ましく、特にウレタン構造を有する樹脂であることが好ましい。
また、前記カルボキシル基含有樹脂（Ａ）は、２個以上のラジカル重合性不飽和二重結合を有する樹脂であることが好ましい。
In another preferred embodiment, the carboxyl group-containing resin (A) is preferably a resin having a structure that is a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, a bixylenol skeleton, or a hydrogenated skeleton thereof. In particular, a resin having a urethane structure is preferable.
The carboxyl group-containing resin (A) is preferably a resin having two or more radically polymerizable unsaturated double bonds.
さらに他の好適な態様においては、前記リン元素含有アクリレート（Ｂ）は、後述する一般式（Ｉ）で示される誘導体であることが好ましい。
さらに（Ｄ）熱硬化成分を含有することが好ましく、それによって諸特性に優れたソルダーレジストを形成することができる。上記熱硬化成分（Ｄ）は、エポキシ樹脂であることが好ましい。
In still another preferred embodiment, the phosphorus element-containing acrylate (B) is preferably a derivative represented by the following general formula (I).
Furthermore, it is preferable to contain (D) a thermosetting component, whereby a solder resist having excellent characteristics can be formed. The thermosetting component (D) is preferably an epoxy resin.
さらに好適な態様においては、有機リン系難燃剤（Ｅ）を含有する。それにより、難燃性をさらに向上させることができる。
上記有機リン系難燃剤（Ｅ）が、エポキシ樹脂と反応可能な反応性基を有する有機リン系難燃剤であることが好ましい。
In a more preferred embodiment, an organic phosphorus flame retardant (E) is contained. Thereby, a flame retardance can be improved further.
The organophosphorus flame retardant (E) is preferably an organophosphorus flame retardant having a reactive group capable of reacting with an epoxy resin.
さらに本発明によれば、前記感光性樹脂組成物を、キャリアフィルムに塗布・乾燥して得られる感光性ドライフィルムが提供される。
さらに本発明の別の態様によれば、前記感光性樹脂組成物又は前記感光性ドライフィルムを、銅上にて光硬化して得られる硬化物、あるいはさらに、前記感光性樹脂組成物又は前記感光性ドライフィルムを、光硬化して得られるレジストパターンを有するフレキシブル配線板が提供される。特に好適には、前記感光性樹脂組成物又は前記感光性ドライフィルムはフレキシブル配線板用ソルダーレジストである。
Furthermore, according to this invention, the photosensitive dry film obtained by apply | coating and drying the said photosensitive resin composition to a carrier film is provided.
Furthermore, according to another aspect of the present invention, a cured product obtained by photocuring the photosensitive resin composition or the photosensitive dry film on copper, or further, the photosensitive resin composition or the photosensitive resin. A flexible wiring board having a resist pattern obtained by photocuring a conductive dry film is provided. Particularly preferably, the photosensitive resin composition or the photosensitive dry film is a solder resist for flexible wiring boards.
本発明の感光性樹脂組成物は、カルボキシル基含有樹脂（Ａ）及び（Ｃ）光重合開始剤、特にオキシム系光重合開始剤、さらには熱硬化成分（Ｄ）と共に、リン元素含有アクリレート（Ｂ）を用いているため、ノンハロゲン組成で環境負荷が少なく、しかも十分な難燃性を発揮すると共に、その硬化物は可撓性に優れている。従って、ＦＰＣ用の感光性樹脂組成物として最適である。 The photosensitive resin composition of the present invention comprises a carboxyl group-containing resin (A) and a photopolymerization initiator (C), particularly an oxime photopolymerization initiator, and further a phosphorus element-containing acrylate (B) together with a thermosetting component (D). ), It has a non-halogen composition, has a low environmental impact, exhibits sufficient flame retardancy, and its cured product has excellent flexibility. Therefore, it is optimal as a photosensitive resin composition for FPC.
本発明者らは、カルボキシル基含有樹脂（Ａ）及び（Ｃ）光重合開始剤、特にオキシム系光重合開始剤、さらには熱硬化成分（Ｄ）と共に、リン元素含有アクリレート（Ｂ）、特に後述する一般式（Ｉ）で示されるリン元素含有アクリレートを用いた場合、ノンハロゲン組成で環境負荷が少なく、しかも十分な難燃性を発揮すると共に、可撓性に優れる硬化物が得られることを見出し、本発明を完成するに至ったものである。
以下、本発明の感光性樹脂組成物の各構成成分について詳しく説明する。
The present inventors, together with carboxyl group-containing resins (A) and (C) photopolymerization initiators, particularly oxime photopolymerization initiators, and thermosetting components (D), phosphorus element-containing acrylates (B), particularly those described later. It has been found that when a phosphorus element-containing acrylate represented by the general formula (I) is used, a cured product having a non-halogen composition with low environmental impact, sufficient flame retardancy, and excellent flexibility can be obtained. The present invention has been completed.
Hereinafter, each structural component of the photosensitive resin composition of this invention is demonstrated in detail.
まず、本発明の感光性樹脂組成物に含まれるカルボキシル基含有樹脂（Ａ）としては、分子中にカルボキシル基を有している従来公知の各種樹脂化合物が使用できる。特に、分子中にエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂（Ａ’）が、光硬化性や耐現像性の面からより好ましい。そして、その不飽和二重結合は、アクリル酸もしくはメタアクリル酸又はそれらの誘導体由来のものが好ましい。 First, as the carboxyl group-containing resin (A) contained in the photosensitive resin composition of the present invention, various conventionally known resin compounds having a carboxyl group in the molecule can be used. In particular, a carboxyl group-containing photosensitive resin (A ′) having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
カルボキシル基含有樹脂（Ａ）の具体例としては、以下に列挙するような化合物が好ましい。
（１）（メタ）アクリル酸と不飽和基含有物との共重合により得られるカルボキシル基含有樹脂。
（２）ジイソシアネートとカルボキシル基含有ジアルコール化合物及びジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂。
（３）ジイソシアネートと２官能エポキシ（メタ）アクリレートもしくはその部分酸無水物変性物及びカルボキシル基含有ジアルコール化合物及びジオール化合物の重付加反応による感光性のカルボキシル基含有ウレタン樹脂。
（４）前記（２）又は（３）の樹脂の合成中に分子内に１つの水酸基と１つ以上の（メタ）アクリル基を有する化合物を加え、末端（メタ）アクリル化したカルボキシル基含有ウレタン樹脂。
（５）前記（２）又は（３）の樹脂の合成中に分子内に１つのイソシアネート基と１つ以上の（メタ）アクリル基を有する化合物を加え、末端（メタ）アクリル化したカルボキシル基含有ウレタン樹脂。
（６）多官能（固形）エポキシ樹脂に（メタ）アクリル酸を反応させ、側鎖に存在する水酸基に２塩基酸無水物を付加させた感光性のカルボキシル基含有樹脂。
（７）２官能（固形）エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に（メタ）アクリル酸を反応させ、生じた水酸基に２塩基酸無水物を付加させた感光性のカルボキシル基含有樹脂。
（８）２官能オキセタン樹脂にジカルボン酸を反応させ、生じた１級の水酸基に２塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。
（９）上記樹脂にさらに１分子内に１つのエポキシ基と１つ以上の（メタ）アクリル基を有する化合物を付加してなる感光性のカルボキシル基含有樹脂。
As specific examples of the carboxyl group-containing resin (A), the following compounds are preferable.
(1) A carboxyl group-containing resin obtained by copolymerization of (meth) acrylic acid and an unsaturated group-containing material.
(2) A carboxyl group-containing urethane resin by a polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound.
(3) Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of diisocyanate and bifunctional epoxy (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound.
(4) A carboxyl group-containing urethane obtained by adding a compound having one hydroxyl group and one or more (meth) acrylic groups in the molecule during the synthesis of the resin of (2) or (3) above, and terminally (meth) acrylated resin.
(5) A carboxyl group containing a terminal (meth) acrylated compound by adding a compound having one isocyanate group and one or more (meth) acrylic groups in the molecule during the synthesis of the resin of (2) or (3). Urethane resin.
(6) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain.
(7) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Carboxyl group-containing resin.
(8) A carboxyl group-containing polyester resin obtained by reacting a difunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
(9) A photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resin.
これらカルボキシル基含有樹脂の中でも好ましいものは、（Ｘ）前記（２）〜（５）の樹脂の合成に用いられるイソシアネート基を有する化合物（ジイソシアネートも含む）が、直接ベンゼン環に結合していないジイソシアネートの場合、及び（Ｙ）前記（６）、（７）の樹脂の合成に用いられる多官能及び２官能エポキシ樹脂がビスフェノールＡ構造、ビスフェノールＦ構造、ビフェニル構造、ビキシレノール構造を有する化合物及びその水添化合物の場合が可撓性等の点で好ましい。また、別の側面では、前記（２）、（３）、（４）、（５）の樹脂及びそれらの前記（９）の如き変性物は、主鎖にウレタン結合を有しており、反りに対して好ましい。特に、ビフェニル構造の多官能エポキシ樹脂を用いた場合、難燃性を向上できるので最適である。また、前記（１）、（２）、（８）以外の樹脂は分子内に感光性基を有しているため好ましい。
なお、本明細書において、（メタ）アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称する用語で、他の類似の表現についても同様である。
Among these carboxyl group-containing resins, preferred are (X) diisocyanates in which the isocyanate group-containing compounds (including diisocyanates) used in the synthesis of the resins of (2) to (5) are not directly bonded to the benzene ring. And (Y) a compound having a bisphenol A structure, a bisphenol F structure, a biphenyl structure, or a bixylenol structure as a polyfunctional or bifunctional epoxy resin used in the synthesis of the resins of the above (6) and (7) and water thereof An additive compound is preferred in terms of flexibility. In another aspect, the resins (2), (3), (4), (5) and the modified products thereof (9) have a urethane bond in the main chain and warp. Is preferable. In particular, when a polyfunctional epoxy resin having a biphenyl structure is used, the flame retardancy can be improved, which is optimal. In addition, the resins other than (1), (2), and (8) are preferable because they have a photosensitive group in the molecule.
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
上記のようなカルボキシル基含有樹脂（Ａ）は、バックボーン・ポリマーの側鎖に多数の遊離のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。
また、上記カルボキシル基含有樹脂（Ａ）の酸価は、４０〜２００ｍｇＫＯＨ／ｇの範囲であり、より好ましくは４５〜１２０ｍｇＫＯＨ／ｇの範囲である。カルボキシル基含有樹脂の酸価が４０ｍｇＫＯＨ／ｇ未満であるとアルカリ現像が困難となり、一方、２００ｍｇＫＯＨ／ｇを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。
Since the carboxyl group-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
Moreover, the acid value of the said carboxyl group-containing resin (A) is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
また、上記カルボキシル基含有樹脂（Ａ）の重量平均分子量は、樹脂骨格により異なるが、一般的に２，０００〜１５０，０００、さらには５，０００〜１００，０００の範囲にあるものが好ましい。重量平均分子量が２，０００未満であると、タックフリー性能が劣ることがあり、露光後の塗膜の耐湿性が悪く現像時に膜減りが生じ、解像度が大きく劣ることがある。一方、重量平均分子量が１５０，０００を超えると、現像性が著しく悪くなることがあり、貯蔵安定性が劣ることがある。 Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeleton, generally what is in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, and the film may be reduced during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
このようなカルボキシル基含有樹脂（Ａ）の配合量は、全組成物中に、２０〜６０質量％、好ましくは３０〜５０質量％である。上記範囲より少ない場合、塗膜強度が低下したりするので好ましくない。一方、上記範囲より多い場合、粘性が高くなったり、塗布性等が低下するので好ましくない。 The compounding quantity of such carboxyl group-containing resin (A) is 20-60 mass% in all the compositions, Preferably it is 30-50 mass%. When the amount is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity becomes high and the coating property and the like deteriorate, which is not preferable.
