JP6512532B2 - Photosensitive resin composition for urethane (meth) acrylate and dry film resist - Google Patents
Photosensitive resin composition for urethane (meth) acrylate and dry film resist Download PDFInfo
- Publication number
- JP6512532B2 JP6512532B2 JP2015114645A JP2015114645A JP6512532B2 JP 6512532 B2 JP6512532 B2 JP 6512532B2 JP 2015114645 A JP2015114645 A JP 2015114645A JP 2015114645 A JP2015114645 A JP 2015114645A JP 6512532 B2 JP6512532 B2 JP 6512532B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- photosensitive resin
- mass
- dry film
- 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.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 37
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 21
- -1 oxypropylene group Chemical group 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 125000006353 oxyethylene group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000036211 photosensitivity Effects 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000010410 layer Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000005187 foaming Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- MHDULSOPQSUKBQ-UHFFFAOYSA-N 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MHDULSOPQSUKBQ-UHFFFAOYSA-N 0.000 description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NPENBPVOAXERED-UHFFFAOYSA-N (4-benzoylphenyl)-phenylmethanone Chemical class C=1C=C(C(=O)C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 NPENBPVOAXERED-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SDTXSEXYPROZSZ-UHFFFAOYSA-N 1,2-dibromo-2-methylpropane Chemical compound CC(C)(Br)CBr SDTXSEXYPROZSZ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- 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
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- FEWDXGMBVQULLN-UHFFFAOYSA-N 1-hydroxy-2-phenyl-1,5,6,7-tetrahydro-4H-benzimidazol-4-one Chemical compound ON1C=2CCCC(=O)C=2N=C1C1=CC=CC=C1 FEWDXGMBVQULLN-UHFFFAOYSA-N 0.000 description 1
- BTUGGGLMQBJCBN-UHFFFAOYSA-N 1-iodo-2-methylpropane Chemical compound CC(C)CI BTUGGGLMQBJCBN-UHFFFAOYSA-N 0.000 description 1
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 description 1
- VYMSWGOFSKMMCE-UHFFFAOYSA-N 10-butyl-2-chloroacridin-9-one Chemical compound ClC1=CC=C2N(CCCC)C3=CC=CC=C3C(=O)C2=C1 VYMSWGOFSKMMCE-UHFFFAOYSA-N 0.000 description 1
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- TZWMFMSDVQGDTC-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-2-[2-(2,4-dichlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC(Cl)=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC(Cl)=CC=2)Cl)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 TZWMFMSDVQGDTC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- FJBTVNOKENFOFP-UHFFFAOYSA-N [1-[6-[4-[(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]-2-methylbenzoyl]-9-ethylcarbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C(C(=C1)C)=CC=C1OCC1COC(C)(C)O1 FJBTVNOKENFOFP-UHFFFAOYSA-N 0.000 description 1
- MKOCCXFKHVQLPW-UHFFFAOYSA-N [[1-oxo-1-(4-phenylsulfanylphenyl)butan-2-ylidene]amino] benzoate Chemical compound C=1C=C(SC=2C=CC=CC=2)C=CC=1C(=O)C(CC)=NOC(=O)C1=CC=CC=C1 MKOCCXFKHVQLPW-UHFFFAOYSA-N 0.000 description 1
- LOCXTTRLSIDGPS-UHFFFAOYSA-N [[1-oxo-1-(4-phenylsulfanylphenyl)octan-2-ylidene]amino] benzoate Chemical compound C=1C=C(SC=2C=CC=CC=2)C=CC=1C(=O)C(CCCCCC)=NOC(=O)C1=CC=CC=C1 LOCXTTRLSIDGPS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- FAJDWNKDRFAWLS-UHFFFAOYSA-N benzyl-[9-(diethylamino)benzo[a]phenoxazin-5-ylidene]azanium;chloride Chemical compound [Cl-].O1C2=CC(N(CC)CC)=CC=C2N=C(C2=CC=CC=C22)C1=CC2=[NH+]CC1=CC=CC=C1 FAJDWNKDRFAWLS-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- OQROAIRCEOBYJA-UHFFFAOYSA-N bromodiphenylmethane Chemical compound C=1C=CC=CC=1C(Br)C1=CC=CC=C1 OQROAIRCEOBYJA-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YDMWUMUNUXUYKT-UHFFFAOYSA-N ethyl [(1-oxo-1-phenylpropan-2-ylidene)amino] carbonate Chemical compound CCOC(=O)ON=C(C)C(=O)C1=CC=CC=C1 YDMWUMUNUXUYKT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は、光硬化およびアルカリ性水溶液による現像でパターン形成可能なドライフィルムレジスト用感光性樹脂組成物に用いられるウレタン（メタ）アクリレートおよびドライフィルムレジスト用感光性樹脂組成物に関する。 The present invention relates to a urethane (meth) acrylate for use in a photosensitive resin composition for a dry film resist which can be patterned by photocuring and development with an alkaline aqueous solution, and a photosensitive resin composition for a dry film resist.
パソコン、携帯電話等の電子機器には、部品や半導体などの実装用としてプリント配線板等が用いられる。プリント配線板等の製造用のレジストとしては、従来、支持体と感光性樹脂層と保護層を積層したドライフィルムレジストが用いられている。ここで用いられる感光性樹脂層は、現像液として弱アルカリ水溶液を用いるアルカリ現像型が一般的である。 In electronic devices such as personal computers and mobile phones, printed wiring boards and the like are used for mounting components and semiconductors. As a resist for manufacturing a printed wiring board etc., the dry film resist which laminated | stacked the support body, the photosensitive resin layer, and the protective layer conventionally is used. The photosensitive resin layer used here is generally an alkali developing type using a weak alkaline aqueous solution as a developer.
露光を行った後、現像液に未露光部分の感光性樹脂層を溶解もしくは分散除去し、ドライフィルムレジストに凹凸のパターンを描く現像工程がある。ドライフィルムレジストの成分はアルカリ可溶のカルボキシル基含有ポリマーと光重合性化合物であり、これが現像液中に溶解、分散をしているが、現像工程を繰返し行うことで、現像液分散性の悪い不溶解成分が増え、凝集物（スカム）が発生する。凝集物は基板上に再付着すると、パターン形成異常を引き起こし断線やショートといった不良原因となることから、凝集物発生は問題となっている。 After the exposure, the photosensitive resin layer in the unexposed area is dissolved or dispersed and removed in a developer, and there is a developing process for drawing a pattern of irregularities on the dry film resist. The components of the dry film resist are an alkali-soluble carboxyl group-containing polymer and a photopolymerizable compound, which are dissolved and dispersed in the developer, but the developer dispersion is poor by repeating the development step. Undissolved components increase and aggregates (scum) are generated. The occurrence of aggregates is a problem because the aggregates re-adhere to the substrate, causing pattern formation abnormalities and causing defects such as disconnections and shorts.
この凝集物発生の問題の解決のため、分子内にオキシアルキレン基を有するウレタン（メタ）アクリレートが光重合性化合物として用いられている（特許文献１〜７）。これらの技術では、オキシアルキレン基の構造に基づく界面活性によって現像液中の不溶性成分の凝集の抑制を図る技術である。 In order to solve the problem of the occurrence of aggregates, urethane (meth) acrylates having an oxyalkylene group in the molecule are used as photopolymerizable compounds (Patent Documents 1 to 7). These techniques are techniques for suppressing the aggregation of insoluble components in the developer by the surface activity based on the structure of the oxyalkylene group.
しかし、一方で、界面活性成分の使用により、現像液中の樹脂成分が泡立ちを起こし、現像液循環の妨げや、現像液と感光性樹脂層との接触を阻害し、未硬化部分の除去効率を下げるため、パターン形成異常の原因となってしまう。泡立ちを押さえようとすると、凝集物の発生を止めることができない。 However, on the other hand, the use of a surface active component causes the resin component in the developer to foam, thereby impeding developer circulation and inhibiting the contact between the developer and the photosensitive resin layer, and the removal efficiency of the uncured portion It causes the pattern formation abnormality to lower the If it is going to hold down foaming, it can not stop generating of an aggregate.