前記リン元素含有アクリレート（Ｂ）は、リン元素を有しており分子内に２個以上の（メタ）アクリレートを含む化合物が良く、具体的には下記一般式（Ｉ）で表されるリン元素含有アクリレートが好ましい。
これらリン元素含有アクリレートは、一般に９，１０−ジヒドロー９−オキサ−１０−フォスファフェナンスレン−１０−オキサイドと慣用公知の多官能アクリレートとのマイケル付加反応により合成することができる。そして、これらは組成物中のリン濃度が２％以上となるとき充分な効力を発揮するが、あまり多くするとはんだ耐熱性が劣るので、多くすることが出来ない。また、アクリレートとしては、反応性が悪いものを使用したり、添加量が少ないと、後で述べるオキシム系光重合開始剤を含むときにのみ充分な硬化性があり、それ以外の光重合開始剤では充分に使用することが難しい。よって、その硬化性を挙げる目的で、従来公知の（メタ）アクリレートモノマーを加えることができる。
リン元素含有アクリレート（Ｂ）の添加量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、１０質量部以上、１００質量部以下が望ましく、好ましくは２０質量部以上、８０質量部以下の割合である。
These phosphorus element-containing acrylates can be generally synthesized by a Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a conventionally known polyfunctional acrylate. And these show sufficient effect when the phosphorus concentration in the composition is 2% or more, but if the amount is too large, the solder heat resistance is inferior, so that it cannot be increased. In addition, as the acrylate, those having poor reactivity or a small addition amount have sufficient curability only when an oxime photopolymerization initiator described later is included, and other photopolymerization initiators. Then it is difficult to use enough. Therefore, conventionally known (meth) acrylate monomers can be added for the purpose of increasing the curability.
The addition amount of the phosphorus element-containing acrylate (B) is desirably 10 parts by mass or more and 100 parts by mass or less, preferably 20 parts by mass or more and 80 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (A). Is the ratio.
前記リン元素含有アクリレート（Ｂ）の合成に用いられ、あるいは添加されるアクリレートモノマーとしては、従来公知の各種アクリレートモノマーを用いることができ、特定のものに限定されないが、例えば、エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類；ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレートなどの多価アルコール又はこれらのエチレオキサイド付加物、プロピレンオキサイド付加物もしくはカプロラクトン付加物などの多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート、及びこれらのフェノール類のエチレンオキサイド付加物もしくはプロピレンオキサイド付加物などの多価アクリレート類；及び上記ポリアルコール類のウレタンアクリレート類、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類；及びメラミンアクリレート、及び／又は上記アクリレートに対応する各メタクリレート類などが挙げられる。 As the acrylate monomer used for or added to the synthesis of the phosphorus element-containing acrylate (B), various conventionally known acrylate monomers can be used and are not limited to specific ones. For example, ethylene glycol, methoxytetra Diacrylates of glycols such as ethylene glycol, polyethylene glycol, propylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene Polyvalent acrylates such as oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and their phenols Polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts; and urethane acrylates of the above polyalcohols, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Examples thereof include polyvalent acrylates of glycidyl ether; and melamine acrylate and / or methacrylates corresponding to the acrylate.
さらに、クレゾールノボラック型エポキシ樹脂などの多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレートなどのヒドロキシアクリレートとイソホロンジイソシアネートなどのジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物などが、挙げられる。このようなエポキシアクリレート系樹脂は、指触乾燥性を低下させることなく、光硬化性を向上させることができる Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
前記光重合開始剤（Ｃ）としては、下記一般式（II）で表される基を有するオキシムエステル系光重合開始剤（Ｃ１）、下記一般式（III）で表される基を有するα−アミノアセトフェノン系光重合開始剤（Ｃ２）、及び下記式（IV）で表される基を有するアシルホスフィンオキサイド系光重合開始剤（Ｃ３）からなる群から選択される１種以上の光重合開始剤を使用することが好ましい。特に、オキシムエステル系光重合開始剤（Ｃ１）、又は、該オキシムエステル系光重合開始剤（Ｃ１）と、α−アミノアセトフェノン系光重合開始剤（Ｃ２）及び／又はアシルホスフィンオキサイド系光重合開始剤（Ｃ３）との混合物が好ましい。
Ｒ３は、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ４及びＲ５は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ６及びＲ７は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、
Ｒ８及びＲ９は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、炭素数１〜１０の直鎖状又は分岐状のアルコキシ基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基若しくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ８及びＲ９の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい）。
As said photoinitiator (C), the oxime ester type photoinitiator (C1) which has group represented by the following general formula (II), and alpha- which has group represented by the following general formula (III) One or more photopolymerization initiators selected from the group consisting of an aminoacetophenone photopolymerization initiator (C2) and an acylphosphine oxide photopolymerization initiator (C3) having a group represented by the following formula (IV) Is preferably used. In particular, the oxime ester photopolymerization initiator (C1), or the oxime ester photopolymerization initiator (C1), the α-aminoacetophenone photopolymerization initiator (C2) and / or the acylphosphine oxide photopolymerization start. A mixture with the agent (C3) is preferred.
R 3 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R 4 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R 8 and R 9 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, aryl Group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that one of R 8 and R 9 is an R—C (═O) — group (where R is a carbon number of 1 to 20 hydrocarbon groups).
前記一般式（II）で表される基を有するオキシムエステル系光重合開始剤（Ｃ１）としては、好ましくは、下記式（Ｖ）で表される２−（アセチルオキシイミノメチル）チオキサンテン−９−オンや、下記一般式（VI）及び（VII）で表される化合物が挙げられる。
Ｒ１1、Ｒ１3は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ１2は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表す。）
R 11 and R 13 are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R 12 is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted). )
Ｒ１6、Ｒ１7、Ｒ18及びＲ19は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、及び
ｎは０〜５の整数を表す）
R 16 , R 17 , R 18 and R 19 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 5)
前記したオキシムエステル系光重合開始剤（Ｃ１）中でも、下記式（Ｖ）で表される２−（アセチルオキシイミノメチル）チオキサンテン−９−オン、及び式（VI）で表される化合物がより好ましい。市販品としては、チバ・スペシャルティ・ケミカルズ社製のＣＧＩ−３２５、イルガキュアー ＯＸＥ０１、イルガキュアー ＯＸＥ０２等が挙げられる。これらのオキシムエステル系光重合開始剤は、単独で又は２種以上を組み合わせて用いることができる。 Among the oxime ester photopolymerization initiator (C1) described above, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V) and a compound represented by the formula (VI) are more preferable. preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.
前記一般式（III）で表される基を有するα−アミノアセトフェノン系光重合開始剤（Ｃ２）としては、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパノン−１、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン、Ｎ，Ｎ−ジメチルアミノアセトフェノンなどが挙げられる。市販品としては、チバ・スペシャルティ・ケミカルズ社製のイルガキュアー９０７、イルガキュアー３６９、イルガキュアー３７９などが挙げられる。 The α-aminoacetophenone photopolymerization initiator (C2) having a group represented by the general formula (III) is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- ( 4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.
前記一般式（IV）で表される基を有するアシルホスフィンオキサイド系光重合開始剤（Ｃ３）としては、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス(２，４，６−トリメチルベンゾイル)−フェニルホスフィンオキサイド、ビス(２，６−ジメトキシベンゾイル)−２，４，４−トリメチル−ペンチルホスフィンオキサイドなどが挙げられる。市販品としては、ＢＡＳＦ社製のルシリンＴＰＯ、チバ・スペシャルティ・ケミカルズ社製のイルガキュアー８１９などが挙げられる。 Examples of the acylphosphine oxide photopolymerization initiator (C3) having the group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.
このような光重合重合開始剤（Ｂ）の配合量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、０．０１〜３０質量部、好ましくは０．５〜１５質量部の範囲が適当である。０．０１質量部未満であると、銅上での光硬化性が不足し、塗膜が剥離したり、耐薬品性等の塗膜特性が低下するので好ましくない。一方、３０質量部を超えると、光重合開始剤（Ｂ）のソルダーレジスト塗膜表面での光吸収が激しくなり、深部硬化性が低下する傾向があるために好ましくない。 The blending amount of such a photopolymerization initiator (B) is in the range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Is appropriate. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (B) becomes violent and the deep curability tends to decrease, which is not preferable.
なお、前記式（II）で表される基を有するオキシムエステル系光重合開始剤の場合、その配合量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは０．０１〜２０質量部、より好ましくは０．０１〜５質量部の範囲から選ぶことが望ましい。 In the case of the oxime ester photopolymerization initiator having a group represented by the formula (II), the blending amount thereof is preferably 0.01 to 100 parts by mass of the carboxyl group-containing resin (A). It is desirable to select from 20 parts by mass, more preferably from 0.01 to 5 parts by mass.
これら光重合開始剤（Ｃ）の中でも、特にオキシム系開始剤が有効である。これはリン元素含有アクリレートの反応性が悪いためであり、オキシム系開始材を用いたときのみ比較的良好な硬化性（実用的な範囲の感度）を示すことが明らかとなった。 Of these photopolymerization initiators (C), oxime initiators are particularly effective. This is because the reactivity of the phosphorus element-containing acrylate is poor, and it has become clear that relatively good curability (sensitivity within a practical range) is exhibited only when an oxime-based initiator is used.
他に本発明の感光性樹脂組成物に好適に用いることができる光重合開始剤、光開始助剤及び増感剤としては、ベンゾイン化合物、アセトフェノン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、キサントン化合物、及び３級アミン化合物等を挙げることができる。 Other photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photosensitive resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds. , Xanthone compounds, and tertiary amine compounds.
ベンゾイン化合物の具体例を挙げると、例えば、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である。
アセトフェノン化合物の具体例を挙げると、例えば、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、１，１−ジクロロアセトフェノンである。
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.
アントラキノン化合物の具体例を挙げると、例えば、２−メチルアントラキノン、２−エチルアントラキノン、２−ｔ−ブチルアントラキノン、１−クロロアントラキノンである。
チオキサントン化合物の具体例を挙げると、例えば、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントンである。
Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
ケタール化合物の具体例を挙げると、例えば、アセトフェノンジメチルケタール、ベンジルジメチルケタールである。
ベンゾフェノン化合物の具体例を挙げると、例えば、ベンゾフェノン、４−ベンゾイルジフェニルスルフィド、４−ベンゾイル−４’−メチルジフェニルスルフィド、４−ベンゾイル−４’−エチルジフェニルスルフィド、４−ベンゾイル−４’−プロピルジフェニルスルフィドである。
Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.
３級アミン化合物の具体例を挙げると、例えば、エタノールアミン化合物、ジアルキルアミノベンゼン構造を有する化合物、例えば、４，４’−ジメチルアミノベンゾフェノン（日本曹達社製ニッソキュアーＭＡＢＰ）、４，４’−ジエチルアミノベンゾフェノン（保土ヶ谷化学社製ＥＡＢ）などのジアルキルアミノベンゾフェノン、７−（ジエチルアミノ）−４−メチル−２Ｈ−１−ベンゾピラン−２−オン（７−（ジエチルアミノ）−４−メチルクマリン）等のジアルキルアミノ基含有クマリン化合物、４−ジメチルアミノ安息香酸エチル（日本化薬社製カヤキュアーＥＰＡ）、２−ジメチルアミノ安息香酸エチル（インターナショナルバイオ−シンセエティックス社製Ｑｕａｎｔａｃｕｒｅ ＤＭＢ）、４−ジメチルアミノ安息香酸（ｎ−ブトキシ）エチル（インターナショナルバイオ−シンセエティックス社製Ｑｕａｎｔａｃｕｒｅ ＢＥＡ）、ｐ−ジメチルアミノ安息香酸イソアミルエチルエステル（日本化薬社製カヤキュアーＤＭＢＩ）、４−ジメチルアミノ安息香酸２−エチルヘキシル（Ｖａｎ Ｄｙｋ社製Ｅｓｏｌｏｌ ５０７）、４，４’−ジエチルアミノベンゾフェノン（保土ヶ谷化学社製ＥＡＢ）である。 Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), dialkylamino group such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).
前記した光重合開始剤の中でも、チオキサントン化合物及び３級アミン化合物が好ましい。本発明の組成物には、チオキサントン化合物が含まれることが深部硬化性の面から好ましく、中でも、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン化合物が好ましい。 Among the photopolymerization initiators described above, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
このようなチオキサントン化合物の配合量としては、上記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは２０質量部以下、より好ましくは１０質量部以下の割合である。チオキサントン化合物の配合量が多すぎると、厚膜硬化性が低下して、製品のコストアップに繋がるので、好ましくない。 The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (A). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.
３級アミン化合物としては、ジアルキルアミノベンゼン構造を有する化合物が好ましく、中でも、ジアルキルアミノベンゾフェノン化合物、最大吸収波長が３５０〜４１０ｎｍにあるジアルキルアミノ基含有クマリン化合物が特に好ましい。ジアルキルアミノベンゾフェノン化合物としては、４，４’−ジエチルアミノベンゾフェノンが、毒性も低く好ましい。最大吸収波長が３５０〜４１０ｎｍにあるジアルキルアミノ基含有クマリン化合物は、最大吸収波長が紫外線領域にあるため、着色が少なく、無色透明な感光性樹脂組成物はもとより、着色顔料を用い、着色顔料自体の色を反映した着色ソルダーレジスト膜を提供することが可能となる。特に、７−（ジエチルアミノ）−４−メチル−２Ｈ−１−ベンゾピラン−２−オンが波長４００〜４１０ｎｍのレーザー光に対して優れた増感効果を示すことから好ましい。 As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds having a maximum absorption wavelength of 350 to 410 nm have a maximum absorption wavelength in the ultraviolet region, so that they are less colored and use a colored pigment as well as a colorless and transparent photosensitive resin composition. It is possible to provide a colored solder resist film reflecting the color of the above. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
このような３級アミン化合物の配合量としては、上記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは０．１〜２０質量部、より好ましくは０．１〜１０質量部の割合である。３級アミン化合物の配合量が０．１質量部以下であると、十分な増感効果を得ることができない傾向にある。２０質量部を超えると、３級アミン化合物による乾燥ソルダーレジスト塗膜の表面での光吸収が激しくなり、深部硬化性が低下する傾向がある。 The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is. When the amount of the tertiary amine compound is 0.1 parts by mass or less, there is a tendency that a sufficient sensitizing effect cannot be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.
前記したような光重合開始剤、光開始助剤及び増感剤は、単独で又は２種類以上の混合物として使用することができる。
また、光重合開始剤、光開始助剤、及び増感剤の総量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して３５質量部以下となる範囲であることが好ましい。３５質量部を超えると、これらの光吸収により深部硬化性が低下する傾向にある。
The photopolymerization initiator, photoinitiator aid and sensitizer as described above can be used alone or as a mixture of two or more.
Moreover, it is preferable that the total amount of a photoinitiator, a photoinitiator adjuvant, and a sensitizer is the range used as 35 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (A). When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
本発明の感光性樹脂組成物には、耐熱性を付与するために、熱硬化性成分（Ｄ）を加えることができる。特に好ましい熱硬化性成分（Ｄ）は、分子中に２個以上の環状エーテル基及び／又は環状チオエーテル基（以下、環状（チオ）エーテル基と略す）を有する熱硬化性樹脂である。これらの中でも２官能性のエポキシ樹脂が好ましく、他にはジイソシアネートやその２官能性ブロックイソシアネートも使用することができる。 A thermosetting component (D) can be added to the photosensitive resin composition of the present invention in order to impart heat resistance. A particularly preferred thermosetting component (D) is a thermosetting resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule. Among these, bifunctional epoxy resins are preferable, and diisocyanate and its bifunctional blocked isocyanate can also be used.
このような分子中に２つ以上の環状（チオ）エーテル基を有する熱硬化性成分（Ｄ）は、分子中に３、４又は５員環の環状エーテル基、又は環状チオエーテル基のいずれか一方又は２種類の基を２個以上有する化合物であり、例えば、分子内に少なくとも２つ以上のエポキシ基を有する化合物、すなわち多官能エポキシ化合物（Ｄ−１）、分子内に少なくとも２つ以上のオキセタニル基を有する化合物、すなわち多官能オキセタン化合物（Ｄ−２）、分子内に２個以上のチオエーテル基を有する化合物、すなわちエピスルフィド樹脂（Ｄ−３）などが挙げられる。 The thermosetting component (D) having two or more cyclic (thio) ether groups in such a molecule is either a three-, four- or five-membered cyclic ether group or a cyclic thioether group in the molecule. Or a compound having two or more of two types of groups, for example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1), at least two oxetanyl in the molecule A compound having a group, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D-3), and the like.
前記多官能エポキシ化合物（Ｄ−１）としては、例えば、ジャパンエポキシレジン社製のＪＥＲ８２８、ＪＥＲ８３４、ＪＥＲ１００１、ＪＥＲ１００４、大日本インキ化学工業社製のエピクロン８４０、エピクロン８５０、エピクロン１０５０、エピクロン２０５５、東都化成社製のエポトートＹＤ−０１１、ＹＤ−０１３、ＹＤ−１２７、ＹＤ−１２８、ダウケミカル社製のＤ．Ｅ．Ｒ．３１７、Ｄ．Ｅ．Ｒ．３３１、Ｄ．Ｅ．Ｒ．６６１、Ｄ．Ｅ．Ｒ．６６４、チバ・スペシャルティ・ケミカルズ社のアラルダイド６０７１、アラルダイド６０８４、アラルダイドＧＹ２５０、アラルダイドＧＹ２６０、住友化学工業社製のスミ−エポキシＥＳＡ−０１１、ＥＳＡ−０１４、ＥＬＡ−１１５、ＥＬＡ−１２８、旭化成工業社製のＡ．Ｅ．Ｒ．３３０、Ａ．Ｅ．Ｒ．３３１、Ａ．Ｅ．Ｒ．６６１、Ａ．Ｅ．Ｒ．６６４等（何れも商品名）のビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ９０３、大日本インキ化学工業社製のエピクロン１５２、エピクロン１６５、東都化成社製のエポトートＹＤＢ−４００、ＹＤＢ−５００、ダウケミカル社製のＤ．Ｅ．Ｒ．５４２、チバ・スペシャルティ・ケミカルズ社製のアラルダイド８０１１、住友化学工業社製のスミ−エポキシＥＳＢ−４００、ＥＳＢ−７００、旭化成工業社製のＡ．Ｅ．Ｒ．７１１、Ａ．Ｅ．Ｒ．７１４等（何れも商品名）のブロム化エポキシ樹脂；ジャパンエポキシレジン社製のＪＥＲ１５２、ＪＥＲ１５４、ダウケミカル社製のＤ．Ｅ．Ｎ．４３１、Ｄ．Ｅ．Ｎ．４３８、大日本インキ化学工業社製のエピクロンＮ−７３０、エピクロンＮ−７７０、エピクロンＮ−８６５、東都化成社製のエポトートＹＤＣＮ−７０１、ＹＤＣＮ−７０４、チバ・スペシャルティ・ケミカルズ社製のアラルダイドＥＣＮ１２３５、アラルダイドＥＣＮ１２７３、アラルダイドＥＣＮ１２９９、アラルダイドＸＰＹ３０７、日本化薬社製のＥＰＰＮ−２０１、ＥＯＣＮ−１０２５、ＥＯＣＮ−１０２０、ＥＯＣＮ−１０４Ｓ、ＲＥ−３０６、住友化学工業社製のスミ−エポキシＥＳＣＮ−１９５Ｘ、ＥＳＣＮ−２２０、旭化成工業社製のＡ．Ｅ．Ｒ．ＥＣＮ−２３５、ＥＣＮ−２９９等（何れも商品名）のノボラック型エポキシ樹脂；大日本インキ化学工業社製のエピクロン８３０、ジャパンエポキシレジン社製ＪＥＲ８０７、東都化成社製のエポトートＹＤＦ−１７０、ＹＤＦ−１７５、ＹＤＦ−２００１、ＹＤＦ−２００４、チバ・スペシャルティ・ケミカルズ社製のアラルダイドＸＰＹ３０６等（何れも商品名）のビスフェノールＦ型エポキシ樹脂；東都化成社製のエポトートＳＴ−２００４、ＳＴ−２００７、ＳＴ−３０００（商品名）等の水添ビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン社製のＪＥＲ６０４、東都化成社製のエポトートＹＨ−４３４、チバ・スペシャルティ・ケミカルズ社製のアラルダイドＭＹ７２０、住友化学工業社製のスミ−エポキシＥＬＭ−１２０等（何れも商品名）のグリシジルアミン型エポキシ樹脂；チバ・スペシャルティ・ケミカルズ社製のアラルダイドＣＹ−３５０（商品名）等のヒダントイン型エポキシ樹脂；ダイセル化学工業社製のセロキサイド２０２１、チバ・スペシャルティ・ケミカルズ社製のアラルダイドＣＹ１７５、ＣＹ１７９等（何れも商品名）の脂環式エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ−９３３、ダウケミカル社製のＴ．Ｅ．Ｎ．、ＥＰＰＮ−５０１、ＥＰＰＮ−５０２等（何れも商品名）のトリヒドロキシフェニルメタン型エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ−６０５６、ＹＸ−４０００、ＹＬ−６１２１（何れも商品名）等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物；日本化薬社製ＥＢＰＳ−２００、旭電化工業社製ＥＰＸ−３０、大日本インキ化学工業社製のＥＸＡ−１５１４（商品名）等のビスフェノールＳ型エポキシ樹脂；ジャパンエポキシレジン社製のＪＥＲ１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ−９３１、チバ・スペシャルティ・ケミカルズ社製のアラルダイド１６３等（何れも商品名）のテトラフェニロールエタン型エポキシ樹脂；チバ・スペシャルティ・ケミカルズ社製のアラルダイドＰＴ８１０、日産化学工業社製のＴＥＰＩＣ等（何れも商品名）の複素環式エポキシ樹脂；日本油脂社製ブレンマーＤＧＴ等のジグリシジルフタレート樹脂；東都化成社製ＺＸ−１０６３等のテトラグリシジルキシレノイルエタン樹脂；新日鉄化学社製ＥＳＮ−１９０、ＥＳＮ−３６０、大日本インキ化学工業社製ＨＰ−４０３２、ＥＸＡ−４７５０、ＥＸＡ−４７００等のナフタレン基含有エポキシ樹脂；大日本インキ化学工業社製ＨＰ−７２００、ＨＰ−７２００Ｈ等のジシクロペンタジエン骨格を有するエポキシ樹脂；日本油脂社製ＣＰ−５０Ｓ、ＣＰ−５０Ｍ等のグリシジルメタアクリレート共重合系エポキシ樹脂；さらにシクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂；エポキシ変性のポリブタジエンゴム誘導体（例えばダイセル化学工業製ＰＢ−３６００等）、ＣＴＢＮ変性エポキシ樹脂（例えば東都化成社製のＹＲ−１０２、ＹＲ−４５０等）等が挙げられるが、これらに限られるものではない。