以上のように、ドライフィルムレジストとしての基本的な物性を維持しつつ、凝集物の発生と、現像液の泡立ちの抑制という、相反する課題を解決することが必要になった。 As described above, it is necessary to solve the contradictory problem of generation of aggregates and suppression of bubbling of the developer while maintaining basic physical properties as a dry film resist.
本発明は上記実情に鑑みてなされたものであり、その目的は、現像液中の凝集物の発生を抑制し、泡立ちを抑えることのできるドライフィルムレジスト用感光性樹脂組成物を提供することにある。 The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide a photosensitive resin composition for dry film resist which can suppress the generation of aggregates in a developer and can suppress foaming. is there.
上記目的を達成するために鋭意検討を重ねた結果、ドライフィルムレジスト用感光性樹脂組成物がオキシエチレン基とオキシプロピレン基をブロック状に連結した構造をもつウレタン（メタ）アクリレートとカルボキシル基を有するポリマーと光重合開始剤を必須の成分とすることにより、アルカリ現像液中の凝集物の発生を抑制し、かつ泡立ちを抑えることができることを見出し、本発明を完成するに至ったものである。 As a result of intensive studies to achieve the above object, the photosensitive resin composition for a dry film resist has a urethane (meth) acrylate having a structure in which an oxyethylene group and an oxypropylene group are linked in a block shape and a carboxyl group. By making a polymer and a photoinitiator into an essential component, it discovers that generation | occurrence | production of the aggregate in alkali developing solution can be suppressed, and foaming can be suppressed, and it came to complete this invention.
すなわち、本発明は次の〔１〕および〔２〕である
〔１〕 下記一般式（１）で示されることを特徴とする、ドライフィルムレジスト用感光性樹脂組成物用ウレタン（メタ）アクリレート。
Ｅ−Ｏはオキシエチレン基を表す。
Ｐ−Ｏはオキシプロピレン基を表す。
ｍは、前記オキシエチレン基の平均付加モル数を表し、ｎは、前記オキシプロピレン基の平均付加モル数を示し、ｍ＝４〜１５、ｎ＝３〜６、かつｍ／ｎ＝１．０〜４．０である。）
That is, the present invention is the following [1] and [2] [1] a urethane (meth) acrylate for a photosensitive resin composition for a dry film resist, which is characterized by the following general formula (1).
E-O represents an oxyethylene group.
PO represents an oxypropylene group.
m represents the average added mole number of the oxyethylene group, n represents the average added mole number of the oxypropylene group, m = 4 to 15, n = 3 to 6, and m / n = 1.0 ~ 4.0. )
［２］ 下記の（Ａ）成分を５〜７５質量％、（Ｂ）成分を２０〜９０質量％および（Ｃ）成分を０．１〜２０質量％含有することを特徴とする、ドライフィルムレジスト用感光性樹脂組成物。
（Ａ） 請求項１記載のウレタン（メタ）アクリレート
（Ｂ） 重量平均分子量が５，０００〜５００，０００であって、共重合成分の含有率が（メタ）アクリル酸１０〜４５質量％、スチレン５〜５５質量％である、カルボキシル基含有ポリマー
（Ｃ） 光重合開始剤
[2] A dry film resist characterized by containing 5 to 75% by mass of the following component (A), 20 to 90% by mass of the component (B) and 0.1 to 20% by mass of the component (C). Photosensitive resin composition.
(A) Urethane (meth) acrylate (B) according to claim 1 wherein the weight average molecular weight is 5,000 to 500,000, and the content of the copolymerization component is 10 to 45% by mass of (meth) acrylic acid, styrene Carboxyl group-containing polymer (C) having 5 to 55% by mass as a photopolymerization initiator
本発明のウレタン（メタ）アクリレートによって、現像液中の凝集物の発生を抑制し、泡立ちを抑えることのできるドライフィルムレジスト用感光性樹脂組成物が提供される。 With the urethane (meth) acrylate of the present invention, a photosensitive resin composition for a dry film resist can be provided which can suppress the generation of aggregates in a developer and can suppress foaming.
なお、特許文献１〜７には、ウレタン（メタ）アクリレートがそれぞれ一般式として記載されている。しかし、式（１）のｍ、ｎについて、実施例に具体的に開示されているのは、ｍ／ｎ＝０．１１の場合、ｍ／ｎ＝０．５６の場合、ｍ／ｎ＝０の場合、ｎ＝０の場合のみであり、本発明の顕著な作用効果については記載も示唆もない。 In each of Patent Documents 1 to 7, urethane (meth) acrylate is described as a general formula. However, for m and n in the formula (1), what is specifically disclosed in the examples is that m / n = 0.11, m / n = 0.56, m / n = 0 In the case of n = 0 only, and the remarkable effects of the present invention are neither described nor suggested.
以下に、本発明を詳細に説明する。
＜ウレタン（メタ）アクリレート：（Ａ）成分＞
（Ａ）成分である本発明のウレタン（メタ）アクリレートは、下記一般式（１）で示される構造を有しており、ドライフィルムレジスト用感光性樹脂組成物に用いられる。
Hereinafter, the present invention will be described in detail.
<Urethane (Meth) Acrylate: (A) Component>
The urethane (meth) acrylate of this invention which is (A) component has a structure shown by following General formula (1), and is used for the photosensitive resin composition for dry film resists.
本発明において、（メタ）アクリレートとは、アクリレートまたはメタクリレートを示す。また（メタ）アクリル酸についてもアクリル酸またはメタクリル酸を示す。 In the present invention, (meth) acrylate refers to acrylate or methacrylate. In addition, (meth) acrylic acid also indicates acrylic acid or methacrylic acid.
Ｅ−Ｏはオキシエチレン基を表す。
Ｐ−Ｏはオキシプロピレン基を表す。
ｍは、前記オキシエチレン基の平均付加モル数を表し、ｎは、前記オキシプロピレン基の平均付加モル数を表し、ｍ＝４〜１５、ｎ＝３〜６、かつｍ／ｎ＝１．０〜４．０である。）
E-O represents an oxyethylene group.
PO represents an oxypropylene group.
m represents the average added mole number of the oxyethylene group, n represents the average added mole number of the oxypropylene group, m = 4 to 15, n = 3 to 6, and m / n = 1.0 ~ 4.0. )
本ウレタン（メタ）アクリレートは、（メタ）アクリレートに基づくα，β光重合可能な不飽和化合物であるウレタン（メタ）アクリレート構造を分子内に含有する。上記一般式（１）で表される化合物において、アルカリ現像液への溶解性を付与する観点から親水性のオキシエチレン基を必要とし、また両親媒性構造により現像液中の凝集物発生の抑制や泡立ちの特性を制御する観点からオキシプロピレン基を必要とする。 The present urethane (meth) acrylate contains in its molecule a urethane (meth) acrylate structure which is an α, β-photopolymerizable unsaturated compound based on (meth) acrylate. In the compound represented by the above general formula (1), a hydrophilic oxyethylene group is required from the viewpoint of imparting solubility to an alkaline developer, and the generation of aggregates in the developer is suppressed by the amphiphilic structure. And oxypropylene groups are required in terms of controlling the foaming characteristics.