これらのエポキシ樹脂は、単独で又は２種以上を組み合わせて用いることができる。これらの中でも特にノボラック型エポキシ樹脂、複素環式エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂又はそれらの混合物が好ましい。 As the polyfunctional epoxy compound (D-1), for example, JER828, JER834, JER1001, JER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epitome 2055 manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Corporation A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); YL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); JER152 and JER154 manufactured by Japan Epoxy Resin, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical Co., Ltd. 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, JER807 manufactured by Japan Epoxy Resin, Epotot YDF-170 manufactured by Toto Kasei Co., YDF- 175, YDF-2001, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST- manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 3000 (trade name); Japan Epoxy Resin JER604, Toto Kasei Epototo YH-434, Ciba Specialty Chemicals Araldide MY720, Sumitomo Chemical Co., Ltd. SUMI-EPOXY ELM Glycidylamine type epoxy resin such as 120 (all trade names); Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty -Alicyclic epoxy resins such as Araldide CY175, CY179, etc. (both trade names) manufactured by Chemicals; YL-933 manufactured by Japan Epoxy Resin; E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Bisphenol A novolak type epoxy resin such as JER157S (trade name) manufactured by Japan Epoxy Resin; YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. (all trade names) Tetraphenylolethane type epoxy resin; Hexacyclic epoxy resins such as Araldide PT810 manufactured by Ba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (both trade names); Diglycidyl phthalate resins such as Bremer DGT manufactured by NOF Corporation; ZX manufactured by Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as -1063; naphthalene group-containing epoxy resins such as Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, Dainippon Ink and Chemicals, Inc. HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; and cyclohexylmaleimide And glycidyl methacrylate Copolymerized epoxy resin; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.
前記多官能オキセタン化合物（Ｄ−２）としては、ビス［（３−メチル−３−オキセタニルメトキシ）メチル］エーテル、ビス［（３−エチル−３−オキセタニルメトキシ）メチル］エーテル、１，４−ビス［（３−メチル−３−オキセタニルメトキシ）メチル］ベンゼン、１，４−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］ベンゼン、（３−メチル−３−オキセタニル）メチルアクリレート、（３−エチル−３−オキセタニル）メチルアクリレート、（３−メチル−３−オキセタニル）メチルメタクリレート、（３−エチル−３−オキセタニル）メチルメタクリレートやそれらのオリゴマー又は共重合体等の多官能オキセタン類の他、オキセタンアルコールとノボラック樹脂、ポリ（ｐ−ヒドロキシスチレン）、カルド型ビスフェノール類、カリックスアレーン類、カリックスレゾルシンアレーン類、又はシルセスキオキサンなどの水酸基を有する樹脂とのエーテル化物などが挙げられる。その他、オキセタン環を有する不飽和モノマーとアルキル（メタ）アクリレートとの共重合体なども挙げられる。 Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.
前記分子中に２個以上の環状チオエーテル基を有する化合物（Ｄ−３）としては、例えば、ジャパンエポキシレジン社製のビスフェノールＡ型エピスルフィド樹脂ＹＬ７０００などが挙げられる。また、同様の合成方法を用いて、ノボラック型エポキシ樹脂のエポキシ基の酸素原子を硫黄原子に置き換えたエピスルフィド樹脂なども用いることができる。 Examples of the compound (D-3) having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
前記分子中に２つ以上の環状（チオ）エーテル基を有する熱硬化性成分（Ｄ）の配合量は、前記カルボキシル基含有樹脂のカルボキシル基１当量に対して、好ましくは０．６〜２．５当量、より好ましくは、０．８〜２．０当量となる範囲にある。分子中に２つ以上の環状（チオ）エーテル基を有する熱硬化性成分（Ｄ）の配合量が０．６未満である場合、ソルダーレジスト膜にカルボキシル基が残り、耐熱性、耐アルカリ性、電気絶縁性などが低下するので、好ましくない。一方、２．５当量を超える場合、低分子量の環状（チオ）エーテル基が乾燥塗膜に残存することにより、塗膜の強度などが低下するので、好ましくない。 The blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2. with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. It is in the range of 5 equivalents, more preferably 0.8 to 2.0 equivalents. When the blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in heat resistance, alkali resistance, electricity This is not preferable because the insulating property is lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
上記分子中に２つ以上の環状（チオ）エーテル基を有する熱硬化性成分（Ｄ）を使用する場合、熱硬化触媒を含有することが好ましい。そのような熱硬化触媒としては、例えば、イミダゾール、２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、４−フェニルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール等のイミダゾール誘導体；ジシアンジアミド、ベンジルジメチルアミン、４−（ジメチルアミノ）−Ｎ，Ｎ−ジメチルベンジルアミン、４−メトキシ−Ｎ，Ｎ−ジメチルベンジルアミン、４−メチル−Ｎ，Ｎ−ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物；トリフェニルホスフィン等のリン化合物など、また市販されているものとしては、例えば四国化成工業社製の２ＭＺ−Ａ、２ＭＺ−ＯＫ、２ＰＨＺ、２Ｐ４ＢＨＺ、２Ｐ４ＭＨＺ（いずれもイミダゾール系化合物の商品名）、サンアプロ社製のＵ−ＣＡＴ３５０３Ｎ、Ｕ−ＣＡＴ３５０２Ｔ（いずれもジメチルアミンのブロックイソシアネート化合物の商品名）、ＤＢＵ、ＤＢＮ、Ｕ−ＣＡＴＳＡ１０２、Ｕ−ＣＡＴ５００２（いずれも二環式アミジン化合物及びその塩）などが挙げられる。特に、これらに限られるものではなく、エポキシ樹脂やオキセタン化合物の熱硬化触媒、もしくはエポキシ基及び／又はオキセタニル基とカルボキシル基の反応を促進するものであればよく、単独で又は２種以上を混合して使用してもかまわない。また、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、２，４−ジアミノ−６−メタクリロイルオキシエチル−Ｓ−トリアジン、２−ビニル−４，６−ジアミノ−Ｓ−トリアジン、２−ビニル−４，６−ジアミノ−Ｓ−トリアジン・イソシアヌル酸付加物、２，４−ジアミノ−６−メタクリロイルオキシエチル−Ｓ−トリアジン・イソシアヌル酸付加物等のＳ−トリアジン誘導体を用いることもでき、好ましくはこれら密着性付与剤としても機能する化合物を前記熱硬化触媒と併用する。 When the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and those that are commercially available ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (both dimethylamine block isocyanate compounds) Product names), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.
これら熱硬化触媒の配合量は、通常の量的割合で充分であり、例えばカルボキシル基含有樹脂（Ａ）又は分子中に２つ以上の環状（チオ）エーテル基を有する熱硬化性成分（Ｄ）１００質量部に対して、好ましくは０．１〜２０質量部、より好ましくは０．５〜１５．０質量部である。 The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, a carboxyl group-containing resin (A) or a thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule. Preferably it is 0.1-20 mass parts with respect to 100 mass parts, More preferably, it is 0.5-15.0 mass parts.
本発明の感光性樹脂組成物は、有機リン系難燃剤（Ｅ）を含むことが好ましい。有機リン系難燃剤（Ｅ）としては、リン酸エステル及び縮合リン酸エステル、環状フォスファゼン化合物、フォスファゼンオリゴマーもしくは下記一般式（VIII）で表される化合物がある。
市販品としては三光社製ＨＣＡ（上記式のＲ２０が水素原子）、ＳＡＮＫＯ−２２０（上記式のＲ２０が３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル基）、Ｍ−ＥＳＴＥＲ（上記式のＲ２０が−ＣＨ２ＣＨ（ＣＯＯＣＨ２ＣＨ２ＯＨ）ＣＨ２ＣＯＯＣＨ２ＣＨ２ＯＨ基）、ＨＣＡ−ＨＱ（上記式のＲ２０が２，５−ベンゼンジオール基）などがある。
The photosensitive resin composition of the present invention preferably contains an organic phosphorus flame retardant (E). Examples of the organic phosphorus flame retardant (E) include phosphoric acid esters and condensed phosphoric acid esters, cyclic phosphazene compounds, phosphazene oligomers, and compounds represented by the following general formula (VIII).
Commercially available products include HCA manufactured by Sanko Co., Ltd. (R 20 in the above formula is a hydrogen atom), SANKO-220 (R 20 in the above formula is 3,5-di-t-butyl-4-hydroxybenzyl group), M-ESTER ( R 20 in the above formula is —CH 2 CH (COOCH 2 CH 2 OH) CH 2 COOCH 2 CH 2 OH group), HCA-HQ (wherein R 20 in the above formula is 2,5-benzenediol group) and the like.
有機リン系難燃剤で特に好ましいものは、前記エポキシ樹脂（Ｄ）と反応性を有するフェノール性水酸基を有する化合物である。このフェノール性水酸基を有する化合物は、疎水性、耐熱性が高く、加水分解による電気特性の低下がなく、はんだ耐熱が高い。また、好適な組み合わせとしてエポキシ樹脂（Ｄ）を使用することによって、エポキシ樹脂と反応してネットワークに取り込まれるので、硬化後にブリードアウトすることがない。しかしながら、フェノール性水酸基は、時には光反応の阻害（ラジカル重合の停止）を引き起こす。この場合にも、好適な組み合わせとして前記オキシム系光重合開始剤（Ｃ’）を使用することにより、その感度低下を抑えることができる。
これら有機リン系難燃剤（Ｅ）の配合量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、０〜３０質量部の範囲が適当であり、特に好ましくは０〜２５質量部である。これ以上多くなると、得られる硬化物の折り曲げ特性等が悪くなるので好ましくない。
A particularly preferable organic phosphorus flame retardant is a compound having a phenolic hydroxyl group having reactivity with the epoxy resin (D). The compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, does not deteriorate electrical characteristics due to hydrolysis, and has high solder heat resistance. Further, by using the epoxy resin (D) as a suitable combination, it reacts with the epoxy resin and is taken into the network, so that it does not bleed out after curing. However, phenolic hydroxyl groups sometimes cause photoreaction inhibition (termination of radical polymerization). Also in this case, the sensitivity fall can be suppressed by using the said oxime type photoinitiator (C ') as a suitable combination.
The blending amount of these organophosphorous flame retardants (E) is suitably in the range of 0 to 30 parts by weight, particularly preferably 0 to 25 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (A). is there. If the amount is more than this, the bending properties and the like of the resulting cured product will deteriorate, such being undesirable.
本発明の感光性樹脂組成物は、その塗膜の物理的強度等を上げるために、必要に応じて、フィラーを配合することができる。このようなフィラーとしては、公知慣用の無機又は有機フィラーが使用できるが、特に硫酸バリウム、球状シリカ及びタルクが好ましく用いられる。さらに、１個以上のエチレン性不飽和基を有する化合物や前記多官能エポキシ樹脂（Ｅ−１）にナノシリカを分散したＨａｎｓｅ−Ｃｈｅｍｉｅ社製のＮＡＮＯＣＲＹＬ（商品名） ＸＰ ０３９６、ＸＰ ０５９６、ＸＰ ０７３３、ＸＰ ０７４６、ＸＰ ０７６５、ＸＰ ０７６８、ＸＰ ０９５３、ＸＰ ０９５４、ＸＰ １０４５（何れも製品グレード名）や、Ｈａｎｓｅ−Ｃｈｅｍｉｅ社製のＮＡＮＯＰＯＸ（商品名） ＸＰ ０５１６、ＸＰ ０５２５、ＸＰ ０３１４（何れも製品グレード名）も使用できる。これらを単独で又は２種以上配合することができる。 The photosensitive resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin (E-1), XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) manufactured by Hanse-Chemie, Inc. XP 0516, XP 0525, XP 0314 (all are product grades) Name) can also be used. These may be used alone or in combination of two or more.
これらフィラーの配合量は、上記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは３００質量部以下、より好ましくは０．１〜３００質量部、特に好ましくは、０．１〜１５０質量部である。フィラーの配合量が、３００質量部を超えた場合、感光性樹脂組成物の粘度が高くなり印刷性が低下したり、硬化物が脆くなるので好ましくない。 The blending amount of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Part. When the blending amount of the filler exceeds 300 parts by mass, the viscosity of the photosensitive resin composition is increased, the printability is lowered, and the cured product becomes brittle.
さらに、本発明の感光性樹脂組成物は、上記カルボキシル基含有樹脂（Ａ）の合成や組成物の調製のため、又は基板やキャリアフィルムに塗布するための粘度調整のため、有機溶剤を使用することができる。 Furthermore, the photosensitive resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (A), the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. be able to.
このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などが挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類；オクタン、デカン等の脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などである。このような有機溶剤は、単独で又は２種以上の混合物として用いられる。 Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.
本発明の感光性樹脂組成物は、さらに必要に応じて、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ−ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、酸化防止剤、防錆剤などのような公知慣用の添加剤類を配合することができる。 If necessary, the photosensitive resin composition of the present invention may be a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, montmorillonite and the like. Conventional thickeners, antifoaming agents and / or leveling agents such as silicones, fluorines and polymers, silane coupling agents such as imidazoles, thiazoles and triazoles, antioxidants, rust inhibitors, etc. Such known and commonly used additives can be blended.
本発明の感光性樹脂組成物は、キャリアフィルムと、該キャリアフィルム上に形成された上記感光性樹脂組成物からなる層とを備えたドライフィルムの形態とすることもできる。
ドライフィルム化に際しては、本発明の感光性樹脂組成物を適切な粘度に前記有機溶剤で希釈し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等で支持体上に均一な厚さに塗布し、通常、５０〜１３０℃の温度で１〜３０分間乾燥して膜を得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で、１０〜１５０μｍ、好ましくは２０〜６０μｍの範囲で適宜選択される。
The photosensitive resin composition of this invention can also be made into the form of the dry film provided with the carrier film and the layer which consists of the said photosensitive resin composition formed on this carrier film.
In forming a dry film, the photosensitive resin composition of the present invention is diluted with the above-mentioned organic solvent to an appropriate viscosity, followed by a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, and a gravure coater. The film can be obtained by applying a uniform thickness on a support with a spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.
キャリアフィルムとしては、プラスチックフィルムが用いられ、ポリエチレンテレフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等のプラスチックフィルムを用いることが好ましい。キャリアフィルムの厚さについては特に制限はないが、一般に、１０〜１５０μｍの範囲で適宜選択される。 As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.
キャリアフィルム上に成膜した後、さらに、膜の表面に塵が付着するのを防ぐなどの目的で、膜の表面に剥離可能なカバーフィルムを積層することが望ましい。
剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、カバーフィルムを剥離するときに膜と支持体との接着力よりも膜とカバーフィルムとの接着力がより小さいものであればよい。
After the film is formed on the carrier film, it is desirable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the support is more than What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
以上のような組成を有する本発明の感光性樹脂組成物は、必要に応じて希釈して塗布方法に適した粘度に調整し、これを例えば、回路形成されたプリント配線板にスクリーン印刷法、カーテンコート法、スプレーコート法、ロールコート法等の方法により塗布し、例えば約６０〜１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥させることにより、タックフリーの塗膜を形成できる。 The photosensitive resin composition of the present invention having the above composition is diluted as necessary and adjusted to a viscosity suitable for the coating method. For example, this is applied to a printed wiring board formed with a circuit by a screen printing method, A tack-free coating film can be formed by applying a curtain coating method, a spray coating method, a roll coating method or the like, and evaporating and drying an organic solvent contained in the composition at a temperature of about 60 to 100 ° C., for example. .
回路形成されたプリント配線板上に塗膜を形成した後（上記ドライフィルムを用いた場合は、回路形成されたプリント配線板上にラミネート後、支持体を剥がさず）、レーザー光等の活性エネルギー線をパターン通りに直接照射するか、又はパターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光し、未露光部を希アルカリ水溶液により現像してレジストパターンを形成できる（上記ドライフィルムを用いた場合、露光後、支持体を剥がし、現像する）。その後さらに、加熱硬化のみ、又は活性エネルギー線の照射後加熱硬化もしくは加熱硬化後活性エネルギー線の照射で最終硬化（本硬化）させることにより、電気絶縁性、密着性、はんだ耐熱性、耐薬品性、無電解金めっき耐性などに優れた硬化膜（硬化物）が形成される。 After forming a coating film on the printed circuit board on which the circuit is formed (when the above dry film is used, after laminating on the printed circuit board on which the circuit has been formed, the support is not peeled off), and then the active energy such as laser light A resist pattern can be formed by directly irradiating a line as a pattern or selectively exposing with an active energy ray through a photomask on which a pattern is formed, and developing an unexposed portion with a dilute alkaline aqueous solution (using the above dry film). If it is, the support is peeled off and developed after exposure). After that, it is further heat-cured only, or heat-cured after irradiation with active energy rays or heat-cured after heat-curing, and finally cured (main-cured) by irradiation with active energy rays, thereby providing electrical insulation, adhesion, solder heat resistance, chemical resistance. A cured film (cured product) excellent in electroless gold plating resistance is formed.
本発明の感光性樹脂組成物は、例えば前記有機溶剤で塗布方法に適した粘度に調整し、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布し、約６０〜１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることにより、タックフリーの塗膜を形成できる。また、前記ドライフィルムの形態の場合、基材上にホットロールラミネーター等を用いて貼り合わせる（前記感光性樹脂組成物層と基材とが接触するように貼り合わせる）。上記フィルムの感光性樹脂組成物層上に、さらに剥離可能なカバーフィルムを備えたドライフィルムの場合、カバーフィルムを剥がした後、上記感光性樹脂組成物層と基材とが接触するようにホットロールラミネーター等を用いて貼り合わせる。 The photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Moreover, in the case of the said dry film form, it bonds together on a base material using a hot roll laminator etc. (It bonds together so that the said photosensitive resin composition layer and a base material may contact). In the case of a dry film having a peelable cover film on the photosensitive resin composition layer of the film, after the cover film is peeled off, the photosensitive resin composition layer and the substrate are hot so that they come into contact with each other. Bond using a roll laminator.
その後、得られた塗膜（感光性樹脂組成物層）に対し、露光（活性エネルギー線の照射）を行う。露光は、接触式（又は非接触方式）により、パターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光する方法、あるいはレーザーダイレクト露光機により直接パターン露光する方法のいずれでもよい。この露光により、塗膜は、露光部（活性エネルギー線により照射された部分）が硬化する。次いで、未露光部を希アルカリ水溶液（例えば０．３〜３％炭酸ソーダ水溶液）により現像してレジストパターンが形成される。さらに、熱硬化性成分（Ｄ）を含有する光硬化性・熱硬化性樹脂組成物の場合、例えば約１４０〜１８０℃の温度に加熱して熱硬化させることにより、前記カルボキシル基含有樹脂（Ａ）のカルボキシル基と、分子中に２個以上の環状エーテル基及び／又は環状チオエーテル基を有する熱硬化性成分（Ｄ）が反応し、耐熱性、耐薬品性、耐吸湿性、密着性、電気特性などの諸特性に優れた硬化塗膜を形成することができる。 Then, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film (photosensitive resin composition layer). The exposure may be either a contact type (or non-contact type) method of selectively exposing with an active energy ray through a photomask on which a pattern has been formed, or a method of direct pattern exposure using a laser direct exposure machine. By this exposure, the exposed portion (portion irradiated with active energy rays) of the coating film is cured. Next, the unexposed portion is developed with a dilute alkaline aqueous solution (for example, a 0.3 to 3% sodium carbonate aqueous solution) to form a resist pattern. Furthermore, in the case of the photocurable thermosetting resin composition containing the thermosetting component (D), for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group-containing resin (A ) And a thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups in the molecule react to produce heat resistance, chemical resistance, moisture absorption resistance, adhesion, electricity A cured coating film excellent in various properties such as properties can be formed.
上記基材としては、紙−フェノール樹脂、紙−エポキシ樹脂、ガラス布−エポキシ樹脂、ガラス−ポリイミド、ガラス布／不繊布−エポキシ樹脂、ガラス布／紙−エポキシ樹脂、合成繊維−エポキシ樹脂、フッ素樹脂・ポリエチレン・ＰＰＯ・シアネートエステル等の複合材を用いた全てのグレード（ＦＲ−４等）の銅張積層板や、ポリイミドフィルム、ＰＥＴフィルム、ガラス基板、セラミック基板、ウエハ板等を用いることができる。 As the substrate, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluorine Use copper graded laminates of all grades (FR-4 etc.) using composite materials such as resin, polyethylene, PPO, cyanate ester, polyimide film, PET film, glass substrate, ceramic substrate, wafer plate, etc. it can.