ｍは、オキシエチレン基の平均付加モル数を表し、４〜１５である。ｍが４より小さい場合は十分な親水性を持たずアルカリ現像液中の凝集物となりやすい。この観点から、ｍを４以上とする。また、ｍが１５より大きい場合は、親水性が高くなり現像残渣の溶け込んだアルカリ現像液が泡立ちしやすくなる。この観点から、ｍを１５以下とするが、１３以下が更に好ましい。 m represents the average added mole number of the oxyethylene group, and is 4 to 15. When m is smaller than 4, it does not have sufficient hydrophilicity and tends to form aggregates in an alkaline developer. From this viewpoint, m is 4 or more. On the other hand, when m is larger than 15, the hydrophilicity is high, and the alkaline developer having the development residue dissolved therein tends to foam. In this respect, m is 15 or less, preferably 13 or less.
ｎは、オキシプロピレン基の平均付加モル数を示し、３〜６であり、３〜５が更に好ましい。ｎが３より小さい場合はアルカリ現像液が泡立ちしやすくなり、ｎが６よりも大きい場合はアルカリ現像液中の凝集物となりやすい。 n represents the average added mole number of the oxypropylene group, and is 3 to 6, and 3 to 5 is more preferable. When n is smaller than 3, the alkaline developer tends to foam, and when n is larger than 6, it tends to be agglomerates in the alkaline developer.
またアルカリ現像液中の凝集物抑制と泡立ちを抑える物性を両立するために、ｍ／ｎ＝１．０〜４．０とする。ｍ／ｎは、１．５以上が更に好ましく、また、３．０以下が更に好ましい。 In addition, in order to achieve both suppression of aggregation in the alkaline developer and physical properties to suppress foaming, m / n is set to 1.0 to 4.0. m / n is more preferably 1.5 or more, and still more preferably 3.0 or less.
本ウレタン（メタ）アクリレートは、水酸基含有（メタ）アクリレート化合物２分子とヘキサメチレンジイソシアネート１分子のウレタン化反応により得られる。該水酸基含有（メタ）アクリレート化合物は、下記式（２）で表される構造を有する。 This urethane (meth) acrylate is obtained by the urethanization reaction of two hydroxyl-containing (meth) acrylate compounds and one molecule of hexamethylene diisocyanate. The hydroxyl group-containing (meth) acrylate compound has a structure represented by the following formula (2).
Ｒ１、Ｅ−Ｏ、Ｐ−Ｏ、ｍ、ｎは、式（１）におけるものと同じである。
この水酸基含有（メタ）アクリレート化合物は、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレートを基質とし、例えば特公昭４３−９０７１号公報に示されているルイス酸触媒を用いたカチオン重合による製法に従い、エチレンオキシドを開環重合させた後に、プロピレンオキシドを開環重合させ、中和剤や吸着剤等を用いて精製して得ることができる。
R 1 , E-O, P-O, m and n are the same as those in the formula (1).
This hydroxyl group-containing (meth) acrylate compound is prepared, for example, using 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate as a substrate, for example, a cationic acid polymerization method disclosed in JP-B-43-9071 using a Lewis acid catalyst. According to this, after ring-opening polymerization of ethylene oxide, it can be obtained by ring-opening polymerization of propylene oxide and purification using a neutralizing agent, an adsorbent and the like.
水酸基含有（メタ）アクリレート化合物とヘキサメチレンジイソシアネートとの反応は、２０〜１２０℃の温度範囲で必要に応じて公知慣用のウレタン化触媒を用いて行うことができる。ウレタン化触媒として塩基性触媒または酸性触媒のいずれかを用いることができる。塩基性触媒としては、例えば、ピリジン、トリエチルアミン、ジエチルアミン、ジブチルアミンなどのアミン類、トリブチルフォスフィン、トリフェニルフォスフィンなどのフォスフィン類を挙げることができる。また、酸性触媒としては、例えば、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、トリブトキシアルミニウム、トリチタニウムテトラブトキシド、ジルコニウムテトラブトキシドなどの金属アルコキシド類、塩化アルミニウムなどのルイス酸類、２−エチルヘキサン錫、オクチル錫トリラウレート、ジブチル錫ジラウレート、オクチル錫ジアセテートなどの錫化合物を挙げることができる。そのうちでも、少量の添加にて反応を加速しうる点から、酸性触媒が好ましく用いられ、特に前記した錫化合物の１種または２種以上がより好ましく用いられる。触媒の使用量は、（メタ）アクリレート化合物とヘキサメチレンジイソシアネートの合計質量に対して０．００５〜１質量％が好ましく、０．０１〜０．５質量％がより好ましい。 The reaction of the hydroxyl group-containing (meth) acrylate compound with hexamethylene diisocyanate can be carried out in the temperature range of 20 to 120 ° C., if necessary, using a known conventional urethanization catalyst. Either a basic catalyst or an acidic catalyst can be used as the urethanization catalyst. Examples of the basic catalyst include amines such as pyridine, triethylamine, diethylamine and dibutylamine, and phosphines such as tributylphosphine and triphenylphosphine. Moreover, as an acidic catalyst, for example, metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexane Mention may be made of tin compounds such as tin, octyltin trilaurate, dibutyltin dilaurate and octyltin diacetate. Among them, an acidic catalyst is preferably used in that it can accelerate the reaction with a small amount of addition, and in particular, one or more of the above-mentioned tin compounds are more preferably used. 0.005-1 mass% is preferable with respect to the total mass of a (meth) acrylate compound and hexamethylene diisocyanate, and, as for the usage-amount of a catalyst, 0.01-0.5 mass% is more preferable.
また、水酸基含有（メタ）アクリレート化合物が有する水酸基のモル数（ＯＨ）とヘキサメチレンジイソシアネートが有するイソシアネート基のモル数（ＮＣＯ）との比〔（ＯＨ）／（ＮＣＯ）〕の値は０．９０〜１．０２の範囲であることが好ましい。 In addition, the ratio [(OH) / (NCO)] of the number of moles of hydroxyl groups (OH) of the hydroxyl group-containing (meth) acrylate compound to the number of moles of isocyanate groups (NCO) of hexamethylene diisocyanate is 0.90. It is preferable to be in the range of -1.02.
水酸基含有（メタ）アクリレート化合物とヘキサメチレンジイソシアネートとの反応は、（メタ）アクリレート化合物とヘキサメチレンジイソシアネートを一括に仕込んで反応させる方法、（メタ）アクリレート化合物をヘキサメチレンジイソシアネートに滴下させる方法またはヘキサメチレンジイソシアネートを（メタ）アクリレート化合物に滴下させる方法等が挙げられる。 The reaction of the hydroxyl group-containing (meth) acrylate compound with hexamethylene diisocyanate is carried out by preparing the (meth) acrylate compound and hexamethylene diisocyanate in one batch and reacting them, a method of dropping the (meth) acrylate compound into hexamethylene diisocyanate or hexamethylene The method etc. which make diisocyanate drip to a (meth) acrylate compound are mentioned.
本発明の樹脂組成物は、上記のウレタン（メタ）アクリレート（Ａ）のほか、下記に説明するカルボキシル基含有ポリマー（Ｂ）、光重合開始剤（Ｃ）を含んでなる。 The resin composition of the present invention comprises, in addition to the above urethane (meth) acrylate (A), a carboxyl group-containing polymer (B) described below and a photopolymerization initiator (C).
＜（Ｂ）成分：カルボキシル基含有ポリマー＞
本発明に用いられるカルボキシル基含有ポリマー（Ｂ）は、アルカリ現像液への溶解性の観点から、共重合性成分として（メタ）アクリル酸およびスチレンから導かれる構成単位を分子中に有する。（メタ）アクリル酸に由来するカルボキシル基は、感光性樹脂にアルカリ水溶液に対する現像性や剥離性を与えるために必要である。
<(B) Component: Carboxyl Group-Containing Polymer>
The carboxyl group-containing polymer (B) used in the present invention has a structural unit derived from (meth) acrylic acid and styrene as a copolymerizable component in the molecule from the viewpoint of solubility in an alkaline developer. The carboxyl group derived from (meth) acrylic acid is necessary to give the photosensitive resin developability and releasability to an aqueous alkali solution.