本発明の感光性樹脂組成物を塗布した後に行う揮発乾燥は、熱風循環式乾燥炉、ＩＲ炉、ホットプレート、コンベクションオーブンなど（蒸気による空気加熱方式の熱源を備えたものを用い、乾燥機内の熱風を向流接触せしめる方法や、ノズルより支持体に吹き付ける方式）を用いて行うことができる。 Volatile drying performed after the photosensitive resin composition of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (with a heat source of an air heating method using steam, It can be carried out using a method in which hot air is brought into countercurrent contact or a method in which a hot air is blown onto a support.
上記活性エネルギー線照射に用いられる露光機としては、高圧水銀灯ランプ、超高圧水銀灯ランプ、メタルハライドランプ、水銀ショートアークランプ等を搭載し、３５０〜４５０ｎｍの範囲で紫外線を照射する装置であればよく、さらに、直接描画装置（例えばコンピューターからのＣＡＤデータにより直接レーザーで画像を描くレーザーダイレクトイメージング装置）も用いることができる。直描機のレーザー光源としては、最大波長が３５０〜４１０ｎｍの範囲にあるレーザー光を用いていれば、ガスレーザー、固体レーザーのどちらでもよい。画像形成のための露光量は膜厚等によって異なるが、一般には２０〜８００ｍＪ／ｃｍ２、好ましくは２０〜６００ｍＪ／ｃｍ２の範囲内とすることができる。 As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As the laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm 2 , preferably 20 to 600 mJ / cm 2 .
前記現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができ、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。 The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
以下に実施例及び比較例を示して本発明について具体的に説明するが、本発明が下記実施例に限定されるものではないことはもとよりである。 EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
合成例
（Ａ−１）前述したカルボキシル基含有樹脂（３）に該当し、感光性基含有、ビスフェノールＡ構造、脂環式ジイソシアネート使用した感光性カルボキシル基含有ウレタン樹脂の合成
セパラブルフラスコ中に、ビスフェノールＡ 型エポキシ化合物として、日本化薬（株）製ＲＥ３１０Ｓ（２官能ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４ｇ／当量）を３６８.０ｇアクリル酸（分子量：７２.０６）を１４２．７ｇ、熱重合禁止剤として２,６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾールを２.９４ｇ及び反応触媒としてトリフェニルフォスフィンを１.５３ｇ仕込み、９８℃の温度で反応液の酸価が０.５ｍｇＫＯＨ／ｇ以下になるまで反応させ、エポキシカルボキシレート化合物（ａ）（理論分子量：５１０.７）を得た。次いでこの反応液に反応用溶媒としてカルビトールアセテートを５８８.２ｇ、ジメチロールプロピオン酸（ｂ）（分子量：１３４．１６）１０５．５ｇを加え、４５℃に昇温させた。この溶液にイソホロンジイソシアネート（ｃ）（分子量： ２２２．２８）２６４.７ｇを反応温度が６５℃を超えないように徐々に滴下した。滴下終了後、温度を８０℃ に上昇させ、赤外吸収スペクトル測定法により、２２５０ｃｍ−１付近の吸収がなくなるまで６時間反応させ、さらに９８℃の温度で２時間反応させ、アルカリ水溶液可溶性ウレタン樹脂を６０重量％含む樹脂溶液を得た。酸価を測定したところ、２８．９ｍｇＫＯＨ／ｇ（固形分酸価：４８．１ｍｇＫＯＨ／ｇ）であった。以下、この反応生成物を樹脂溶液（Ａ−１）とする。
Synthesis Example (A-1) Synthesis of a photosensitive carboxyl group-containing urethane resin that corresponds to the carboxyl group-containing resin (3) and uses a photosensitive group, a bisphenol A structure, and an alicyclic diisocyanate In a separable flask, As a bisphenol A type epoxy compound, Nippon Kayaku Co., Ltd. RE310S (bifunctional bisphenol A type epoxy resin, epoxy equivalent: 184 g / equivalent) is 368.0 g acrylic acid (molecular weight: 72.06) is 142.7 g, heat 2.94 g of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor and 1.53 g of triphenylphosphine as a reaction catalyst were charged, and the acid value of the reaction solution at a temperature of 98 ° C. was 0.5 mgKOH / It was made to react until it became g or less, and the epoxy carboxylate compound (a) (theoretical molecular weight: 510.7) was obtained. Next, 588.2 g of carbitol acetate and 105.5 g of dimethylolpropionic acid (b) (molecular weight: 134.16) were added to the reaction solution as a reaction solvent, and the temperature was raised to 45 ° C. To this solution, 264.7 g of isophorone diisocyanate (c) (molecular weight: 222.28) was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropwise addition, the temperature is raised to 80 ° C., and the reaction is performed for 6 hours until the absorption near 2250 cm −1 disappears by infrared absorption spectrum measurement, and the reaction is further performed for 2 hours at a temperature of 98 ° C. A resin solution containing 60 wt% was obtained. When the acid value was measured, it was 28.9 mgKOH / g (solid content acid value: 48.1 mgKOH / g). Hereinafter, this reaction product is referred to as a resin solution (A-1).
（Ａ−２）前記カルボキシル基含有樹脂（６）に該当し、感光性基含有でビフェニル骨格を有するビフェニルノボラックエポキシ樹脂を使用した感光性カルボキシル基含有樹脂日本化薬社製ＺＣＲ−１６０１Ｈ（固形分６５％樹脂としての酸価は９８ｍｇＫＯＨ／ｇ）この樹脂溶液をＡ−２とする。 (A-2) A photosensitive carboxyl group-containing resin that corresponds to the carboxyl group-containing resin (6) and uses a biphenyl novolac epoxy resin containing a photosensitive group and having a biphenyl skeleton, manufactured by Nippon Kayaku Co., Ltd. ZCR-1601H (solid content The acid value as a 65% resin is 98 mgKOH / g) This resin solution is designated as A-2.
（Ａ−３）前記カルボキシル基含有樹脂（７）に該当し、感光性基含有でビスフェノールＦ構造の多官能エポキシを使用した感光性カルボキシル基含有樹脂：日本化薬社製ＺＦＲ−１１２４（固形分６３％樹脂としての酸価は１０２ｍｇＫＯＨ／ｇ）。この樹脂溶液をＡ−３とする。 (A-3) Photosensitive carboxyl group-containing resin corresponding to the carboxyl group-containing resin (7) and containing a photosensitive group and using a polyfunctional epoxy having a bisphenol F structure: ZFR-1124 manufactured by Nippon Kayaku Co., Ltd. (solid content The acid value as 63% resin is 102 mgKOH / g). This resin solution is designated as A-3.
実施例１〜８、比較例１
上記各樹脂溶液（Ａ−１）〜（Ａ−３）を用い、表１に示す種々の成分とともに表１に示す割合（質量部）にて配合し、攪拌機にて予備混合した後、３本ロールミルで混練し、ソルダーレジスト用感光性樹脂組成物を調製した。ここで、得られた感光性樹脂組成物の分散度をエリクセン社製グラインドメータによる粒度測定にて評価したところ１５μｍ以下であった。
Examples 1-8, Comparative Example 1
Using each of the above resin solutions (A-1) to (A-3), the various components shown in Table 1 were blended in the proportions (parts by mass) shown in Table 1, and premixed with a stirrer, then three A photosensitive resin composition for a solder resist was prepared by kneading with a roll mill. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the Grindometer by Eriksen.
性能評価：
＜最適露光量＞
前記実施例及び比較例の感光性樹脂組成物を、銅厚３５μｍの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスクリーン印刷法により全面に塗布し、８０℃の熱風循環式乾燥炉で３０分間乾燥させる。乾燥後、メタルハライドランプ搭載の露光装置（ＨＭＷ−６８０−ＧＷ２０）を用いてステップタブレット（コダック Ｎｏ．２）を介して露光し、現像（３０℃、０．２ＭＰａ、１質量％炭酸ナトリウム水溶液）を６０秒で行った際残存するステップタブレットのパターンが６段の時を最適露光量とした。
Performance evaluation:
<Optimum exposure amount>
The photosensitive resin compositions of the above examples and comparative examples were coated with a screen printing method on the entire surface of a circuit pattern substrate having a copper thickness of 35 μm after buffing, washed with water, dried and then dried at 80 ° C. For 30 minutes. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) is performed. When the pattern of the step tablet remaining at the time of 60 seconds was 6 steps, the optimum exposure amount was set.
＜解像性＞
実施例及び比較例の感光性樹脂組成物を、ライン／スペースが３００／３００μｍ、銅厚３５μｍの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスクリーン印刷法により塗布し、８０℃の熱風循環式乾燥炉で３０分間乾燥させる。乾燥後、最大波長３５５ｎｍの半導体レーザーを搭載した直接描画装置を用いて露光した。露光パターンはスペース部に２０／３０／４０／５０／６０／７０／８０／９０／１００μｍのラインを描画させる直描用データを使用した。露光量は感光性樹脂組成物の最適露光量となるように活性エネルギー線を照射した。露光後、３０℃の１質量％炭酸ナトリウム水溶液によって現像を行ってパターンを描き、１５０℃×６０分の熱硬化をすることにより硬化塗膜を得た。
得られたソルダーレジスト用感光性樹脂組成物の硬化塗膜の最小残存ラインを２００倍に調整した光学顕微鏡を用いて求めた（解像性）。
<Resolution>
The circuit pattern substrates of 300/300 μm in line / space and 35 μm in copper thickness were coated with the photosensitive resin compositions of Examples and Comparative Examples by buffing, washed with water, dried and then applied by screen printing. Dry in a hot air circulating drying oven for 30 minutes. After drying, exposure was performed using a direct drawing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm. As the exposure pattern, direct drawing data for drawing a 20/30/40/50/60/70/80/90/100 μm line in the space portion was used. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes.
It calculated | required using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times (resolution).
特性試験：
上記各実施例及び比較例の組成物を、パターン形成されたポリイミドフィルム基板上にスクリーン印刷で全面塗布し、８０℃で２０分乾燥し、（ドライフィルムの場合は熱ラミネートし）室温まで放冷する。この基板にメタルハライドランプ搭載の露光装置（ＨＭＷ−６８０−ＧＷ２０）をもちいて最適露光量でソルダーレジストパターンを露光し、３０℃の１％Ｎａ２ＣＯ３水溶液をスプレー圧０．２ＭＰａの条件で６０秒間現像を行い、レジストパターンを得た。この基板を、１５０℃で６０分加熱して硬化した。得られたプリント基板（評価基板）に対して以下のように特性を評価した。
Characteristic test:
The composition of each of the above examples and comparative examples was applied on the entire surface of a patterned polyimide film substrate by screen printing, dried at 80 ° C. for 20 minutes, and then allowed to cool to room temperature (heat laminated in the case of a dry film). To do. The substrate is exposed to a solder resist pattern with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1% Na 2 CO 3 aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Development was performed for 2 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The characteristic was evaluated as follows with respect to the obtained printed circuit board (evaluation board).
＜はんだ耐熱性＞
ロジン系フラックスを塗布した評価基板を、予め２６０℃に設定したはんだ槽に浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
○：１０秒間浸漬を１回で剥がれが認められない。
△：１０秒間浸漬を１回で少し剥がれる。
×：１０秒間浸漬を１回でレジスト層に膨れ、剥がれがある。
<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed after one immersion for 10 seconds.
(Triangle | delta): It peels for a while for 10 seconds for a while.
X: The resist layer swells and peels off once in 10 seconds.
＜耐無電解金めっき性＞
評価基板に、市販品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い、テープピーリングにより、レジスト層の剥がれの有無やめっきのしみ込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
○：染み込み、剥がれが見られない。
△：めっき後にほんの僅かしみ込みが見られ、テープピール後に剥がれも見られる。
×：めっき後に剥がれが有る。
<Electroless gold plating resistance>
The evaluation substrate is plated using commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel 0.5 μm and gold 0.03 μm. After evaluating the presence or absence of penetration, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Infiltration and peeling are not seen.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.
＜電気特性＞
銅箔基板に代えてＩＰＣ Ｂ−２５のクシ型電極Ｂクーポンを用い、上記の条件で評価基板を作製し、このクシ型電極にＤＣ１００Ｖのバイアス電圧を印加し、８５℃、８５％Ｒ．Ｈ．の恒温恒湿槽にて１，０００時間後のマイグレーションの有無を確認した。判定基準は以下のとおりである。
○：全く変化が認められないもの
△：ほんの僅か変化したもの
×：マイグレーションが発生しているもの
<Electrical characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of a copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The presence or absence of migration after 1,000 hours was confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
○: No change at all △: Only a slight change ×: Migration has occurred
＜耐酸性＞
評価基板を１０ｖｏｌ％Ｈ２ＳＯ４水溶液に室温で３０分間浸漬し、染み込みや塗膜の溶け出し、さらにテープビールによる剥がれを確認した。判定基準は以下のとおり。
○：染み込み、溶け出し、剥がれなし。
△：染み込み、溶け出し、もしくは剥がれが少し確認される。
×：染み込み、溶け出し、もしくは剥がれが大きく確認される。
<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling by tape beer was confirmed. Judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.
＜難燃性＞
各実施例及び比較例の組成物を、２５μｍ厚のポリイミドフィルム（カプトン１００Ｈ）にスクリーン印刷で全面塗布し、８０℃で２０分乾燥して室温まで放冷する。さらに裏面を同様にスクリーン印刷で全面塗布し、８０℃で２０分乾燥して室温まで放冷し両面塗布基板を得た。この基板にメタルハライドランプ搭載の露光装置（ＨＭＷ−６８０−ＧＷ２０）を用いて最適露光量でソルダーレジストを全面露光し、３０℃の１％Ｎａ２ＣＯ３水溶液をスプレー圧０．２ＭＰａの条件で６０秒間現像を行い、１５０℃で６０分間熱硬化を行い評価サンプルとした。この難燃性評価用サンプルついて、ＵＬ９４規格に準拠した薄材垂直燃焼試験を行った。評価はＵＬ９４規格に基づいて、ＶＴＭ−０又はＶＴＭ−１と表した。
<Flame retardance>
The composition of each Example and Comparative Example is applied to a 25 μm-thick polyimide film (Kapton 100H) by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. Using this exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the entire surface of the solder resist was exposed to this substrate at an optimum exposure amount, and a 1% Na 2 CO 3 aqueous solution at 30 ° C. was applied under a spray pressure of 0.2 MPa. Development was performed for 1 second, and thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample. This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. Evaluation was expressed as VTM-0 or VTM-1 based on the UL94 standard.
＜可撓性（耐折性）の評価＞
難燃性評価用サンプルと同様に作成したサンプルを、ハゼ折りにより１８０°折り曲げを数回繰り返して行い、その際のカバーレイにおけるクラック発生状況を目視及びｘ２００の光学顕微鏡で観察し、クラックが発生し無かった回数を評価した。
<Evaluation of flexibility (fold resistance)>
A sample prepared in the same manner as the sample for flame retardancy evaluation was repeatedly bent 180 ° by goblet folding several times, and the crack occurrence in the coverlay at that time was observed visually and with an optical microscope of x200, and cracks were generated. We evaluated the number of times we did not.
前記各評価試験の結果を表２にまとめて示す。
実施例９
表１に示す実施例４に従って調製した感光性樹脂組成物をメチルエチルケトンで希釈し、キャリアフィルム上に塗布し、加熱乾燥して、厚さ２０μｍの感光性樹脂組成物層を形成し、その上にカバーフィルムを貼り合わせてドライフィルムを得た。その後、カバーフィルムを剥がし、パターン形成された銅箔基板に、フィルムを貼り合わせ、次いで、キャリアフィルムを剥がし、８０℃の熱風乾燥器で３０分、乾燥させ、その後、１５０℃の熱風乾燥器で６０分加熱硬化を行ない、試験基板を作製した。得られた硬化皮膜を有する試験基板について、前述した試験方法及び評価方法にて、各特性の評価試験を行なった。結果は、実施例４と同等であった。
Example 9
A photosensitive resin composition prepared according to Example 4 shown in Table 1 was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating to form a photosensitive resin composition layer having a thickness of 20 μm, on which A cover film was bonded to obtain a dry film. Thereafter, the cover film is peeled off, the film is bonded to the patterned copper foil substrate, and then the carrier film is peeled off and dried in a hot air dryer at 80 ° C. for 30 minutes, and then in a hot air dryer at 150 ° C. Heat curing was performed for 60 minutes to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The result was equivalent to Example 4.
Claims (17)
Ｒ３は、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ４及びＲ５は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ６及びＲ７は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、
Ｒ８及びＲ９は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、炭素数１〜１０の直鎖状又は分岐状のアルコキシ基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基若しくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ８及びＲ９の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい）。 The photopolymerization initiator (C) is an oxime ester photopolymerization initiator (C1) represented by the following general formula (II), or the oxime ester photopolymerization initiator (C1) and the following general formula ( It is a mixture with an aminoacetophenone photopolymerization initiator (C2) represented by III) and / or an acylphosphine oxide photopolymerization initiator (C3) represented by the following general formula (IV). The photosensitive resin composition as described in any one of Claims 1 thru | or 6.
R 3 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R 4 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R 8 and R 9 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, aryl Group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that one of R 8 and R 9 is an R—C (═O) — group (where R is a carbon number of 1 to 20 hydrocarbon groups).
Ｒ１1、Ｒ１3は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ１2は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表す。） The oxime ester photopolymerization initiator (C1) represented by the general formula (II) is an oxime ester photopolymerization initiator represented by the following formula (VI). Photosensitive resin composition
R 11 and R 13 are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R 12 is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted). )
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007148647A JP4616863B2 (en) | 2007-06-04 | 2007-06-04 | Photosensitive resin composition and flexible wiring board obtained using the same |
| TW097120484A TWI426347B (en) | 2007-06-04 | 2008-06-02 | A photosensitive resin composition, and a flexible circuit board using the same |
| KR1020080052168A KR100997862B1 (en) | 2007-06-04 | 2008-06-03 | Photosensitive resin composition, and flexible wiring board obtained by using the same |
| CN2008101086803A CN101320213B (en) | 2007-06-04 | 2008-06-04 | Light sensitive resin composition and flexible printed circuit board produced with the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007148647A JP4616863B2 (en) | 2007-06-04 | 2007-06-04 | Photosensitive resin composition and flexible wiring board obtained using the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2008299293A true JP2008299293A (en) | 2008-12-11 |
| JP2008299293A5 JP2008299293A5 (en) | 2010-07-15 |
| JP4616863B2 JP4616863B2 (en) | 2011-01-19 |
Family
ID=40172833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007148647A Active JP4616863B2 (en) | 2007-06-04 | 2007-06-04 | Photosensitive resin composition and flexible wiring board obtained using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4616863B2 (en) |
| KR (1) | KR100997862B1 (en) |
| CN (1) | CN101320213B (en) |
| TW (1) | TWI426347B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009031665A (en) * | 2007-07-30 | 2009-02-12 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using the same |
| JP2009251585A (en) * | 2008-04-11 | 2009-10-29 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using the same |
| JP2010191215A (en) * | 2009-02-18 | 2010-09-02 | Kyocera Chemical Corp | Photosensitive thermosetting resin composition and flexible printed wiring board |
| JP2010224168A (en) * | 2009-03-23 | 2010-10-07 | Taiyo Ink Mfg Ltd | Photo-curing thermosetting resin composition, its dry film, cured product, and printed wiring board using them |
| JP2010237488A (en) * | 2009-03-31 | 2010-10-21 | Toppan Printing Co Ltd | Photosensitive resin composition, color filter, and method of manufacturing the same |
| WO2010125720A1 (en) * | 2009-04-27 | 2010-11-04 | 太陽インキ製造株式会社 | Photo-curable and heat-curable resin composition |
| JP2011028129A (en) * | 2009-07-28 | 2011-02-10 | Kyocera Chemical Corp | Photosensitive heat curing-type resin composition and flexible printed wiring board |
| WO2011021350A1 (en) * | 2009-08-19 | 2011-02-24 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP2011099919A (en) * | 2009-11-04 | 2011-05-19 | Mitsubishi Chemicals Corp | Colored resin composition, color filter, liquid crystal display device, and organic el display |
| WO2011074528A1 (en) * | 2009-12-14 | 2011-06-23 | 太陽ホールディングス株式会社 | Photosensitive resin composition, dry film thereof, and printed wiring board formed using same |
| CN102741751A (en) * | 2010-02-01 | 2012-10-17 | 富士胶片株式会社 | Photosensitive composition, photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed board |
| JP2013049856A (en) * | 2012-10-01 | 2013-03-14 | Taiyo Holdings Co Ltd | Curable resin composition, and dry film and printed wiring board using the same |
| JP2013174920A (en) * | 2013-05-13 | 2013-09-05 | Taiyo Holdings Co Ltd | Photocurable thermosetting resin composition, dry film and cured product of the composition, and printed wiring board using the same |
| JP2013228722A (en) * | 2012-03-27 | 2013-11-07 | Taiyo Ink Mfg Ltd | Fire retardant curable resin composition, dry film, fire retardant coating and print circuit board |
| JP2013228723A (en) * | 2012-03-27 | 2013-11-07 | Taiyo Ink Mfg Ltd | Fire retardant curable resin composition, dry film, fire retardant coating and print circuit board |
| JP2015141303A (en) * | 2014-01-28 | 2015-08-03 | 太陽インキ製造株式会社 | Photosensitive thermosetting resin composition and flexible printed wiring board |
| WO2020080352A1 (en) * | 2018-10-19 | 2020-04-23 | 株式会社カネカ | Resin composition, cured film, printed wiring board with cured film, and method for producing same |
| CN116107163A (en) * | 2022-12-28 | 2023-05-12 | 上海玟昕科技有限公司 | Nanoparticle-containing positive photoresist composition |
| US11714033B2 (en) * | 2019-04-12 | 2023-08-01 | Gourgen AMBARTSOUMIAN | Tissue embedding cassette with shield |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5261242B2 (en) * | 2009-03-23 | 2013-08-14 | 太陽ホールディングス株式会社 | Curable resin composition, dry film and printed wiring board using the same |
| JP5377021B2 (en) * | 2009-03-23 | 2013-12-25 | 太陽ホールディングス株式会社 | Curable resin composition, dry film and printed wiring board using the same |