カルボキシル基含有ポリマー（Ｂ）中の（メタ）アクリル酸の共重合成分としての含有率は１０〜４５質量％である。アルカリ現像液中の凝集物発生および泡立ち抑制の観点から２０〜４５質量％が好ましい。 The content rate as a copolymerization component of (meth) acrylic acid in a carboxyl group-containing polymer (B) is 10-45 mass%. 20-45 mass% is preferable from a viewpoint of aggregate generation | occurrence | production and bubbling suppression in alkali developing solution.
スチレンに由来する構成単位から、カルボキシル基含有ポリマー（Ｂ）の疎水性やドライフィルムレジストとしての物性が導かれる。カルボキシル基含有ポリマー（Ｂ）のスチレンの共重合成分としての含有率は５〜５５質量％である。アルカリ現像液中の凝集物発生および泡立ち抑制の観点から５〜４０質量％が好ましい。 The hydrophobicity of the carboxyl group-containing polymer (B) and the physical properties as a dry film resist are derived from the structural unit derived from styrene. The content of the carboxyl group-containing polymer (B) as a copolymerization component of styrene is 5 to 55% by mass. 5-40 mass% is preferable from a viewpoint of aggregate generation | occurrence | production and bubbling suppression in alkali developing solution.
カルボキシル基含有ポリマー（Ｂ）の重量平均分子量は、５０００〜５０００００である。カルボキシル基含有ポリマー（Ｂ）の重量平均分子量は、アルカリ現像液への溶解性の観点から５０００００以下であり、感光性樹脂の硬さの観点から５０００以上であり、１００００〜３０００００であることが好ましく、より好ましくは１００００〜１０００００である。重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）、移動層溶媒：テトラヒドロフラン、ポリスチレン標準サンプルにより重量平均分子量（ポリスチレン換算）として求められる。 The weight average molecular weight of the carboxyl group-containing polymer (B) is 5,000 to 500,000. The weight average molecular weight of the carboxyl group-containing polymer (B) is 500000 or less from the viewpoint of solubility in an alkaline developer, 5000 or more from the viewpoint of the hardness of the photosensitive resin, and preferably 10000-300000. More preferably, it is 10000-100000. The weight average molecular weight is determined as a weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC), mobile phase solvent: tetrahydrofuran, polystyrene standard sample.
本発明に用いられるカルボキシル基含有ポリマー（Ｂ）は、（メタ）アクリル酸、スチレンに加え、下記の単量体の中より、少なくとも一種の単量体を共重合させることができる。単量体として、分子中に重合性不飽和基を一個有するカルボン酸または酸無水物、例えば、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、マレイン酸無水物、マレイン酸半エステル等が挙げられ、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート等のアルキル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、（メタ）アクリロニトリル、フルフリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェニル（メタ）アクリレート、クレジル（メタ）アクリレート、ナフチル（メタ）アクリレート等のアリール（メタ）アクリレート、フェニル基を有するビニル化合物（例えば、スチレン）、メトキシベンジル（メタ）アクリレートやクロロベンジル（メタ）アクリレート等のベンジル（メタ）アクリレートの芳香環にアルコキシ基、ハロゲン、アルキル基等が置換した化合物等を用いることができる。 In addition to (meth) acrylic acid and styrene, the carboxyl group-containing polymer (B) used in the present invention can copolymerize at least one monomer out of the following monomers. Examples of the monomer include carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule, such as fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, etc. Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, Aryl (meth) acrylates such as furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, etc., having a phenyl group vinyl Compounds (eg, styrene), compounds in which an alkoxy group, a halogen, an alkyl group or the like is substituted on the aromatic ring of benzyl (meth) acrylate such as methoxybenzyl (meth) acrylate or chlorobenzyl (meth) acrylate can be used .
カルボキシル基含有ポリマー（Ｂ）は、（メタ）アクリル酸とスチレンと、必要に応じて上記の単量体を混合し、アセトン、メチルエチルケトン、またはイソプロパノール等の溶剤で希釈した溶液に、過酸化ベンゾイル、アゾイソブチロニトリル等のラジカル重合開始剤を適量添加し、加熱撹拌することにより合成を行うことが好ましい。混合物の一部を反応液に滴下しながら合成を行う場合もある。反応終了後、さらに溶剤を加えて、所望の濃度に調整する場合もある。合成手段としては、溶液重合以外に、塊状重合、懸濁重合、または乳化重合を用いてもよい。 The carboxyl group-containing polymer (B) is prepared by mixing (meth) acrylic acid and styrene and, if necessary, the above-mentioned monomers, and diluting with a solvent such as acetone, methyl ethyl ketone or isopropanol, benzoyl peroxide, It is preferable to carry out the synthesis by adding an appropriate amount of a radical polymerization initiator such as azoisobutyronitrile and heating and stirring. In some cases, synthesis is performed while a portion of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a synthesis means, bulk polymerization, suspension polymerization or emulsion polymerization may be used other than solution polymerization.
＜（Ｃ）成分：光重合開始剤＞
本発明に用いる光重合開始剤（Ｃ）としては、活性光線（例えば紫外線等）の作用により活性化されて（メタ）アクリル化合物の重合反応を開始させる化合物として一般に知られている光重合開始剤であれば特に限定されることはなく。例えば、アルキルフェノン化合物、ビイミダゾール化合物、トリアジン化合物、アシルホスフィンオキサイド化合物、オキシム化合物が挙げられる。
<(C) Component: Photopolymerization Initiator>
The photopolymerization initiator (C) to be used in the present invention is a photopolymerization initiator generally known as a compound which is activated by the action of an actinic ray (for example, ultraviolet light) to initiate the polymerization reaction of the (meth) acrylic compound. If it is, it will not be limited in particular. For example, an alkyl phenone compound, a biimidazole compound, a triazine compound, an acyl phosphine oxide compound, and an oxime compound are mentioned.
これらの光重合開始剤のうちでも、ビイミダゾール化合物、アルキルフェノン化合物およびオキシム化合物からなる群から選ばれる少なくとも１種を含む重合開始剤であることが好ましく、特にオキシム化合物およびビイミダゾール化合物からなる群から選ばれる少なくとも１種を含む重合開始剤であることがより好ましい。これらの重合開始剤であると、特に、高感度になる傾向があるため好ましい。 Among these photopolymerization initiators, a polymerization initiator containing at least one selected from the group consisting of biimidazole compounds, alkylphenone compounds and oxime compounds is preferable, and in particular, a group consisting of oxime compounds and biimidazole compounds It is more preferable that it is a polymerization initiator containing at least one selected from These polymerization initiators are particularly preferable because they tend to be highly sensitive.
前記のオキシム化合物としては、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−エトキシカルボニルオキシ−１−フェニルプロパン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン等が挙げられる。 Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropan-1-one-2-imine, N-Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- [I] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl}- 9H-carbazol-3-yl] ethane-1-imine and the like.
前記のビイミダゾール化合物としては、２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２，３−ジクロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール（例えば、特開平６−７５３７２号公報、特開平６−７５３７３号公報等参照）、２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラ（アルコキシフェニル）ビイミダゾール、２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラ（ジアルコキシフェニル）ビイミダゾール、２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラ（トリアルコキシフェニル）ビイミダゾール（例えば、特公昭４８−３８４０３号公報、特開昭６２−１７４２０４号公報等参照）、４，４’，５，５’−位のフェニル基がカルボアルコキシ基により置換されているイミダゾール化合物（例えば、特開平７−１０９１３号公報等参照）等が挙げられる。好ましくは２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２、３−ジクロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（２、４−ジクロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾールが挙げられる。 Examples of the above-mentioned biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,2, 3-Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) bi Imidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole (eg, JP-B-48-38403, JP-A-62-1) Referring 4204 JP, etc.), 4,4 ', phenyl 5,5'-position imidazole compound substituted by carbalkoxy group (for example, see Publication No. Hei 7-10913) and the like. Preferably, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4 And 4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.
さらに光重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４−ベンゾイル−４’−メチルジフェニルサルファイド、３，３’，４，４’−テトラ（ｔｅｒｔ−ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６−トリメチルベンゾフェノン等のベンゾフェノン化合物；９，１０−フェナンスレンキノン、２−エチルアントラキノン、カンファーキノン等のキノン化合物；１０−ブチル−２−クロロアクリドン、ベンジル、フェニルグリオキシル酸メチル、チタノセン化合物等が挙げられる。 Further, as a photopolymerization initiator, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ′ Benzophenone compounds such as -methyl diphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- And quinone compounds such as ethyl anthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
＜ドライフィルムレジスト用感光性樹脂組成物＞
以下に本発明のドライフィルムレジスト用感光性樹脂組成物の配合に関して説明する。
<Photosensitive resin composition for dry film resist>
The formulation of the photosensitive resin composition for a dry film resist of the present invention will be described below.
本発明に用いられるウレタン（メタ）アクリレート（Ａ）の割合は、ドライフィルムレジスト用感光性樹脂組成物の（Ａ）成分、（Ｂ）成分および（Ｃ）成分の合計量を１００質量％としたとき、５〜７５質量％の範囲である。ウレタン（メタ）アクリレート（Ａ）が５質量％未満では感度が不十分であり、また硬化物の硬さが不十分であるため現像時に正常なパターンが形成されない。この観点から、（Ａ）成分の割合を５質量％以上とするが、１５質量％以上が更に好ましい。また、（Ａ）成分の割合が７５質量％を超えると、感光性樹脂層が柔らかくなり過ぎ、支持体、感光性樹脂層、保護層の３層構造としたドライフィルムレジストをロールの形態で保存した時に感光性樹脂層がはみ出しを起こす現象が発生する。この観点から、（Ａ）成分の割合を７５質量％以下とするが、６０質量％以下が更に好ましい。 The proportion of the urethane (meth) acrylate (A) used in the present invention was 100 mass% of the total amount of the components (A), (B) and (C) of the photosensitive resin composition for dry film resist. When it is in the range of 5 to 75% by mass. When the amount of the urethane (meth) acrylate (A) is less than 5% by mass, the sensitivity is insufficient, and the hardness of the cured product is insufficient, so that a normal pattern is not formed during development. From this viewpoint, although the proportion of the component (A) is 5% by mass or more, 15% by mass or more is more preferable. When the proportion of the component (A) exceeds 75% by mass, the photosensitive resin layer becomes too soft, and the dry film resist having a three-layer structure of a support, a photosensitive resin layer, and a protective layer is stored in the form of a roll. When this occurs, a phenomenon occurs in which the photosensitive resin layer is pushed out. From this viewpoint, although the proportion of the component (A) is 75% by mass or less, 60% by mass or less is more preferable.
本発明に用いられるカルボキシル基含有ポリマー（Ｂ）の割合は、（Ａ）成分、（Ｂ）成分および（Ｃ）成分の合計量を１００質量％としたとき、２０〜９０質量％の範囲とする。カルボキシル基含有ポリマー（Ｂ）の割合が２０質量％未満では硬化物が脆くなりやすい。この観点から、カルボキシル基含有ポリマー（Ｂ）の割合を２０質量％以上とするが、４０質量％以上が更に好ましい。また、カルボキシル基含有ポリマー（Ｂ）の割合が９０質量％を超えると光感度が不十分になる。この観点から、カルボキシル基含有ポリマー（Ｂ）の割合を９０質量％以下とするが、７０質量％以下が更に好ましい。 The proportion of the carboxyl group-containing polymer (B) used in the present invention is in the range of 20 to 90% by mass, assuming that the total amount of the components (A), (B) and (C) is 100% by mass. . If the proportion of the carboxyl group-containing polymer (B) is less than 20% by mass, the cured product tends to be brittle. From this viewpoint, the proportion of the carboxyl group-containing polymer (B) is 20% by mass or more, and 40% by mass or more is more preferable. When the proportion of the carboxyl group-containing polymer (B) exceeds 90% by mass, the photosensitivity becomes insufficient. From this viewpoint, the proportion of the carboxyl group-containing polymer (B) is 90% by mass or less, preferably 70% by mass or less.
本発明に用いられる光重合開始剤（Ｃ）の割合は、ドライフィルムレジスト用感光性樹脂組成物の（Ａ）成分、（Ｂ）成分および（Ｃ）成分の合計量を１００質量％としたとき、０．１〜２０質量％の範囲とする。光感度の観点からは、光重合開始剤（Ｃ）の割合を０．１質量％以上とすることが好ましく、１．０質量％以上とすることが更に好ましい。また、光重合開始剤の割合が２０質量％を超えると感光性樹脂層の表層部での光吸収が増大して、底部の光硬化が不十分となる。この観点から、光重合開始剤（Ｃ）の割合を２０質量％以下とするが、１０質量％以下が更に好ましい。 The proportion of the photopolymerization initiator (C) used in the present invention is 100% by mass as the total of the components (A), (B) and (C) of the photosensitive resin composition for a dry film resist. And 0.1 to 20% by mass. From the viewpoint of photosensitivity, the proportion of the photopolymerization initiator (C) is preferably 0.1% by mass or more, and more preferably 1.0% by mass or more. In addition, when the proportion of the photopolymerization initiator exceeds 20% by mass, light absorption in the surface layer portion of the photosensitive resin layer is increased, and photocuring of the bottom portion becomes insufficient. From this viewpoint, the proportion of the photopolymerization initiator (C) is set to 20% by mass or less, and 10% by mass or less is more preferable.
上記（Ａ）、（Ｂ）、（Ｃ）の成分をはじめとする各成分を一括配合しても良いし、各成分を溶剤に溶解した後に逐次配合しても良い。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解して樹脂組成物を調製しても良いし、必要に応じては各成分を適宜２つ以上の溶液としておいて、使用時（塗布時）にこれらの溶液を混合して樹脂組成物として調製しても良い。 The respective components including the components (A), (B) and (C) may be blended at one time, or may be sequentially blended after the respective components are dissolved in a solvent. In addition, the order of introduction and working conditions at the time of blending are not particularly limited. For example, all components may be simultaneously dissolved in a solvent to prepare a resin composition, or, if necessary, each component may be appropriately prepared as two or more solutions, and these solutions may be used at the time of application (at the time of application) May be mixed to prepare a resin composition.
本発明のドライフィルムレジスト用感光性樹脂組成物には、前述した成分以外に加えて、染料、顔料等の着色物質を添加してもよい。このような着色物質としては、例えば、フタロシアニングリーン、クリスタルバイオレット、メチルオレンジ、ナイルブルー２Ｂ、ビクトリアブルー、マラカイトグリーン、ベイシックブルー２０、およびダイアモンドグリーン等が挙げられる。 In addition to the components described above, a coloring substance such as a dye or a pigment may be added to the photosensitive resin composition for a dry film resist of the present invention. As such a coloring substance, for example, phthalocyanine green, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green and the like can be mentioned.
また露光により可視像を与えることができるように、本発明のドライフィルムレジスト用感光性樹脂組成物には発色剤を添加しても良い。このような発色系染料としては、ロイコ染料または、フルオラン染料とハロゲン化合物との組み合わせが挙げられる。該ハロゲン化合物としては、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンザル、臭化メチレン、トリブロモメチルフェニルスルホン、四臭化炭素、トリス（２，３−ジブロモプロピル）ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、１，１，１−トリクロロ−２，２−ビス（ｐ−クロロフェニル）エタン、ヘキサクロロエタン、およびクロル化トリアジン化合物等が挙げられる。 In addition, a color former may be added to the photosensitive resin composition for a dry film resist of the present invention so that a visible image can be given by exposure. As such a color forming dye, a leuco dye or a combination of a fluoran dye and a halogen compound can be mentioned. Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethyl phenyl sulfone, carbon tetrabromide, tris (2, 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, chlorinated triazine compounds, and the like. .
さらに本発明のドライフィルムレジスト用感光性樹脂組成物の熱安定性、保存安定性を向上させる目的で、ドライフィルムレジスト用感光性樹脂組成物にラジカル重合禁止剤を添加することもできる。 Furthermore, for the purpose of improving the thermal stability and storage stability of the photosensitive resin composition for dry film resist of the present invention, a radical polymerization inhibitor may be added to the photosensitive resin composition for dry film resist.
本発明のドライフィルムレジスト用感光性樹脂組成物は、溶媒を添加したドライフィルムレジスト用感光性樹脂組成物溶液としても良い。好適な溶媒として、メチルエチルケトンに代表されるケトン系溶媒、並びにメタノール、エタノール、およびイソプロパノール等に代表されるアルコール類が挙げられる。ドライフィルムレジスト用感光性樹脂組成物溶液の粘度は２５℃で５００〜４０００ｍＰａ・ｓｅｃとなるように溶媒を添加することが好ましい。 The photosensitive resin composition for a dry film resist of the present invention may be a solution of a photosensitive resin composition for a dry film resist to which a solvent is added. Suitable solvents include ketone solvents represented by methyl ethyl ketone, and alcohols represented by methanol, ethanol, isopropanol and the like. It is preferable to add a solvent so that the viscosity of the photosensitive resin composition solution for dry film resist becomes 500 to 4000 mPa · sec at 25 ° C.
本発明のドライフィルムレジスト用感光性樹脂組成物は、支持体上に本発明のドライフィルムレジスト用感光性樹脂組成物を塗布および乾燥してなるドライフィルムレジスト用感光性樹脂組成物層を形成し、必要により感光性樹脂層の支持体と反対側の表面に保護層を有する積層体とすることでドライフィルムレジストとして使用できる。ここで用いられる支持体は、露光光源からの光を透過する透明なものが望ましく、例えば、ポリエチレンテレフタレートフィルム、ポリビニルアルコールフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリ塩化ビニリデンフィルム、塩化ビニリデン共重合フィルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、およびセルロース誘導体フィルム等が挙げられる。これらのフィルムは、必要に応じて延伸されたものを使用することができる。ヘーズは５以下のものが好ましい。フィルムの厚みは、薄い方が画像形成性および経済性の観点から好ましいが、強度を維持する必要等から、１０〜３０μｍのものが好ましく使用される。 The photosensitive resin composition for dry film resist of the present invention forms a photosensitive resin composition layer for dry film resist, which is obtained by applying and drying the photosensitive resin composition for dry film resist of the present invention on a support. If necessary, it can be used as a dry film resist by forming a laminate having a protective layer on the surface of the photosensitive resin layer opposite to the support. The support used herein is preferably a transparent one that transmits light from an exposure light source, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, chloride A vinylidene copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film etc. are mentioned. These films can be stretched if necessary. The haze is preferably 5 or less. The thickness of the film is preferably as thin as possible from the viewpoint of image formability and economy, but from the viewpoint of necessity to maintain the strength, a film of 10 to 30 μm is preferably used.
保護層について、ポリエチレンフィルムやポリプロピレンフィルム等が好ましく使用できる。保護層の厚みは１０〜１００μｍが好ましく、１０〜５０μｍがさらに好ましい。 A polyethylene film, a polypropylene film, etc. can be preferably used about a protective layer. 10-100 micrometers is preferable and, as for the thickness of a protective layer, 10-50 micrometers is more preferable.
本発明のドライフィルムレジスト用感光性樹脂組成物を用いた積層体の厚みは、好ましくは５〜１００μｍ、より好ましくは７〜６０μｍである。厚みが薄いほど解像度は向上し、厚みが厚いほど膜強度が増すため、用途に応じて適宜選択することができる。 The thickness of the laminate using the photosensitive resin composition for a dry film resist of the present invention is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the thickness, the higher the film strength. Therefore, the thickness can be appropriately selected according to the application.
支持体、感光性樹脂層、必要に応じて保護層を順次積層して、ドライフィルムレジスト用感光性樹脂組成物の積層体を作成する方法は、従来知られている方法を採用することができる。例えば、感光性樹脂層に用いるドライフィルムレジスト用感光性樹脂組成物を、前述のドライフィルムレジスト用感光性樹脂組成物溶液に調製しておき、支持体上にバーコーターやロールコーターを用いて塗布して乾燥させ、支持体上に該ドライフィルムレジスト用感光性樹脂組成物からなる感光性樹脂層を積層する。次いで、必要に応じて感光性樹脂層の上に保護層を積層することにより感光性樹脂積層体を作成することができる。 A conventionally known method can be employed as a method of forming a laminate of a photosensitive resin composition for a dry film resist by sequentially laminating a support, a photosensitive resin layer, and a protective layer as necessary. . For example, the photosensitive resin composition for a dry film resist used for the photosensitive resin layer is prepared in the above-mentioned photosensitive resin composition solution for a dry film resist, and coated on a support using a bar coater or a roll coater. Dried, and a photosensitive resin layer composed of the photosensitive resin composition for dry film resist is laminated on a support. Subsequently, a photosensitive resin laminated body can be created by laminating | stacking a protective layer on the photosensitive resin layer as needed.
以下に、実施例を挙げて本発明をさらに詳細に説明する。
（合成例１）
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、ポリオキシエチレンポリオキシプロピレンモノメタクリレート（オキシエチレン基の繰り返し単位数＝１２、オキシプロピレン基の繰り返し単位数＝５、水酸基価＝６５ｍｇＫＯＨ／ｇ；実測値、ブロック付加）４５６部、ヘキサメチレンジイソシアネート（デュラネートＨＤＩ−５０Ｍ、旭化成ケミカルズ（株）製、ＮＣＯ含量５０％（質量％））４４部、ジブチルスズジラウレート（以下、「ＤＢＴＤＬ」という。）０．０１部、ハイドロキノンモノメチルエーテル（以下、「ＭＥＨＱ」という。）０．０１部を投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
Hereinafter, the present invention will be described in more detail by way of examples.
Synthesis Example 1
A polyoxyethylene polyoxypropylene monomethacrylate (number of repeating units of oxyethylene group = 12, number of repeating units of oxypropylene group = 5, hydroxyl value = 65 mg KOH / g; measured value, block addition) 456 parts hexamethylene diisocyanate (Duranate HDI-50M, manufactured by Asahi Kasei Chemicals, NCO content 50% (% by mass)) 44 parts dibutyltin dilaurate (hereinafter referred to as "DBTDL" ) 0.01 parts of hydroquinone monomethyl ether (hereinafter referred to as "MEHQ") was added. The equivalent ratio of isocyanate group / hydroxyl group at this time is 1.0.
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ １６０３−１の方法でイソシアネート基含有量が０．０５％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、ウレタンアクリレート（ａ−１）を５００部得た。 Next, while blowing air, the internal temperature is maintained at 60 ° C. and the reaction is performed for 5 hours, and the isocyanate group content is 0.05% or less by the method of JIS K 1603-1, and almost all of the isocyanate groups are hydroxyl groups. It confirmed that it reacted and urethane bond was formed, and 500 parts of urethane acrylate (a-1) were obtained.
得られたウレタン（メタ）アクリレート（ａ−１）は、一般式（１）においてＲ１がメチル基、ｍが１２、ｎが５である化合物である。２５℃における粘度は１２５０ｍＰａ・ｓであった。 The obtained urethane (meth) acrylate (a-1) is a compound in which R 1 is a methyl group, m is 12 and n is 5 in the general formula (1). The viscosity at 25 ° C. was 1250 mPa · s.
（合成例２、３）
ＥＯとＰＯの鎖長の異なるポリオキシエチレンポリオキシプロピレンモノメタクリレートと、成分配合量を変えた以外は合成例１と同じにして、本発明に用いるウレタン（メタ）アクリレート（ａ−２）、（ａ−３）の合成を行った。配合量を合成結果とともに表１に示す。
(Composition examples 2 and 3)
Urethane (meth) acrylates (a-2), (a-2), ((a-2), (a-2), (a-2), (a-2), used in the present invention) The synthesis of a-3) was performed. The compounding amounts are shown in Table 1 together with the synthesis results.
（比較合成例１〜３）
ＥＯとＰＯの鎖長の異なるポリオキシエチレンポリオキシプロピレンモノメタクリレートと、成分配合量を変えた以外は合成例１と同じにして、本発明に用いるのとは異なるウレタン（メタ）アクリレート（ａ’−１）〜（ａ’−３）の合成を行った。配合量を合成結果とともに表１に示す。
(Comparative synthesis examples 1 to 3)
A urethane (meth) acrylate (a ') different from that used in the present invention is the same as in Synthesis Example 1 except that polyoxyethylene polyoxypropylene monomethacrylates having different chain lengths of EO and PO and the component blending amounts are changed. -1) to (a'-3) were synthesized. The compounding amounts are shown in Table 1 together with the synthesis results.
表１のウレタン（メタ）アクリレートを用いたドライフィルムレジスト用感光性樹脂組成物の配合を表２に示す。 The composition of the photosensitive resin composition for dry film resist using the urethane (meth) acrylate of Table 1 is shown in Table 2.
表中に記載した使用材料の詳細は次の通りである。
カルボキシル基含有ポリマー（Ｂ）
（ｂ−１）：
メタクリル酸／メタクリル酸メチル／スチレン＝４０／５０／１０（質量比）、重量平均分子量＝５０，０００
（ｂ−２）：
メタクリル酸／メタクリル酸メチル／スチレン＝３０／４０／３０（質量比）、重量平均分子量＝８０，０００
光重合開始剤（Ｃ）
（ｃ−１）：
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール
The details of the materials used in the table are as follows.
Carboxyl group-containing polymer (B)
(B-1):
Methacrylic acid / methyl methacrylate / styrene = 40/50/10 (mass ratio), weight average molecular weight = 50,000
(B-2):
Methacrylic acid / methyl methacrylate / styrene = 30/40/30 (mass ratio), weight average molecular weight = 80,000
Photopolymerization initiator (C)
(C-1):
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole
＜アルカリ現像液とドライフィルムレジスト用感光性樹脂組成物による配合液＞
１％炭酸ナトリウム水溶液／ドライフィルムレジスト用感光性樹脂組成物＝４００／１（ｗｔ）とした配合液を調製した。
＜泡立ち評価＞
３０℃に温調した配合液を５０ｍＬスクリュー管に４０ｍＬ充填し、蓋をして１００回／３０秒の速さで上下に振とうし、振とう終了直後から発生した気泡が完全に消失するまでの時間を測定した。発生した気泡が消失するまでの時間が短いほど、低起泡性であることを表す。３０秒以内に泡が消失するものを◎、６０秒以内に泡が消失するものを○、６０秒を超えるものを×と評価した。
<Composition of alkaline developer and photosensitive resin composition for dry film resist>
A mixed solution of 1% aqueous sodium carbonate solution / photosensitive resin composition for dry film resist = 400/1 (wt) was prepared.
<Fathering evaluation>
Fill 50 mL of the mixed solution that has been thermostated at 30 ° C in 40 mL, cover it, shake up and down 100 times / 30 seconds, and until bubbles generated immediately after the end of shaking completely disappear Time was measured. The shorter the time until the generated air bubbles disappear, the lower the foamability. Evaluations were made as も の for foams that disappeared within 30 seconds, ○ for foams that disappeared within 60 seconds, and × for those that exceeded 60 seconds.
＜分散性評価＞
３０℃に温調した配合液を５０ｍＬスクリュー管に４０ｍＬ充填し、蓋をして１００回／３０秒の速さで上下に振とうし、振とう後３０分間静置して下部の沈殿物を目視にて確認した。沈殿物の量が少量ほど、分散性が良好であることを表す。沈殿物が全く認められないものを◎、沈殿物が僅かに認められるものを○、沈殿物が多量に認められるものを×と評価した。
<Dispersibility evaluation>
Fill 40 mL of the mixed solution thermostated at 30 ° C in a 50 mL screw tube, shake the lid up and down 100 times / 30 seconds, shake and let stand for 30 minutes after shaking. It confirmed visually. The smaller the amount of precipitate, the better the dispersibility. Those with no precipitate at all were evaluated as ◎, those with slight precipitates were evaluated as ○, and those with a large amount of precipitates were evaluated as x.
実施例１〜４は、本発明のドライフィルムレジスト用感光性樹脂組成物を用いることにより、現像液中での凝集物の発生を抑え、泡立ちが低いことがわかった。 By using the photosensitive resin composition for dry film resists of this invention, Examples 1-4 suppressed generation | occurrence | production of the aggregate in a developing solution, and it turned out that foaming is low.
比較例１ではｎが本発明の範囲外であり、泡立ちが高い。
比較例２ではｍ、ｎが範囲外かつｍ／ｎが範囲外であり、泡立ちがあり、分散性が不良である。
比較例３ではｎが範囲外かつｍ／ｎが範囲外であり、泡立ちがあり、分散性が不良である。
In Comparative Example 1, n is outside the scope of the present invention, and bubbling is high.
In Comparative Example 2, m and n are out of the range and m / n is out of the range, and there is foaming and the dispersibility is poor.
In Comparative Example 3, n is out of the range and m / n is out of the range, and there is foaming and the dispersibility is poor.
＜ドライフィルムレジスト用感光性樹脂組成物としての評価＞
実施例１〜４に、着色剤ロイコクリスタルバイオレットを混合したドライフィルムレジスト用感光性樹脂組成物を使用し、厚さ２０μｍのポリエチレンテレフタレートフィルム上にバーコーターを用いて厚さ４０μｍの感光性樹脂層を作製した。銅張積層板上にラミネーターによりラミネートして積層体を得た後、ラインとスペース幅が１：１のライン＆スペースパターンをパターンマスクとして用いて、超高圧水銀ランプにより５０ｍＪ／ｃｍ２の露光量で露光した。ポリエチレンテレフタレートフィルムを剥離した後、３０℃の１質量％炭酸ナトリウム水溶液を所定時間スプレーし、感光性樹脂層の未露光部分を溶解除去した。この結果、現像後の銅張積層板への密着性、硬化レジストラインが正常に形成されており、設計どおりのドライフィルムレジストを得ることができた。
<Evaluation as a photosensitive resin composition for dry film resists>
The photosensitive resin composition for dry film resists which mixed the coloring agent leuco crystal violet is used for Examples 1-4, and a photosensitive resin layer with a thickness of 40 micrometers using a bar coater on a polyethylene terephthalate film with a thickness of 20 micrometers. Was produced. After laminating with a laminator on a copper-clad laminate to obtain a laminate, the exposure amount of 50 mJ / cm 2 with a super high pressure mercury lamp using a line & space pattern with a line and space width of 1: 1 as a pattern mask Exposed. After peeling the polyethylene terephthalate film, a 1% by mass sodium carbonate aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove the unexposed part of the photosensitive resin layer. As a result, adhesion to a copper-clad laminate after development and a cured resist line were formed properly, and a dry film resist as designed could be obtained.
本発明のドライフィルムレジスト用感光性樹脂組成物を用いたドライフィルムレジストは、現像時の現像液中の凝集物の発生を抑制し、泡立ちを抑えることができるため、アルカリ現像型プリント配線板、リードフレームおよび半導体パッケージ用基板を作製するためのドライフィルムレジストとして有用である。
The dry film resist using the photosensitive resin composition for a dry film resist of the present invention can suppress the generation of aggregates in a developing solution at the time of development and can suppress foaming, so an alkali development type printed wiring board, It is useful as a dry film resist for producing a lead frame and a substrate for a semiconductor package.
Claims (2)
Ｅ−Ｏはオキシエチレン基を表す。
Ｐ−Ｏはオキシプロピレン基を表す。
ｍは、前記オキシエチレン基の平均付加モル数を表し、ｎは、前記オキシプロピレン基の平均付加モル数を示し、ｍ＝４〜１５、ｎ＝３〜６、かつｍ／ｎ＝１．０〜４．０である。）
Urethane (meth) acrylate for photosensitive resin composition for dry film resists characterized by having the following general formula (1).
E-O represents an oxyethylene group.
PO represents an oxypropylene group.
m represents the average added mole number of the oxyethylene group, n represents the average added mole number of the oxypropylene group, m = 4 to 15, n = 3 to 6, and m / n = 1.0 ~ 4.0. )
（Ａ） 請求項１記載のウレタン（メタ）アクリレート
（Ｂ） 重量平均分子量が５，０００〜５００，０００であって、共重合成分の含有率が（メタ）アクリル酸１０〜４５質量％、スチレン５〜５５質量％である、カルボキシル基含有ポリマー
（Ｃ） 光重合開始剤
Photosensitivity for dry film resist characterized by containing 5 to 75% by mass of the following component (A), 20 to 90% by mass of the component (B) and 0.1 to 20% by mass of the component (C) Resin composition.
(A) Urethane (meth) acrylate (B) according to claim 1 wherein the weight average molecular weight is 5,000 to 500,000, and the content of the copolymerization component is 10 to 45% by mass of (meth) acrylic acid, styrene Carboxyl group-containing polymer (C) having 5 to 55% by mass as a photopolymerization initiator
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015114645A JP6512532B2 (en) | 2015-06-05 | 2015-06-05 | Photosensitive resin composition for urethane (meth) acrylate and dry film resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015114645A JP6512532B2 (en) | 2015-06-05 | 2015-06-05 | Photosensitive resin composition for urethane (meth) acrylate and dry film resist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017003641A JP2017003641A (en) | 2017-01-05 |
| JP6512532B2 true JP6512532B2 (en) | 2019-05-15 |
Family
ID=57752006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015114645A Active JP6512532B2 (en) | 2015-06-05 | 2015-06-05 | Photosensitive resin composition for urethane (meth) acrylate and dry film resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6512532B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111123647B (en) * | 2020-01-14 | 2023-04-25 | 广东省石油与精细化工研究院 | Dry film photoresist and application thereof |
| WO2021220980A1 (en) * | 2020-04-28 | 2021-11-04 | 富士フイルム株式会社 | Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel |
| CN113126434B (en) * | 2021-04-14 | 2023-08-29 | 福斯特(安吉)新材料有限公司 | Dry film resist |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3251446B2 (en) * | 1994-12-21 | 2002-01-28 | 日立化成工業株式会社 | Photosensitive resin composition and photosensitive element |
| US6069217A (en) * | 1997-03-07 | 2000-05-30 | Rheox, Inc. | Urethane-acrylic copolymer thickening compositions for aqueous systems |
| JP2001117225A (en) * | 1999-10-14 | 2001-04-27 | Asahi Kasei Corp | Photosensitive resin composition |
| JP3775174B2 (en) * | 2000-06-08 | 2006-05-17 | 日立プラント建設株式会社 | Microorganism immobilization carrier in which microorganisms are comprehensively immobilized |
| JP2002023351A (en) * | 2000-07-05 | 2002-01-23 | Toray Ind Inc | Photosensitive paste and member for display |
| JP2002216845A (en) * | 2001-01-18 | 2002-08-02 | Nippon Synthetic Chem Ind Co Ltd:The | Solid polymer electrolyte, electrochemical element using the same, and secondary cell |
| JP4352663B2 (en) * | 2001-07-31 | 2009-10-28 | 東レ株式会社 | Photosensitive ceramic composition |
| JP3883540B2 (en) * | 2002-03-12 | 2007-02-21 | 旭化成エレクトロニクス株式会社 | Photosensitive resin composition and use thereof |
| JP2005044681A (en) * | 2003-07-24 | 2005-02-17 | Nippon Synthetic Chem Ind Co Ltd:The | Binder composition for lithium secondary battery electrode, electrode for lithium secondary battery, and lithium secondary battery and manufacturing method thereof |
| JP5025894B2 (en) * | 2004-04-06 | 2012-09-12 | 住友ベークライト株式会社 | UV curable antifogging composition, cured product and molded product |
| JP4749270B2 (en) * | 2006-08-03 | 2011-08-17 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and laminate |
| JP2008090223A (en) * | 2006-10-05 | 2008-04-17 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern and method for producing printed wiring board |
| JP4979391B2 (en) * | 2007-01-17 | 2012-07-18 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
| JP5465928B2 (en) * | 2009-06-01 | 2014-04-09 | 旭化成イーマテリアルズ株式会社 | Photopolymerizable resin composition and use thereof |
| JP5921914B2 (en) * | 2012-03-01 | 2016-05-24 | ハリマ化成株式会社 | Coating material, method for producing the same, and coating composition |
-
2015
- 2015-06-05 JP JP2015114645A patent/JP6512532B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017003641A (en) | 2017-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5155853B2 (en) | Photosensitive resin laminate | |
| JP4781434B2 (en) | Photosensitive resin composition and laminate | |
| JP4761909B2 (en) | Photosensitive resin composition and laminate | |
| CN105474094B (en) | Photosensitive resin element | |
| JP6207654B2 (en) | Photosensitive resin composition | |
| JPWO2017043544A1 (en) | Photosensitive resin composition | |
| JP6512532B2 (en) | Photosensitive resin composition for urethane (meth) acrylate and dry film resist | |
| JP5777461B2 (en) | Photosensitive resin composition | |
| JP4395384B2 (en) | Photosensitive resin composition and laminate | |
| JP4578269B2 (en) | Photopolymerizable resin composition | |
| JP2006234995A5 (en) | ||
| JP2010286796A (en) | Photosensitive resin composition | |
| JP5948543B2 (en) | Photosensitive resin composition | |
| CN108375874B (en) | Photosensitive resin composition, photosensitive resin laminate, substrate having resist pattern formed thereon, and method for producing circuit board | |
| JP5260745B2 (en) | Photosensitive resin composition, photosensitive resin laminate, and resist pattern forming method | |
| JP4535851B2 (en) | Photopolymerizable resin composition | |
| JP6981864B2 (en) | A method for manufacturing a photosensitive resin composition, a photosensitive resin laminate, a substrate on which a resist pattern is formed, and a circuit board. | |
| JP5646873B2 (en) | Photosensitive resin composition and laminate thereof | |
| JP2009229655A (en) | Photosensitive resin composition and laminated body | |
| TW202331417A (en) | Photosensitive resin multilayer body and method for producing same | |
| JP5612862B2 (en) | Dry film resist roll | |
| JP4716347B2 (en) | Dry film resist | |
| WO2003077035A1 (en) | Photosensitive resin composition and use thereof | |
| JP4488601B2 (en) | Photosensitive resin laminate | |
| JP5469399B2 (en) | Photosensitive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180409 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190307 |
|
| 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: 20190318 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6512532 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190331 |
|
| 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 |