| JP5349113B2 (en) * | 2009-03-30 | 2013-11-20 | 太陽ホールディングス株式会社 | Photosensitive resin composition, dry film and printed wiring board using the same |
| JP5475350B2 (en) * | 2009-07-02 | 2014-04-16 | 太陽ホールディングス株式会社 | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them |
| WO2011034124A1 (en) * | 2009-09-18 | 2011-03-24 | 太陽インキ製造株式会社 | Photosensitive resin composition, dry film and cured product thereof, and printed wiring board using the same |
| JP5537566B2 (en) * | 2009-12-14 | 2014-07-02 | 太陽ホールディングス株式会社 | Solder resist ink composition and cured product thereof |
| JP6061440B2 (en) * | 2010-02-25 | 2017-01-18 | 太陽ホールディングス株式会社 | Resin composition for polyester substrate, dry film and printed wiring board using the same |
| KR101473556B1 (en) * | 2012-03-27 | 2014-12-16 | 다이요 잉키 세이조 가부시키가이샤 | Flame-retardant curable resin composition, dry film, flame-retardant coat and printed wiring board |
| JP5632978B1 (en) * | 2013-06-28 | 2014-11-26 | 太陽インキ製造株式会社 | Photocurable composition and cured product thereof |
| CN109957283B (en) * | 2019-02-27 | 2021-09-10 | 江苏艾森半导体材料股份有限公司 | High-flame-retardance solder resist ink |
| CN111665685A (en) * | 2019-03-08 | 2020-09-15 | 株式会社田村制作所 | Photosensitive resin composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006251715A (en) * | 2005-03-14 | 2006-09-21 | Kaneka Corp | Photosensitive resin composition having flame resistance and photosensitive dry film resist |
| WO2006129697A1 (en) * | 2005-05-31 | 2006-12-07 | Taiyo Ink Manufacturing Co., Ltd. | Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same |
| JP2007133377A (en) * | 2005-10-12 | 2007-05-31 | Toray Ind Inc | Photosensitive resin composition |
| JP2007304542A (en) * | 2006-04-13 | 2007-11-22 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element |
| WO2008066101A1 (en) * | 2006-12-01 | 2008-06-05 | Kyocera Chemical Corporation | Photosensitive heat curing-type resin composition and flexible printed wiring board |
| WO2008087812A1 (en) * | 2007-01-18 | 2008-07-24 | Showa Highpolymer Co., Ltd. | Phosphorus-containing flame retardant and curable flame -retarded resin compositions containing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001213889A (en) * | 2000-01-28 | 2001-08-07 | Nippon Shokubai Co Ltd | Reactive phosphorus compound |
| TW200417294A (en) * | 2002-11-28 | 2004-09-01 | Taiyo Ink Mfg Co Ltd | Photo- and thermo-setting resin composition and printed wiring boards made by using the same |
| CN100578359C (en) * | 2003-03-06 | 2010-01-06 | 日本化药株式会社 | Photosensitive resin composition and curing product thereof |
-
2007
- 2007-06-04 JP JP2007148647A patent/JP4616863B2/en active Active
-
2008
- 2008-06-02 TW TW097120484A patent/TWI426347B/en active
- 2008-06-03 KR KR1020080052168A patent/KR100997862B1/en active IP Right Grant
- 2008-06-04 CN CN2008101086803A patent/CN101320213B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006251715A (en) * | 2005-03-14 | 2006-09-21 | Kaneka Corp | Photosensitive resin composition having flame resistance and photosensitive dry film resist |
| WO2006129697A1 (en) * | 2005-05-31 | 2006-12-07 | Taiyo Ink Manufacturing Co., Ltd. | Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same |
| JP2007133377A (en) * | 2005-10-12 | 2007-05-31 | Toray Ind Inc | Photosensitive resin composition |
| JP2007304542A (en) * | 2006-04-13 | 2007-11-22 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element |
| WO2008066101A1 (en) * | 2006-12-01 | 2008-06-05 | Kyocera Chemical Corporation | Photosensitive heat curing-type resin composition and flexible printed wiring board |
| WO2008087812A1 (en) * | 2007-01-18 | 2008-07-24 | Showa Highpolymer Co., Ltd. | Phosphorus-containing flame retardant and curable flame -retarded resin compositions containing the same |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009031665A (en) * | 2007-07-30 | 2009-02-12 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using the same |
| JP2009251585A (en) * | 2008-04-11 | 2009-10-29 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using the same |
| JP2010191215A (en) * | 2009-02-18 | 2010-09-02 | Kyocera Chemical Corp | Photosensitive thermosetting resin composition and flexible printed wiring board |
| JP2010224168A (en) * | 2009-03-23 | 2010-10-07 | Taiyo Ink Mfg Ltd | Photo-curing thermosetting resin composition, its dry film, cured product, and printed wiring board using them |
| JP2010237488A (en) * | 2009-03-31 | 2010-10-21 | Toppan Printing Co Ltd | Photosensitive resin composition, color filter, and method of manufacturing the same |
| WO2010125720A1 (en) * | 2009-04-27 | 2010-11-04 | 太陽インキ製造株式会社 | Photo-curable and heat-curable resin composition |
| JP2010256728A (en) * | 2009-04-27 | 2010-11-11 | Taiyo Ink Mfg Ltd | Photocurable thermosetting resin composition, its dry film and cured product, and printed wiring board using the same |
| JP2011028129A (en) * | 2009-07-28 | 2011-02-10 | Kyocera Chemical Corp | Photosensitive heat curing-type resin composition and flexible printed wiring board |
| WO2011021350A1 (en) * | 2009-08-19 | 2011-02-24 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP2011099919A (en) * | 2009-11-04 | 2011-05-19 | Mitsubishi Chemicals Corp | Colored resin composition, color filter, liquid crystal display device, and organic el display |
| US20120250268A1 (en) * | 2009-12-14 | 2012-10-04 | Taiyo Holdings Co., Ltd. | Photosensitive resin composition, dry film thereof, and printed wiring board using them |
| WO2011074528A1 (en) * | 2009-12-14 | 2011-06-23 | 太陽ホールディングス株式会社 | Photosensitive resin composition, dry film thereof, and printed wiring board formed using same |
| JP2011123420A (en) * | 2009-12-14 | 2011-06-23 | Taiyo Holdings Co Ltd | Photosensitive resin composition, dry film thereof and printed wiring board using the same |
| US8962712B2 (en) | 2009-12-14 | 2015-02-24 | Taiyo Holdings Co., Ltd. | Photosensitive resin composition, dry film thereof, and printed wiring board using them |
| CN102741751B (en) * | 2010-02-01 | 2014-07-16 | 富士胶片株式会社 | Photosensitive composition, photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed board |
| CN102741751A (en) * | 2010-02-01 | 2012-10-17 | 富士胶片株式会社 | Photosensitive composition, photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed board |
| JP2013228722A (en) * | 2012-03-27 | 2013-11-07 | Taiyo Ink Mfg Ltd | Fire retardant curable resin composition, dry film, fire retardant coating and print circuit board |
| JP2013228723A (en) * | 2012-03-27 | 2013-11-07 | Taiyo Ink Mfg Ltd | Fire retardant curable resin composition, dry film, fire retardant coating and print circuit board |
| JP2013049856A (en) * | 2012-10-01 | 2013-03-14 | Taiyo Holdings Co Ltd | Curable resin composition, and dry film and printed wiring board using the same |
| JP2013174920A (en) * | 2013-05-13 | 2013-09-05 | Taiyo Holdings Co Ltd | Photocurable thermosetting resin composition, dry film and cured product of the composition, and printed wiring board using the same |
| JP2015141303A (en) * | 2014-01-28 | 2015-08-03 | 太陽インキ製造株式会社 | Photosensitive thermosetting resin composition and flexible printed wiring board |
| WO2020080352A1 (en) * | 2018-10-19 | 2020-04-23 | 株式会社カネカ | Resin composition, cured film, printed wiring board with cured film, and method for producing same |
| JPWO2020080352A1 (en) * | 2018-10-19 | 2021-09-30 | 株式会社カネカ | Resin composition, hardened film, printed wiring board with hardened film and its manufacturing method |
| JP7418343B2 (en) | 2018-10-19 | 2024-01-19 | 株式会社カネカ | Resin composition, cured film, printed wiring board with cured film, and manufacturing method thereof |
| US11714033B2 (en) * | 2019-04-12 | 2023-08-01 | Gourgen AMBARTSOUMIAN | Tissue embedding cassette with shield |
| CN116107163A (en) * | 2022-12-28 | 2023-05-12 | 上海玟昕科技有限公司 | Nanoparticle-containing positive photoresist composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI426347B (en) | 2014-02-11 |
| CN101320213A (en) | 2008-12-10 |
| TW200912533A (en) | 2009-03-16 |
| KR20080106855A (en) | 2008-12-09 |
| KR100997862B1 (en) | 2010-12-01 |
| CN101320213B (en) | 2012-07-04 |
| JP4616863B2 (en) | 2011-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4616863B2 (en) | Photosensitive resin composition and flexible wiring board obtained using the same | |
| JP5043516B2 (en) | Photocurable / thermosetting resin composition and printed wiring obtained using the same | |
| JP5513711B2 (en) | Photosensitive resin composition and cured product thereof | |
| JP5301915B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
| KR101073792B1 (en) | Photocurable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using the same | |
| JP5183073B2 (en) | Photocurable / thermosetting resin composition and cured product thereof | |
| JP5567543B2 (en) | Resin composition, cured product thereof and printed wiring board obtained using the same | |
| US20080096133A1 (en) | Photocurable and thermosetting resin composition, cured product thereof and printed circuit board obtained using the same | |
| JP5183425B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
| JP4831786B2 (en) | Photocurable / thermosetting resin composition, cured product and printed wiring board | |
| JP5384785B2 (en) | Resin composition, cured product thereof and printed wiring board obtained using the same | |
| JP2010113241A (en) | Photosetting resin composition, dry film and cured product of the same, and printed wiring board using them | |
| JP5043775B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
| JP5660690B2 (en) | Photosensitive resin composition and cured product thereof | |
| JP5113298B2 (en) | Photocurable / thermosetting resin composition and printed wiring board obtained using the same | |
| JP5164386B2 (en) | Photocurable / thermosetting resin composition and cured product thereof | |
| JP5575858B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
| JP5433209B2 (en) | Photocurable resin composition, dry film and cured product thereof, and printed wiring board using them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100128 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100602 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20100602 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20100617 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100629 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100830 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101005 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101022 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4616863 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131029 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |